Tkachuk O. Scientific bases for increasing functional properties of surface layers of titanium alloys for medical applications
Українська версіяThesis for the degree of Doctor of Science (DSc)
State registration number
0526U000064
Applicant for
Specialization
- 05.02.01 - Матеріалознавство
15-04-2026
Specialized Academic Board
Д. 35.226.02
Physico-Mechanical Institute named after GV Karpenko of the National Academy of Sciences of Ukraine
Essay
The dissertation presents a solution of an important scientific and technical problem – increasing the complex of biocompatibility, wear- and anti-corrosion characteristics of titanium alloys for medical applications using surface engineering by forming the appropriate phase-structural state of nitride and oxynitride layers by diffusion saturation from a controlled gas environment and hydroxyapatite coatings of regulated parameters by plasma electrolytic oxidation. The general regularities of the formation of the phase-structural state of the modified layers on the titanium alloys for medical applications by the diffusion saturation from a controlled nitrogen-containing gas environment, and its effect on the wear and corrosion resistance in physiological solutions were established. It was determined that the wear resistance of nitrided BT6 titanium alloy in a tribo-pair with UHMWPE in a 10% aqueous solution of chondroitin sulfate is better when a nitride layer based on the Ti2N phase with lower roughness and surface microhardness is formed on the surface, the formation of which is provided by the saturation in the range of low temperatures and long exposures in a rarefied nitrogen. It was shown that the corrosion resistance of nitrided BT6 titanium alloy in physiological solutions that simulate the physiological environment of a human body is better when a nitride layer based on titanium mononitride TiNx is formed on the surface, the formation of which is ensured by the saturation in the range of high temperatures and short exposures at atmospheric pressure of the nitrogen. The stage nitriding regime for commercially pure titanium BT1-0 was developed. It provides high leveling of tribological and anti-corrosion characteristics of the surface in physiological solutions. Testing by using the T-24 simulator of the biomechanical human motion showed that the wear intensity of the UHMWPE cup in a tribo-pair with a nitrided titanium head is 3 times lower than that of a tribo-pair with CoCrMo. It was established that the surface nitrided by developed saturation method improves the cytocompatibility of titanium, which allows to conduct studies in vivo. The scientific approaches to the formation of oxynitride layers on titanium alloys from a controlled nitrogen-oxygen-containing gas environment, both in a rarefied (0.001…0.1 Pa) nitrogen-oxygen-containing gas environment (an air) and saturation in rarefied nitrogen with the addition of 20 and 30 vol.% of oxygen (nitrogen-oxygen-containing gas mixture) were developed. The temperature range (500...750 °C) for the formation of oxynitride layers was established. It was determined that with a decrease of the oxygen content in the nitrogen-oxygen gas mixture from 30 to 20 vol.%, the corrosion resistance of oxynitrided titanium is increased regardless of the oxynitriding temperature. It was established that by influencing the ratio of nitrogen and oxygen in titanium oxynitride, it is possible to form both oxynitrides of equiatomic composition and those enriched with nitrogen or oxygen, while changing the surface colour from violet, gray-violet to golden or green, blue, aquamarine, which has the prospect of use for implants and medical instruments, parts of which are given colour to simplify the selection of required shape and size. It was determined that when modifying non-stoichiometric titanium nitride with oxygen, nitrogen atoms are replaced by oxygen atoms with the formation of titanium oxynitride TiNxO1-x on the surface, in which the nitrogen content is decreased, up to the formation of titanium oxide TiO2. It was determined that by increasing the oxygen content in titanium oxynitride and the appearance of the TiO2 oxide phase, the corrosion resistance of the BT6 titanium alloy in a physiological environment is improved due to an increase of the proportion of the ionic bonding in the coating compounds. It was established that an increase of the oxygen content in the oxynitride leads to an increase of the cytocompatibility of the BT6 titanium alloy, and the oxynitride layers of composition TiN0.42O0.58 and TiN0.36O0.64 can be recommended for further testing of their biological action in vivo. The optimal composition of the electrolyte of (1М КОН + hydroxyapatite) for the formation of HA coating on the titanium alloys for medical applications by the PEO method was determined, which allows to form a porous HA coating with a spheroidal structure and an optimal Ca/P ratio at a voltage of 160 V in a pulsed regime. The regularities of formation of HA coatings on preformed nitride layers of Ti2N and TiNx were established. It was shown that the corrosion resistance of the Ti2N+HA coating in Ringer's solution is higher compared to TiNx+HA. It was established that the value of Young's modulus for the HA coating deposited on the Ti2N nitride layer is close to the corresponding value for a cortical bone.
