The long-range attraction between hydrophobic macroscopic surfaces

Abstract

Direct measurements of the long-range strongly attractive force observed between macroscopic hydrophobic surfaces across aqueous solutions are reexamined in light of recent experiments and theoretical developments. The focus is on systems in the absence of submicroscopic bubbles (preexistent or induced) to avoid capillary bridging forces. Other possible interferences to the measurements are also eliminated. The force-distance profiles are obtained directly (no contributions from electrical double layer or hydrodynamics) between symmetric identical hydrophobic surfaces, overall charge-neutral, at the thermodynamic equilibrium and in a quenched state. Therefore in the well-defined geometry of crossed-cylinders, sphere-flat, or sphere-sphere, there is no additional interaction to be considered except the ever-present dispersion forces, negligible at large separations. For the three main categories of substrates rendered hydrophobic, namely surfaces obtained with surfactant monolayers physically adsorbed from solution to deposited ones, and substrates coated with a hydrophobizing agent bonded chemically onto the surface, the interaction energy scales as A exp (−2κD)/2κD at large separations, with measured decay lengths in accord with theoretical predictions, simply being half the Debye screening length, κ−1/2, at least in non vanishing electrolyte. Taken together with the prefactor A scaling as the ionic strength, the interaction energy is demonstrated to have an electrostatic origin in all the systems. Thanks to our recent SFAX coupling force measurements with x-ray solution scattering under controlled nano-confinement, the microstructuration of the adsorbed film emerges as an essential feature in the molecular mechanism for explaining the observed attraction of larger magnitude than dispersion forces. The adsorption of pairs of positive and negative ions on small islands along the interface, the fluctuation of the surface charge density around a zero mean-value with desorption into or adsorption from the electrolyte solution, the correlations in the local surface ion concentrations along the surfaces, the redistribution of counterions upon intersurface variation, all contribute and are tuned finely by the inhomogeneities and defects present in the hydrophobic layers. It appears that the magnitude of the interacting energy can be described by a single master curve encompassing all the systems.