Please wait a minute...
Acta Metall Sin  2018, Vol. 54 Issue (7): 1019-1030    DOI: 10.11900/0412.1961.2017.00437
Current Issue | Archive | Adv Search |
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
Download:  HTML  PDF(9560KB) 
Export:  BibTeX | EndNote (RIS)      

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:     OR

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
[1] Martínez-Cazares G M, Almanza A, Almanza E, et al. Enhanced hardenability and tempering resistance of AISI 4130 steel by Ni addition[J]. Mater. Perform. Charact., 2016, 5: 202
[2] Danaee I, Khomami M N, Attar A A.Corrosion behavior of AISI 4130 steel alloy in ethylene glycol-water mixture in presence of molybdate[J]. Mater. Chem. Phys., 2012, 135: 658
[3] Hutasoit N, Luzin V, Blicblau A, et al.Fatigue life of laser clad hardfacing alloys on AISI 4130 steel under rotary bending fatigue test[J]. Int. J. Fatigue, 2015, 72: 42
[4] Katakam S, Santhanakrishnan S, Dahotre N B.Fe-based amorphous coatings on AISI 4130 structural steel for corrosion resistance[J]. JOM, 2012, 64: 709
[5] Abioye T E, McCartney D G, Clare A T. Laser cladding of Inconel 625 wire for corrosion protection[J]. J. Mater. Process. Technol., 2015, 217: 232
[6] Li Q H, Savalani M M, Zhang Q M, et al.High temperature wear characteristics of TiC composite coatings formed by laser cladding with CNT additives[J]. Surf. Coat. Technol., 2014, 239: 206
[7] Pereira J, Zambrano J, Licausi M, et al. Tribology and high temperature friction wear behavior of MCrAlY laser cladding coatings on stainless steel [J]. Wear, 2015, 330-331: 280
[8] Kusmoko A, Dunne D P, Li H.A Comparative study for wear resistant of Stellite 6 coatings on nickel alloy substrate produced by laser cladding, HVOF and plasma spraying techniques[J]. Int. J. Curr. Eng. Technol., 2014, 4: 32
[9] Pan J, Zhang M, Chen Q, et al.Study of anticorrosion ability of Fe43.7Co7.3Cr14.7Mo12.6C15.5B4.3Y1.9 bulk metallic glass in strong acid solutions[J]. Rare Met. Mater. Eng., 2008, 37(Suppl.4): 805(潘杰, 张猛, 谌祺等. FeCoCrMoCBY块体非晶合金在强酸介质中的耐蚀性能[J]. 稀有金属材料与工程, 2008, 37(增刊4): 805)
[10] Zhou Z, Wang L, Wang F C, et al.Formation and corrosion behavior of Fe-based amorphous metallic coatings by HVOF thermal spraying[J]. Surf. Coat. Technol., 2009, 204: 563
[11] Fan H B, Zheng W, Wang G Y, et al.Corrosion behavior of Fe41Co7Cr15Mo14C15B6Y2 bulk metallic glass in sulfuric acid solutions[J]. Metall. Mater. Trans., 2011, 42A: 1524
[12] Liu L, Zhang C.Fe-based amorphous coatings: Structures and properties[J]. Thin Solid Films, 2014, 561: 70
[13] Huang Y J, Guo Y Z, Fan H B, et al.Synthesis of Fe-Cr-Mo-C-B amorphous coating with high corrosion resistance[J]. Mater. Lett., 2012, 89: 229
[14] Wang Y, Zheng Y G, Wang J Q, et al.Passivation behavior of Fe-based amorphous metallic coating in NaCl and H2SO4 solutions[J]. Acta Metall. Sin., 2015, 51: 49(王勇, 郑玉贵, 王建强等. 铁基非晶涂层在NaCl和H2SO4溶液中的钝化行为[J]. 金属学报, 2015, 51: 49)
[15] Long Z L, Chang C T, Ding Y H, et al.Corrosion behavior of Fe-based ferromagnetic (Fe, Ni)-B-Si-Nb bulk glassy alloys in aqueous electrolytes[J]. J. Non-Cryst. Solids, 2008, 354: 4609
[16] Li J W, Yang L J, Ma H R, et al.Improved corrosion resistance of novel Fe-based amorphous alloys[J]. Mater. Des., 2016, 95: 225
[17] Wang W, Zhang C, Xu P, et al.Enhancement of oxidation and wear resistance of Fe-based amorphous coatings by surface modification of feedstock powders[J]. Mater. Des., 2015, 73: 35
[18] Ma H R, Chen X Y, Li J W, et al.Fe-based amorphous coating with high corrosion and wear resistance[J]. Surf. Eng., 2017, 33: 56
