Effect of nitrogen addition on the structural, mechanical and corrosion properties of FeCoCrMnNiN_x high-entropy nitride ceramic thin films

Abstract

FeCoCrMnNiN_x high entropy nitride ceramics thin films were prepared using the magnetron sputtering method, and the effects of nitrogen content on the thin films’ properties were later examined. The addition of N₂ affected the microstructures of the thin films and their mechanical and corrosion properties. Compared with the FeCoCrMnNi thin films with 1-sccm N₂, the addition of 2 and 3 sccm of N₂ by as much as 5.45at% and 6.34at% changed the solid solution’s crystalline structure into an amorphous structure. The addition of nitrogen caused drastic changes to the surface morphology, creating a smoother and more uniform surface without cauliflower units. The atomic force microscopy image analysis indicated that the addition of nitrogen reduced the surface roughness from 5.58 to 1.82 nm. Adding N₂ to the CoCrFeMnNi thin film helped increase its mechanical properties, such as hardness and strength, while the Young’s modulus decreased. The hardness of (8.75 ± 0.5) GPa and the reduced Young’s modulus of (257.37 ± 11.4) GPa of the FeCoCrMnNi thin film reached (12.67 ± 1.2) and (194.39 ± 12.4) GPa, respectively, with 1 sccm N₂. The applied coating of the CoCrFeMnNi thin film on 304SUS increased the corrosion resistance, whereas the addition of nitrogen to the CoCrFeMnNi thin film also improved its corrosion resistance compared with that of the CoCrFeMnNi thin film without nitrogen.

Keywords

thin films / sputtering / high-entropy nitride ceramics / structural properties / corrosion behavior / mechanical properties

References

[1] HuangKH, YehJWA Study on the Multicomponent Alloy Systems Containing Equal-Mole Elements, 1996, Hsinchu, National Tsing Hua University

[2] TsaiMH, YehJW. High-entropy alloys: A critical review. Mater. Res. Lett., 2014, 2(3): 107

[3] YehJW, ChenSK, LinSJ, et al.. Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes. Adv. Eng. Mater., 2004, 6(5): 299

[4] G.D. Sim, J.A. Krogstad, K.M. Reddy, et al., Nanotwinned metal MEMS films with unprecedented strength and stability, Sci. Adv., 3(2017), No. 6, art. No. e1700685.

[5] Z. Wang, C. Wang, Y.L. Zhao, et al., Growth, microstructure and mechanical properties of CoCrFeMnNi high entropy alloy films, Vacuum, 179(2020), art. No. 109553.

[6] YeQF, FengK, LiZG, et al.. Microstructure and corrosion properties of CrMnFeCoNi high entropy alloy coating. Appl. Surf. Sci., 2017, 396: 1420

[7] HuoWY, LiuXD, TanSY, et al.. Ultrahigh hardness and high electrical resistivity in nano-twinned, nanocrystalline high-entropy alloy films. Appl. Surf. Sci., 2018, 439: 222

[8] FuZQ, ChenWP, XiaoHQ, ZhouLW, ZhuDZ, YangSF. Fabrication and properties of nanocrystalline Co_0.5FeNiCrTi_0.5 high entropy alloy by MA–SPS technique. Mater. Des., 2013, 44: 535

[9] KaoYF, ChenTJ, ChenSK, YehJW. Microstructure and mechanical property of as-cast, -homogenized, and-deformed Al_xCoCrFeNi (0≤x≤2) high-entropy alloys. J. Alloy. Compd., 2009, 488(1): 57

[10] G. Radnóczi, R. Dedoncker, G.Z. Radnóczi, et al., The growth of a multi-principal element (CoCrFeMnNi) oxynitride film by direct current magnetron sputtering using air as reactive gas, Surf. Coat. Technol., 421(2021), art. No. 127433.

[11] Z.J. Zhang, M.M. Mao, J.W. Wang, et al., Nanoscale origins of the damage tolerance of the high-entropy alloy CrMnFeCoNi, Nat. Commun., 6(2015), No. 1, art. No. 10143.

[12] H. Feng, Y. Han, H.B. Li, et al., Enhancement in impact toughness of CoCrFeMnNi high-entropy alloy via nitrogen addition, J. Alloy. Compd., 932(2023), art. No. 167615.

