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.

Cleaning is a fundamental phase of the conservation and maintenance activity of the cultural heritage. It is required to be highly effective in the removal of undesired deposits, controllable at every stage and gradable, selective, and completely respectful of the substrate. Moreover, cleaning procedures which can also assure to be harmless to the environment and the operators are particularly valued nowadays. According to these general guidelines, in the present work a sustainable approach for the cleaning of indoor surfaces of the cultural heritage is presented. A methodology based on agar gel was setup and preliminary tested on pilot areas. It has been then applied to the stone sculpted surfaces of the “Fuga in Egitto” high-relief of the Duomo of Milan. A multi-analytical approach was carried out during the setup phase to compare the efficacy of different cleaning conditions in terms of agar concentration, application time and presence of additives. Hence, spectrophotometric measurements, optical observations, ESEM-EDX analyses, Fourier Transform Infrared Spectroscopy, and X-Ray Diffraction were performed. Specific attention was paid to the aesthetic features of the sculpted surfaces before and after the cleaning. For this purpose, spectrophotometric data have been analysed by multivariate analysis techniques such as Principal Component Analysis and Hierarchic Cluster Analysis. The overall intervention has been monitored to evaluate the cleaning results and to confirm the absence of any damage to the stone substrate. The application of agar gel proved to be effective in removing soluble salts and soot particles, as well as very respectful of the valuable sculpted surfaces. This methodology is also totally safe for both the operators and the visitors, it is based on a natural and low-cost raw material, and it is low time-consuming. It can be therefore considered as a sustainable alternative to the traditional procedures.

It is known that oil paintings containing zinc white are subject to rapid degradation. This is caused by the interaction between the active groups of binder and the metal ions of the pigment, which gives rise to the formation of new zinc complexes (metal soaps). Ongoing studies on zinc white paints have been limited to the chemical mechanisms that lead to the formation of zinc complexes. On the contrary, little is known of the photo-physical changes induced in the zinc oxide crystal structure following this interaction. Time-resolved photoluminescence spectroscopy has been applied to follow modifications in the luminescent zinc white pigment when mixed with binder. Significant changes in trap state photoluminescence emissions have been detected: the enhancement of a blue emission combined with a change of the decay kinetic of the well-known green emission. Complementary data from molecular analysis of paints using Fourier transform infrared spectroscopy confirms the formation of zinc carboxylates and corroborates the mechanism for zinc complexes formation. We support the hypothesis that zinc ions migrate into binder creating novel vacancies, affecting the photoluminescence intensity and lifetime properties of zinc oxide. Here, we further demonstrate the advantages of a time-resolved photoluminescence approach for studying defects in semiconductor pigments.

Innovative nanostructured treatments for stone conservation, based on dispersions of photoactive TiO₂ nanoparticles, recently studied in our research group, provided interesting results after laboratory testing. Unfortunately, it is almost impossible to accurately reproduce in the lab the complexity of field exposure conditions. It is then of crucial importance to evaluate the behaviour and durability of new treatments in situ, once they are applied to real deteriorated surfaces of the architectural heritage exposed in outdoor. In the present research, the effectiveness of a TEOS-nano-TiO₂ treatment and of two nanocomposites based on nano-TiO₂ dispersion in organosiloxane and functionalized SiO₂ for the protection of two specific marbles—Candoglia and Crevoladossola—has been evaluated on-site. The effect of the introduction of innovative titania nanoparticles in selected commercial products has been examined focusing on compatibility and protection efficacy in real exposure condition. An on-site testing protocol has been defined and carried out for 12 months after the application, considering colour and morphology changes and water absorption by capillarity. The nano-TiO₂ addition does not hinder the performance of the protective treatments while it provides a positive contribution in soiling reduction. The results will be implemented in the operative framework of the ongoing conservation project of the considered historical façade.