Structure of hydroxyapatite coatings produced by electrodeposition on stainless steel and titanium nickelide substrates

Cover Page

Cite item

Full Text

Abstract

Problem. Hydroxyapatite (HA, chemical formula Ca10(PO4)6(OH)2) is widely used as a biocompatible and
bioactive ceramic due to its structural and chemical similarity to the main mineral component of human hard tissues.
A disadvantage of hydroxyapatite is its low mechanical properties (strength, crack resistance, and impact resistance),
which undoubtedly limits its use as a structural material but not as a bioactive coating on metal implant surfaces.
Electrodeposition is one of the most promising methods for forming bioactive calcium-phosphate coatings on metal
implants due to the ability to control the composition, structure, and thickness of the coating at low process temperatures.
Aim. The aim of this work is to identify patterns in the formation of the composition and structure of hydroxyapatite coatings produced by electrodeposition on 12X18H10T stainless steel and titanium nickelide substrates, and to optimize
the deposition modes. Methods. The influence of electrolyte parameters (Ca2+ and PO4
3
ion concentration, pH, H2O2
and NaOH additives), temperature (23–85 °C), potential and deposition time on the stoichiometry, crystallinity, texture
and crystallite size of HA coatings was studied using X-ray fluorescence (XRF), X-ray diffraction (XRD), and
IR-spectroscopy. Results. It was shown that the brushite phase (CaHPO4·2H2O) is formed at room temperature regardless
of the electrolyte composition. Increasing the temperature to 65 °C or higher, when combined with optimization of pH
(4.1–6.0) and potential (−1.7…−3.4 V), allows the synthesis of coatings with a composition close to stoichiometric
hydroxyapatite. The regimes ensuring the production of single-phase, highly-crystalline HA coatings with a texture coefficient of up to 2.6, which corresponds to the structure most conducive to osseointegration, were experimentally determined.
Conclusions. The best coating characteristics (high crystallinity CI=9.1, crystallite size along the c-axis ~70 nm, c/a
ratio=0.730) were achieved for the sample synthesized at T=75 °C, pH=5.0, and U=−1.7 V.

About the authors

Vasili V. Rubanik

Institute of Technical Acoustics of the NAS of Belarus

Email: v.v.rubanik@tut.by
ORCID iD: 0000-0002-0350-1180

Doctor of Sciences (Engineering), Professor,
Corresponding Member of the National Academy of Sciences of Belarus,
Head of the Department – Head of the Laboratory

Belarus, 210009, Belarus, Vitebsk, General Lyudnikov Prospekt, 13

Dzmitry A. Bahrets

Institute of Technical Acoustics of the NAS of Belarus

Author for correspondence.
Email: bagurets@gmail.com
ORCID iD: 0009-0009-2632-5464
Belarus, 210009, Belarus, Vitebsk, General Lyudnikov Prospekt, 13

