Search Results (20)

The erosion phenomena of the natural stone in cultural heritage are induced by various sources. Consequently, the development of multifunctional protective materials that combine two or more useful properties is an effective strategy in addressing the synergistic effects of various erosion mechanisms. A multifunctional coating, consisting of a silane-based precursor and zinc oxide (ZnO) nanoparticles (NPs), is produced and tested for the protection of limestone. The hybrid coating combines the following three properties: superhydrophobicity, including water-repellency, photocatalytic self-cleaning and biocidal activity. The relative concentration of the NPs (0.8% w/w), used for the suggested composite coating, is carefully selected according to wetting studies, colourimetric measurements and durability (tape peeling) tests. The non-wetting state is evidenced on the surface of the composite coating by the large contact angle of water drops (≈153°) and the small contact angle hysteresis (≈5°), which gives rise to a physical self-cleaning scenario (lotus effect). The photocatalytic chemical self-cleaning is shown with the removal of methylene blue, induced by UV-A radiation. Moreover, it is shown that the suggested coating hinders the incubation of E. coli and S. aureus, as the inhibitions are 94.8 and 99.9%, respectively. Finally, preliminary studies reveal the chemical stability of the suggested coating. Full article

The purpose of this research was to study the influence of multifunctional anatase–silica photocatalytic materials (ASPMs) with various photocatalytic and pozzolanic activities on the properties of white portland cement and fine-grained concrete. ASPMs were synthesized by a sol–gel method, during which the levels of photocatalytic and pozzolanic activity were regulated by a certain amount of solvent. ASPMb, obtained with the use of a smaller amount of solvent, was characterized by increased pozzolanic activity due to the lower degree of coating of the surface of diatomite particles with titanium dioxide and the higher content of an opal–cristobalite–tridymite-phase and Bronsted acid sites. They promoted the reaction of diatomite with portlandite of cement stone and allowed significant decreases in the strength of cement–sand mortar to be avoided when replacing 15% of the cement with ASPMs. This allowed self-cleaning fine-grained concrete to be produced, which, after forced carbonization, simulating the natural aging of the product during operation, retained the ability of self-cleaning without changes. ASPMc, produced with the use of a larger amount of solvent with a more uniform distribution of titanium dioxide on the surface of diatomite, allowed fine-grained concrete with a high self-cleaning ability to be obtained, but with a lesser manifestation of the pozzolanic effect. Full article

Due to the ongoing threat of degradation of artefacts and monuments, the conservation of cultural heritage items has been gaining prominence on the global scale. Thus, finding suitable approaches that can preserve these materials while keeping their natural aspect of is crucial. In particular, preventive conservation is an approach that aims to control deterioration before it happens in order to decrease the need for the intervention. Several techniques have been developed in this context. Notably, the application of coatings made of metal oxide nanomaterials dispersed in polymer matrix can be effectively address stone heritage deterioration issues. In particular, metal oxide nanomaterials (TiO₂, ZnO, CuO, and MgO) with self-cleaning and antimicrobial activity have been considered as possible cultural heritage conservative materials. Metal oxide nanomaterials have been used to strengthen heritage items in several studies. This review seeks to update the knowledge of different kinds of metal oxide nanomaterials, especially nanoparticles and nanocomposites, that have been employed in the preservation and consolidation of heritage items over the last 10 years. Notably, the transport of nanomaterials in diverse environments is undoubtedly not well understood. Therefore, controlling their effects on various neighbouring non-target organisms and ecological processes is crucial. Full article

