几种金属在海水中阴极保护数值计算及瞬态激励影响研究
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摘要
对于阴极保护下海洋钢结构物(如海洋环境中的管线、船体、储油罐和油气平台等)的电位分布情况,国内外已有较多研究报道。其研究主要集中在稳态下海洋钢结构物的电位和电流分布特征,外加条件通常只有阴极保护而没考虑其它附加激励影响。海洋工程结构的阴极保护系统设计和监、检测较复杂,实海工程造价成本高、工作量大、周期长。数值模拟方法能够减少或避免经验估算法造成的局部区域过保护和欠保护状态,能够计算预测监、检测过程中遗漏的数据和实验手段无法测试的数据。本论文采用理论分析、预实验、模拟计算、实验验证等研究流程,分别对铝基牺牲阳极阴极保护Q275钢、Q275钢保护紫铜、缝隙腐蚀、小尺度激励实验模拟、大尺度激励实验模拟进行了研究。主要工作如下:
1、设计了海水中铝基牺牲阳极保护Q275钢的电极电位分别处于保护范围内、过保护、欠保护状态下的物理模型,推导Laplace方程的弱形式方便了有限元程序设计。利用Kriging网格化插值法比较了有限元计算和实验数据。结果表明,有限元法模拟计算三种保护状态下的电位分布接近测量值。
2、在海水中使用Q275钢作为牺牲阳极保护紫铜,建立了6个二维物理模型。用有限元法模拟计算了各物理模型阴极保护体系的电位分布,并进行实验验证。结果表明,二维有限元法能很好地模拟该阴极保护体系的电位分布。在小范围内Q275钢和紫铜电偶对的距离远近对电位分布影响不大。各模型中具有代表性的X轴、Y轴方向的电位模拟计算值与实测值接近。Q275钢阴极保护紫铜具有可行性,有限元法计算能够为其阴极保护设计提供依据。
3、研究建立了薄、窄缝隙内的化学反应机理模型,该稳态模型细致的描述了缝隙内溶解氧、氢离子反应。模型包括了缝隙内六个平行的电化学反应:多电极反应(Fe、Cr、Ni的溶解氧化反应)和三个阴极反应(氧还原反应、氢还原、水解离)。计算中认为阳极金属反应对腐蚀过程的影响与金属中各元素成分的摩尔比成正比。计算得到了缝隙内pH值、电压、电流密度和氧浓度分布,并进行了实验验证。经分析,计算值和实验验证值接近。
4、提出了阴极保护下海洋钢结构物电化学瞬态响应研究,探讨了在附加恒电量瞬态激励下,钢结构物表面的电位和电流密度分布的响应变化规律。研究介质为海水,分别建立了304不锈钢和Q235钢在不同几何结构、尺寸等边界条件下电位和电流密度随时间的变化响应数值模型。用自制矩阵电极和多通道腐蚀监测器进行了相应的测试实验。进行了附加电化学瞬态激励钢结构物的电位分布实验,并对各模型进行数值模拟。
5、完成了海水中大尺度钢架在有或无阴极保护下,受附加电化学瞬态激励后的电位响应实验。分别建立不同瞬态激励实验模型,通过模拟计算,初步研究了各模型的钢架表面电位和电流密度分布随时间延迟的响应变化规律。
There are many researches on the potential distributions of marine steel structure under cathodic protection (CP) condition, such as pipelines, hulls, oil tanks and oil/gas platforms in marine environment. These researches were focused on the study of potential distributions and current distributions of marine structures which were under steady state condition of CP, and other transient impulses were not considered. It is difficult to design an effective cathodic protection system and corrosion detection and monitoring system for complicated and huge steel structures in marine environment. The engineering will cost a lot of time and money with a lot of works. Numerical simulation method could decrease over-protection or defective protection in local area of the traditional methods based on experiential estimate in real marine environment. The calculation could offer lost collecting data of detection and monitoring, and could get the data which experiments could not test. The study of the paper follows the following order: theory analysis, pre-experiments, numerical simulation, and verification test. The study has learned Q275 steel protected by aluminum sacrificial anode, copper protected by medium carbon steel, crevice corrosion, small scale electrochemical transient impulse test, and large scale electrochemical transient impulse test. The highlights are summarized as follows:
1. Physical models of cathodic protection for Q275 steel by aluminum sacrificial anode in seawater were built, under different conditions of normal cathodic protection, over-protection and under-protection, respectively. And the weak form of Laplace equation was deduced to make finite element method (FEM) numerical calculation conveniently. The comparison of FEM data and measured experimental data was made by Kriging gridding interpolation. The results show that the potential distributions under three protection conditions simulated by FEM approximated to measured experimental results.
