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Substitution of carbonate has long been recognized in both synthetic and natural biologically and geologically precipitated forms of hydroxylapatite. Although the predominant substitution mechanism in all of the calcium members of the apatite group formed below 100 °C is substitution of carbonate for phosphate (B-type), small amounts of A-type substitution of carbonate in the channel sites also occur. The present study focuses on the effect of cation size on the type of substitution of carbonate in members of the apatite group. The barium and lead members offer a larger channel site, which potentially could stabilize A-type substitution. A series of carbonated barium and lead fluorapatites were synthesized in aqueous solution and characterized by powder X-ray diffraction, and infrared and Raman spectroscopy. Carbonate content was determined by combustion analysis.

Synthesis and structure of carbonated barium and lead fluorapatites: Effect of cation size on A-type carbonate substitution