Constitutive response and mechanical properties of PFSA membranes in liquid water

The mechanical properties and swelling behavior of perfluorosulfonic acid (PFSA) membranes in liquid water have been investigated using a custom-built, temperature-controlled water bath. Interestingly, the theoretical models of Mooney–Rivlin and Ogden for rubber elasticity are shown to reproduce the major features of the experimentally obtained stress–strain relationships. In addition, stress relaxation of the membrane subjected to a fixed strain at room temperature fits time-dependent constitutive models used to describe nonlinear rubber elasticity. Thus, the experimental results suggest that even though PFSA is not an elastomer, the constitutive models developed for rubber-like behavior can be used for describing the ex situ constitutive response of PFSA membranes with high water content. This response is in contrast to the constitutive behavior of PFSA membranes swollen in water vapor (e.g. humid air and consequently lower water absorption in the membrane) where studies have suggested constitutive behavior corresponding to that of semicrystalline polymers, including distinct features such as a linear regime followed by onset of nonlinearity.