By Michael E. Fleet
content material: 1. creation --
2. Apatite-type constitution --
three. Crystal chemistry and geochemistry --
four. Synthesis of carbonate apatites --
five. X-ray buildings --
6. Chemical spectroscopy --
7. Carbonate apatite crystal chemistry --
eight. organic apatites.
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Additional resources for Carbonated hydroxyapatite : materials, synthesis, and applications
60 The lanthanides (La to Lu) are 4 f transition 03-Michael-Fleet-c03 31 September 23, 2014 16:41 PSP Book - 9in x 6in 32 Crystal Chemistry and Geochemistry metals, and represent the progressive ﬁlling of the 4 f electron shell. The progressive decrease in ionic radius through the series arises from imperfect shielding of one 4 f electron by another 4 f electron, so that the eﬀective nuclear charge increases through the series, pulling the entire 4 f n shell inward toward the nucleus. The absolute abundance of rare earths in rocks and minerals decreases through the lanthanide series.
75. 2 Summary of some apatite substitutions relative to ideal FAP, Ca10 (PO4 )6 F2 1 Channel (X ) anion X − = F− = 2F− X 2− + A+ + = Ca2+ + F− +2 = Ca2+ + 2F− = PO4 3− + F− A + + BO4 2− = Ca2+ + PO4 3− = 2F− BO4 2− + BO4 4− = 2PO4 3− CrO4 2− + SiO4 4− = 2PO4 3− +2 = Ca 2+ = Ca 2+ − + 2F A+ + = Ca2+ + F− 3+ = 2Ca A + BO4 2− = Ca A +A + + PO4 2A + BO4 = 2Ca 2+ 2A 3+ + = 3Ca2+ 2RE3+ + = 3Ca2+ + PO4 3− RE3+ + X 2− = Ca2+ + F− RE3+ + A + = 2Ca2+ RE3+ + SiO4 4− = Ca2+ + PO4 3− 2RE3+ + = PO4 3− + F− = 3Ca2+ Bi3+ + O2− = Ca2+ + F− VO4 3− = PO4 3− SO4 2− + SiO4 4− = 2PO4 3− A 3+ + BO4 4− = Ca2+ + PO4 3− 5− + A 3+ + BO4 4− = Ca2+ + PO4 3− AsO4 3− = PO4 3− 3− Bi3+ + O2− = Ca2+ + F− 3+ = PO4 3− + F− 4− 2A 3+ + BO4 5− = 2Ca2+ + PO4 3− 2+ 2+ BO4 4− + SiO4 + 2BO4 2− = Ca2+ + 2PO4 3− + = 2Ca2+ BO4 3− = PO4 3− Large ( A) cation A U4+ + + 2BO4 2− = Ca2+ + 2PO4 3− A 3+ + X 2− = Ca2+ + F− 2+ = 2Ca2+ = 2Ca2+ Phosphate group (BO4 ) BO4 4− + CO3 2− + A 4+ + Th4+ + Na+ + SO4 2− = Ca2+ + PO4 3− K+ + SeO4 2− = Ca2+ + PO4 3− SiO4 4− + (SO4 ,CO3 )2− = 2PO4 3− 2RE3+ + BO4 5− = 2Ca2+ + PO4 3− Type B carbonate + 2CO3 2− = Ca2+ + 2PO4 3− CO3 2− + SiO4 4− = 2PO4 3− Na+ + CO3 2− = Ca2+ + PO4 3− H3 O+ + CO3 2− = Ca2+ + PO4 3− 1.
The ﬁgure clearly discriminates, on the basis of atomic size, the metalloid cations which form tetrahedral complexes in apatites from those which do not: Te6+ , Ga3+ , Sn4+ , Sb5+ , Pb4+ , and Bi5+ are apparently too big to form tetrahedral complexes with oxygen in densely packed structures and C3+ is too small, except at very high pressure. 5 ). However, the limiting values of atomic radius for tetrahedral coordination, as represented by radius ratio in Fig. 414) are attributed to covalence eﬀects.
Carbonated hydroxyapatite : materials, synthesis, and applications by Michael E. Fleet