Self-cleaning and hydrophobic treatments based on TiO₂ and SiO₂ nanoparticles are widely applied for the preservation of cultural heritage materials, to improve their resilience in polluted environments. Excellent results have been obtained on stone materials, but experiments on painted stone surfaces, such as wall paintings and polychrome plasters used in historic buildings, are still limited. In this work, we present a study on the use of water dispersions of TiO₂ nanoparticles obtained via sol-gel and organically modified silica (OrMoSil) for cleaning and protective purposes on Lecce stone, a carbonate stone, widely used for its excellent workability but easily attacked by atmospheric agents and pollutants. First, we evaluated the harmlessness of the treatment on Lecce stone through colorimetric tests, water absorption by capillarity and permeability to water vapor. The photocatalytic activity of the TiO₂ nanoparticles was assessed by photo-degradation of methyl orange and methylene blue dyes. The dispersion was then applied on painted samples prepared according to ancient recipes to confirm the effectiveness of the cleaning. The proposed TiO₂/OrMoSil-based coating can act as a self-cleaning and protective treatment on lithic surfaces to prevent degradation phenomena and preserve the original appearance of the monument. Full article

The aim of this study was to develop versatile coatings that can protect the stone surfaces of Architectural Heritage. Two different 3D media, namely superhydrophobic (SPHB) and hydro-oleophobic (OHB), were utilized as host matrices for nanostructured photocatalysts (Bi₂O₃-ZnO 8/92). These photocatalysts were sensitive to visible light to enhance their efficiency when exposed to sunlight. To prevent the nanophotocatalyst from clumping together in the 3D media, non-ionic dispersant additives (Tween20, TritonX-100, and Brij35) were incorporated. The optimized suspensions were then applied to various substrates such as sandstone, limestone, and granite. The effectiveness of the coatings was assessed by evaluating the hydrophobicity, oleophobicity, and photocatalytic activity of the coated substrates. The Bi₂O₃-ZnO photocatalyst exhibited higher activity in the SPHB medium compared to the OHB medium. To simulate real-life conditions, the coated substrates were subjected to accelerated weathering tests to predict their durability. Despite a significant reduction in their thickness, the coatings demonstrated sustained hydrophobic efficiency and self-cleaning capability after the accelerated ageing tests. Full article

Stones are ones of the most ancient natural materials exploited by humans, with different uses, from tools to buildings, that have endured over time in better conditions than other objects belonging to cultural heritage. Given the importance of those silent witnesses of our past, as well as our duty to preserve all parts of cultural heritage for future generations, much effort was put into the development of materials for their consolidation, protection, self-cleaning, or restoration. Protection of ancient stone monuments and objects has gained the interest of researchers in the last decades in the field of conservation of cultural heritage. In this respect, the present paper aims to be a critical discussion regarding potential polymeric materials, which can be used in restorative and conservative approaches for stone materials of cultural heritage importance, against physical degradation phenomena. Recent advances in this area are presented, as well as the current bottle-necks and future development perspectives. Full article

Heritage buildings and monuments are mostly made from natural stone, which undergoes irreversible decay under outdoor conditions. The main reason for the contamination, degradation, and cracking of natural stones is water and oil permeation. Hence, modifications on stones rendering their surface self-cleaning are effective for stone protection. Reported in this paper is the development of a bionic approach to enabling self-cleaning stone surface via growing self-assembled polydopamine (PDA) as the adhesive layer on the stone surface, followed by depositing Al₂O₃ nanoparticles derivatized by self-assembled monolayers of a fluorophosphonic acid (FPA). This approach ensured a robust surface modification that realized superhydrophobicity, as demonstrated on natural marbles, Hedishi, and Qingshi. The surface modification was thermally stable up to 400 °C. Full article

Nowadays, durable protective coatings receive more attention in the field of conservation for several reasons (they are cost effective, time consuming, more resistance, etc.). Hence, this study was focused on producing a multi-functional, durable coating to protect different stone materials, especially, Lecce stone, bricks, and marble. For this purpose, ZrO₂-doped-ZnO-PDMS nanocomposites (PDMS, polydimethylsiloxane used as the binder) were synthesized by in situ reaction (doped nanoparticles were inserted into the polymer matrix during the synthesis of PDMS) and the performances of resulting coatings were examined by handling different experimental analyses. In particular, the study aimed to evaluate the durability properties of the coating along with the self-cleaning effect. As a result, the durability of the nanocomposite coating with respect to the well-known PDMS coating was assessed after exposure to two different ageing cycles: solar ageing (300 W, 1000 h) and humid chamber ageing (RH > 80%, T = 22 ± 3 °C, desiccator, 2 years). All the results were in good agreement with each other providing that newly prepared nanocomposite coating can be used as a durable protective coating for different stone materials. Full article

