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中国腐蚀与防护学报  2015, Vol. 35 Issue (2): 113-121    DOI: 10.11902/1005.4537.2013.262
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环境因素对X100钢表面钝化膜性能的影响
赵阳1, 梁平1(), 史艳华1, 张云霞2
1. 辽宁石油化工大学机械工程学院 抚顺 113001
2. 辽宁石油化工大学继续教育学院 抚顺 113001
Influence of Environmental Factors on Property of Passive Film Formed on X100 Pipeline Steel
ZHAO Yang1, LIANG Ping1(), SHI Yanhua1, ZHANG Yunxia2
1. School of Mechanical Engineering, Liaoning Shihua University, Fushun 113001, China
2. Continual Education Institute, Liaoning Shihua University, Fushun 113001, China
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摘要: 

利用极化曲线、电化学阻抗和电容法研究了温度、pH值和Cl-浓度对X100管线钢在高pH值土壤模拟溶液中所成钝化膜性能的影响。结果表明：X100管线钢在不同的介质中都可以发生钝化,但随着温度从20 ℃升到60 ℃、Cl-浓度从0.001 mol/L增大到0.005 mol/L以及pH值从10.84下降到9.27时,X100管线钢的钝化区间范围减小,抗腐蚀性能下降。电化学阻抗结果表明：随着温度升高、Cl-浓度增大和pH值下降,钝化膜的致密性下降,而温度是影响钝化膜致密性的最主要因素；电容测试和理论计算表明：Cl-浓度是影响钝化膜厚度的最主要因素,而温度则是影响钝化膜缺陷密度和缺陷扩散系数的最主要因素。
关键词 ： X100管线钢,  环境因素,  半导体特性,  Mott-Schottky分析,  电化学阻抗谱    
Abstract：

Effect of temperature, pH and chloride ion concentration on the property of passive films formed on X100 pipeline steel were investigated in an artificial soil solution by polarization curves, electrochemical impedance spectroscopy (EIS) and capacitance measurements technique. The results polarization measurement showed that the range of passive potential and the corrosion resistance of the steel decreased with the increasing temperature from 20 to 60 ℃, the increasing Cl- concentration from 0.001 to 0.005 mol/L and the decreasing pH value from 10.84 to 9.27 respectively. EIS results displayed that the compactness of passive films decreased with the increasing temperature and Cl- concentration, and the decreasing pH respectively, while temperature exhibited the strongest effect among the three factors on the compactness of the passive films. The results of capacitance measurement and theoretical calculation implied that the Cl- concentration exhibited the strongest effect on the thickness of passive film, while temperature exhibited the strongest effect on the defect density and diffusion coefficient of the passive films.
Key words： X100 pipeline steel    environmental factor    semi-conductive property    Mott-Schottky analysis    EIS
收稿日期: 2013-12-10     
ZTFLH:  TG142.71  
基金资助:辽宁省教育厅2012年科学研究一般项目 (L2012127)资助
作者简介: null

赵阳，男，1989年生，硕士生
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引用本文:

赵阳, 梁平, 史艳华, 张云霞. 环境因素对X100钢表面钝化膜性能的影响[J]. 中国腐蚀与防护学报, 2015, 35(2): 113-121.
Yang ZHAO, Ping LIANG, Yanhua SHI, Yunxia ZHANG. Influence of Environmental Factors on Property of Passive Film Formed on X100 Pipeline Steel. Journal of Chinese Society for Corrosion and protection, 2015, 35(2): 113-121.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2013.262      或      https://www.jcscp.org/CN/Y2015/V35/I2/113

