Protective ALD Thin Films for Morphologically Diverse Types of Limestone

We report on the results of investigations of atomic layer deposited (ALD) amorphous alumina (Al2O3) coatings for the protection of limestone with a wide range of porosity against acid-based dissolution. The protective effects of the ALD coatings were investigated by aqueous acid immersion. The solution pH was tracked over time for a constant volume of acetic acid solution with an initial pH of 4 with the stone samples immersed. We find the protective effect of ALD alumina coatings is extremely promising, with 90 nm thick coatings slowing the initial and total rate of substrate mass loss significantly by up to two orders of magnitude. The eventual failure of the ALD coatings during immersion was also investigated. Pitted areas on the substrate were discovered and were found to have an area fraction that correlates to the changing pH of the acid solution during immersion. The variation of the protective action of the films with thickness is consistent with kinetics, which are limited by diffusion within the pits rather than through the films. Our findings point to the dominant role of defects in the coatings in their eventual failure. We also show that the appearance of the stone does not change significantly for the thickest and most protective ALD films, making the treatment promising for cultural heritage applications.