Crystal morphology, composition, and dissolution behavior of carbonated apatites prepared at controlled pH and temperature

A range of carbonated apatites was prepared by aqueous precipitation at 37, 60, and 85°C and at controlled pH values varying from 6.00–9.50 in 0.25 increments. The products were analyzed for Ca, P, Sr, Mg, Na, F, and carbonate. Their initial dissolution rates were measured in a pH 4.5, 0.01 mol · liter−1 acetate buffer. Information about crystal morphologies and crystal defects was obtained by x-ray diffraction and high-resolution transmission electron microscopy (TEM). The CaP molar ratios of the products, together with their Sr and Mg contents, increased with increasing pH. Initial dissolution rates of the products, when adjusted for carbonate content, were in the order 37 > 60 > 85°C whereas apparent particle sizes determined by TEM and x-ray diffraction were ordered 37 < 60 < 85°C. Carbonated apatites precipitated at pHs of 7.0 or less were observed to have planar defects parallel to (100) that were identified as unit-cell-thick intergrowths of octacalcium phosphate. Carbonated apatites precipitated at higher pHs and noncarbonated apatites did not have these defects. A crystal growth mechanism is proposed to account for the presence of the (100) defects.