Superhydrophobicity, Photocatalytic Self-Cleaning and Biocidal Activity Combined in a Siloxane-ZnO Composite for the Protection of Limestone.

The erosion phenomena of the natural stone in cultural heritage are induced by various sources. Consequently, the development of multifunctional protective materials that combine two or more useful properties is an effective strategy in addressing the synergistic effects of various erosion mechanisms. A multifunctional coating, consisting of a silane-based precursor and zinc oxide (ZnO) nanoparticles (NPs), is produced and tested for the protection of limestone. The hybrid coating combines the following three properties: superhydrophobicity, including water-repellency, photocatalytic self-cleaning and biocidal activity. The relative concentration of the NPs (0.8% w/w), used for the suggested composite coating, is carefully selected according to wetting studies, colourimetric measurements and durability (tape peeling) tests. The non-wetting state is evidenced on the surface of the composite coating by the large contact angle of water drops (≈153°) and the small contact angle hysteresis (≈5°), which gives rise to a physical self-cleaning scenario (lotus effect). The photocatalytic chemical self-cleaning is shown with the removal of methylene blue, induced by UV-A radiation. Moreover, it is shown that the suggested coating hinders the incubation of E. coli and S. aureus, as the inhibitions are 94.8 and 99.9%, respectively. Finally, preliminary studies reveal the chemical stability of the suggested coating.