Abstract

A number of theoretical molecular energetics-based models of polar/nonpolar aggregation in ionomers have developed in concert with the proliferation of an experimental structure/properties database in this area. This manuscript is a critical review of these contributions with a view toward identifying areas that demand improvement or development as well as provide a general enumeration of concepts for the uninformed. A distinction is made between dry vs. hydrated ionomers and hydrocarbon-based ionomers with low ionic mole fractions vs. perfluorinated ionomers. It is also concluded that, while the existing models have come a long way in explaining observed overall structural features and properties trends, the goal of fine-tuning novel ionomer materials for a broad range of applications, using a comprehensive model, remains unattained.

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