Plazma Nitrürlenmiş X153CrMoV12 Soğuk İş Takım Çeliği Üzerine Tetrahedral Amorf Karbon (ta-C) Kaplamalarının Tribolojik Performansı

Abstract

Elmas benzeri karbon (DLC) kaplamalar, tetrahedral amorf karbon (ta-C) gibi, zorlu endüstriyel ortamlardaki tribolojik uygulamalar için uygun, sert ve düşük sürtünmeli karbon filmler sağlamaktadır. Bu çalışmada, PVD ark teknolojisiyle (Ionbond Tetrabond) biriktirilmiş elmas benzeri karbon (ta-C), kalitesi ve X153CrMoV12 takım çeliklerine uygulanabilirliği araştırılmıştır. Plazma nitrürleme (535°C, 9 saat), DLC kaplama ve dupleks plazma nitrürleme ile DLC kaplama olmak üzere üç farklı yüzey işlemi uygulanmıştır. Bu işlemlerin kimyasal ve fiziksel özellikleri Raman, XPS, SEM ve XRD gibi karakterizasyon teknikleri kullanılarak karşılaştırılmıştır. XPS analizi, yalnızca DLC kaplama için yaklaşık %60, dupleks nitrürleme + DLC kaplama için %62 oranında sp3 fraksiyon değerlerini ortaya koymuş; bu sonuçlar yüksek kaliteli ta-C filmlerini doğrulamaktadır. Aşınma testleri, 10 N ve 20 N yükler altında, 0,04 m/s hız ve 100 m mesafede gerçekleştirilmiştir. Düşük kaplama kalınlığı (~400 nm), yük taşıma kapasitesini sınırlamış; erken aşınmaya ve alt tabakanın açığa çıkmasına yol açmış, aynı zamanda sürekli yükler altında artan sürtünmeye neden olmuştur. Kaplanmamış numunelerle karşılaştırıldığında, ta-C kaplamanın nitrürlü bir alt tabaka üzerine biriktirildiğinde delaminasyona karşı gelişmiş yapışma direnci sergilediği görülmektedir. Dupleks nitrürleme ve DLC kaplama konfigürasyonu, kaplanmamış referans numuneye kıyasla aşınma izi genişliğinde %78'e varan en belirgin azalmayı sağlamış ve endüstriyel soğuk şekillendirme uygulamaları için en uygun yüzey işleme stratejisi olarak öne çıkmıştır. Dupleks işlem uygulanmış numunenin sürtünme katsayısı (CoF), test boyunca en düşük değerde kalmış; bu durum söz konusu numunenin üstün tribolojik performansını doğrulamaktadır. Bu araştırma, takım çeliklerinde ve elmas benzeri karbon kaplama teknolojisindeki ilerlemelere zemin hazırlamaktadır.

Keywords

• Elmas benzeri karbon
• Tetrahedral amorf karbon
• Soğuk iş takım çelikleri
• Aşınma
• plazma nitrürleme
• Yüzey karakterizasyonu

Project Number

KUBAP-01/2021-23

Tribological Performance of Tetrahedral Amorphous Carbon (ta-C) Coatings on Plasma-Nitrided X153CrMoV12 Cold Work Tool Steel

Abstract

Diamond-like carbon (DLC) coatings, specifically tetrahedral amorphous carbon (ta-C), provide hard, low-friction carbon films suitable for tribological applications in demanding industrial environments. In this study, we investigated diamond-like carbon (ta-C) deposited by PVD arc technology (Ionbond Tetrabond), its quality, and applicability on tool steels, X153CrMoV12. Three different surface treatments were applied: plasma nitriding (535 °C, 9 h), DLC coating, and duplex plasma nitriding combined with DLC coating. The DLCs were characterized using characterization techniques, such as Raman, XPS, SEM, and XRD. XPS analysis reveals sp3 fractions of approximately 60% (DLC-only coating) and 62% (duplex nitrided + DLC coating) which confirm the high quality of the deposited ta-C films. Wear tests were conducted under loads of 10 N and 20 N, with a speed of 0.04 m/s and a distance of 100 m. Low coating thickness (~400 nm) limited load-carrying capacity, leading to premature wear and substrate exposure, as well as increased friction under continuous loads. Compared to non-coated samples, ta-C coating exhibits improved adhesion resistance to delamination if deposited on a nitrided substrate. The duplex nitrided and DLC-coated configuration achieved the most significant reduction in wear track width of up to 78% compared to the uncoated baseline, establishing it as the optimal surface treatment strategy for industrial cold-forming applications. The coefficient of friction (CoF) for the duplex-treated sample remained the lowest throughout testing, confirming its superior tribological performance. This research paves the way to improvements in tool steels and coating technology of diamond-like carbon.

