Enhanced resistance of 2205 Cu-bearing duplex stainless steel towards microbiologically influenced corrosion by marine aerobic Pseudomonas aeruginosa biofilms

doi:10.1016/j.jmst.2017.11.025

Abstract

Abstract:

An antibacterial 2205-Cu duplex stainless steel (DSS) was shown to inhibit the formation and growth of corrosive marine biofilms by direct contact with copper-rich phases and the release of Cu²⁺ ions from the 2205-Cu DSS surface. In this work, the microbiologically influenced corrosion (MIC) resistance of 2205-Cu DSS in the presence of the corrosive marine bacterium Pseudomonas aeruginosa was investigated. The addition of copper improved the mechanical properties such as the yield strength, the tensile strength and the hardness of 2205 DSS. Electrochemical test results from linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS) and critical pitting temperature (CPT) measurements showed that 2205-Cu DSS possessed a larger polarization resistance (R_p), charge transfer resistance (R_ct) and CPT values, indicating the excellent MIC resistance of 2205-Cu DSS against the corrosive P. aeruginosa biofilm. The live/dead staining results and the SEM images of biofilm confirmed the strong antibacterial ability of 2205-Cu DSS. The largest pit depth of 2205-Cu DSS was considerably smaller than that of 2205 DSS after 14 d in the presence of P. aeruginosa (2.2 μm vs 12.5 μm). 2205-Cu DSS possessed a superior MIC resistance to regular 2205 DSS in the presence of aerobic P. aeruginosa.

Key words: Microbiologically influenced corrosion, Cu-bearing, uplex stainless steel, Pseudomonas aeruginosa, Antibacterial

Dake Xu, Enze Zhou, Ying Zhao, Huabing Li, Zhiyong Liu, Dawei Zhang, Chunguang Yang, Hai Lin, Xiaogang Li, Ke Yang. Enhanced resistance of 2205 Cu-bearing duplex stainless steel towards microbiologically influenced corrosion by marine aerobic Pseudomonas aeruginosa biofilms[J]. J. Mater. Sci. Technol., 2018, 34(8): 1325-1336.

Figures/Tables 21

Table 1 Chemical composition of 2205-Cu DSS and 2205 DSS (wt%).

Sample	Si	Mn	C	P	S	Ni	Cr	Mo	Cu	N	Fe
2205-Cu DSS	0.04	0.01	0.005	0.006	0.0034	6.03	23.63	2.90	3.02	0.23	Bal.
2205 DSS	0.51	1.14	0.039	0.030	0.001	5.89	23.22	3.10	-	0.17	Bal.

Fig. 1. Microstructures of 2205-Cu DSS after solution treatment at 1050 °C (a), solution treatment at 1050 °C and aging treatment at 540 °C for 4 h (b).

Table 2 Volume fraction (%) of phases of 2205-Cu DSS after solution treatment at 1050 °C, and aging treatment at 540 °C for 4 h.

Phase	Solution treatment	Solution + aging treatment
α	51.92 ± 0.06	43.82 ± 0.08
γ	48.08 ± 0.06	56.18 ± 0.08

Table 3 Mechanical properties of regular 2205 DSS (a), 2205-Cu DSS after solution treatment at 1050 °C and aging treatment at 540 °C for 4 h (b) and 2205-Cu DSS after solution treatment at 1050 °C (c).

Sample	δ_s (MPa)	δ_b (MPa)	σ (%)	ψ (%)	H (HV)
a	540	770	76	38	380
b	636	886	74	32	471
c	571	810	77	30	369

Fig. 2. Variations of Eocp with exposure time for 2205 DSS and 2205-Cu DSS coupons in sterile medium and in the presence of P. aeruginosa in 2216E medium at 30 °C.

Fig. 3. Variations of Rp with exposure time for 2205 DSS and 2205-Cu DSS coupons in 2216E medium with and without P. aeruginosa at 30 °C.

Fig. 4. Nyquist and Bode plots of 2205 DSS and 2205-Cu DSS coupons with and without exposure to P. aeruginosa in 2216E medium at 30 °C: (a, a’) 2205-Cu DSS in the medium inoculated with P. aeruginosa, (b, b’) 2205 DSS in the medium inoculated with P. aeruginosa, (c, c’) 2205 DSS in the uninoculated medium; (d, d’) 2205-Cu DSS in the uninoculated medium (f: frequency; Z’: real part of impedance; Z”: imaginary part of impedance; |Z|: impedance).

Fig. 5. Equivalent physical models and corresponding circuit models used for fitting experimental impedance diagrams of coupons in abiotic medium (a) and P. aeruginosa broth (b).

Table 4 EIS parameters of 2205 and 2205-Cu DSS in sterile medium and in the presence of P. aeruginosa.

