Water uptake and swelling hysteresis in a nafion thin film measured with neutron reflectometry

Water uptake and swelling in a thin (∼15 nm) Nafion film on SiO2 native oxide on a Si wafer is studied as a function of relative humidity (8-97%) at room temperature and as a function of temperature (25-60 °C) at 97% relative humidity by neutron reflectometry. This is the first report on the behavior of thin Nafion films at elevated temperatures and high humidity. Large hysteresis is observed during the temperature cycle. The observed swelling strain in the film at 60 °C is 48% as compared to the as-deposited state, which is far above any previously observed trend at room temperature. A small decrease in the average SLD suggests that part of the additional swelling is due to thermal expansion, but the estimated D2O/SO3 ratio also increases by 70%. Half of the "excess" absorption and 73% of the additional swelling are retained during cooling back to room temperature. The results provide new insights into the dynamics of Nafion on nanometer scales under fuel cell operating conditions.