Tailoring the microstructure, mechanical and tribocorrosion performance of (CrNbTiAlV)Nx high-entropy nitride films by controlling nitrogen flow

doi:10.1016/j.jmst.2021.08.032

Abstract

Abstract:

The (CrNbTiAlV)N_x high-entropy nitride films were fabricated by adjusting nitrogen flow via magnetron sputtering. The microstructure, mechanical, electrochemical and tribocorrosion performances of the films were studied. The results show that the films transform from amorphous to nanocrystalline structure as nitrogen flow increased. The nanocrystalline films show super hardness (> 40 GPa) and adhesion strength (> 50 N). The amorphous film has a pretty anti-corrosion in static corrosion, while not in tribocorrosion condition. The film deposited at nitrogen flow of 38 sccm exhibits the optimal tribocorrosion performance in artificial seawater, with the highest open circuit potential (- - 0.1 V vs. Ag/AgCl), the lowest friction coefficient (- 0.162) and wear rate (- 7.48 × 10^-7 mm³ N^-1 m^-1).

Key words: High-entropy nitride films, Nitrogen flow, Tribocorrosion performance, Magnetron sputtering

Cunxiu Zhang, Xiaolong Lu, Cong Wang, Xudong Sui, Yanfang Wang, Haibin Zhou, Junying Hao. Tailoring the microstructure, mechanical and tribocorrosion performance of (CrNbTiAlV)N_x high-entropy nitride films by controlling nitrogen flow[J]. J. Mater. Sci. Technol., 2022, 107: 172-182.

Figures/Tables 16

Table 1 The details of the process parameters.

Process parameters	Pre-cleaning	Deposited films
Process parameters	Pre-cleaning	Cr	HEFNs
Current (A)	0.4	4.5	4.5	4.5	4.5	4.5	4.5
N₂ flow (sccm)	0	0	0	8	18	38	58
Ar flow (sccm)	18	18	18	18	18	18	18
Working Pressure (Torr)	2.5 × 10^-3	2.5 × 10^-3	2.5 × 10^-3	2.6 × 10^-3	3.2 × 10^-3	4.1 × 10^-3	5.1 × 10^-3
Bias (V)	- 450	- 60	- 126	- 126	- 126	- 126	- 126
Time (min)	30	8	240	240	240	240	240

Fig. 1. Schematic diagram of (a) static electrochemical test setup and (b) the reciprocating tribocorrosion device.

Fig. 2. Element compositions (a), and deposition rate (b) of the (CrNbTiAlV)Nx high-entropy films as a function of N2 flow.

Fig. 3. SEM cross-section and surface morphology of (CrNbTiAlV)Nx high-entropy films deposited under different nitrogen flows: (a, f) S0; (b, g) S8; (c, h) S18; (d, i) S38; (e, j) S58; (k) high magnification SEM image of S38 (in order to improve the resolution of the image, the sample was sprayed with gold for 60 s in advance).

Fig. 4. XRD patterns of (CrNbTiAlV)Nx films deposited under different nitrogen flows.

Table 2 Relative intensity of diffraction peaks, average grain sizes and lattice constant of (CrNbTiAlV)Nx films.

Sample	Relative intensity				Average grain size (nm)	Lattice constant (Å)
Sample	(111)	(200)	(220)	(311)
S8	216	41	24	5	12.41	4.26015
S18	680	152	182	28	14.05	4.31748
S38	25	5	7	-	11.74	4.32233
S58	114	8	35	9	13.30	4.30363

Table 3 The radius of elements in (CrNbTiAlV)Nx system.

Element	Cr	Nb	Ti	Al	V	N
Radius(pm)	124.9	142.9	146.2	143.2	131.6	75

Table 4 The nitrogen content, δ and ΔSmix value of the (CrNbTiAlV)Nx high-entropy films at different N2 flows.

N₂ flow	N content (at.%)	δ (%)	ΔS_mix (kJ mol^-1)
S0	0	6.41	13.01
S8	29.8	24.42	11.25
S18	31.4	24.51	10.52
S38	35.7	25.64	10.13
S58	40.9	27.04	9.88

Fig. 5. The residual stress (a), hardness and elastic modulus (b), load-displacement curves (c) and H/E and H3/E2 (d) of (CrNbTiAlV)Nx films deposited under different nitrogen flows.

Fig. 6. The experimental curves (a: S0, b: S8, c: S18, d: S38, e: S58), adhesion LC2 (f) and scratch morphologies (g) of (CrNbTiAlV)Nx high-entropy films deposited under different nitrogen flows using a scratch tester with a diamond indenter (loading rate and termination load are 80 N/min and 100 N, respectively).

