The Nonequilibrium Crystallization Force

Abstract

The forces exerted by growing crystals on the surrounding materials play a major role in many geological processes, from diagenetic replacement to rock weathering and uplifting of rocks and soils. Although crystallization is a nonequilibrium process, the available theoretical prediction for these forces are based on equilibrium thermodynamics. Here we show that nonequilibrium effects can lead to a drop of the crystallization force in large pores where the crystal surface dissociates from the surrounding walls during growth. The critical pore size above which such detachment can be observed depends only on the ratio of kinetic coefficients and cannot be predicted from thermodynamics. Our conclusions are based on a physical model which accounts for the nonequilibrium kinetics of mass transport, and disjoining pressure effects within the thin liquid film separating the crystal and the surrounding walls. Our results suggest that the maximum size of the pores that can sustain crystallization forces close to the equilibrium prediction ranges from micrometers for salts to a millimetre for low solubility minerals such as calcite. These results are discussed in the light of recent experimental observations of the growth of confined salt crystals.

References in corpus (5)

• Ion Transport and Precipitation Kinetics as Key Aspects of Stress Generation on Pore Walls Induced by Salt Crystallization
• Cavity formation in confined growing crystals
• Thin film modeling of crystal dissolution and growth in confinement
• Crystal growth in nano-confinement: Subcritical cavity formation and viscosity effects
• Confined Growth with slow surface kinetics: a Thin Film Model approach

Cited by in corpus (2)

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