A mechanism for the formation of hydroxyapatite (HAp) surface layers compositionally different from the bulk compositions is described. Surface layer formation is a consequence of HAp being a compound of variable composition: Ca 10 (PO 4 ) 6 (OH) 2 to ∼Ca 9 HPO 4 (PO 4 ) 5 OH, existing over Ca/P ratio from 1.67 for stoichiometric to ∼1.5 for fully calcium-deficient HAp. One consequence of this compositional variability is that only one HAp composition (Ca/P ratio) dissolves congruently (the solution and solid have the same Ca/P ratio). HAp compositions having Ca/P ratios different from the congruently dissolving composition will form surface layers. Equilibration of stoichiometric HAp with water will result in the formation of a surface layer having a Ca/P ratio of less than 1.67. In general, for solid HAp compositions having Ca/P ratios greater than that of the congruently dissolving composition, a nonstoichiometric surface layer will form and the Ca/P ratio in solution will exceed that of the surface layer. For solid compositions having lower Ca/P ratios than the congruently dissolving composition, the opposite will be true.
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Brown et al. (1999) studied this question.
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