Location and size of nanoscale free-volume holes in crosslinked- polytetrafluoroethylene-based graft-type polymer electrolyte membranes determined by positron annihilation lifetime spectroscopy

The location and size of nanoscale free-volume holes (nanoholes) in graft-type polymer electrolyte membranes (PEMs), which were prepared by radiation-induced graft polymerization (grafting) of styrene into crosslinked-polytetrafluoroethylene (cPTFE) films and subsequent sulfonation, were investigated using positron annihilation lifetime (PAL) spectroscopy. The PAL spectra of the PEMs indicated the existence of two types of ortho-positronium (o-Ps) species, corresponding to nanoholes with volumes of 0.11 and 0.38 nm3. A comparison of the PAL data of the PEMs with that of the precursor original cPTFE and polystyrene-grafted films demonstrated the probability that the smaller holes were located in both the PTFE crystalline phases and the poly(styrene sulfonic acid) graft regions, whereas the larger holes are potentially localized in the PTFE amorphous phases. Taking into account both the size and the location of the nanoholes, it was concluded that gas transport through the larger holes in the amorphous PTFE phases was dominant over permeation through the smaller holes in the PTFE crystals and grafted regions. - Highlights: ► Positron annihilation lifetime measurement of graft-type electrolyte membrane. ► There were two types of free-volume holes with different sizes. ► The smaller holes were located in the PTFE crystalline phases and grafted regions. ► The larger holes were located in the PTFE amorphous phases