磁处理与缓蚀剂2-巯基苯并噻唑结合对铜的缓蚀效能与机理

doi:10.11949/j.issn.0438-1157.20171062

摘要/Abstract

摘要：

为了考察磁处理与缓蚀剂2-巯基苯并噻唑（MBT）是否具有协同缓蚀作用，采用腐蚀失重法，测试了恒磁场、交变磁场、缓蚀剂MBT以及磁处理与MBT结合作用下紫铜挂片的腐蚀速率，并通过SEM、XRD、ATR-FTIR等分析方法研究了缓蚀作用机理。研究结果表明恒磁场缓蚀作用较小，而交变磁场具有一定缓蚀作用，其缓蚀机理是生成致密氧化物膜覆盖在金属表面。交变磁场能够降低水分子的极性，给水分子以能量和活性，从而增加了有机缓蚀剂MBT在水中的溶解度，在铜片上吸附的MBT量也相应增加了，因此，交变磁场与MBT具有协同缓蚀作用。达到同等缓蚀效能，协同作用可使得MBT用量减少60%。由于MBT是溶解在氢氧化钠溶液中，用量少则引入的碱含量随之降低，客观上降低了发电机内冷液的电导率。

关键词: 交变磁场, 缓蚀剂, 腐蚀, 表面, 吸附

Abstract:

In order to investigate whether magnetic treatment and 2-mercaptobenzothiazole (MBT) have synergistic effect on corrosion inhibition, corrosion rate of red copper was measured under different treatment conditions by weight loss method. The treatments included permanent magnetic field, alternative magnetic field, corrosion inhibitor MBT, and combination of MBT and magnetic field. Mechanism of corrosion inhibition was studied with assistance of SEM, XRD and ATR-FTIR. The results showed that permanent magnetic field had little effect on corrosion inhibition, but alternative magnetic field had some improvement on corrosion inhibition by forming compact oxide film on copper surface. Alternative magnetic field reduced water polarity and gave water molecules power and activity, which increased MBT solubility in water and adsorbance on copper surface. Therefore, combination of alternative magnetic field and MBT has synergistic effect on corrosion inhibition. To achieve same corrosion inhibition effect as MBT itself, synergistic effect could decrease MBT usage by 60%. Because MBT is dissolved in NaOH solution, less MBT will reduce alkali consumption and lower conductivity of cooling water in power generator.

Key words: alternating magnetic field, corrosion inhibitor, corrosion, surface, adsorption

中图分类号:

TQ172.4

孙旭辉, 齐原, 董书玉. 磁处理与缓蚀剂2-巯基苯并噻唑结合对铜的缓蚀效能与机理[J]. 化工学报, 2018, 69(5): 2120-2126.

SUN Xuhui, QI Yuan, DONG Shuyu. Copper corrosion inhibition mechanism by combination of 2-mercaptobenzothiazole and magnetic treatment[J]. CIESC Journal, 2018, 69(5): 2120-2126.

