A Green Conversion Coating on a Magnesium Alloy for Corrosion Protection

doi:10.1007/s40195-023-01582-z

Abstract

Abstract:

A novel coating on the Mg1Mn alloy was produced by anodic polarization combined with hydrothermal treatment (AP + H) in 0.1 M Na₂CO₃ solution. The microstructure and protection of the coating were evaluated. The coating consisted of MgCO₃, Mg(OH)₂ and MgO, and provided satisfactory protection in 3.5 wt% NaCl with a corrosion rate of 0.07 mm y⁻¹ in 72 h. However, after that period, the corrosion rate of the specimen increased due to the damage of the coating. The failure of the coating was strongly related to the second phase particles (e.g. Zr particles) or impurities in the matrix. The AP + H coating is supposed to be used as a primer coating for Mg applications in kitchen ware, biomedical areas or industry.

Key words: Coating, Magnesium alloy, Hydrothermal, Corrosion resistance

Tong Bu, Ruijie Jia, Tao Ying, Andrej Atrens, Pengbo Chen, Dajiang Zheng, Fuyong Cao. A Green Conversion Coating on a Magnesium Alloy for Corrosion Protection[J]. Acta Metallurgica Sinica (English Letters), 2023, 36(10): 1630-1648.

Figures/Tables 23

Fig. 1 Surface morphologies before the immersion test of the Mg1Mn alloy: a-c untreated, d-f AP treated, g-i AP + H treated

Fig. 2 Cross-sections and EDS mapping of the coated Mg1Mn alloy: a AP treated, b AP + H treated

Fig. 3 X-ray diffraction (XRD) patterns of the Mg1Mn alloy

Fig. 4 EDS of Mg1Mn alloy: a untreated, b AP treated, c AP + H treated

Table 1 Element concentration analysis of Mg1Mn alloy (wt%)

Sample	Mg	O	C	Mn
Untreated	99	-	-	1
AP treated	93	4	3	-
AP + H treated	46	49	5	-

Fig. 5 XPS spectra of the Mg1Mn alloy

Fig. 6 XPS of C 1s, Mg 1s and O 1s of Mg1Mn alloy before immersion testing: a-c AP treated, d-f AP + H treated

Fig. 7 Hydrogen evolution volume for the Mg1Mn alloy specimens during immersion testing at the OCP in 3.5 wt% NaCl solution for 7 days at 25 ± 1 °C

Fig. 8 OCP of Mg1Mn alloy specimens at the initial period of the immersion testing in 3.5 wt% NaCl solution

Fig. 9 Equivalent circuits used for EIS data fitting: a for EIS data with two capacitance arcs, b for EIS data with two capacitance arcs and an inductance arc

Fig. 10 Nyquist plots and the Rf of Mg1Mn specimens at the OCP in 3.5 wt% NaCl solution for 7 days at 25 ± 1 °C: a untreated Mg1Mn specimen, b AP treated specimen, c AP + H treated specimen, and d the film resistance, Rf, of the specimens versus immersion time

Table 2 Data from EIS fitting of the untreated Mg1Mn, AP and AP + H treated specimens at OCP in 3.5 wt% NaCl for 7 d

