Santosh R. Patil,
Rajanikant M. Kurane,
Suyog Sutar,
- Associate Professor, Department of Mechatronics Engineering, Rajarambapu Institute of Technology, Rajaramnagar, Islampur, Maharashtra, India
- Assistant Professor, Department of Sciences and Humanities, Rajarambapu Institute of Technology, Rajaramnagar, Islampur, Maharashtra, India
- Research Scholar, Department of Mechanical Engineering, Rajarambapu Institute of Technology, Rajaramnagar, Islampur, Maharashtra, India
Abstract
Developing bone implant materials that combine biological compatibility with mechanical strength remains a major challenge in orthopedic research. Hydroxyapatite (HAp) closely mimics bone mineral and supports cell growth, but its brittleness limits load-bearing applications. To address this, a quaternary nanocomposite of hydroxyapatite (HAp), graphene (Gr), zirconia (ZrO2), and ferrocene (Fc) (Hap-Gr-ZrO₂-Fc) was synthesized through a one-step hydrothermal process. Graphene and zirconia provided reinforcement, while ferrocene contributed structural stability and carbon functionality. Comprehensive characterization confirmed a crystalline, multi-phase composite with strong interfacial bonding. BET analysis showed a high surface area (89.4 m² g⁻¹) and mesoporous structure (0.1537 cm³ g⁻¹), favorable for cell adhesion. Thermal analysis revealed excellent stability with 81.6 % residue at 500 °C. MTT assays on L929 fibroblast cells indicated high biocompatibility, maintaining greater than 82 % viability up to 100 µg mL⁻¹. Finite element analysis of a bone-pin model predicted a maximum von Mises stress of 9.45 MPa under a 70 kg load, lower than that of natural bone (12.42 MPa), confirming superior load distribution and durability. The HAp-Gr-ZrO₂-Fc nanocomposite integrates mechanical strength, stability, and cytocompatibility, demonstrating strong potential for next-generation load-bearing orthopedic implants.
Keywords: Biocompatibility, bone pin, FCA analysis, ferrocene, graphene, hydrothermal synthesis, hydroxyapatite, nanocomposite, zirconia.
[This article belongs to Journal of Polymer & Composites ]
Santosh R. Patil, Rajanikant M. Kurane, Suyog Sutar. Synthesis and Characterization of Graphene-Based Hydroxyapatite Using Hydrothermal Method for Its Biomedical Application. Journal of Polymer & Composites. 2025; 14(01):120-135.
Santosh R. Patil, Rajanikant M. Kurane, Suyog Sutar. Synthesis and Characterization of Graphene-Based Hydroxyapatite Using Hydrothermal Method for Its Biomedical Application. Journal of Polymer & Composites. 2025; 14(01):120-135. Available from: https://journals.stmjournals.com/jopc/article=2025/view=234436
References
- Sadat-Shojai M, Khorasani MT, Dinpanah Khoshdargi E, Jamshidi A. Synthesis methods for nanosized hydroxyapatite with diverse structures. Acta Biomater. 2013;9(8):7591–7621. doi:10.1016/j.actbio.2013.04.012.
- Sadat-Shojai M, Khorasani MT, Dinpanah-Khoshdargi E, Jamshidi A. Hydroxyapatite nanoparticles: a review of synthesis, properties, and applications. Biomaterials. 2013;34(28):6679–6711. doi:10.1016/j.biomaterials.2013.05.036.
- Dorozhkin SV. Bioceramics of calcium orthophosphates. Biomaterials. 2010;31(7):1465–1485. doi:10.1016/j.biomaterials.2009.11.050.
- Dorozhkin SV. Calcium orthophosphates in nature, biology and medicine. Materials (Basel). 2009;2(2):399–498. doi:10.3390/ma2020399.
- Vallet-Regí M, González-Calbet JM. Calcium phosphates as substitution of bone tissues. Prog Solid State Chem. 2004;32(1–2):1–31. doi:10.1016/j.progsolidstchem.2004.07.001.
