Received 17.12.2023, Revised 20.02.2024, Accepted 26.04.2024
One of the most promising directions of modern materials science is the search for methods of improving the biocompatibility properties of metals used in implantology, which will allow to reduce the percentage of rejection of implants by the living organism. Therefore, it is promising to use processing methods to change the state of the surface of metals due to surface modification, which includes the method of plasma electrolytic oxidation. The main goal of this work was to develop a technological process for obtaining coatings with higher biocompatibility compared to the base metal due to the introduction of natural components into the coating. The presence of elements in biocoatings and their quantity was determined using a scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS), which allowed for targeted analysis of the surface of the samples. The elemental composition of coatings synthesised on the basis of titanium alloy in alkaline electrolytes based on KOH, liquid glass of calcium hydroxide, sodium polyphosphate and sodium pyrophosphate with the addition of hydroxyapatite and diatomite was researched in the work. A direct relationship between the composition of the electrolyte and the Ca/P ratio was established. It has been proven that biocoatings synthesised in alkaline solutions by the PEO method satisfy the conditions of biocompatibility. It has been established that in an environment containing alkalis and phosphates, coatings are synthesised for which Ca/P = 1.21. The introduction of hydroxyapatite into the electrolyte leads to an increase in the Ca/P ratio to a value of 1.28, and an increase in the concentration of the electrolyte and the addition of diatomite increases this ratio to a value of 1.57. The obtained results establish the possibility of a wide range of regulation of the Ca/P ratio in the biocoating
elemental analysis; biocompatibility; chemical properties; synthesis modes; coating composition
[1] Azmat, A., Asrar, S., Channa, I.A., Ashfaq, J., Chandio, I.A., Chandio, A.D., Shar, M.A., AlSalhi, M.S., & Devanesan, S. (2023). Comparative study of biocompatible titanium alloys containing non-toxic elements for orthopedic implants. Crystals, 13(3), article number 467. doi: 10.3390/cryst13030467.
[2] Fazel, M., Salimijazi, H.R., Shamanian, M., Apachitei, I., & Zadpoor, A.A. (2019). Influence of hydrothermal treatment on the surface characteristics and electrochemical behavior of Ti-6Al-4V bio-functionalized through plasma electrolytic oxidation. Surface and Coatings Technology, 374, 222-231. doi: 10.1016/j.surfcoat.2019.05.088.
[3] Ghobara, M., El-Sheekh, M., Hamed, A.F., Abdelhamid, M.A.A., & Pack, S.P. (2024). Diatom nanostructured biosilica. In A. Abomohra & S. Ende (Eds.), Value-added products from algae (pp. 461-492). New York: Springer.
[4] Gibbs, J.W. (1878). On the equilibrium of heterogeneous substances. American Journal of Science, s3-16(96), 441-458.
[5] Gu, Y., Ma, A., Jiang, J., Li, H., Song, D., Wu, H., & Yuan, Y. (2018). Simultaneously improving mechanical properties and corrosion resistance of pure Ti by continuous ECAP plus short-duration annealing. Materials Characterization, 138, 38-47. doi: 10.1016/j.matchar.2018.01.050.
[6] Hanawa, T. (2022). Biocompatibility of titanium from the viewpoint of its surface. Science and Technology of Advanced Materials, 23(1), 457-472. doi: 10.1080/14686996.2022.2106156.
[7] Imbirovych, N.Y., Zvirko, O.I., & Kurzydlowski, K.J. (2023). Morphology and porosity of titanium alloys surface after plasma-electrolytic oxidation in an alkaline environment with diatomite. Materials Science, 58(4).
[8] Jakubowicz, J. (2020). Special issue: Ti-based biomaterials: Synthesis, properties and applications. Materials, 13(7), article number 1696. doi: 10.3390/ma13071696.
[9] Jovović, J., Stojadinović, S., Šišović, N.M., & Konjević, N. (2012). Spectroscopic study of plasma during electrolytic oxidation of magnesium- and aluminium-alloy. Journal of Quantitative Spectroscopy and Radiative Transfer, 113(15), 1928-1937. doi: 10.1016/j.jqsrt.2012.06.008.
[10] Korzhyk, V., Berdnikova, O., Stukhliak, P., Kushnarova, O., Zhao, J., & Skachkov, І. (2024). Strength and crack resistance structural criteria of composite coatings produced by the method of multi-chamber detonation spraying. Solid State Phenomena, 355, 123-129. doi: 10.4028/p-qjM7yA.
[11] Li, L., Shi, J., Zhang, K., Yang, L., Yu, F., Zhu, L., Liang, H., Wang, X., & Jiang, Q. (2019). Early osteointegration evaluation of porous Ti6Al4V scaffolds designed based on triply periodic minimal surface models. Journal of Orthopedic Translation, 19, 94-105. doi: 10.1016/j.jot.2019.03.003.
