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Title: Frank–Kasper Phases Identified in PDMS‐ b‐PTFEA Copolymers with High Conformational Asymmetry

Abstract

In the search for the formation of Frank-Kasper phases from diblock copolymer self-assembly, a series of compositionally asymmetric poly(dimethylsiloxane)- b-poly(2,2,2-triflouroethyl acrylate)s (PDMS- b-PTFEAs) are synthesized to produce PDMS-rich phases with PDMS volume fractions ( f PDMS) ranging from 0.746 to 0.869. As determined by small-angle X-ray scattering analysis, the Frank-Kasper sigma and C14 phases are identified at f PDMS = 0.796 and 0.851, respectively, plausibly due to high conformational asymmetry (ϵ ≈ 2.20) between the two blocks. Intriguingly, the σ phase develops during heating from a short-range liquid-like packing (LLP) state, whereas the C14 phase is achieved at room temperature, which are both followed by a disordering at higher temperatures. Finally, based on thermal experiments from a super cooled disordered state, the findings further provide compelling evidence of an LLP-hexagonally packed cylinder-σ transition and a direct pathway to the C14 phase during heating from an LLP state.

Authors:
 [1];  [1];  [2];  [3];  [4];  [5]; ORCiD logo [1]
  1. Yonsei Univ., Seoul (South Korea). Dept. of Chemical and Biomolecular Engineering
  2. S. Jeon, T. Jun, S. Jo, Prof. D. Y. RyuDepartment of Chemical and Biomolecular EngineeringYonsei University 50 Yonsei‐ro Seodaemun‐gu Seoul 03722 Korea
  3. Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of). Pohang Accelerator Lab.
  4. Korea Univ., Seoul (South Korea). HU-KIST Graduate School of Converging Science and Technology, and Dept. of Biomicrosystem Technology
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Samsung Electronics, Seoul (South Korea)
OSTI Identifier:
1574376
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecular Rapid Communications
Additional Journal Information:
Journal Volume: 40; Journal Issue: 19; Journal ID: ISSN 1022-1336
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING; Frank-Kasper phases; block copolymers; conformational asymmetry; quasicrystals; self-assembly

Citation Formats

Jeon, Seungbae, Jun, Taesuk, Jo, Seongjun, Ahn, Hyungju, Lee, Seungwoo, Lee, Byeongdu, and Ryu, Du Yeol. Frank–Kasper Phases Identified in PDMS‐b‐PTFEA Copolymers with High Conformational Asymmetry. United States: N. p., 2019. Web. doi:10.1002/marc.201900259.
Jeon, Seungbae, Jun, Taesuk, Jo, Seongjun, Ahn, Hyungju, Lee, Seungwoo, Lee, Byeongdu, & Ryu, Du Yeol. Frank–Kasper Phases Identified in PDMS‐b‐PTFEA Copolymers with High Conformational Asymmetry. United States. doi:10.1002/marc.201900259.
Jeon, Seungbae, Jun, Taesuk, Jo, Seongjun, Ahn, Hyungju, Lee, Seungwoo, Lee, Byeongdu, and Ryu, Du Yeol. Wed . "Frank–Kasper Phases Identified in PDMS‐b‐PTFEA Copolymers with High Conformational Asymmetry". United States. doi:10.1002/marc.201900259.
@article{osti_1574376,
title = {Frank–Kasper Phases Identified in PDMS‐b‐PTFEA Copolymers with High Conformational Asymmetry},
author = {Jeon, Seungbae and Jun, Taesuk and Jo, Seongjun and Ahn, Hyungju and Lee, Seungwoo and Lee, Byeongdu and Ryu, Du Yeol},
abstractNote = {In the search for the formation of Frank-Kasper phases from diblock copolymer self-assembly, a series of compositionally asymmetric poly(dimethylsiloxane)-b-poly(2,2,2-triflouroethyl acrylate)s (PDMS-b-PTFEAs) are synthesized to produce PDMS-rich phases with PDMS volume fractions (fPDMS) ranging from 0.746 to 0.869. As determined by small-angle X-ray scattering analysis, the Frank-Kasper sigma and C14 phases are identified at fPDMS = 0.796 and 0.851, respectively, plausibly due to high conformational asymmetry (ϵ ≈ 2.20) between the two blocks. Intriguingly, the σ phase develops during heating from a short-range liquid-like packing (LLP) state, whereas the C14 phase is achieved at room temperature, which are both followed by a disordering at higher temperatures. Finally, based on thermal experiments from a super cooled disordered state, the findings further provide compelling evidence of an LLP-hexagonally packed cylinder-σ transition and a direct pathway to the C14 phase during heating from an LLP state.},
doi = {10.1002/marc.201900259},
journal = {Macromolecular Rapid Communications},
number = 19,
volume = 40,
place = {United States},
year = {2019},
month = {7}
}

