Crystallographic study of hydrothermal synthesis of Hydroxyapatite nano-rods using Brushite precursors

Document Type : Original Article


1 Department of Materials Engineering, Tarbiat Modares University, Tehran, Iran

2 Non-metallic Materials Group, Niroo Research Institute, Tehran, Iran



Introduction: Being known for an array of properties that favor hard tissue regeneration, ranging from osteoconductivity to biocompatibility to non-immunogenicity, and being the natural bone mineral phase hydroxyapatite (HA, Ca10(PO4)6(OH)2) is the natural bioceramic of choice for the reinforcement phase of biocomposites.
Objective: The main objective of this study is to successfully synthesize uniform one dimensional HA nano-structures using a gram-scale hydrothermal batch process.
Material and Methods: Brushite used as a precursor for HA synthesis. The powders obtained after washing and drying were evaluated. The analysis performed in the sample includes inductively coupled plasma (ICP), Raman Spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, Field Emission Scanning Electron Microscope (FE-SEM), and high-resolution TEM.
Result: The results of this study showed that the initial brushite used in the hydrothermal process was dissolved, followed by the nucleation process and the growth of hydroxyapatite. The synthesized powders in this study were rod-shaped, with 35 nm in diameter and between 50 and 250 nm in length. The main direction of rod growth was , which is C axis.
Conclusion: The powders synthesized in this research have the potential to be used in bone tissue engineering, implantation, and drug delivery.

Graphical Abstract

Crystallographic study of hydrothermal synthesis of Hydroxyapatite nano-rods using Brushite precursors


