The morphology and elemental compositions at the surface of poly(styrene sulfonic acid) (PSSA) grafted poly(ethylene‐co‐tetrafluoroethylene) polymer electrolyte membranes (ETFE‐PEMs) in a grafting degree (GD) range of 0%–127% are investigated by using FE‐SEM and XPS analyses. The concentrations of elemental components at the surface are not a linear function of GDs, resulting from different grafting speeds at the surface and bulk. In addition, low accumulation of PSSA grafts on the surface of ETFE‐PEMs in the low GDs of 0%–19%, as well as their homogeneous distribution through the membranes at least at a GD of 19% are observed. At higher GDs of 19%–127%, the PSSA accumulation on the surface is relatively limited, indicating the presence of more PSSA grafts inside the bulk than on the surface. The surface signatures of ETFE‐PEMs over the entire GD range can be determined based on the grafting process. These interesting observations suggest the significant advantages of interfacial properties of ETFE‐PEMs for fuel cell applications.
The subnano free‐volume hole features of Nafion‐212 and poly(styrene sulfonic acid) grafted poly(ethylene‐co‐tetrafluoroethylene) polymer electrolyte membranes are investigated by using the positron annihilation lifetime spectroscopic analyses with three‐ and four‐component models (i.e., one‐ and two‐ortho‐positronium [o‐Ps] components). The four‐component model provides a more adequate description of free‐volume hole features for both membranes, in which the longer o‐Ps lifetime is assigned to the larger free volume hole sizes in the mobile side chains, while the shorter o‐Ps lifetime is associated with the smaller free volume hole sizes within the backbones (the rigid amorphous fractions and the crystalline‐amorphous interfaces) and the interfaces between the main chains and the side chains. The o‐Ps annihilation is found to occur primarily in the side chains. The subnano volume hole features revealed by the positron annihilation lifetime (PAL) spectra suggest the primary water uptake and conductance in the side chains and the possible presence of water molecules in the rigid amorphous fractions and the interfaces. Note that the three‐component model as usually reported in the literature may underestimate the lifetime and intensity of ortho‐positronium annihilation.
The extensive ultrasmall-angle X-ray scattering measurements are performed in order to investigate the changes of lamellar grains of poly(styrenesulfonic acid)-grafted poly(ethylene-co-tetrafluoroethylene) polymer electrolyte membranes (ETFE-PEMs) that occur during the alteration of grafting degree (GD) under dry and immersed conditions. The lamellar grains of three series of the samples (polystyrene-grafted ETFE films and dry and hydrated ETFE-PEMs) are formed during the grafting process and develop independently with the change of the lamellar stacks. Interestingly, three series of samples exhibit a very similar trend of lamellar grain at any GD and a significant amount of graft chains is observed directly in the region between the grains (GD £ 59%) and outside of the grain network structures (GD > 59%). This observation indicates: i) The formation of the lamellar grains; ii) The rapid changes in characteristic sizes of the lamellar grains compared with the lamellar stacks; and iii) The newly generated phases consisting of only the graft materials. These findings explain why the lamellar grains and the graft chains play an important role in the higher proton conductivity and compatible tensile strengths of the membranes, compared with Nafion, at the immersed and severe operating conditions.
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