New Triple Metallic Carbonated Hydroxyapatite for Stone Surface Preservation

This paper presents the synthesis of the triple substituted carbonated hydroxyapatite with magnesium, strontium and zinc (Mg-Sr-Zn-CHAp), as well as its structural, morphological and compositional characterization. The analytical techniques used (WDXRF, XRD and FTIR) highlighted, on the one hand, the B form for the apatite structure, as well as the presence of the three metal ions in the apatite structure, on the other hand (small shifts of 1120–900 cm⁻¹ and 500–600 cm⁻¹ absorption peaks due to the metals incorporated into the CHAp structure). The ratio between the metallic ions that substitute calcium and Ca²⁺, and phosphorus is increased, the value being 2.11 in comparison with CHAp and pure hydroxyapatite. Also, by using imaging techniques such as optical microscopy and SEM, spherical nanometric particles (between 150 and 250 nm) with a large surface area and large pores (6 m²/g surface area, pores with 6.903 nm diameters and 0.01035 cm³/g medium volume, determined by nitrogen adsorption/desorption analysis) and a pronounced tendency of agglomeration was highlighted. Also, the triple substituted carbonated hydroxyapatite was tested as an inorganic consolidant by using stone specimens prepared in the laboratory. The efficiency of Mg-Sr-Zn-CHAp in the consolidation processes was demonstrated by specific tests in the field: water absorption, peeling, freeze–thaw behavior, chromatic parameters as well as mechanical strength. All these tests presented conclusive values for the use of this consolidant in the consolidation procedures of stone surfaces (lower water absorption, increased mechanical strength, higher consolidation percent, decreased degradation rate by freeze–thaw, no significant color changes).