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Effect of pH and temperature on the morphology and phases of co-precipitated hydroxyapatite

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Abstract

This paper reports a high-yield process to fabricate biomimetic hydroxyapatite nano-particles or nano-plates. Hydroxyapatite is obtained by simultaneous dripping of calcium chloride and ammonium hydrogen phosphate solutions into a reaction vessel. Reactions were carried out under various pH and temperature conditions. The morphology and phase composition of the precipitates were investigated using scanning electron microscope and X-ray diffraction. The analyses showed that large plates of calcium hydrophosphate are formed at neutral or acidic pH condition. Nanoparticles of hydroxyapatite were obtained in precipitates prepared at pH 9–11. Hydroxyapatite plates akin to seashell nacre were obtained at 40 °C and pH 9. This material holds promise to improve the strength of hydroxyapatite containing composites for bone implant or bone cement used in orthopaedic surgeries. The thermodynamics of the crystal growth under these conditions was discussed. An assembly mechanism of the hydroxyapatite plates was proposed according to the nanostructure observations.

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References

  1. Meyers MA, Chen P-Y, Lin AY, Seki Y (2008) Biological materials: structure and mechanical properties. Prog Mater Sci 53:1–206

    Article  CAS  Google Scholar 

  2. Gentleman E, Lay AN, Dickerson DA, Nauman EA, Livesay GA, Dee KC (2003) Mechanical characterization of collagen fibers and scaffolds for tissue engineering. Biomaterials 24:3805–3813

    Article  CAS  Google Scholar 

  3. Yana J, Daga A, Kumar R, Mecholsky JJ (2008) Fracture toughness and work of fracture of hydrated, dehydrated, and ashed bovine bone. J Biomech 41:1929–1936

    Article  Google Scholar 

  4. Kikuchi M, Ikoma T, Itoh S, Matsumoto H, Koyama Y, Takakuda K, Shinomiya K, Tanaka J (2004) Biomimetic synthesis of bone-like nanocomposites using the self-organization mechanism of hydroxyapatite and collagen. Compos Sci Technol 64:819–825

    Article  CAS  Google Scholar 

  5. Kim H-W, Kim H-E, Salih V (2005) Stimulation of osteoblast responses to biomimetic nanocomposites of gelatin-hydroxyapatite for tissue engineering scaffolds. Biomaterials 26:5221–5230

    Article  CAS  Google Scholar 

  6. Kikuchi M, Itoh S, Ichinose S, Shinomiya K, Tanaka J (2001) Self organisation mechanism in bone-like hydroxyapatite/collagen nanocomposite synthesized in vitro and its biological reaction in vivo. Biomaterials 22:1705–1711

    Article  CAS  Google Scholar 

  7. Kikuchi M, Matsumoto HN, Yamada T, Koyama Y, Takakuda K, Tanaka J (2004) Glutaraldehyde cross-linked hydroxyapatite/collagen self-organized nanocomposites. Biomaterials 25:63–69

    Article  CAS  Google Scholar 

  8. Zhang W, Liao SS, Cui FZ (2003) Hierarchical self-assembly of nano-fibrils in mineralised collagen. Chem Mater 15:3221–3226

    Article  CAS  Google Scholar 

  9. Manara S, Paolucci F, Palazzo B, Marcaccio M, Foresti E, Tosi G, Sabbatini S, Sabatino P, Altankov G, Roveri N (2008) Electrochemically-assisted deposition of biomimetic hydroxyapatite–collagen coatings on titanium plate. Inorg Chim Acta 361:1634–1645

    Article  CAS  Google Scholar 

  10. Muller FA, Muller L, Caillard D, Conforto E (2007) Preferred growth orientation of biomimetic apatite crystals. J Cryst Growth 304:464–471

    Article  Google Scholar 

  11. Liu C, Huang Y, Shen W, Cui J (2001) Kinetics of hydroapatite precipitation at pH 10 to 11. Biomaterials 22:301–306

    Article  CAS  Google Scholar 

  12. Liao S, Ngiam M, Watari F, Ramakrishna S, Chan CK (2007) Systematic fabrication of nano-carbonated hydroxyapatite/collagen composites for biomimetic bone grafts. Bioinspir Biomim 2:37–41

    Article  CAS  Google Scholar 

  13. Rusu VM, Ng C-H, Wilke M, Tiersch B, Fratzl P, Peter MG (2005) Size-controlled hydroxyapatite nanoparticles as self-organized organic–inorganic composite materials. Biomaterials 26:5414–5426

    Article  CAS  Google Scholar 

  14. Yunoki S, Ikoma T, Monkawa A, Ohta K, Kikuchi M, Sotome S, Shinomiya K, Tanaka J (2006) Control of pore structure and mechanical property in hydroxyapatite/collagen composite using unidirectional ice growth. Mater Lett 60:999–1002

    Article  CAS  Google Scholar 

  15. Yoon B-H, Kim H-W, Lee S-H, Bae C-J, Koh Y-H, Kong Y-M, Kim H-E (2005) Stability and cellular responses to fluorapatite–collagen composites. Biomaterials 26:2957–2963

    Article  CAS  Google Scholar 

  16. Viswanath B, Ravishankar N (2008) Controlled synthesis of plate—shaped hydroxyapatite and implications for the morphology of the apatite phase in bone. Biomaterials 29:4855–4863

    Article  CAS  Google Scholar 

  17. Neira IS, Kolenko YV, Lebedev OL, Van Tendeloo G, Gupta HS, Guitian F, Yoshimura M (2009) An efficient morphology control of hydroxyapatite crystal via hydrothermal synthesis. Cryst Growth Des 9:466–474

    Article  CAS  Google Scholar 

  18. Ma T, Xia Z, Liao L (2011) Effect of reaction systems and surfactant additives on the morphology evolution of hydroxyapatite nanorods obtained via a hydrothermal route. Appl Surf Sci 257:4384–4388

    Article  CAS  Google Scholar 

  19. Rajkumar M, Sundaram NM, Rajendran V (2011) Preparation of size controlled, stoichiometric and bioresorbable hydroxyapatite nanorod by varying initial pH, Ca/P ratio and sintering temperature. Dig J Nanomater Biostruct 6:169–179

    Google Scholar 

  20. Zhang H-B, Zhou K, Li Z, Huang S (2000) Plate-like hydroxyapatite nanoparticles synthesized by the hydrothermal method. J Phys Chem Solids 70:243–248

    Article  CAS  Google Scholar 

  21. Wang RZ, Suo Z, Evans AG, Yao N, Aksay IA (2001) Deformation mechanisms in nacre. J Mater Res 16:2485

    Article  CAS  Google Scholar 

  22. Evans AG, Suo Z, Wang RZ, Aksay IA, He MY, Hutchinson JW (2001) Model for the robust mechanical behavior of nacre. J Mater Res 16:2475

    Article  CAS  Google Scholar 

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Acknowledgements

The financial support from Tsinghua University National Key Lab of Advanced Ceramics and Fine Processing through National Laboratory Fund is gratefully acknowledged. The authors are obliged to colleagues at Tsinghua University, Dundee University and Plymouth University for their assistance with XRD and SEM analysis.

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Correspondence to H. R. Le.

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Le, H.R., Chen, K.Y. & Wang, C.A. Effect of pH and temperature on the morphology and phases of co-precipitated hydroxyapatite. J Sol-Gel Sci Technol 61, 592–599 (2012). https://doi.org/10.1007/s10971-011-2665-7

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  • DOI: https://doi.org/10.1007/s10971-011-2665-7

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