[13] YueYY, YanXH, ZhangY. Nano-fiber-structured Cantor alloy films prepared by sputtering. J. Mater. Res. Technol., 2022, 21: 1120

[14] KarriSNS, RamaduraiR, BhattacharjeePPPulsed Laser Deposition of CoCrFeMnNi High Entropy Alloy and Its Stability, 2018, Telangana, Indian Institute of Technology Hyderabad

[15] XuZL, ZhangH, LiWH, et al.. Microstructure and nanoindentation creep behavior of CoCrFeMnNi high-entropy alloy fabricated by selective laser melting. Addit. Manuf., 2019, 28: 766

[16] YoosefanF, AshrafiA, VaghefiSMM. Characterization of Co–Cr–Fe–Mn–Ni high-entropy alloy thin films synthesized by pulse electrodeposition: Part 2: Effect of pulse electrodeposition parameters on the wettability and corrosion resistance. Met. Mater. Int., 2021, 27(1): 106

[17] MahaffeyJ, VackelA, WhettenS, MeliaM, KustasAB. Structure evolution and corrosion performance of CoCrFeMnNi high entropy alloy coatings produced via plasma spray and cold spray. J. Therm. Spray Technol., 2022, 31(4): 1143

[18] S.K. Padamata, A. Yasinskiy, V. Yanov, and G. Saevarsdottir, Magnetron sputtering high-entropy alloy coatings: A mini-review, Metals, 12(2022), No. 2, art. No. 319.

[19] BraeckmanBR, BoydensF, HidalgoH, et al.. High entropy alloy thin films deposited by magnetron sputtering of powder targets. Thin Solid Films, 2015, 580: 71

[20] X. Yu, J.J. Wang, L.Q. Wang, and W.J. Huang, Fabrication and characterization of CrNbSiTiZr high-entropy alloy films by radio-frequency magnetron sputtering via tuning substrate bias, Surf. Coat. Technol., 412(2021), art. No. 127074.

[21] C.Q. Dang, J.U. Surjadi, L.B. Gao, and Y. Lu, Mechanical properties of nanostructured CoCrFeNiMn high-entropy alloy (HEA) coating, Front. Mater., 5(2018), art. No. 41.

[22] HsuYJ, ChiangWC, WuJK. Corrosion behavior of FeCoNiCrCu_x high-entropy alloys in 3.5% sodium chloride solution. Mater. Chem. Phys., 2005, 92(1): 112

[23] LinCM, TsaiHL, BorHY. Effect of aging treatment on microstructure and properties of high-entropy Cu_0.5CoCrFeNi alloy. Intermetallics, 2010, 18(6): 1244

[24] LeeCP, ChangCC, ChenYY, YehJW, ShihHC. Effect of the aluminium content of Al_xCrFe_1.5MnNi_0.5 high-entropy alloys on the corrosion behaviour in aqueous environments. Corros. Sci., 2008, 50(7): 2053

[25] KaoYF, LeeTD, ChenSK, ChangYS. Electrochemical passive properties of Al_xCoCrFeNi (x =0, 0.25, 0.50, 1.00) alloys in sulfuric acids. Corros. Sci., 2010, 52(3): 1026

[26] C.W. Lu, Y.S. Lu, Z.H. Lai, H.W. Yen, and Y.L. Lee, Comparative corrosion behavior of Fe₅₀Mn₃₀Co₁₀Cr10 dual-phase high-entropy alloy and CoCrFeMnNi high-entropy alloy in 3.5wt% NaCl solution, J. Alloy. Compd., 842(2020), art. No. 155824.

[27] Z. Wang, D.Y. Li, Y.Y. Yao, Y.L. Kuo, and C.H. Hsueh, Wettability, electron work function and corrosion behavior of CoCrFeMnNi high entropy alloy films, Surf. Coat. Technol., 400(2020), art. No. 126222.

[28] E.M. Paschalidou, R. Lindblad, L.Z. Medina, D. Karlsson, U. Jansson, and L. Nyholm, Corrosion studies on multicomponent CoCrFeMnNi(C) thin films in acidic environments, Electrochim. Acta, 404(2022), art. No. 139756.

[29] L.Z. Medina, M.V.T. da Costa, E.M. Paschalidou, et al., Enhancing corrosion resistance, hardness, and crack resistance in magnetron sputtered high entropy CoCrFeMnNi coatings by adding carbon, Mater. Des., 205(2021), art. No. 109711.

[30] OttoF, YangY, BeiH, GeorgeEP. Relative effects of enthalpy and entropy on the phase stability of equiatomic high-entropy alloys. Acta Mater., 2013, 61(7): 2628

[31] Y. Wu, W.H. Liu, X.L. Wang, et al., In-situ neutron diffraction study of deformation behavior of a multi-component high-entropy alloy, Appl. Phys. Lett., 104(2014), No. 5, art. No. 051910.

