4 years ago

Ionomer Solution to Film Solidification Dependence upon Solvent Type and Its Impact Upon Morphology and Ion Transport

Ionomer Solution to Film Solidification Dependence upon Solvent Type and Its Impact Upon Morphology and Ion Transport
Ionomer chain and solvent molecule interactions during solution-casting, solvent evaporation, and solidification impacts chain entanglements, spatial arrangement of functional groups, microstructure development, morphology, and physical properties. These concepts were investigated using poly(t-butylstyrene-b-ethylene-alt-propylene-b-sulfonatedstyrene-b-ethylene-alt-propylene-b-t-butylstyrene) with a fixed ion-exchange capacity of 1.0, and estimated solubility parameter of 21.8 (J/cm3)1/2. Films were solution-cast using an equal volume cyclohexane:heptane mixture (C:H), chloroform (CHCl3), and tetrahydrofuran (THF). Subsequent film structures were evaluated using transmission electron microscopy (TEM), small-angle x-ray scattering (SAXS), FT-IR, and electrochemical impedance spectroscopy. A commercially supplied film had sulfonated domains randomly distributed throughout it, and its initial proton conductivity was 11.8 mS/cm. A film created by solution-casting from C:H had a morphology containing randomly distributed sulfonated domains. This random morphology became more ordered with a lamella-like morphology when solution-cast using THF. The film produced from CHCl3 had a morphology that was between random and ordered. Film morphology differences were attributed to a poorer solvent system that inhibited chain solvation. The solution-cast film’s proton conductivity was 1.0 mS/cm for a random morphology, and 15.3 mS/cm with a lamella-like structure. Increasing the ionomer-THF solution-casting temperature to 40 °C produced a film with a 103% increase in conductivity (31.2 mS/cm). This led to a water uptake change from 29 wt% to 80 wt%. Cycling a THF solution-cast film from its dry to a wet state revealed that a lamella-like morphology would maintain its conductivity, but the commercial film’s conductivity decreased from 11.8 mS/cm to 0.98 mS/cm. Ionomer film properties were found to be dependent upon solvent quality and processing.

Publisher URL: www.sciencedirect.com/science

DOI: S001430571731162X

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