vestiftИзвестия Национальной академии наук Беларуси. Серия физико-технических наукProceedings of the National Academy of Sciences of Belarus. Physical-technical series1561-83582524-244XThe Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8358-2026-71-1-18-30vestift-924Research ArticleМАТЕРИАЛОВЕДЕНИЕ, МЕТАЛЛУРГИЯMATERIALS SCIENCES AND ENGINEERING, METALLURGYВлияние азотирования на структуру и механические свойства углеродных покрытий, легированных цирконием и кремниемInfluence of heat treatment on the structure and mechanical properties of carbon coatings doped with zirconium and siliconhttps://orcid.org/0000-0001-5171-188XРуденковА. С.RudenkovA. S.

Руденков Александр Сергеевич – кандидат технических наук, доцент, заведующий кафедрой радиофизики и электроники 

ул. Советская, 104, 246028, Гомель 

Alexander S. Rudenkov – Cand. Sci. (Engineering), Associate Professor, Head of the De­ partment of Radiophysics and Electronics 

104, Sovetskaya St., 246028, Gomel 

rudenkov@gsu.byhttps://orcid.org/0000-0001-7206-3092РогачевА. В.RogachevA. V.

Рогачев Александр Владимирович – член-корреспондент Национальной академии наук Беларуси, доктор химических наук, профессор, директор Научно-исследовательского физико-химического института 

ул. Советская, 104, 246028, Гомель 

Alexander V. Rogachev – Сorresponding Member of the National Academy of Sciences of Belarus, Dr. Sci. (Chemistry), Professor, Director of the Research Institute of Physics  

104, Sovetskaya St., 246028, Gomel 

rogachevav@mail.ruhttps://orcid.org/0000-0001-5930-4066ПилипцовД. Г.PiliptsouD. G.

Пилипцов Дмитрий Геннадьевич – доктор технических наук, доцент, заместитель декана факультета физики и информационных технологий 

ул. Советская, 104, 246028, Гомель 

Dzmitry G. Piliptsou – Dr. Sci. (Engineering), Deputy Dean of Faculty of Physics and Information Technology

104, Sovetskaya St., 246028, Gomel  

pdg_@mail.ruГомельский государственный университет имени Франциска СкориныFrancisk Scorina Gomel State University2026310320267111830Copyright © Руденков А.С., Рогачев А.В., Пилипцов Д.Г., 20262026Руденков А.С., Рогачев А.В., Пилипцов Д.Г.Rudenkov A.S., Rogachev A.V., Piliptsou D.G.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vestift.belnauka.by/jour/article/view/924

Исследованы структурные особенности и определены механические свойства композиционных угле­ родных покрытий, сформированных из плазменных потоков сложного состава, которые генерируются импульсным электродуговым и электроискровым испарением в присутствии молекулярного азота. Концентрация азота в покры­ тии варьировалась путем изменения значения его парциального давления в остаточной атмосфере вакуумной камеры. Установлено, что азотирование при парциальном давлении азота 0,08 Па углеродных покрытий, легированных цирконием и кремнием, приводит к увеличению дисперсности, уменьшению их шероховатости и размеров отдельных структурных образований. Средствами рентгеновской фотоэлектронной спектроскопии определены особенности процессов химического взаимодействия. Азотирование способствует увеличению степени структурной упорядоченности sp2-кластеров, образованию соединений на основе CNx, нитридов легирующих элементов и росту соотношения sp3/sp2-гибридизированных атомов углерода, что приводит к увеличению нанотвердости композиционных углеродных покрытий до 15,3 ГПа. Показано, что образование твердых фаз на основе карбидов и нитридов легирую­ щих элементов обусловливает увеличение значений коэффициентов трения и объемного изнашивания контртела при азотировании композиционных углеродных покрытий. Установлен химический состав композиционных углеродных покрытий, обеспечивающий оптимальное сочетание их нанотвердости и триботехнических свойств за счет наиболее высокой доли кластеров на основе Csp2–N-связей, трансформирующихся при трении в графит, который выполняет роль твердой смазки. Полученные результаты могут быть использованы при модифицировании поверхности металлообрабатывающего инструмента и деталей специализированной оснастки с целью улучшения их механических характеристик и увеличения срока эксплуатации. 

