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Here, we report a study on the structural characteristics of membrane electrode assembly (MEA) samples obtained from a low-temperature (LT) polymer electrolyte membrane (PEM) fuel cell (FC) stack subjected to long-term durability testing for ∼18,500 h of nominal operation along with ∼900 on/off cycles accumulated over the operation time, with the total power production being 3.39 kW h/cm 2 of MEA and the overall degradation being 87% based on performance loss. The chemical and physical states of the degraded MEAs were investigated through structural characterizations aiming to probe their different components, namely the cathode and anode electrocatalysts, the Nafion ionomer in the catalyst layers (CLs), the gas diffusion layers (GDLs), and the PEM. Surprisingly, X-ray diffraction and electron microscopy studies suggested no significant degradation of the electrocatalysts. Similarly, the cathode and anode GDLs exhibited no significant change in porosity and structure as indicated by BET analysis and helium ion microscopy. Nevertheless, X-ray fluorescence spectroscopy, elemental analysis through a CHNS analyzer, and comprehensive investigations by X-ray photoelectron spectroscopy suggested significant degradation of the Nafion, especially in terms of sulfur content, that is, the abundance of the -SO 3 - conduction. Hence, the degradation of the Nafion, in both of the CLs and in the PEM, was found to be the principal mechanism for performance degradation, while the Pt/C catalyst degradation in terms of particle size enlargement or mass loss was minimal. The study suggests that under real-life operating conditions, ionomer degradation plays a more significant role than electrocatalyst degradation in LT-PEMFCs, in contrast to many scientific studies under artificial stress conditions. Mitigation of the ionomer degradation must be emphasized as a strategy to improve the PEMFC's durability.+ conduction. Hence, the degradation of the Nafion, in both of the CLs and in the PEM, was found to be the principal mechanism for performance degradation, while the Pt/C catalyst degradation in terms of particle size enlargement or mass loss was minimal. The study suggests that under real-life operating conditions, ionomer degradation plays a more significant role than electrocatalyst degradation in LT-PEMFCs, in contrast to many scientific studies under artificial stress conditions. Mitigation of the ionomer degradation must be emphasized as a strategy to improve the PEMFC's durability.

This work explores a new technique for the out-of-plane patterning of metal thin films prefabricated on the surface of a polymer substrate. This technique is based on an ion-beam-induced material modification in the bulk of the polymer. Effects of subsurface and surface processes on the surface morphology have been studied for three polymer materials: poly(methyl methacrylate), polycarbonate, and polydimethylsiloxane, by using focused ion beam irradiation with He + , Ne + , and Ga + . Thin films of a Pt 60 Pd 40 alloy and of pristine Au were used to compare the patterning of thin films with different microstructures. We show that the height of Pt 60 Pd 40 thin films deposited onto poly(methyl methacrylate) and polycarbonate substrates can be patterned by He + ion beams with ultrahigh precision (nanometers) while preserving in-plane features, at the nanoscale, of the pre-deposited films. Ion irradiation of the Au-coated samples results in delamination, bulging, and perforation of the Au film, which is attributed to the accumulation of gases from radiolysis at the film-substrate interface. The irradiation with Ne + and Ga + ions destroys the films and roughens the surface due to dominating sputtering processes. A very different behavior, resulting in the formation of complex, multiscale 3D patterns, is observed for polydimethylsiloxane samples. The roles of the metal film structure, elastic properties of the polymer substrate, and irradiation-induced mechanical strain in the patterning process are elaborated and discussed., (Copyright © 2020, Chiriaev et al.; licensee Beilstein-Institut.)

Adding roughness to hydrophilic surfaces is generally expected to enhance their wetting by water. Indeed, global free energy minimization predicts decreasing contact angles when roughness factor or surface energy increases. However, experimentally it is often found that water spreading on rough surfaces is impeded by pinning effects originating from local free energy minima; an effect, largely neglected in scientific literature. Here, we utilize Laplace pressure as a proxy for these local minima, and we map the transition to a superwetting state of hydrophilic nano-textured surfaces in terms of surface chemistry and texture geometry. We demonstrate the effect for polymer model surfaces templated from block-copolymer self-assembly comprising dense, nano-pillar arrays exhibiting strong pinning in their pristine state. By timed argon plasma exposure, we tune surface chemistry to map the transition into the superwetting state of low contact angle, which we show coincide with the surface supporting hemiwicking flow. For the near-ideal model surfaces, the transition to the superwetting state occurs below a critical material contact angle of ∼50°. We show that superwetting surfaces possess anti-fogging properties, and demonstrate long term stability of the superwetting effect by coating the nanotextured surfaces with ∼10 nm thin films of either tungsten or silica.