Molecular Dynamics Simulations of Calcite Fracture in Water

QY Wang and J Rimsza and JA Harvey and P Newell and M Grünwald and AG Ilgen, JOURNAL OF PHYSICAL CHEMISTRY C, 128, 375-383 (2023).

DOI: 10.1021/acs.jpcc.3c05702

Calcite (CaCO3) is one of the most common minerals in geologic and engineered systems. It is often in contact with aqueous solutions, causing chemically assisted fracture that is critical to understanding the stability of subsurface systems and manmade structures. Calcite fracture was evaluated with reactive molecular dynamics simulations, including the impacts of crack tip geometry (notch), the presence of water, and surface hydroxyl groups. Chemo-mechanical weakening was assessed by comparing the loads where fracture began to propagate. Our analyses show that in the presence of a notch, the load at which crack growth begins is lower, compared to the effect of water or surface hydroxyls. Additionally, the breaking of two adjacent Ca-O bonds is the kinetic limitation for crack initiation, since transiently broken bonds can reform, not resulting in crack growth. In aqueous environments, fresh (not hydroxylated) calcite surfaces exhibited water strengthening. Manual addition of H+ and/or OH- species on the (104) calcite surface resulted in chemo-mechanical weakening of calcite by 9%. Achieving full hydroxylation of the calcite surface was thermodynamically and kinetically limited, with only 0.17-0.01 OH/nm(2) surface hydroxylation observed on the (104) surface at the end of the simulations. The limited reactivity of pure water with the calcite surface restricts the chemo- mechanical effects and suggests that reactions between physiosorbed water and localized structural defects may be dominating the chemo- mechanical process in the studies where water weakening has been reported.

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