Keywords

• Diamond-like carbon
• Tetrahedral amorphous carbon
• Cold work tool steels
• Wear
• Plasma nitriding
• Surface characterization

Project Number

KUBAP-01/2021-23

References

1. S. Jie, H. Tian, J. Li, P. Zhang, Z. Hong, S. An, Study on the working performance of CrAlCN coated and uncoated carbide twist drill, Optik (Stuttg). 270 (2022) 169948. https://doi.org/10.1016/j.ijleo.2022.169948.
2. P.A. Primeaux, B. Zhang, W.J. Meng, Performance of micro-drilling of hard Ni alloys using coated and uncoated WC/Co bits, Engineering Research Express 1 (2019) 0–18. https://doi.org/10.1088/2631-8695/ab383e.
3. N. Mokas, S. Bouadila, A. Amirat, Contradictory effects of machining conditions on wear in the main cutting zones of the twist drill, Journal of the Brazilian Society of Mechanical Sciences and Engineering 45 (2023) 1–15. https://doi.org/10.1007/s40430-023-04459-5.
4. R. Zhang, Z. Liang, L. Yi, J. Hu, Y. Du, L. Guo, Y. Ma, R. Cai, Q. Zhao, L. Xiong, Research on the design and cutting performance of a novel BTA boring tool intended for machining of nickel-based superalloys, Journal of Materials Research and Technology 36 (2025) 7980–7995. https://doi.org/10.1016/j.jmrt.2025.05.022.
5. J.E. Field, Natural Diamond: The Standard, in: 1991: pp. 17–35. https://doi.org/10.1007/978-1-4684-5967-8_2.
6. P.K. Bachmann, R. Messier, Emerging Technology of Diamond Thin Films, Chemical & Engineering News Archive 67 (1989) 24–38. https://doi.org/10.1021/cen-v067n020.p024.
7. M. Amaral, D.J. Carreira, A.J.S. Fernandes, C.S. Abreu, F.J. Oliveira, J.R. Gomes, R.F. Silva, A DLC/diamond bilayer approach for reducing the initial friction towards a high bearing capacity, Wear 290–291 (2012) 18–24. https://doi.org/10.1016/j.wear.2012.05.026.
8. X. Meng, K. Zhang, X. Guo, C. Wang, L. Sun, Preparation of micro-textures on cemented carbide substrate surface by plasma-assisted laser machining to enhance the PVD tool coatings adhesion, J. Mater. Process. Technol. 288 (2021) 116870. https://doi.org/10.1016/j.jmatprotec.2020.116870.