Research papers
1. Погрелюк І.М., Ткачук О.В. Хіміко-термічна обробка титанових сплавів. Оксинітрування. Л.: Простір-М, 2021. с. 204.
2. Sheykin S.Ye., Pohrelyuk I.M., Tkachuk O.V. The use of c.p. titanium in medical friction pairs (Chapter 6). In book Biotribology: Emerging Technologies and Applications, editors Rao T.V.V.L.N., Kasolang S.B., Guoxin X., Kumar Katiyar J., Abdul Rani A.M. CRC Press. Boca Raton. United States of America. 2021. P. 147–177.
3. Tkachuk O.V., Sheykin S.E., Lavrys S.M., Rostotskii I.Yu., Danyliak M.-O.M., Pohrelyuk I.M., Proskurnyak R.V. Effect of stage gas nitriding on corrosion and wear resistance of Ti6Al4V alloy in physiological environment. Vacuum. 2024. Vol. 230. Article number 113713.
4. Proskurnyak R.V, Tkachuk O.V., Pohrelyuk I.M, Padgurskas J., Kuznietsov O.V, Gnilitskyi I.M. Characterization of hydroxyapatite coatings deposited on gas nitrided Ti-6Al-4V alloy. Materials Today Communications. 2025. Vol. 46. Article number 112771.
5. Pohrelyuk I., Morgiel J., Tkachuk O., Szymkiewicz K. Effect of temperature on gas oxynitriding of Ti-6Al-4V alloy. Surface & Coatings Technology. 2019. Vol. 360. P. 103–109.
6. Pohrelyuk I.M., Fedirko V.M., Tkachuk O.V., Proskurnyak R.V. Corrosion resistance of Ti-6Al-4V alloy with nitride coatings in Ringer's solution. Corrosion Science. 2013. Vol. 66. P. 392–398.
7. Pohrelyuk I.M., Tkachuk O.V., Proskurnyak R.V., Boiko N.M., Kluchivska O.Yu., Stoika R.S. Effect of thermodiffusion nitriding on cytocompatibility of Ti-6Al-4V titanium alloy. JOM. 2016. Vol. 68. P. 1109–1115.
8. Pohrelyuk I.M., Tkachuk O.V., Proskurnyak R.V. Corrosion resistance of the Ti-6Al-4V titanium alloy with nitride coatings in 0.9 % NaCl. JOM. 2011. Vol. 63. P. 35–40.
9. Tkachuk O.V., Pohrelyuk I.M., Proskurnyak R.V., Danyliak M.-O.M., Vynar V.A. Influence of concentration of potassium hydroxide in electrolyte on formation of hydroxyapatite coatings on titanium. JOM. 2023. Vol. 75. P. 5088–5095.
10. Tkachuk O.V., Pohrelyuk I.M., Proskurnyak R.V., Morgiel J., Faryna M., Goral A. Morphology and corrosion resistance of hydroxyapatite coatings formed on commercially pure titanium. Journal of Materials Engineering and Performance. 2023. Vol. 32. P. 11040–11049.
11. Lavrys S., Pohrelyuk I., Tkachuk O., Padgurskas J., Trush V., Proskurnyak R. Comparison of friction behaviour of titanium Grade 2 after non-contact boriding in oxygen-containing medium with gas nitriding. Coatings. 2023. Vol. 13. Article number 282.
12. Pohrelyuk I.M., Tkachuk O.V., Proskurnyak R.V., Boiko N.M., Kluchivska O.Yu., Stoika R.S., Ozga P. Cytocompatibility evaluation of Ti-6Al-4V alloy after gas oxynitriding. Journal of Materials Engineering and Performance. 2020. Vol. 29. P. 7785–7792.
