Reasearch on Corrosion Resistance of Containment Steel Liner in Simulated Concrete Pore Solution
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摘要: 针对核电厂安全壳钢衬里专用P265GH低合金钢（CSL），采用电化学和X射线光电子能谱（XPS）分析方法探究其在饱和Ca(OH)2溶液中的钝化和破钝效应，并与Q235B低碳钢（Q235B）和304不锈钢（304SS）耐腐蚀性能进行对比分析。结果表明：与Q235B和304SS相比，CSL在模拟混凝土孔溶液中钝化效率更高，但钝化膜中Fe2+/Fe3+比值较低导致其耐蚀性较差，CSL的临界氯离子浓度（0.16~0.2 mol/L）远小于Q235B（0.3 mol/L）；氯离子的破钝效应主要影响试件表面的双电层结构，导致其有效电容增大，电荷转移电阻急剧下降；304SS的钝化膜为Fe和Cr的氧化物和羟基氧化物，具有更高的耐腐蚀性。Abstract: Aiming at the special P265GH low alloy steel (CSL) for nuclear power plant containment steel liner, the passivation and de-passivation effects of CSL in saturated Ca(OH)2 solution were investigated using electrochemical and X-ray photoelectron spectroscopy (XPS) analysis methods, and the corrosion resistance of CSL was compared with that of low carbon steel (Q235B) and 304 stainless steel (304SS). The results show that, compared with Q235B and 304SS, CSL has higher passivation efficiency in simulated concrete pore solution, but the low Fe2+/Fe3+ ratio in the passivation film leads to poor corrosion resistance, and the critical chloride ion concentration of CSL (0.16~0.2 mol/L) is much smaller than that of Q235b (0.3 mol/L). The de-passivation effect of chloride ions mainly affects the electric double layer structure on the surface of the specimen, which leads to the increase of its effective capacitance and the sharp decrease of charge transfer resistance. The passive film formed on the surface of 304SS is composed of Fe and Cr oxide and hydroxide, which has higher corrosion resistance.
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图 5 不同钝化时间下试件CSL、Q235B和304SS的EIS曲线
Zre—阻抗实部；Zim—阻抗虚部；φ—相位角
Figure 5. EIS Curves of CSL, Q235B and 304SS in Different Passivation Time
图 6 等效电路图
$ {R_{\text{s}}} $—模拟混凝土孔溶液电阻；常相位角元件CPEf 和CPEdl—表征钢板表面钝化膜和双电层特征；W—Warburg阻抗；Rf、Rct—钝化膜电阻、电荷转移电阻
Figure 6. Equivalent Circuit Diagram
图 7 钝化10 d后3种试件XPS 拟合图谱
Figure 7. XPS Peak Fitting of the Three Tested Specimens after 10 Days' Passivation
图 8 腐蚀电位及极化电阻随氯离子浓度变化曲线
Figure 8. Curves of Corrosion Potential and Polarization Resistance with Chloride Ion Concentration
图 9 不同氯离子浓度条件下试件EIS曲线
Figure 9. EIS Curves of Specimens under Different Chloride Ion Concentrations
图 10 CSL、Q235B和304SS在碱性溶液钝化和破钝机理示意图
Figure 10. Passivation and Depassivtion Mechanisms of CSL, Q235B and 304SS in Alkaline Solutions
表 1 不同钢材的化学成分
Table 1. Chemical Composition of Different Steels
试件 化学成分/（质量百分数，%） Fe C Si Mn P S Cr Ni N Cu Alt Nb V Ti Mo CSL 余量 0.11 0.21 0.84 0.013 0.002 0.04 0.14 0.003 0.02 0.032 0.003 0.002 0.002 0.01 Q235B 余量 0.15 0.12 0.36 0.024 0.009 304SS 余量 0.034 0.45 1.42 0.018 0.003 18.1 8.13 0.054 
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表 2 氯离子浓度增长制度
