• Energy Research

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.

Cleaning is one of the most important, essential, and delicate operation which has to be handled by conservators before applying new materials to any substrates. In past decades, nanotechnology introduced new concepts and materials in the conservation field, which have been providing many advantageous performances, especially higher than older materials. As a result, the conservators have already started to use nanomaterials in the cleaning processes of artifacts. Taking into consideration this new approach, our study has focused on using nano-structured emulsions (NSE) as smart cleaning materials for removing polymer coatings (e.g., acrylic polymers). For this purpose, Paraloid B-72 was applied on three different substrates (glass, Lecce stone, and Arenaria stone) and cleaning was performed by a specific nano-structured emulsion (NSE) based on an eco-friendly surfactant (EcoSurf) and two organic solvents in different proportions. In order to better understand the interaction of surfactant and organic solvents with polymer coating, plain EcoSurf in water was also used for comparison. In this study, the decay process of the considered polymer was also deeply studied, because it directly affects the cleaning effectiveness. Coated specimens of the different substrates were artificially aged and examined by different techniques: chromatic variations and contact angle measurements, optical microscopy, FTIR, and SEM-EDS. This material characterization process is important to understand the colour, morphology, and micro-structural difference, and the changes of hydrophobic behaviour as well as chemical composition of Paraloid B-72 polymer due to different ageing processes. After that, substrates coated with both unaged and aged polymer were cleaned by NSE according to the direct-contact procedure and cellulose pulp method. Preliminary analyses suggested that the direct-contact cleaning performed by nano-emulsion (i.e., NSE) induced a complete removal of the acrylic polymer, despite that this method is not recommended for the artifacts and can be hardly applicable in real cases. On the other hand, experimental results showed that satisfactory cleaning of stone substrates can be obtained by using NSE/the cellulose pulp system.

In a MeOH solution the complex [ZnII(L)]2+ gives an adduct with the coumarin-343 anion and an electronic energy transfer process takes place from the fluorophore placed on the ligand L to the fluorescent anion, according to a mechanism which can be reversively switched OFF–ON following an acid–base input.

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