Preparation of a nano aluminum phosphate enhanced hydroxyapatite coating for marble conservation

Open-air marble relics in Beijing are experiencing degradation due to sugaring, dissolution and other illnesses. Therefore, it is necessary to apply a protective and reinforcing coating to the weathered surface. Hydroxyapatite (HAP) has significantly lower solubility and dissolution rate compared to calcite. Additionally, HAP has similar lattice parameters with calcite, suggesting that a cohesive layer of HAP can be formed over calcite. In fact, HAP exhibits a lattice mismatch of 5 % with calcite, which might potentially lead to stress if the layer exceeds a few nanometre in thickness. On the other hand, aluminum phosphates (ideally, B-AlPO₄) only exhibit a 1 % mismatch with calcite and have a solubility lower than that of calcite. In this study, in order to improve the property of HAP in marble conservation, sol–gel method was employed to synthesize nano AlPO₄, which were then incorporated into the phosphate solution to produce protective coating on the stone surface. The coatingʼs morphology and the structure were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), high capacity 3D X-ray microscopy (XRM), optical microscope, and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). Moreover, the color, the contact angle, the three-point bending strength measurements, as well as the simulated acid rain test and freeze–thaw treatment were performed to assess the chromatic aberration, hydrophilicity, reliability, and durability of the coating. Results indicated that the nano AlPO₄, with its matched lattice parameters and nucleation site provision, facilitated the formation a coherent HAP layer of crystal flakes. Subsequently, the anti‑corrosion property, freeze-thaw resistance and consolidation property of the coating were improved, demonstrating the potential application the hybrid of HAP with nano AlPO₄ in the preservation of marble.