ABSTRACT
Hysteresis in the saturation versus capillary pressure curves of neutrally wettable fibrous media was simulated with a random pore network model using a Voronoi diagram approach. The network was calibrated to fit experimental air-water capillary pressure data collected for carbon fibre paper commonly used as a gas diffusion layer in fuel cells. These materials exhibit unusually strong capillary hysteresis, to the extent that water injection and withdrawal occur at positive and negative capillary pressures, respectively. Without the need to invoke contact angle hysteresis, this capillary behaviour is re-produced when using a pore-scale model based on the curvature of a meniscus passing through the centre of a toroid. The classic Washburn relation was shown to produce erroneous results, and its use is not recommended when modelling fibrous media. The important effect of saturation distribution on the effective diffusivity of the medium was also investigated for both water injection and withdrawal cases. The findings have bearing on the understanding of both capillarity in fibrous media and fuel cell design.
ABSTRACT
Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.
