Diffusion in thin films on the surface of a porous solid

A water-wet mono-dispersed glass bead system is saturated with two phases, a wetting phase of water and a non-wetting phase of tetrachloroethylene (no 1H signal). Pulsed field gradient NMR measurements of the one-dimensional probability density distribution P(Delta) (X) for the diffusive displacements of water molecules in times, Delta, are presented for the whole accessible water saturation range. At lower water contents the distributions show a distinctive shape, which is attributed to the distribution of the aqueous phase in thin surface wetting films connecting pendular rings where the beads are in contact. The data are reproduced well by a computer simulation of a random walk model based on diffusion of molecules within such a structure, allowing determination of the surface film thickness.