Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

Chao Wang, Clinton G. Wiener, Pablo I. Sepulveda-Medina, Changhuai Ye, David S. Simmons, Ruipeng Li, Masafumi Fukuto, R. A. Weiss, Bryan D. Vogt

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

Prevention of ice formation is a critical issue for many applications, but routes to overcome the large thermodynamic driving force for crystallization of water at significant supercooling are limited. Here, we demonstrate that supramolecular hydrogels formed from statistical copolymers of 2-hydroxyethyl acrylate (HEA) and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM) exhibit a degree of ice formation suppression unprecedented in a synthetic material. The mechanisms of ice prevention by these hydrogels mimic two methods used by nature: (1) hydrogen bonding of water to highly hydrophilic macromolecular chains and (2) nanoconfinement of water between hydrophobic moieties. From systematic variation in the copolymer composition to control the nanoscale (<4 nm) separation of the self-assembled hydrophobic nanodomains, the main mechanism by which these supramolecular hydrogels inhibit large amounts of water from freezing appears to be soft nanoconfinement. Nearly complete ice inhibition was achieved in hydrogels when the nanodomain separation was <3 nm (i.e., confinement volume ∼15 nm 3 ) where <290 water molecules are present. Dielectric spectroscopy is consistent with two primary populations of water: a population of water with a bulk-like dynamics as well as T g (136 K) and a minority population of water with suppressed dynamics and an enhanced T g near 151 K that is attributed to interfacial water. The nanostructured design of these supramolecular hydrogels provides a blueprint concept for controlling and manipulating ice formation in concentrated soft matter using the length scale between hydrophobic domains and the hydrophilicity of the network water-soluble component. These insights have the potential to provide solutions to challenges with ice in engineering applications where confinement of water to nanoscale dimensions is possible.

Original languageEnglish (US)
Pages (from-to)135-145
Number of pages11
JournalChemistry of Materials
Volume31
Issue number1
DOIs
StatePublished - Jan 8 2019

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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