The structural features and mechanical properties of composite carbon coatings formed from plasma flows of complex composition generated by pulsed electric arc and spark evaporation in the presence of molecular nitrogen were investigated. The nitrogen concentration in the coating was varied by changing its partial pressure in the residual atmosphere of the vacuum chamber. It was found that nitriding of carbon coatings doped with zirconium and silicon at a nitrogen partial pressure of 0.08 Pa leads to an increase in dispersion, a decrease in their roughness and the size of individual structural formations. The features of chemical interaction processes were determined using X-ray photoelectron spectroscopy. Nitriding promotes an increase in the degree of structural ordering of sp2-clusters, the formation of compounds based on CNx, nitrides of alloying elements and an increase in the ratio of sp3/sp2-hybridized carbon atoms, which leads to an increase in the nanohardness of composite carbon coatings to 15.3 GPa. It has been shown that the formation of hard phases based on alloying element carbides and nitrides leads to increased friction coefficients and volumetric wear of the counterface during nitriding of composite carbon coatings. The chemical composition of the composite carbon coatings has been determined, providing an optimal combination of nanohardness and tribological properties due to the highest proportion of clusters based on Csp2–N-bonds, which are transformed during friction into graphite, which acts as a solid lubricant. The obtained results can be used to modify the surface of metalworking tools and specialized equipment parts in order to improve their mechanical characteristics and increase their service life. 