Experimental condition Solution composition
Temperature / ℃ 20 0.5 mol/L NaHCO3
40 0.5 mol/L NaHCO3
60 0.5 mol/L NaHCO3
pH 9.27 0.05 mol/L NaHCO3＋0.25 mol/L Na2CO3
9.78 0.25 mol/L NaHCO3＋0.25 mol/L Na2CO3
10.84 0.05 mol/L NaHCO3＋0.5 mol/L Na2CO3
Cl-/molL-1 0.001 0.5 mol/L NaHCO3＋0.001 mol/L NaCl
0.003 0.5 mol/L NaHCO3＋0.003 mol/L NaCl
0.005 0.5 mol/L NaHCO3＋0.005 mol/L NaCl
表1  不同实验条件下的溶液组成
图1  温度、pH值和Cl-浓度对X100管线钢在高pH值溶液中极化曲线的影响
图2  不同温度各成膜电位下X100钢表面钝化膜的Nyquist 曲线
图3  等效模拟电路
Temperature
℃ 		Formation
potential / V 		RS
Ωcm2 		Qf×10-4
Fcm2 		n1 Rf×104
Ωcm2 		Qdl×10-4
Fcm2 		n2 Rct×103
Ωcm2
20 0.1 11.82 5.750 0.927 3.170 6.82 0.912 5.360
0.2 14.14 5.403 0.926 3.581 6.88 0.911 9.761
0.3 10.67 5.359 0.929 4.057 5.68 0.920 12.19
0.4 6.058 5.074 0.927 5.233 4.28 0.937 14.01
40 0.1 8.932 5.970 0.901 1.588 4.63 0.901 2.491
0.2 6.027 7.249 0.917 2.652 5.54 0.945 5.854
0.3 5.469 6.542 0.913 4.414 6.87 0.916 6.542
0.4 5.285 5.536 0.904 5.125 7.72 0.925 6.933
60 0.1 4.311 4.942 0.945 1.088 6.70 0.914 2.246
0.2 5.124 5.893 0.913 2.430 7.75 0.946 4.562
0.3 3.461 5.714 0.925 4.018 6.21 0.936 5.623
0.4 6.156 6.321 0.905 5.048 5.45 0.906 5.825
表2  电化学阻抗图的拟合结果
图4  X100钢表面钝化膜在不同pH值溶液中的Nyquist曲线
图5  X100钢表面钝化膜在不同Cl-浓度溶液中的Nyquist曲线
pH Formation
potential / V 		Rf×104
Ωcm2 		[Cl-]
mol/L 		Formation potential / V Rf×103
Ωcm2 		Temperature
℃ 		Formation potential / V Rf×104
Ωcm2
9.27 0.1 1.112 0.001 0.1 9.621 20 0.1 11.82
0.2 1.652 0.2 9.758 0.2 14.14
0.3 3.626 0.3 9.898 0.3 10.67
0.4 4.009 0.4 10.257 0.4 6.058
9.78 0.1 1.217 0.003 0.1 7.913 40 0.1 8.932
0.2 1.897 0.2 8.345 0.2 6.027
0.3 4.654 0.3 9.165 0.3 5.469
0.4 6.568 0.4 9.752 0.4 5.285
10.84 0.1 1.362 0.005 0.1 6.586 60 0.1 4.311
0.2 3.288 0.2 7.894 0.2 5.124
0.3 5.678 0.3 8.965 0.3 3.461
0.4 7.895 0.4 9.968 0.4 6.156
表3  不同条件下电化学阻抗谱的拟合结果
图6  不同温度下钝化膜厚度与成膜电位之间的关系曲线
Experimental condition Fitting equation x =0.1
Temperature 20 ℃ y =1.8836x+0.4924 y =0.6808
40 ℃ y =1.9230x+0.3765 y =0.5688
60 ℃ y =1.7752x+0.3528 y =0.5303
pH 9.27 y =3.3452x+0.9599 y =1.2944
9.78 y =3.2542x+1.2753 y =1.6007
10.84 y =3.2473x+1.5822 y =1.9069
Cl- 0.001 y =1.338x+0.1403 y =0.2741
0.003 y =0.6380x+0.1302 y =0.1940
0.005 y =0.2870x+0.1276 y =0.1563
表4  不同条件下钝化膜厚度与成膜电位之间的拟合曲线
图7  不同温度下X100钢表面钝化膜的Mott-Schottky曲线
Formation potential / V 20 ℃ 40 ℃ 60 ℃
10-21 ND/cm-3 10-21 ND/cm-3 10-21 ND'/cm-3 10-21 (ND+ND')/cm-3 10-21 ND/cm-3 10-21 ND'/cm-3 10-21 (ND+ND')/cm-3
0.1 1.584 2.957 2.472 5.429 2.976 2.653 5.629
0.2 1.247 2.919 1.754 4.637 2.938 1.984 4.922
0.3 0.996 2.570 1.263 3.833 2.677 1.493 4.170
0.4 0.904 2.350 1.024 3.374 2.556 1.186 3.742
表5  不同温度下钝化膜内的施主密度
图8  不同pH值溶液中X100钢表面钝化膜的Mott-Schottky曲线
图9  X100钢在不同Cl-浓度溶液中所成钝化膜的Mott-Schottky曲线
Temperature
℃ 		Formation potential / V 10-21
(ND+ND')/cm-3 		pH Formation potential / V 10-21
(ND+ND')/cm-3 		[Cl-]
mol/L 		Formation potential / V 10-21
(ND+ND')/cm-3
20 0.1 1.584 9.27 0.1 7.955 0.001 0.1 7.017
0.2 1.247 0.2 5.824 0.2 6.034
0.3 0.996 0.3 5.204 0.3 5.031
0.4 0.904 0.4 4.674 0.4 4.254
40 0.1 5.429 9.78 0.1 5.893 0.003 0.1 21.76
0.2 4.637 0.2 4.929 0.2 11.13
0.3 3.833 0.3 4.418 0.3 7.741
0.4 3.374 0.4 3.724 0.4 6.537
60 0.1 5.629 10.84 0.1 5.612 0.005 0.1 45.108
0.2 4.922 0.2 4.219 0.2 25.246
0.3 4.170 0.3 3.715 0.3 18.997
0.4 3.742 0.4 3.198 0.4 14.621
表6  不同条件下钝化膜内施主密度计算结果
Environmental parameter Experimental condition D0 / 10-17cm2s-1
Temperature 20 ℃ 1.755×10-17
40 ℃ 3.264×10-17
60 ℃
5.147×10-17
pH 9.27 1.551×10-17
9.78 0.847×10-17
10.84 0.553×10-17
Cl- 0.001 mol/L 1.076×10-17
0.003 mol/L 1.906×10-17
0.005 mol/L 3.568×10-17
表7  不同条件下钝化膜的缺陷扩散系数
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