Organic/inorganic hybrid membranes based on poly(vinyl alcohol) (PVA) and sulfonated polyhedral oligosilsesquioxane (sPOSS), crosslinked by ethylenediaminetetraacetic dianhydride (EDTAD), were prepared as candidate materials for proton exchange membranes in direct methanel fuel cell (DMFC) applications. Fourier transform infrared (FT-IR) spectroscopy and ion exchange capacity measurements for the prepared networks clearly revealed sPOSS incorporation. We found that proton conductivity increased and methanol permeability decreased with increasing sPOSS content in the hybrid membrane. In particular, our hybrid membranes demonstrated proton conductivities as high as 0.042 S/cm, which is comparable to that of Nafion TM , while exhibiting two orders of magnitude lower methanol permeability as compared to Nafion TM . We postulate that the polar sulfonic acid groups of the incorporated sPOSS cages assemble to provide ion conduction paths while the hydrophobic portions of the same sPOSS cages combine to form a barrier to methanol permeation with improved thermal stability of the hybrid membrane.

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Polyurethane (PU)/organoclay nanocomposites were prepared by mixing UV curable urethane acrylate oligomer with organoclay, and a subsequent curing by UV irradiation. As organoclays, commercially available Cloisite 20A (C20A) and acrylsilane modified C20A were used. XRD and TEM analyses revealed that the UV cured PU/clay nanocomposites formed intercalated nanocomposites, and acrylsilane modified C20A are dispersed more finely than unmodified C20A in PU matrix. DMTA, pencil hardness and adhesion test onto PET substrate showed that the clay nanolayers induced an increase in the properties, and the enhancement in the properties was more pronounced in the PU/acrylsilane modified C20A nanocomposites than in the PU/unmodified C20A nanocomposites. It was also observed that the PU/surface modified clay nanocomposites showed remarkably lower shrinkage upon UV curing than the unfilled PU. The nanocomposites showed excellent optical transparency but lower gloss as compared to unfilled PU.