Carbonated calcium apatites doped with a monovalent cation (Li+, Na+, or K+) or a divalent cation (Mg2+ or Zn2+) were prepared in aqueous solution and analysed by powder X-ray diffraction, inductively coupled plasma atomic emission spectroscopy and infrared spectroscopy. The hypothesis that the location of carbonate in the apatite structure, either in place of hydroxide ions in the c-axis channels (A-type substitution) or in place of phosphate (B-type substitution), is affected by the solution energetics of the cation (specifically its enthalpy of hydration) was strengthened by the observation of larger amounts of A-type carbonate in apatites containing the monovalent cations in aqueous solution. It is shown that cations with low negative enthalpies of hydration favour A-type substitution, whereas cations with higher negative hydration enthalpies, such as divalent cations (Mg2+, Zn2+), favour B-type substitution.

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