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金属学报  2015, Vol. 51 Issue (2): 191-200    DOI: 10.11900/0412.1961.2014.00407
  本期目录 | 过刊浏览 |
模拟工业-海岸大气中pH值对Q235B钢腐蚀行为的影响*
陈文娟(), 郝龙, 董俊华, 柯伟, 文怀梁
中国科学院金属研究所材料环境腐蚀研究中心, 沈阳 110016
EFFECT OF pH VALUE ON THE CORROSION EVOLUTION OF Q235B STEEL IN SIMULATED COASTAL-INDUSTRIAL ATMOSPHERES
CHEN Wenjuan(), HAO Long, DONG Junhua, KE Wei, WEN Huailiang
Environmental Corrosion Research Center of Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016
引用本文:

陈文娟, 郝龙, 董俊华, 柯伟, 文怀梁. 模拟工业-海岸大气中pH值对Q235B钢腐蚀行为的影响*[J]. 金属学报, 2015, 51(2): 191-200.
Wenjuan CHEN, Long HAO, Junhua DONG, Wei KE, Huailiang WEN. EFFECT OF pH VALUE ON THE CORROSION EVOLUTION OF Q235B STEEL IN SIMULATED COASTAL-INDUSTRIAL ATMOSPHERES[J]. Acta Metall Sin, 2015, 51(2): 191-200.

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摘要: 

采用干/湿交替腐蚀增重模拟实验、XRD以及EIS等方法, 研究了模拟工业-海岸大气中pH值变化对Q235B钢腐蚀行为的影响. 结果表明, 当SO2浓度较低时, pH值变化对Q235B钢腐蚀速率的影响不明显; 当SO2浓度较高时, pH值变化对Q235B钢腐蚀速率的影响存在极值现象, 即: 当pH值处于“较高”和“较低”之间某一值时, Q235B钢的腐蚀速率达到极大值. 当模拟工业-海岸大气中SO2浓度一定时, pH值变化对Q235B钢表面锈层相组成的影响不明显. 分析表明, 模拟工业-海岸大气环境中SO2的存在一定程度上抑制了β-FeOOH的形成. 随着SO2浓度的升高, 锈层中β-FeOOH和ϒ-FeOOH的相对含量在减少, ϒ-FeOOH可能发生了向Fe3O4的还原或向α-FeOOH的相变转化. 随着腐蚀时间的延长, 锈层相组成的演化呈现出相似的规律. 此外, 当模拟工业-海岸大气中SO2浓度较低时, Q235B钢腐蚀主要遵循Cl-的循环机制, 改变pH值对钢腐蚀行为的影响不明显; SO2浓度较高时, Q235B钢腐蚀初期主要遵循Cl-的循环机制, 随着腐蚀时间的延长, SO2对腐蚀的影响逐渐显著, 并以H2SO4再生循环的方式加速钢的腐蚀。
关键词 ： Q235B钢,  干/湿交替实验,  工业-海岸大气腐蚀,  锈层    
Abstract：