- Kokubo T, Kim HM, Kawashita M. Novel bioactive materials with different mechanical properties. Biomaterials. 2003;24(13):2161–2175. doi:10.1016/S0142-9612(03)00044-9.
- Garvie RC. Stabilization of the tetragonal structure in zirconia microcrystals. J Phys Chem. 1978;82(2):218–224. doi:10.1021/j100491a016.
- Garvie RC. Metastable tetragonal zirconia. J Phys Chem. 1965;69(4):1238–1243. doi:10.1021/j100888a024.
- Garvie RC, Hannink RHJ, Pascoe RT. Ceramic steel. Nature. 1975;258:703–704. doi:10.1038/258703a0.
- Hannink RHJ, Kelly PM, Muddle BC. Transformation toughening in zirconia-containing ceramics. J Am Ceram Soc. 2000;83(3):461–487. doi:10.1111/j.1151-2916.2000.tb01221.x.
- Chevalier J, Gremillard L, Virkar AV, Clarke DR. The tetragonal–monoclinic transformation in zirconia: lessons learned and future trends. J Am Ceram Soc. 2009;92(9):1901–1920. doi:10.1111/j.1551-2916.2009.03278.x.
- Chevalier J, Gremillard L. Ceramics for medical applications: a picture for the next 20 years. J Eur Ceram Soc. 2009;29(7):1245–1255. doi:10.1016/j.jeurceramsoc.2008.08.025.
- Kelly JR, Denry I. Stabilized zirconia as a structural ceramic: an overview. Dent Mater. 2008;24(3):289–298. doi:10.1016/j.dental.2007.05.005.
- Ramesh S, Tan CY, Bhaduri SB, Teng WD. Processing and properties of nanocrystalline hydroxyapatite derived from wet-chemical synthesis. J Mater Process Technol. 2007;206(1–3):221–230. doi:10.1016/j.jmatprotec.2007.12.019.
- Balasubramanian P, et al. Zirconia–alumina composites for orthopaedic applications. J Eur Ceram Soc. 2014;34(12):2915–2926. doi:10.1016/j.jeurceramsoc.2014.04.013.
- Anselme K. Osteoblast adhesion on biomaterials. Biomaterials. 2000;21(7):667–681. doi:10.1016/S0142-9612(99)00242-2.
- Anselme K, Bigerelle M. Effect of surface topography on cell–biomaterial interactions. J Biomed Mater Res A. 2005;75(1):89–97. doi:10.1002/jbm.a.30563.
- Anselme K, et al. The interaction of cells and bacteria with surfaces structured at the nanometre scale. Acta Biomater. 2010;6(10):3824–3846. doi:10.1016/j.actbio.2010.04.001.
- Webster TJ, Ergun C, Doremus RH, Siegel RW, Bizios R. Enhanced osteoclast-like cell functions on nanophase ceramics. Biomaterials. 2000;22(11):1327–1333. doi:10.1016/S0142-9612(00)00275-2.
- Ren F, Leng Y, Xin R, Ge X. Synthesis, characterization and ab initio simulation of magnesium-substituted hydroxyapatite. Acta Biomater. 2010;6(7):2787–2796. doi:10.1016/j.actbio.2010.01.042.
- Dorozhkin SV. Biphasic, triphasic and multiphasic calcium orthophosphates. Acta Biomater. 2012;8(3):963–977. doi:10.1016/j.actbio.2011.09.003.
- Wu VM, Uskoković V. Is there a relationship between solubility and resorbability of different calcium phosphate phases in vitro? Biochim Biophys Acta Gen Subj. 2015;1850(8):1648–1658. doi:10.1016/j.bbagen.2015.04.009.
- Dorozhkin SV. Calcium orthophosphate-based bioceramics. Materials (Basel). 2013;6(9):3840–3942. doi:10.3390/ma6093840.
- Dorozhkin SV. Calcium orthophosphates in nature, biology and medicine. Materials (Basel). 2011;4(6):1057–1111. doi:10.3390/ma4061057.
