Corrosion Behavior of Zn-2.0Al-1.5Mg Coatings in Simulated Marine Atmosphere
GU Tianzhen1,2,3, LIU Yuwei1,3(), PENG Can1,2,3, ZHANG Peng4, WANG Zhenyao1,3(), WANG Chuan1,3, MA Cheng4, CAO Hongwei4
1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China 2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China 3 Liaoning Shenyang Soil and Atmosphere Corrosion of Materials National Observation and Research Station, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China 4 HBIS Group Technology Research Institute, Shijiazhuang 050023, China
Cite this article:
GU Tianzhen, LIU Yuwei, PENG Can, ZHANG Peng, WANG Zhenyao, WANG Chuan, MA Cheng, CAO Hongwei. Corrosion Behavior of Zn-2.0Al-1.5Mg Coatings in Simulated Marine Atmosphere. Acta Metall Sin, 2025, 61(2): 278-286.
As the service environment changes, the widely used galvanized coating faces challenges due to its overly thick coating and insufficient corrosion resistance. Zn-2.0Al-1.5Mg coatings have emerged as an alternative to conventional galvanizing because of their excellent corrosion resistance and are extensively used in buildings, home appliances, and automobiles in harsh environments. The marine environment, known for its high corrosiveness, faces considerable material corrosion problems. Highly resistant materials, such as Zn-2.0Al-1.5Mg coating, stainless steel, have found applications in the marine environment. However, the development period of Zn-2.0Al-1.5Mg coating is short, and further research is required to determine its suitability for highly corrosive marine atmospheric environments. Consequently, the laboratory dry-wet alternating cycle corrosion test method, corrosion mass loss, SEM, XRD, EIS, and potentiodynamic polarization were used to investigate the corrosion behavior (e.g., corrosion kinetics, corrosion product evolution, corrosion morphology, and electrochemical behavior) of Zn-2.0Al-1.5Mg coatings in a simulated marine atmosphere. Results show that the initial corrosion product is ZnO at 168 h, with Zn5(OH)8Cl2·H2O appearing after 168 h of corrosion cycles (336, 504, 672, 840, and 1848 h). The emergence of ZnO at 168 h is attributed to the shortened dry-wet alternating cycle time, while that of Zn(OH)2·0.5H2O at 1848 h is attributed to the depletion of Mg or Al elements. The corrosion rate of Zn-2.0Al-1.5Mg coatings in the simulated marine atmosphere exhibited an M-shaped curve over time, closely related to the evolution of corrosion products. Between 0 and 840 h, the corrosion rate increased, except for a decrease between 336 and 504 h; this trend may be attributed to the disappearance of ZnO and an increase in the amount of Zn5(OH)8Cl2·H2O. Combined with the electrochemical results, it is speculated that the corrosion will accelerate with further exposure after 1848 h.
Corresponding Authors:
LIU Yuwei, associate professor, Tel: (024)23893544, E-mail: ywliu12s@imr.ac.cn; WANG Zhenyao, professor, Tel: (024)23893544, E-mail: zhywang@imr.ac.cn
Fig.1 Mass losses (a) and average corrosion rates (b) of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time (V—corrosion rate, t—corrosion time)
Fig.2 XRD spectra of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time
Fig.3 Macromorphologies of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time (a) 168 h (b) 840 h (c) 1848 h
Fig.4 Surface SEM images of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time (a) 168 h (b) 336 h (c) 504 h (d) 672 h (e) 840 h (f) 1848 h
Fig.5 Cross-sectional SEM images of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time (a) 168 h (b) 336 h (c) 504 h (d) 672 h (e) 840 h (f) 1848 h
Fig.6 SEM image and corresponding EDS mappings of elements of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at 1848 h
Fig.7 Potentiodynamic curves of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time (E—potential, i—current density, SCE—saturated calomel electrode)
Fig.8 Corrosion current density (icorr) of Zn-2.0Al-1.5Mg coating obtains by Tafel extrapolation after different exposure periods
Fig.9 Nyquist (a) and Bode (b) diagrams of Zn-2.0Al-1.5Mg coating in the simulated marine atmosphere at different time (Z'—impedance real part, Z"—impedance imaginary part, Z—impedance)
