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材料研究学报  2016, Vol. 30 Issue (4): 241-247    DOI: 10.11901/1005.3093.2015.507
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海洋用高强钢E690氧浓差腐蚀行为研究
邢佩1, 卢琳1(), 李晓刚1,2
1. 北京科技大学腐蚀与防护中心 北京 100083
2. 中国科学院宁波材料技术与工程研究所 宁波 315201
Oxygen-concentration Cell Induced Corrosion of E690 Steel for Ocean Platform
XING Pei1, LU Lin1,**(), LI Xiaogang1,2
1. Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China
2. Ningbo Institute of Material Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, China
引用本文:

邢佩, 卢琳, 李晓刚. 海洋用高强钢E690氧浓差腐蚀行为研究[J]. 材料研究学报, 2016, 30(4): 241-247.
Pei XING, Lin LU, Xiaogang LI. Oxygen-concentration Cell Induced Corrosion of E690 Steel for Ocean Platform[J]. Chinese Journal of Materials Research, 2016, 30(4): 241-247.

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摘要: 

为了考察新型海洋平台用E690钢在海水环境中的耐蚀性能, 采用动电位极化曲线、电偶电流测量以及扫描电镜和拉曼光谱分析法研究了其在溶氧量为0.3-8 mg/L之间的3.5%NaCl溶液中的氧浓差腐蚀行为, 并讨论了溶氧量差值、阴阳极面积比以及锈层等因素对E690钢氧浓差腐蚀的影响。结果表明: 当阴阳极面积比Sc/a≤4时, 阴阳极面积比是影响氧浓差腐蚀的主要因素, 当Sc/a>4, 阴极区溶氧量是影响氧浓差腐蚀的主要因素; 锈层氧浓差腐蚀的影响与所处的环境有关, 处于贫氧条件下时, 对锈层下的金属有保护作用, 而处于富氧氧条件下, 锈层会参与阴极反应, 加速金属腐蚀, 并且由于锈层的不均匀性, 还会造成阳极金属的不均匀腐蚀, 产生点蚀坑。
关键词 ： 材料失效与保护,  E690钢,  氧浓差电池,  阴阳极面积比,  锈层,  Raman光谱    
Abstract：

In order to investigate the corrosion resistance of ocean platform steel E690 in sea water, the corrosion induced by oxygen-concentration cell of E690 steel in 3.5%NaCl with oxygen concentration within a range of 0.3 to 8 mg/L was investigated by means of electrochemical measurement techniques, scanning electron microscopy and Raman spectroscopy. The influence of the difference in dissolved oxygen, the ratio of cathode area to anode area and the corrosion product on the corrosion behavior of E690 steel was examined respectively. It was found that: when the ratio of cathode area to anode area was less than four (Sc/a≤4), the cathode and these ratios would be the main factor that influenced the oxygen-concentration cell corrosion; when Sc/a>4, the dissolved oxygen would be the main factor that influenced the oxygen-concentration cell corrosion; How the corrosion product influenced the oxygen-concentration cell corrosion depends on the dissloved oxygen. When the rusted metal under an oxygen-deficient condition, the rust layer would prevent the substrate from corrosion; when the rusted metal was immersed in an aerated condition, the corrosion product would participate in the cathodic reaction process, which would accelerate the anode dissolution and resulted in localized corrosion, such as pitting.
Key words： materials failure and protection    E690 steel    oxygen concentration cell    area ration between cathode and anode    rust layer    Raman spectroscopy
收稿日期: 2015-09-14     
ZTFLH:  TG172.4  
基金资助:国家重点基础研究发展计划2014CB643300和国家材料环境腐蚀平台资助项目
作者简介: 本文联系人: 卢琳
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https://www.cjmr.org/CN/10.11901/1005.3093.2015.507      或      https://www.cjmr.org/CN/Y2016/V30/I4/241

C Si Mn P S Alt V Cr Ni Cu Mo B Ti
0.095 0.21 1.47 0.009 0.0012 0.0236 0.033 0.45 0.32 0.31 0.46 0.0018 0.015
表1  实验用E690钢化学成分
图1  模拟氧浓差腐蚀的实验装置
图2  E690钢试样显微组织
图3  E690在不同溶解氧的3.5%NaCl溶液中的动电位极化曲线
DO/(mg/L) Ecorr/VSCE Icorr/Acm-2 Ba/(V/dec) Bc/(V/dec)
0.3 -0.825 5.04×10-7 0.0319 -0.3803
1 -0.770 2×10-6 0.0473 -0.2894
2 -0.768 2.65×10-6 0.1017 -0.2327
3 -0.752 3.08×10-6 0.1100 -0.2064
6 -0.510 8.61×10-6 0.1002 -0.1428
8 -0.462 9.19×10-6 0.0828 -0.0990
表2  3.5%NaCl中的电化学测试拟合结果
DO in the two
containers		 Oxygen concentration
difference		 OCP difference
0.3-2 mg/L 1.7 mg/L 54 mV
2-6 mg/L 4 mg/L 95 mV
0.3-6 mg/L 5.7 mg/L 149 mV
0.3-8 mg/L 7.7 mg/L 170 mV
表3  氧浓差电池基本参数
图4  面积比对氧浓差腐蚀电流的影响
DO/(mg/L) OCP/V
Rusted sample Unrusted sample
0.3 -0.698 -0.741
6.0 -0.656 -0.556
表4  不同溶氧量下试样的开路电位
The cathode and anode are
respectively in each solution		 The cathode and anode are in the same solution
Group one Group two Group three
Anode Fresh steel
(solution with
0.3 mg/L DO)		 Rusty metal
(solution with
0.3 mg/L DO)		 Rusty metal
(solution with 6.0 mg/L DO)
Cathode Rysty metal
(solution with
6.0 mg/L DO)		 Fresh steel
(solution with
6.0 mg/L DO)		 Fresh steel
(solution with 6.0 mg/L DO)
表5  三组氧浓差腐蚀电池的设置
图5  3组氧浓差电池电流和电位随时间的变化
图6  3组氧浓差电池阳极表面除锈前、后的腐蚀形貌
图7  试样表面锈层成分激光拉曼光谱
Raman peak frequencies of corrosion products / cm-1 Raman peak frequencies
of standard rust phase / cm-1		 Corrosion products
Corrosion products made
by polarization		 218, 286, 489, 225, 245, 295, 415, 500, 615, α-Fe2O3
328, 406 330, 415, 745 β-FeOOH
Corrosion products on the cathode surface of the oxygenconcentration
corrosion cell		 319, 680 298, 319, 420, 560, 680, 1322 Fe3O4
Corrosion products after immersed in solution 265, 345, 386, 265, 300, 345, 395, 515, 645, 670, 715, γ-Fe2O3
485, 680 248, 303, 397, 485, 554, 680, 1002 α-FeOOH
表6  产物拉曼峰和标准特征峰位的对应表
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