参考文献 32

[1]	濮文虹, 杨道武, 庹文群, 等. WY-1复合缓蚀剂用于发电机内冷水系统防腐蚀[J]. 长沙水电师院学报(自然科学版), 1995, (3):248-252. PU W H, YANG D W, TUO W Q, et al. Study on compound inhibitor WY-1 used in anticorrosion of cooling water system for generator stator winding in copper[J]. Journal of Changsha University of Electric Power (Natural Science), 1995, (3):248-252.
[2]	闫爱军, 路育龙. 发电机内冷水处理技术的研究进展[J]. 陕西电力, 2006, 34(1):5-7. YAN A J, LU Y L. Study development of generator inner cooling water treatment technology[J]. Northwest China Electric Power, 2006, 34(1):5-7.
[3]	白亚民, 戴骥, 宋朝晖. 优化发电机内冷却水防止铜腐蚀的方法和措施[J]. 电力设备, 2006, 7(4):76-78. BAI Y M, DAI J, SONG Z H. Method and measures of optimizing generator cooling-water to prevent copper corrosion[J]. Electrical Equipment, 2006, 7(4):76-78.
[4]	范圣平, 苏伟, 曹顺安. 发电机内冷水处理技术研究进展[J]. 广东电力, 2015, (4):7-11. FAN S P, SU W, CAO S A. Research development of treatment technology for generator inner cooling water[J]. Guangdong Electric Power, 2015, (4):7-11.
[5]	严川伟, 程明, 赵珲. MBT、BTA和MBO对铜缓蚀性能的电化学研究[J]. 腐蚀与防护, 2000, 21(6):255-256. YAN C W, CHENG M, ZHAO H. Inhibition of 2-mercaptobenzoxazole(MBO) for copper corrosion in NaCl and HCl solutions[J]. Corrosion & Protection, 2000, 21(6):255-256.
[6]	贺甜, 谭澄宇, 唐娟, 等. 铜经MBT和HQ钝化处理后在3.5% NaCl溶液中的电化学行为[J]. 中国有色金属学报, 2013, (5):1388-1395. HE T, TAN C Y, TANG J, et al. Electrochemical behavior of copper passivated by MBT and HQ in 3.5% NaCl solution[J]. The Chinese Journal of Nonferrous Metals, 2013, (5):1388-1395.
[7]	崔航, 谭澄宇, 郑勇, 等. 铜经BTA和MBT钝化处理后在NaCl溶液中电化学行为分析[J]. 中南大学学报(自然科学版), 2011, 42(11):3336-3341. CUI H, TAN C Y, ZHENG Y, et al. Electrochemical behavior of copper passivated by BTA and MBT in NaCl solution[J]. Journal of Central South University (Science and Technology), 2011, 42(11):3336-3341.
[8]	孙旭辉, 李文超, 李冰, 等. 高铁酸盐的制备、性质及在水处理中的应用[J]. 东北电力大学学报, 2015, 35(4):33-39. SUN X H, LI W C, LI B, et al. Preparation, properties and application of ferrate in water treatment[J]. Journal of Northeast Dianli University, 2015, 35(4):33-39.
[9]	FATHI A, MOHAMED T, CLAUDE G, et al. Effect of a magnetic water treatment on homogeneous and heterogeneous precipitation of calcium carbonate[J]. Water Research, 2006, 40(10):1941-1950.
[10]	ZAIDI N S, SOHAILI J, MUDA K, et al. Magnetic field application and its potential in water and wastewater treatment systems[J]. Separation & Purification Reviews, 2014, 43(3):206-240..
[11]	王建国, 梁延东, 尹钊, 等. 电磁抑垢效果及其机理研究进展[J]. 东北电力大学学报, 2016, 36(6):1-6. WANG J G, LIANG Y D, YIN Z, et al. A research review of electromagnetic anti-scale effect and its mechanism[J]. Journal of Northeast Dianli University, 2016, 36(6):1-6.
[12]	MADSEN H E L. Crystallization of calcium carbonate in magnetic field in ordinary and heavy water[J]. Journal of Crystal Growth, 2004, 267(1/2):251-255..
[13]	CHANG M C, TAI C Y. Effect of the magnetic field on the growth rate of aragonite and the precipitation of CaCO3[J]. Chemical Engineering Journal, 2010, 164(1):1-9.
[14]	王建国, 李斌, 梁延东, 等. 基于介稳区的电磁抑垢最佳磁场强度探寻[J]. 化工学报, 2016, 67(9):3658-3662. WANG J G, LI B, LIANG Y D, et al. Detecting the best electromagnetic field intensity in experiment of electromagnetic anti-fouling based on metastable zone[J]. CIESC Journal, 2016, 67(9):3658-3662.
[15]	GONCHARUK V V, BAGRⅡ V A, BASHTAN S Y. Crystallization of calcium carbonate from aqueous solutions in superimposition of electric and magnetic fields[J]. Journal of Water Chemistry & Technology, 2012, 34(3):133-135.
[16]	张欣, 黑田正和. 利用磁场处理水的研究[J]. 给水排水, 2001, 27(4):18-21. ZHANG X, KURODA M. Approach to water treatment in magnetic field[J]. Water and Wastewater Engineering, 2001, 27(4):18-21.
[17]	刘卫国, 孙祖芳. 磁处理的缓蚀试验[J]. 石油化工腐蚀与防护, 2008, 25(4):11-13. LIU W G, SUN Z F. Test of corrosion inhibition by magnetic treatment[J]. Corrosion & Protection in Petrochemical Industry, 2008, 25(4):11-13
