Directing Polymorphism of Colloid Crystals Using Conformational Entropy of Polymer Chains

Ahn, Juhong; Lee, Hanseung; Wąsik, Patryk; Lee, Sangwoo

doi:10.1021/acs.macromol.5c00749

Directing Polymorphism of Colloid Crystals Using Conformational Entropy of Polymer Chains

Journal Article · Wed Jun 11 00:00:00 EDT 2025 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5c00749· OSTI ID:2570565

Ahn, Juhong ^[1]; Lee, Hanseung ^[2]; ^[3]; ^[1]

Rensselaer Polytechnic Inst., Troy, NY (United States)
Univ. of Minnesota, Minneapolis, MN (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Controlling the polytypes of close-packed structures of spherical colloids is still a challenging problem despite their wide occurrence. Here, in this work, we show that systematic engineering of the polytype structures of close-packed colloids is possible by using the conformational entropy of polymer chains confined in the interstitial space of colloid crystals. Our interstitial space analysis shows that the hexagonal close-packed (HCP) structures offer larger local interstitial space domains, and the structure director chains in favor of HCP counteract the entropic advantages of the face-centered cubic (FCC) lattices. Using model block copolymer colloids and the known lattice entropy of FCC, a proportionality parameter, β_CP = 1.91 × 10^–3 ± 3.67 × 10^–4, for quantifying the conformational entropy contribution toward HCP structures is extracted. This work demonstrates that the interstitial space of colloid crystals serves as a new structure engineering tool for the self-assembly of colloids.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2570565

Report Number(s):: BNL--228367-2025-JAAM

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 12 Vol. 58; ISSN 1520-5835; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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