期刊
ACS MACRO LETTERS
卷 8, 期 11, 页码 1522-1527出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsmacrolett.9b00783
关键词
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资金
- National Institutes of Health [RR023614]
- National Science Foundation [CHE-0840501, CBET-1510772]
- North Carolina Biotechnology Center (NCBC) [2009-IDG-1015]
- U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) [DE-FG02-02ER15354]
- Korea Coast Guard of the Korean government
- National Research Foundation [NRF-2016M3C1B5906481]
Sonication of gallium or gallium-based liquid metals in an aqueous solution of vinyl monomers leads to rapid free radical polymerization (FRP), without the need for conventional molecular initiators. Under ambient conditions, a passivating native oxide separates these metals from solution and renders the metal effectively inert. However, sonication generates liquid metal nanoparticles (LMNPs) of similar to 100 nm diameter and thereby increases the surface area of the metal. The exposed metal initiates polymerization, which proceeds via a FRP mechanism and yields high molecular weight polymers that can form physical gels. Spin trapping EPR reveals the generation of free radicals. Time-of-flight secondary ion mass spectrometry measurements confirm direct polymer bonding to gallium, verifying the formation of surface-anchored polymer grafts. The grafted polymers can modify the interfacial properties, that is, the preference of the metal particles to disperse in aqueous versus organic phases. The polymer can also be degrafted and isolated from the particles using strong acid or base. The concept of physically disrupting passivated metal surfaces offers new routes for surface-initiated polymerization and has implications for surface modification, reduction reactions, and fabrication of mechanically responsive materials.
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