Fig. 7. The potentiodynamic polarization curves of the substrate and (CrNbTiAlV)Nx films at different N2 flows in artificial seawater at room temperature.

Table 5 The electrochemical parameters fitted from the polarization curve by Cview software.

Sample	E_corr (V_SCE)	E_pit (V_SCE)	i_corr (μA/cm²)	R_corr (μm/PY)
S0	-0.344	0.833	0.038	0.44
S8	-0.227	-	0.019	0.23
S18	-0.509	0.666	0.344	4.05
S38	-0.091	-	0.015	0.18
S58	-0.427	0.811	0.271	3.19
Substrate	-0.597	0.423	0.337	3.96

Fig. 8. The evolution of open circuit potential and coefficient of friction in the soaking, sliding, and passivation (a, c), the wear rate and COF (b) of the substrate and (CrNbTiAlV)Nx films in artificial seawater, and the enlarged view of S58 and substrate in loading, stabilizing and unloading stages (c-1, c-2, c-3).

Fig. 9. Three-dimensional profiles, SEM, EDS of wear tracks obtained from the steel substrate (a, f, k) and S0 (b, g, l), S18 (c, h, m), S38 (d, i, n), S58 (e, j, o) films after tribocorrosion test.

Table 6 EDS results of selected points on the wear track after the tribocorrosion tests (at.%).

Sample	Point	Cr	Nb	Ti	Al	V	N	Cl	O	Fe
Substrate	1	24.9	-	-	-	-	-	-	-	75.1
Substrate	2	23.4	-	-	-	-	-	0.3	12.7	63.6
S0	3	8.8	12.1	8.4	14.9	3.1	-	1.1	39.9	11.7
S18	4	1.7	-	-	-	-	-	-	21.3	77.0
S18	5	22.4	9.0	8.3	11.9	1.3	43.7	0.2	3.1	-
S38	6	25.8	9.0	8.1	7.1	9.8	40.2	-	-	-
S58	7	-	7.1	-	4.7	-	-	-	86.5	-
S58	8	26.6	9.6	6.9	9.6	-	47.3	-	-	-

Fig. 10. Schematic of the static corrosion and tribocorrosion mechanism of (CrNbTiAlV)Nx high-entropy films under different work environments.