- Bose S, Tarafder S. Calcium phosphate ceramic systems in growth factor and drug delivery for bone tissue engineering: a review. Acta Biomater. 2012;8(4):1401–1421. doi:10.1016/j.actbio.2011.11.017.
- Webster TJ, Siegel RW, Bizios R. Osteoblast adhesion on nanophase ceramics. Biomaterials. 1999;20(13):1221–1227. doi:10.1016/S0142-9612(99)00020-4.
- Shi Z, Huang X, Cai Y, Tang R, Yang D. Size effect of hydroxyapatite nanoparticles on proliferation and apoptosis of osteoblast-like cells. Acta Biomater. 2009;5(1):338–345. doi:10.1016/j.actbio.2008.07.023.
- Cai Y, et al. Role of hydroxyapatite nanoparticle size in bone cell proliferation. J Mater Chem. 2007;17(36):3780–3787. doi:10.1039/B705129H.
- Boanini E, Gazzano M, Bigi A. Ionic substitutions in calcium phosphates synthesized at low temperature. Acta Biomater. 2010;6(6):1882–1894. doi:10.1016/j.actbio.2009.12.041.
- Dey A, et al. The role of prenucleation clusters in surface-induced calcium phosphate crystallization. Nat Mater. 2010;9:1010–1014. doi:10.1038/nmat2900.
- Dorozhkin SV. Calcium orthophosphates in dentistry. J Mater Sci Mater Med. 2009;20(4):819–837. doi:10.1007/s10856-008-3639-7.
- Penel G, Leroy G, Rey C, Bres E. MicroRaman spectral study of the PO₄ and CO₃ vibrational modes in synthetic and biological apatites. Calcif Tissue Int. 1998;63(6):475–481. doi:10.1007/s002239900561.
- De Aza PN, Santos C, Pazo A, de Aza S, Cuscó R, Artús L. Vibrational properties of calcium phosphate compounds. 1. Raman spectrum of β-tricalcium phosphate. Chem Mater. 1997;9(4):912–915. doi:10.1021/cm960425d.
- Bouvier P, Lucazeau G. Raman spectra and vibrational analysis of nanometric tetragonal zirconia under high pressure. J Phys Chem Solids. 2000;61(4):569–578. doi:10.1016/S0022-3697(99)00242-5.
- Ferrari AC, Robertson J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B. 2000;61(20):14095–14107. doi:10.1103/PhysRevB.61.14095.
- Suchanek W, Yoshimura M. Processing and properties of hydroxyapatite-based biomaterials for use as hard tissue replacement implants. J Mater Res. 1998;13(1):94–117. doi:10.1557/JMR.1998.0016.
- Sopyan I, Mel M, Ramesh S, Khalid KA. Porous hydroxyapatite for artificial bone applications. Sci Technol Adv Mater. 2007;8(1–2):116–123. doi:10.1016/j.stam.2006.11.017.
- LeGeros RZ. Calcium phosphate-based osteoinductive materials. Chem Rev. 2008;108(11):4742–4753. doi:10.1021/cr800427g.
- Raynaud S, Champion E, Bernache-Assollant D, Thomas P. Calcium phosphate apatites with variable Ca/P atomic ratio I. Biomaterials. 2002;23(4):1065–1072. doi:10.1016/S0142-9612(01)00218-6.
- Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A. 1976;32(5):751–767. doi:10.1107/S0567739476001551.
- Kim HW, Koh YH, Kong YM, Kang JG, Kim HE. Strontium substituted calcium phosphate biphasic ceramics for bone tissue engineering. Biomaterials. 2004;25(17):3403–3411. doi:10.1016/j.biomaterials.2003.09.048.
- Bigi A, Boanini E, Gazzano M. Strontium-substituted hydroxyapatite nanocrystals. Inorg Chem. 2007;46(15):6200–6206. doi:10.1021/ic700426j.
- Pan HH, et al. Nucleation of amorphous calcium phosphate on negatively charged surfaces involves a two-step mechanism. J Phys Chem C. 2007;111(28):10219–10225. doi:10.1021/jp0722405.
