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钙、镁离子对NC-55E油套管钢CO2腐蚀产物膜性能的影响
其他题名The effect of Ca2+ and Mg2+ ions on the performance of corrosion product scale of NC-55E steel for CO2 corrosion
马丽
学位类型硕士
导师郑玉贵
2007-06-06
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业腐蚀科学与防护★
关键词Co2腐蚀 ca2+浓度 mg2+浓度 腐蚀产物膜 极化电阻 电化学阻抗谱 点蚀 预腐蚀 冲刷
摘要在油气生产和输运过程中,各种管道和设备遭受严重的CO2腐蚀。特别是在流动条件下,由于冲刷作用,腐蚀速率往往比静态下的更高。腐蚀速率的大小经常和腐蚀产物膜的保护性相关。当介质中有Ca2+、Mg2+存在时,静态条件下生成的腐蚀产物膜主要由CaCO3、MgCO3和FeCO3组成,这些腐蚀产物膜有时对基体有保护作用,有必要研究腐蚀产物膜的保护性与介质中Ca2+、Mg2+浓度间的关系,尤其是能否利用短期停工的静态条件来生成腐蚀产物膜,以便达到抵抗随后的冲刷腐蚀。本文通过线性极化、电化学阻抗谱测试和SEM观察,研究了80℃条件下Ca2+、Mg2+浓度对NC-55E套管钢CO2腐蚀产物膜的形成过程和保护性能的影响,以及静态条件下形成的腐蚀产物膜耐动态冲刷的性能。 1. Ca2+对腐蚀产物膜性能的影响 对0.6%、1.5%、2%、3%、4%五种Ca2+浓度下所测得的Rp和电化学阻抗谱结果表明:随着Ca2+浓度增加,Rp和根据阻抗谱拟合后的膜电阻Rf的最大值逐渐增大。在4%的CaCl2溶液中生成的腐蚀产物膜相对更具有保护性。从4%CaCl2腐蚀产物膜的表面和截面形貌可以看出,在浸泡40h左右,腐蚀产物膜保护性能较好,浸泡时间到61h时,腐蚀产物膜开始发生点蚀。为了模拟油田现场介质,研究Ca2+对腐蚀产物膜的影响,采用了3%NaCl +1.5%CaCl2和与之相同Cl-浓度的4.6%NaCl溶液。比较80℃条件下的实验结果发现:Ca2+的加入减缓了材料的腐蚀,延长了点蚀的孕育期;Cl-的加入则加快了腐蚀,缩短了点蚀的孕育期。 2. Mg2+对腐蚀产物膜性能的影响 对0.6%、1.5%、2%、3%、4%五种Mg2+浓度下所测得的Rp和电化学阻抗谱表明:随着Mg2+浓度增加,Rp和根据阻抗谱拟合后的膜电阻Rf的最大值逐渐增大。在4%的MgCl2溶液中生成的腐蚀产物膜相对更具有保护性。从4% MgCl2腐蚀产物膜的表面和截面形貌可以看出,在浸泡48h左右,腐蚀产物膜保护性能较好,浸泡时间到62h时,腐蚀产物膜开始发生点蚀。同样采用了3%NaCl +1.5%MgCl2和浓度与之相同Cl-浓度的4.8%NaCl溶液。比较80℃条件下的实验结果发现:Mg2+的加入也减缓了材料的腐蚀,延长了点蚀的孕育期。 3. 静态条件下形成的腐蚀产物膜在动态条件下的抗冲刷性能 为了研究静态条件下形成的腐蚀产物膜在动态条件下的保护性能,预先在4%CaCl2和4%MgCl2中静态浸泡40h和48h,生成腐蚀产物膜,然后分别在流速为3m/s和5m/s的动态条件下进行冲刷实验。结果表明:经过4%CaCl2和4%MgCl2静态预腐蚀的试样经过3m/s和5m/s冲刷后,在一定的时间内Rp和Rf都要高于没有经过静态预腐蚀的试样。说明,静态预腐蚀所形成的表面膜在一定程度上对基体起到一定的保护作用。在4%CaCl2中静态浸泡40h后的试样,在3m/s和5m/s流速下冲刷,极化电阻Rp在7h和6h时开始明显减小,说明表面膜的保护性发生恶化;类似地,在4%MgCl2中静态浸泡48h的试样,在3m/s和5m/s流速下冲刷,极化电阻Rp在大约6h和4h时开始明显减小,说明表面膜的保护性发生恶化。流速越高,表面膜保护性恶化时间越短。相对来说,CaCO3膜比MgCO3膜的抗冲刷性能略好。
其他摘要The effect of Ca2+ and Mg2+ ions on the performance of corrosion product scale of NC-55E steel for CO2 corrosion Ma Li (Materials Science) Directed by Prefessor Zheng Yugui Abstact In this dissertation, the polarization resistance technique, electrochemical impedance spectroscopy (EIS) and SEM observation were used to investigate the effect of calcium and magnesium ions on the formation process and the protective performance of the corrosion product scale of NC-55E steel for CO2 corrosion at 80℃. The erosion corrosion resistance of the above mentioned corrosion product scale formed under static conditions was also investigated by modified rotating disk rig at 3m/s and 5m/s. 1. The effect of Ca2+ ions on the protective performance of the corrosion product scale The test results in 0.6%、1.5%、2%、3%、4% CaCl2 five solutions showed that under static condition the maximum value of Rp and Rf obtained from EIS increased with the increasing of Ca2+ ion concentration. The corrosion product scale formed in 4%CaCl2 solution had better protective ability. The surface morphologies and cross-section morphologies showed that the corrosion product scale after immersion for about 40h presented better protective ability. But, the corrosion scale was degraded due to pitting corrosion after immersion for 61h. In order to simulate the possible oil field medium containing Ca2+ ions and differentiate the effects of Ca2+ ion and Cl- ion on pitting corrosion, 3%NaCl + 1.5%CaCl2 solution as well as 4.6% NaCl solution, which had the same Cl- concentration as 3%NaCl + 1.5%CaCl2 solution, were chosen to compare with 3%NaCl solution. The results showed that the adding of Ca2+ ion decreased the corrosion rate and prolonged the incubation time of pitting corrosion. Conversely, Cl- ion severely increased the corrosion rate and shortened the incubation time of pitting corrosion. 