Table 2. Schedule of the Increase of Chloride Concentration
阶段 时间/d 浓度梯度/
（mol·L−1）初始浓度/
（mol·L−1）终止浓度/
（mol·L−1）阶段一 6 0.01 0 0.06 阶段二 7 0.02 0.06 0.2 阶段三 6 0.05 0.2 0.5 阶段四 3 0.5 0.5 2.0
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表 3 钝化阶段等效电路拟合参数值
Table 3. EIS Fitting Values of Parameters of Equivalent Circuit in Passivation Stage
试件 钝化时间/h Rs/（Ω·cm2） CPEf Rf/(kΩ·cm2) CPEdl Rct/(kΩ·cm2) Qf /
(10−7 $ {\text{Ω}}^{{-1}}\cdot {\text{cm}}^{{-2}}\cdot {\text{s}}^{{n}_{\text{f}}}） $nf $C_{{\text{CPE}}_{\mathrm{f}}} $/
($ {\text{μF}} \cdot {\text{c}}{{\text{m}}^{ - 2}} $)Qdl/
(10−5 $ {{{\Omega }}^{{{ - 1}}}} \cdot {\text{c}}{{\text{m}}^{{{ - 2}}}} \cdot {{\text{s}}^{{n_{{\text{dl}}}}}} $)ndl $C_{{\text{CPE}}_{\mathrm{dl}}} $/
($ \mu{\text{F}} \cdot {\text{c}}{{\text{m}}^{ - 2}} $)CSL 8 14.95 1.48 1.00 1.48 11.37 8.60 0.90 30.81 1760.45 120 19.14 9.03 1.00 9.03 5.02 8.91 0.93 19.95 4469.18 240 16.93 2.68 1.00 2.68 9.09 9.00 0.95 16.32 3842.10 Q235B 8 17.35 4.08 1.00 4.08 7.84 7.71 0.91 22.89 926.93 120 18.21 5.41 1.00 5.41 7.37 6.64 0.92 16.98 5269.28 240 14.65 2.00 1.00 2.00 1.13 6.72 0.95 10.75 4252.95 304SS 8 26.50 9.29 1.00 9.29 52.70 10.86 0.79 9.32 2152.51 120 26.16 10.59 1.00 10.59 78.84 11.09 0.81 10.68 3623.63 240 26.16 13.93 1.00 13.93 52.70 10.03 0.75 8.08 4726.13 表中数据均为每组3个试件的平均值
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表 4 Fe2+/Fe3+、FeOX/FeM 比值
Table 4. Values of Fe2+/Fe3+ and FeOX/FeM
试件 Fe2+/Fe3+ FeOX/FeM CSL 0.19 66.56 Q235B 0.21 49.01 304SS 0.61 1.89
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表 5 腐蚀阶段等效电路拟合参数值
Table 5. EIS Fitting Values of Parameters of Equivalent Circuit in Corrosion Stage
试件 ${C_{{\text{C}}{{\text{l}}^{{ - }}}}}$/(mol·L−1) Rs/
（Ω·cm2）CPEf Rf /
（KΩ·cm2）CPEdl Rct/
（kΩ·cm2）Qf/
$ (10^{-7}\Omega^{-1}\cdot\text{c}\text{m}^{-2}\cdot\text{s}^{n_{\mathrm{f}}} $)nf $C_{{\text{CPE}}_{\mathrm{f}}} $/
$ （\text{μF}\cdot\text{c}\text{m}^{-2}） $Qdl /
$ \left(10^{-5}\Omega^{-1}\cdot\text{c}\text{m}^{-2}\cdot\text{s}^{n_{\mathrm{dl}}}\right) $ndl $C_{{\text{CPE}}_{\mathrm{dl}}} $/
$ （\text{μF}\cdot\text{c}\text{m}^{-2}） $CSL 0.1 18.71 18.2 1.00 18.2 3.15 10.00 0.94 19.37 3525.10 0.2 16.62 7.14 1.00 7.14 4.47 12.61 0.93 28.66 135.63 0.5 13.36 8.70 1.00 8.70 3.06 19.22 0.87 98.00 36.52 Q235B 0.3 14.81 12.00 1.00 12.00 3.09 7.92 0.95 13.48 3779.30 0.4 22.31 0.92 1.00 0.92 18.10 22.60 0.87 92.04 0.55 0.5 12.04 6.85 1.00 6.85 3.47 30.10 0.84 181.41 0.47 304SS 0.1 24.62 12.63 1.00 12.63 118.17 11.24 0.73 12.39 4848.30 0.4 28.18 9.47 1.00 9.47 5.19 15.09 0.70 5.07 5577.30 0.5 17.66 7.79 1.00 7.79 4.95 17.73 0.72 6.88 5681.30 表中数据均为每组3个试件的平均值；${C_{{\text{C}}{{\text{l}}^{{ - }}}}}$为氯离子浓度
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