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金属学报  2017, Vol. 53 Issue (6): 677-683    DOI: 10.11900/0412.1961.2016.00412
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Cr含量和pH值对低铬管线钢半钝化行为的影响
许立宁(),朱金阳,王贝
北京科技大学新材料技术研究院腐蚀与防护中心 北京100083
Influence of Cr Content and pH Value on the Semi-Passivation Behavior of Low Cr Pipeline Steels
Lining XU(),Jinyang ZHU,Bei WANG
Corrosion and Protection Center, Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
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摘要: 

针对油气管道CO2腐蚀环境,研究了Cr含量为1%~5% (质量分数)的5种低铬钢的阳极极化行为,讨论了半钝化行为受Cr含量的影响规律。测试了不同pH值下5种低铬钢的极化曲线,探究了不同Cr含量的低铬钢出现明显半钝化的临界pH值。利用Raman光谱,对比了在不同pH值溶液中极化生成的腐蚀膜的成分。结果表明,随着Cr含量的升高,低铬钢半钝化特征变得更加明显。在CO2环境下,溶液pH值的升高对Cr(OH)3沉积有利,基体中Cr的溶解导致低铬钢表面生成了Cr(OH)3膜,在极化曲线测试过程中,显示出半钝化的特征。

关键词 低铬钢Cr含量pH值半钝化Cr(OH)3    
Abstract

More than 60% corrosion failure of oil/gas pipeline happened in carbon steel pipeline transporting fluid containing CO2. Adding appropriate amount of Cr to carbon steel can greatly suppress localized corrosion. So, anti-CO2 low Cr steel and its corrosion mechanism become research hotspot. This work found that active-passive transition region occurred when low Cr steel was anodic polarized. But stable broad passive region like typical passivation was not found. This phenomenon was called semi-passivation. The anodic polarization behavior of low Cr steels with Cr content of 1%~5% and the effect of Cr content on semi-passivation in CO2 corrosion environment had been studied and discussed respectively. The anode potentiodynamic polarization curves of five kinds of low Cr steels in solutions with different pH values had been tested, subsequently the critical pH value which made the occurrence of the semi-passivation of low Cr steels with different Cr contents had been explored. The components of the corrosion product films on the low Cr steel samples polarized in solutions with various pH values had been compared through the Raman spectroscopy. The results showed that with the increase of Cr content, the semi-passivation characteristics was more obvious. The pH value of solutions in the CO2 environment contributes to the precipitation of Cr(OH)3. The Cr3+ ions dissolved from the substrate generate the corrosion films of Cr(OH)3 on the surface, resulting in the semi-passivation characteristics in the tests of anode potentiodynamic polarization.

Key wordslow Cr steel    Cr content    pH value    semi-passivation    Cr(OH)3
收稿日期: 2016-09-13      出版日期: 2017-03-31
基金资助:国家科技支撑计划项目No.2012BAK13B04

引用本文:

许立宁,朱金阳,王贝. Cr含量和pH值对低铬管线钢半钝化行为的影响[J]. 金属学报, 2017, 53(6): 677-683.
Lining XU,Jinyang ZHU,Bei WANG. Influence of Cr Content and pH Value on the Semi-Passivation Behavior of Low Cr Pipeline Steels. Acta Metall Sin, 2017, 53(6): 677-683.

链接本文:

http://www.ams.org.cn/CN/10.11900/0412.1961.2016.00412      或      http://www.ams.org.cn/CN/Y2017/V53/I6/677

