DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials

Abstract

Frank–Kasper phases are tetrahedrally packed structures occurring in numerous materials, from elements to intermetallics to self-assembled soft materials. They exhibit complex manifolds of Wigner–Seitz cells with many-faceted polyhedra, forming an important bridge between the simple close-packed periodic and quasiperiodic crystals. The recent discovery of the Frank–Kasper σ-phase in diblock and tetrablock polymers stimulated the experiments reported here on a poly(isoprene-b-lactide) diblock copolymer melt. Thus, analysis of small-angle X-ray scattering and mechanical spectroscopy exposes an undiscovered competition between the tendency to form self-assembled particles with spherical symmetry, and the necessity to fill space at uniform density within the framework imposed by the lattice. We thus deduce surprising analogies between the symmetry breaking at the body-centered cubic phase to σ-phase transition in diblock copolymers, mediated by exchange of mass, and the symmetry breaking in certain metals and alloys (such as the elements Mn and U), mediated by exchange of charge. Similar connections are made between the role of sphericity in real space for polymer systems, and the role of sphericity in reciprocal space for metallic systems such as intermetallic compounds and alloys. These findings establish new links between disparate materials classes, provide opportunities to improve the understanding of complex crystallization by buildingmore » on synergies between hard and soft matter, and, perhaps most significantly, challenge the view that the symmetry breaking required to form reduced symmetry structures (possibly even quasiperiodic crystals) requires particles with multiple predetermined shapes and/or sizes.« less

Authors:
 [1];  [2];  [2]
  1. Rensselaer Polytechnic Inst., Troy, NY (United States); Univ. of Minnesota, Minneapolis, MN (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1168557
Grant/Contract Number:  
AC02-06CH11357; FG02-06ER46275
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 111; Journal Issue: 50; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
ENGLISH
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; symmetry breaking; sphericity; Frank-Kasper phases; block polymers

Citation Formats

Lee, Sangwoo, Leighton, Chris, and Bates, Frank S. Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials. United States: N. p., 2014. Web. doi:10.1073/pnas.1408678111.
Lee, Sangwoo, Leighton, Chris, & Bates, Frank S. Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials. United States. https://doi.org/10.1073/pnas.1408678111
Lee, Sangwoo, Leighton, Chris, and Bates, Frank S. Wed . "Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials". United States. https://doi.org/10.1073/pnas.1408678111. https://www.osti.gov/servlets/purl/1168557.
@article{osti_1168557,
title = {Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials},
author = {Lee, Sangwoo and Leighton, Chris and Bates, Frank S.},
abstractNote = {Frank–Kasper phases are tetrahedrally packed structures occurring in numerous materials, from elements to intermetallics to self-assembled soft materials. They exhibit complex manifolds of Wigner–Seitz cells with many-faceted polyhedra, forming an important bridge between the simple close-packed periodic and quasiperiodic crystals. The recent discovery of the Frank–Kasper σ-phase in diblock and tetrablock polymers stimulated the experiments reported here on a poly(isoprene-b-lactide) diblock copolymer melt. Thus, analysis of small-angle X-ray scattering and mechanical spectroscopy exposes an undiscovered competition between the tendency to form self-assembled particles with spherical symmetry, and the necessity to fill space at uniform density within the framework imposed by the lattice. We thus deduce surprising analogies between the symmetry breaking at the body-centered cubic phase to σ-phase transition in diblock copolymers, mediated by exchange of mass, and the symmetry breaking in certain metals and alloys (such as the elements Mn and U), mediated by exchange of charge. Similar connections are made between the role of sphericity in real space for polymer systems, and the role of sphericity in reciprocal space for metallic systems such as intermetallic compounds and alloys. These findings establish new links between disparate materials classes, provide opportunities to improve the understanding of complex crystallization by building on synergies between hard and soft matter, and, perhaps most significantly, challenge the view that the symmetry breaking required to form reduced symmetry structures (possibly even quasiperiodic crystals) requires particles with multiple predetermined shapes and/or sizes.},
doi = {10.1073/pnas.1408678111},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 50,
volume = 111,
place = {United States},
year = {Wed Nov 05 00:00:00 EST 2014},
month = {Wed Nov 05 00:00:00 EST 2014}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 175 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Quasicrystals
journal, November 2001

