Nucleation in Confinement Generates Long-range Repulsion between Rough Calcite Surfaces

Abstract

Fluid-induced alteration of rocks and mineral-based materials often starts at confined mineral interfaces where nm-thick water films can persist even at high overburden pressures and at low vapor pressures. These films enable transport of reactants and affect forces acting between mineral surfaces. However, the feedback between the surface forces and reactivity of confined solids is not fully understood. We used the surface forces apparatus (SFA) to follow surface reactivity in confinement and measure nm-range forces between two rough calcite surfaces in NaCl, CaCl$_2$, or MgCl$_2$ solutions with ionic strength of 0.01, 0.1 or 1 M. We observed long-range repulsion that could not be explained by changes in calcite surface roughness, surface damage, or by electrostatic or hydration repulsion, but was correlated with precipitation events which started at ${\mu}$m-thick separations. We observed a poorly crystalline or amorphous precipitate that formed in the confined solution. This liquid-like precipitate did not undergo any spontaneous ripening into larger crystals, which suggested that confinement prevented its dehydration. Nucleation was significantly postponed in the presence of Mg$^{2+}$. The long-range repulsion generated by nucleation between confined mineral surfaces can have a crucial influence on the evolution of the microstructure and therefore the macroscopic strength of rocks and materials.