船用钢海水腐蚀与检测研究
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摘要
海洋环境是一种非常严酷的腐蚀环境,各种材料在使用过程中始终面临着恶劣的海洋腐蚀环境,由海水腐蚀所引发事故的经济损失所占的比例相当高。目前对船用钢耐蚀性能的评价方法主要是实海挂片试验,该方法的优点是实验环境条件真实,操作简单,结果比较可靠。但是该试验方法还存在以下不足:试验周期长,一般最短试验周期为1年;环境因素无法控制;试验结果的重现性较差;由于试样丢失而造成试验失败的风险较高。这些不足是制约新材料新工艺快速应用的主要问题。
本文主要研究三种典型船用钢A、B、C在不同实验环境条件下的耐蚀性能。通过电化学试验,探讨了不同的实验环境条件对材料的腐蚀的影响,得到了材料在不同实验条件下的腐蚀规律,并从数学的角度,找出不同试验条件下的腐蚀速度随时间变化的函数关系,得到了适合于所选材料在本地区海水环境腐蚀的模拟公式。本文的主要结论如下:
1.通过实海腐蚀电位监测,B的稳定电位最正,C次之,A最负。其结果与室内模拟静水条件下得到的结果有差别。
2.分别对实海全浸的试样进行了线性极化以及交流阻抗测试,得到瞬时腐蚀速度(i_(corr))和极化电阻(R_P)随浸泡时间的变化,表明其变化是表面锈层的堆积与海水温度变化所带来的影响的共同作用的结果。
3.采用四种阻抗模型对EIS数据进行了拟和,表明全浸可分为四个阶段,浸泡初期,等效电路仅由双电层电容(C_(dl))和电荷转移电阻(R_t)构成。随时间延长,等效电路中出现了反映界面性质的腐蚀产物层电容(C_f)和电阻(R_f)。随时间的进一步延长,阻抗模型中出现了由于微生物而导致的电容及电阻,通过C_(dl)和R_t随浸泡时间的变化表征了材料的腐蚀行为。
4.对腐蚀产物进行激光拉曼分析,得到腐蚀产物的结构成分,外层腐蚀产物主要由γ-FeOOH构成,并有少量α-Fe_2O_3,内锈层主要由α-Fe_2O_3、Fe_3O_4构成,其中也伴有少量γ-FeOOH。
5.室内模拟充气搅拌条件下,材料的稳定电位排序与实海全浸一致,并且其瞬时腐蚀速度(icorr)和极化电阻(RP)随浸泡时间的变化也与实海一致,这说明室内充气搅拌条件得到的实验结果可以很好的重现实海条件下的实验结果。
6.两种室内模拟方法得到的交流阻抗结果与实海有较大差别,原因可能是海水中微生物的影响不同,实海中微生物的影响较强,室内模拟较弱。
7.通过积分拟合的方法分别得到三种实验条件下的腐蚀速度随时间变化的数学公式,通过与失重方法得到的数学公式相对比,可以看出室内充气搅拌实验结果与相应条件下的失重实验结果较好的吻合,说明由电化学方法得到的积分拟合值来计算腐蚀速度的方法完全可以替代失重挂片实验方法。
8.本文的研究表明,由室内模拟充气条件下的电化学实验得到的腐蚀速度完全可以预测材料的腐蚀速度,从而可以替代挂片失重实验。但监测频率要更为密集,才能保证结果的准确性。
Marine environmental is a rigorous corrosion environmental, materials in the process of using is confronted with badly ocean corrosion circumstance all the time. The proportion of accident’s economic loss caused by seawater corrosion is quite high.
At present, the method which appraise the anti-corrode performance of vessel steel is loss weight in natural seawater. The measurement’s merit is experiment condition’s reality, operation simple and result credibility. While there are many shortages in the measurement. For example, the periods of experiment are very long, usually, the shortest experiment periods are one year; the circumstance factors are out of control; consequential the recurrence is bad; the risk caused by losing sample in the process of experiment is high. All shortages above, are mostly issues which restrict the use of new material, new craftwork.
This paper mostly research the anti-corrode performance of three representative vessel steel: A, B, C in different experiment circumstances. Through electrochemistry experiment, we probe into the influence of different experiment circumstances with the corrosion of material, find material corrosion disciplinarian in different experiment circumstances, the function relation between corrosion rate and time in different experiment circumstances from mathematical view and simulation formula which simulate material corrosion in this region. The conclusions of this paper are as follows:
1) Through monitoring corrosion potential in natural seawater, we find that the stabilization potential of B is most positive, the second is C, and A is most negative. While the result gained by natural seawater is different from the conclusion gained by indoor static seawater.