[12] Li, T., Yan, Z., Liu, Z., He, M., Yan, Y., & Chen, Y. (2022). High corrosion resistance and surface conductivity of (Ti1-xCrx)N coating for titanium bipolar plate. Corrosion Science, 200, article number 110256. doi: 10.1016/j.corsci.2022.110256.
[13] Li, X., Dong, C., Zhao, Q., Pang, Y., Cheng, F., & Wang, S. (2018) Characterization of microstructure and wear resistance of PEO coatings containing various microparticles on Ti6Al4V alloy. Journal of Materials Engineering and Performance, 27, 1642-1653. doi: 10.1007/s11665-018-3249-2.
[14] Maj, Ł., Muhaffel, F., Jarzębska, A., Trelka, A., Balin, K., Bieda, M., & Cimenoglu, H. (2024). Unveiling the mechanisms of coating formation during micro-arc oxidation of titanium in Na2HPO4 electrolyte. Surface and Coatings Technology, 476, article number 130224. doi: 10.1016/j.surfcoat.2023.130224.
[15] Malekmohammadi, F., Razaghian, A., & Dehghanian, C. (2020). Effect of Cl– and NO–3 ions on microstructure and properties of TiO2-CeO2 nanostructured composite coatings obtained through plasma electrolytic oxidation (PEO) on Ti6Al4V. Protection of Metals and Physical Chemistry of Surfaces, 56, 103-112. doi: 10.1134/S2070205120010153.
[16] Markashova, L., Tyurin, Y., Berdnikova, O., Kolisnichenko, O., Polovetskyi, I., & Titkov, Y. (2019). Effect of nano-structured factors on the properties of the coatings produced by detonation spraying method. In Advances in thin films, nanostructured materials, and coatings (рp.109-117). Singapore: Springer. doi: 10.1007/978-981-13-6133-3_11.
[17] Molaei, M., Nouri, M., Babaei, K., & Fattah-Alhosseini, A. (2021). Improving surface features of PEO coatings on titanium and titanium alloys with zirconia particles: A review. Surfaces and Interfaces, 22, article number 100888. doi: 10.1016/j.surfin.2020.100888.
[18] Montes-Hernandez, G., & Renard, F. (2020). Nucleation of brushite and hydroxyapatite from amorphous calcium phosphate phases revealed by dynamic in situ raman spectroscopy. The Journal of Physical Chemistry C, 124, 28, 15302-15311. doi: 10.1021/acs.jpcc.0c04028.
[19] Pesode, P., & Barve, S. (2021). Surface modification of titanium and titanium alloy by plasma electrolytic oxidation process for biomedical applications: A review. Materials Today: Proceedings, 46(1), 594-602. doi: 10.1016/j.matpr.2020.11.294.
[20] Povstyanoy, O., Imbirovych, N., Redko, R., Redko, O., & Savaryn, P. (2024). Numerical evaluation of the properties of highly efficient titanium porous materials. In Advanced manufacturing processes V (pp. 307-317). New York: Springer. doi: 10.1007/978-3-031-42778-7_28.
[21] Subbotina, V., Bilozerov, V., Subbotin, O., Barmin, O., Hryhorieva, S., & Pysarska, N. (2022). Investigation of the influence of electrolyte composition on the structure and properties of coatings obtained by microarc oxidation. Physics and Chemistry of Solid State, 23(2), 380-386. doi: 10.15330/pcss.23.2.380-386.
[22] Subha, V., Raj, J.S., Anand, R.V., Sathya, S., Jothikumar, R., & Anusuya, M. (2023). Electrical discharge machining of titanium alloy using diatomite powder-mixed dielectric fluid based on response surface methodology. Materials Today: Proceedings. doi: 10.1016/j.matpr.2023.06.256.
[23] Tzaphlidou, M., Speller, R., Royle, G., Griffiths, J., Olivo, A., Pani, S., & Longo, R. (2005). High resolution Ca/P maps of bone architecture in 3D synchrotron radiation microtomographic images. Applied Radiation and Isotopes, 62(4), 569-575. doi: 10.1016/j.apradiso.2004.10.003.
[24] Yang, X., Ma, A., Liu, H., Jiang, J., Li, Y., & Sun, J. (2019). Microstructure and corrosion resistance of yellow MAO coatings. Surface Engineering, 35(4), 334-342. doi: 10.1080/02670844.2018.1445939.
[25] Zglobicka, I., Chmielewska, A., Topal, E., Kutukova, K., Gluch, J., Krüger, P., Kilroy, C., Swieszkowski, W., Kurzydlowski, K.J., & Zschech, E. (2019). 3D diatom-designed and selective laser melting (SLM) manufactured metallic structures. Scientific Reports, 9, article number 19777. doi: 10.1038/s41598-019-56434-7.
[26] Zhou, J., Wang, X., & Zhao, L. (2019). Antibacterial, angiogenic, and osteogenic activities of Ca, P, Co, F, and Sr compound doped titania coatings with different Sr content. Scientific Reports, 9, article number 14203. doi: 10.1038/s41598-019-50496-3.