The atmosphere in many cities along the coastal lines such as Qingdao in China has been polluted with SO2 due to the development of industry, and the atmosphere therefore has been changed to coastal-industrial atmosphere. The corrosion behavior and mechanism of steels in coastal-industrial atmosphere with the co-existence of SO2 and Cl- are different from that in the coastal atmosphere containing only Cl- or the industrial atmosphere containing only SO2. In addition, pH value is diverse in different coastal-industrial atmosphere. However, there are only few researches on the effect of pH value on the corrosion evolution of steels in the coastal-industrial atmosphere. Almost all the atmospheric corrosion data of steels were obtained by the field exposure test, which could not reflect the dependence of the atmospheric corrosion evolution of steels on pH value due to the difficulties in controlling the field conditions. In this work, the effect of pH value on the corrosion evolution of Q235B steel in the simulated coastal-industrial atmospheres has been investigated by the dry/wet cyclic corrosion test (CCT), XRD and EIS. The results indicate that, when the content of SO2 is lower, changing pH value has no effect on the corrosion of the steel. When the content of SO2 is higher, the corrosion rate of Q235B steel influenced by changing pH value shows an extreme phenomenon, that is, when the pH value being a certain value between the "higher" and the "lower", the corrosion rate of Q235B steel reaches the maximum value. When the SO2 content is certain, changing pH value almost has no effect on the rust composition. To some extent, the existence of SO2 inhibits the formation of β-FeOOH. With the increasing of SO2 content, the relative contents of β-FeOOH and ϒ-FeOOH are decreasing, and ϒ-FeOOH maybe reduced back to Fe3O4 or transform to α-FeOOH. With the corrosion process prolongs, the rust evolution shows almost the same trend. In addition, when the content of SO2 in the simulated coastal-industrial atmosphere is lower, the Q235B steel mainly follows Cl- corrosion mechanism, and the influence of pH value on corrosion behavior of the steel is not obvious. When the content of SO2 is higher, the Q235B steel also follows Cl- corrosion mechanism in the early stage; with prolonging the dry/wet cyclic corrosion test number, H2SO4 regeneration mechanism accelerates corrosion of the steel as the effect of SO2 on corrosion increasing significantly。
Key words： Q235B steel    dry/wet cyclic test    coastal-industrial atmosphere    atmospheric corrosion    rust layer
收稿日期: 2014-07-23     
ZTFLH:  TG172.3  
基金资助:*国家自然科学基金项目 51201170和51131007, 国家重点基础研究发展计划项目2014CB643300 和国家材料环境腐蚀平台项目资助
作者简介: null

陈文娟, 女, 1986年生, 博士生
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https://www.ams.org.cn/CN/10.11900/0412.1961.2014.00407      或      https://www.ams.org.cn/CN/Y2015/V51/I2/191

Atmosphere Na2SO3 / (mol·L-1) NaCl / (mol·L-1) pH value
No.1 0.001 0.050 3.5
No.2 0.001 0.050 4.5
No.3 0.001 0.050 6.0
No.4 0.010 0.050 3.5
No.5 0.010 0.050 4.5
No.6 0.010 0.050 6.0
No.7 0.150 0.050 3.5
No.8 0.150 0.050 4.5
No.9 0.150 0.050 6.0
表1  模拟工业-海岸大气环境所用电解质溶液浓度与pH值
图1  Q235B钢在模拟工业-海岸大气中的腐蚀增重结果线性坐标曲线
图2  Q235B钢在模拟工业-海岸大气中的腐蚀增重结果对数坐标曲线
Atmosphere 1st stage 2nd stage 3rd stage 4th stage
No.1 y=-0.108+0.991x - - -
R2=0.998
No.2 y=-0.069+0.958x - - -
R2=0.998
No.3 y=-0.122+0.996x - - -
R2=0.999
No.4 y=-0.094+1.039x - - -
R2=0.999
No.5 y=-0.044+1.006x - - -
R2=0.999
No.6 y=-0.072+1.031x - - -
R2=0.999
No.7 y=0.057+0.772x y=0.232+0.566x y=-0.725+1.401x y=-0.176+0.994x
R2=0.977 R2=0.992 R2=0.996 R2=0.999
No.8 y=0.062+0.849x y=0.256+0.605x y=-0.664+1.405x y=-0.096+1.007x
R2=0.997 R2=0.992 R2=0.996 R2=0.995
No.9 y=0.047+0.795x y=0.199+0.614x y=-0.705+1.398x y=-0.014+0.877x
R2=0.981 R2=0.964 R2=0.995 R2=0.998
表2  Q235B钢在模拟工业-海岸大气中9条腐蚀增重曲线的分段拟合结果
图3  Q235B钢在模拟工业-海岸大气中腐蚀速率随干/湿交替次数变化的曲线
图4  Q235B钢在模拟工业-海岸大气中腐蚀不同周期后腐蚀产物的XRD谱
图5  Q235B钢在模拟工业-海岸大气中腐蚀120 cyc后腐蚀产物的同步辐射XRD谱
图6  Q235B钢带锈电极在0.150 mol/L Na2SO3工业-海岸大气模拟液中的EIS的Bode图
图7  拟合Q235B钢带锈电极在0.150 mol/L Na2SO3工业-海岸大气模拟液中EIS的等效电路示意图
图8  Q235B钢带锈电极在0.150 mol/L Na2SO3工业-海岸大气模拟液中EIS拟合结果
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