Crystal growth of calcium apatites in dilute solutions containing fluoride.

The kinetics of seeded crystal growth of calcium apatites were studied in dilute supersaturated solutions at various levels of fluoride concentrations. Initial precipitation rates were enhanced by fluoride concentrations higher than 0.05 ppm. The analytical results are consistent with the precipitation of fluoridated hydroxyapatites, Ca5Fx-(OH)1-x(PO4)3, FHA. The degree of fluoridation, X, appears to be determined by the activity of HF in solution, which varies for the various initial fluoride levels but remains fairly constant during precipitation. Thus the composition of the precipitating phase was the same for a given solution whether 25 or 10 mg of hydroxyapatite was added as seeds. All the experimental results are consistent with the BCF theory, which relates the mean linear rate of growth, RL, to the supersaturation, DS, by the expression RL = C1T(DS-1)1n(DS)tanh(C2/T 1n DS), in which DS is the supersaturation defined by mean molar activities with respect to the precipitating FHA, T the absolute temperature, and C1 and C2 are constants calculated from the experimental results. Consequently, the crystal growth appears to take place in surface kinks and to be controlled by surface diffusion. Since crystal growth in most biological systems takes place at fluoride concentrations within the experimental range used, it seems probable that it occurs along the model advanced in the present investigation.