  • Cahn, J. W.
  • Journal of Research of the National Institute of Standards and Technology, Vol. 106, Issue 6
  • DOI: 10.6028/jres.106.049

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


Colloidal quasicrystals with 12-fold and 18-fold diffraction symmetry
journal, January 2011

  • Fischer, Steffen; Exner, Alexander; Zielske, Kathrin
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 5
  • DOI: 10.1073/pnas.1008695108

Brillouin Zone Concept And Crystal Structures Of sp Metals Under High Pressure
journal, September 2003


Crystal Structure Variations in Alpha Uranium at Low Temperatures
journal, January 1963


Giant Supramolecular Liquid Crystal Lattice
journal, February 2003


The space groups of icosahedral quasicrystals and cubic, orthorhombic, monoclinic, and triclinic crystals
journal, January 1992


Multiblock Polymers: Panacea or Pandora's Box?
journal, April 2012


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

Roles of icosahedral and crystal-like order in the hard spheres glass transition
journal, January 2012

  • Leocmach, Mathieu; Tanaka, Hajime
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1974

On the Origins of Morphological Complexity in Block Copolymer Surfactants
journal, April 2003


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


The Order−Disorder Transition and the Disordered Micelle Regime for Poly(ethylenepropylene- b -dimethylsiloxane) Spheres
journal, December 2002

  • Wang, Xiaohui; Dormidontova, Elena E.; Lodge, Timothy P.
  • Macromolecules, Vol. 35, Issue 26
  • DOI: 10.1021/ma021009j

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

Supramolecular dendritic liquid quasicrystals
journal, March 2004

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

Diffusionless Crystal Growth from Glass Has Precursor in Equilibrium Liquid
journal, January 2008

  • Sun, Ye; Xi, Hanmi; Ediger, M. D.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 3
  • DOI: 10.1021/jp709616c

Experimental measurement of the photonic properties of icosahedral quasicrystals
journal, August 2005

  • Man, Weining; Megens, Mischa; Steinhardt, Paul J.
  • Nature, Vol. 436, Issue 7053
  • DOI: 10.1038/nature03977

A unified picture of the crystal structures of metals
journal, April 1995

  • Söderlind, Per; Eriksson, Olle; Johansson, Börje
  • Nature, Vol. 374, Issue 6522
  • DOI: 10.1038/374524a0

Predictive Self-Assembly of Polyhedra into Complex Structures
journal, July 2012


Maximizing Entropy by Minimizing Area:  Towards a New Principle of Self-Organization
journal, October 2001

  • Ziherl, P.; Kamien, Randall D.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 42
  • DOI: 10.1021/jp010944q

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


Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990


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


Understanding the Complex Phase Diagram of Uranium: The Role of Electron-Phonon Coupling
journal, September 2011


Block Copolymers—Designer Soft Materials
journal, February 1999

  • Bates, Frank S.; Fredrickson, Glenn H.
  • Physics Today, Vol. 52, Issue 2
  • DOI: 10.1063/1.882522

Double-diamond NaAl via pressure: Understanding structure through Jones zone activation
journal, March 2010

  • Feng, Ji; Hoffmann, Roald; Ashcroft, N. W.
  • The Journal of Chemical Physics, Vol. 132, Issue 11
  • DOI: 10.1063/1.3328198

Jamming phase diagram for attractive particles
journal, June 2001

  • Trappe, V.; Prasad, V.; Cipelletti, Luca
  • Nature, Vol. 411, Issue 6839
  • DOI: 10.1038/35081021

