Investigation of the physicochemical properties of composite materials based on hydroxyapatite doped with individual substances and their combinations
K.I. Sabanin2, V.M. Skachkov1, E.A. Bogdanova3, N.A. Sabirzyanov1
1 Institute of Solid State Chemistry of the Ural Branch of RAS
2 Ural Federal University named after the first President of Russia B. N. Yeltsin
3 JSC «Giredmet»
DOI: 10.26456/pcascnn/2025.17.875
Original article
Abstract: The paper studies the effect of reinforcing additives of titanium and zirconium oxides, as in individually and with their combined effect, on the physico-chemical properties of dispersed-hardened composite materials based on nanoscale hydroxyapatite obtained by precipitation from solution, followed by a heat treatment over a wide temperature range from 25 to 1200°C. The composite materials under study have been obtained by means of mechanochemical synthesis with simultaneous mixing and grinding of materials. The synthesized samples were certified by X-ray phase analysis, differential thermal analysis, and dispersion analysis. The influence of the qualitative and quantitative composition of the composite material on the sintering processes, strength characteristics and morphology of studied samples is shown. It has been experimentally established that the introduction of reinforcing additives, both individually and in combination, makes it possible to thermally stabilize the material up to temperatures of ~1200°C, while maintaining a constant phase composition, preventing the decomposition of hydroxyapatite into tricalcium phosphate. It is shown that the presence of zirconium dioxide in the sample composition makes it possible to significantly increase the compressive strength of the material. However, it was found that the combined presence of titanium and zirconium oxides in the ceramic material leads to a decrease in the microhardness of the composite, which in the case of these additives makes the use of double composites as medical materials more promising.
Keywords: hydroxyapatite, nonstoichiometric titanium oxide, zirconium dioxide, composite biomaterials, microhardness
- Kirill I. Sabanin – 1st year graduate student, Department of Experimental Physics, Ural Federal University named after the first President of Russia B. N. Yeltsin
- Vladimir M. Skachkov – Ph. D., Senior Researcher, Laboratory of heterogeneous processes chemistry, Institute of Solid State Chemistry of the Ural Branch of RAS
- Ekaterina A. Bogdanova – Ph. D., Leading Researcher, Laboratory of materials and technologies of the fourth energy transition, JSC «Giredmet»
- Nail A. Sabirzyanov – Dr. Sc., Chief Researcher, Laboratory of heterogeneous processes chemistry, Institute of Solid State Chemistry of the Ural Branch of RAS
For citation:
Sabanin K.I., Skachkov V.M., Bogdanova E.A., Sabirzyanov N.A. Issledovanie fiziko-khimicheskikh svojstv kompozitsionnykh materialov na osnove gidroksiapatita pri dopirovanii ego individualnymi veshchestvami i ikh kombinatsiyami [Investigation of the physicochemical properties of composite materials based on hydroxyapatite doped with individual substances and their combinations], Fiziko-khimicheskie aspekty izucheniya klasterov, nanostruktur i nanomaterialov [Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials], 2025, issue 17, pp. 875-886. DOI: 10.26456/pcascnn/2025.17.875. ⎘
Full article (in Russian): download PDF file
References:
1. Verma S., Sharma N. Evaluating the mechanical properties of novel HAp reinforced polyaryletherketone biocomposites via molecular dynamics simulation, Materials Chemistry and Physics, 2023, vol. 307, art. no. 28106, 9 p. DOI: 10.1016/j.matchemphys.2023.128106.
2. Barinov S.M., Komlev V.S. Biokeramika na osnove fosfatov kal'tsiya [Calcium phosphate bioceramics]. Moscow, Nauka Publ., 2006, 204 p. (In Russian).
3. Suresh S., Sun C-N., Tekumalla S. et al. Mechanical properties and in vitro cytocompatibility of dense and porous Ti–6Al–4V ELI manufactured by selective laser melting technology for biomedical applications, Journal of the Mechanical Behavior of Biomedical Materials, 2021, vol. 123, art. no. 104712, 12 p. DOI: 10.1016/j.jmbbm.2021.104712.
4. Cai D., Zhao X., Yang L. et al. A novel biomedical titanium alloy with high antibacterial property and low elastic modulus, Journal of Materials Science & Technology, 2021, vol. 81, pp. 13-25. DOI: 10.1016/j.jmst.2021.01.015.
5. Shekhawat D., Singh A., Banerjee M.K. et al. Bioceramic composites for orthopaedic applications: A comprehensive review of mechanical, biological, and microstructural properties, Ceramics International, 2021, vol. 47, issue 3, pp. 3013-3030. DOI: 10.1016/j.ceramint.2020.09.214.
6. Kim H-W., Noh Y-J., Koh Y-H. et al. Effect of CaF2 on densification and properties of hydroxyapatite–zirconia composites for biomedical applications, Biomaterials, 2002, vol. 23, issue 20, pp. 4113-4121. DOI: 10.1016/s0142-9612(02)00150-3.
7. Mobasherpour I., Solati Hashjin M., Razavi Toosi S.S., Darvishi Kamachali R. Effect of the addition ZrO2-Al2O3 on nanocrystalline hydroxyapatite bending strength and fracture toughness, Ceramics International, 2009, vol. 35, issue 4, pp. 1569-1574. DOI: 10.1016/j.ceramint.2008.08.017.
8. Htun Z.L., Ahmad N., Thant A.A., Noor A.-F.M. Characterization of CaO-ZrO2 reinforced hap biocomposite for strength and toughness improvement, Procedia Chemistry, 2016, vol. 19, pp. 510-516. DOI: 10.1016/j.proche.2016.03.046.
9. Khalajabadi S.Z., Ahmad N., Izman S. et al. In vitro biodegradation, electrochemical corrosion evaluations and mechanical properties of an Mg/HA/TiO2 nanocomposite for biomedical applications, Journal of Alloys and Compounds, 2017, vol. 696, pp. 768-781. DOI: 10.1016/j.jallcom.2016.11.106.
10. He Y., Zhang Y., Jiang Y. et al. Microstructure evolution, electrochemical properties and in-vitro properties of Ti-Nb-Zr based biocomposite by hydroxyapatite bioceramic, Journal of Alloys and Compounds, 2018, vol. 764, pp. 987-1002. DOI: 10.1016/j.jallcom.2018.06.132.
11. Rempel S.V., Bogdanova Е.А., Valeeva А.А. et al. The effect of substoichiometric nanocrystalline titanium monoxide (TiOy) additions on the strength properties of hydroxyapatite (HAp), Inorganic Materials. 2016, vol. 52, issue 5, pp. 476-482. DOI: 10.1134/S0020168516050137.
12. Rempel S.V., Valeeva А.А., Bogdanova Е.А. et al. Vacuum-made nanocomposite of low-temperature hydroxyapatite (HAp) and hard nonstoichiometric titanium monoxide (TiOy) with enhanced mechanical properties, Mendeleev Communications, 2016, vol. 26, issue 6, pp. 543-545. DOI: 10.1016/j.mencom.2016.11.029.
13. Sabirzyanov N.A., Bogdanova E.A., Khonina T.G. Sposob polucheniya suspenzii gidroksiapatita [A method of obtaining a suspension of hydroxyapatite]. Patent RF, no. 2406693, 2010. (In Russian).
14. Bogdanova E.A., Skachkov V.М., Medyankina I.S. et al. Formation of nanodimensional structures in precipitated hydroxyapatite by fluorine substitution, SN Applied Sciences, 2020, vol. 2, issue 9, art. no. 1565, 7 p. DOI: 10.1007/s42452-020-03388-5.