海洋浪花飞溅区钢铁腐蚀过程和修复技术研究
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摘要
海洋浪花飞溅区由于干湿交替频率高、供氧充分、含盐粒子量高、来自太阳的紫外线等因素,是海洋腐蚀环境最苛刻的区带。另外浪溅区防腐也是防腐蚀技术的难题,解决该部位的腐蚀控制问题将会大大延长钢结构设施服役寿命。
本文通过对海洋用钢浪溅区带锈试样的电化学极化试验和电化学阻抗试验,考察钢铁在浪溅区腐蚀过程,并采用电子扫描电镜、X射线衍射、激光拉曼光谱分析了试样的腐蚀形貌及成分,探讨了其在浪溅区的腐蚀机理。结果表明,浪花飞溅区之所以腐蚀严重,是因为在海洋浪花飞溅区钢铁表面干湿交替,不仅有溶解氧的还原反应,还存在着锈层自身氧化剂的作用。海洋浪花飞溅区锈层内层为Fe3O4和生长于其上的细小片状γ-FeOOH晶体组成,外锈层由鳞片状γ-FeOOH和少量钟乳石状α-FeOOH组成。γ-FeOOH为海洋环境中钢铁腐蚀的特征产物,其作为氧化剂参与了阴极过程加速了钢铁的腐蚀。在湿润的情况下,金属基体发生腐蚀并与γ-FeOOH发生阴极反应,生成Fe3O4。在干燥阶段末期,Fe3O4又被氧化为γ-FeOOH,形成化学氧化—电化学还原自循环过程,Fe3O4和γ-FeOOH起到催化剂作用。
通过选择缓蚀剂、增稠剂和抗氧剂等,研制了一系列的防锈脂,通过电化学试验和盐雾试验研究了其防锈机理和防锈性能,并确定了各种缓蚀剂和增稠剂等的最佳配方,加工了一种防锈性能优异的防锈脂;选定了缓蚀油脂缠带的基础材料,利用设计的油脂浸胶机,加工了防锈缠带;使用加工的防锈脂和防锈缠带对钢样进行保护,在模拟海洋环境中进行挂片试验后发现施加保护后钢样腐蚀速率比未加保护钢样的腐蚀速率降低了2~4个数量级,说明其具有优异的耐海洋环境腐蚀能力,可以对海洋环境,尤其是浪溅区钢铁结构物进行更长时间的保护。
The splash zone is the most corrosive area in the marine environment due to higher frequency of alternation of wetting and drying, abundant oxygen supply, high amount of oxygen supply, large amount of salt deposition, high irradiation intensity of ultraviolet, etc. The materials exposed in this area would suffer from serious corrosion and it was very difficult to protect the materials exposed in this region. If appropriate protection methods were applied, it would greatly prolong the service lifetime of the whole offshore steel structures exposed in this area.
In the present dissertation, the corrosion processes and mechanisms of steels in splash zone were studied using polarization curve, electrochemical impedance spectroscopy (EIS). The electrochemical results were obtained from the corroded steel samples exposed in splash zone, while, the corrosion morphologies and corrosion products of the steel samples exposed in splash zone were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman.
The reason, which the steel samples suffered from serious corrosion in splash zone, was the alternation of wetting and drying. During the drying process, the electrolyte thickness decreased and chloride concentration increased. Oxygen would be much easier to diffuse into the interface of electrolyte/metal, which improved the cathodic reduction processes. Except for this, the rust itself took part in the reduction processes and hence increased the corrosion rate of the steel samples.
The composition of the inner layer of the rust formed on the steel samples in splash zone were magnetite(Fe3O4), with tiny flaky lepidocrocite(γ-FeOOH) crystal growing on Fe3O4. The composition of the outer rust layer consisted of scaly sliceγ-FeOOH and small amount of stalactitic goethite(α-FeOOH).γ-FeOOH, which is the typical rust of steel in marine envirnment, took part in the cathodic processes as an oxidant and accelerated the corrosion processes of steel. The metal corroded and reacted withγ-FeOOH and Fe3O4 appeared in wet process, while Fe3O4 was oxidized toγ-FeOOH again during dry process. This consisted a self circulation of electrochemical reduction and chemical oxidization, and Fe3O4 andγ-FeOOH acted as catalysts.
Corrosion inhibitors, thickening agents and antioxidants were chosen and series of anti-corrosion grease were produced in the present dissertation. Their anti-corrosion performances were studied using electrochemical methods and salt spray tests. The optimal formula was obtained and one of the anticorrosion greases with best anti-corrosion property was selected. The basic material of anticorrosion tape was selected, and anti-corrosion tape was prepared with the designed dipping machine. With the protection of the prepared grease and tape, the corrosion rate of steels exposed in marine environment was reduced 2~4 orders of magnitude. That is to say, using the anticorrosion grease with the anticorrosion tape could provide effective long term corrosion protection for the steel structure exposed in splash zone.
