Micellar Mimicry of Intermetallic C14 and C15 Laves Phases by Aqueous Lyotropic Self-Assembly

Baez-Cotto, Carlos M.; Mahanthappa, Mahesh K.

doi:10.1021/acsnano.7b07475

Title: Micellar Mimicry of Intermetallic C14 and C15 Laves Phases by Aqueous Lyotropic Self-Assembly

Journal Article · Tue Apr 03 00:00:00 EDT 2018 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.7b07475· OSTI ID:1435815

^[1];

^[2]

Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, and Dept. of Chemical Engineering and Materials Science

Concentration-dependent supramolecular self-assembly of amphiphilic molecules in water furnishes a variety of nanostructured lyotropic liquid crystals (LLCs), which typically display high symmetry bicontinuous network and discontinuous micellar morphologies. Aqueous dispersions of soft spherical micelles derived from small molecule amphiphile hydration typically pack into exemplary body-centered cubic and closest-packed LLCs. However, investigations of hydrated mixtures of the ionic surfactant tetramethylammonium decanoate loaded with 40 wt % n-decane (TMADec-40) revealed the formation of a high symmetry bicontinuous double diamond LLC, as well as cubic C15 and hexagonal C14 Laves LLC phases that mirror the MgCu₂ and MgZn₂ intermetallic structure types, respectively. Detailed small-angle X-ray scattering analyses demonstrate that the complex C15 and C14 LLCs exhibit large unit cells, in which 12 or more ~3–4 nm diameter micelles of multiple discrete sizes arrange into tetrahedral close packing arrangements with exceptional long-range translational order. The symmetry breaking that drives self-assembly into these low-symmetry LLC phases is rationalized in terms of a frustrated balance between maximizing counterion-mediated micellar cohesion within the ensemble of oil-swollen particles, while simultaneously optimizing local spherical particle symmetry to minimize molecular-level variations in surfactant solvation.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1435815

Journal Information:: ACS Nano, Vol. 12, Issue 4; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 50 works

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Group theory
Lattices
X-ray scattering
Micelles
Surfactants
liquid crystals
self-assembly
surfactants
Frank−Kasper phases
lyotropic phase
superlattices