No abstract

Solutions of Nafion® with an ion exchange capacity (IEC) of 0.91 meq g(-1), which are on the verge of the formation of SO(3)H nanoclusters, were spin coated on silicon (Si), glassy carbon (GC) and platinum/silicon (Pt/Si) substrates to form films of up to 256 nm thickness. Nanostructure of the films was studied using Doppler broadening of annihilation radiation (DBAR), positron annihilation lifetime (PAL), X-ray photoelectron spectroscopy (XPS), an atomic force microscope (AFM) and contact angle measurements. Contact angles as low as 10 degrees indicate that the surface of dry ultrathin Nafion® films on Si is highly hydrophilic. XPS data of 10 nm thick, ultrathin film on Si show that oxygen concentration is enhanced and the SO(3)H group concentration, in other words, IEC on the surface is much higher than other films. The S parameter measured by DBAR of an ultrathin Nafion® film on Si is much higher than that of the films on the other substrates. We consider that a large number of hydrophilic, reversed micelle like SO(3)H groups are on the surface of the ultrathin Nafion® film on Si but not on the surface of other films. Positrons implanted into the film are trapped by the SO(3)H clusters, annihilating with the electrons of oxygen and exhibit the high S parameter. The SO(3)H concentration on the surface of thin Nafion® films on GC and Pt/Si substrates may not be so high as the threshold for the formation of a large number of SO(3)H clusters. Positrons implanted into the films annihilate mostly with fluorine atoms, resulting in a low S parameter. The film-substrate interaction plays an essential role in nanostructuring of Nafion® thin films, which may also be the case for Nafion® on the catalysts of polymer electrolyte fuel cells.

To understand the relationship between surface morphology and proton conduction of polymer electrolyte thin films, perfluorinated ionomer Nafion® thin films were prepared on different substrates such as glassy carbon (GC), hydrophilic-GC (H-GC), and platinum (Pt) as models for the ionomer film within a catalyst layer. Atomic force microscopy coupled with an electrochemical (e-AFM) technique revealed that proton conduction decreased with film thickness; an abrupt decrease in proton conductance was observed when the film thickness was less than ca. 10 nm on GC substrates in addition to a significant change in surface morphology. Furthermore, thin films prepared on H-GC substrates with UV-ozone treatment exhibited higher proton conduction than those on untreated GC substrates. However, Pt substrates exhibited proton conduction comparable to that of GCs for films thicker than 20 nm; a decrease in proton conduction was observed at ∼5 nm thick film but was still much higher than for carbon substrates. These results indicate that the number of active proton-conductive pathways and/or the connectivity of the proton path network changed with film thickness. The surface morphology of thinner films was significantly affected by the film/substrate interface and was fundamentally different from that of the bulk thick membrane.

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