Water and Ion Transport through the Glass Transition in Polyelectrolyte Complexes

被引:23
作者
Abou Shaheen, Samir [1 ]
Yang, Mo [1 ]
Chen, Banghao [1 ]
Schlenoff, Joseph B. [1 ]
机构
[1] Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32308 USA
基金
美国国家科学基金会;
关键词
MULTILAYER FILMS; DIFFUSION; TEMPERATURE; MEMBRANES; POLYMERS; RELAXATION; HYDRATION; SALT;
D O I
10.1021/acs.chemmater.0c01217
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Polyelectrolyte complexes or coacervates, PECs, represent one of the many families of ion-containing polymers proposed or in use for applications requiring mobile ions, including fuel cells, water purification, and rechargeable batteries. Interest in these materials has focused on how ion transport is coupled to, and limited by, polymer dynamics, which slow considerably below the glass transition, T-g. Unlike many other polymer systems, ion conductivity in hydrated PECs remains high above and below T-g. In this work, we investigate the transport of water and ions within a PEC as the polymer host passes through T-g. We find no evidence of a response in the transport of water and small univalent ions, such as Na+ and Cl-, as the hydrated PEC goes through T-g. In contrast, triple-charged ions ferricyanide and ruthenium hexamine experience a second-order change in transport rate at T-g. This response is interpreted to show that these ions engage enough polyelectrolyte repeat units to experience the highly localized cooperative rearrangement thought to be responsible for the glass transition.
引用
收藏
页码:5994 / 6002
页数:9
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