13. Pohrelyuk I., Tkachuk O., Proskurnyak R., Guspiel J., Beltowska-Lehman E., Morgiel J. Influence of regulated modification of nitride layer by oxygen on the electrochemical behavior of Ti-6Al-4V alloy in the Ringer's solution. Materials and Corrosion. 2019. Vol. 70. P. 2320–2325.
14. Pohrelyuk I.M., Sheykin S.E., Dub S.M., Mamalis A.G., Rostotskii I.Yu., Tkachuk O.V., Lavrys S.M. Increasing of functionality of c.p. titanium/UHMWPE tribo-pairs by thermodiffusion nitriding of titanium component. Biotribology. 2016. Vol. 7. P. 38–45.
15. Pohrelyuk I., Tkachuk O., Proskurnyak R. Effect of oxidation of nitride coatings on corrosion properties of Ti-6Al-4V alloy in 0.9% NaCl at 40°С. Central European Journal of Chemistry. 2014. Vol. 12. P. 260–265.
16. Tkachuk O.V., Proskurnyak R.V., Holovchuk M.Ya. Morphology of hydroxyapatite coatings formed on VT1-0 titanium as a result of combined treatment. Materials Science. 2022. Vol. 58. P. 75–79.
17. Tkachuk O.V., Pohrelyuk I.M., Proskurnyak R.V., Guspiel J., Beltowska-Lehman E., Morgiel J. Electrochemical behavior of Ti-6Al-4V alloy in Ringer's solution after oxynitriding. Materials Science. 2019. Vol. 54. P. 542–546.
18. Ткаchuk O.V., Proskurnyak R.V., Pohrelyuk I.M. Analysis of the surface and corrosion resistance of nitrided and oxynitrided VT6C alloys in a physiological solution at 36 and 40°C. Materials Science. 2015. Vol. 50. P. 882–888.
19. Tkachuk O., Proskurnyak R., Pohrelyuk I., Fedirko V. Corrosion behaviour of thermodiffusion coatings on titanium implants in simulated body fluids. Solid State Phenomena. 2015. Vol. 227. P. 503–506.
20. Tkachuk O., Pohrelyuk I., Proskurnyak R. Surface modification of titanium implants. Key Engineering Materials. 2019. Vol. 813. P. 215–220.
21. Proskurnyak R.V., Tkachuk O.V., Student M.M., Padgurskas J. Structure and mechanical properties of hydroxyapatite coating deposited on nitrogen-modified titanium surface. Materials Science. 2025. Vol. 60. P. 634–639.
22. Pohrelyuk I.M., Tkachuk O.V., Proskurnyak, R.V., Kuznetsov O.V, Gnilitskyi Ya.M. Morphology and corrosion properties of hydroxyapatite coating on VT6 titanium alloy. Materials Science. 2023. Vol. 58. P. 781–787.
23. Pohrelyuk І.М., Proskurnyak R.V., Ткаchuk O.V., Obukh Yu.V. Formation of hydroxyapatite coatings on titanium by plasma-electrolytic oxidation in alkaline electrolytes. Materials Science. 2020. Vol. 55. P. 563–568.
24. Pohrelyuk І.М., Proskurnyak R.V., Ткаchuk O.V., Goral A. Influence of the parameters of plasma-electrolytic oxidation on the formation of calcium-phosphate coatings on titanium. Materials Science. 2019. Vol. 54. P. 789–795.
25. Pohrelyuk І.М., Fedirko V.M., Ткаchuk O.V., Proskurnyak R.V., Korol'ova T.V. Corrosion behavior of VT6S titanium alloy in a physiological solution after chemicothermal treatment. Materials Science. 2018. Vol. 53. P. 796–804.
26. Fedirko V.M., Pohrelyuk І.М., Ткаchuk O.V., Proskurnyak R.V. Corrosion behavior of VT6S titanium alloy with oxidized nitride layers in 0.9% NaCl at 36°С. Materials Science. 2013. Vol. 48. P. 769–775.