9. T. Katoh, T. Aizawa, T. Yamaguchi, Plasma assisted nitriding for micro-texturing onto martensitic stainless steels ∗, Manuf. Rev. (Les. Ulis). 2 (2015). https://doi.org/10.1051/mfreview/2015004.
10. V. Kundrát, X. Zhang, K. Cooke, H. Sun, J. Sullivan, H. Ye, A novel Mo-W interlayer approach for CVD diamond deposition on steel, AIP Adv. 5 (2015). https://doi.org/10.1063/1.4918969.
11. A.M. Grishin, V. V Putrolaynen, Hard and Highly Adhesive AlMgB14 Coatings RF Sputtered on Tungsten Carbide and High-Speed Steel, Materials 16 (2023) 6930. https://doi.org/10.3390/ma16216930.
12. T. Hao, J. Du, G. Su, P. Zhang, Y. Sun, J. Zhang, Mechanical and cutting performance of cemented carbide tools with Cr/x/DLC composite coatings, International Journal of Advanced Manufacturing Technology 106 (2020) 5241–5254. https://doi.org/10.1007/s00170-020-05014-5.
13. Z. Zeng, L. Yang, Q. Zeng, H. Lou, H. Sheng, J. Wen, D.J. Miller, Y. Meng, W. Yang, W.L. Mao, H.K. Mao, Synthesis of quenchable amorphous diamond, Nat. Commun. 8 (2017) 322. https://doi.org/10.1038/s41467-017-00395-w.
14. T.A. Friedmann, J.P. Sullivan, J.A. Knapp, D.R. Tallant, D.M. Follstaedt, D.L. Medlin, P.B. Mirkarimi, Thick stress-free amorphous-tetrahedral carbon films with hardness near that of diamond, Appl. Phys. Lett. 71 (1997) 3820–3822. https://doi.org/10.1063/1.120515.
15. P.H. Gaskell, A. Saeed, P. Chieux, D.R. McKenzie, The structure of highly tetrahedral amorphous diamond-like carbon: I. Neutron scattering studies, Philosophical Magazine B: Physics of Condensed Matter; Statistical Mechanics, Electronic, Optical and Magnetic Properties 66 (1992) 155–169. https://doi.org/10.1080/13642819208224580.
16. T. Miyazawa, S. Misawa, S. Yoshida, S.I. Gonda, Preparation and structure of carbon film deposited by a mass-separated C+ ion beam, J. Appl. Phys. 55 (1984) 188–193. https://doi.org/10.1063/1.332862.
17. B. Rothammer, M. Schwendner, M. Bartz, S. Wartzack, T. Böhm, S. Krauß, B. Merle, S. Schroeder, M. Uhler, J.P. Kretzer, V. Weihnacht, M. Marian, Wear Mechanism of Superhard Tetrahedral Amorphous Carbon (ta-C) Coatings for Biomedical Applications, Adv. Mater. Interfaces 10 (2023). https://doi.org/10.1002/admi.202202370.
18. A. Götze, S. Makowski, T. Kunze, M. Hübner, H. Zellbeck, V. Weihnacht, A. Leson, E. Beyer, J. Joswig, G. Seifert, G. Abrasonis, M. Posselt, J. Fassbender, W. Möller, S. Gemming, M. Krause, Tetrahedral Amorphous Carbon Coatings for Friction Reduction of the Valve Train in Internal Combustion Engines, Adv. Eng. Mater. 16 (2014) 1226–1233. https://doi.org/10.1002/adem.201400188.
19. A. Iyer, A. Kaskela, S. Novikov, J. Etula, X. Liu, E.I. Kauppinen, J. Koskinen, Effect of tetrahedral amorphous carbon coating on the resistivity and wear of single-walled carbon nanotube network, J. Appl. Phys. 119 (2016). https://doi.org/10.1063/1.4948672.
20. N. Wester, J. Etula, T. Lilius, S. Sainio, T. Laurila, J. Koskinen, Selective detection of morphine in the presence of paracetamol with anodically pretreated dual layer Ti/tetrahedral amorphous carbon electrodes, Electrochem. Commun. 86 (2018) 166–170. https://doi.org/10.1016/j.elecom.2017.12.014.
21. P.A. Romero, L. Pastewka, J. Von Lautz, M. Moseler, Surface passivation and boundary lubrication of self-mated tetrahedral amorphous carbon asperities under extreme tribological conditions, Friction 2 (2014) 193–208. https://doi.org/10.1007/s40544-014-0057-z.
22. P. Fabisch, V. Voropai, M. Nieher, A. Buchholz, S. Weissmantel, C.H. Lohmann, J. Bertrand, J. Döring, Biocompatibility and Antibacterial Potential of Tetrahedral Amorphous Carbon (ta-C) Coatings on CoCrMo Alloy for Articulating Implant Surfaces, J. Biomed. Mater. Res. A 113 (2025). https://doi.org/10.1002/jbm.a.37815.