[18]	李克娟, 郑碧娟, 陈碧, 等. 磁场对Q235钢微生物腐蚀行为的影响[J]. 中国腐蚀与防护学报, 2013, 33(6):463-469. LI K J, ZHENG B J, CHEN B, et al. Effect of magnetic field on microbiologically-influenced corrosion behavior of Q235 steel[J]. Journal of Chinese Society for Corrosion and Protection, 2013, 33(6):463-469.
[19]	KELLY E J. Magnetic field effects on electrochemical reactions occurring at metal/flowing-electrolyte interfaces[J]. J. Electrochem. Soc., 1977, 124(7):987-994.
[20]	田光, 魏爱军, 霍富永, 等. 磁场对金属腐蚀的实验研究[J]. 管道技术与设备, 2010, (1):50-52. TIAN G, WEI A J, HUO F Y, et al. An experiment study of the magnetic field on metal corrosion[J]. Pipeline Technique and Equipment, 2010, (1):50-52.
[21]	王红萍, 许崇武. 静电场和磁场对碳钢表面结垢和腐蚀的影响[J]. 武汉大学学报(工学版), 2002, 35(6):68-76. WANG H P, XU C W. Effect of electrostatic and magnetic field on scaling and corrosion on surface of carbon steel[J]. Engineering Journal of Wuhan University, 2002, 35(6):68-76.
[22]	ZHANG P, ZHU Q, QIAN S U, et al. Corrosion behavior of T2 copper in 3.5% sodium chloride solution treated by rotating electromagnetic field[J]. Transactions of Nonferrous Metals Society of China, 2016, 26(5):1439-1446.
[23]	孙旭辉, 李迎, 常星岚, 等. 低强度交变磁场对盐水中紫铜的缓蚀作用[J]. 东北电力大学学报, 2015, 5(35):27-32. SUN X H, LI Y, CHANG X L, et al. The Effects of low-intensity alternating magnetic field on corrosion inhibition of copper in NaCl solution[J]. Journal of Northeast Dianli University, 2015, 5(35):27-32.
[24]	韩建勋, 葛红花, 叶明君, 等. 磁场作用下苯并三氮唑对黄铜的缓蚀性能研究[J]. 上海电力学院学报, 2014, 30(2):145-148. HAN J X, GE H H, YE M J, et al. Corrosion inhibitor performance research of brass electrode under the action of BTA and magnetic treatment[J]. Journal of Shanghai University of Electric Power, 2014, 30(2):145-148.
[25]	孟媛媛, 张国福, 宋天民, 等. 磁场在工业用水缓蚀方面的研究[J]. 化工时刊, 2007, 21(10):10-13. MENG Y Y, ZHANG G F, SONG T M, et al. Study of magnetic treatment on defending corrosion of industrial water[J]. Chemical Industry Times, 2007, 21(10):10-13.
[26]	迟金宝, 张雪峰, 苍大强, 等. 低频电磁场处理中水的静态阻垢缓蚀试验研究[J]. 钢铁, 2009, 44(6):89-93. CHI J B, ZHANG X F, CANG D Q, et al. Experimental research on static scale and corrosion inhibition using low frequency electromagnetic treatment of reclaimed water[J]. Iron and Steel, 2009, 44(6):89-93.
[27]	刘卫国, 刘建东, 赵陈龙. 水的磁处理防腐蚀机理研究[J]. 腐蚀与防护, 2006, 27(4):196-198. LIU W G, LIU J D, ZHAO C L. Corrosion-prevention mechanism in magnetic treatment of water[J]. Corrosion & Protection, 2006, 27(4):196-198.
[28]	李风亭, 张冰如. 2-巯基苯并噻唑在铜表面的吸附状态[J]. 腐蚀与防护, 2002, 23(8):344-344. LI F T, ZHANG B R. Adsorption of 2-mercaptobenzothiazole on copper surface[J]. Corrosion and Protection, 2002, 23(8):344-348.
[29]	TOLEDO E J L, RAMALHO T C, MAGRIOTIS Z M. Influence of magnetic field on physical-chemical properties of the liquid water:insights from experimental and theoretical models[J]. Journal of Molecular Structure, 2008, 888(1/2/3):409-415.
[30]	徐群杰, 周国定, 陆柱, 等. 苯并三氮唑与5-羧基苯并三氮唑在NaCl溶液中对铜缓蚀作用的SERS研究[J]. 华东理工大学学报(自然科学版), 2001, 27(2):181-185. XU Q J, ZHOU G D, LU Z, et al. SERS Studies of the corrosion inhibition of BTA and its derivative 5-CBTA on copper electrode in NaCl solution[J]. Journal of East China University of Science and Technology(Natural Science), 2001, 27(2):181-185.
[31]	韦萍洁, 袁亚仙, 顾仁敖, 等. N-甲基咪唑与2, 2'-联吡啶在铜表面共吸附的SERS研究[J]. 光谱学与光谱分析, 2008, 28(12):2868-2871. WEI P J, YUAN Y X, GU R A, et al. Surface enhanced Raman spectroscopic studies on the coadsorption of N-methylimidazole and 2, 2'-bipyridine at Cu electrode[J]. Spectroscopy and Spectral Analysis, 2008, 28(12):2868-2871.
[32]	霍胜娟, 陈利红, 祝卿, 等. 2-巯基苯并噻唑对铜缓蚀行为的表面增强红外光谱研究[J]. 物理化学学报, 2013, 29 (12):2565-2572. HUO S J, CHEN L H, ZHU Q, et al. Surface-enhanced infrared absorption spectroscopy study of anticorrosion behavior of 2-mercaptobenzothiazole on copper[J]. Acta Physico-Chimica Sinica, 2013, 29(12):2565-2572.