2) Linear polarization test and AC impedance test have been separately carried out on samples immersing entirely in natural seawater, and it give us the change of instantaneous corrosion rate(i_(corr)) vs. immersing time and polarization resistance(R_P) vs. immersing time, it dedicates that the changes are the result caused by the accumulation of surface rust layer and seawater temperature’s change together.
3) Four kinds of impedance models are adopted to fit EIS plot which represent four different stages. At the early stage, the equivalent circuit only includes double electricity layer capacitance (C_(dl)) and charge transfer resistance(R_t). Following the time’s fluid, rust layer capacitance (C_f) and rust layer resistance (R_f) appear in equivalent circuit. And then, as time’s more prolonging, there are capacitance and resistance caused by microorganism. And the corrosion behaviour of rust-layer/metal system is characterized by the changing trend of Cdl and Rct on time.
4) The corrosion production has been analysed by laser Raman technology and it gives us that the structure and component of corrosion production, while the outer corrosion production is mostlyγ-FeOOH and smackα-Fe_2O_3 and inner corrosion production is mostlyα-Fe_2O_3, Fe_3O_4 and littleγ-FeOOH.
5) The order of stabilization potential tested by indoor aerated seawater condition is consistent with that in natural seawater circumstance. And that the instantaneous corrosion rate(i_(corr)) and polarization resistance(R_P) vs. immersing time are as same as that in natural seawater. The result gained by indoor aerated seawater experiment can recure the result of natural seawater experiment.
6) There are more difference between two indoor experiment and natural seawater experiment. The reason of above issue may be the difference influence of microorganism. The microorganism influence made by natural seawater is strong, and the other is less.
7) Through integral fit, we find the mathematics formulas between corrosion rate and immersing time in three corrode circumstance separately and then contrast them with the mathematics formulas gained by weight loss experiment in three different corrode circumstance. After that, only indoor aerated condition, we find out the result gained by integral fit is inosculating with that gained by weight loss. It shows the method that forecasting corrosion rate gained by integral fit the data of electrochemical test can substitute the method of weight loss’s.
8) The research of this paper show that the integral fit corrosion rate gained by indoor aerated condition can forecast material’s corrosion rate and thereby substitute weight loss experiment. But only the frequency of monitoring is more coarctation, can we assure the veracity of forecasting result.
本文主要研究三种典型船用钢A、B、C在不同实验环境条件下的耐蚀性能。通过电化学试验,探讨了不同的实验环境条件对材料的腐蚀的影响,得到了材料在不同实验条件下的腐蚀规律,并从数学的角度,找出不同试验条件下的腐蚀速度随时间变化的函数关系,得到了适合于所选材料在本地区海水环境腐蚀的模拟公式。本文的主要结论如下:
1.通过实海腐蚀电位监测,B的稳定电位最正,C次之,A最负。其结果与室内模拟静水条件下得到的结果有差别。
2.分别对实海全浸的试样进行了线性极化以及交流阻抗测试,得到瞬时腐蚀速度(i_(corr))和极化电阻(R_P)随浸泡时间的变化,表明其变化是表面锈层的堆积与海水温度变化所带来的影响的共同作用的结果。
3.采用四种阻抗模型对EIS数据进行了拟和,表明全浸可分为四个阶段,浸泡初期,等效电路仅由双电层电容(C_(dl))和电荷转移电阻(R_t)构成。随时间延长,等效电路中出现了反映界面性质的腐蚀产物层电容(C_f)和电阻(R_f)。随时间的进一步延长,阻抗模型中出现了由于微生物而导致的电容及电阻,通过C_(dl)和R_t随浸泡时间的变化表征了材料的腐蚀行为。
4.对腐蚀产物进行激光拉曼分析,得到腐蚀产物的结构成分,外层腐蚀产物主要由γ-FeOOH构成,并有少量α-Fe_2O_3,内锈层主要由α-Fe_2O_3、Fe_3O_4构成,其中也伴有少量γ-FeOOH。
5.室内模拟充气搅拌条件下,材料的稳定电位排序与实海全浸一致,并且其瞬时腐蚀速度(icorr)和极化电阻(RP)随浸泡时间的变化也与实海一致,这说明室内充气搅拌条件得到的实验结果可以很好的重现实海条件下的实验结果。
6.两种室内模拟方法得到的交流阻抗结果与实海有较大差别,原因可能是海水中微生物的影响不同,实海中微生物的影响较强,室内模拟较弱。
7.通过积分拟合的方法分别得到三种实验条件下的腐蚀速度随时间变化的数学公式,通过与失重方法得到的数学公式相对比,可以看出室内充气搅拌实验结果与相应条件下的失重实验结果较好的吻合,说明由电化学方法得到的积分拟合值来计算腐蚀速度的方法完全可以替代失重挂片实验方法。
8.本文的研究表明,由室内模拟充气条件下的电化学实验得到的腐蚀速度完全可以预测材料的腐蚀速度,从而可以替代挂片失重实验。但监测频率要更为密集,才能保证结果的准确性。
Marine environmental is a rigorous corrosion environmental, materials in the process of using is confronted with badly ocean corrosion circumstance all the time. The proportion of accident’s economic loss caused by seawater corrosion is quite high.
