A computational investigation of stoichiometric and calcium-deficient oxy- and hydroxy-apatites.

Computer modelling techniques have been employed to qualitatively and quantitatively investigate the dehydration of hydroxyapatite to oxyapatite and the defect chemistry of calcium-deficient hydroxyapatite, where a number of vacancy formation reactions are considered. The dehydration of hydroxyapatite into oxyhydroxyapatite is calculated to be endothermic by E = +83.2 kJ mol(-1) in agreement with experiment, where thermal treatment is necessary to drive this process. Calcium vacancies are preferentially charge-compensated by carbonate ions substituting for phosphate groups (E = -5.3 kJ mol(-1)), whereas charge-compensating reactions involving PO4 vacancies are highly endothermic (E > or =652 kJ mol(-1)). The exothermicity of the charge compensation of a Ca vacancy accompanied by a PO4/CO3 substitution agrees with their co-occurrence in natural bone tissue and tooth enamel. Our calculations of a range of defect structures predict (i) that calcium vacancies as well as substitutional sodium and potassium ions would occur together with carbonate impurities at phosphate sites, but that other charge compensations by replacement of the phosphate groups are unfavourable, and (ii) that the hydroxy ions in the channel are easily replaced by carbonate groups, but that the formation of water or oxygen defects in the channels is thermodynamically unfavourable. Calculated elastic constants are reported for the defect structures.