本文通过对海洋用钢浪溅区带锈试样的电化学极化试验和电化学阻抗试验,考察钢铁在浪溅区腐蚀过程,并采用电子扫描电镜、X射线衍射、激光拉曼光谱分析了试样的腐蚀形貌及成分,探讨了其在浪溅区的腐蚀机理。结果表明,浪花飞溅区之所以腐蚀严重,是因为在海洋浪花飞溅区钢铁表面干湿交替,不仅有溶解氧的还原反应,还存在着锈层自身氧化剂的作用。海洋浪花飞溅区锈层内层为Fe3O4和生长于其上的细小片状γ-FeOOH晶体组成,外锈层由鳞片状γ-FeOOH和少量钟乳石状α-FeOOH组成。γ-FeOOH为海洋环境中钢铁腐蚀的特征产物,其作为氧化剂参与了阴极过程加速了钢铁的腐蚀。在湿润的情况下,金属基体发生腐蚀并与γ-FeOOH发生阴极反应,生成Fe3O4。在干燥阶段末期,Fe3O4又被氧化为γ-FeOOH,形成化学氧化—电化学还原自循环过程,Fe3O4和γ-FeOOH起到催化剂作用。
通过选择缓蚀剂、增稠剂和抗氧剂等,研制了一系列的防锈脂,通过电化学试验和盐雾试验研究了其防锈机理和防锈性能,并确定了各种缓蚀剂和增稠剂等的最佳配方,加工了一种防锈性能优异的防锈脂;选定了缓蚀油脂缠带的基础材料,利用设计的油脂浸胶机,加工了防锈缠带;使用加工的防锈脂和防锈缠带对钢样进行保护,在模拟海洋环境中进行挂片试验后发现施加保护后钢样腐蚀速率比未加保护钢样的腐蚀速率降低了2~4个数量级,说明其具有优异的耐海洋环境腐蚀能力,可以对海洋环境,尤其是浪溅区钢铁结构物进行更长时间的保护。
The splash zone is the most corrosive area in the marine environment due to higher frequency of alternation of wetting and drying, abundant oxygen supply, high amount of oxygen supply, large amount of salt deposition, high irradiation intensity of ultraviolet, etc. The materials exposed in this area would suffer from serious corrosion and it was very difficult to protect the materials exposed in this region. If appropriate protection methods were applied, it would greatly prolong the service lifetime of the whole offshore steel structures exposed in this area.
In the present dissertation, the corrosion processes and mechanisms of steels in splash zone were studied using polarization curve, electrochemical impedance spectroscopy (EIS). The electrochemical results were obtained from the corroded steel samples exposed in splash zone, while, the corrosion morphologies and corrosion products of the steel samples exposed in splash zone were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman.
The reason, which the steel samples suffered from serious corrosion in splash zone, was the alternation of wetting and drying. During the drying process, the electrolyte thickness decreased and chloride concentration increased. Oxygen would be much easier to diffuse into the interface of electrolyte/metal, which improved the cathodic reduction processes. Except for this, the rust itself took part in the reduction processes and hence increased the corrosion rate of the steel samples.
The composition of the inner layer of the rust formed on the steel samples in splash zone were magnetite(Fe3O4), with tiny flaky lepidocrocite(γ-FeOOH) crystal growing on Fe3O4. The composition of the outer rust layer consisted of scaly sliceγ-FeOOH and small amount of stalactitic goethite(α-FeOOH).γ-FeOOH, which is the typical rust of steel in marine envirnment, took part in the cathodic processes as an oxidant and accelerated the corrosion processes of steel. The metal corroded and reacted withγ-FeOOH and Fe3O4 appeared in wet process, while Fe3O4 was oxidized toγ-FeOOH again during dry process. This consisted a self circulation of electrochemical reduction and chemical oxidization, and Fe3O4 andγ-FeOOH acted as catalysts.
Corrosion inhibitors, thickening agents and antioxidants were chosen and series of anti-corrosion grease were produced in the present dissertation. Their anti-corrosion performances were studied using electrochemical methods and salt spray tests. The optimal formula was obtained and one of the anticorrosion greases with best anti-corrosion property was selected. The basic material of anticorrosion tape was selected, and anti-corrosion tape was prepared with the designed dipping machine. With the protection of the prepared grease and tape, the corrosion rate of steels exposed in marine environment was reduced 2~4 orders of magnitude. That is to say, using the anticorrosion grease with the anticorrosion tape could provide effective long term corrosion protection for the steel structure exposed in splash zone.
引文
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