Abstract
Hydroxyapatite [Ca10(PO4)6(OH)2], Ca-HA, is the emblematic mineral phase of bones, and is known for its complexity and difficult to reproduce chemical synthesis. Among the routes developed for obtaining this calcium phosphate, the so-called double-decomposition method is well described and often utilized. However, the Ca-HA synthesized by this way forms a larger mass of ammonium nitrate by-product than the desired product itself. Pure Ca-HA for orthopedic or dental applications usually uses thermal treatment to eliminate residual nitrogen compounds by releasing them in the atmosphere. Contemporary sol–gel methods currently in fashion produce even more degradation products including solvents and precursor organics. We now report on a green synthesis procedure which makes pure Ca-HA with minimum by-product. The synthesis calls for reacting phosphoric acid with calcium carbonate in water suspension to form a Ca-HA gel of fine particles. This gel can be filtered and the solids recovered, dried, and sintered, but can also be used as-is for environmental applications such as heavy metal ions or textile dye removal from polluted waste streams. This green Ca-HA has been used to trap heavy metals in flue gases and in municipal waste water treatment plants. This low-cost and low-environmental impact material can be developed for medical use because of its absence of impurities, and in catalytic productions for remediation of many environmental problems. Recent results show Ca-HA can also serve in reforming biogas compositions into useful products, after deposition of selected metal elements. Some of these results will be communicated in this paper.
Similar content being viewed by others
References
Pham Minh D, Lyczko N, Sebei H, Nzihou A, Sharrock P (2012) Synthesis of calcium hydroxyapatite from calcium carbonate and different orthophosphate sources: a comparative study. Mater Sci Eng B 177:1080–1089
Morgan H, Wilson RM, Elliott JC, Dowker SEP, Anderson P (2000) Preparation and characterisation of monoclinic hydroxyapatite and its precipitated carbonate apatite intermediate. Biomaterials 21:617–627
Murakami S, Kato K, Enari Y, Kamitakahara M, Watanabe N, Ioku K (2012) Hydrothermal synthesis of porous hydroxyapatite ceramics composed of rod-shaped particles and evaluation of their fracture behavior. Ceram Int 38:1649–1654
http://www.innophos.com/en/products-and-markets/browse-product-categories/phosphate-salt/tricalcium-phosphates/calipharm-t. Accessed Feb 2013
Rodriguez-Lorenzo LM, Vallet-Regi M, Ferreira JMF (2001) Fabrication of hydroxyapatite bodies by uniaxial pressing from a precipitated powder. Biomaterials 22:583–588
Matsumura Y, Moffat JB (1993) Catalytic oxidative coupling of methane over hydroxyapatite modified with lead. Catal Let 17:197–204
Tsuchida T, Kubo J, Yoshioka T, Sakuma S, Takeguchi T, Ueda W (2008) Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst. J Catal 259:183–189
Verwilghen C, Rio S, Nzihou A, Gauthier D, Flamant G, Sharrock PJ (2007) Preparation of high specific surface area hydroxyapatite for environmental applications. J Mater Sci 42:6062–6066. doi:10.1007/s10853-006-1160-y
Venugopal A, Scurrell MS (2003) Hydroxyapatite as a novel support for gold and ruthenium catalysts behaviour in the water gas shift reaction. Appl Catal A Gen 245:137–147
Kanai H, Nakao M, Imamura S (2003) Selective photoepoxidation of propylene over hydroxyapatite–silica composites. Catal Com 4:405–409
Baillez S, Nzihou A, Bernache-Assolant D, Champion E, Sharrock P (2007) Removal of aqueous lead ions by hydroxyapatites: equilibria and kinetic processes. J Hazard Mater 139:443–446
Fernane F, Mecherri MO, Sharrock P, Hadioui M, Lounici H, Fedoroff M (2008) Sorption of cadmium and copper ions on natural and synthetic hydroxylapatite particles. Mater Charact 59:554–559
Nzihou A, Sharrock P (2010) Role of phosphate in the remediation and reuse of heavy metal polluted wastes and sites. Waste Biomass Valor 1:163–174
Fernane F, Mecherri MO, Sharrock P, Fiallo M, Sipos R (2010) Mater Sci Eng C 30:1060–1064
Pham Minh D, Sebei H, Nzihou A, Sharrock P (2012) Apatitic calcium phosphates: synthesis, characterization and reactivity in the removal of lead(II) from aqueous solution. Chem Eng J 198–199:180–190
Sharrock P, Brumas V, Fiallo MML (2013) Wastewater sorption on HA: old recipes for new tastes. Proc Earth Planet Sci 7:256–259
Oliva J, De Pablo J, Cortina J-L, Cama J, Ayora C (2011) Removal of cadmium, copper, nickel, cobalt and mercury from water by Apatite IITM: column experiments. J Hazard Mater 194:312–323
Jarcho M, Bolen CH (1976) Hydroxylapatite synthesis and characterization in dense polycrystalline form. J Mater Sci 11:2027–2035. doi:10.1007/BF02403350