- Gibson IR, Bonfield W. Novel synthesis and characterization of an AB-type carbonate-substituted hydroxyapatite. J Biomed Mater Res. 2002;59(4):697–708. doi:10.1002/jbm.10044.
- Camire CL, et al. In vivo evaluation of injectable calcium phosphate cement with biodegradable fibers. J Biomed Mater Res B Appl Biomater. 2006;76(2):424–431. doi:10.1002/jbm.b.30398.
- Elliott JC. Structure and chemistry of the apatites and other calcium orthophosphates. Amsterdam: Elsevier; 1994.
- Ohtsuki C, Kokubo T, Yamamuro T. Mechanism of apatite formation on CaO–SiO₂–P₂O₅ glasses in a simulated body fluid. J Non-Cryst Solids. 1992;143(1–3):84–92. doi:10.1016/S0022-3093(05)80556-3.
- Kokubo T, Takadama H. How useful is SBF in predicting in vivo bone bioactivity? Biomaterials. 2006;27(15):2907–2915. doi:10.1016/j.biomaterials.2006.01.017.
- Dalchiele EA, et al. XPS and electrochemical studies of ferrocene derivatives anchored on n- and p-Si(100) by Si–O or Si–C bonds. J Electroanal Chem. 2005;579(1):133–142. doi:10.1016/j.jelechem.2005.02.002.
- Lu HB, Campbell CT, Graham DJ, Ratner BD. Surface characterization of hydroxyapatite and related calcium phosphates by XPS and TOF-SIMS. Anal Chem. 2000;72(13):2886–2894. doi:10.1021/ac990812h.
- Azdad Z, et al. Valence band behaviour of zirconium oxide: photoelectron and Auger spectroscopy study. Sci Rep. 2018;8:16251. doi:10.1038/s41598-018-34570-w.
- Wang P, et al. Fabrication of hydroxyapatite/hydrophilic graphene composites and their modulation to cell behavior toward bone reconstruction engineering. Colloids Surf B Biointerfaces. 2019;173:512–520. doi:10.1016/j.colsurfb.2018.10.027.
- Patil SR, Shirguppikar SS, Dong PV. Synthesis and characterization of artificial human bone developed using nanocomposite. EUREKA Phys Eng. 2022;3:131–139. doi:10.21303/2461-4262.2022.002432.
- Karuppiah G, et al. Multiobjective optimization of fabrication parameters of jute fibre/polyester composites with egg shell powder and nanoclay filler. Molecules. 2020;25(23):5579. doi:10.3390/molecules25235579.
- Padmanabhan RG, et al. Evaluation of mechanical properties and Fick’s diffusion behaviour of aluminum-DMEM reinforced with hemp/bamboo/basalt woven fiber metal laminates. Ain Shams Eng J. 2024;15(7):102759. doi:10.1016/j.asej.2024.102759.
- Ayrilmis N, et al. Utilizing waste manhole covers and fibreboard as reinforcing fillers for thermoplastic composites. J Reinf Plast Compos. 2024;0(0):e-pub ahead of print. doi:10.1177/07316844241238507.
- Ramasubbu R, et al. Mechanical properties of epoxy composites reinforced with Areca catechu fibers containing silicon carbide. BioResources. 2024;19(2):2353–2370. doi:10.15376/biores.19.2.2353-2370.
- Aruchamy K, et al. Enhancement of mechanical properties of hybrid polymer composites using palmyra palm and coconut sheath fibers. BioResources. 2024;20(1):698–724. doi:10.15376/biores.20.1.698-724.
- Kar A, et al. Effect of fiber loading on the mechanical, morphological, and dynamic mechanical characteristics of Calamus tenuis fiber-reinforced epoxy composites. J Vinyl Addit Technol. 2024;31(1):224–240. doi:10.1002/vnl.22167.

Journal of Polymer & Composites
| Volume | 14 |
| Issue | 01 |
| Received | 19/11/2025 |
| Accepted | 01/12/2025 |
| Published | 16/12/2025 |
| Publication Time | 27 Days |
Login
PlumX Metrics