Sample	Time	R_s (Ω cm²)	CPE_f		R_f (Ω cm²)	CPE_dl		R_ct (Ω cm²)	R_L (Ω cm²)	L (H cm⁻²)	R_p (Ω cm²)
Sample	Time	R_s (Ω cm²)	Y_f (Ω⁻¹ cm⁻² sⁿ)	n	R_f (Ω cm²)	Y_dl (Ω⁻¹ cm⁻² sⁿ)	n	R_ct (Ω cm²)	R_L (Ω cm²)	L (H cm⁻²)	R_p (Ω cm²)
Untreated	1 h	19	1.25 × 10^-5	0.92	1493	1.55 × 10^-3	0.84	5989			2060
	6 h	18	1.13 × 10^-5	0.93	2526	8.85 × 10^-4	0.73	1902			3984
	1 d	18	1.08 × 10^-5	0.93	1809	1.13 × 10^-3	0.11	2343	3	4234	2000
	2 d	19	8.57 × 10^-6	0.93	698	1.68 × 10^-6	1.00	1564	1758	12,770	1647
	3 d	20	8.23 × 10^-6	0.91	620	1.98 × 10^-6	0.98	1338	353	19,370	1627
	4 d	20	9.13 × 10^-6	0.89	1024	2.57 × 10^-6	1.00	1171	2	13,040	1820
	5 d	21	1.14 × 10^-5	0.86	2589	3.14 × 10^-3	0.98	400	3	1184	2544
	6 d	24	1.07 × 10^-5	0.87	2612	1.17 × 10^-3	0.81	1086	796	3322	3017
	7 d	23	1.10 × 10^-5	0.87	2971	7.09 × 10^-4	0.98	975			3995
AP	1 h	16	1.12 × 10^-5	0.93	1740	1.61 × 10^-3	0.57	1255			2318
	6 h	18	9.95 × 10^-6	0.93	3028	7.37 × 10^-4	0.75	1913			4694
	1 d	20	1.11 × 10^-5	0.93	3300	7.18 × 10^-4	0.70	2142			4997
	2 d	23	1.13 × 10^-5	0.94	2860	1.98 × 10^-3	0.74	825	202	6189	3504
	3 d	24	7.66 × 10^-6	0.96	788	2.52 × 10^-6	0.96	1625	208	3152	2461
	4 d	27	1.02 × 10^-5	0.90	3067	1.24 × 10^-3	0.80	980	225	4245	3152
	5 d	32	9.72 × 10^-6	0.90	3384	5.81 × 10^-4	0.91	1708			5225
	6 d	34	8.23 × 10^-6	0.91	3174	4.66 × 10^-4	0.74	2931			5607
	7 d	36	7.95 × 10^-6	0.91	3725	3.96 × 10^-4	0.69	3641			6621
AP + H	1 h	19	2.41 × 10^-6	0.80	9841	3.10 × 10^-5	0.74	16,150			23,832
	6 h	20	4.18 × 10^-6	0.87	4783	6.53 × 10^-5	0.51	10,980			14,035
	1d	19	1.01 × 10^-5	0.91	3589	1.41 × 10^-4	0.66	800			4730
	2 d	17	1.18 × 10^-5	0.91	2977	1.38 × 10^-4	0.14	1012	98	18,080	2875
	3 d	17	1.24 × 10^-5	0.90	1626	2.00 × 10^-4	0.10	2040	200	11,990	2621
	4 d	18	1.06 × 10^-5	0.90	3332	4.78 × 10^-3	1.00	124			3667
	5 d	19	9.00 × 10^-6	0.90	3513	6.86 × 10^-4	0.74	1563			4895
	6 d	19	9.19 × 10^-6	0.91	3658	7.07 × 10^-4	0.76	1679			5140
	7 d	22	9.26 × 10^-6	0.91	3966	6.06 × 10^-4	0.76	1886			5653

Table 2 Data from EIS fitting of the untreated Mg1Mn, AP and AP + H treated specimens at OCP in 3.5 wt% NaCl for 7 d

