Inhibition effect on microbiologically influenced corrosion of Ti-6Al-4V-5Cu alloy against marine bacterium Pseudomonas aeruginosa

doi:10.1016/j.jmst.2021.08.084

Abstract

Abstract:

With rapid development of marine infrastructures, materials with better biocorrosion resistance and antibiofouling performance will be highly demanded. Ti6Al4V alloy is susceptible to the above. The inhibition to the microbiologically influenced corrosion of Ti6Al4V-5Cu alloy against Pseudomonas aeruginosa was investigated using antibacterial test, electrochemical techniques, surface analysis, and weight loss test conducted for 2.5 months. At a sputtering depth of 0 nm, the passive film of Ti6Al4V-5Cu alloy was mainly composed of ideal oxide TiO₂. With increasing sputtering thickness to 6 nm, Ti₂O₃ and TiO were detected with a relative fraction of 14.6% and 14.8%, respectively, in the oxide layer of Ti6Al4V-5Cu alloy. In contrast, the outermost layer of Ti6Al4V alloy was predominantly composed of TiO₂ but Ti₂O₃ (22.8%), Al₂O₃ and V₂O₅ were also detected. With increasing sputtering depth to 6 nm, fitting revealed the presence of Ti₂O₃ and TiO with relative fractions of 25.3% and 35.8%, respectively. Yet, a spot of TiO (8%) was also observed at 12 nm in the oxide layer of Ti6Al4V alloy. Although the addition of Cu into Ti6Al4V alloy generated the self-healing property of passive film in the presence of P. aeruginosa, it also reduced resistance to corrosion in general condition.

Key words: Titanium alloy, Biocorrosion inhibition, Passive film, P. aeruginosa

Mohammed Arroussi, Qing Jia, Chunguang Bai, Shuyuan Zhang, Jinlong Zhao, Zhizhou Xia, Zhiqiang Zhang, Ke Yang, Rui Yang. Inhibition effect on microbiologically influenced corrosion of Ti-6Al-4V-5Cu alloy against marine bacterium Pseudomonas aeruginosa[J]. J. Mater. Sci. Technol., 2022, 109: 282-296.

Figures/Tables 18

Table 1. Actual chemical compositions (wt%) of Ti6Al4V-5Cu and Ti6Al4V alloy.

Samples	Al	V	Fe	Cu	H	C	N	O	Ti
Ti6Al4V-5Cu alloy	6.03	4.15	0.17	5.26	0.001	0.014	0.0063	0.1	Bal.
Ti6Al4V alloy	6.40	4.08	0.16	0.001	0.0028	0.0087	0.009	0.12	Bal.

Fig. 1. Typical photographs of P. aeruginosa biofilm and planktonic colonization for Ti6Al4V-5Cu and Ti6Al4V alloys after 24 h and 7 days of incubation.

Fig. 2. SEM images of P. aeruginosa cells morphology and biofilms on the surfaces of Ti6Al4V after 7 days (a), 14 days (b), and Ti6Al4V-5Cu after 7 days (c) and 14 days (d).

Fig. 3. Variations of Rp for Ti6Al4V-5Cu and Ti6Al4V coupons during 14 days of incubation in different culture media, where error bars introduce the standard deviations of three replicate measurements.

Fig. 4. Nyquist and Bode plots of Ti6Al4V-5Cu and Ti6Al4V alloys: (a, a’) Ti6Al4V-5Cu in the biotic medium, (b, b’) Ti6Al4V in the biotic medium, (c, c’) Ti6Al4V-5Cu in the sterile medium, and (d, d’) Ti6Al4V in the sterile medium.

Table 2. EIS fitting results for Ti6Al4V-5Cu and Ti6Al4V alloys immersed in abiotic and biotic media.

