• Energy Research

Stone surfaces and façades of historic buildings, due to their predominately outdoor location, suffer from many deterioration factors, including air pollution, soluble salts, relative humidity (RH)/temperature, and biodeterioration, which are the main causes of decay. In particular, the façades of the buildings deteriorate with direct exposure to these factors; deformation and disfiguration of superficial decoration and formation of black crusts are often observed on the stones. The development and application of self-cleaning and protection treatments on historical and architectural stone surfaces could be a significant improvement in the conservation, protection and maintenance of Cultural Heritage. A titanium dioxide nanoparticle has become a promising photocatalytic material, owing to its ability to catalyze the complete degradation of many organic contaminants and environmental factors. In this study, TiO2 nanoparticles, dispersed in an aqueous colloidal suspension, were applied directly to historic marble stone surfaces, by spray-coating, in order to obtain a nanometric film over the stone surface. The study started with an investigation of some properties of TiO2 nanoparticles, to assess the feasibility of the use of TiO2 on historic stone and architectural surfaces. Scanning electron microscopy (SEM) was, coupled with energy dispersive X-ray (EDX) microanalysis, (SEM-EDX), in order to obtain information on coating homogeneity and surface morphology, before and after artificial aging; the activity of the coated surface was evaluated through UV-light exposure, to evaluate photo-induced effects. The changes of molecular structure occurring in treated samples were spectroscopically studied by attenuated total reflection infrared spectroscopy (ATR-FTIR); activity of the hydrophobic property of the coated surface was evaluated by Sterio microscopy, model Zeiss 2010 from Munich, Germany, equipped with photo camera S23 under 80X magnification. The efficacy of the treatments was evaluated through capillary water absorption, and colorimetric measurements, performed to evaluate the optical appearance. Results showed that TiO2 nanoparticles are good candidates for coating applications on historic stone surfaces, where self-cleaning photo-induced effects are well evident; they enhanced the durability of stone surfaces toward UV aging, improved resistance to relative humidity (RH)/temperature and abrasion affect, reduced accumulation of dirt on stone surfaces when left in open air for 6 months, and did not alter the original features.

The unwanted changes in valuable historic calcareous stone monuments due to exposure to many physical and chemical effects may lead to its deterioration. The growing interest in the field of conservation of stone monuments encourages the development of consolidation and water-repellent materials. The aim of this study is to evaluate the effectiveness of CaCO3 nanoparticles as a consolidation and protection material for calcareous stone monuments, when those nanoparticles used are dispersed in acrylic copolymer; polyethylmethacrylate (EMA)/methylacrylate (MA) (70/30), respectively. Samples were subjected to artificial aging by relative humidity/temperature to show the optimum conditions of durability and the effectiveness of the nano-mixture in improving the physical and mechanical properties of the stone material. The synthesis process of CaCO3 nanoparticles/polymer nanocomposite has been prepared by in situ emulsion polymerization system. The prepared nanocomposites with 0.15 g CaCO3 nanoparticles showed obvious transparency features and represent nanocomposites coating technology with hydrophobic, consolidating and good protection properties. Some tests were performed in order to estimate the superficial consolidating and protective effect of the treatment. The obtained nanocomposites have been characterized by TEM, while the surface morphology before and after treatment and homogeneous distribution of used consolidation materials on stone surface were examined by SEM. Improvement of stone mechanical properties was evaluated by compressive strength tests. Change in water-interaction properties was evaluated by water absorption capillarity measurements, and colorimetric measurements were used to evaluate the optical appearance. Taken together, the results indicate that CaCO3/polymer nanocomposite is a completely compatible, efficient material for the consolidation of artistic and architectural limestone monuments capable of enhancing the durability of limestone toward artificial aging and improving the stone mechanical properties compared to the samples treated with pure acrylic copolymer without Calcium carbonate nanoparticles.