Hydroxyapatite and Other Calcium Phosphates for the Conservation of Cultural Heritage: A Review

The present paper reviews the methods and the performance of in situ formation of calcium phosphates (CaP) for the conservation of materials belonging to cultural heritage. The core idea is to form CaP (ideally hydroxyapatite, HAP, the most stable CaP at pH > 4) by reaction between the substrate and an aqueous solution of a phosphate salt. Initially proposed for the conservation of marble and limestone, the treatment has been explored for a variety of different substrates, including sandstones, sulphated stones, gypsum stuccoes, concrete, wall paintings, archaeological bones and paper. First, the studies aimed at identifying the best treatment conditions (e.g., nature and concentration of the phosphate precursor, solution pH, treatment duration, ionic and organic additions to the phosphate solution, mineralogical composition of the new CaP phases) are summarized. Then, the treatment performance on marble and limestone is reviewed, in terms of protective and consolidating effectiveness, compatibility (aesthetic, microstructural and physical) and durability. Some pilot applications in real case studies are also reported. Recent research aimed at extending the phosphate treatment to other substrates is then illustrated. Finally, the strengths of the phosphate treatment are summarized, in comparison with alternative products, and some aspects needing future research are outlined

Mineral consolidants

Inorganic consolidants, such as ethyl silicate, nanolime and ammonium oxalate, have proven to be effective for certain materials, but each has its drawbacks. This has recently led to the investigation of hydroxyapatite (HAP) as a novel inorganic consolidant, which demonstrated excellent performance on carbonate stones. Considering that a mineral that matched calcite crystal lattice parameters even more closely than HAP would be expected to provide a consolidating action even greater than HAP, in this study aluminum phosphate (AP) was investigated as a potential new consolidant. Indeed, AP has lattice parameters differing from those of calcite by only 1%. The consolidating ability of AP was preliminarily investigated here in comparison with HAP. Both treatments were tested on artificially weathered marble samples, in the view of their application for conservation of sugaring marble. A novel method is also proposed for producing samples with near-surface damage similar to that of sugaring marble in the field. The results of the study point out that the novel weathering method is able to provide samples with tailored gradient in dynamic elastic modulus, closely resembling naturally sugaring marble. The AP treatment was found to significantly improve the dynamic elastic modulus of weathered marble, at least as efficiently as the HAP treatment investigated in this study. This confirmed the high potential of AP as a new inorganic consolidant

Consolidation of porous carbonate stones by an innovative phosphate treatment: Mechanical strengthening and physical-microstructural compatibility in comparison with TEOS-based treatments

For preservation of stones used in Cultural Heritage, affected by weathering processes that threaten their cohesion and mechanical properties, the application of consolidants is a common practice. However, available consolidating products generally exhibit some drawbacks that hinder their performance, in terms of either mechanical efficacy, compatibility with the substrate and/or durability. Ethyl silicate is currently the most widely used among stone consolidants; nevertheless, its reduced efficacy on calcitic substrates, together with its temporary hydrophobicity, its tendency to crack and its common formulation with volatile organic solvent, make the research for alternative consolidants for carbonate stones necessary. In this paper, a recently proposed new consolidation treatment based on the formation of hydroxyapatite inside the stone was tested on two different porous carbonate stones (Globigerina Limestone and Giallo Terra di Siena), and compared with TEOS-based treatments, frequently used for the consolidation of these lithotypes. The results show that the hydroxyapatite treatment exhibits a good efficacy in terms of mechanical properties and, compared to TEOS, it causes less pronounced alterations in open porosity and water transport properties. This makes the new treatment a potentially valid alternative to TEOS, especially in those situations where the possible presence of water behind the consolidated layer (e.g. in case of rising damp, condensation or infiltration) might threaten the durability of the consolidation intervention

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

Preliminary study on the use of ammonium phosphate for the conservation of marble-imitating gypsum-stuccoes

In this study, a novel method for consolidation and improvement of resistance to water of gypsum-stuccoes was preliminarily investigated. The idea is treating gypsum with an aqueous solution of diammonium hydrogen phosphate (DAP, (NH4)2HPO4) to form hydroxyapatite (HAP, Ca10(PO4)6(OH)2), which has much lower solubility than gypsum. Tests carried out on gypsum paste samples, manufactured to resemble historic stuccoes, showed that, after treatment with the DAP solution, a significant improvement in mechanical properties was achieved and brushite (CaHPO4∙2H2O) was formed (alongside some other by-products, that can be removed by an additional poultice treatment). Even if brushite is more soluble than HAP, still its formation is expected to be beneficial for stuccoes conservation, as brushite is significantly less soluble than gypsum

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

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

Durable self-cleaning coatings for architectural surfaces by incorporation of TiO2 nano-particles into hydroxyapatite films

To prevent soiling of marble exposed outdoors, the use of TiO2 nano-particles has been proposed in the literature by two main routes, both raising durability issues: (i) direct application to marble surface, with the risk of particle leaching by rainfall; (ii) particle incorporation into inorganic or organic coatings, with the risk of organic coating degradation catalyzed by TiO2 photoactivity. Here, we investigated the combination of nano-TiO2 and hydroxyapatite (HAP), previously developed for marble protection against dissolution in rain and mechanical consolidation. HAP-TiO2 combination was investigated by two routes: (i) in series application of HAP followed by nano-TiO2 (“H+T”); (ii) simultaneous application by introducing nano-TiO2 into the phosphate solution used to form HAP (“HT”). The self-cleaning ability was evaluated before and after prolonged exposure to simulated rain. “H+T” and “HT” coatings exhibited much better resistance to nano-TiO2 leaching by rain, compared to TiO2 alone. In “H+T” samples, TiO2 nano-particles adhere better to HAP (having flower-like morphology and high specific surface area) than to marble. In “HT” samples, thanks to chemical bonds between nano-TiO2 and HAP, the particles are firmly incorporated in the HAP coating, which protects them from leaching by rain, without diminishing their photoactivity and without being degraded by them