环己胺甲基脲气相缓蚀剂的缓蚀作用研究
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摘要
目的考察环己胺甲基脲(CAU)气相缓蚀剂的防腐蚀性能和成膜特性。方法采用密闭空间挥发减量实验考察了CAU气相挥发能力,通过气相缓蚀能力实验和气相防锈甄别实验研究了它对碳钢的气相缓蚀保护作用,采用ACM电极技术考察了CAU预膜对碳钢电极腐蚀电化学行为的影响,通过XPS技术分析了其在碳钢表面的吸附成膜特性。结果环己胺甲基脲的挥发性较小,72 h、50℃条件下密闭空间挥发减量大约为1.0%。经过20 h诱导期,气相缓蚀实验的碳钢试片无锈蚀。气相防锈甄别实验中,CAU可以使碳钢的腐蚀率从311.9 mg/(m~2·h)降低至64.76 mg/(m~2·h),对碳钢缓蚀效率为79.24%。CAU预膜电极电化学阻抗谱呈现弥散效应,经过30 min的CAU预膜,碳钢电极的电荷传递电阻从1.32 k?·cm~2提高到3.81 k?·cm~2。环己胺甲基脲可以挥发到达碳钢表面,通过分子中的N原子、O原子和Fe原子发生化学配位作用,吸附在碳钢表面形成保护膜。结论环己胺甲基脲是性能优良的碳钢气相缓蚀剂。
The work aims to investigate the anticorrosion properties and film formation properties of cyclohexyl-aminoethyl-urea(CAU)as a volatile corrosion inhibitor(VCI).The gas volatility of CAU was investigated by volatility reduction experiment in confined space and the corrosion inhibition for mild steel was evaluated by volatile inhibiting ability(VIA)test and volatile inhibiting sieve(VIS)test.ACM scanning vibrating electrode technique was applied to study the effect of CAU on the corrosion inhibition of mild steel under a thin electrolyte layer.In addition,X-ray photoelectron spectrometry(XPS)was used to illuminate the mechanism of the film formation for CAU on the steel surface.The volatility of CAU was less and the volatile quantity was about 1.0%after 72 h in a closed space at 50℃.The steel specimens had no rust after 20 h volatilization period in the VIA test.CAU promoted the corrosion rate of mild steel to decrease from 311.9 mg/(m~2·h)to 64.76 mg/(m~2·h)in the VIS test and the corrosion inhibition rate of CAU on mild steel was 79.24%.Nyquist plots of EIS rendered a dispersion effect and the charge transfer resistance of mild steel increased from 1.32 k?·cm~2 to 3.81 k?·cm~2 after 30 min CAU pre-film process.CAU could volatilize to the surface of mild steel and formed chemical coordination on the surface through atoms N,O and Fe to form a protective film.CAU has good inhibition effect against the atmospheric corrosion of mild steel.
The work aims to investigate the anticorrosion properties and film formation properties of cyclohexyl-aminoethyl-urea(CAU)as a volatile corrosion inhibitor(VCI).The gas volatility of CAU was investigated by volatility reduction experiment in confined space and the corrosion inhibition for mild steel was evaluated by volatile inhibiting ability(VIA)test and volatile inhibiting sieve(VIS)test.ACM scanning vibrating electrode technique was applied to study the effect of CAU on the corrosion inhibition of mild steel under a thin electrolyte layer.In addition,X-ray photoelectron spectrometry(XPS)was used to illuminate the mechanism of the film formation for CAU on the steel surface.The volatility of CAU was less and the volatile quantity was about 1.0%after 72 h in a closed space at 50℃.The steel specimens had no rust after 20 h volatilization period in the VIA test.CAU promoted the corrosion rate of mild steel to decrease from 311.9 mg/(m~2·h)to 64.76 mg/(m~2·h)in the VIS test and the corrosion inhibition rate of CAU on mild steel was 79.24%.Nyquist plots of EIS rendered a dispersion effect and the charge transfer resistance of mild steel increased from 1.32 k?·cm~2 to 3.81 k?·cm~2 after 30 min CAU pre-film process.CAU could volatilize to the surface of mild steel and formed chemical coordination on the surface through atoms N,O and Fe to form a protective film.CAU has good inhibition effect against the atmospheric corrosion of mild steel.
引文
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[2]张大全.气相防锈材料的开发与应用[J].腐蚀与防护,2007(7):325-328.ZHANG Da-quan. Application and development of volatile corrosion inhibition materials[J]. Corrosion&protection, 2007(7):325-328.
[3]张阔,杜敏,张静.在模拟酸性海洋大气环境中锌缓蚀剂的研制[J].装备环境工程, 2016, 13(5):140-146.ZHANGKuo,DUMin,ZHANGJing.Thedevelopment of corrosion inhibitor for zinc in simulated acidic marine atmosphere[J]. Equipment enviromental engineering, 2016,13(5):140-146.