[19] Chen Q J, Hu L L, Zhou X L, et al. Effect of corrosive medium on the corrosion resistance of FeCrMoCB amorphous alloy coating [J]. Adv. Mater. Res., 2011, 291-294: 65
[20] Veinthal R, Sergejev F, Zikin A, et al.Abrasive impact wear and surface fatigue wear behaviour of Fe-Cr-C PTA overlays[J]. Wear, 2013, 301: 102
[21] Hou Q Y.Influence of molybdenum on the microstructure and properties of a FeCrBSi alloy coating deposited by plasma transferred arc hardfacing[J]. Surf. Coat. Technol., 2013, 225: 11
[22] Lou M.Microstructure, mechanical properties and wear resistance of Fe-based coating deposited by PTA hardfacing [D]. Changsha: Central South University, 2014(娄明. 等离子堆焊Fe基涂层结构、力学性能和耐磨性的研究 [D]. 长沙: 中南大学, 2014)
[23] Wang Y B.Laser cladding prepare coating with wear resistance and corrosion resistance [D]. Harbin: Harbin Engineering University, 2009(王一博. 激光熔覆制备耐磨耐蚀涂层 [D]. 哈尔滨: 哈尔滨工程大学, 2009)
[24] Sun H Y, Zhou Z J, Wang M, et al.Microstructures and mechanical properties of a new 310 austenitic stainless steel during long term aging[J]. Chin. J. Eng., 2015, 37: 600(孙红英, 周张健, 王曼等. 改进310奥氏体不锈钢长期时效后的组织与性能[J]. 工程科学学报, 2015, 37: 600)
[25] Rojacz H, Zikin A, Mozelt C, et al.High temperature corrosion studies of cermet particle reinforced NiCrBSi hardfacings[J]. Surf. Coat. Technol., 2013, 222: 90
[26] Sun Y Z, Liu S, Li J B, et al.Effect of Fe content on microstructure and properties of laser clad layer[J]. Mater. Rev., 2017, 31(4): 75(孙有政, 刘帅, 李进宝等. 铁含量对激光熔覆层微结构及性能的影响[J]. 材料导报, 2017, 31(4): 75)
[27] Zhang H, Zhang C H, Wang Q, et al.Effect of Ni content on stainless steel fabricated by laser melting deposition[J]. Opt. Laser Technol., 2018, 101: 363
[28] Xu Q G.Study on laser cladding layer of iron based alloy reinforced by ceramic particle [D]. Ji'nan: Shandong University, 2012(徐勤官. 陶瓷颗粒增强铁基合金激光熔覆层的研究 [D]. 济南: 山东大学, 2012)
[29] Jiang C P.The microstructure and properties of Fe-based amorphous coatings fabricated by plasma spraying [D]. Xi'an: Chang'an University, 2015(姜超平. 等离子喷涂铁基非晶涂层结构与性能研究 [D]. 西安: 长安大学, 2015)
[30] Hu Y B, Dong C F, Sun M, et al.Effects of solution pH and Cl- on electrochemical behaviour of an Aermet100 ultra-high strength steel in acidic environments[J]. Corros. Sci., 2011, 53: 4159
[31] Cao C N.Principles of electrochemistry of corrosion [M]. 3rd Ed., Beijing: Chemical Industry Press., 2008: 176(曹楚南. 腐蚀电化学原理 [M]. 第3版. 北京: 化学工业出版社2008: 176)
[32] Kocijan A, Merl D K, Jenko M.The corrosion behaviour of austenitic and duplex stainless steels in artificial saliva with the addition of fluoride[J]. Corros. Sci., 2011, 53: 776
[33] Ma H R.Fabrication, corrosion and wear properties of Fe-based amorphous coatings [D]. Shanghai: Shanghai University, 2016(马浩然. Fe基非晶涂层的制备及其耐磨防腐性能研究 [D]. 上海: 上海大学, 2016)
[34] Yamashita T, Hayes P.Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials[J]. Appl. Surf. Sci., 2008, 254: 2441
[35] Wu Q L, Li W G, Zhong N.Corrosion behavior of TiC particle-reinforced 304 stainless steel[J]. Corros. Sci., 2011, 53: 4258
[36] Lv J L, Luo H Y.Electrochemical investigation of passive film in pre-deformation AISI 304 stainless steels[J]. Appl. Surf. Sci., 2012, 263: 29
[37] Yuan L, Wang H M.Corrosion properties of a Cr13Ni5Si2-based metal silicide alloy[J]. Intermetallics, 2008, 16: 1149
[38] Hu G.Preparation and properties of Ni based and Fe based clad coating using ultrasonic frequency induction cladding [D]. Beijing: University of Science and Technology Beijing, 2015(胡舸. 超音频感应熔覆镍基和铁基涂层制备及性能研究 [D]. 北京: 北京科技大学, 2015)
[1] CHEN Yongjun, BAI Yan, DONG Chuang, XIE Zhiwen, YAN Feng, WU Di. Passivation Behavior on the Surface of Stainless Steel Reinforced by Quasicrystal-Abrasive via Finite Element Simulation[J]. 金属学报, 2020, 56(6): 909-918.
