Enhanced antibacterial behavior of a novel Cu-bearing high-entropy alloy

doi:10.1016/j.jmst.2022.02.001

Abstract

Abstract:

Contact infection of bacteria and viruses has been a critical threat to human health. The worldwide outbreak of COVID-19 put forward urgent requirements for the research and development of the self-antibacterial materials, especially the antibacterial alloys. Based on the concept of high-entropy alloys, the present work designed and prepared a novel Co_0.4FeCr_0.9Cu_0.3 antibacterial high-entropy alloy with superior antibacterial properties without intricate or rigorous annealing processes, which outperform the antibacterial stainless steels. The antibacterial tests presented a 99.97% antibacterial rate against Escherichia coli and a 99.96% antibacterial rate against Staphylococcus aureus after 24 h. In contrast, the classic antibacterial copper-bearing stainless steel only performed the 71.50% and 80.84% antibacterial rate, respectively. The results of the reactive oxygen species analysis indicated that the copper ion release and the immediate contact with copper-rich phase had a synergistic effect in enhancing antibacterial properties. Moreover, this alloy exhibited excellent corrosion resistance when compared with the classic antibacterial stainless steels, and the compression test indicated the yield strength of the alloy was 1015 MPa. These findings generate fresh insights into guiding the designs of structure-function-integrated antibacterial alloys.

Key words: High-entropy alloy, Antibacterial property, Corrosion resistance, Mechanical property

Guangyu Ren, Lili Huang, Kunling Hu, Tianxin Li, Yiping Lu, Dongxu Qiao, Haitao Zhang, Dake Xu, Tongmin Wang, Tingju Li, Peter K. Liaw. Enhanced antibacterial behavior of a novel Cu-bearing high-entropy alloy[J]. J. Mater. Sci. Technol., 2022, 117: 158-166.

Figures/Tables 11

Fig. 1. X-ray diffraction patterns of the Cu0.3 and Cu0.5 alloys.

Fig. 2. SEM images and elemental mapping analysis. (a-b) Backscattered electron images of the Cu0.3 alloy. (c-d) Backscattered electron images of the Cu0.5 alloy. (e) The corresponding elemental mapping of the Cu0.3 alloy.

Fig. 3. The images of the bacterial colony growth after co-culture with alloys. (a) Coupon biofilm and planktonic colonies of E. coli after incubation for 2, 6, 12, 24, and 48 h. (b) Coupon biofilm and planktonic colonies of S. aureus after incubation for 2, 6, 12, 24, and 48 h.

Fig. 4. The CLSM images of live/dead cell staining test. (a) Live/Dead cell staining of E. coli biofilms after incubation with 304 SS, 304-Cu SS, Cu0.3, and Cu0.5. (b) Live/Dead cell staining results of S. aureus biofilms after incubation with 304 SS, 304-Cu SS, Cu0.3, and Cu0.5 alloys.

Fig. 5. The SEM images of bacteria morphology. The SEM images of (a-d) E. coli and (e-h) S. aureus cultured on 304 SS, 304-Cu SS, Cu0.3, and Cu0.5 samples after 24 h.

Fig. 6. The results of Cu-releasing tests, ROS activity tests, and the schematic diagram of germicidal mechanism. (a) The Cu-releasing profile in the DI water. (b) The Cu-releasing profile in bacterial suspension of E. coli. (c) The Cu-releasing profile in bacterial suspension of S. aureus. (d) ROS activity of bacterial suspension after co-culturing with 304 SS, 304-Cu SS, Cu0.3, and Cu0.5 alloys after 24 h (n = 3) (Sidak's multiple comparisons test, two-way ANOVA. 304 vs. 304-Cu, *p < 0.05; 304 vs. Cu0.3, **p < 0.001; 304 vs. Cu0.5, **p < 0.001). Data are displayed as mean ± SD and analyzed by the GraphPad Prism software [2].

Fig. 7. The electrochemical-polarization curves of the 304 SS, 304-Cu SS, Cu0.3, and Cu0.5 alloys.

Table 1. Electrochemical parameters of 304 SS, 304-Cu SS, Cu0.3, and Cu0.5 alloys.

Alloys	304	304-Cu	Cu0.3	Cu0.5
E_corr (mV)	-153	-135	-115	-111
i_corr (μA/cm²)	2.35	2.11	2.71	2.46

Fig. 8. Images of salt spray test of the 304 SS, 304-Cu SS, Cu0.3 and Cu0.5 alloys after 7 days.