Duration (day)	R_s (Ω cm²)	Q_f (10^-5 Ω^-1 Sⁿ cm^-2)	n_f	R_f (Ω cm²)	Q_dl (10^-5 Ω^-1 Sⁿ cm^-2)	n_dl	R_ct (MΩ cm²)	χ² × 10^-4
Ti6Al4V-5Cu in the presence of P. aeruginosa
1	8.85 ± 0.42	1.42	0.94	6.22 ± 0.15	1.41	0.91	1.848 ± 0.03	1.33
2	9.60 ± 0.33	1.44	0.92	9.11 ± 0.38	0.69	0.91	7.338 ± 0.35	0.72
4	9.65 ± 0.23	3.06	0.88	588 ± 20.4	0.25	0.92	5.119 ± 0.08	0.71
7	8.74 ± 0.36	2.87	0.87	801 ± 49.0	0.17	0.90	6.859 ± 0.19	1.61
14	9.12 ± 0.38	2.27	0.89	328 ± 36.0	0.14	0.96	6.624 ± 0.13	2.00
Ti6Al4V in the presence of P. aeruginosa
1	6.06 ± 0.71	28.1	0.57	1.133 ± 0.15	3.13	0.90	5.911 ± 0.11	0.36
2	6.07 ± 0.20	8.62	0.69	39.12 ± 2.5	3.90	0.90	1.869 ± 0.03	0.41
4	6.48 ± 0.43	7.77	0.80	468.5 ± 25.1	0.39	0.89	0.317 ± 0.02	1.97
7	7.21 ± 0.64	3.68	0.86	167.2 ± 36.0	0.41	0.93	3.169 ± 0.19	5.21
14	7.89 ± 0.61	3.19	0.87	474.6 ± 40.6	0.22	0.93	4.533 ± 0.22	4.98
Ti6Al4V-5Cu in the sterile medium
1	11.8 ± 0.74	-	-	-	2.85	0.92	3.250 ± 0.14	1.10
2	12.1 ± 0.67	-	-	-	2.47	0.92	8.447 ± 0.29	8.88
4	11.5 ± 0.47	-	-	-	1.22	0.80	7.428 ± 0.35	3.10
7	11.2 ± 1.54	-	-	-	2.89	0.92	4.811 ± 0.01	1.08
14	10.9 ± 0.31	-	-	-	3.63	0.87	3.491 ± 0.09	1.75
Ti6Al4V in the sterile medium
1	14.8 ± 0.37	-	-	-	2.90	0.93	1.793 ± 0.04	2.98
2	15.9 ± 3.26	-	-	-	2.38	0.93	3.671 ± 0.61	2.20
4	17.8 ± 2.99	-	-	-	2.11	0.93	6.817 ± 0.91	1.83
7	15.2 ± 1.82	-	-	-	2.82	0.89	8.507 ± 0.98	0.64
14	16.8 ± 0.26	-	-	-	2.65	0.89	5.005 ± 0.42	1.31

Table 3. Inhibition based-efficiency of Ti6Al4V-5Cu alloy against P. aeruginosa.

Day	2	4	7	14
η_i(%)	74.52	93.79	53.79	31.56

Fig. 5. Polarization curves of Ti6Al4V-5Cu and Ti6Al4V alloys in the biotic and abiotic media after 14 days of incubation (a), high resolution for Tafel-extrapolation on the cathodic region (b).

Table 4. Corrosion parameters obtained from polarization curves of Ti6Al4V-5Cu and Ti6Al4V alloys after 14 days of incubation (Standard deviations were calculated from three replicate tests).

Samples	E_corr (mV vs. SCE)	i_corr (nA cm^-2)	E_pit (V) vs. SCE	IE (%)
Ti6Al4V-5Cu in the biotic medium	-211.01 ± 18	8.40 ± 0.5	1.28 ± 0.01	70.62
Ti6Al4V in the biotic medium	-344.99 ± 13	28.6 ± 3.8	1.18 ± 0.02	-
Ti6Al4V-5Cu in the sterile medium	-359.81 ± 4	4.52 ± 0.3	1.30 ± 0.01	-
Ti6Al4V in the sterile medium	-389.70 ± 2	3.09 ± 0.1	1.47 ± 0.05	-

Fig. 6. CLSM images of largest pits depth measured on surfaces of Ti6Al4V-5Cu (a) and Ti6Al4V alloy (b) in the biotic medium, and scan profiles for Ti6Al4V-5Cu (c) and Ti6Al4V alloy (d) in the abiotic medium after 14 days of incubation.

Fig. 7. XPS spectra of Ti 2p on the surfaces (without sputtering) of Ti6Al4V-5Cu and Ti6Al4V alloys after 14 days of incubation in different culture media: (a) Ti6Al4V-5Cu in the abiotic medium, (b) Ti6Al4V in the abiotic medium, (c) Ti6Al4V-5Cu in the biotic medium, (d) Ti6Al4V in the biotic medium.

Fig. 8. XPS spectra at various sputtering depths (from 0 to 18 nm) for Ti6Al4V-5Cu and Ti6Al4V alloys (marked in the figure) immersed in biotic medium for 14 days: (a, d) Ti 2p binding energy-region, (b, e) Al 2p region, (c, f) V 2p region.

Fig. 9. Passive films analysis of Ti 2p region for (a-c) Ti6Al4V-5Cu alloy, (d-f) Ti6Al4V alloy at the sputtering depth of (a, d) 0 nm, (b, e) 6 nm. (c) and (f) represent the content of the corresponding oxide at the sputtering thickness of 6 nm.

Fig. 10. Quantitative analysis of Cu 2p (at the sputtering depth of 6 nm) for sample immersed in the biotic medium for different time: (a) 1 day, (b), 7 days, and (c) 14 days.

Table 5. Weight loss results for samples exposed to biotic medium for 2.5 months.

Samples	D (mg cm^-2)	δ (%)
Ti6Al4V-5Cu alloy	18.500 ± 0.2	70.58
Ti6Al4V alloy	62.23 ± 2.0	-

Fig. 11. 3D roughness profiles of samples exposed to biotic medium for 2.5 months: (a) Ti6Al4V alloy, (b) Ti6Al4V-5Cu alloy.

Table 6. Surface roughness parameters of samples exposed to biotic medium for 2.5 months.

Samples	S_a (nm)	S_q (nm)
Ti6Al4V-5Cu alloy	80.7	109
Ti6Al4V alloy	103	144

Fig. 12. Schematic illustration of MIC inhibition mechanism for Ti6Al4V-5Cu alloy against P. aeruginosa.

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