How does your gyroid grow? A mesoatomic perspective on supramolecular, soft matter network crystals

Grason, Gregory M.; Thomas, Edwin L.

doi:10.1103/physrevmaterials.7.045603

Title: How does your gyroid grow? A mesoatomic perspective on supramolecular, soft matter network crystals

Journal Article · 21 April 2023 · Physical Review Materials

DOI: https://doi.org/10.1103/physrevmaterials.7.045603 · OSTI ID:1971165

Grason, Gregory M. ^[1];

^[2]

Univ. of Massachusetts, Amherst, MA (United States)
Texas A & M Univ., College Station, TX (United States)

We propose and describe a framework to understand the structure of supramolecular network crystals formed in soft matter in terms of mesoatomic building blocks, collective groupings of amphiphilic molecules that play a role analogous to atomic or molecular subunits of hard matter crystals. While the concept of mesoatoms is intuitive and widely invoked in crystalline arrangements of spherelike or cylinderlike (micellelike) domains, analogous notions of natural and physically meaningful building blocks of triply periodic network (TPN) crystals, like the double-gyroid or double-diamond structures are obscured by the complex, bicontinuous domain shapes and intercatenated topologies of the double networks. Focusing on the specific example of diblock copolymer melts, we propose generic rules for decomposing TPN crystals into a unique set of mesoatomic building blocks. Based on physically motivated principles, the combination of symmetries and topologies of these structures point to mesoatomic elements associated with the nodal connections, leading to mesoatomic volumes that are nonconvex and bound by smoothly curved faces, unlike the more familiar Voronoi polyhedral shapes associated with spherelike and cylinderlike mesoatoms. We analyze the shapes of these mesoatoms, their internal structure, and importantly, their local packing with neighbor mesoatomic units. Importantly, we hypothesize that mesoatoms are kinetically favored intermediate structures whose local shapes and packing template network crystal assembly on long time scales. We propose and study a minimal energetic model of mesoatom assembly for three different cubic double-network crystals, based on local shape packing, which predicts a detailed picture for kinetics of intercatenation and surface growth. Based on these analyses, we discuss several possible extensions and elaborations of the mesoatomic description of supramolecular soft matter network crystals, most notably the implications of mesoatomic malleability, a feature that distinguishes soft matter from hard matter crystals. We describe experimental observations of malleable mesoatomic units in the precursor sponge phase as well as in ordered cubic networks and suggest possibilities for observing mesoatoms in primordial, precrystalline states.

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Research Organization:: Univ. of Massachusetts, Amherst, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022229

OSTI ID:: 1971165

Alternate ID(s):: OSTI ID: 2422100

Journal Information:: Physical Review Materials, Vol. 7, Issue 4; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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