Superhydrophobic films for the protection of outdoor cultural heritage assets

A very simple method that can be used to impart superhydrophobicity to stone surfaces of monuments using common and low-cost materials that are already employed or are easy to be found by conservators is presented. A siloxane-nanoparticle dispersion is sprayed on a stone, and this process can result in the formation of a rough two-length-scale hierarchical structure that exhibits water repellent properties, provided that the nanoparticle concentration in the dispersion is higher than a critical value. Superhydrophobicity (static contact angle >150° and contact angle hysteresis <7°) is achieved, by this simple method (i) on the surfaces of three types of stones, Opuka, Božanovský and Hoř ický, which have been used for the restoration of the castle of Prague, (ii) using two poly (alkyl siloxane) products such as Rhodorsil 224 and Porosil VV plus, which are utilized by conservators and (iii) using common nanoparticles such as silica (SiO₂), alumina (Al₂O₃), tin oxide (SnO₂) and titanium oxide (TiO₂). It is shown that the stone substrate and the nanoparticle size (5-50 nm) or type have almost no effect on the wettability of the superhydrophobic surfaces, as comparable contact angles were measured on the three stone substrates, treated with any siloxane-particle composite. Treatments of the stones with pure (hydrophobic) siloxanes and siloxane-SiO₂ (superhydrophobic) composites result in comparable reductions of the water vapor permeability and the water amounts absorbed by capillarity. Consequently, the use of nanoparticles in the protective coatings does not have any obvious effect on the results of the aforementioned tests. However, the aesthetic appearance of the three stones, included in this study, is highly affected by the nanoparticles.