Simulated and Experimental Trends Regarding Water Uptake in Polymeric Electrolyte Membranes.

Polymeric membranes in an anion or a proton exchange membrane fuel cell need sufficient hydration in order to provide a high hydroxide ion or proton conductivity. The water uptake for six model ionomer membranes, all of the same ion exchange capacity, is modeled by dissipative particle dynamics. The architectures cover three types of families that are of potential interest in fuel cell membrane research. All architectures consist of connected hydrophobic backbone A beads, to which side chains are grafted. For the type I family, the hydrophilic (functional) C beads are pendent on (amphiphilic) [AxC] side chains. The type II architecture contains both hydrophobic [A4] and short hydrophilic [C] side chains. For type III, the C beads are embedded along various locations within the [AxCAy] side chains (x + y = constant). For similar equilibrium time, the membrane water volume fraction increases with side chain length x for type I, and for type III, it increases with the distance x that C beads are separated from the backbone. Among the architectures (types I and III) for which the number of covalent C-A bonds are the same, the water uptake increases with the average number of A-A and A-C bonds (dpd springs) between A beads and the nearest C bead. A picture emerges in which for similar ion exchange capacity model membranes water uptake increases as a function of ⟨Nbondphob-phyl⟩.