Quasicrystalline order in self-assembled binary nanoparticle superlattices
journal, October 2009

  • Talapin, Dmitri V.; Shevchenko, Elena V.; Bodnarchuk, Maryna I.
  • Nature, Vol. 461, Issue 7266
  • DOI: 10.1038/nature08439

Mosaic two-lengthscale quasicrystals
journal, February 2014


Polymeric Quasicrystal: Mesoscopic Quasicrystalline Tiling in A B C Star Polymers
journal, May 2007


Comparison of the Site Occupancies Determined by Combined Rietveld Refinement and Density Functional Theory Calculations: Example of the Ternary Mo–Ni–Re σ Phase
journal, February 2012

  • Yaqoob, Khurram; Crivello, Jean-Claude; Joubert, Jean-Marc
  • Inorganic Chemistry, Vol. 51, Issue 5
  • DOI: 10.1021/ic202479y

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


Nature of Disordered Micelles in Sphere-Forming Block Copolymer Melts
journal, March 2005

  • Wang, Jiafang; Wang, Zhen-Gang; Yang, Yuliang
  • Macromolecules, Vol. 38, Issue 5
  • DOI: 10.1021/ma047990j

Micellar Cubic Phases and Their Structural Relationships:  The Nonionic Surfactant System C 12 EO 12 /Water
journal, July 1997

  • Sakya, P.; Seddon, J. M.; Templer, R. H.
  • Langmuir, Vol. 13, Issue 14
  • DOI: 10.1021/la9701844

Block copolymer microstructures in the intermediate-segregation regime
journal, February 1997

  • Matsen, M. W.; Bates, F. S.
  • The Journal of Chemical Physics, Vol. 106, Issue 6
  • DOI: 10.1063/1.473153

Should All Crystals Be bcc? Landau Theory of Solidification and Crystal Nucleation
journal, September 1978


Site occupation in the Cr-Ru and Cr-Os σ phases
journal, October 2009


Structure of β-uranium
journal, April 1988

  • Lawson, A. C.; Olsen, C. E.; Richardson, J. W.
  • Acta Crystallographica Section B Structural Science, Vol. 44, Issue 2
  • DOI: 10.1107/S0108768187009406

Pseudo-Fivefold Diffraction Symmetries in Tetrahedral Packing
journal, June 2013

  • Lee, Stephen; Henderson, Ryan; Kaminsky, Corey
  • Chemistry - A European Journal, Vol. 19, Issue 31
  • DOI: 10.1002/chem.201203758

Granulation, Phase Change, and Microstructure Kinetics of Phase Change. III
journal, February 1941

  • Avrami, Melvin
  • The Journal of Chemical Physics, Vol. 9, Issue 2, p. 177-184
  • DOI: 10.1063/1.1750872

Crystallization near Glass Transition:  Transition from Diffusion-Controlled to Diffusionless Crystal Growth Studied with Seven Polymorphs
journal, May 2008

  • Sun, Ye; Xi, Hanmi; Chen, Shuang
  • The Journal of Physical Chemistry B, Vol. 112, Issue 18
  • DOI: 10.1021/jp7120577

Fluctuations, Order, and Disorder in Short Diblock Copolymers
journal, February 2013

  • Lee, Sangwoo; Gillard, Timothy M.; Bates, Frank S.
  • AIChE Journal, Vol. 59, Issue 9
  • DOI: 10.1002/aic.14023

Frank–Kasper, quasicrystalline and related phases in liquid crystals
journal, January 2005

  • Ungar, Goran; Zeng, Xiangbing
  • Soft Matter, Vol. 1, Issue 2
  • DOI: 10.1039/b502443a

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


Tuning the structure of non-equilibrium soft materials by varying the thermodynamic driving force for crystal ordering
journal, January 2011

  • Tegze, György; Gránásy, László; Tóth, Gyula I.
  • Soft Matter, Vol. 7, Issue 5
  • DOI: 10.1039/C0SM00944J