[2] Lin WEI,Zhijun WANG,Qingfeng WU,Xuliang SHANG,Junjie LI,Jincheng WANG. Effect of Mo Element and Heat Treatment on Corrosion Resistance of Ni2CrFeMox High-Entropy Alloyin NaCl Solution[J]. 金属学报, 2019, 55(7): 840-848.
[3] Xiubing LIANG, Jianwen FAN, Zhibin ZHANG, Yongxiong CHEN. Microstructure and Corrosion Properties of Aluminum Base Amorphous and Nanocrystalline Composite Coating[J]. 金属学报, 2018, 54(8): 1193-1203.
[4] Haiou YANG, Xuliang SHANG, Lilin WANG, Zhijun WANG, Jincheng WANG, Xin LIN. Effect of Constituent Elements on the Corrosion Resistance of Single-Phase CoCrFeNi High-Entropy Alloys in NaCl Solution[J]. 金属学报, 2018, 54(6): 905-910.
[5] Jiang XU, Xike BAO, Shuyun JIANG. In Vitro Corrosion Resistance of Ta2N Nanocrystalline Coating in Simulated Body Fluids[J]. 金属学报, 2018, 54(3): 443-456.
[6] Ke YANG, Mengchao U, Jialong AN, Wei NG. Research and Development of Maraging Stainless Steel Used for New Generation Landing Gear[J]. 金属学报, 2018, 54(11): 1567-1585.
[7] Yinghua LIN, Ying YUAN, Liang WANG, Yong HU, Qunli ZHANG, Jianhua YAO. Effect of Electric-Magnetic Compound Field on the Microstructure and Crack in Solidified Ni60 Alloy[J]. 金属学报, 2018, 54(10): 1442-1450.
[8] Wenhui TONG,Zilong ZHAO,Xinyuan ZHANG,Jie WANG,Xuming GUO,Xinhua DUAN,Yu LIU. Microstructure and Properties of TiC/Co-Based Alloyby Laser Cladding on the Surface of NodularGraphite Cast Iron[J]. 金属学报, 2017, 53(4): 472-478.
[9] Erlin ZHANG, Xiaoyan WANG, Yong HAN. Research Status of Biomedical Porous Ti and Its Alloy in China[J]. 金属学报, 2017, 53(12): 1555-1567.
[10] Chao XIA, Shi QIAN, Donghui WANG, Xuanyong LIU. Properties of Carbon Ion Implanted Biomedical Titanium[J]. 金属学报, 2017, 53(10): 1393-1401.
[11] Muqin LI, Haitao YAO, Fanghong WEI, Mingda LIU, Zan WANG, Shuhao PENG. The Microstructure and in Vivo and in Vitro Property of Multi-Component Composite Films on the Biomedical Pure Magnesium Surface[J]. 金属学报, 2017, 53(10): 1337-1346.
[12] Cong PENG, Shuyuan ZHANG, Ling REN, Ke YANG. Effect of Cooling Rate on Microstructure and Properties ofa Cu-Containing Titanium Alloy[J]. 金属学报, 2017, 53(10): 1377-1384.
[13] Wei XU,Xin LU,Yanxia DU,Qingyu MENG,Ming LI,Xuanhui QU. Corrosion Resistance of Ti-Fe Binary Alloys Fabricated by Powder Metallurgy[J]. 金属学报, 2017, 53(1): 38-46.
No Suggested Reading articles found!