The development of nanocomposite materials with multifunctional protective features is an urgent need in many fields. However, few works have studied the durability of these materials. Even though TiO₂ nanoparticles have been extensively applied for self-cleaning effect, it displays a weak activity under visible light. Hence, in this study, pure and Gd-doped TiO₂ nanoparticles (molar ratios of doping ions/Ti are 0.1 and 1) were synthesised, characterised, and then mixed with polydimethylsiloxane (PDMS), used as a binder, in order to produce a homogenised thin film on a very porous stone substrate. To our knowledge, Gd-doped TiO₂/PDMS protective coatings are studied for the first time for application on historic structures. The protective coatings developed in this work are intended to reduce the surface wettability of the stone and protect the historic stones from dye pollution and microorganism colonisation. Moreover, in this study, the durability of the developed nanocomposite was deeply studied to evaluate the stability of the coatings. Results confirmed that samples treated with the lowest concentrations of Gd ions (0.1 mol%) showed acceptable chromatic variations, a good repellent feature, acceptable water vapour permeability, good durability, the highest self-cleaning activity, and good inhibitory behaviour against microbial colonisation. Full article

This study evaluated the self-cleaning ability and durability of Si-based consolidants (an ethyl silicate consolidant and a consolidant based on nanosized silica) spiked with nanocrystalline TiO₂ activated by either UV-A radiation (spectral region between 340 and 400 nm, and main peak at 365 nm) or UV-B radiation (spectral region between 270 and 420 nm, and main peak at 310 nm). Granite samples were coated with consolidant, to which nanocrystalline TiO₂ was added at different concentrations (0.5, 1, and 3%, by wt.). Diesel soot was then applied to the coated surfaces, and the samples were exposed to UV-A or UV-B radiation for 1650 h. The surface color changes, relative to the color of untreated granite, were determined every 330 h by color spectrophotometry. Slight color changes indicated a recovery of the reference color due to the degradation of the soot. The final surfaces of both the untreated and treated surfaces were compared by stereomicroscopy and scanning electron microscopy. The main findings were that: (1) In general, the consolidant containing nanosized silica induced the most intense photocatalytic activity. In the more compact xerogel coating formed by the nanosized silica, more TiO₂ nanoparticles were available to interact with the radiation. (2) For all consolidant mixtures, soot degradation remained constant or decreased over time, except with ethyl silicate with 0.5 wt % TiO₂ (no self-cleaning capacity). (3) Soot degradation increased with the concentration of TiO₂. (4) The UV-B radiation was the most effective in terms of soot degradation, except for the surface coated with the ethyl silicate and 3% wt. TiO₂. Full article

The development of innovative materials is one of the most important focus areas in heritage conservation research. Eligible materials can not only protect the physical and chemical integrity of artworks but also preserve their artistic and aesthetic features. Recently, as one of the hot research topics in materials science, biomimetic superhydrophobic materials have gradually attracted the attention of conservation scientists due to their unique properties. In fact, ultra-repellent materials are particularly suitable for hydrophobization treatments on outdoor artworks. Owing to their excellent hydrophobicity, superhydrophobic materials can effectively prevent the absorption and penetration of liquid water as well as the condensation of water vapor, thus greatly relieving water-induced decay phenomena. Moreover, in the presence of liquid water, the superhydrophobic surfaces equipped with a self-cleaning property can clean the dirt and dust deposited spontaneously, thereby restoring the artistic features simultaneously. In the present paper, besides the basic principles of wetting on solid surfaces, materials, and methods reported for preparing bioinspired ultra-repellent materials, the recently proposed materials for art conservation are also introduced and critically reviewed, along with a discussion on the droplet impact and durability of the artificial superhydrophobic surfaces. Lastly, the current status and the problems encountered in practical application are also pointed out, and the focus of future research is presented as well. Full article