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Works referenced in this record:

Metallic Phase with Long-Range Orientational Order and No Translational Symmetry
journal, November 1984


Fluorine-Containing Styrenic Block Copolymers toward High χ and Perpendicular Lamellae in Thin Films
journal, September 2018


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
  • DOI: 10.1073/pnas.1408678111

Conformational Asymmetry and Quasicrystal Approximants in Linear Diblock Copolymers
journal, May 2017


Giant Supramolecular Liquid Crystal Lattice
journal, February 2003


Nonclassical Spherical Packing Phases Self-Assembled from AB-Type Block Copolymers
journal, October 2017


Counterion-Dependent Access to Low-Symmetry Lyotropic Sphere Packings of Ionic Surfactant Micelles
journal, January 2018


Dodecagonal Quasicrystalline Morphology in a Poly(styrene- b -isoprene- b -styrene- b -ethylene oxide) Tetrablock Terpolymer
journal, April 2012

  • Zhang, Jingwen; Bates, Frank S.
  • Journal of the American Chemical Society, Vol. 134, Issue 18
  • DOI: 10.1021/ja301770v

Complex alloy structures regarded as sphere packings. II. Analysis and classification of representative structures
journal, July 1959


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
  • DOI: 10.1073/pnas.1809655115

Cornucopia of Nanoscale Ordered Phases in Sphere-Forming Tetrablock Terpolymers
journal, April 2016


Thermal processing of diblock copolymer melts mimics metallurgy
journal, May 2017


The AFLOW Library of Crystallographic Prototypes: Part 1
journal, August 2017


SUPERFLIP – a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions
journal, July 2007


Origins of low-symmetry phases in asymmetric diblock copolymer melts
journal, January 2018

  • Kim, Kyungtae; Arora, Akash; Lewis, Ronald M.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 5
  • DOI: 10.1073/pnas.1717850115

Quasicrystals: A New Class of Ordered Structures
journal, December 1984


Laves Phases Formed in the Binary Blend of AB 4 Miktoarm Star Copolymer and A-Homopolymer
journal, February 2019


Measurement of molecular dimensions of polystyrene chains in the bulk polymer by low angle neutron diffraction
journal, September 1973


New Types of Multishell Nanoclusters with a Frank–Kasper Polyhedral Core in Intermetallics
journal, June 2011

  • Blatov, Vladislav A.; Ilyushin, Gregory D.; Proserpio, Davide M.
  • Inorganic Chemistry, Vol. 50, Issue 12
  • DOI: 10.1021/ic2005024

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
  • DOI: 10.1039/c3sm51238j

Supramolecular dendritic liquid quasicrystals
journal, March 2004

  • Zeng, Xiangbing; Ungar, Goran; Liu, Yongsong
  • Nature, Vol. 428, Issue 6979
  • DOI: 10.1038/nature02368

Crystallization of polydimethylsiloxane: effect of silica filler and curing
journal, September 1998


Dispersion atom transfer radical polymerization of methyl methacrylate with bromo-terminated poly(dimethylsiloxane) in supercritical carbon dioxide
journal, January 2004

  • Minami, Hideto; Kagawa, Yasuyuki; Kuwahara, Shintaro
  • Designed Monomers and Polymers, Vol. 7, Issue 6
  • DOI: 10.1163/1568555042474103

Discovery of a Frank-Kasper   Phase in Sphere-Forming Block Copolymer Melts
journal, October 2010


Complex alloy structures regarded as sphere packings. I. Definitions and basic principles
journal, March 1958


Unifying Weak- and Strong-Segregation Block Copolymer Theories
journal, January 1996

  • Matsen, M. W.; Bates, F. S.
  • Macromolecules, Vol. 29, Issue 4
  • DOI: 10.1021/ma951138i

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
  • DOI: 10.1021/mz500445v

Understanding the complex metallic element Mn. I. Crystalline and noncollinear magnetic structure of α-Mn
journal, July 2003


Dodecagonal quasicrystalline order in a diblock copolymer melt
journal, April 2016

  • Gillard, Timothy M.; Lee, Sangwoo; Bates, Frank S.
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 19
  • DOI: 10.1073/pnas.1601692113

Stabilizing the Frank-Kasper Phases via Binary Blends of AB Diblock Copolymers
journal, September 2016


Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity
journal, April 2017

  • Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 16
  • DOI: 10.1073/pnas.1701608114