Roles of icosahedral and crystal-like order in hard spheres glass transition
text, January 2013


Works referencing / citing this record:

Breaking Parallel Orientation of Rods via a Dendritic Architecture toward Diverse Supramolecular Structures
journal, July 2019

  • Zhang, Ruimeng; Feng, Xueyan; Zhang, Rui
  • Angewandte Chemie International Edition, Vol. 58, Issue 34
  • DOI: 10.1002/anie.201904749

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

Mapping the phase behavior of coacervate-driven self-assembly in diblock copolyelectrolytes
journal, January 2019

  • Ong, Gary M. C.; Sing, Charles E.
  • Soft Matter, Vol. 15, Issue 25
  • DOI: 10.1039/c9sm00741e

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

Which Wave Numbers Determine the Thermodynamic Stability of Soft Matter Quasicrystals?
journal, October 2019


A few rediscovered and challenging topics in polymer crystals and crystallization
journal, December 2018

  • Yue, Kan; Liu, Gengxin; Feng, Xueyan
  • POLYMER CRYSTALLIZATION, Vol. 1, Issue 4
  • DOI: 10.1002/pcr2.10053

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


Complex Crystals from Size-Disperse Spheres
journal, March 2019


An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase
journal, January 2020

  • Lachmayr, Kätchen K.; Wentz, Charlotte M.; Sita, Lawrence R.
  • Angewandte Chemie International Edition, Vol. 59, Issue 4
  • DOI: 10.1002/anie.201912648

Frank-Kasper and related quasicrystal spherical phases in macromolecules
journal, December 2017


Rapid One-Step Synthesis of Complex-Architecture Block Polymers Using Inductively “Armed-Disarmed” Monomer Pairs
journal, March 2018

  • Chang, Boyce S.; Oyola-Reynoso, Stephanie; Cutinho, Joel
  • Macromolecular Rapid Communications, Vol. 39, Issue 8
  • DOI: 10.1002/marc.201800026

Nanoparticle Superlattices as Quasi-Frank-Kasper Phases
journal, September 2017


Emergent symmetries in block copolymer epitaxy
journal, July 2019

  • Ding, Yi; Gadelrab, Karim R.; Mizrahi Rodriguez, Katherine
  • Nature Communications, Vol. 10, Issue 1
  • DOI: 10.1038/s41467-019-10896-5

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

Multiple-scale structures: from Faraday waves to soft-matter quasicrystals
journal, March 2018


Stability of the Frank–Kasper σ-phase in BABC linear tetrablock terpolymers
journal, January 2016

  • Liu, Meijiao; Li, Weihua; Qiu, Feng
  • Soft Matter, Vol. 12, Issue 30
  • DOI: 10.1039/c6sm00798h

Shaping micro-clusters via inverse jamming and topographic close-packing of microbombs
journal, September 2017


Small‐Molecule Modulation of Soft‐Matter Frank–Kasper Phases: A Method for Adding Function to Form
journal, January 2020

  • Lachmayr, Kätchen K.; Sita, Lawrence R.
  • Angewandte Chemie International Edition, Vol. 59, Issue 9
  • DOI: 10.1002/anie.201915416

A new framework for X-ray photon correlation spectroscopy analysis from polycrystalline materials
journal, December 2018

  • Lewis, Ronald M.; Jackson, Grayson L.; Maher, Michael J.
  • Review of Scientific Instruments, Vol. 89, Issue 12
  • DOI: 10.1063/1.5051451

Frank–Kasper Phases Identified in PDMS‐ b ‐PTFEA Copolymers with High Conformational Asymmetry
journal, July 2019

  • Jeon, Seungbae; Jun, Taesuk; Jo, Seongjun
  • Macromolecular Rapid Communications, Vol. 40, Issue 19
  • DOI: 10.1002/marc.201900259

Controlling the Periodically Ordered Nanostructures in Ceramics: A Macromolecule‐Guided Strategy
journal, November 2019