23. S. Sainio, D. Nordlund, M.A. Caro, R. Gandhiraman, J. Koehne, N. Wester, J. Koskinen, M. Meyyappan, T. Laurila, Correlation between sp 3 -to-sp 2 Ratio and Surface Oxygen Functionalities in Tetrahedral Amorphous Carbon (ta-C) Thin Film Electrodes and Implications of Their Electrochemical Properties, The Journal of Physical Chemistry C 120 (2016) 8298–8304. https://doi.org/10.1021/acs.jpcc.6b02342.
24. J. Wei, P. Guo, L. Liu, H. Li, H. Li, S. Wang, P. Ke, H. Saito, A. Wang, Corrosion resistance of amorphous carbon film in 3.5 wt% NaCl solution for marine application, Electrochim. Acta 346 (2020). https://doi.org/10.1016/j.electacta.2020.136282.
25. M. Muhammed, M. Javidani, T. Ebrahimi Sadrabadi, M. Heidari, T. Levasseur, M. Jahazi, A Comprehensive Review of Cathodic Arc Evaporation Physical Vapour Deposition (CAE-PVD) Coatings for Enhanced Tribological Performance, Coatings 14 (2024). https://doi.org/10.3390/coatings14030246.
26. I.P. Filos, R. Sesana, M. Di Biase, R. Lupoi, New abrasive coatings: Abraded volume measurements in ceramic ball production, Journal of Manufacturing and Materials Processing 5 (2021). https://doi.org/10.3390/jmmp5030081.
27. S. Sharma, S. Sangal, K. Mondal, On the optical microscopic method for the determination of ball-on-flat surface linearly reciprocating sliding wear volume, Wear 300 (2013) 82–89. https://doi.org/10.1016/j.wear.2013.01.107.
28. P. Pawlus, R. Reizer, Accurate determination of wear volume of ball employed as counter sample in reciprocating sliding tests, Wear 580–581 (2025) 206309. https://doi.org/10.1016/j.wear.2025.206309.
29. A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B 61 (2000) 14095–14107. https://doi.org/10.1103/PhysRevB.61.14095.
30. A.C. Ferrari, J. Robertson, Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon, Phys. Rev. B Condens. Matter Mater. Phys. 64 (2001) 1–13. https://doi.org/10.1103/PhysRevB.64.075414.
31. C. Casiraghi, A.C. Ferrari, J. Robertson, Raman spectroscopy of hydrogenated amorphous carbons, Phys. Rev. B Condens. Matter Mater. Phys. 72 (2005) 1–14. https://doi.org/10.1103/PhysRevB.72.085401.
32. F. Alvarez-Antolin, A. Gonzalez-Pociño, A. Cofiño-Villar, C.H. Alvarez-Perez, Optimisation of Thermal Processes with Plasma Nitriding on Vanadis 4 High Speed Steel, Materials 15 (2022) 906. https://doi.org/10.3390/ma15030906.
33. E.A. dos Santos de Almeida, J.C.G. Milan, C.E. da Costa, C. Binder, J.D.B. de Mello, H.L. Costa, Combined Use of Surface Texturing, Plasma Nitriding and DLC Coating on Tool Steel, Coatings 11 (2021) 201. https://doi.org/10.3390/coatings11020201.
34. I. Gómez, J.A. García, J.A. Santiago, I. Fernandez, P. Jose Fernandez, I. Braceras, Adhesion Enhancement on a Duplex DLC HiPIMS Positive Pulse Coating Performed by Active Screen Plasma Nitriding Pretreatment on 316L Stainless Steel Substrate, Advances in Materials Science and Engineering 2022 (2022) 1–11. https://doi.org/10.1155/2022/5621154.
35. A. Mannan, M.F.M. Sabri, Md.A. Kalam, H.H. Masjuki, Tribological Properties of Steel/Steel, Steel/DLC and DLC/DLC Contacts in the Presence of Biodegradable Oil, Journal of the Japan Petroleum Institute 62 (2019) 11–18. https://doi.org/10.1627/jpi.62.11.
36. T.F. Zhang, K.-W. Kim, K.H. Kim, Nitrogen-Incorporated Hydrogenated Amorphous Carbon Film Electrodes on Ti Substrates by Hybrid Deposition Technique and Annealing, J. Electrochem. Soc. 163 (2016) E54–E61. https://doi.org/10.1149/2.0051603jes.
37. X. Chen, X. Wang, D. Fang, A review on C1s XPS-spectra for some kinds of carbon materials, Fullerenes Nanotubes and Carbon Nanostructures 0 (2020) 1048–1058. https://doi.org/10.1080/1536383X.2020.1794851.
