Adsorption of water and organic solvents on the calcite [101¯4] surface: Implications for marble conservation treatments

When exposed outdoors, marble artefacts are subject to degradation caused by dissolution in rain. To improve acid-resistance of marble, surface treatments involving the in situ formation of a passivating calcium phosphate (CaP) layer have been developed. Adding alcohol to the treatment improves CaP coverage but the reason is still unclear. Here, we use computational and experimental studies to ascertain whether the interaction of the organic additives with the marble surface plays a role in determining the treatment outcome. Density functional theory calculations are employed to determine the binding energy of additives on the calcite [101¯4] surface and identify acetone as a promising new additive due to its weak adsorption. Molecular dynamics calculations show that ethanol and isopropanol displace water from the calcite [101¯4] surface forming an immobile, ordered, and hydrophobic layer, while acetone and water form a mixed, dynamic environment. In experimental trials, a continuous (yet cracked) layer of carbonate hydroxyapatite is formed after 24 h, with all organic additives improving the final coating. This result suggests that the interaction of the additive with the marble surface does not play a major role in determining treatment outcomes and other factors should be investigated for the design of improved treatments.