Mesoscale modeling of hydrated morphologies of sulfonated polysulfone ionomers

The hydrated morphologies of sulfonated poly(phenylene) sulfone (sPSO2) ionomers as a function of equivalent weight (EW), molecular weight (MW), and water content were investigated by using mesoscale dissipative particle dynamics (DPD) simulations. The morphological changes were characterized by analyzing the water distribution and plotting the radial distribution functions for the water particles. The results were compared to typical PFSA ionomers (i.e., Nafion and Aquivion) to evaluate the effects of backbone and side chain chemistry. Our results show that water is more likely to be equally distributed within the hydrophilic domains of the sPSO2 ionomers particularly at low water content, which is in contrast to strong phase separation observed in PFSA ionomers at the same level of hydration. As the degree of sulfonation is increased (i.e., decreasing the EW), well-connected water clusters develop in the sPSO2 ionomers even at low water content which are less affected by changes in the MW than observed for PFSA ionomers. The size of the water clusters is estimated to be from 1.2 to 1.5 nm (compared to ∼ 3.5 nm in Nafion) at a water content of 7H2O/SO3H, which is consistent with results determined from previous experiments. This suggests that the high proton conductivity observed in the sPSO2 ionomers is due to the well-connected hydrophilic pathways.