Growth units and nucleation: The case of calcium phosphates

Abstract

Calcium phosphates are precipitated at 37°C from solutions the pH of which ranges from 5.0 to 11.0. Despite the fact that the supersaturations of hydroxyapatite HAP, octocalcium phosphate OCP and brushite B are often in the order HAP⪢OCP⪢B, brushite nucleates more easily than OCP and HAP at low pH, while OCP nucleates more easily than HAP at mean to high pH. These facts cannot be explained, as usually, by the only differences in the surface free energies of the three solid phases. On the other hand, they may be explained by assuming that the values of the kinetic coefficients change as a function of the concentration in the proper growth units which have to integrate in the nuclei of either phase. In the model we propose, the kinetic coefficients of OCP and HAP are smaller than that of B by 10 and 18 orders of magnitude at pH=6.5, differences which reduce to 3 orders of magnitude at pH=10.0. Accordingly, nucleation of OCP and HAP is favoured with increasing pH.