27. Pohrelyuk I.M., Tkachuk O.V., Proskurnyak R.V. Corrosion behaviour of Ti-6Al-4V alloy with nitride coatings in simulated body fluids at 36°С and 40°С. ISRN Corrosion. 2013. Vol. 2013. Article number 241830.
28. Pohrelyuk I., Fedirko V., Tkachuk O., Proskurnyak R. Corrosion resistance of Ti-6Al-4V alloy with oxidized nitride coatings in Ringer's solution. Inżynieria Powierzchni. 2015. Nr 1. P. 38–46.
29. Tkachuk O. Corrosion properties of Ti-6Al-4V alloy with nitride and oxynitride coatings in physiological solutions. Machines, Technologies, Materials. 2015. Iss. 1. P. 29–31.
30. Ткачук О.В., Погрелюк І.М., Проскурняк Р.В. Вплив температури на термодифузійне насичення титану в азоткисневмісному середовищі. Наукові нотатки. 2011. Вип. 31. С. 380–383.
31. Погрелюк І.М., Ткачук О.В., Проскурняк Р.В. Вплив температури фізіологічного розчину на корозійну стійкість титанових імплантатів з покриттями. Літопис травматології та ортопедії. 2014. № 1–2. С. 66–68.
32. Tkachuk O. Surface engineering of titanium alloys in controlled gas environments for aviation and medicine. 2017 Qingdao International Technology Transfer Conference & Aoshan Eurasian Science and Technology Forum: project book, Qingdao, China, 27 November – 01 December 2017. # 2017QD-Ukraine-050
33. Tkachuk O. Corrosion properties of Ti-6Al-4V alloy with nitride and oxynitride coatings in physiological solutions. Technical Science and Industrial Management: proceedings of VIII International Science Conference for Young Researchers. Varna, Bulgaria, 15–16.09.2014. P. 6–8.
34. Tkachuk O., Proskurnyak R., Pohrelyuk I., Fedirko V. Corrosion behaviour of thermodiffusion coatings on titanium implants in simulated body fluids. Corrosion 2014: book of abstracts of International Scientific Conference, Gliwice, Poland, 18–21 November 2014. P. 89.
35. Tkachuk O., Proskurnyak R. Formation of hydroxyapatite coatings on previous nitrided titanium surface. Materials Science and Surface Engineering: proceedings of International Young Scientists Conference, Lviv, Ukraine, 22–24 September 2021. Materials Science and Surface Engineering (MSSE2021), Lviv, 2021. P. 30–33.
36. Tkachuk O., Proskurnyak R. Deposition of calcium phosphate coating on titanium depends on electrolyte composition. Materials Science and Surface Engineering: proceedings of International Young Scientists Conference, Lviv, Ukraine, 27–29 September 2023. Materials Science and Surface Engineering (MSSE2023), Lviv, 2023. P. 76–79.
37. Tkachuk O., Proskurnyak R. Regularities of oxynitride layer formation on VT6s titanium alloy. Welding and Related Technologies: proceedings of 9th International Conference of Young Scientists, Kyiv, Ukraine, 23–26 May 2017. PWI NASU, 2017. P. 194–197.
38. Tkachuk O., Proskurnyak R. Influence of initial surface topography of titanium on formation of hydroxyapatite coatings. Materials Science and Surface Engineering MSSE2019: abstracts of Young Scientists Conference, Lviv, Ukraine, 25–27 September 2019. Problems of Materials Science and Surface Engineering, Lviv, 2019. P. 116–119.
39. Погрелюк І.М., Ткачук О.В., Проскурняк Р.В. Вплив температури фізіологічного розчину на корозійну стійкість титанових імплантатів з покриттями. Проблеми біомеханіки та медичного матеріалознавства: міжнародна науково-практична конференція, м. Київ, 21–22 листопада 2013 р. Літопис травматології та ортопедії. 2014. № 1–2. С. 204.
40. Труш В.С., Ткачук О.В., Проскурняк Р.В. Корозійна стійкість у фізіологічних розчинах азотованого титанового сплаву медичного призначення. КМН-2015: матеріали XXIV Відкритої науково-технічної конференції молодих науковців і спеціалістів, м. Львів, 20–22 жовтня 2015 р. Фізико-механічний інститут ім. Г.В. Карпенка НАН України, 2015 р. С. 119–122.