At present, the method which appraise the anti-corrode performance of vessel steel is loss weight in natural seawater. The measurement’s merit is experiment condition’s reality, operation simple and result credibility. While there are many shortages in the measurement. For example, the periods of experiment are very long, usually, the shortest experiment periods are one year; the circumstance factors are out of control; consequential the recurrence is bad; the risk caused by losing sample in the process of experiment is high. All shortages above, are mostly issues which restrict the use of new material, new craftwork.
This paper mostly research the anti-corrode performance of three representative vessel steel: A, B, C in different experiment circumstances. Through electrochemistry experiment, we probe into the influence of different experiment circumstances with the corrosion of material, find material corrosion disciplinarian in different experiment circumstances, the function relation between corrosion rate and time in different experiment circumstances from mathematical view and simulation formula which simulate material corrosion in this region. The conclusions of this paper are as follows:
1) Through monitoring corrosion potential in natural seawater, we find that the stabilization potential of B is most positive, the second is C, and A is most negative. While the result gained by natural seawater is different from the conclusion gained by indoor static seawater.
2) Linear polarization test and AC impedance test have been separately carried out on samples immersing entirely in natural seawater, and it give us the change of instantaneous corrosion rate(i_(corr)) vs. immersing time and polarization resistance(R_P) vs. immersing time, it dedicates that the changes are the result caused by the accumulation of surface rust layer and seawater temperature’s change together.
3) Four kinds of impedance models are adopted to fit EIS plot which represent four different stages. At the early stage, the equivalent circuit only includes double electricity layer capacitance (C_(dl)) and charge transfer resistance(R_t). Following the time’s fluid, rust layer capacitance (C_f) and rust layer resistance (R_f) appear in equivalent circuit. And then, as time’s more prolonging, there are capacitance and resistance caused by microorganism. And the corrosion behaviour of rust-layer/metal system is characterized by the changing trend of Cdl and Rct on time.
4) The corrosion production has been analysed by laser Raman technology and it gives us that the structure and component of corrosion production, while the outer corrosion production is mostlyγ-FeOOH and smackα-Fe_2O_3 and inner corrosion production is mostlyα-Fe_2O_3, Fe_3O_4 and littleγ-FeOOH.
5) The order of stabilization potential tested by indoor aerated seawater condition is consistent with that in natural seawater circumstance. And that the instantaneous corrosion rate(i_(corr)) and polarization resistance(R_P) vs. immersing time are as same as that in natural seawater. The result gained by indoor aerated seawater experiment can recure the result of natural seawater experiment.
6) There are more difference between two indoor experiment and natural seawater experiment. The reason of above issue may be the difference influence of microorganism. The microorganism influence made by natural seawater is strong, and the other is less.
7) Through integral fit, we find the mathematics formulas between corrosion rate and immersing time in three corrode circumstance separately and then contrast them with the mathematics formulas gained by weight loss experiment in three different corrode circumstance. After that, only indoor aerated condition, we find out the result gained by integral fit is inosculating with that gained by weight loss. It shows the method that forecasting corrosion rate gained by integral fit the data of electrochemical test can substitute the method of weight loss’s.
8) The research of this paper show that the integral fit corrosion rate gained by indoor aerated condition can forecast material’s corrosion rate and thereby substitute weight loss experiment. But only the frequency of monitoring is more coarctation, can we assure the veracity of forecasting result.
引文
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