Enhanced Bio-corrosion Resistance by Cu Alloying in a Micro-alloyed Pipeline Steel

doi:10.1007/s40195-022-01392-9

Abstract

Abstract:

On the composition base of commercial X65 grade pipeline steels, a Cu modified pipeline steel was designed to show improved resistance to microbially induced corrosion (MIC). The mechanical properties of the Cu-added steel and its corrosion behavior in a soil solution inoculated with sulfate-reducing bacteria (SRB) were investigated in this work. The results demonstrated that Cu-added steel exhibits a good combination of strength and toughness. Cu ions released from the Cu-added steel could effectively kill the SRB attaching on the steel surface, thus evidently decreased the pit depth and diameter of Cu-added steel. Furthermore, during the long-term immersion, the Cu-rich film formed by the enrichment of Cu in the corrosion product layer on the steel surface could also contribute to the improvement of the bio-corrosion resistance of Cu-added steel.

Key words: Pipeline steel, Mechanical property, Microbiologically influenced corrosion, Cu alloyed steel, Corrosion mechanism, Sulfate-reducing bacteria (SRB)

Yunpeng Zeng, Wei Yan, Xianbo Shi, Maocheng Yan, Yiyin Shan, Ke Yang. Enhanced Bio-corrosion Resistance by Cu Alloying in a Micro-alloyed Pipeline Steel[J]. Acta Metallurgica Sinica (English Letters), 2022, 35(10): 1731-1743.

Figures/Tables 18

Table 1 Chemical compositions of the experimental steels (wt%)

Steel	C	Si	Mn	S	P	Cu	Nb	Ti	Mo	Fe
Cu-added steel	0.02	0.010	0.07	0.002	0.005	1.34	0.04	0.017	0.1	Bal.
Cu-free steel	0.06	0.014	1.64	0.001	0.010	< 0.01	0.04	0.013	0.1	Bal.

Table 2 Physicochemical properties of the dried soil

Soil type	pH	Chemical composition (mg kg^-1 soil)
Soil type	pH	${\text{NO}}_{3}^{ - }$	${\text{Cl}}^{ - }$	${\text{SO}}_{4}^{2 - }$	${\text{HCO}}_{3}^{ - }$	${\text{Ca}}^{2 + }$	${\text{Mg}}^{2 + }$	${\text{K}}^{ + }$	${\text{Na}}^{ + }$	Organic content	Whole nitrogen content	Total salt content
Meadow soil	7.75	46	31	48	234	57	32	2	4	2.26 × 10⁴	910	464

Fig. 1 Optical microstructures and the corresponding TEM images of Cu-added steel a, b; Cu-free steel c, d. Inset of b shows the EDS mapping image of Cu in b

Table 3 Mechanical properties of Cu-added steel and Cu-free steel

Steel	YS (MPa)	UTS (MPa)	EL (%)	CVN (J)
Cu-added steel	606	670	23.5	324
Cu-free steel	480	602	26.2	350

Fig. 2 Variations of open circuit potential (EOCP) and linear polarization resistance (Rp) with immersion time for Cu-added and Cu-free steels: a EOCP; b Rp

Fig. 3 Electrochemical impedance spectra of Cu-free steel a, b; Cu-added steel c, d exposed to the SRB-incubated soil solution for different time

Fig. 4 Equivalent circuit models used for EIS fitting analysis: a equivalent circuit for one-time constant, b equivalent circuit for two-time constant, c time dependence of Rct + Rf derived from EIS date of SRB-containing SES

Table 4 Parameters derived from EIS data of Cu-free steel and Cu-added steel after immersions in SRB-incubated soil solution

Time (d)	R_s (Ω cm²⁾	Y_f (S sⁿ cm^-2)	n_f	R_f (Ω cm²)	Y_dl (S sⁿ cm^-2)	n_dl	R_ct (Ω cm²)	∑χ
Cu-free steel
1	353.3	-	-	-	1.170 × 10^-4	0.8508	7.782 × 10⁴	5.12 × 10^-4
3	318.7	-	-	-	1.072 × 10^-4	0.8902	1.443 × 10⁴	6.13 × 10^-4
5	291.0	-	-	-	1.261 × 10^-4	0.8857	2.797 × 10⁴	9.69 × 10^-4
7	281.4	-	-	-	1.577 × 10^-4	0.8396	3.644 × 10⁴	7.85 × 10^-4
14	227.4	8.017 × 10^-4	0.7838	25.47	6.945 × 10^-4	0.8598	1.290 × 10⁴	9.64 × 10^-5
21	202.7	7.521 × 10^-4	0.9547	11.59	8.729 × 10^-4	0.8511	2.699 × 10⁴	1.19 × 10^-4
28	180.2	7.756 × 10^-4	0.9873	7.153	9.662 × 10^-4	0.8447	3.642 × 10⁴	2.08 × 10^-4
Cu-added steel
1	336.7	-	-	-	1.202 × 10^-4	0.8096	5.465 × 10⁴	5.74 × 10^-4
3	311.7	-	-	-	7.821 × 10^-5	0.8763	4.314 × 10⁴	1.34 × 10^-3
5	278.2	-	-	-	6.829 × 10^-5	0.8613	6.920 × 10⁴	7.08 × 10^-4
7	275.6	-	-	-	1.856 × 10^-4	0.7191	6.015 × 10⁴	7.22 × 10^-4
14	217.9	1.123 × 10^-3	0.7236	2803	1.986 × 10^-3	0.9837	2.498 × 10⁴	5.29 × 10^-5
21	194.6	1.256 × 10^-3	0.9329	3335	2.094 × 10^-3	0.9388	4.088 × 10⁴	2.60 × 10^-4
28	176.4	1.128 × 10^-3	0.6510	3369	2.650 × 10^-3	0.9950	4.182 × 10⁴	5.06 × 10^-4

Fig. 5 Potentiodynamic polarization curves of Cu-added and Cu-free steels after 28-day immersion

Fig. 6 CLSM images of live/dead staining biofilms on the steel surface of Cu-free steel a, Cu-added steel b after 14 days incubation with SRB

Fig. 7 SEM images of surface morphologies of Cu-free steel a, Cu-added steel c after 28 days immersion in the SRB-incubated soil solution; b, d magnified images of a, c, respectively

Fig. 8 EDS elemental analyses of films formed on surfaces of Cu-free steel a, Cu-added steel b after 28 days immersion in SRB culture medium

Table 5 Quantitative analysis results of films formed on Cu-free steel and Cu-added steel surfaces (wt%)

Steels	Fe	C	O	S	Cu	Al	Si	Mn
Cu-free steel	49.74	14.78	26.88	5.25	-	1.25	1.59	0.5
Cu-added steel	76.45	9.12	8.79	3.32	2.00	-	0.32	-

Fig.9 EPMA mapping data of the cross section of corrosion products on Cu-free steel a, Cu-added steel b after 28 days immersion in SRB-incubated soil solution

Fig. 10 SEM images of surface morphologies of Cu-free steel a, Cu-added steel b after 28 days immersion in the SRB-incubated soil solution after removing biofilm and corrosion products

Fig. 11 Maximum pit depths and the corresponding data (red line) on the surface of Cu-free steel a, b, Cu-added steel c, d after 28 days immersion in the SRB-incubated soil solution

Fig. 12 Pit depths and pit diameters (${D}_{\mathrm{eq}}$) of two steels after 28 days immersion in SRB culture medium

Fig. 13 Schematic illustrations of SRB corrosion mechanisms for Cu-free steel a, Cu-added steel b

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