38. S. Bhattacharyya, J. Hong, G. Turban, Determination of the structure of amorphous nitrogenated carbon films by combined Raman and x-ray photoemission spectroscopy, J. Appl. Phys. 83 (1998) 3917–3919. https://doi.org/10.1063/1.367312.
39. J. Zhu, B. Liu, L. Li, Z. Zeng, W. Zhao, G. Wang, X. Guan, Simple and Green Fabrication of a Superhydrophobic Surface by One-Step Immersion for Continuous Oil/Water Separation, J. Phys. Chem. A 120 (2016) 5617–5623. https://doi.org/10.1021/acs.jpca.6b06146.
40. K. Yamamoto, Chemical bond analysis of amorphous carbon films, Vacuum 84 (2009) 638–641. https://doi.org/10.1016/j.vacuum.2009.10.016.
41. M. Kano, J.M. Martin, M.I. De Barros Bouchet, Green Superlubrication by Hydrogen-Free Amorphous Carbon with Human Friendly Lubricants, Sensors and Materials (2017) 771. https://doi.org/10.18494/SAM.2017.1630.
42. E.C.T. Ba, P.S. Martins, M.B. da Silva, A.J. dos Santos, M.R. Dumont, P.M. Firpe, G.F.S. de Melo Nogueira, P.A.A. Magalhães Júnior, Study of the structural and tribological characteristics of hydrogenated diamond-like carbon coatings for high-speed steel substrate applications, Tribol. Int. 212 (2025). https://doi.org/10.1016/j.triboint.2025.110941.
43. S.N. Grigoriev, M.A. Volosova, S. V. Fedorov, M. Mosyanov, Influence of DLC Coatings Deposited by PECVD Technology on the Wear Resistance of Carbide End Mills and Surface Roughness of AlCuMg2 and 41Cr4 Workpieces, Coatings 10 (2020) 1038. https://doi.org/10.3390/coatings10111038.
44. J. Decrozant-Triquenaux, L. Pelcastre, C. Courbon, B. Prakash, J. Hardell, High temperature tribological behaviour of PVD coated tool steel and aluminium under dry and lubricated conditions, Friction 9 (2021) 802–821. https://doi.org/10.1007/s40544-020-0435-7.
45. L. Chagas da Silva, M.S. Libório, P.A. Radi, D.A. Pereira Reis, V.J. Trava-Airoldi, T.F. da Conceição Hermenegildo, S.M. Alves, DLC/a-Si:H multilayers films to improve wear resistance of components of common rail injection system, Journal of Materials Research and Technology 26 (2023) 2617–2628. https://doi.org/10.1016/j.jmrt.2023.08.078.
46. A. Claver, E. Jiménez-Piqué, J.F. Palacio, E. Almandoz, J. Fernández de Ara, I. Fernández, J.A. Santiago, E. Barba, J.A. García, Comparative Study of Tribomechanical Properties of HiPIMS with Positive Pulses DLC Coatings on Different Tools Steels, Coatings 11 (2020) 28. https://doi.org/10.3390/coatings11010028.
47. H. Paschke, M. Weber, P. Kaestner, G. Braeuer, Influence of different plasma nitriding treatments on the wear and crack behavior of forging tools evaluated by Rockwell indentation and scratch tests, Surf. Coat. Technol. 205 (2010) 1465–1469. https://doi.org/10.1016/j.surfcoat.2010.07.053.
48. C. Zhao, C.X. Li, H. Dong, T. Bell, Study on the active screen plasma nitriding and its nitriding mechanism, Surf. Coat. Technol. 201 (2006) 2320–2325. https://doi.org/10.1016/j.surfcoat.2006.03.045.
49. A.K. Gonzalez-Moran, M. Naeem, H.M. Hdz-García, E.E. Granda-Gutiérrez, J.J. Ruíz-Mondragón, M. Alvarez-Vera, J.C. Díaz-Guillén, Improved mechanical and wear properties of H13 tool steel by nitrogen-expanded martensite using current-controlled plasma nitriding, Journal of Materials Research and Technology 25 (2023) 4139–4153. https://doi.org/10.1016/j.jmrt.2023.06.221.
50. O. Kubaschewski, C.B. Alcock, Metallurgical Thermochemistry, Pergamon Press, 1979. https://onlinelibrary.wiley.com/doi/10.1002/crat.19800150208.
51. E.J. Mittemeijer, Fundamentals of Nitriding and Nitrocarburizing, in: Steel Heat Treating Fundamentals and Processes, ASM International, 2013: pp. 619–646. https://doi.org/10.31399/asm.hb.v04a.a0005818.