Functional nano-hydroxyapatite for applications in conservation of stony monuments of cultural heritage

Stone is one of the most durable construction materials used in historic buildings all over the world. However, over time, the stone can be subject to various degradation processes leading to physical and chemical modifications. Although these effects may be limited to the surface and negligible to the structural stability of the affected buildings, they can represent a major problem in decorative elements of artistic value, where any detail should be preserved [1]. The challenge for conservators and material scientists involved in stone conservation has always been to find a way to stop or delay the effects of these degradation processes. The basic principle of the patrimony is that the cultural heritage is an incalculable and integral legacy to our future: observing and knowing the past, will help next generations to better challenge the future. Thus, conservation of stone heritage is always a delicate and complex task, due to the multiple variables that have to be taken into account to identify the problems, and to define the necessary conservation actions and to select materials and best procedures to be used. The variety of factors to be analyzed includes the intrinsic stone properties (from geological features up to mechanical behavior), the state of conservation, the degradation mechanisms and the environmental factors. One of the most promising technology employed for lowering the previously described degradation processes, is that of nanomaterials, nowadays largely applied in the maintenance of the world cultural heritage, with the aim of improving the consolidation and protection treatments of damaged stone materials they are made of [2]. Such nanomaterials display important advantages that could solve many problems found in the traditional interventions, that often showed the serious bias of the lack the vital compatibility with the original substrate and a durable performance: application of nanotechnology in the cultural heritage conservation is characterized by the possibility to design consolidant products strongly compatible with the original stone substrate. Moreover, when particles have dimensions of about 100 nanometers, the material properties change significantly from those at larger scales. The nanoparticles must show: stability and sustained photoactivity; biological and chemical inactivity nontoxicity, as well as antimicrobial properties for lowering ecotoxicological impact on animals and plants [3]; low cost suitability towards visible or near UV light; high conversion efficiency and high quantum yield. In addition, these treatments can also have water repellent properties which favor this self-cleaning action and prevent the generation of damage caused by water. The most commonly used inorganic consolidant agents are the products based on Ca(OH)2 calcium hydroxide nanoparticles [4], due to their compatibility with a large part of the built and sculptural heritage. As well as other hydroxides (Mg(OH)2, Sr(OH)2), metal oxides (TiO2, ZnO), and metal nanoparticles (Au, Ag, Pt)) have been reported in the literature, focusing on their potential as consolidants on different artifacts of cultural heritage [2, 5]. But one of the most challenging nanomaterial is Ca10(PO4)6(OH)2 hydroxyapatite (HAP), already applied in a large variety of technological and biomedical applications, mainly due to its close relationship with mineral component of hard human tissues [6-7], and in cultural heritage conservation used for carbonate stone consolidation [2]. HAP can be applied for the consolidation of limestones, marbles and sandstones with different carbonate contents. This product is not introduced directly into stone material, but it comes from the reaction between phosphate ions from an aqueous solution of diammonium hydrogen phosphate applied to the stone and calcium ions coming from substrate. Among its advantages, HAP has a similar crystal structure and close lattice parameters of CaCO3 calcite, the main constituents of marbles and limestone. Thanks to its low viscous nature, this aqueous consolidant product is able to penetrate deeply into the stone, generating a significant improvement in mechanical properties of the same stone. The HAP has been tested as a protective treatment for marble against acid rain corrosion [8]. The study of compatibility and adaptability requires that the physical and chemical properties of both consolidator products and stone substrate are well known. Such a knowledge plays a very important role for the good outcome of the present project. Materials of interest, synthesized in our labs has been analysed by using: 1) X-ray diffraction (XRD), effective on crystalline materials and able to carry out information on chemical composition, size, shape and atomic structure, 2) small- and/or wide-angle scattering (SAXS/WAXS), powerful tool to investigate the domain of phosphate particles as a function of their optical properties; in the case of SAXS the technique can be applied to HAp nanoparticles characterization; 3) Fourier-Transform Infrared (FTIR) spectroscopy, reliable techniques for investigating hydroxyl anions and variations within anionic and cationic groups in the obtained materials; 4) scanning electron microscopy for checking morphologies of nanonparticles; 5) biological evaluation of the antimicrobial properties of obtained HAp materials, through direct contact and disc diffusion methods versus most common gram + and gram - bacteria present in human or animal biosystems 6) Laser Induced Breakdown Spectroscopy (LIBS), a non-destructive technique able to get quali-quantitative informations on museal artifacts. 1 - Pesce C., Moretto L.M., Orsega E.F., Pesce G.L., Corradi M., Weber J. Effectiveness and Compatibility of a Novel Sustainable Method for Stone Consolidation Based on Di-Ammonium Phosphate and Calcium-Based Nanomaterials. Materials 12 (2019) 3025. 2 - David, M.E., Ion, R.-M., Grigorescu, R.M., Iancu, L., Andrei, E.R. Nanomaterials Used in Conservation and Restoration of Cultural Heritage: An Up-to-Date Overview. Materials 13 (2020) 2064. 3 - Reyes-Estebanez, M., Ortega-Morales, B.O., Chan-Bacab, M., Granados-Echegoyen, C., Camacho-Chab, J.C., Pereanez-Sacarias J.E., Gaylarde C. Antimicrobial engineered nanoparticles in the built cultural heritage context and their ecotoxicological impact on animals and plants: a brief review. Heritage Science 6 (2018) 52. 4 - El Bakkari M, Bindiganavile V, Boluk Y. Facile Synthesis of Calcium Hydroxide Nanoparticles onto TEMPO-Oxidized Cellulose Nanofibers for Heritage Conservation. ACS Omega 4 (2019) 20606-20611. 5 - Dida B., Siliqi D., Baldassarre, F., Karaj D., Hasimi A., Kasemi V., Nika V., Vozga I. “Nanomaterialet per Konservimin e Trashegimise Kulturore”, SHLBSH, Tirana (2020), ISBN 978-99943-2-468-2 6 - Rakovan J.R., Pasteris J.D. A technological gem: Materials, Medical, and Environmental Mineralogy of Apatite. Elements 11 (2015) 195-200. 7 - Baldassarre F., Altomare A., Corriero N., Mesto E., Lacalamita M., Bruno G., Sacchetti A., Dida B., Karaj D., Della Ventura G.D., Capitelli, F., Siliqi, D. Crystal Chemistry and Luminescence Properties of Eu-Doped Polycrystalline Hydroxyapatite Synthesized by Chemical Precipitation at Room Temperature. Crystals 10 (202) 250. 8 - Graziani G., Sassoni E., Franzoni E., Scherer G.W. Hydroxyapatite Coatings for Marble Protection: Optimization of Calcite Covering and Acid Resistance. Applied Surface Science 368 (2016) 241-257.