Time	R_s	C_p	R_p	C_b	R_b	C_dl	R_ct
	(Ω cm²)	(μF cm^-2)	(Ω cm²)	(μF cm^-2)	(Ω cm²)	(μF cm^-2)	(Ω cm²)
2205-Cu DSS in the presence of P. aeruginosa
1 d	8.01	-	-	25.26	1166.0	41.16	1.68 × 10⁵
7 d	7.30	-	-	13.46	831.5	23.85	1.36 × 10⁵
14 d	9.42	-	-	57.63	340.4	25.01	4.79 × 10⁵
2205 DSS in the presence of P. aeruginosa
1 d	7.86	-	-	27.16	993.5	94.40	8.31 × 10⁴
7 d	9.32	-	-	20.88	442.6	83.83	6.78 × 10⁴
14 d	8.40	-	-	13.70	340.3	74.73	5.67 × 10⁴
2205 DSS in the uninoculated medium
1 d	12.15	27.79	1.109 × 10⁵	-	-	-	-
7 d	15.60	21.72	3.447 × 10⁵	-	-	-	-
14 d	14.54	14.29	2.868 × 10⁵	-	-	-	-
2205-Cu DSS in the uninoculated medium
1 d	9.83	28.55	8.574 × 10⁴	-	-	-	-
7 d	8.47	15.28	2.543 × 10⁵	-	-	-	-
14 d	9.48	10.10	4.328 × 10⁵	-	-	-	-

Table 5 Inhibition efficiency of 2205-Cu DSS in the presence of P. aeruginosa (ηp was calculated according to the icorr of 2205 DSS in the presence of P. aeruginosa; ηR was calculated according to the Rct of 2205 DSS in the presence of P. aeruginosa).

Time (d)	7	12	13	14
η_p (%)	N/A	N/A	N/A	89
η_R (%)	57	67	81	88

Fig. 6. CPT values of 2205 DSS and 2205-Cu DSS in sterile and P. aeruginosa inoculated in 2216E medium for 14 d.

Fig. 7. Polarization curves at the 14th day for 2205 DSS and 2205-Cu DSS coupons in 2216E medium with and without P. aeruginosa at 30 °C.

Table 6 Polarization parameters of 2205 and 2205-Cu DSS in sterile medium and in the presence of P. aeruginosa (icorr: corrosion current density; Ecorr: corrosion potential; Epit: pitting potential).

	i_corr (μA cm^-2)	E_corr (V vs SCE)	E_pit (V vs SCE)
2205 DSS in the sterile medium	0.046	-0.560	1.089
2205 DSS in the presence of P. aeruginosa	0.106	-0.390	1.018
2205-Cu DSS in the presence of P. aeruginosa	0.011	-0.259	1.002
2205-Cu DSS in the sterile medium	0.025	-0.203	0.839

Fig. 8. Representative SEM images of biofilm on different coupon surfaces in 2216E medium at 30 °C for 2205 (a, c) and 2205-Cu (b, d) DSS in the presence of P. aeruginosa after 7 d (a, b) and 14 d (c, d) (The insets show the enlarged views).

Fig. 9. CLSM images of 2205 (a, b) and 2205-Cu (c, d) DSS surfaces after live/dead staining after 7 d (a, c) and 14 d (b, d).

Table 7 Biofilm thickness on 2205 and 2205-Cu coupon surface in the P. aeruginosa broth for 7 and 14 d.

Sample	Duration (d)	Largest biofilm thickness (μm)	Average biofilm thickness (μm)
2205 DSS	7	39.3	31.0 ± 5.1
2205 DSS	14	26.3	21.4 ± 3.0
2205-Cu DSS	7	24.3	22.1 ± 1.9
2205-Cu DSS	14	20.9	17.7 ± 2.1

Fig. 10. Pit profile of the largest pit measured by CLSM on (a) 2205 DSS and (b) 2205-Cu DSS surface incubated in 2216E medium with P. aeruginosa for 14 d.

Table 8 Pit depths measured by CLSM on 2205 DSS and 2205-Cu DSS surface inoculated with P. aeruginosa for 14 d.

Sample	Largest pit depth (μm)	Average pit depth (μm)
2205-Cu DSS	2.2	1.4 ± 0.4
2205 DSS	12.5	4.8 ± 3.6

Fig. 11. Stochastic probability for pit depth of 2205 DSS and 2205-Cu DSS surface inoculated in 2216E medium with P. aeruginosa for 14 d: (a) cumulative probability plots showing the pit of a certain depth; (b) Gumbel probability plots; (c) pit probability.

Table 9 Relative atomic concentrations of main elements (at.%) of 2205-Cu DSS and 2205 DSS in the P. aeruginosa inoculated medium after 7 d and 14 d immersion.

Sample	Cl	C	N	O	Cr	Fe	Cu	Mg
2205-Cu DSS (7 d)	16.70	27.70	3.46	48.10	0.25	0.36	0.22	3.30
2205 DSS (7 d)	1.98	40.00	6.16	42.60	0	0	-	3.79
2205-Cu DSS (14 d)	5.97	35.30	3.47	44.10	0.68	0.89	0.45	3.99
2205 DSS (14 d)	2.51	58.60	6.37	26.30	0.20	0.22	-	2.11

Fig. 12. High resolution spectra of Cl 2p for 2205 DSS and 2205-Cu DSS with exposure to P. aeruginosa after 7 d (a) and 14 d (b) of incubation in 2216E medium.

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