Considering that consolidant products are commonly used in the cultural heritage field and the titanium oxide nanoparticles (TiO₂) have been used to develop photocatalyst films to induce self-cleaning property, the scientific research on consolidants doped with TiO₂ is justified. However, the addition of TiO₂ can affect to the physical properties of the cultural heritage object, questioning the adequacy of the procedure. In this paper, we evaluated the influence of nanoparticle TiO₂ addition to two different commercial consolidant products (ethyl silicate or nano-sized silica) on the appearance and the color of a granite and the penetration through its fissure system. The stone was previously subjected to high temperature simulating the effect of a fire and the subsequent tap water jet to cool down. Therefore, different concentrations of nanocrystalline TiO₂ (0.5, 1, and 3 wt %) were considered. The different compositions were also studied considering the compactness, the extent and the thickness of the superficial xerogel coating, and as well the penetration of the consolidant. The minimal TiO₂ concentration tested (0.5 wt %) implied a low-medium risk of incompatibility as an intervention in cultural heritage field, because its low-medium potential as inducer of visible color changes of the granite surface. Regardless of the TiO₂ content, the nano-sized silica induced surface xerogel coatings more compact and continue than those formed in the ethyl silicate coated surfaces. Higher penetration rates were identified in the granite treated with nano-sized silica colloidal solution, while ethyl silicate was only found in the first few µm. It was found that penetration could depend on the application procedure, the solvent of the consolidant and the silica particle size. The TiO₂ addition reduced the penetration of the nano-sized silica consolidant. Full article

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. Full article

In this work, the self-cleaning and photocatalytic properties of mesoporous TiO₂/AuNRs-SiO₂ composites (namely UCA–TiO₂Au) prepared by a simple and low-cost technique were investigated toward application in building materials. Mesoporous photocatalytic nanocomposites coating the surface of stone and other building materials are a very promising approach to address relevant questions connected with the increasing atmospheric pollution. We tested three types of preformed TiO₂/AuNRs nanostructures in order to evaluate the effect of AuNRs on the photocatalytic activity of resulting coatings deposited on the surface of a popular building limestone. The resulting nanocomposites provide crack-free surface coatings on limestone, effective adhesion, improve the stone mechanical properties and impart hydrophobic and self-cleaning properties. Photocatalytic characterization involved the degradation of a target compound (Methylene blue; MB) under direct exposure to simulated solar light using TiO₂ P25 Evonik (TiO₂ P25) as a reference material. Moreover, these coatings upon irradiation by simulated solar light were successfully employed for the photocatalytic oxidation of carbon soot. The experimental results revealed that UCA–TiO₂Au samples are the best performing coating in both MB bleaching and soot degradation. Full article

The high pollution levels in our cities are producing a significant increase of dust on buildings. An application of photoactive coatings on building materials can produce buildings with self-cleaning surfaces. In this study, we have developed a simple sol-gel route for producing Au-TiO₂/SiO₂ photocatalysts with application on buildings. The gold nanoparticles (AuNPs) improved the TiO₂ photoactivity under solar radiation because they promoted absorption in the visible range. We varied the content of AuNPs in the sols under study, in order to investigate their effect on self-cleaning properties. The sols obtained were sprayed on a common building stone, producing coatings which adhere firmly to the stone and preserve their aesthetic qualities. We studied the decolourization efficiency of the photocatalysts under study against methylene blue and against soot (a real staining agent for buildings). Finally, we established that the coating with an intermediate Au content presented the best self-cleaning performance, due to the role played by its structure and texture on its photoactivity. Full article