Hygro-thermal mechanical behavior of Nafion during constrained swelling

Abstract Durability is a major limitation of current proton exchange membrane fuel cells. Mechanical stress due to hygro-thermal cycling is one failure mechanism of the polymer electrolyte membrane. In previous work the cyclic rate, temperature, and hydration dependent elastic–viscoplastic mechanical behavior of Nafion has been extensively investigated in uniaxial and biaxial tension, serving as a data basis and means of validation for a three-dimensional constitutive model. Here, the important effect of loading via constrained swelling is studied. Specifically, two types of loading are investigated: partially constrained swelling via a bimaterial swelling test and hygro-thermal cycling within a fuel cell. The bimaterial swelling conditions are examined via experiments in conjunction with modeling. Nafion/GDL bimaterial strips were hydrated and observed to curl significantly with the membrane on the convex side due to the large Nafion hygro-expansion coefficient. Upon drying the bimaterial strips developed a slight reverse curvature with the membrane on the concave side due to the plastic deformation which had occurred in the membrane during hydration. Finite element simulations utilizing the Nafion constitutive model successfully predicted the behavior during hydration and drying, providing insight on the constrained swelling physics and the ability of the model to predict such events. Simulations of in situ fuel cell hygro-thermal cycling are performed via a simplified two-dimensional fuel cell model. The simulation results confirm the finding of other studies that a tensile stress develops in the membrane during drying. Further, a concentration of negative hydrostatic pressure is found to develop just inside the channel region in the dried state supporting the theory of hygro-thermal driven mechanical stresses causing pinhole formation in the channel. The amplitude of the pressure cycling is found to be large and sensitive to both hygro-thermal ramp time and hold time. This finding is important for guiding both start-up and shut-down procedures and accelerated lifetime testing.