[1]    D.E. Aston, J.R. Bow, D.N. Gangadean, Mechanical properties of selected nanostructured materials and complex bio-nano, hybrid and hierarchical systems, Int.
[2]    Mater. Rev. 58 (2013) 167–202, R.K. Roeder, G.L. Converse, R.J. Kane, W. Yue, Hydroxyapatite-reinforced polymer biocomposites for synthetic bone substitutes, JOM 60 (2008) 38–45.
[3]    F. Munarin, P. Petrini, R. Gentilini, R.S. Pillai, S. Dirè, M.C. Tanzi, V.M. Sglavo, Microand nano-hydroxyapatite as active reinforcement for soft biocomposites, Int. J. Biol. Macromol. 72 (2015) 199–209,
[4]    Z. Fang, Q. Feng, Improved mechanical properties of hydroxyapatite whiskerreinforced poly(l-lactic acid) scaffold by surface modification of hydroxyapatite, Mater. Sci. Eng. C 35 (2014) 190–194,
[5]    V. Uskoković, D.P. Uskoković, Nanosized hydroxyapatite and other calcium phosphates: chemistry of formation and application as drug and gene delivery agents, J. Biomed. Mater. Res. B Appl. Biomater. 96B (2011) 152–191,
[6]    X. Li, Y. Yang, Y. Fan, Q. Feng, F. Cui, F. Watari, Biocomposites reinforced by fibers or tubes as scaffolds for tissue engineering or regenerative medicine: biocomposites reinforced by fibers or tubes, J. Biomed. Mater. Res. A 102 (2014) 1580–1594,
[7]    T. Liu, X. Ding, D. Lai, Y. Chen, R. Zhang, J. Chen, X. Feng, X. Chen, X. Yang, R. Zhao, K. Chen, X. Kong, Enhancing in vitro bioactivity and in vivo osteogenesis of organic–inorganic nanofibrous biocomposites with novel bioceramics, J. Mater. Chem. B 2 (2014) 6293,
[8]    C.Z. Liao, K. Li, H.M.Wong, W.Y. Tong, K.W.K. Yeung, S.C. Tjong, Novel polypropylene biocomposites reinforced with carbon nanotubes and hydroxyapatite nanorods for bone replacements, Mater. Sci. Eng. C 33 (2013) 1380–1388,
[9]    C. Wan, B. Chen, Poly(ε-caprolactone)/graphene oxide biocomposites: mechanical properties and bioactivity, Biomed. Mater. 6 (2011) 055010,
[10] P. Wang, L. Zhao, J. Liu, M.D. Weir, X. Zhou, H.H.K. Xu, Bone tissue engineering via nanostructured calcium phosphate biomaterials and stem cells, Bone Res. 2 (2014) 14017,
[11] D.S.H. Lee, Y. Pai, S. Chang, D.H. Kim, Microstructure, physical properties, and bone regeneration effect of the nano-sized β-tricalcium phosphate granules, Mater. Sci. Eng. C 58 (2016) 971–976,
[12] F. Peng, X. Yu, M. Wei, In vitro cell performance on hydroxyapatite particles/poly(Llactic acid) nanofibrous scaffolds with an excellent particle along nanofiber orientation, Acta Biomater. 7 (2011) 2585–2592,
[13] Y. Deng, H.Wang, L. Zhang, Y. Li, S. Wei, In situ synthesis and in vitro biocompatibility of needle-like nano-hydroxyapatite in agar–gelatin co-hydrogel, Mater. Lett. 104 (2013) 8–12,
[14] M. Jevtić, M. Mitrić, S. Škapin, B. Jančar, N. Ignjatović, D. Uskoković, Crystal structure of hydroxyapatite nanorods synthesized by Sonochemical homogeneous precipitation, Cryst. Growth Des. 8 (2008) 2217–2222,
[15] D.O. Costa, S.J. Dixon, A.S. Rizkalla, One- and three-dimensional growth of hydroxyapatite nanowires during sol–gel–hydrothermal synthesis, ACS Appl. Mater. Interfaces 4 (2012) 1490–1499,
[16] Q. Sun, J.-T. Lou, F. Kang, J.-F. Chen, J.-X.Wang, Facile preparation of hydroxyapatite nanotubes assisted by needle-like calcium carbonate, Powder Technol. 261 (2014) 49–54,
[17] B.B. Chandanshive, P. Rai, A.L. Rossi, O. Ersen, D. Khushalani, Synthesis of hydroxyapatite nanotubes for biomedical applications,Mater. Sci. Eng. C 33 (2013) 2981–2986,
[18] Y. Zhang, J. Lu, J. Wang, S. Yang, Y. Chen, Synthesis of nanorod and needle-like hydroxyapatite crystal and role of pH adjustment, J. Cryst. Growth 311 (2009) 4740–4746,
[19] L. Xia, K. Lin, X. Jiang, B. Fang, Y. Xu, J. Liu, D. Zeng, M. Zhang, X. Zhang, J. Chang, Z. Zhang, Effect of nano-structured bioceramic surface on osteogenic differentiation of adipose derived stem cells, Biomaterials 35 (2014) 8514–8527,
[20] B.-Q. Lu, Y.-J. Zhu, F. Chen, C. Qi, X.-Y. Zhao, J. Zhao, Solvothermal transformation of calcium oleate precursor into large-sized highly ordered arrays of ultralong hydroxyapatite Microtubes, Chem. Eur. J. (2014) 1–7,
[21] B. Jokić, M. Mitrić, V. Radmilović, S. Drmanić, R. Petrović, D. Janaćković, Synthesis and characterization ofmonetite and hydroxyapatite whiskers obtained by a hydrothermal method, Ceram. Int. 37 (2011) 167–173,
[22] X. Guo, L. Yu, L. Chen, H. Zhang, L. Peng, X. Guo,W. Ding, Organoamine-assisted biomimetic synthesis of faceted hexagonal hydroxyapatite nanotubes with prominent stimulation activity for osteoblast proliferation, J. Mater. Chem. B 2 (2014) 1760,
[23] M.-G.Ma, Y.-J. Zhu, J. Chang, Monetite formed inmixed solvents of water and ethylene glycol and its transformation to hydroxyapatite, J. Phys. Chem. B 110 (2006) 14226–14230,
[24] I.S. Neira, Y.V. Kolen'ko, O.I. Lebedev, G. Van Tendeloo, H.S. Gupta, F. Guitián, M. Yoshimura, An effective morphology control of hydroxyapatite crystals via hydrothermal synthesis, Cryst. Growth Des. 9 (2008) 466–474.
[25] F.Mohandes,M. Salavati-Niasari, Particle size and shapemodification of hydroxyapatite nanostructures synthesized via a complexing agent-assisted route, Mater. Sci. Eng. C 40 (2014) 288–298,
[26] F. Mohandes, M. Salavati-Niasari, Z. Fereshteh, M. Fathi, Novel preparation of hydroxyapatite nanoparticles and nanorods with the aid of complexing agents, Ceram. Int. 40 (2014) 12227–12233,
[27] F. Mohandes, M. Salavati-Niasari, Simple morphology-controlled fabrication of hydroxyapatite nanostructures with the aid of new organic modifiers, Chem. Eng. J. 252 (2014) 173–184,
[28] H. Nosrati, D. Q. S. Le, R. Z. Emameh, C. E. Bunger, Characterization of the Precipitated Dicalcium Phosphate Dehydrate on the Graphene Oxide Surface as a Bone Cement Reinforcement, Journal of Tissues and Materials, 2(1), (2019) 33-46, DOI: 10.22034/jtm.2019.173565.1013.   
[29] H. Nosrati, R. Sarraf Mamoory, F. Dabir, M. Canillas Perez, M. A. Rodriguez, D. Q. Svend Le, C. E. Bunger, In situ synthesis of three dimensional graphene-hydroxyapatite nano powders via hydrothermal process, Materials Chemistry and Physics, 222, (2019) 251–255,
[30] H. Nosrati, R. Sarraf Mamoory, F. Dabir, D. Q. Svend Le, C. E. Bunger, M. Canillas Perez, M. A. Rodriguez, Effects of hydrothermal pressure on in situ synthesis of 3D graphene/hydroxyapatite nano structured powders, Ceramics International, 45, (2019) 1761–1769,