Sample	Time	R_s (Ω cm²)	CPE_f		R_f (Ω cm²)	CPE_dl		R_ct (Ω cm²)	R_L (Ω cm²)	L (H cm⁻²)	R_p (Ω cm²)
Sample	Time	R_s (Ω cm²)	Y_f (Ω⁻¹ cm⁻² sⁿ)	n	R_f (Ω cm²)	Y_dl (Ω⁻¹ cm⁻² sⁿ)	n	R_ct (Ω cm²)	R_L (Ω cm²)	L (H cm⁻²)	R_p (Ω cm²)
Untreated	1 h	19	1.25 × 10^-5	0.92	1493	1.55 × 10^-3	0.84	5989			2060
	6 h	18	1.13 × 10^-5	0.93	2526	8.85 × 10^-4	0.73	1902			3984
	1 d	18	1.08 × 10^-5	0.93	1809	1.13 × 10^-3	0.11	2343	3	4234	2000
	2 d	19	8.57 × 10^-6	0.93	698	1.68 × 10^-6	1.00	1564	1758	12,770	1647
	3 d	20	8.23 × 10^-6	0.91	620	1.98 × 10^-6	0.98	1338	353	19,370	1627
	4 d	20	9.13 × 10^-6	0.89	1024	2.57 × 10^-6	1.00	1171	2	13,040	1820
	5 d	21	1.14 × 10^-5	0.86	2589	3.14 × 10^-3	0.98	400	3	1184	2544
	6 d	24	1.07 × 10^-5	0.87	2612	1.17 × 10^-3	0.81	1086	796	3322	3017
	7 d	23	1.10 × 10^-5	0.87	2971	7.09 × 10^-4	0.98	975			3995
AP	1 h	16	1.12 × 10^-5	0.93	1740	1.61 × 10^-3	0.57	1255			2318
	6 h	18	9.95 × 10^-6	0.93	3028	7.37 × 10^-4	0.75	1913			4694
	1 d	20	1.11 × 10^-5	0.93	3300	7.18 × 10^-4	0.70	2142			4997
	2 d	23	1.13 × 10^-5	0.94	2860	1.98 × 10^-3	0.74	825	202	6189	3504
	3 d	24	7.66 × 10^-6	0.96	788	2.52 × 10^-6	0.96	1625	208	3152	2461
	4 d	27	1.02 × 10^-5	0.90	3067	1.24 × 10^-3	0.80	980	225	4245	3152
	5 d	32	9.72 × 10^-6	0.90	3384	5.81 × 10^-4	0.91	1708			5225
	6 d	34	8.23 × 10^-6	0.91	3174	4.66 × 10^-4	0.74	2931			5607
	7 d	36	7.95 × 10^-6	0.91	3725	3.96 × 10^-4	0.69	3641			6621
AP + H	1 h	19	2.41 × 10^-6	0.80	9841	3.10 × 10^-5	0.74	16,150			23,832
	6 h	20	4.18 × 10^-6	0.87	4783	6.53 × 10^-5	0.51	10,980			14,035
	1d	19	1.01 × 10^-5	0.91	3589	1.41 × 10^-4	0.66	800			4730
	2 d	17	1.18 × 10^-5	0.91	2977	1.38 × 10^-4	0.14	1012	98	18,080	2875
	3 d	17	1.24 × 10^-5	0.90	1626	2.00 × 10^-4	0.10	2040	200	11,990	2621
	4 d	18	1.06 × 10^-5	0.90	3332	4.78 × 10^-3	1.00	124			3667
	5 d	19	9.00 × 10^-6	0.90	3513	6.86 × 10^-4	0.74	1563			4895
	6 d	19	9.19 × 10^-6	0.91	3658	7.07 × 10^-4	0.76	1679			5140
	7 d	22	9.26 × 10^-6	0.91	3966	6.06 × 10^-4	0.76	1886			5653

Fig. 11 Polarization curves of the Mg1Mn after immersion in 3.5 wt% NaCl for 30 min at 25 ± 1 °C

Table 3 Electrochemical data evaluated by Tafel fitting of the Mg1Mn specimen

Sample	i_corr (μA cm⁻²)	E_corr (V, Ag/AgCl/Sat KCl)	β_a (mV dec⁻¹)	β_c (mV dec⁻¹)
Untreated	29	− 1.61	104	− 213
AP	13	− 1.58	118	− 256
AP + H	0.3	− 1.54	161	− 148

Fig. 12 Surface of the Mg1Mn alloy with corrosion products after immersion testing at OCP in 3.5 wt% NaCl for 7 days: a, d, g Untreated, b, e, h AP treated and c, f, i AP + H treated

Fig. 13 Surface appearance of untreated Mg1Mn specimen without the corrosion products after immersion testing in 3.5 wt% NaCl for 7 days: a,b optical image, c, d SEM image

Fig. 14 Surface appearance of AP treated Mg1Mn specimen without the corrosion products after immersion testing in 3.5 wt% NaCl for 7 days: a,b optical images, c, d SEM images

Fig. 15 Surface appearance of AP + H treated Mg1Mn specimen without the corrosion products after immersion testing in 3.5 wt% NaCl for 7 days: a b optical images, c d SEM images

Fig. 16 X-ray diffraction (XRD) patterns of the Mg1Mn specimens containing corrosion products after immersion testing at OCP in 3.5 wt% NaCl for 7 days

Fig. 17 XPS of C 1s, Mg 1s O 1s and Mn 2p of the corrosion products for Mg1Mn specimens after immersion testing: a-d Untreated, e-g AP treated, h-j AP + H treated

Fig. 18 a Surface morphology of the AP + H treated specimen with the corrosion products after immersion at OCP in 3.5 wt% NaCl for 1 day, b the corresponding elemental mapping of region D

Fig. 19 a Surface morphology of the AP + H treated specimen without corrosion product, b the corresponding elemental mapping of Region E and the content of the elements

Fig. 20 Schematic diagram of failure for the coating prepared by AP + H in 3.5 wt% NaCl solution

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