Antifreeze Hydrogels from Amphiphilic Statistical Copolymers
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 nm3) 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 Tg (136 K) and a minority population of water with suppressed dynamics and an enhanced Tg near 151 K that is attributedmore »
- Authors:
-
- Univ. of Akron, Akron, OH (United States)
- Univ. of Akron, Akron, OH (United States); 3M Center St., St. Paul, MN (United States)
- Univ. of South Florida, Tampa, FL (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1493571
- Report Number(s):
- BNL-211245-2019-JAAM
Journal ID: ISSN 0897-4756
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 1; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Wang, Chao, Wiener, Clinton G., Sepulveda-Medina, Pablo I., Ye, Changhuai, Simmons, David S., Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., and Vogt, Bryan D. Antifreeze Hydrogels from Amphiphilic Statistical Copolymers. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b03650.
Wang, Chao, Wiener, Clinton G., Sepulveda-Medina, Pablo I., Ye, Changhuai, Simmons, David S., Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., & Vogt, Bryan D. Antifreeze Hydrogels from Amphiphilic Statistical Copolymers. United States. doi:10.1021/acs.chemmater.8b03650.
Wang, Chao, Wiener, Clinton G., Sepulveda-Medina, Pablo I., Ye, Changhuai, Simmons, David S., Li, Ruipeng, Fukuto, Masafumi, Weiss, R. A., and Vogt, Bryan D. Thu .
"Antifreeze Hydrogels from Amphiphilic Statistical Copolymers". United States. doi:10.1021/acs.chemmater.8b03650. https://www.osti.gov/servlets/purl/1493571.
@article{osti_1493571,
title = {Antifreeze Hydrogels from Amphiphilic Statistical Copolymers},
author = {Wang, Chao and Wiener, Clinton G. and Sepulveda-Medina, Pablo I. and Ye, Changhuai and Simmons, David S. and Li, Ruipeng and Fukuto, Masafumi and Weiss, R. A. and Vogt, Bryan D.},
abstractNote = {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 nm3) 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 Tg (136 K) and a minority population of water with suppressed dynamics and an enhanced Tg 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. Furthermore, these insights have the potential to provide solutions to challenges with ice in engineering applications where confinement of water to nanoscale dimensions is possible.},
doi = {10.1021/acs.chemmater.8b03650},
journal = {Chemistry of Materials},
number = 1,
volume = 31,
place = {United States},
year = {2018},
month = {12}
}
Web of Science
Works referencing / citing this record:
Biomimetic Extreme‐Temperature‐ and Environment‐Adaptable Hydrogels
journal, August 2019
- Zhou, Dan; Chen, Fan; Handschuh‐Wang, Stephan
- ChemPhysChem, Vol. 20, Issue 17
Kinetically controlled morphology in copolymer-based hydrogels crosslinked by crystalline nanodomains determines efficacy of ice inhibition
journal, January 2020
- Sepulveda-Medina, Pablo I.; Wang, Chao; Li, Ruipeng
- Molecular Systems Design & Engineering, Vol. 5, Issue 3
Poly(ionic liquid) hydrogel-based anti-freezing ionic skin for a soft robotic gripper
journal, January 2020
- Liu, Ziyang; Wang, Yue; Ren, Yongyuan
- Materials Horizons, Vol. 7, Issue 3