Sergey E. Mozzharov

Institute of Technical Acoustics of the NAS of Belarus

Email: lkm_ita@vitebsk.by

Senior Researcher

Belarus, 210009, Belarus, Vitebsk, General Lyudnikov Prospekt, 13

Thi Anh Tuyet Ngo

Institute of Material Science of Vietnam Academy of Science and Technology

Email: tuyetnta@ims.vast.vn
ORCID iD: 0000-0001-9792-5613

PhD, Senior Researcher

Viet Nam, Вьетнам, г. Ханой, улица Хоанг Куок Вьет, 18

References

  1. Kareem R.O., Bulut N., Kaygili O. Hydroxyapatite Biomaterials: A Comprehensive Review of their Properties, Structures, Medical Applications, and Fabrication Methods. Journal of Chemical Reviews, 2024, vol. 6, no. 1, pp. 1‒26. doi: 10.48309/JCR.2024.415051.1253.
  2. Rios-Pimentel F.F., Méndez-González M.M., García-Rocha M. A short review: hydroxyapatite coatings for metallic implants. Heat Treatment and Surface Engineering, 2023, vol. 5, no. 1, article number 2202002. doi: 10.1080/25787616.2023.2202002.
  3. Safavi M.S., Walsh F.C., Surmeneva M.A., Surmenev R.A., Khalil-Allafi J. Electrodeposited Hydroxyapatite‐Based Biocoatings: Recent Progress and Future Challenges. Coatings, 2021, vol. 11, no. 1, article number 110. doi: 10.3390/coatings11010110.
  4. Ting-Ting Li, Lei Ling, Mei-Chen Lin, Hao-Kai Peng, Hai-Tao Ren, Ching-Wen Lou, Jia-Horng Lin. Recent advances in multifunctional hydroxyapatite coating by electrochemical deposition. Journal of Materials Science, 2020, vol. 55, pp. 6352‒6374. doi: 10.1007/s10853-020-04467-z.
  5. Drevet R., Benhayoune H. Electrodeposition of Calcium Phosphate Coatings on Metallic Substrates for Bone Implant Applications: A Review. Coatings, 2022, vol. 12, no. 4, article number 539. doi: 10.3390/coatings12040539.
  6. Zhitomirsky I. Electrolytic deposition of oxide films in the presence of hydrogen peroxide. Journal of the European Ceramic Society, 1999, vol. 19, no. 15, pp. 2581‒2587. doi: 10.1016/S0955-2219(99)00023-0.
  7. Dev P.R., Anand C.P., Michael D.S., Wilson P. Hydroxyapatite coatings: a critical review on electrodeposition parametric variations influencing crystal facet orientation towards enhanced electrochemical sensing. Materials Advances, 2022, vol. 3, no. 21, pp. 7773‒7809. doi: 10.1039/D2MA00620K.
  8. Yue Sa, Yaru Guo, Xiaowei Feng, Man Wang, Ping Li, Yixue Gao, Xu Yang, Tao Jiang. Are different crystallinity-index-calculating methods of hydroxyapatite efficient and consistent? New Journal of Chemistry, 2017, vol. 41, no. 13, pp. 5723‒5731. doi: 10.1039/C7NJ00803A.
  9. Gopi D., Kanimozhi K., Bhuvaneshwari N., Indira J., Kavitha L. Novel banana peel pectin mediated green route for the synthesis of hydroxyapatite nanoparticles and their spectral characterization. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 118, pp. 589‒597. doi: 10.1016/j.saa.2013.09.034.
  10. Shamray V.F., Kalita V.I., Sirotinkin V.P., Gordeev A.S., Radyuk A.A., Komlev D.I. Study of the influence of heating the substrate to 550°C on the structure of plasma hydroxyapatite coatings. Neorganicheskie materialy, 2022, vol. 58, no. 12, pp. 1361‒1369. doi: 10.31857/S0002337X22120120.
  11. Shamray V.F., Sirotinkin V.P., Smirnov I.V., Kalita V.I., Fedotov A.Yu., Barinov S.M., Komlev V.S. Structure of the Hydroxyapatite Plasma-sprayed Coatings Deposited on Pre-heated Titanium Substrates. Ceramics International, 2017, vol. 43, no. 12, pp. 9105‒9109. doi: 10.1016/J.CERAMINT.2017.04.057.
  12. Janusz W., Skwarek E. Comparison of Oxalate, Citrate and Tartrate Ions Adsorption in the Hydroxyapatite/Aqueous Electrolyte Solution System. Colloids and Interfaces, 2020, vol. 4, no. 4, article number 45. doi: 10.3390/colloids4040045.
  13. Coşkun M., Karahan I.H., Yücel Y. Optimized Electrodeposition Concentrations for Hydroxyapatite Coatings on CoCrMo biomedical alloys by computational techniques. Electrochimica Acta, 2014, vol. 150, pp. 46‒54. doi: 10.1016/j.electacta.2014.10.120.
  14. Kuo M.C., Yen S.K. The process of electrochemical deposited hydroxyapatite coatings on biomedical titanium at room temperature. Materials Science and Engineering: C, 2002, vol. 20, no. 1-2, pp. 153‒160. doi: 10.1016/S0928-4931(02)00026-7.
  15. Weilong Zhao, Zhijun Xu, Yang Yang, Nita Sahai. Surface Energetics of the Hydroxyapatite Nanocrystal–Water Interface: A Molecular Dynamics Study. Langmuir, 2014, vol. 30, no. 44, pp. 13283‒13292. doi: 10.1021/la503158p.
  16. Nguyen Huu Thong, Bui Thi Hue, Le Quynh Duong, Le Van Toan, Hoang Nhu Van, Duong Thanh Tung, Cao Xuan Thang, Nguyen Viet Tung, Nguyen Thi Lan, Hoang Van Vuong, Le Thai Hung, Pham Hung Vuong. Synthesis of Hydroxyapatite Coatings with Hexagonal Crystal Structure on Etched Titanium by Hydrothermal Method. VNU Journal of Science: Mathematics – Physics, 2022, vol. 38, no. 4, pp. 85‒92. doi: 10.25073/2588-1124/vnumap.4740.
  17. Zakharov N.A., Sentsov M.Yu., Demina L.I., Zakharova T.V., Kalinnikov V.T. Synthetical calcium hydroxyapatite and its natural analogues. Sorbtsionnye i khromatograficheskie protsessy, 2010, vol. 10, no. 6, pp. 879‒886. EDN: NCVBOX.
  18. Neira I.S., Kolen’ko Y.V., Lebedev O.I., Van Tendeloo G., Gupta H.S., Guitián F., Yoshimura M. An Effective Morphology Control of Hydroxyapatite Crystals via Hydrothermal Synthesis. Crystal Growth & Design, 2009, vol. 9, no. 1, pp. 466‒474. doi: 10.1021/cg800738a.

Supplementary files

Supplementary Files
Action
1. JATS XML
Download

Copyright (c) 2026 Rubanik V.V., Bahrets D.A., Mozzharov S.E., Ngo T.T.

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.