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Sub-µm CaCO 3  (calcite; CC) particles were converted to calcium monohydrogenphosphate dihydrate (DCPD) and hydroxyapatite (HAp) via soaking treatments in K 2 HPO 4  solutions with varied pH (3–12) and concentrations (0.1–1.5 M) at 37°C for up to 10 days. DCPD was derived from the solutions with pH ≤ 6; while hollow HAp was yielded when pH ≥ 7 in assemblies of petal-like crystallites. Results of magic angle spinning (MAS) and cross-polarization magic angle spinning (CP-MAS) NMR studies have shown that the HAp lattice has only PO 42−  but no HPO 42−  at B (phosphate) sites. Trace amounts of CO 32−  have occupied both A (OH) and B (PO 4 ) sites, and H 2 O is adsorbed on surface crystallites. The primary crystallite size of HAp derived from Scherrer equation increases quickly in a 12 h period and becomes gradually stable afterward. Samples of particles soaked within 3 h in a temperature range of 20–80°C were analyzed by X-ray diffraction. It is shown that the rate constant of 1 M solution is about an order of magnitude greater than that of 0.1 M solution and the apparent activation energy is 33 kJ/mol. In this work, the conversion of CC to HAp can be quantitatively controlled to solve the problem of slow degradation of HAp.

Conversion of sub-µm calcium carbonate (calcite) particles to hollow hydroxyapatite agglomerates in K 2 HPO 4 solutions