Adsorption of water and organic solvents on the calcite [101¯4] surface: Implications for marble conservation treatments

When exposed outdoors, marble artefacts are subject to degradation caused by dissolution in rain. To improve acid-resistance of marble, surface treatments involving the in situ formation of a passivating calcium phosphate (CaP) layer have been developed. Adding alcohol to the treatment improves CaP coverage but the reason is still unclear. Here, we use computational and experimental studies to ascertain whether the interaction of the organic additives with the marble surface plays a role in determining the treatment outcome. Density functional theory calculations are employed to determine the binding energy of additives on the calcite [101¯4] surface and identify acetone as a promising new additive due to its weak adsorption. Molecular dynamics calculations show that ethanol and isopropanol displace water from the calcite [101¯4] surface forming an immobile, ordered, and hydrophobic layer, while acetone and water form a mixed, dynamic environment. In experimental trials, a continuous (yet cracked) layer of carbonate hydroxyapatite is formed after 24 h, with all organic additives improving the final coating. This result suggests that the interaction of the additive with the marble surface does not play a major role in determining treatment outcomes and other factors should be investigated for the design of improved treatments

Consolidation of sugaring marble by hydroxyapatite: some recent developments on producing and treating decayed samples

Consolidation of sugaring marble (i.e., marble affected by granular disaggregation) still lacks fully effective solutions. Consequently, the use of an innovative phosphate-based treatment, aimed at bonding calcite grains by formation of hydroxyapatite at grain boundaries, has recently been proposed. In this paper, firstly a novel method for producing artificially decayed marble samples, by contact with a heating plate, is proposed. Then, some results are presented about the effectiveness and the compatibility of two different formulations of the phosphate treatment, differing in terms of concentration of the phosphate precursor (3.0 M or 0.1 M aqueous solutions of diammonium hydrogen phosphate, DAP), possible ethanol addition to the DAP solution and number of DAP solution applications (1 or 2). The results of the study point out that the new weathering method allows to obtain specimens with a gradient in microstructural and mechanical properties with thickness, just like naturally weathered samples. Both phosphate treatments were able to significantly improve marble cohesion, without causing significant changes in thermal behaviour and aesthetic appearance after treatment. The addition of small quantities of ethanol to the DAP solution seems to be a very promising method for favouring HAP formation and improving the treatment performance

Electrodeposition of hydroxyapatite coatings for marble protection: Preliminary results

Surface coatings made of hydroxyapatite (HAP) have been proposed to protect marble artworks from dissolution in rain, originated by the aqueous solubility of calcite. However, HAP coatings formed by wet chemistry exhibit incomplete coverage of marble surface, which results in limited protective efficacy. In this study, electrodeposition was explored as a new route to possibly form continuous coatings over the marble surface, leaving no bare areas. Electrodeposition was performed by placing marble samples in poultices containing the electrolyte (an aqueous solution with calcium and phosphate precursors) and the electrodes. The influence of several parameters was investigated, namely the role of the working electrode (cathode or anode), the distance between the marble sample and the working electrode, the deposition conditions (potentiostatic or galvanostatic), the electrolyte composition and concentration, the applied voltage, and time. The coating morphology and composition were assessed by SEM/EDS and FT-IR. The protective ability of the most promising formulations was then evaluated, in all cases comparing electrodeposition with traditional wet synthesis methods. The results of the study suggest that electrodeposition is able to accelerate and improve formation of HAP coatings over the marble surface, even though the obtained protective efficacy is not complete yet

Resistance of consolidated lime mortars to freeze-thaw and salt crystallization cycles by different accelerated durability tests

The present study aimed at evaluating the performance of untreated and consolidated lime mortars, in terms of durability and possible "delayed incompatibility" of the consolidants. Lime mortars samples were treated by an aqueous solution of diammonium hydrogen phosphate (DAP treatment) and a dispersion of nanolimes (NL treatment). The samples were then subjected to accelerated ageing by different methods: (1) freeze-thaw cycles; (2) salt crystallization cycles based on the European standard EN 12370 (often considered as highly aggressive); (3) salt crystallization cycles according to a new recommendation proposed by the RILEM TC 271-ASC (designed to provide less aggressive and more reliable ageing). The results of the study showed that the DAP-based treatment was able to significantly reduce damage caused by freeze-thaw cycles and salt weathering cycles by the RILEM procedure. In the case of salt weathering by the EN procedure, some risk of "delayed incompatibility" was highlighted for DAP, which can be considered an outcome of the combination between the salt weathering procedure itself and the consolidating treatment. For both freeze-thaw and salt weathering by either procedure, the residual mechanical properties of DAP samples at the end of the cycles were significantly higher than those of the untreated references and of the NL samples, for which the effects of the NL treatment were very modest

Synthetic or Natural (Bio-Based) Hydroxyapatite? A Systematic Comparison between Biomimetic Nanostructured Coatings Produced by Ionized Jet Deposition