[32] YehJW. Recent progress in high-entropy alloys. Ann. Chim. Sci. Mat., 2006, 31(6): 633

[33] HeJY, LiuWH, WangH, et al.. Effects of Al addition on structural evolution and tensile properties of the FeCoNiCrMn high-entropy alloy system. Acta Mater., 2014, 62: 105

[34] XianX, ZhongZH, LinLJ, ZhuZX, ChenC, WuYC. Tailoring strength and ductility of high-entropy CrMnFeCoNi alloy by adding Al. Rare Met., 2022, 41(3): 1015

[35] Y.C. Hsu, C.L. Li, and C.H. Hsueh, Effects of Al addition on microstructures and mechanical properties of CoCrFeMnNiAl_x high entropy alloy films, Entropy, 22(2020), No. 1, art. No. 2.

[36] QinG, ChenRR, ZhengHT, et al.. Strengthening FCC-CoCrFeMnNi high entropy alloys by Mo addition. J. Mater. Sci. Technol., 2019, 35(4): 578

[37] Y.C. Hsu, C.L. Li, and C.H. Hsueh, Modifications of microstructures and mechanical properties of CoCrFeMnNi high entropy alloy films by adding Ti element, Surf. Coat. Technol., 399(2020), art. No. 126149.

[38] A. Obeydavi, A. Rezaeian, A. Shafyei, P. Kameli, and J.W. Lee, Prediction of amorphous phase formation by thermodynamic and kinetic analysis, a Fe-based thin film metallic glass deposited by direct current magnetron sputtering, Mater. Res. Express, 6(2019), No. 9, art. No. 096407.

[39] A. Obeydavi, A. Shafyei, A. Rezaeian, P. Kameli, and J.W. Lee, Fabrication and properties evaluation of novel Fe_46−XCr₂₃Mo₁₄Co₇P_XB₅Si₅ (X = 0, 6) metallic glasses deposited by DC magnetron sputtering, Intermetallics, 131(2021), art. No. 107120.

[40] A. Obeydavi, A. Shafyei, A. Rezaeian, P. Kameli, and J.W. Lee, Microstructure, mechanical properties and corrosion performance of Fe₄₄Cr₁₅Mo₁₄Co₇C₁₀B₅Si₅ thin film metallic glass deposited by DC magnetron sputtering, J. Non Cryst. Solids, 527(2020), art. No. 119718.

[41] MusilJ, KuncF, ZemanH, PolákováH. Relationships between hardness, Young’s modulus and elastic recovery in hard nanocomposite coatings. Surf. Coat. Technol., 2002, 154(2–3): 304

[42] M. Hu, Q.P. Cao, X.D. Wang, D.X. Zhang, and J.Z. Jiang, Tuning nanostructure and mechanical property of Fe–Co–Ni–Cr–Mn high-entropy alloy thin films by substrate temperature, Mater. Today Nano, 15(2021), art. No. 100130.

[43] TaborDThe Hardness of Metals, 2000, Oxford, Oxford University Press

[44] JenkinsR, SnyderRLIntroduction to X-ray Powder Diffractometry, 1996, New York, Wiley

[45] StokesAR, WilsonAJC. The diffraction of X rays by distorted crystal aggregates - I. Proc. Phys. Soc., 1944, 56(3): 174

[46] HallEO. The deformation and ageing of mild steel: III discussion of results. Proc. Phys. Soc. B, 1951, 64(9): 747

[47] PetchNJ. The cleavage strength of polycrystals. J. Iron Steel Inst., 1953, 174: 25

[48] CaronA, WunderlichR, Louzguine-LuzginDV, XieG, InoueA, FechtHJ. Influence of minor aluminum concentration changes in zirconium-based bulk metallic glasses on the elastic, anelastic, and plastic properties. Acta Mater., 2010, 58(6): 2004

[49] ZengF, GaoY, LiL, LiDM, PanF. Elastic modulus and hardness of Cu–Ta amorphous films. J. Alloy. Compd., 2005, 389(1–2): 75

[50] KuoYC, WangCJ, LeeJW. The microstructure and mechanical properties evaluation of CrTiAlSiN coatings: Effects of silicon content. Thin Solid Films, 2017, 638: 220

[51] StansburyEE, BuchananRAFundamentals of Electrochemical Corrosion, 2000, Materials Park, OH, ASM International

[52] SouzaCAC, RibeiroDV, KiminamiCS. Corrosion resistance of Fe–Cr-based amorphous alloys: An overview. J. NonCryst. Solids, 2016, 442: 56

[53] ChenLT, LeeJW, YangYC, LouBS, LiCL, ChuJP. Microstructure, mechanical and anti-corrosion property evaluation of iron-based thin film metallic glasses. Surf. Coat. Technol., 2014, 260: 46

RIGHTS & PERMISSIONS

University of Science and Technology Beijing