Hayek E, Newesely H (1965) Pentacalcium monohydroxyorthophosphate (Hydroxylapatite). Inorg Synth 7:63–65
Eanes ED, Gillessen IH, Posner AS (1965) Intermediate states in the precipitation of hydroxyapatite. Nature 208:365–367
Bezzi G, Celotti G, Landi E, La Torretta TMG, Sopyan I, Tampieri A (2003) A novel sol–gel technique for hydroxyapatite preparation. Mater Chem Phys 78:816–824
Anee TK, Ashok M, Palanichamy M, Narayana Kalkura S (2003) A novel technique to synthesize hydroxyapatite at low temperature. Mater Chem Phys 80:725–730
Tredwin CJ, Young AN, Georgiou G, Shin S-H, Kim H-W, Knowles J-C (2013) Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol–gel method. Optimisation, characterisation and rheology. Dental Mater 29:166–173
Bakan F, Laçin O, Sarac H (2013) A novel low temperature sol–gel synthesis process for thermally stable nano crystalline hydroxyapatite. Powder Technol 233:295–302
Saha SK, Banerjee A, Banerjee S, Bose S (2009) Synthesis of nanocrystalline hydroxyapatite using surfactant template systems: role of templates in controlling morphology. Mater Sci Eng C 29:2294–2301
Gopi D, Indira J, Kavitha L, Sekara M, Mudali UK (2012) Synthesis of hydroxyapatite nanoparticles by a novel ultrasonic assisted with mixed hollow sphere template method. Spectrochim Acta A 93:131–134
Silva CC, Pinheiro AG, Miranda MAR, Góes JC, Sombra ASB (2003) Structural properties of hydroxyapatite obtained by mechanosynthesis. Solid State Sci 5:553–558
Nasiri-Tabrizi B, Fahami A, Ebrahimi-Kahrizsangi R (2014) A comparative study of hydroxyapatite nanostructures produced under different milling conditions and thermal treatment of bovine bone. J Ind Eng Chem 20:245–258
Conn JF, Jessen LA (1980) Process for producing hydroxyapatite. US Patent 4,324,772
Lazic S, Zec S, Miljevic N, Milonjic S (2001) The effect of temperature on the properties of hydroxyapatite precipitated from calcium hydroxide and phosphoric acid. Thermochim Acta 374:13–22
Elliott JC (1994) Studies in inorganic chemistry 18: structure and chemistry of the apatites and other calcium orthophosphates. Elsevier, Amsterdam
Pham Minh D, Tran ND, Nzihou A, Sharrock P (2013) Carbonate-containing apatite (CAP) synthesis under moderate conditions starting from calcium carbonate and orthophosphoric acid. Mater Sci Eng C 33:2971–2980
Liao CJ, Lin FH, Chen KS, Sun JS (1999) Thermal decomposition and reconstitution of hydroxyapatite in air atmosphere. Biomaterials 20:1807–1813
Parhi P, Ramanan A, Ray AR (2004) A convenient route for the synthesis of hydroxyapatite through a novel microwave-mediated metathesis reaction. Mater Lett 58:3610–3612
Lim GK, Wang J, Ng SC, Gan LM (1999) Formation of nanocrystalline hydroxyapatite in nonionic surfactant emulsions. Langmuir 15:7472–7477
Jillavenkatesa A, Condrate RA (1998) Sol–gel processing of hydroxyapatite. J Mater Sci 33:4111–4119. doi:10.1023/A:1004436732282
Rey C, Combes C, Drouet C, Lebugle A, Sfihi H, Barroug A (2007) Nanocrystalline apatites in biological systems: characterisation, structure and properties. Mater Sci Eng Technol 38:996–1002
Banu M (2005) Mise en forme d’apatites nanocristallines : céramiques et ciments. PhD dissertation, Institut National Polytechnique de Toulouse, France
Miyake M, Watanabe K, Nagayama Y, Nagasawa H, Suzuki T (1990) Synthetic carbonate apatites as inorganic cation exchangers: exchange characteristics for toxic ions. J Chem Soc Faraday Trans 86:2303–2306
Rio S, Verwilghen C, Ramaroson J, Nzihou A, Sharrock P (2007) Heavy metal vaporization and abatement during thermal treatment of modified wastes. J Hazard Mater 148:521–528
Rodrigues CVM, Serricella P, Linhares ABR, Guerdes RM, Borojevic R, Rossi MA, Duarte MEL, Farina M (2003) Characterization of a bovine collagen–hydroxyapatite composite scaffold for bone tissue engineering. Biomaterials 24:4987–4997
Thian ES, Ahmad Z, Huang J, Edirisinghe MJ, Jayasinghe SN, Ireland DC, Brooks RA, Rushton N, Bonfield W, Best SM (2008) The role of electrosprayed apatite nanocrystals in guiding osteoblast behavior. Biomaterials 29:1833–1843
Jalota S, Bhaduri SB, Tas AC (2008) Using a synthetic body fluid (SBF) solution of 27 mM HCO3 − to make bone substitutes more osteointegrative. Mater Sci Eng C 28:129–140
Acknowledgements
The authors thank gratefully colleagues at RAPSODEE Center, Christine Rolland, Céline Boachon, Bernard Auduc, Denis Marty, for their technical help.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Pham Minh, D., Rio, S., Sharrock, P. et al. Hydroxyapatite starting from calcium carbonate and orthophosphoric acid: synthesis, characterization, and applications. J Mater Sci 49, 4261–4269 (2014). https://doi.org/10.1007/s10853-014-8121-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-014-8121-7