Fig.10 Equivalent circuit of EIS (Rs—electrolyte resistance, Rr—rust layer resistance, Rct—charge transfer resistance, Qr—rust layer capacitance, Qdl—double layer capacitance, EIS—electrical impedance spectroscopy)
Time
h
Rs
Ω·cm2
Qr
Rr
Ω·cm2
Qdl
Rct
Ω·cm2
Chi-squared
Rp (= Rr + Rct)
Ω·cm2
yr
Ω-1·cm-2·S
nr
ydl
Ω-1·cm-2·S
ndl
0
4.33 × 101
1.30 × 10-5
6.56 × 10-1
7.20 × 103
6.26 × 10-5
9.71 × 10-1
6.44 × 103
9.29 × 10-3
1.36 × 104
168
5.05 × 101
1.48 × 10-5
6.81 × 10-1
8.26 × 102
2.05 × 10-3
5.23 × 10-1
8.94 × 102
5.87 × 10-3
1.72 × 103
336
8.53 × 10-4
2.02 × 10-5
4.65 × 10-1
2.31 × 102
6.74 × 10-7
9.60 × 10-1
2.87 × 104
2.39 × 10-2
2.89 × 104
504
2.51 × 101
1.07 × 10-5
6.95 × 10-1
2.84 × 103
1.19 × 10-4
6.36 × 10-1
5.52 × 103
7.11 × 10-3
8.36 × 103
672
4.21 × 10-3
3.03 × 10-5
4.58 × 10-1
7.89 × 102
2.09 × 10-7
1.00 × 100
6.33 × 103
6.47 × 10-3
7.12 × 103
840
3.07 × 101
1.77 × 10-5
5.50 × 10-1
5.52 × 103
4.13 × 10-4
8.78 × 10-1
4.59 × 103
4.34 × 10-2
1.01 × 104
1848
3.14 × 10-23
1.51 × 10-3
8.38 × 10-2
4.70 × 10-19
4.63 × 10-7
7.34 × 10-1
5.95 × 102
7.36 × 10-4
5.95 × 102
Table 1 Impedance parameters of Zn-2.0Al-1.5Mg coating after being fitted
Fig.11 Variations of 1/ Rp after different corrosion periods
Fig.12 Variations of the equilibrium concentration of chloride solution () of NaCl solution with different relative humidities[37]
1
Gong J J, Li W T, Zhou Y. Development of hot dip galvanized aluminum and magnesium coated plate and application status of Hegang and Tangshan Steel [J]. Hebei Metall., 2020, 12: 9
Prosek T, Nazarov A, Goodwin F, et al. Improving corrosion stability of Zn-Al-Mg by alloying for protection of car bodies [J]. Surf. Coat. Technol., 2016, 306: 439
3
Prosek T, Nazarov A, Le Gac A, et al. Coil-coated Zn-Mg and Zn-Al-Mg: Effect of climatic parameters on the corrosion at cut edges [J]. Prog. Org. Coat., 2015, 83: 26
4
LeBozec N, Thierry D, Peltola A, et al. Corrosion performance of Zn-Mg-Al coated steel in accelerated corrosion tests used in the automotive industry and field exposures [J]. Mater. Corros., 2013, 64: 969
5
Ahmadi M, Salgın B, Kooi B J, et al. Genesis and mechanism of microstructural scale deformation and cracking in ZnAlMg coatings [J]. Mater. Des., 2020, 186: 108364
6
Van Schaik M, Dane C, Berkhout B. MagiZinc—The new high performance coating for steel in the BIW and closures [A]. SAE 2016 World Congress and Exhibition [C]. New York: SAE, 2016: 0537
7
Schürz S, Luckeneder G H, Fleischanderl M, et al. Chemistry of corrosion products on Zn-Al-Mg alloy coated steel [J]. Corros. Sci., 2010, 52: 3271
8
Prosek T, Larché N, Vlot M, et al. Corrosion performance of Zn-Al-Mg coatings in open and confined zones in conditions simulating automotive applications [J]. Mater. Corros., 2010, 61: 412
9
Thierry D, LeBozec N, Le Gac A, et al. Long-term atmospheric corrosion rates of hot dip galvanised steel and zinc-aluminium-magnesium coated steel [J]. Mater. Corros., 2019, 70: 2220
10
Keppert T A, Luckeneder G, Stellnberger K H, et al. The effect of sulphate, phosphate, nitrate and acetate on the corrosion behaviour of Zn-Al-Mg hot-dip galvanised steel [J]. Mater. Corros., 2014, 65: 560
11
Bobzin K, Oete M, Linke T F, et al. Corrosion of wire arc sprayed ZnMgAl [J]. Mater. Corros., 2015, 66: 520
12
Dutta M, Halder A K, Singh S B. Morphology and properties of hot dip Zn-Mg and Zn-Mg-Al alloy coatings on steel sheet [J]. Surf. Coat. Technol., 2010, 205: 2578
13
Yao C Z, Tay S L, Zhu T P, et al. Effects of Mg content on microstructure and electrochemical properties of Zn-Al-Mg alloys [J]. J. Alloys Compd., 2015, 645: 131
14
Schuerz S, Fleischanderl M, Luckeneder G H, et al. Corrosion behaviour of Zn-Al-Mg coated steel sheet in sodium chloride-containing environment [J]. Corros. Sci., 2009, 51: 2355
15
Liu Y, Ooi A, Tada E, et al. Electrochemical monitoring of the degradation of galvanized steel in simulated marine atmosphere [J]. Corros. Sci., 2019, 147: 273
doi: 10.1016/j.corsci.2018.11.013
16
Zhang X, Leygraf C, Wallinder I O. Atmospheric corrosion of Galfan coatings on steel in chloride-rich environments [J]. Corros. Sci., 2013, 73: 62
17
Wallinder I O, Leygraf C. A critical review on corrosion and runoff from zinc and zinc-based alloys in atmospheric environments [J]. Corrosion, 2017, 73: 1060
18
