In the field of stone protection, the introduction of inorganic nanoparticles, such as TiO2, ZnO, and Ag in polymeric blends can enhance the protective action of pristine treatments, as well as confer additional properties (photocatalytic, antifouling, and antibacterial). In the framework of the “Nano-Cathedral” European project, nanostructured photocatalytic protective treatments were formulated by using different TiO2 nanoparticles, solvents, and silane/siloxane systems in the blends. The results about the characterization and application of two promising nano-TiO2 based products applied on Apuan marble and Ajarte limestone are here reported, aiming at investigating the complex system “treatment/stone-substrate”. The nanocomposites show better performances when compared to a commercial reference siloxane based protective treatment, resulting in different performances once applied on different carbonatic substrates, with very low and high open porosity, confirming the necessity of correlating precisely the characteristics of the stone material to those of the protective formulations. In particular, the TiO2 photocatalytic behavior is strictly linked to the amount of available nanoparticles and to the active surface area. The alkyl silane oligomers of the water-based formulation have a good penetration into the microstructure of Ajarte limestone, whereas the solvent-based and small size monomeric formulation shows better results for Apuan marble, granting a good coverage of the pores. The encouraging results obtained so far in lab will be confirmed by monitoring tests aiming at assessing the effectiveness of the treatments applied in pilot sites of historical Gothic Cathedrals.

The use of hybrid nanocoatings for the protection of natural stones has received increasing attention over the last years. However, the interaction of these materials with stones and, in particular, its modification resulting from the blending of nanoparticles and matrices, are yet little explored. In this work, the interaction of two nanocomposite coatings (based on alkylalkoxysilane matrices and TiO2 nanoparticles in water and 2-propanol) with two different porous stones is examined in detail by comparing their absorption behaviour and protection performance with those of the respective TiO2-free matrices. It is shown that the protective effectiveness of both matrices is not negatively affected by the presence of TiO2, as the desired water barrier effect is retained, while a significant photocatalytic activity is achieved. The addition of titania leads to a partial aggregation of the water-based matrix and accordingly reduces the product penetration into stones. On the positive side, a chemical interaction between titania and this matrix is observed, probably resulting in a greater stability of nanoparticles inside the protective coating. Moreover, although an effect of TiO2 on the chemical stability of matrices is observed upon UV light exposure, the protective performance of coatings is substantially maintained after ageing, while the interaction between matrices and nanoparticles results in a good retention of the latter upon in-lab simulated rain wash-out.

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Protective coatings, in recent years also from nanocomposite formulations, are commonly applied onto architectural stone and stone artefacts, mainly to prevent absorption of condensed water and dissolved atmospheric pollutants into the porous stone structure. While standard protocols to assess a coating’s performance are available, understanding the response of the coating-stone system is a complex task, due to the interplay of various factors determining the overall behaviour. Characterization techniques allowing one to correlate the extent and nature of surface modification upon treatment with the most relevant physical properties (i.e., water absorption and surface wettability) are thus of great interest. Electrokinetic analysis based on streaming current measurements, thanks to its sensitivity towards even minor changes in the surface chemical composition, may fulfil such requirement. Indeed, by involving the interaction with a testing aqueous electrolyte solution, this technique allows one to probe not only the outer surface, but also the outermost layer of the pore network, which plays a crucial role in the interaction of the stone with condensed atmospheric water. In this work, a correlation was found between the extent of surface modification, as determined by streaming current measurements, surface wettability and capillary water absorption, for three lithotypes with different mineralogical and microstructural properties treated with two nanocomposite formulations (one water based and one in alcoholic solvent) containing organosilica precursors and titania nanoparticles.