2. The effect of Mg2+ ions on the protective performance of the corrosion product scale The test results in 0.6%、1.5%、2%、3%、4% MgCl2 five solutions showed that under static condition the maximum value of Rp and Rf obtained from EIS increased with the increasing of Mg2+ ion concentration. The corrosion product scale formed in 4%MgCl2 solution had better protective ability. The surface morphologies and cross-section morphologies showed that the corrosion product scale after immersion for about 48h presented better protective ability. But, the corrosion scale was degraded due to pitting corrosion after immersion for 62h. In order to simulate the possible oil field medium containing Mg2+ ions and differentiate the effects of Mg2+ ion and Cl- ion on pitting corrosion, 3%NaCl +1.5%MgCl2 solution as well as 4.8% NaCl solution, which had the same Cl- concentration as 3%NaCl + 1.5%MgCl2 solution, were chosen to compare with 3%NaCl solution. The results showed that the adding of Mg2+ ion also decreased the corrosion rate and prolonged the incubation time of pitting corrosion. 3. Erosion corrosion resistance of the corrosion product scale formed under static condition In order to investigate the erosion corrosion resistance of the corrosion product scale formed under static condition, the samples were firstly immersed in the 4%CaCl2 and 4%MgCl2 for 40h and 48h respectively to form the corrosion product scale, and then eroded at flow velocity of 3m/s and 5m/s in 3%NaCl. The results showed that the Rp and Rf of samples with pre-formed corrosion product scale were higher than the samples without the precorrosion which indicated that the pre-formed corrosion product scales did provide some protection to the steel. But, the Rp of the samples with pre-formed corrosion product scale in 4%CaCl2 deteriorated after erosion corrosion tests for 7h and 6h respectively at 3m/s and 5m/s. Similarly, the Rp of the samples with pre-formed corrosion product scale in 4%MgCl2 deteriorated after erosion corrosion tests for 6h and 4h respectively at 3m/s and 5m/s. The higher the flow velocity was, the shorter the time to deteriorate for the scales. Comparatively, the CaCO3 scale provided a little bit better protection to the steel than the MgCO3 scale under dynamic condition. Key Words: CO2 corrosion, the concentration of Ca2+ ion, the concentration of Mg2+ ion, corrosion product scale, polarization resistance, electrochemical impedance spectroscopy, pitting corrosion, precorrosion, erosion.
页数96
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/17088
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
马丽. 钙、镁离子对NC-55E油套管钢CO2腐蚀产物膜性能的影响[D]. 金属研究所. 中国科学院金属研究所,2007.
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