The biomimetic synthesis and phase transformation of XRD amorphous calcium phosphate were studied by application of kinetic, chemical and spectral (XRD and IR) methods and thermodynamic simulations. Two SBFs (SBFc and SBFr), differing in their HCO(3)(-) and Cl(-) ion contents, were used in the maturation studies. It has been proven that the biomimetic maturation accelerated the phase transformation of less thermodynamically stable amorphous calcium phosphate to poorly crystalline hydroxyapatite. Several regularities have been found: (i) kinetic reasons determined the biomimetic precipitation of XRD-amorphous calcium deficient phosphate (ACP); (ii) the precipitated ACP always contained impurities due to co-precipitation, ion substitution and incorporation phenomena; (iii) the increased content of HCO(3)(-) ions in the surrounding microenvironments increased the rate of phase transformation and the concentration of MeHCO(3)(+) (Me = Ca, Mg) species in the solution, but the solubility of CaCO(3) has only been decreased and its precipitation accelerated, thus playing a crucial role in the process under study.

The metastable and stable equilibria of a precipitation in the biomimetic system Simulated Body Fluid (SBF)–CaCl2–K2HPO4–KOH–H2O were modeled in the pH region 3–7 at a Ca/P molar ratio of 1 using a thermodynamic approach. Saturation indices (SI) of the solid phases were calculated and used to prognose the salt precipitation/dissolution processes. At рН < 4, the solutions are undersaturated (SI < 0) in respect of all solid phases; co‐precipitation of dicalcium phosphate dihydrate (DCPD) and hydroxyapatite (HA) occurs at рН 4 while at рН > 4 the stable phase is DCPD but the number of other co‐precipitated solid phases increases. This result is associated with the increase in HPO42−, CaHPO40, and KНРО4− species in the studied solution. The phase transformations of five model DCPD‐based calcium phosphate precursors in three simulated body fluids differing in their composition, to more stable octacalcium phosphate and hydroxyapatite was thermodynamically prognosed and experimentally confirmed by kinetic studies, as well as by chemical, XRD, SEM, and IR methods.

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Powders of magnesium-modified as well as zinc-modified calcium phosphates (Me-β-TCP and HA) with a (Ca(2+)+Mg(2+)+Zn(2+)+Na(+)+K(+))/P ratio of 1.3-1.4 and various Me(2+)/(Me(2+)+Ca(2+)) ratios (from 0.005 to 0.16) were prepared in biomimetic electrolyte systems at pH 8, mother liquid maturation and further syntering at 600-1000°C. Some differences in zinc and magnesium modifications have been prognosed on the basis of thermodynamic modeling of the studied systems and explained by the Mg(2+) and Zn(2+) ion chemical behaviour. The temperature as well as the degree of Zn(2+) and Mg(2+) ions substitutions were found to stabilize the β-TCP structure and this effect was more prononced for zinc. Thus, zinc-modified β-TCP powders consisting of idiomorphic crystals were obtained through sintering of Zn(2+) ion substituted calcium phosphates precursors at 800-1000°C. The Mg(2+) ion substitution leads to obtaining magnesium-modified β-TCP with spherical grains.

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