Tetracalcium phosphate

Tetracalcium phosphate is the compound Ca4(PO4)2O, (4CaO·P2O5). It is the most basic of the calcium phosphates, and has a Ca/P ratio of 2, making it the most phosphorus poor phosphate.[1] It is found as the mineral hilgenstockite, which is formed in industrial phosphate rich slag (called "Thomas slag"). This slag was used as a fertiliser due to the higher solubility of tetracalcium phosphate relative to apatite minerals.[2] Tetracalcium phosphate is a component in some calcium phosphate cements that have medical applications.[1]

Tetracalcium phosphate
Names
Other names
Tetracalcium diphosphorus nonaoxide, tetracalcium oxygen(2-) diphosphate, calcium oxide phosphate, TTCP, TetCP, Thomas phosphate
Identifiers
3D model (JSmol)
ECHA InfoCard 100.013.767
EC Number
  • 215-143-6
UNII
Properties
Ca4(PO4)2O
Molar mass 366.254124 g/mol
Appearance white
Melting point decomp
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Preparation and reactions

Tetracalcium phosphate cannot be prepared in aqueous solution, any precipitates having the correct Ca/P ratio contain hydroxide ions in apatitic phases. Solid state reactions are used, one example is:[1]

2 CaHPO4 + 2 CaCO3 → Ca4(PO4)2O + CO2 + H2O (1450-1500 °C for up to 12 hours)

As tetracalcium phosphate is metastable the molten reaction mixture has to be quenched to rapidly, reduce the temperature and prevent the formation of other compounds such as Ca3(PO4)2, CaO, CaCO3 and Ca5(PO4)3(OH).[1]

Unwanted tetracalcium phosphate can be formed when metal alloy implants (orthopaedic and dental) are plasma spayed with hydroxyapatite.[1]

Tetracalcium phosphate is stable in water at room temperature for up to four weeks, but at higher temperatures hydrolyses to hydroxyapatite and calcium hydroxide:[1]

3 Ca4(PO4)2O + 3 H2O → 2 Ca5(PO4)3(OH) + 2 Ca(OH)2

Tetracalcium phosphate is a component used in the formation of some hydroxyapatite calcium phosphate cements that used for the repair of bone defects.[3] One example of a hydroxyapatite cement forming reaction is that of tetracalcium phosphate and dicalcium diphosphate dihydrate:[4]

Ca4(PO4)2O + CaHPO4·2H2O → Ca5(PO4)3(OH) + 2 H2O

Structure

Crystalline tetracalcium phosphate is monoclinic, and has close similarities to hydroxyapatite. The similarity is such that it has been suggested that there is an epitactic relationship between the structures enabling direct conversion of tetracalcium phosphate to hydroxyapatite.[1] [5]

References
  1. Moseke, C.,Gbureck, U. (October 2010). "Tetracalcium phosphate: Synthesis, properties and biomedical applications". Acta Biomaterialia. 6 (10): 3815–3823. doi:10.1016/j.actbio.2010.04.020. PMID 20438869.CS1 maint: uses authors parameter (link)  – via ScienceDirect (Subscription may be required or content may be available in libraries.)
  2. Walter E.Brown and Earl F. Epstein (November–December 1965). "Crystallography of Tetracalcium Phosphate". Journal of Research of the National Bureau of Standards Section A. 69A (6): 547–551. doi:10.6028/jres.069a.059. PMC 6599098. PMID 31927823.CS1 maint: uses authors parameter (link)
  3. Bohner, M., Gbureck, U., Barralet, J.E. (November 2005). "Technological issues for the development of more efficient calcium phosphate bone cements: A critical assessment". Biomaterials. 26 (33): 6423–6429. doi:10.1016/j.biomaterials.2005.03.049. PMID 15964620.CS1 maint: uses authors parameter (link)  – via ScienceDirect (Subscription may be required or content may be available in libraries.)
  4. Bohner, Marc (2007). "Reactivity of calcium phosphate cements". Journal of Materials Chemistry. 17 (38): 3980–3986. doi:10.1039/B706411J.
  5. Dickens, B.; Brown, W. E.; Kruger, G. J.; Stewart, J. M. (1973). "Ca4(PO4)2O, tetracalcium diphosphate monoxide. Crystal structure and relationships to Ca5(PO4)3OH and K3Na(SO4)2". Acta Crystallographica Section B. 29 (10): 2046–2056. doi:10.1107/S0567740873006102. ISSN 0567-7408.
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