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Acta Metall Sin  2018, Vol. 54 Issue (7): 1019-1030    DOI: 10.11900/0412.1961.2017.00437
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Corrosion Behavior of Fe-Based Laser Cladding Coating in Hydrochloric Acid Solutions
Li FAN1,2, Haiyan CHEN1(), Yaohua DONG1,3, Xueying LI1, Lihua DONG1, Yansheng YIN1
1 College of Ocean Science and Engineering, Shanghai Maritime University, Shanghai 201306, China
2 Department of Marine Engineering, Nantong Shipping College, Nantong 226010, China
3 School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
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Abstract  

30CrMo alloy steel has a wide range of applications in the petrochemical industry such as the valve bodies and valve covers of subsea Christmas tree, and oil drilling pipes that working in strong acid environment. Therefore, the methods to improve the corrosion resistance of 30CrMo steel by surface modification techniques have become a hot topic of research. Laser cladding Fe-based coatings are regarded as promising materials, because of their high bonding strength, good hardness and excellent wear and corrosion resistance, and they might replace more expensive Co-based or Ni-based alloys. Additions of Cr, Mo, Y, Co and Ni are benefit to improve the corrosion resistance of Fe-based coatings. However, Cr, Y, Co and Mo are expensive. With consideration of reducing the materials cost, and at the same time maintaining the excellent corrosion resistance, a novel Fe-based alloy without, Y, Co and minor Mo content is synthesized. Therefore, in this study, to improve the corrosion resistance of 30CrMo alloy, the novel synthesized Fe-based powder was prepared on the surface by laser cladding. The microstructure, chemical and phase compositions of the fabricated coating were measured systemically by using a SEM equipment with EDS spectrometer, and XRD. The corrosion behavior of this Fe-based coating in 0.5 mol/L HCl solution were studied by polarization curve and EIS measurements, combined with immersion tests. The passive film formed on the surface of the alloy after immersion in the 0.5 mol/L HCl solution for 3 d was analyzed by XPS. The microstructure is mainly composed of dendrites and interdendritic phases, which are confirmed as austenite γ-Fe phase and the eutectics γ-Fe/M23C6. Similar to 304 stainless steel, the Fe-based alloy coating with a very broad passive region, shows positive corrosion potential and less corrosion current density than that of 30CrMo alloy steel. This indicates that the corrosion resistance of the Fe-based coating is superior to 30CrMo alloy steel, and almost the same as 304 stainless steel. The immersion tests show that the corrosion mechanisms of the coating are the combination of anodic dissolution and passive film protection. As for the eutectic region rich in Cr and Mo, the destruction and corrosion of this area in HCl solution are slowed down due to the passivation of Cr and Mo. The passive film is mainly composed of Cr2O3, FeCr2O4 and MoO3. The main reason for the excellent corrosion resistance of the coating is the mechanical barrier effect of the passivation effect of the high density composite oxide film.

Key words:  Fe-based alloy coating      laser cladding      electrochemical corrosion      passivation film      corrosion resistance     
Received:  20 October 2017     
ZTFLH:  TG174.44  
Fund: Supported by National Natural Science Foundation of China (No.51609133), China Postdoctoral Science Foundation (No.2017M620153), Ocean Public Science and Technology Research Fund Projects of China (No.201405013-3) and Science and Technology Program of Shanghai Maritime University (No.20130448)

Cite this article: 

Li FAN, Haiyan CHEN, Yaohua DONG, Xueying LI, Lihua DONG, Yansheng YIN. Corrosion Behavior of Fe-Based Laser Cladding Coating in Hydrochloric Acid Solutions. Acta Metall Sin, 2018, 54(7): 1019-1030.

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2017.00437     OR     https://www.ams.org.cn/EN/Y2018/V54/I7/1019

Material C Si Mn P S Cr Mo Ni Fe
Fe-based powder 0.20 1.20 1.50 - - 16.80 2.60 11.50 Bal.
304SS 0.07 0.90 2.00 0.03 0.03 19.00 - 10.00 Bal.
30CrMo 0.30 0.17~0.37 0.40~0.70 <0.025 <0.025 0.80~1.10 0.15~0.25 ≤0.03 Bal.
Table 1  Chemical compositions of the Fe-based powder, 304 stainless steel (304SS) and 30CrMo (mass fraction / %)
Fig.1  SEM image (a) and particle size distribution (b) of Fe-based powder (Inset in Fig.1a show the enlarged view)
Fig.2  XRD spectra of the Fe-based powder and coating
Fig.3  Schaeffler diagram of the coating (Creq—chromium equivalent; Nieq—nickel equivalent)
Fig.4  Low (a) and high (b) magnified surface SEM images of the coating, and EDS analyses of dentritic region (c) and interdendritic region (d) in Fig.4b
Fig.5  Cross-section SEM images of whole section (a), interface of coating and substrate (b), middle part of the coating (c) and top surface of the coating (d)
Fig.6  Potentiodynamic polarization curves of Fe-based coating, 304SS and 30CrMo steel in 0.5 mol/L HCl solution (E—potential; i—current density; ip—passive current density)
Material Ecorr / mV icorr / (μAcm-2) Rp / Ω βa / (mVdec-1) βc / (mVdec-1)
Fe-based coating -365.12 78.18 186.68 70.238 64.440
304SS -380.68 112.73 113.16 87.571 44.202
30CrMo -448.90 365.59 71.70 213.810 84.089
Table 2  Fitting results of potention dynamic polarization curves in 0.5 mol/L HCl solution
Fig.7  Nyquist plots (a), Bode impedance plots (b) of different alloys in 0.5 mol/L HCl solution (θmax—maximum phase angle)
Fig.8  Equivalent electric circuit of EIS fitting for Fe-based coating and 304SS (a), equivalent electric circuit of EIS fitting for 30CrMo (b) (Rs—solution resistance; Qdl—electric double layer capacitance; Rct—charge transfer resistance; L—inductance; RL—resistance of corrosion product layer)
Material Rs Qdl Rct L RL
Ωcm2 Y0 / (Ω-1cm-2sn) n Ωcm2 Hcm-2 Ωcm2
Fe-based coating 2.438 2.11×10-4 0.9609 519.8 - -
304SS 2.452 2.32×10-4 0.9236 473.2 - -
30CrMo 1.966 3.94×10-5 0.8359 94.8 134.9 73.49
Table 3  EIS fitting results of Fe-based coating, 304SS and 30CrMo in 0.5 mol/L HCl solution
Fig.9  Full survey (a) and O (b), Fe (c), Cr (d), Ni (e) and Mo (f) high resolution XPS spectra of passive film of Fe-based coating exposed to 0.5 mol/L HCl solution for 3 d
Fig.10  Low (a, c, e) and high (b, d, f) magnified surface corrosion SEM images of Fe-based coating exposed to 0.5 mol/L HCl solution for 1 d (a, b), 3 d (c, d) and 7 d (e, f), and EDS of regions A (g) and B (h) marked in Fig.10d
Fig.11  2D (a, c, e) and 3D (b, d, f) corroded surfaces of Fe-based coating exposed to 0.5 mol/L HCl solution for 1 d (a, b), 3 d (c, d) and 7 d (e, f) scanned using a profilometer
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