углеродные покрытияазоткремнийцирконийкарбиднитриднанотвердостьмодуль упругостикоэффициент тренияcarbon coatingsnitrogensiliconzirconiumcarbidenitridenanohardnesselastic modulusfriction coefficientработа выполнена при финансовой поддержке Министерства образования Республики Беларусь в рамках Государственной программы научных исследований «Современное материаловедение, перспективные материалы и новые технологии» на 2026–2030 годы, научно-исследовательская работа «Формирование и физикохимические свойства нанокомпозиционных углеродных покрытий, содержащих кластеры тугоплавких металлов и их соединений».ReferencesDonnet, C. Tribology of Diamond-like Carbon Films: Fundamentals and Applications / C. Donnet, A. Erdemir. – Springer Science & Business Media, 2007. – 680 p. https://doi.org/10.1007/978-0-387-49891-1Donnet C., Erdemir A. Tribology of Diamond-like Carbon Films: Fundamentals and Applications. New York, Springer New York, 2007. 680 p. https://doi.org/10.1007/978-0-387-49891-1Рогачев, А. В. Триботехнические свойства композиционных покрытий, осаждаемых вакуумно-плазменными методами / А. В. Рогачев // Трение и износ. – 2008. – Т. 29, № 3. – С. 285–592.Rogachev A. V. Triboengineering properties of composite coating sputtered with vacuum plasma techniques. Journal of Friction and Wear, 2008, vol. 29, iss. 3, pp. 218–223. https://doi.org/10.3103/S1068366608030112Robertson, J. Diamond-like amorphous carbon / J. Robertson // Materials Science and Engineering: R: Reports. – 2002. – Vol. 37, iss. 4–6. – P. 129–281. https://doi.org/10.1016/S0927-796X(02)00005-0Robertson J. Diamond-like amorphous carbon. Materials Science and Engineering: R: Reports, 2002, vol. 37, iss. 4–6, pp. 129–281. https://doi.org/10.1016/S0927-796X(02)00005-0Композиционные углеродные покрытия, осажденные из импульсной катодной плазмы / Д. Г. Пилипцов, А. С. Руденков, П. А. Лучников [и др.]. – М.: Радиотехника, 2020. – 283 с.Pilipcov D. G., Rudenkov A. S., Luchnikov P. A., Rogachev A. V., Syao Hun Czyan, Bin Chzhou. Composite Carbon Coatings Deposited from Pulsed Cathodic Plasma. Moscow, Radiotekhnika Publ., 2020. 283 p. (in Russian).Пилипцов, Д. Г. Влияние термообработки на механические свойства слоистых углеродных покрытий / Д. Г. Пилипцов // Проблемы физики, математики и техники. – 2021. – № 3 (48). – С. 29–37. https://doi.org/10.54341/20778708_2021_4_49_29Piliptsou D. G. Influence of heat treatment on the mechanical properties of layered carbon coatings. Problemy fiziki, matematiki i tekhniki = Problems of Physics, Mathematics and Technics, 2021, no. 4 (49), pp. 29–37 (in Russian). https://doi.org/10.54341/20778708_2021_4_49_29Mabuchi, Y. Effects of sp2/sp3 bonding ratio and nitrogen content on friction properties of hydrogen-free DLC coatings / Y. Mabuchi, T. Higuchi, V. Weihnacht // Tribology International. – 2013. – Vol. 62. – P. 130–140. https://doi.org/10.1016/j.triboint.2013.02.007Mabuchi Y., Higuchi T., Weihnacht V. Effects of sp2/sp3 bonding ratio and nitrogen content on friction properties of hydrogen-free DLC coatings. Tribology International, 2013, vol. 62, pp. 130–140. https://doi.org/10.1016/j.triboint.2013.02.007Wongpanya, P. Nanomechanical properties and thermal stability of Al–N-co-doped DLC films prepared by filtered cathodic vacuum arc deposition / P. Wongpanya, P. Silawong, P. Photongkam // Surface and Coatings Technology. – 2021. – Vol. 424. – Art. ID 127655. https://doi.org/10.1016/j.surfcoat.2021.127655Wongpanya P., Silawong P., Photongkam P. Nanomechanical properties and thermal stability of Al–N-co-doped DLC films prepared by filtered cathodic vacuum arc deposition. Surface and Coatings Technology, 2021, vol. 424, art. ID 127655. https://doi.org/10.1016/j.surfcoat.2021.127655Effects of source gases on the properties of silicon/nitrogen-incorporated diamond-like carbon films prepared by plasmaenhanced chemical vapor deposition / H. Nakazawa, K. Magara, T. Takami [et al.] // Thin Solid Films. – 2017. – Vol. 636. – P. 