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中国腐蚀与防护学报  2016, Vol. 36 Issue (6): 535-542    DOI: 10.11902/1005.4537.2016.190
  研究报告 本期目录 | 过刊浏览 |
模拟海水中HSO3-对2205双相不锈钢钝化膜成分及耐蚀性能的影响
张天翼,吴俊升(),郭海龙,李晓刚
北京科技大学新材料技术研究院 腐蚀与防护中心 北京 100083
Influence of HSO3- on Passive Film Composition and Corrosion Resistance of 2205 Duplex Stainless Steelin Simulated Seawater
Tianyi ZHANG,Junsheng WU(),Hailong GUO,Xiaogang LI
Corrosion and Protection Center, Institute of Advanced Materials, University of Science and Technology Beijing, Beijing 100083, China
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摘要: 

在含有不同浓度NaHSO3的模拟海水溶液中系统考察了2205双相不锈钢的腐蚀行为。利用动电位极化曲线和电化学阻抗谱测试,研究模拟海水中不同浓度HSO3-对2205双相不锈钢腐蚀行为的影响。通过Mott-Schottky和XPS测试,分析了2205不锈钢在不同浓度HSO3-模拟海水溶液中钝化膜的缺陷浓度和成分。结果表明,模拟海水溶液中HSO3-的存在会提高2205不锈钢钝化膜中金属氧化物的含量。在含有0.01 mol/L HSO3-的模拟海水溶液中,2205双相不锈钢表现出较差的耐蚀性,其表面钝化膜中的缺陷浓度计算结果也与电化学测试结果相吻合。主要是由于HSO3-在溶液中极易被氧化为HSO4-,电离出H+,会对2205不锈钢钝化膜产生破坏作用;而当模拟海水中HSO3-浓度低于0.01 mol/L时,材料阻抗呈上升趋势,HSO3-会在2205不锈钢表面和Cl-产生竞争吸附,阻碍Cl-在不锈钢表面的吸附,从而减少点蚀发生的可能。
关键词 ： 2205双相不锈钢,  钝化膜,  缺陷,  模拟海水,  竞争吸附    
Abstract：

Corrosion behavior of 2205 duplex stainless steel in simulated seawater containing different concentration of NaHSO3 has been systemically investigated by means of potentiodynamic polarization and electrochemical impedance spectrum (EIS) measurements. While the defects and the compositions of the formed passive films on the steel were characterized by Mott-Schottky and XPS respectively. The results demonstrate that the existence of HSO3- in the simulated seawater contributes to the increase of metal oxide content in the passive film formed on 2205 stainless steel. In the simulated seawater containing 0.01 mol/L HSO3-, 2205 duplex stainless steel presents the worst corrosion resistant performance, correspondingly the calculated defect concentration for the formed passive film is consistent to the electrochemical test results. The oxidation of HSO3- induces the formation of HSO4- in aqueous solution, which will give rise to the releasing of hydrogen ions, leading to the increase of acidity of the solution and thus induces the damage of the passive film on 2205 stainless steel. However, when the concentration of HSO3- in simulated seawater is less than 0.01 mol/L, the corrosion resistance of the steel will rise again. This is because the competitive adsorption between HSO3- and Cl- on the 2205 stainless steel surface can inhibit the adsorption of Cl-, which then results in the decline of the pitting corrosion probability.
Key words： 2205 duplex stainless steel    passive film    defect    simulated seawater    competitiveadsorption
    
基金资助:国家自然科学基金项目 (51271031),国家重点基础研究发展计划项目 (2014CB643300) 和国家科技基础条件平台项目 (2005DKA10400) 资助
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张天翼
吴俊升
郭海龙
李晓刚

引用本文:

张天翼,吴俊升,郭海龙,李晓刚. 模拟海水中HSO3-对2205双相不锈钢钝化膜成分及耐蚀性能的影响[J]. 中国腐蚀与防护学报, 2016, 36(6): 535-542.
Tianyi ZHANG, Junsheng WU, Hailong GUO, Xiaogang LI. Influence of HSO3- on Passive Film Composition and Corrosion Resistance of 2205 Duplex Stainless Steelin Simulated Seawater. Journal of Chinese Society for Corrosion and protection, 2016, 36(6): 535-542.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2016.190      或      https://www.jcscp.org/CN/Y2016/V36/I6/535

图1  2205不锈钢试样在模拟海水溶液中的动电位极化曲线和NaHSO3浓度与不锈钢点蚀电位的关系图
图2  2205不锈钢在不同浓度HSO3-模拟海水溶液中的电化学阻抗谱及相应的等效电路
Concentration of NaHSO3 / molL-1 Rs / Ω CPEdl / F ndl Rct / Ω CPEfilm / F nfilm Rfilm / Ω
0 5.805 5.06×10-5 0.8924 2.34×105 1.68×10-5 0.7992 2.20×105
0.005 5.597 5.97×10-5 0.8798 3.05×104 2.10×10-3 1 3.77×104
0.01 6.235 6.19×10-5 0.8587 2.50×104 3.36×10-3 1 1.82×104
0.05 6.106 6.34×10-5 0.8976 6.20×104 1.90×10-3 0.8670 2.23×104
0.1 5.456 5.83×10-5 0.8608 9.70×104 8.47×10-4 1 6.14×104
表2  不同HSO3-浓度条件下2205双相不锈钢的电化学阻抗谱拟合结果
图3  Rfilm与NaHSO3浓度之间的关系
图4  2205双相不锈钢在不同浓度HSO3-模拟海水溶液中的Mott-Schottky曲线及NaHSO3浓度与所形成的钝化膜中点缺陷浓度Nd的变化关系
Concentration of NaHSO3 / molL-1 Fit-slope Nd / cm-3
0 5.83×109 1.55×1021
0.0050 3.84×109 2.36×1021
0.010 2.35×109 3.84×1021
0.050 4.26×109 2.13×1021
0.10 5.71×109 1.59×1021
表3  Mott-schottky曲线计算结果
图5  0.01 mol/L HSO3-模拟海水溶液中不锈钢表面钝化膜的XPS总谱图及Cr, Fe和S分谱拟合图
Concentration of HSO3- / molL-1 Cr Cr2O3 Cr(OH)3 CrO3
0 0.384 0.272 0.179 0.164
0.005 0.174 0.307 0.333 0.186
0.01 0.139 0.310 0.327 0.224
0.05 0.157 0.300 0.344 0.200
0.1 0.161 0.312 0.309 0.218
表4  不同浓度HSO3-模拟海水溶液中不锈钢表面钝化膜中不同价态Cr的含量
Concentration of HSO3- / molL-1 Fe Fe3O4 FeO Fe2O3 FeOOH
0 0.531 0.228 0.039 0.083 0.119
0.005 0.302 0.303 0.180 0.097 0.117
0.01 0.304 0.296 0.185 0.101 0.113
0.05 0.347 0.345 0.108 0.095 0.105
0.1 0.286 0.292 0.185 0.089 0.148
表5  不同浓度HSO3-模拟海水溶液中不锈钢表面钝化膜中不同价态Fe的含量
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