  • Guo, Qing‐Yun; Zhang, Bo‐xing; Feng, Xueyan
  • Macromolecular Rapid Communications, Vol. 41, Issue 1
  • DOI: 10.1002/marc.201900534

Small‐Molecule Modulation of Soft‐Matter Frank–Kasper Phases: A Method for Adding Function to Form
journal, January 2020


Role of Chain Length in the Formation of Frank-Kasper Phases in Diblock Copolymers
journal, November 2018


Selective assemblies of giant tetrahedra via precisely controlled positional interactions
journal, April 2015


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
  • DOI: 10.1073/pnas.1609422113

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


Machine-learning solver for modified diffusion equations
journal, November 2018


Formation pathways of mesoporous silica nanoparticles with dodecagonal tiling
journal, August 2017


Breaking Parallel Orientation of Rods via a Dendritic Architecture toward Diverse Supramolecular Structures
journal, July 2019


Recent applications of synchrotron radiation and neutrons in the study of soft matter
journal, February 2017


An Exceptionally Stable and Scalable Sugar–Polyolefin Frank–Kasper A15 Phase
journal, December 2019

  • Lachmayr, Kätchen K.; Wentz, Charlotte M.; Sita, Lawrence R.
  • Angewandte Chemie, Vol. 132, Issue 4
  • DOI: 10.1002/ange.201912648

Multiple-scale structures: from Faraday waves to soft-matter quasicrystals
conference, January 2018


Low-Temperature Crystal Structures of the Hard Core Square Shoulder Model
journal, November 2017

  • Gabriëlse, Alexander; Löwen, Hartmut; Smallenburg, Frank
  • Materials, Vol. 10, Issue 11
  • DOI: 10.3390/ma10111280

Identification of a Frank–Kasper Z phase from shape amphiphile self-assembly
journal, September 2019


Stability of the A15 phase in diblock copolymer melts
journal, June 2019

  • Bates, Morgan W.; Lequieu, Joshua; Barbon, Stephanie M.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 27
  • DOI: 10.1073/pnas.1900121116

Giant molecules: where chemistry, physics, and bio-science meet
journal, February 2017

  • Yin, Guang-Zhong; Zhang, Wen-Bin; Cheng, Stephen Z. D.
  • Science China Chemistry, Vol. 60, Issue 3
  • DOI: 10.1007/s11426-016-0436-x

Four-Phase Morphologies in Blends of ABC and BAC Triblock Terpolymers
journal, July 2017

  • Haenelt, Taida Gil; Abetz, Clarissa; Abetz, Volker
  • Macromolecular Chemistry and Physics, Vol. 219, Issue 1
  • DOI: 10.1002/macp.201700241

Multiple-scale structures: from Faraday waves to soft-matter quasicrystals
text, January 2017


Stable Frank-Kasper phases of self-assembled, soft matter spheres
text, January 2018


A machine-learning solver for modified diffusion equations
text, January 2018


Complex Crystals from Size-disperse Spheres
text, January 2018


Which wavenumbers determine the thermodynamic stability of soft matter quasicrystals?
text, January 2019


Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomer
journal, February 2019


Evidence for a C14 Frank–Kasper Phase in One-Size Gold Nanoparticle Superlattices
journal, July 2015


Shaping micro-clusters via inverse jamming and topographic close-packing of microbombs
journal, September 2017


Emergent symmetries in block copolymer epitaxy
journal, July 2019

  • Ding, Yi; Gadelrab, Karim R.; Mizrahi Rodriguez, Katherine
  • Nature Communications, Vol. 10, Issue 1
  • DOI: 10.1038/s41467-019-10896-5

Disorder to Order Transition and Ordered Morphology of Coil-Comb Block Copolymer by Self-Consistent Field Theory
journal, August 2015


Low-temperature crystal structures of the hard core square shoulder model
text, January 2017