177–182. https://doi.org/10.1016/j.tsf.2017.05.046Nakazawa H., Magara K., Takami T., Ogasawara H., Enta Y., Suzuki Y. Effects of source gases on the properties of silicon/nitrogen-incorporated diamond-like carbon films prepared by plasma-enhanced chemical vapor deposition. Thin Solid Films, 2017, vol. 636, pp. 177–182. https://doi.org/10.1016/j.tsf.2017.05.046Synergistic effect of Cu/Cr co-doping on the wettability and mechanical properties of diamond-like carbon films / L. Sun, P. Guo, P. Ke [et al.] // Diamond and Related Materials. – 2016. – Vol. 68. – P. 1–9. https://doi.org/10.1016/j.diamond.2016.05.006Sun L., Guo P., Ke P., Li X., Wang A. Synergistic effect of Cu/Cr co-doping on the wettability and mechanical properties of diamond-like carbon films. Diamond and Related Materials, 2016, vol. 68, pp. 1–9. https://doi.org/10.1016/j.diamond.2016.05.006Руденков, А. С. Влияние концентрации металла на фазовый состав, структуру и свойства углерод-металлических покрытий / А. С. Руденков // Проблемы физики, математики и техники. – 2015. – № 3 (24). – С. 26–32.Rudenkov A. S. Influence of metal concentration on the phase composition, structure and properties of carbon-metal coating. Problemy fiziki, matematiki i tekhniki = Problems of Physics, Mathematics and Technics, 2015, no. 3 (24), pp. 26–32 (in Russian).Effects of silicon doping on the chemical bonding states and properties of nitrogen-doped diamond-like carbon films by plasma-enhanced chemical vapor deposition / K. Nakamura, H. Ohashi, Y. Enta [et al.] // Thin Solid Films. – 2021. – Vol. 736. – Art. ID 138923. https://doi.org/10.1016/j.tsf.2021.138923Nakamura K., Ohashi H., Enta Y., Kobayashi Y., Suzuki Y., Suemitsu M., Nakazawa H. Effects of silicon doping on the chemical bonding states and properties of nitrogen-doped diamond-like carbon films by plasma-enhanced chemical vapor deposition. Thin Solid Films, 2021, vol. 736, art. ID 138923. https://doi.org/10.1016/j.tsf.2021.138923Tribological characterization of carbon-nitrogen coatings deposited by using vacuum arc discharge / J. Koskinen, J.-P. Hirvonen, J. Levoska, P. Torri // Diamond and Related Materials. – 1996. – Vol. 5. – P. 669–673. https://doi.org/10.1016/0925-9635(95)00382-7Koskinen J., Hirvonen J.-P., Levoska J., Torri P. Tribological characterization of carbon-nitrogen coatings deposited by using vacuum arc discharge. Diamond and Related Materials, 1996, vol. 5, iss. 6–8, pp. 669–673. https://doi.org/10.1016/0925-9635(95)00382-7Long-term thermal stability of Si-containing diamond prepared by plasma source ion implantation / R. Hatada, K. Baba, S. Flege [et al.] // Surface and Coatings Technology. – 2016. – Vol. 305. – P. 93–98. https://doi.org/10.1016/j.surfcoat.2016.08.011Hatada R., Baba K., Flege S., Ensinger W. Long-term thermal stability of Si-containing diamond prepared by plasma source ion implantation. Surface and Coatings Technology, 2016, vol. 305, pp. 93–98. https://doi.org/10.1016/j.surfcoat. 2016.08.011Effect of nitrogen doping on the microstructure and thermal stability of diamond-like carbon coatings containing silicon and oxygen / J. Peng, Y. Xiao, M. Yang, J. Liao // Surface and Coatings Technology. – 2021. – Vol. 421. – Art. ID 127479. https://doi.org/10.1016/j.surfcoat.2021.127479Peng J., Xiao Y., Yang M., Liao J. Effect of nitrogen doping on the microstructure and thermal stability of diamondlike carbon coatings containing silicon and oxygen. Surface and Coatings Technology, 2021, vol. 421, art. ID 127479. https://doi.org/10.1016/j.surfcoat.2021.127479Mechanical properties of d.c. magnetron-sputtered and pulsed vacuum arc deposited ultra-thin nitrogenated carbon coatings / A. Wienss, M. Neuhäuser, H.-H. Schneider [et al.] // Diamond and Related Materials. – 2001. – Vol. 10, iss. 3–7. – P. 1024–1029. https://doi.org/10.1016/S0925-9635(00)00512-4Wienss A., Neuhäuser M., Schneider H.