Fig. 9. The mechanical properties of the Cu-containing HEAs. (a) Compression engineering stress-strain curves of Cu0.3 and Cu0.5 alloys, and (b) the comparison of the specific yield strength and antibacterial rates between Cu-containing HEAs and the traditional antibacterial stainless steel.

Fig. 10. The possible schematic illustration for the contact killing mechanism of Cu-HEAs. (EMP, Embden-Meyerhof-Pranas pathway; PPP, pentose phosphate pathway; TCA, tricarboxylic acid cycle; PTS, phosphotransferase system).

References 41

[1]	R. Akid, H. Wang, T.J. Smith, D. Greenfield, J.C. Earthman, Adv. Funct. Mater. 18 (2008) 203-211. DOI URL
[2]	J.Y. Xie, M. Zhou, Y.X. Qian, Z.H. Cong, S. Chen, W.J. Zhang, W.N. Jiang, C.Z. Dai, N. Shao, Z.M. Ji, J.C. Zou, X.M. Xiao, L.Q. Liu, M.Z. Chen, J. Li, R.H. Liu, Nat. Commun. 12 (2021) 5898. DOI URL
[3]	T.M. Gross, J. Lahiri, A. Golas, J. Luo, F. Verrier, J.L. Kurzejewski, D.E. Baker, J. Wang, P.F. Novak, M.J. Snyder, Nat. Commun. 10 (2019) 1979. DOI URL
[4]	W.X. Xi, V. Hegde, S.D. Zoller, H.Y. Park, C.M. Hart, T. Kondo, C.D. Hamad, Y. Hu, A.H. Loftin, D.O. Johansen, Z. Burke, S. Clarkson, C. Ishmael, K. Hori, Z. Mamouei, H. Okawa, I. Nishimura, N.M. Bernthal, T. Segura, Nat. Commun. 12 (2021) 5473. DOI URL
[5]	H.L. Karlsson, P. Cronholm, Y. Hedberg, M. Tornberg, L. De Battice, S. Svedhem, I.O. Wallirider, Toxicology 313 (2013) 59-69. DOI PMID
[6]	K.S. Chaturvedi, J.P. Henderson, Front. Cell. Infect. Microbiol. 4 (2014) 1-12.
[7]	M. Vincent, R.E. Duval, P. Hartemann, M. Engels-Deutsch, J. Appl. Microbiol. 124 (2018) 1032-1046. DOI PMID
[8]	S.A. Yavari, S.M. Castenmiller, J.A.G. van Strijp, M. Croes, Adv. Mater. 32 (2020) 2002962. DOI URL
[9]	Y.F. Zhuang, S.Y. Zhang, K. Yang, L. Ren, K.R. Dai, J. Biomed. Mater. Res. Part B 108 (2020) 484-495. DOI URL
[10]	D. Sun, D.K. Xu, C.G. Yang, J. Chen, M.B. Shahzad, Z.Q. Sun, J.L. Zhao, T.Y. Gu, K. Yang, G.X. Wang, Mater. Sci. Eng. C 69 (2016) 744-750. DOI URL
[11]	L. Nan, D.K. Xu, T.Y. Gu, X. Song, K. Yang, Mater. Sci. Eng. C 48 (2015) 228-234. DOI URL
[12]	Z. Ma, M. Li, R. Liu, L. Ren, Y. Zhang, H.B. Pan, Y. Zhao, K. Yang, J. Mater. Sci. 27 (2016) 91.
[13]	B. Bai, E.L. Zhang, J.C. Liu, J.T. Zhu, Dent. Mater. J. 35 (2016) 659-667. DOI URL
[14]	Z.Y. Ke, C.B. Yi, L. Zhang, Z.Y. He, J. Tan, Y.H. Jiang, Mater. Lett. 253 (2019) 335-338. DOI URL
[15]	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) 299-303. DOI URL
[16]	B. Cantor, I.T.H. Chang, P. Knight, A.J.B. Vincent, Mater. Sci. Eng. A 375 (2004) 213-218.
[17]	S.L. Wei, S.J. Kim, J.Y. Kang, Y. Zhang, Y.J. Zhang, T. Furuhara, E.S. Park, C.C. Tasan, Nat. Mater. 19 (2020) 1175-1181. DOI URL
