Bowing of thin marble slabs is a phenomenon affecting both historic monuments and modern buildings. In spite of the ubiquity and destructiveness of this phenomenon, no fully satisfactory treatment is currently available to arrest and/or prevent bowing. In this study, a treatment based on formation of hydroxyapatite (HAP) was investigated as a possible route to arrest and possibly prevent bowing of Carrara marble slabs. Four different formulations of the HAP-treatment were tested and compared to ammonium oxalate and ethyl silicate (widely used in the practice of marble conservation). The treatments were applied onto pre-weathered and unweathered specimens to investigate their ability to arrest and prevent bowing, respectively. Marble behavior was studied in terms of residual strain and bowing after thermal cycles up to 90°C in dry and wet conditions. Marble cohesion was assessed before and after the thermal cycles by ultrasound. The HAP-treatments exhibited promising results, as the residual strain and the bowing after the cycles were always lower or equal to the untreated references, while marble cohesion was always higher. Surprisingly, ammonium oxalate caused marked worsening of marble thermal behavior. In the case of ethyl silicate, most of the initial benefit after consolidation was lost after the thermal cycles. In general, the results of the study point out the importance of evaluating marble thermal behavior to assess the suitability of any conservation treatment and suggest that treatments able to strengthen marble without causing excessive pore occlusion and stiffening are preferable to enhance durability to thermal cycles.

Reversibility is a mandatory requirement for materials used in heritage conservation, including hydrophobic protectives. Nevertheless, current protectives for stone are not actually reversible as they remain on the surfaces for a long time after their hydrophobicity is lost and can hardly be removed. Ineffective and aged coatings may jeopardise the stone re-treatability and further conservation interventions. This paper aims at investigating the performance of PHAs-based coatings for stone protection, their main potential being the ‘reversibility by biodegradation’ once water repellency ended. The biopolymer coatings were applied to three different kinds of stone, representative of lithotypes used in historic architecture: sandstone, limestone and marble. Spray, poultice and dip-coating were tested as coating techniques. The effectiveness and compatibility of the protectives were evaluated in terms of capillary water absorption, static and dynamic contact angles, water vapour diffusion, colour alteration and surface morphology. The stones’ wettability after application of two commercial protectives was investigated too, for comparison. Finally, samples were subjected to artificial ageing to investigate their solar light stability. Promising results in terms of efficacy and compatibility were obtained, although the PHAs-based formulations developed here still need improvement for increased durability and on-site applicability.

Salt crystallization can produce severe damage in porous stones, with a dramatic impact on cultural heritage conservation. Such damage is related to the fact that repulsive forces arise between the salt crystals and the pore wall, generating a disjoining pressure that frequently exceeds the tensile strength of stone. In this paper, new treatments are proposed, aimed at preventing salt damage by depositing a thin layer of polymeric coatings over the stone's pore surfaces. These coating are expected to change the surface chemistry, eliminating the repulsion between the growing crystals and the pore wall and hence the development of the disjoining pressure. Several biopolymers were tested on these substrates: silica glass, calcite, and calcite subjected to a pre-treatment with diammonium hydrogen phosphate (DAP), aimed at preventing calcite dissolution and acting as an anchoring substrate for the polymer coating. Selected polymer treatments were applied to porous Globigerina limestone samples, which were subjected to crystallization tests with sodium sulfate, obtaining promising results (i.e., significant reduction in stone damage), especially when the polymers were applied after the DAP treatment.

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