Xie Y X, Jin X Y, Wang L. Development and application of hot-dip galvanized zinc-aluminum-magnesium coating [J]. J. Iron Steel Res., 2017, 29: 167
Sullivan J, Cooze N, Gallagher C, et al. In situ monitoring of corrosion mechanisms and phosphate inhibitor surface deposition during corrosion of zinc-magnesium-aluminium (ZMA) alloys using novel time-lapse microscopy [J]. Faraday Discuss., 2015, 180: 361
doi: 10.1039/c4fd00251b
pmid: 25912828
20
Sullivan J, Mehraban S, Elvins J. In situ monitoring of the microstructural corrosion mechanisms of zinc-magnesium-aluminium alloys using time lapse microscopy [J]. Corros. Sci., 2011, 53: 2208
21
Li F, Lv J S, Yang H G, et al. The corrosion behavior for Zn-Al-Mg coating in NaCl system [J]. China Surf. Eng., 2011, 24(4): 25
Oh M S, Kim S H, Kim J S, et al. Surface and cut-edge corrosion behavior of Zn-Mg-Al Alloy-coated steel sheets as a function of the alloy coating microstructure [J]. Met. Mater. Int., 2016, 22: 26
23
Zhou H, Zhao A M, Xiao J, et al. Advances in continuous hot dip galvanizing of advanced high strength steels [A]. The Chinese Society for Metals. The 13th China Steel Annual Conference 5. Surface and Coating [C]. Beijing: Metallurgical Industry Press, 2022: 119
Persson D, Prosek T, LeBozec N, et al. Initial SO2-induced atmospheric corrosion of ZnAlMg coated steel studied with in situ Infrared Reflection Absorption Spectroscopy [J]. Corros. Sci., 2015, 90: 276
25
Prosek T, Hagström J, Persson D, et al. Effect of the microstructure of Zn-Al and Zn-Al-Mg model alloys on corrosion stability [J]. Corros. Sci., 2016, 110: 71
26
Salgueiro Azevedo M, Allély C, Ogle K, et al. Corrosion mechanisms of Zn(Mg,Al) coated steel: The effect of HCO 3 - and NH 4 + ions on the intrinsic reactivity of the coating [J]. Electrochim. Acta, 2015, 153: 159
27
Thierry D, Persson D, Luckeneder G, et al. Atmospheric corrosion of ZnAlMg coated steel during long term atmospheric weathering at different worldwide exposure sites [J]. Corros. Sci., 2019, 148: 338
28
Salgueiro Azevedo M, Allély C, Ogle K, et al. Corrosion mechanisms of Zn(Mg, Al) coated steel: 2. The effect of Mg and Al alloying on the formation and properties of corrosion products in different electrolytes [J]. Corros. Sci., 2015, 90: 482
29
Volovitch P, Vu T N, Allély C, et al. Understanding corrosion via corrosion product characterization: II. Role of alloying elements in improving the corrosion resistance of Zn-Al-Mg coatings on steel [J]. Corros. Sci., 2011, 53: 2437
30
Salgueiro Azevedo M, Allély C, Ogle K, et al. Corrosion mechanisms of Zn(Mg, Al) coated steel in accelerated tests and natural exposure: 1. The role of electrolyte composition in the nature of corrosion products and relative corrosion rate [J]. Corros. Sci., 2015, 90: 472
31
Diler E, Rouvellou B, Rioual S, et al. Characterization of corrosion products of Zn and Zn-Mg-Al coated steel in a marine atmosphere [J]. Corros. Sci., 2014, 87: 111
32
Li F, Lv J S, Yang H G, et al. Research on ZnAlMg coated steel sheet [J]. Steel Rolling, 2013, 30(2): 45
Liu Y W, Zhao H T, Wang Z Y. Initial corrosion behavior of carbon steel and weathering steel in Nansha Marine atmosphere [J]. Acta Metall. Sin., 2020, 56: 1247
doi: 10.11900/0412.1961.2020.00013
Liu Y W, Gu T Z, Wang Z Y, et al. Corrosion behavior of Q235 and Q450NQR1 exposed to marine atmospheric environment in Nansha, China for 34 months [J]. Acta Metall. Sin., 2022, 58: 1623
doi: 10.11900/0412.1961.2021.00576
Hosking N C, Ström M A, Shipway P H, et al. Corrosion resistance of zinc-magnesium coated steel [J]. Corros. Sci., 2007, 49: 3669
36
Bernard M C, Goff A H L, Phillips N. In situ Raman study of the corrosion of zinc-coated steel in the presence of chloride: I. Characterization and stability of zinc corrosion products [J]. J. Electrochem. Soc., 1995, 142: 2162
37
Graedel T E. Corrosion mechanisms for zinc exposed to the atmosphere [J]. J. Electrochem. Soc., 1989, 136: 193C
38
Chen Z Y, Cui F, Kelly R G. Calculations of the cathodic current delivery capacity and stability of crevice corrosion under atmospheric environments [J]. J. Electrochem. Soc., 2008, 155: C360
39
Gu T Z, Zhang P, Guo M X, et al. Corrosion behavior of zinc-aluminum-magnesium coated steel in simulated marine atmosphere [J]. Int. J. Electrochem. Sci., 2022, 17: 22054