2. Six different 2-D physical models for cathodic protection of copper by medium carbon steel as sacrificial anode in seawater are built in this paper. Potential distribution of various physical models was computed by FEM, and followed by experimental measurements for validation. The results show clearly that potential distribution of the cathodic protection system could be well simulated by the 2-D FEM solution. The distance of the galvanic couples is not a key factor influencing potential distribution in small range. Typical simulation data (along X-axis and Y-axis) of different models are consistent with the experimentally measured results. Therefore, it should be feasible to protect copper with medium carbon steel as sacrificial anode, and FEM could afford well a basis for cathodic protection design.
3. A mechanistic model was presented to describe the chemical reactions within the corroding thin and narrow crevice. In the mathematical model, a two-dimensional steady-state was used to predict the crevice pH profile by taking into account dissolved oxygen and hydrogen ions within the crevice. It consists of six parallel electrochemical reactions: multi-anodic reactions (Fe, Cr, Ni dissolution reactions) and three cathodic reactions (the oxygen reduction, the hydrogen reaction and water dissociation). Current density distributions and oxygen concentration distribution were determined to be corresponding to the evolution of potential distribution within the crevice. The contribution of each metal reaction to the overall corrosion process was in proportion to the mole fraction, and the simulation provided a good agreement with published experimental results for the crevice corrosion of stainless steel in sodium chloride solution.
4. The electrochemical response behaviors on marine structures by electrochemical transient impulse were studied in this paper. The law of potential and current density distributions of steel structure surface with coulostatic impulse response was discussed. The numerical simulation models of potential vs. time for 304 stainless steel and Q235 steel were established in seawater. Its boundary includes different geometry structures and sizes. The self-made array electrodes and multi-channel corrosion monitor were used for tests. Potential distribution of steel structures was impulsed by electrochemical transient response. And all models were calculated by numerical simulation.
5. The paper has accomplished the tests of potential responses for large scale steel frame which were with or without cathodic protection influenced by electrochemical transient impulse. Different transient impulse models of experiments were respectively established. The variation laws of potential and current distributions of steel frame surfaces as time delayed were studied by numerical simulation.
1、设计了海水中铝基牺牲阳极保护Q275钢的电极电位分别处于保护范围内、过保护、欠保护状态下的物理模型,推导Laplace方程的弱形式方便了有限元程序设计。利用Kriging网格化插值法比较了有限元计算和实验数据。结果表明,有限元法模拟计算三种保护状态下的电位分布接近测量值。
2、在海水中使用Q275钢作为牺牲阳极保护紫铜,建立了6个二维物理模型。用有限元法模拟计算了各物理模型阴极保护体系的电位分布,并进行实验验证。结果表明,二维有限元法能很好地模拟该阴极保护体系的电位分布。在小范围内Q275钢和紫铜电偶对的距离远近对电位分布影响不大。各模型中具有代表性的X轴、Y轴方向的电位模拟计算值与实测值接近。Q275钢阴极保护紫铜具有可行性,有限元法计算能够为其阴极保护设计提供依据。
3、研究建立了薄、窄缝隙内的化学反应机理模型,该稳态模型细致的描述了缝隙内溶解氧、氢离子反应。模型包括了缝隙内六个平行的电化学反应:多电极反应(Fe、Cr、Ni的溶解氧化反应)和三个阴极反应(氧还原反应、氢还原、水解离)。计算中认为阳极金属反应对腐蚀过程的影响与金属中各元素成分的摩尔比成正比。计算得到了缝隙内pH值、电压、电流密度和氧浓度分布,并进行了实验验证。经分析,计算值和实验验证值接近。
4、提出了阴极保护下海洋钢结构物电化学瞬态响应研究,探讨了在附加恒电量瞬态激励下,钢结构物表面的电位和电流密度分布的响应变化规律。研究介质为海水,分别建立了304不锈钢和Q235钢在不同几何结构、尺寸等边界条件下电位和电流密度随时间的变化响应数值模型。用自制矩阵电极和多通道腐蚀监测器进行了相应的测试实验。进行了附加电化学瞬态激励钢结构物的电位分布实验,并对各模型进行数值模拟。
5、完成了海水中大尺度钢架在有或无阴极保护下,受附加电化学瞬态激励后的电位响应实验。分别建立不同瞬态激励实验模型,通过模拟计算,初步研究了各模型的钢架表面电位和电流密度分布随时间延迟的响应变化规律。