Steel C Cr Mo Si Mn S P Fe
1Cr 0.07 1.01 0.16 0.20 0.52 0.005 0.004 Bal.
2Cr 0.05 2.06 0.18 0.14 0.53 0.004 0.003 Bal.
3Cr 0.07 2.96 0.15 0.20 0.55 0.003 0.003 Bal.
4Cr 0.05 4.06 0.21 0.13 0.53 0.002 0.009 Bal.
5Cr 0.07 5.00 0.15 0.20 0.55 0.004 0.005 Bal.
表1  实验用低铬钢的化学成分
图1  Cr含量对低铬钢阳极动电位极化曲线的影响
图2  不同Cr含量下低铬钢半钝化电位区间(|Eps-Epf|)及电流密度下降幅度(imax-imin)/imax的对比
图3  不同pH值溶液中低铬钢的阳极动电位极化曲线
图4  3Cr钢在不同pH值溶液中从自腐蚀电位极化至-500 mV表面生成腐蚀膜的Raman光谱
[1] Zhang Z H, Huang Z Y, Sun Y N, et al.Development of 3Cr series oil pipes with good CO2 and H2S corrosion resistant properties[J]. Baosteel Technol., 2006, (3): 5
[1] (张忠铧, 黄子阳, 孙元宁等. 3Cr抗CO2和H2S腐蚀系列油套管开发[J]. 宝钢技术, 2006, (3): 5)
[2] Liang M H, Zhao G X, Feng Y R, et al.The influence of Cr on CO2 corrosion behavior of P110 steel[J]. J. Mater. Eng., 2006, (suppl.1): 31
[2] (梁明华, 赵国仙, 冯耀荣等. 添加Cr元素对P110钢CO2腐蚀行为的影响[J]. 材料工程, 2006, (增刊1): 31)
[3] Xu L N, Wang B, Zhu J Y, et al.Effect of Cr content on the corrosion performance of low-Cr alloy steel in a CO2 environment[J]. Appl. Surf. Sci., 2016, 379: 39
[4] Pfennig A, Kranzmann A.Effect of CO2 and pressure on the stability of steels with different amounts of chromium in saline water[J]. Corros. Sci., 2012, 65: 441
[5] Wu Q L, Zhang Z H, Dong X M, et al.Corrosion behavior of low-alloy steel containing 1% chromium in CO2 environments[J]. Corros. Sci., 2013, 75: 400
[6] Ko M, Ingham B, Laycock N, et al.In situ synchrotron X-ray diffraction study of the effect of chromium additions to the steel and solution on CO2 corrosion of pipeline steels[J]. Corros. Sci., 2014, 80: 237
[7] Kermani B, Gonzales J C, Turconi G L, et al.In-field corrosion performance of 3%Cr steels in sweet and sour downhole production and water injection [A]. Corrosion 2004[C]. New Orleans, LA: NACE International, 2004: 04111
[8] Nyborg R, Dugstad A.Understanding and prediction of mesa corrosion attack [A]. Corrosion 2003[C]. San Diego, CA: NACE International, 2003: 03642
[9] Nice P I, Ueda M.The effect of microstructure and chromium alloying content to the corrosion resistance of low-alloy steel well tubing in seawater injection service [A]. Corrosion 1998[C]. San Diego, CA: NACE International, 1998: 98003
[10] Ueda M, Takabe H.Corrosion resistance of low Cr bearing steel in sour and sweet environments [A]. Corrosion 2002[C]. Denver, CO: NACE International, 2002: 02041
[11] Kermani B, Dougan M, Gonzales J C, et al.Development of low carbon Cr-Mo steels with exceptional corrosion resistance for oilfield applications [A]. Corrosion 2001[C]. Houston, TX: NACE International, 2001: 01065
[12] Paolinelli L D, Simison S N, Pérez T E.The influence of Cr content on the efficiency of inhibitor of C-Mn steel CO2 corrosion [A]. Corrosion 2006[C]. San Diego, CA: NACE International, 2006: 06369
[13] Paolinelli L D, Simison S N, Pérez T E.The influence of steel microstructure, chemical composition and precorrosion on CO2 corrosion inhibitor efficiency [A]. Corrosion 2007[C]. Nashville, TN: NACE International, 2007: 07311
[14] Scoppio L, Piccolo E L, Cristofaro N D, et al.Corrosion problem and its countermeasure of 3Cr production tubing in NaCl completion brine on the Statfjord field [A]. Corrosion 2006[C]. San Diego, CA: NACE International, 2006: 06134
[15] Ueda M, Takabe H, Nice P I.The development and implementation of a new alloyed steel for oil and gas production wells [A]. Corrosion 2000[C]. Orlando, FL: NACE International, 2000: 00154
[16] Kermani B, Gonzales J C, Turconi G L, et al.Window of application and operational track record of low carbon 3Cr steel tubular [A]. Corrosion 2006[C]. San Diego, CA: NACE International, 2006: 06133
[17] Chen C F, Lu M X, Zhao G X, et al.The ion passing selectivity of CO2 corrosion scale on N80 tube steel [A]. Corrosion 2003[C]. San Diego, CA: NACE International, 2003: 03342
[18] Ueda M, Takabe H.The formation behavior of corrosion protective films of low Cr bearing steels in CO2 environments [A]. Corrosion 2001[C]. Houston, TX: NACE International, 2001: 01066
[19] Chen C F, Lu M X, Sun D B, et al.Effect of chromium on the pitting resistance of oil tube steel in a carbon dioxide corrosion system[J]. Corrosion, 2005, 61: 594
[20] Guo S Q, Xu L N, Zhang L, et al.Corrosion of alloy steels containing 2% chromium in CO2 environments[J]. Corros. Sci., 2012, 63: 246
[21] Zhu J Y, Xu L N, Lu M X, et al.Cathodic reaction mechanism of 3Cr low alloy steel corroded in CO2-saturated high salinity solutions[J]. Int. J. Electrochem. Sci., 2015, 10: 1434
[22] Dugstad A.Fundamental aspects of CO2 metal loss corrosion-Part I: Mechanisms [A]. Corrosion 2006[C]. San Diego, CA: NACE International, 2006: 06111
[23] Sidorin D, Pletcher D, Hedges B.The electrochemistry of 13% chromium stainless steel in oilfield brines[J]. Electrochim. Acta, 2005, 50: 4109
[24] Kocijan A, Donik ?, Jenko M.Electrochemical and XPS studies of the passive film formed on stainless steels in borate buffer and chloride solutions[J]. Corros. Sci., 2007, 49: 2083
[25] Jung R H, Tsuchiya H, Fujimoto S.XPS characterization of passive films formed on type 304 stainless steel in humid atmosphere[J]. Corros. Sci., 2012, 58: 62
[26] Ueda M, Ikeda A.Effect of microstructure and Cr content in steel on CO2 corrosion [A]. Corrosion 1996[C]. Denver, Colorado: NACE International, 1996: 96013
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