References 60

[1]	K. Rohith, S. Shreyas, K.B. Vishnu Appaiah, R.V. Sheshank, B.B. Ganesha, B. Vinod, Mater. Today: Proc., 18 (2019), pp. 4854-4859.
[2]	B.R. Hou, X.G. Li, X.M. Ma, C.W. Du, D.W. Zhang, M. Zheng, W.C. Xu, D.Z. Lu, F.B. Ma, NPJ Mater. Degrad., 1 (2017), pp. 4-13. DOI URL
[3]	S. Jin, A. Atrens, Appl. Phys. A, 50 (1990), pp. 287-300. DOI URL
[4]	M. Santamaria, G. Tranchida, F.D. Franco, Corros. Sci., 173 (2020), Article 108778. DOI URL
[5]	X.J. Yang, C.W. Du, H.X. Wan, Z.Y. Lu, X.G. Li, Appl. Surf. Sci., 458 (2018), pp. 198-209. DOI URL
[6]	J.J. Pang, D.J. Blackwood, Corros. Sci., 105 (2016), pp. 17-24. DOI URL
[7]	X.D. Sui, R.N. Xu, J. Liu, S.T. Zhang, Y. Wu, J. Yang, J.Y. Hao, ACS Appl. Mater. Interfaces, 10 (2018), pp. 36531-36539. DOI URL
[8]	H. Kovacı, Y.B. Bozkurt, A.F. Yetim, O. Baran, A. Çelik, Tribol. Int., 156 (2021), Article 106823. DOI URL
[9]	P.A. Dearnley, B. Mallia, Wear, 306 (2013), pp. 263-275. DOI URL
[10]	M.M. Liu, H.X. Hua, Y.G. Zheng, Surf. Coat. Technol., 309 (2017), pp. 579-589. DOI URL
[11]	X.L. Huang, L. Yua, Y.S. Dong, Prog. Org. Coat., 139 (2020), Article 105446.
[12]	A.S.M. Ang, C.C. Berndt, M.L. Sesso, A. Anupam, S. Praveen, R.S. Kottda, B.S. Murty, Metall. Mater. Trans. A, 46 (2015), pp. 791-800. DOI URL
[13]	J.K. Xiao, H. Tan, Y.Q. Wu, Surf. Coat. Technol., 385 (2020), Article 125430. DOI URL
[14]	S. Yin, W. Li, B.O. Song, X.C. Yan, M. Kuang, Y.X. Xu, K. Wen, R. Lupoi, J. Mater. Sci. Technol., 35 (2019), pp. 1003-1007. DOI URL
[15]	Y.L. Li, P. Song, W.Q. Wang, M. Lei, X.W. Li, Mater. Charact., 170 (2020), Article 110674. DOI URL
[16]	A. Baptista, F.J.G. Silva, J. Porteiro, J.L. Míguez, G. Pinto, L. Fernandes, Proc. Manuf, 17 (2018), pp. 746-757.
[17]	F. Zhou, Q. Ma, Q.Z. Wang, L.K.Y. Li, J.W. Yan, Tribol. Int., 116 (2017), pp. 19-25. DOI URL
[18]	Y. Wang, J.L. Li, C.Q. Dang, Y.X. Wang, Y.J. Zhu, Tribol. Int., 109 (2017), pp. 285-296. DOI URL
[19]	Y. Zhang, T.T. Zuo, Z. Tang, M.C. Gao, K.A. Dahmen, P.K. Liaw, Z.P. Lu, Prog. Mater. Sci., 61 (2014), pp. 1-93. DOI URL
[20]	X.H. Yan, J.S. Li, W.R. Zhang, Y. Zhang, Mater. Chem. Phys., 210 (2018), pp. 12-19. DOI URL
[21]	Y. Fu, J. Li, H. Luo, C.W. Du, X.G. Li, J. Mater. Sci. Technol., 80 (2021), pp. 217-233. DOI URL
[22]	H. Luo, Z. Li, A.M. Mingers, D. Raabe, Corros. Sci., 134 (2018), pp. 131-139. DOI URL
[23]	S. Alvi, D.M. Jarzabek, M.G. Kohan, D. Hedman, P. Jenczyk, M. Natile, A. Vomiero, F. Akhtar, ACS Appl. Mater. Interfaces, 12 (2020), pp. 21070-21079. DOI URL
[24]	N.A. Khan, B. Akhavan, H.R. Zhou, L. Chang, Y. Wang, L.X. Sun, M.M. Bilek, Z.W. Liu, Appl. Surf. Sci., 495 (2019), Article 143560. DOI URL
[25]	Y.S. Kim, H.J. Park, S.C. Mun, E. Jumaev, S.H. Hong, G. Song, J.T. Kim, Y.K. Park, K.S. Kim, S. Jeong, Y.H. Kwon, K.B. Kim, J. Alloys Compd., 797 (2019), pp. 834-841. DOI URL
[26]	N.A. Khan, B. Akhavan, C.F. Zhou, L. Chang, Y. Wang, L.X. Sun, M.M. Bilek, Z.W. Liu, Surf. Coat. Technol., 402 (2020), Article 126327. DOI URL
[27]	L.Q. Chen, W. Li, P. Liu, K. Zhang, F.C. Ma, X.H. Chen, H.L. Zhou, X.K. Liu, Vacuum, 181 (2020), Article 109706. DOI URL
[28]	P.P. Cui, W. Li, P. Liu, K. Zhang, F.C. Ma, X.H. Chen, R. Feng, P.K. Liaw, J. Alloys Compd., 834 (2020), Article 155063. DOI URL
[29]	A.D. Pogrebnjak, I.V. Yakushchenko, A.A. Bagdasaryan, O.V. Bondar, R. Krause-Rehberg, G. Abadias, P. Chartier, K. Oyoshi, Y. Takeda, V.M. Beresnev, O.V. Sobol, Mater. Chem. Phys., 147 (2014), pp. 1079-1091. DOI URL
