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Structure, Thermodynamics, and Dynamics of Thin Brine Films in Oil-Brine-Rock Systems.

Thin brine films are ubiquitous in oil-brine-rock systems such as oil reservoirs and play a crucial role in applications such as enhanced oil recovery. We report the results of molecular simulations of brine films that are confined between model oil (n-decane) and rock (neutral or negatively charged quartz slabs), with a focus on their structure, electrical double layers, disjoining pressure, and dynamics. As brine films are squeezed to ~0.7 nm (~3 water molecule layers), the structures of the water-rock and water-oil interfaces change only marginally, except that the oil surface above the brine film becomes less diffuse. As the film is thinned from ~1.0 to ~0.7 nm, ions are enriched (depleted) near the rock (oil) surface, especially at a bath ion concentration of 0.1 M. These changes are caused primarily by the reduced dielectric screening of water and the weakened ion hydration near water-oil interfaces and, to a smaller extent, by the increased confinement. When the brine film is ~1.0-nm thick, hydration and EDL forces contribute to the disjoining pressure between the charged rock and the oil. The EDL forces are reduced substantially as the ion concentration increases from 0.1 to 1.0 M and the magnitude of the reduction is close to that predicted by the Poisson-Boltzmann equation. When the brine film is thinned from ~1.0 to ~0.7 nm, the disjoining pressure increases by ~10 MPa, which is mostly due to an increase in the hydration forces. The first layer of water on the rock surface is nearly stagnant, even in 0.74-nm-thick brine films, whereas the viscosity of water beyond the first layer is bulk-like and the slip coefficient of oil-water interfaces is close to that under unconfined conditions. The insights that are obtained here help lay a foundation for the rational application of technologies such as low-salinity waterflooding.