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金属学报  2018, Vol. 54 Issue (7): 1019-1030    DOI: 10.11900/0412.1961.2017.00437
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激光熔覆铁基合金涂层在HCl溶液中的腐蚀行为
范丽1,2, 陈海龑1(), 董耀华1,3, 李雪莹1, 董丽华1, 尹衍升1
1 上海海事大学海洋科学与工程学院 上海 2013062
2 南通航运职业技术学院轮机工程系 南通 2260103
3 上海交通大学机械与动力工程学院 上海 200240
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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摘要: 

采用激光熔覆方法在30CrMo合金钢表面制备了一种铁基合金耐腐蚀涂层,利用EIS、极化曲线、浸泡腐蚀实验等测试方法,结合XPS研究了该涂层在0.5 mol/L HCl溶液中的腐蚀行为,并与304不锈钢和30CrMo钢进行对比。电化学结果表明,在0.5 mol/L HCl溶液中,与30CrMo钢相比,铁基合金涂层极化曲线出现了明显的钝化区,且具有较低的腐蚀电流密度和较高的自腐蚀电位,熔覆层的耐腐蚀性能显著提高。与304不锈钢相比,铁基合金涂层维钝电流略微变小,钝化区变宽,其耐蚀性与304不锈钢相当。涂层钝化膜主要由Cr2O3、FeCr2O4和MoO3组成,涂层具有优良耐蚀性能的本质原因是复合氧化膜的钝化作用对腐蚀介质产生机械阻隔作用。

关键词 铁基合金涂层激光熔覆电化学腐蚀钝化膜耐蚀性    
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 wordsFe-based alloy coating    laser cladding    electrochemical corrosion    passivation film    corrosion resistance
收稿日期: 2017-10-20     
ZTFLH:  TG174.44  
基金资助:国家自然科学基金项目No.51609133,中国博士后科学基金项目No.2017M620153,海洋公益性行业科研专项经费项目No.201405013-3和上海海事大学科研基金项目No.20130448
作者简介:

作者简介 范 丽,女,1983年生,博士生

引用本文:

范丽, 陈海龑, 董耀华, 李雪莹, 董丽华, 尹衍升. 激光熔覆铁基合金涂层在HCl溶液中的腐蚀行为[J]. 金属学报, 2018, 54(7): 1019-1030.
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.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2017.00437      或      https://www.ams.org.cn/CN/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.
表1  铁基合金粉末、304不锈钢和30CrMo基体的化学成分
图1  铁基合金粉末的SEM像和粉末粒度分布图
图2  铁基粉末和涂层的XRD谱
图3  涂层的Schaeffler组织图
图4  铁基涂层表面的SEM像和EDS分析
图5  铁基涂层截面的SEM像
图6  铁基涂层、304不锈钢和30CrMo钢在0.5 mol/L HCl溶液中的动电位极化曲线
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
表2  铁基涂层、304不锈钢和30CrMo钢在0.5 mol/L HCl溶液中的极化曲线拟合结果
图7  铁基涂层、304不锈钢和30CrMo钢在0.5 mol/L HCl溶液中的EIS
图8  铁基涂层、304不锈钢和30CrMo钢在0.5 mol/L HCl溶液中的EIS拟合采用的等效电路
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
表3  铁基涂层、304不锈钢和30CrMo钢在0.5 mol/L HCl溶液中的电化学阻抗谱拟合数据
图9  铁基涂层表面在0.5 mol/L HCl溶液中浸泡3 d后的XPS全谱及精细谱峰
图10  铁基涂层在0.5 mol/L HCl溶液中浸泡1、3和7 d后的腐蚀形貌和EDS
图11  铁基涂层在0.5 mol/L HCl溶液中浸泡1、3和7 d后的白光干涉腐蚀形貌
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