-H., Persch-Schuy G., Windeln J., Witke T., Hartman U. Mechanical properties of d.c. magnetron-sputtered and pulsed vacuum arc deposited ultra-thin nitrogenated carbon coatings. Diamond and Related Materials, 2001, vol. 10, iss. 3–7, pp. 1024–1029. https://doi.org/10.1016/S0925-9635(00)00512-4Влияние ионного азотирования на фазовый состав, структуру и свойства углеродных покрытий / А. С. Руденков, А. В. Рогачев, Д. Г. Пилипцов [и др.] // Проблемы физики, математики и техники. – 2016. – № 1 (26). – С. 37–42.Rudenkov A. S., Rogachev A. V., Piliptsov D. G., Fedosenko N. N., Xiaohong Jiang. Influence of ion nitriding on the phase composition, structure and properties of carbon coatings. Problemy fiziki, matematiki i tekhniki = Problems of Physics, Mathematics and Technics, 2016, no. 1 (26), pp. 37–42 (in Russian).Evolution of Phase Composition and Antibacterial Activity of Zr–C Thin Films / K. Mydlowska, E. Czerwińska, A. Gilewicz [et al.] // Processes. – 2020. – Vol. 8. – Art. ID 260. https://doi.org/10.3390/pr8030260Mydlowska K., Czerwińska E., Gilewicz A., Dobruchowska E., Jakubczyk E., Szparaga L., Ceynowa P., Ratajski J. Evolution of Phase Composition and Antibacterial Activity of Zr–C Thin Films. Processes, 2020, vol. 8, art. ID 260. https://doi.org/10.3390/pr8030260Ray, S. C. Iron, nitrogen and silicon doped diamond like carbon (DLC) thin films: A comparative study / S. C. Ray, W. F. Pong, P. Papakonstantinou // Thin Solid Films. – 2016. – Vol. 610. – P. 42–47. https://doi.org/10.1016/j.tsf.2016.04.048Ray S. C., Pong W. F., Papakonstantinou P. Iron, nitrogen and silicon doped diamond like carbon (DLC) thin films: A comparative study. Thin Solid Films, 2016, vol. 610, pp. 42–47. https://doi.org/10.1016/j.tsf.2016.04.048Paik, N. Raman and XPS studies of DLC films prepared by a magnetron sputter-type negative ion source / N. Paik // Surface and Coatings Technology. – 2005. – Vol. 200, iss. 7. – P. 2170–2174. https://doi.org/10.1016/j.surfcoat.2004.08.073Paik N. Raman and XPS studies of DLC films prepared by a magnetron sputter-type negative ion source. Surface and Coatings Technology, 2005, vol. 200, iss. 7, pp. 2170–2174. https://doi.org/10.1016/j.surfcoat.2004.08.073Trusso, S. CNx thin films grown by pulsed laser deposition: Raman, infrared and X-ray photoelectron spectroscopy study / S. Trusso, C. Vasi, F. Neri // Thin Solid Films. – 1999. – Vol. 355–356. – P. 219–222. https://doi.org/10.1016/S0040-6090(99)00503-9Trusso S., Vasi C., Neri F. CNx thin films grown by pulsed laser deposition: Raman, infrared and X-ray photoelectron spectroscopy study. Thin Solid Films, 1999, vol. 355–356, pp. 219–222. https://doi.org/10.1016/S0040-6090(99)00503-9Mirenghi, L. An Accurate Quantitative X-ray Photoelectron Spectroscopy Study of Pure and Homogeneous ZrN Thin Films Deposited Using BPDMS / L. Mirenghi, A. Rizzo // Applied Sciences. – 2023. – Vol. 13. – Art. ID 1271. https://doi.org/10.3390/app13031271Mirenghi L., Rizzo A. An Accurate Quantitative X-ray Photoelectron Spectroscopy Study of Pure and Homogeneous ZrN Thin Films Deposited Using BPDMS. Applied Sciences, 2023, vol. 13, art. ID 1271. https://doi.org/10.3390/app13031271Biomineralization of osteoblasts on DLC coated surfaces for bone implants / B. Subramanian, S. Thanka Rajan, P. J. Martin [et al.] // Biointerphases. – 2018. – Vol. 13, iss. 4. – Art. ID 041002. https://doi.org/10.1116/1.5007805Subramanian B., Thanka Rajan S., Martin P. J., Vaithilingam V., Bean P. A., Evans M. D. M., Bendavid A. Biomineralization of osteoblasts on DLC coated surfaces for bone implants. Biointerphases, 2018, vol. 13, iss. 4, art. ID 041002. https://doi.org/10.1116/1.5007805Using photoelectron spectroscopy to observe oxygen spillover to zirconia / P. Lackner, Z. Zou, S. Mayr [et al.] // Physical Chemistry Chemical Physics. – 2019. – Vol. 32. – P. 17613–17620. https://doi.org/10.1039/C9CP03322JLackner P., Zou Z., Mayr S., Diebold U., Schmid M. Using photoelectron spectroscopy to observe oxygen spillover to zirconia. Physical Chemistry Chemical Physics, 2019, vol. 32, pp. 17613–17620. https://doi.org/10.1039/C9CP03322JWong, P. C. XPS studies of the stability