A colloidal route was exploited to synthesize TiO₂ anisotropic nanocrystal rods in shape (TiO₂ NRs) with a surface chemistry suited for their dispersibility and processability in apolar organic solvents. TiO₂ NRs were dispersed in chloroform and n-heptane, respectively, and the two resulting formulations were investigated to identify the optimal conditions to achieve high-quality TiO₂ NR-based coatings by the spray-coating application. In particular, the two types of TiO₂ NR dispersions were first sprayed on silicon chips as a model substrate in order to preliminarily investigate the effect of the solvent and of the spraying time on the morphology and uniformity of the resulting coatings. The results of the SEM and AFM characterizations of the obtained coatings indicated n-heptane as the most suited solvent for TiO₂ NR dispersion. Therefore, an n-heptane dispersion of TiO₂ NRs was sprayed on a highly porous limestone—Lecce stone—very commonly used as building material in historic constructions and monuments present in Apulia Region (Italy). A comprehensive physical-chemical investigation of the TiO₂ NR based treatment on the surface of the stone specimens, including measurements of colour variation, static contact angle, water transfer properties, and morphological characterization were performed. Finally, the photocatalytic properties of the coatings were assessed under solar irradiation by using Lecce stone specimens and Methyl Red as a model target compound. The obtained results demonstrated that TiO₂ NRs based coatings can be successfully applied by spray-coating resulting in an effective photocatalytic and hydrophobic treatment, which holds great promise as a material for the environmental protection of architectural stone in the field of cultural heritage conservation.

Many polymers, able to confer a hydrophobicity to treated surfaces, have been proposed for the restoration and conservation of civil and monumental buildings. Polysiloxanes, and their precursors, the silanes, have been frequently employed for stone protection. To avoid decay of the treated surfaces, the effectiveness and harmlessness of the treatment need to be carefully evaluated before application in the field. In this study, a commercial alkyl-siloxane was tested as a protective treatment on a highly porous stone, starting from water solutions with different contents of the product. The treatments have been devised to try to balance the requirements and the sustainability of the conservative actions. Sustainability, in terms of costs and environmental impact, is regarded as a key factor in the 21st century. Morphological observations of the stone surface, static contact angle and colour measurements, water vapour transmission test, and tests of water absorption were carried out to characterize the untreated and treated stones. A concentration below the minimum level suggested by the manufacturer was still able to act as a good barrier against water. More concentrated solutions produced polymer accumulation and coatings with extended cracks. The properties of the treated stone were affected by the presence of cracks in the coating.

Conservation strategies to limit the degradation of stone materials are being constantly developed. To this aim, new materials are designed to confer hydrophobic properties and anti-graffiti protection to the treated surfaces. Hybrid nanocomposites, based on inorganic nano-particles added to an organic matrix, have been recently proposed for treatments of stone surfaces, obtaining promising and innovative properties. In the present paper, an experimental product based on fluorine resin containing SiO₂ nano-particles, a commercial fluorine-based product and a silicon-based material were applied as protective coatings on two calcareous stones (compact and porous) widely employed in the Mediterranean region. All the studied products are expected to provide both water and anti-graffiti protection to both stones’ surfaces. The rheological characterization of the liquid products, changes in color of the surfaces, and variations in water vapor permeability allowed the compatibility of the protective systems applied to stones to be evaluated. Water–stone contact angle measurements and water absorption by capillarity were used to control the action against water ingress. The oleophobicity was assessed by measuring the oil–stone contact angle. The experimental nano-filled product proved to be a suitable hydrophobic coating for compact and porous stones; furthermore, it provides high oleophobicity to the treated surfaces, as required for anti-graffiti systems.

The application of hydrophobic treatments to stone surfaces is the most common proven method to prevent, or at least limit, the degradation of stone-made constructions and artworks brought about by the ingress and action of water, in particular in the case of very porous stone materials. To avoid the use of protective products containing harmful solvents, new green products have been proposed. In this paper, an eco-friendly hydrophobic coating, based on a fluorine polymer dispersed in water, was deeply analyzed to evaluate its protective properties, especially for very porous stone substrates. To this aim, a wide characterization of treated and untreated Lecce stone elements, i.e., a stone typical of the Apulia region, was carried out to assess the optimum required amount, the effectiveness and the protective capability, even against graffiti staining, of the green hydrophobic treatment, still allowing the stone to retain adequate vapor permeability. The efficacy of the eco-friendly product was analyzed also after a short time (four weeks) of outdoor exposure. Suitable performance and short-term durability of the green hydrophobic coating were found, comparable or even greater than those reported in the current literature for other widespread commercial products, confirming the capability of the product to preserve porous stone surfaces even in absence of solvents in its formulation. The study also allowed to experiment with the “contact sponge” test as an appropriate method for evaluating the water absorption properties of the stone.

In recent years, graffiti writings are increasingly regarded as a form of art. However, their presence on historic building remains a vandalism and different strategies have been developed to clean or, preferably, protect the surfaces. In this study, an experimental nano-filled coating, based on fluorine resin containing SiO₂ nano-particles, and two commercial products have been applied on compact and porous calcareous stones, representative of building materials used in the Mediterranean basin, and their anti-graffiti ability has been analyzed. All the tested experimental and commercial coatings exhibited high hydrophobicity and oleophobicity, thus meeting one of the basic requirements for anti-graffiti systems. The effects of staining by acrylic blu-colored spray paint and felt-tip marker were, then, assessed; the properties of the treated stone surfaces after cleaning by acetone were also investigated. Visual observations, contact angle measurements and color evaluations were performed to this aim. It was found that the protective coatings facilitated the spray paint removal; however high oleophobicity or paint repellence did not guarantee a complete cleaning. The stain from the felt-tip marker was confirmed to be extremely difficult to remove. The cleaning with a neat unconfined solvent promoted the movement of the applied polymers (and likely of the paint, as well) in the porous structure of the stone substrate.

An experimental nano-filled coating, based on a fluorine resin containing SiO₂ nano-particles, was applied on calcareous stones, representative of materials used in buildings and monuments of the Mediterranean basin; for comparison purposes, two commercial products were applied on the same substrates. The efficacy of the protective treatments was assessed by analyzing different characteristics of the three experimental/commercial products, i.e., color changes and permeability to water vapor to evaluate the treatments’ harmlessness; capillary water absorption and water stone contact angle to evaluate the protection against water ingress; oleophobicity of the treated surfaces and the behavior under staining by acrylic blue-colored spray paint and felt-tip marker to verify the anti-graffiti action. Finally, the properties of the treated stone surfaces were analyzed also after the application of pancreatin, used to simulate bird excreta (guano). The protective coatings were found to promote graffiti removal, reducing also the detrimental effects due to simulated guano. The experimental nano-filled product, in addition, was able to provide outstanding performance but using smaller amounts of product in comparison to commercial systems.