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

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [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)

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; FG02-06ER46275
OSTI ID:
1168557
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 111, Issue 50; ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)Copyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 175 works
Citation information provided by
Web of Science

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Cited By (46)

Breaking Parallel Orientation of Rods via a Dendritic Architecture toward Diverse Supramolecular Structures journal July 2019
Stable Frank–Kasper phases of self-assembled, soft matter spheres journal September 2018
Mapping the phase behavior of coacervate-driven self-assembly in diblock copolyelectrolytes journal January 2019
Origins of low-symmetry phases in asymmetric diblock copolymer melts journal January 2018
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
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
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
Nanoparticle Superlattices as Quasi-Frank-Kasper Phases journal September 2017
Emergent symmetries in block copolymer epitaxy journal July 2019
Dodecagonal quasicrystalline order in a diblock copolymer melt journal April 2016
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
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
A new framework for X-ray photon correlation spectroscopy analysis from polycrystalline materials journal December 2018
Frank–Kasper Phases Identified in PDMS‐ b ‐PTFEA Copolymers with High Conformational Asymmetry journal July 2019
Controlling the Periodically Ordered Nanostructures in Ceramics: A Macromolecule‐Guided Strategy journal November 2019
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
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
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
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
Giant molecules: where chemistry, physics, and bio-science meet journal February 2017
Four-Phase Morphologies in Blends of ABC and BAC Triblock Terpolymers journal July 2017
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
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

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