Aspects of fatigue failure mechanisms in polymer fuel cell membranes

The swelling‐driven fatigue behavior of polymer fuel cell membranes during relative humidity (RH) cycling is investigated. In particular, swelling‐induced membrane stresses are obtained from a numerical model simulating fuel cell RH cycle tests, and compared to the lifetimes obtained experimentally from tests conducted in the absence of electrochemical effects. A strong correlation between the lifetimes of the membranes in the actual tests and model results is obtained. In general, higher RH (or swelling) amplitude results in larger stress amplitudes and shorter lifetime, that is, fewer cycles to failure. Tensile stresses are needed for forming local cavities in the membrane, which may eventually lead to craze formation. Cavitation is less likely to occur in compressed membrane at high humidities. The stress–lifetime plots for polymer fuel cell membranes exhibit similar features to those observed for other polymers. The crazing criterion for polymers suggests that craze initiation during RH cycling is more likely to occur in the low compression regions, such as under the channels, which is in agreement with experimental observations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1506–1517, 2011