Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

doi:10.1021/acs.chemmater.8b03650

This content will become publicly available on December 13, 2019

Title: Antifreeze Hydrogels from Amphiphilic Statistical Copolymers

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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 151more »« less

Authors:

^[1]; Wiener, Clinton G. ^[2]; Sepulveda-Medina, Pablo I. ^[1]; Ye, Changhuai ^[1];

^[3]; Li, Ruipeng ^[4]; Fukuto, Masafumi ^[4];

^[1];

^[1]

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:: 2018-12-13

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

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

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.

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                    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.

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                    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.

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@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}

}

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