of a zirconium carbide film in the presence of zirconium oxide and hydrogen / P. C. Wong, Y. S. Li, K. A. R. Mitchell // Surface Review and Letters. – 1995. – Vol. 2, № 3. – P. 297–303. https://doi.org/10.1142/S0218625X95000315Wong P. C., Li Y. S., Mitchell K. A. R. XPS studies of the stability of a zirconium carbide film in the presence of zirconium oxide and hydrogen. Surface Review and Letters, 1995, vol. 2, no. 3, pp. 297–303. https://doi.org/10.1142/S0218625X95000315Prieto, P. Interaction of Oxygen with ZrN at Room Temperature: an XPS Study / P. Prieto, L. Galan, J. M. Sanz // Surface and Interface Analysis. – 1994. – Vol. 21. – P. 395–399. https://doi.org/10.1002/sia.740210612Prieto P., Galan L., Sanz J.M. Interaction of Oxygen with ZrN at Room Temperature: an XPS Study. Surface and Interface Analysis, 1994, vol. 21, pp. 395–399. https://doi.org/10.1002/sia.740210612Muneshwar, T. Comparing XPS on bare and capped ZrN films grown by plasma enhanced ALD: Effect of ambient oxidation / T. Muneshwar, K. Cadien // Applied Surface Science. – 2018. – Vol. 435. – P. 367–376. https://doi.org/10.1016/j.apsusc.2017.11.104Muneshwar T., Cadien K. Comparing XPS on bare and capped ZrN films grown by plasma enhanced ALD: Effect of ambient oxidation. Applied Surface Science, 2018, vol. 435, pp. 367–376. https://doi.org/10.1016/j.apsusc.2017.11.104Cubillos, G. ZrN-ZrOxNy vs ZrO2-ZrOxNy coatings deposited via unbalanced DC magnetron sputtering / G. Cubillos, E. Romero, A. Umaña-Perez // Scientific Reports. – 2021. – Vol. 11. – Art. ID 18926. https://doi.org/10.1038/s41598-021-98052-2Cubillos G., Romero E., Umaña-Perez A. ZrN-ZrOxNy vs ZrO2-ZrOxNy coatings deposited via unbalanced DC magnetron sputtering. Scientific Reports, 2021, vol. 11, art. ID 18926. https://doi.org/10.1038/s41598-021-98052-2X ray photoelectron spectroscopy (XPS) analysis of Photosensitive ZrO2 array / Y. Li, G. Zhao, R. Zhu [et al.] // IOP Conference Series: Materials Science and Engineering. – 2018. – Vol. 322. – Art. ID 022043. https://doi.org/10.1088/1757-899X/322/2/022043Li Y., Zhao G., Zhu R., Kou Z. X ray photoelectron spectroscopy (XPS) analysis of Photosensitive ZrO2 array. IOP Conference Series: Materials Science and Engineering, 2018, vol. 322, art. ID 022043. https://doi.org/10.1088/1757-899X/322/2/022043Modulation of Si on microstructure and tribo-mechanical properties of hydrogen-free DLC films prepared by magnetron sputtering / C.-Q. Guo, S. Sh. Lin, D. Gao [et al.] // Applied Surface Science. – 2020. – Vol. 509. – Art. ID 145381. https://doi.org/10.1016/j.apsusc.2020.145381Guo C.-Q., Lin S. Sh., Gao D., Shi Q., Wei Ch.-B., Dai M.-J., Su Y. F. [et al.]. Modulation of Si on microstructure and tribo-mechanical properties of hydrogen-free DLC films prepared by magnetron sputtering. Applied Surface Science, 2020, vol. 509, art. ID 145381. https://doi.org/10.1016/j.apsusc.2020.145381A concise review of the Raman spectra of carbon allotropes / V. Thapliyal, M. E. Alabdulkarim, D. R. Whelan [et al.] // Diamond and Related Materials. – 2022. – Vol. 127. – Art. ID 109180. https://doi.org/10.1016/j.diamond.2022.109180Thapliyal V., Alabdulkarim M. E., Whelan D. R. A concise review of the Raman spectra of carbon allotropes. Diamond and Related Materials, 2022, vol. 127, art. ID 109180. https://doi.org/10.1016/j.diamond.2022.109180Structure and properties of Si incorporated tetrahedral amorphous carbon films prepared by hybrid filtered vacuum arc process / C. S. Lee, K.-R. Lee, K. E. Eun [et al.] // Diamond and Related Materials. – 2002. – Vol. 11, iss. 2. – P. 198–203. https://doi.org/10.1016/S0925-9635(01)00666-5Lee C. S., Lee K.-R., Eun K. E., Yoon K. H., Han J. H. Structure and properties of Si incorporated tetrahedral amorphous carbon films prepared by hybrid filtered vacuum arc process. Diamond and Related Materials, 2002, vol. 11, iss. 2, pp. 198–203. https://doi.org/10.1016/S0925-9635(01)00666-5

The authors declare that there are no conflicts of interest present.