Issue 10, 2024

Unimer suppression enables supersaturated homopolymer swollen micelles with long-term stability after glassy entrapment

Abstract

Micelle sizes are critical for a range of applications where the simple ability to adjust and lock in specific stable sizes has remained largely elusive. While micelle swelling agents are well-known, their dynamic re-equilibration in solution implies limited stability. Here, a non-equilibrium processing sequence is studied where supersaturated homopolymer swelling is combined with glassy-core (“persistent”) micelles. This path-dependent process was found to sensitively depend on unimer concentration as revealed by DLS, SAXS, and TEM analysis. Here, lower-selectivity solvent combinations led to the formation of unimer-homopolymer aggregates and eventual precipitation, reminiscent of anomalous micellization. In contrast, higher-selectivity solvents enabled supersaturated homopolymer loadings favored by rapid homopolymer insertion. The demonstrated ∼40–130 nm core-size tuning exceeded prior equilibrium demonstrations and subsequent core-vitrification enabled size persistence beyond 6 months. Lastly, the linear change in micelle diameter with homopolymer addition was found to correlate with a plateau in the interfacial area per copolymer chain.

Graphical abstract: Unimer suppression enables supersaturated homopolymer swollen micelles with long-term stability after glassy entrapment

Supplementary files

Article information

Article type
Paper
Submitted
26 Dec 2023
Accepted
07 Feb 2024
First published
08 Feb 2024
This article is Open Access
Creative Commons BY license

Soft Matter, 2024,20, 2288-2300

Unimer suppression enables supersaturated homopolymer swollen micelles with long-term stability after glassy entrapment

E. R. Williams, C. X. Ruff and M. Stefik, Soft Matter, 2024, 20, 2288 DOI: 10.1039/D3SM01754K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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