[18]	W.D. Li, D. Xie, D.Y. Li, Y. Zhang, Y.F. Gao, P.K. Liaw, Prog. Mater. Sci. 118 (2021) 100777. DOI URL
[19]	Z.M. Li, K.G. Pradeep, Y. Deng, D. Raabe, C.C. Tasan, Nature 534 (2016) 227. DOI URL
[20]	Y. Zhang, T.T. Zuo, Z. Tang, M.C. Gao, K.A. Dahmen, P.K. Liaw, Z.P. Lu, Prog. Mater. Sci. 61 (2014) 1-93. DOI URL
[21]	DIN EN ISO 9227, in: Corrosion Tests in Artificial Atmospheres-Salt Spray Tests, Deutsches Institut für Normung e.V. (DIN), 2006, pp. 1-24.
[22]	E.Z. Zhou, D.X. Qiao, Y. Yang, D.K. Xu, Y.P. Lu, J.J. Wang, J.A. Smith, H.B. Li, H.L. Zhao, P.K. Liaw, F.H. Wang, J. Mater. Sci. Technol. 46 (2020) 201-210. DOI URL
[23]	Y. Yu, N.N. Xu, S.Y. Zhu, Z.H. Qiao, J.B. Zhang, J. Yang, W.M. Liu, J. Mater. Sci. Technol. 69 (2021) 48-59. DOI URL
[24]	H.T. Zhang, K.W. Siu, W.B. Liao, Q. Wang, Y. Yang, Y. Lu, Mater. Res. Express 3 (2016) 094002. DOI URL
[25]	A. Verma, P. Tarate, A.C. Abhyankar, M.R. Mohape, D.S. Gowtam, V.P. Desh-mukh, T. Shanmugasundaram, Scr. Mater. 161 (2019) 28-31. DOI URL
[26]	J.F. Jiang, M.J. Huang, Y. Wang, G.F. Xiao, Y.Z. Liu, Y. Zhang, J. Alloy Compd. 876 (2021) 160102. DOI URL
[27]	H.J. Wang, Z.Y. Wu, H. Wu, H.G. Zhu, W.C. Tang, Trans. Indian Inst. Met. 74 (2021) 267-272. DOI URL
[28]	Y.K. Kim, B.J. Lee, S.K. Hong, S.I. Hong, Mater. Sci. Eng. A 781 (2020) 139241. DOI URL
[29]	X.F. Wang, Y. Zhang, Y. Qiao, G.L. Chen, Intermetallics 15 (2007) 357-362. DOI URL
[30]	S.M. Oh, S.I. Hong, Mater. Chem. Phys. 210 (2018) 120-125. DOI URL
[31]	A. Shabani, M.R. Toroghinejad, A. Shafyei, R.E. Loge, J. Mater. Eng. Perform. 28 (2019) 2388-2398. DOI
[32]	H. Qiu, H.G. Zhu, J.F. Zhang, Z.H. Xie, Mater. Sci. Eng. A 769 (2020) 138514. DOI URL
[33]	S. Samal, S. Mohanty, A.K. Mishra, K. Biswas, B. Govind, Mater. Sci. Forum 790-791 (2014) 503-508. DOI URL
[34]	C.J. Tong, Y.L. Chen, S.K. Chen, J.W. Yeh, T.T. Shun, C.H. Tsau, S.J. Lin, S.Y. Chang, Metall. Mater. Trans. A 36 (2005) 881-893. DOI URL
[35]	A.V. Kuznetsov, D.G. Shaysultanov, N.D. Stepanov, G.A. Salishchev, O.N. Senkov, Mater. Sci. Eng. A 533 (2012) 107-118. DOI URL
[36]	N. Deng, J. Wang, J.X. Wang, Y.X. He, Z.Y. Lan, R.F. Zhao, E. Beaugon, J.S. Li, Mater. Lett. 285 (2021) 129182. DOI URL
[37]	C. Liu, W.Y. Peng, C.S. Jiang, H.M. Guo, J. Tao, X.H. Deng, Z.X. Chen, J. Mater. Sci. Technol. 35 (2019) 1175-1183. DOI URL
[38]	J.H. Pi, Y. Pan, H. Zhang, L. Zhang, Mater. Sci. Eng. A 534 (2012) 228-233. DOI URL
[39]	L. Nan, Y.Q. Liu, M.Q. Lu, K. Yang, J. Mater. Sci. Mater. Med. 19 (2008) 3057-3062. DOI URL
[40]	H.Y. Zhao, Y.P. Sun, L. Yin, Z. Yuan, Y.L. Lan, D.K. Xu, C.G. Yang, K. Yang, J. Mater. Sci. Technol. 66 (2021) 112-120. DOI URL
[41]	X.R. Zhang, C.G. Yang, K. Yang, ACS Appl. Mater. Interfaces 12 (2020) 361-372. DOI URL