41. Федірко В.М., Погрелюк І.М., Ткачук О.В., Проскурняк Р.В., Труш В.С. Корозійна поведінка титанового сплаву ВТ6с з нітридними покриттями у фізіологічних розчинах. Проблеми корозії та протикорозійного захисту матеріалів: спецвипуск журналу Фізико-хімічна механіка матеріалів. № 9. Львів: Фізико-механічний інститут ім. Г.В. Карпенка НАН України, 2012. Т. 2. С. 475–479.
42. Труш В., Ткачук О., Проскурняк Р., Погрелюк І. Вплив модифікованого поверхневого шару на корозійні властивості титанового сплаву ВТ6 у фізіологічному розчині. Проблеми корозії та протикорозійного захисту матеріалів: спецвипуск журналу “Фізико-хімічна механіка матеріалів”. № 11. Львів: Фізико-механічний інститут ім. Г.В. Карпенка НАН України, 2016. С. 193–197.
43. Ткачук О., Проскурняк Р. Вплив температури окиснення нітриду титану на корозійну тривкість сплаву Ti64 у 0,9% розчині хлориду натрію. Проблеми корозії та протикорозійного захисту матеріалів: спецвипуск журналу Фізико-хімічна механіка матеріалів. № 13. Львів: Фізико-механічний інститут ім. Г.В. Карпенка НАН України, 2020. С. 56–59.
44. Проскурняк Р.В., Ткачук О.В. Корозійна стійкість титанового сплаву ВТ6с з термодифузійними покриттями у 0,9% NaCl. КМН–2017: XXV відкрита науково-технічна конференція молодих науковців і спеціалістів Фізико-механічного інституту ім. Г.В. Карпенка НАН України, м. Львів, 27–29 вересня 2017 року. Проблеми корозійно-механічного руйнування, інженерія поверхні, діагностичні системи, Львів, 2017. С. 76–79.
45. Проскурняк Р., Ткачук О. Кальцій-фосфатні покриття на титані. Сучасні технології в механіці: збірник наукових праць наукової конференції, м. Хмельницький, 19–21 квітня 2018 р. Хмельницький: ФОП Мельник А.А., 2018. С. 106–107.
46. Pohrelyuk I.M., Tkachuk O.V., Proskurnyak R.V. Formation of hydroxyapatite coatings on dental titanium implants. HighMathTech 2019: book of abstracts of 6th International Conference, Kyiv, Ukraine, October 28–30, 2019. P. 167.
47. Pohrelyuk I., Tkachuk O., Proskurnyak R. Effect of temperature of nitride oxidation on corrosion resistance of Ti64 alloy in 0,9% sodium chloride solution. Problems of Corrosion and Corrosion Protection of Materials (Corrosion-2020): abstract book of XV International Conference, Lviv, Ukraine, October 15–16, 2020. Karpenko Physico-Mechanical Institute of NAS of Ukraine. Lviv, 2020. P. 20.
48. Проскурняк Р.В., Ткачук О.В. Вплив напруги осадження на формування кальцій-фосфатних покриттів на титані. Надтверді, композиційні матеріали та покриття: отримання, властивості, застосування: тези доповідей Дванадцятої конференції молодих вчених та спеціалістів, м. Київ, 19–20 жовтня 2023 р. Київ: ІНМ ім. В.М. Бакуля НАН України, 2023. С. 77.
49. Федірко В.М., Погрелюк І.М., Ткачук О.В. Спосіб хіміко-термічної обробки титанових сплавів. Патент на корисну модель № 65352 Україна. Заявл. 17.02.2011 р. Публ. 12.12.2011 р. Бюл. № 23. с. 4.
50. Погрелюк І.М., Ткачук О.В., Лаврись С.М. Спосіб поверхневого модифікування титанових сплавів. Патент на корисну модель № 159948 Україна. Заявл. 29.10.2024 р. Публ. 24.07.2025 р. Бюл. № 30/25. с. 4.
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