[30]	R. Chen, Z.B. Cai, J.B. Pu, Z.Y. Lu, S.Y. Chen, S.J. Zheng, C. Zeng, J. Alloys Compd., 827 (2020), Article 153836. DOI URL
[31]	H.T. Hsueh, W.J. Shen, M.H. Tsai, J.W. Yeh, Surf. Coat. Technol., 206 (2012), pp. 4106-4112. DOI URL
[32]	X.G. Feng, K.F. Zhang, Y.G. Zheng, H. Zhou, Z.H. Wan, Mater. Chem. Phys., 239 (2020), Article 121991. DOI URL
[33]	B. Ren, S.Q. Yan, R.F. Zhao, Z.X. Liu, Surf. Coat. Technol., 235 (2013), pp. 764-772. DOI URL
[34]	Z.C. Chang, S.C. Liang, S. Han, Y.K. Chen, F.S. Shieu, Nucl. Instrum. Methods Phys. B, 268 (2010), pp. 2504-2509. DOI URL
[35]	F. Rovere, D. Music, S. Ershov, M. Baben, H.G. Fuss, P.H. Mayrhofer, J.M. Schneider, J. Phys. D: Appl. Phys., 43 (2010), Article 035302. DOI URL
[36]	S.M. Wang, X.H. Yu, J.Z. Zhang, L.P. Wang, K. Leinenweber, D. He, Y.S. Zhao, Cryst. Growth Des., 16 (2016), pp. 351-358. DOI URL
[37]	M. Adamik, P.B. Barna, I. Tomov, Thin Solid Films, 317 (1998), pp. 64-68. DOI URL
[38]	D.C. Tsai, Z.C. Chang, B.H. Kuo, M.H. Shiao, S.Y. Chang, F.S. Shieu, Appl. Surf. Sci., 282 (2013), pp. 789-797. DOI URL
[39]	C.H. Lai, S.J. Lin, J.W. Yeh, S.Y. Chang, Surf. Coat. Technol., 201 (2006), pp. 3275-3280. DOI URL
[40]	D.C. Tsai, Y.L. Huang, S.R. Lin, S.C. Liang, F.S. Shieu, Appl. Surf. Sci., 257 (2010), pp. 1361-1367. DOI URL
[41]	P.K. Huang, J.W. Yeh, Surf. Coat. Technol., 203 (2009), pp. 1891-1896. DOI URL
[42]	Y. Zhang, Y.J. Zhou, J.P. Lin, G.L. Chen, P.K. Liaw, Adv. Eng. Mater., 10 (2008), pp. 534-538. DOI URL
[43]	J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau, S.Y. Chang, Adv. Eng. Mater., 6 (2004), pp. 299-303. DOI URL
[44]	Y. Zhang, X.H. Yan, W.B. Liao, K. Zhang, Entropy, 20 (2018), pp. 624-635. DOI URL
[45]	L. Karlsson, L. Hultman, J.E. Sundgren, Thin Solid Films, 371 (2000), pp. 167-177. DOI URL
[46]	S. Suresha, R. Gunda, V. Jayaram, J. Mater. Res., 22 (2007), pp. 3501-3506. DOI URL
[47]	Y. Niu, J. Wei, Z. Yu, Surf. Coat. Technol., 275 (2015), pp. 332-340. DOI URL
[48]	Y.Q. Fu, F. Zhou, Q.Z. Wang, M.D. Zhang, Z.F. Zhou, L. Kwork, Y. Li, J. Alloys Compd., 791 (2019), pp. 800-813. DOI URL
[49]	S.J. Zheng, Z.B. Cai, J.B. Pu, C. Zeng, S.Y. Chen, R. Chen, L.P. Wang, Appl. Surf. Sci., 483 (2019), pp. 870-874. DOI URL
[50]	J. Ding, L. Zhang, M.U. Lu, J. Wang, Z.B. Wen, W.H. Hao, Appl. Surf. Sci., 289 (2014), pp. 33-41. DOI URL
[51]	S.J. Zheng, Z.B. Cai, J.B. Pu, C. Zeng, L.P. Wang, Appl. Surf. Sci., 483 (2021), Article 148520.
[52]	J. Dai, H. Feng, H.B. Li, Z.H. Jiang, H. Li, S.C. Zhang, P. Zhou, T. Zhang, Corros. Sci., 174 (2020), Article 108792. DOI URL
[53]	R. Bayón, A. Igartua, J.J. González, U.R.D. Gopegui, Tribol. Int., 88 (2015), pp. 115-125. DOI URL
[54]	Y.X. Wang, J.W. Zhang, S.G. Zhou, Y.C. Wang, C.T. Wang, Y.X. Wang, Y.F. Sui, J.B. Lan, Q.J. Xue, Appl. Surf. Sci., 528 (2020), Article 147061. DOI URL
[55]	Y. Sun, E. Haruman, Corros. Sci., 53 (2011), pp. 4131-4140. DOI URL
[56]	J.P. Celis, P. Ponthiaux, F. Wenger, Wear, 261 (2006), pp. 939-946. DOI URL
[57]	Y.Q. Fu, F. Zhou, Q.Z. Wang, M.D. Zhang, Z.F. Zhou, Corros. Sci., 165 (2020), Article 108385. DOI URL
[58]	A. Hatem, J.L. Lin, R.H. Wei, R.D. Torres, C. Laurindo, G.B.D. Souza, P. Soares, Surf. Coat. Technol., 347 (2018), pp. 1-12. DOI URL
[59]	A. López-Ortega, R. Bayón, J.L. Arana, Surf. Coating. Technol., 349 (2018), pp. 1083-1097. DOI URL
[60]	X. Dai, M. Wen, K.K. Huang, X. Wang, L.N. Yang, J. Wang, K. Zhang, Appl. Surf. Sci., 447 (2018), pp. 886-893. DOI URL