There are many researches on the potential distributions of marine steel structure under cathodic protection (CP) condition, such as pipelines, hulls, oil tanks and oil/gas platforms in marine environment. These researches were focused on the study of potential distributions and current distributions of marine structures which were under steady state condition of CP, and other transient impulses were not considered. It is difficult to design an effective cathodic protection system and corrosion detection and monitoring system for complicated and huge steel structures in marine environment. The engineering will cost a lot of time and money with a lot of works. Numerical simulation method could decrease over-protection or defective protection in local area of the traditional methods based on experiential estimate in real marine environment. The calculation could offer lost collecting data of detection and monitoring, and could get the data which experiments could not test. The study of the paper follows the following order: theory analysis, pre-experiments, numerical simulation, and verification test. The study has learned Q275 steel protected by aluminum sacrificial anode, copper protected by medium carbon steel, crevice corrosion, small scale electrochemical transient impulse test, and large scale electrochemical transient impulse test. The highlights are summarized as follows:
1. Physical models of cathodic protection for Q275 steel by aluminum sacrificial anode in seawater were built, under different conditions of normal cathodic protection, over-protection and under-protection, respectively. And the weak form of Laplace equation was deduced to make finite element method (FEM) numerical calculation conveniently. The comparison of FEM data and measured experimental data was made by Kriging gridding interpolation. The results show that the potential distributions under three protection conditions simulated by FEM approximated to measured experimental results.
2. Six different 2-D physical models for cathodic protection of copper by medium carbon steel as sacrificial anode in seawater are built in this paper. Potential distribution of various physical models was computed by FEM, and followed by experimental measurements for validation. The results show clearly that potential distribution of the cathodic protection system could be well simulated by the 2-D FEM solution. The distance of the galvanic couples is not a key factor influencing potential distribution in small range. Typical simulation data (along X-axis and Y-axis) of different models are consistent with the experimentally measured results. Therefore, it should be feasible to protect copper with medium carbon steel as sacrificial anode, and FEM could afford well a basis for cathodic protection design.
3. A mechanistic model was presented to describe the chemical reactions within the corroding thin and narrow crevice. In the mathematical model, a two-dimensional steady-state was used to predict the crevice pH profile by taking into account dissolved oxygen and hydrogen ions within the crevice. It consists of six parallel electrochemical reactions: multi-anodic reactions (Fe, Cr, Ni dissolution reactions) and three cathodic reactions (the oxygen reduction, the hydrogen reaction and water dissociation). Current density distributions and oxygen concentration distribution were determined to be corresponding to the evolution of potential distribution within the crevice. The contribution of each metal reaction to the overall corrosion process was in proportion to the mole fraction, and the simulation provided a good agreement with published experimental results for the crevice corrosion of stainless steel in sodium chloride solution.
4. The electrochemical response behaviors on marine structures by electrochemical transient impulse were studied in this paper. The law of potential and current density distributions of steel structure surface with coulostatic impulse response was discussed. The numerical simulation models of potential vs. time for 304 stainless steel and Q235 steel were established in seawater. Its boundary includes different geometry structures and sizes. The self-made array electrodes and multi-channel corrosion monitor were used for tests. Potential distribution of steel structures was impulsed by electrochemical transient response. And all models were calculated by numerical simulation.
5. The paper has accomplished the tests of potential responses for large scale steel frame which were with or without cathodic protection influenced by electrochemical transient impulse. Different transient impulse models of experiments were respectively established. The variation laws of potential and current distributions of steel frame surfaces as time delayed were studied by numerical simulation.
引文
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