Calcium phosphate (CaP)-based materials are largely explored in orthopedics, to increase osseointegration of the prostheses and specifically in spine surgery, to permit better fusion. To address these aims, nanostructured biogenic apatite coatings are emerging, since they better mimic the characteristics of the host tissue, thus potentially being better candidates compared to their synthetic counterpart. Here, we compare hydroxyapatite (HA) nanostructured coatings, obtained by ionized jet deposition, starting from synthetic and natural sources. The starting materials and the corresponding films are characterized and compared from a compositional and morphological point of view, then their stability is studied after post-treatment annealing. Although all the films are formed by globular aggregates and show morphological features at different scales (from nano to micro), significant differences are found in composition between the synthetic and naturally derived HA in terms of magnesium and sodium content, carbonate substitution and Ca/P ratio, while differences between the coatings obtained by the different natural HA sources are minor. In addition, the shape of the aggregates is also target-dependent. All coatings have a good stability after over 14 days of immersion in medium, with natural apatite coatings showing a better behavior, as no cracking and detachments are observed during immersion. Based on these results, both synthetic and naturally derived apatitic materials appear promising for applications in spine surgery, with coatings from natural sources possessing physiochemical properties more similar to the mineral phase of the human bone tissue

Choosing the consolidant for carbonate substrates: Technical performance and environmental sustainability of selected inorganic and organic products

This study aims at providing a dataset for selecting the most suitable consolidant for marble, limestone and lime mortar. Diammonium hydrogen phosphate (DAP), nanolimes (NL), ethyl silicate (ES) and acrylic resin (B72) were compared. Application was performed by brushing in different amounts to investigate the influence of the product consumption. Effectiveness, compatibility, durability and sustainability were evaluated. DAP showed several advantages over the alternative consolidants, in terms of both technical performance and sustainability. ES exhibited high efficacy but also risks of poor compatibility and durability, together with a high global warming potential. NL and B72 provided the least promising results

A natural biogenic fluorapatite as a new biomaterial for orthopedics and dentistry: antibacterial activity of lingula seashell and its use for nanostructured biomimetic coatings

Calcium phosphates are widely studied in orthopedics and dentistry, to obtain biomimetic and antibacterial implants. However, the multi-substituted composition of mineralized tissues is not fully reproducible from synthetic procedures. Here, for the first time, we investigate the possible use of a natural, fluorapatite-based material, i.e., Lingula anatina seashell, resembling the composition of bone and enamel, as a biomaterial source for orthopedics and dentistry. Indeed, thanks to its unique mineralization process and conditions, L. anatina seashell is among the few natural apatite-based shells, and naturally contains ions having possible antibacterial efficacy, i.e., fluorine and zinc. After characterization, we explore its deposition by ionized jet deposition (IJD), to obtain nanostructured coatings for implantable devices. For the first time, we demonstrate that L. anatina seashells have strong antibacterial properties. Indeed, they significantly inhibit planktonic growth and cell adhesion of both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. The two strains show different susceptibility to the mineral and organic parts of the seashells, the first being more susceptible to zinc and fluorine in the mineral part, and the second to the organic (chitin-based) component. Upon deposition by IJD, all films exhibit a nanostructured morphology and sub-micrometric thickness. The multi-doped, complex composition of the target is maintained in the coating, demonstrating the feasibility of deposition of coatings starting from biogenic precursors (seashells). In conclusion, Lingula seashell-based coatings are non-cytotoxic with strong antimicrobial capability, especially against Gram-positive strains, consistently with their higher susceptibility to fluorine and zinc. Importantly, these properties are improved compared to synthetic fluorapatite, showing that the films are promising for antimicrobial applications.Lingula anatina seashell is an apatite-based shells, and naturally contains fluorine and zinc alongside an organic part (chitin). For the first time, we demonstrate that it has strong antibacterial properties, and that it can be used as nanostructured coatings for orthopaedics and dentistry

Self-cleaning and colour-preserving efficiency of photocatalytic concrete: case study of the Jubilee Church in Rome

The Jubilee Church in the south-eastern outskirts of Rome is one of the first buildings constructed with super white reinforced concrete with self-cleaning photocatalytic cement. However, 16 years after the opening of the building, the self-cleaning and colour-preserving properties arising from the titania particles (TiO2) within the concrete mix are not meeting the design requirements and the concrete is showing premature evidence of decay. While the form of the decay is affecting the appearance of the building and not its structural soundness, the ageing pattern of the building's components is resulting in a high maintenance cost, one not easily affordable within the ordinary budget supported by a small parish. This study comprises the first comprehensive step in understanding the causes of the accelerated ageing pattern of the concrete, highlighting methods to improve the long-term durability of the concrete and therefore reduce the cost of its maintenance. Moreover, this research offered the opportunity to test the durability and the effectiveness of the TiO2 in the real conditions on an actual building featuring non-standard geometries. The findings highlight how the ageing pattern directly connects with the geometry of the building and inadequate consideration of the local weathering at the design stage

Recommendation of RILEM TC 271-ASC: New accelerated test procedure for the assessment of resistance of natural stone and fired-clay brick units against salt crystallization

This recommendation is devoted to testing the resistance of natural stone and fired-clay brick units against salt crystallization. The procedure was developed by the RILEM TC 271-ASC to evaluate the durability of porous building materials against salt crystallization through a laboratory method that allows for accelerated testing without compromising the reliability of the results. The new procedure is designed to replicate salt damage caused by crystallization near the surface of materials as a result of capillary transport and evaporation. A new approach is proposed that considers the presence of two stages in the salt crystallization test. In the first, the accumulation stage, salts gradually accumulate on or near the surface of the material due to evaporation. In the second, the propagation stage, damage initiates and develops due to changes in moisture content and relative humidity that trigger salt dissolution and crystallization cycles. To achieve this, two types of salt were tested, namely sodium chloride and sodium sulphate, with each salt tested separately. A methodology for assessing the salt-induced damage is proposed, which includes visual and photographical observations and measurement of material loss. The procedure has been preliminarily validated in round robin tests