To prevent soiling of marble exposed outdoors, the use of TiO₂ nano-particles has been proposed in the literature by two main routes, both raising durability issues: (i) direct application to marble surface, with the risk of particle leaching by rainfall; (ii) particle incorporation into inorganic or organic coatings, with the risk of organic coating degradation catalyzed by TiO₂ photoactivity. Here, we investigated the combination of nano-TiO₂ and hydroxyapatite (HAP), previously developed for marble protection against dissolution in rain and mechanical consolidation. HAP-TiO₂ combination was investigated by two routes: (i) sequential application of HAP followed by nano-TiO₂ ("H+T"); (ii) simultaneous application by introducing nano-TiO₂ into the phosphate solution used to form HAP ("HT"). The self-cleaning ability was evaluated before and after prolonged exposure to simulated rain. "H+T" and "HT" coatings exhibited much better resistance to nano-TiO₂ leaching by rain, compared to TiO₂ alone. In "H+T" samples, TiO₂ nano-particles adhere better to HAP (having flower-like morphology and high specific surface area) than to marble. In "HT" samples, thanks to chemical bonds between nano-TiO₂ and HAP, the particles are firmly incorporated in the HAP coating, which protects them from leaching by rain, without diminishing their photoactivity and without being degraded by them.
Keywords: anatase; calcium phosphates; consolidation; cultural heritage; leaching; marble; photocatalytic activity; protection; rain; soiling.