[4]张军锋,李晓妮,张小红,等.曼尼希碱类缓蚀剂缓蚀性能及其影响因素[J].清洗世界, 2016, 32(2):18-26. ZHANG Jun-feng, LI Xiao-ni, ZHANG Xiao-hong, et al.Corrosioninhibitionperformanceandinfluencingfactors ofmannichbasecorrosioninhibitors[J].Cleaningworld,2016, 32(2):18-26.
[5]BELARBIZ,FARELASF,SINGERM,etal.Roleof aminesinthemitigationofCO2topofthelinecorrosion[J]. Corrosion, 2016, 72(10):1300-1310.
[6]张大全.缓蚀技术研究进展及在能源工业中的应用[J].上海电力学院学报, 2013, 29(4):355-363.ZHANGDa-quan.Researchprogressforcorrosioninhibitorscienceandtechnologyanditsapplicationinenergy industry[J]. Journal of Shanghai university of electric power, 2013, 29(4):355-363.
[7]刘志辉,王霞,吴艺琛.曼尼希碱型酸化缓蚀剂研究进展[J].应用化工, 2014, 43(1):148-150.LIUZhi-hui,WANGXia,WUYi-chen.Researchprogressofmannichbaseinhibitorsforacidification[J].Applied chemical industry, 2014, 43(1):148-150.
[8]李海清,钱静,王彤.一种气相缓蚀剂的密闭空间定量评价方法[J].包装工程, 2012, 33(19):94-98.LI Hai-qing, QIAN Jing, WANG Tong. A confined space quantitativeevaluationmethodofvaporphasecorrosion inhibitors[J]. Packaging engineering, 2012, 33(19):94-98.
[9]GAO Guo, LIANG Cheng-hao, WANG Hua. Synthesis of tertiary amines and their inhibitive performance on carbon steelcorrosion[J].Corrosionscience,2007,49(4):1833-1846.
[10]陶蕾,郑书忠,秦立娟,等.电化学测试技术在缓蚀剂缓蚀行为研究中的应用[J].工业水处理,2010,30(8):1-5.TAO Lei, ZHENG Shu-zhong, QIN Li-juan, et al. Application of electrochemical measurement technology in the inhibitionbehaviorresearchofcorrosioninhibitors[J].Industrial water treatment, 2010, 30(8):1-5.
[11]BELARBI Z, VU T N, FARELAS F, et al. Thiols as volatilecorrosioninhibitorsfortop-of-the-linecorrosion[J].Corrosion, 2017, 73(7):892-899.
[12]滕飞,胡钢.WB-1复合气相缓蚀剂对清代带锈铁质钱币文物的保护研究[J].文物保护与考古科学,2016,28(1):18-23.TENG Fei, HU Gang. Performance of volatile compound WB-1 corrosion inhibitor on rusty iron coins of qing dynasty[J].Scienceofconservationandarchaeology,2016,28(1):18-23.
[13]安仲勋,潘庆谊,张大全,等.新型吗啉类气相缓蚀剂的电化学阻抗研究[J].材料保护, 2003(5):14-16.ANZhong-xun,PANQing-yi,ZHANGDa-quan,etal.Electrochemicalbehaviorofmorpholinederivativevolatilecorrosioninhibitor[J].Materialsprotection,2003(5):14-16.
[14]张大全,高立新,周国定.多单元气相缓蚀剂的合成,气相缓蚀能力及电化学研究[J].电化学,2003(3):308-313.ZHANGDa-quan,GAOLi-xin,ZHOUGuo-ding.Synthesisofpolyunitvaporphaseinhibitoranditsvolatile corrosioninhibitionperformance[J].Journalofelectrochemistry, 2003(3):308-313.
[15]EIBL S, REINER D. Correlation of content and corrosion protectionofvolatilecorrosioninhibitorsinpackaging material-regaining trust in VCI[J]. Materials&corrosion,2011, 62(8):745-752.
[16]ZHANGDa-quan,GAOLi-xin,ZHOUGuo-ding.Polyaminecompoundasavolatilecorrosioninhibitorforatmosphericcorrosionofmildsteel[J].Materials&corrosion, 2007, 58(8):594-598.
[17]董晓静.乙醇胺化合物缓蚀性能的研究[D].哈尔滨:哈尔滨工业大学, 2007.DONGXiao-jing.Thestudyoninhibitorcapabilityof ethanolaminescompound[D].Harbin:HarbinInstituteof Technology, 2007.
[18]VALENTE M A G, TEIXEIRA D A, AZEVEDO D L, et al.Caprylatesaltsbasedonaminesasvolatilecorrosion inhibitors for metallic zinc:Theoretical and experimental studies[J]. Frontiers in chemistry, 2017, 5:1-18.
[19]ZHANGDa-quan,GAOLi-xin,ZHOUGuo-ding.Self-assembledurea-aminecompoundasvaporphase corrosioninhibitorformildsteel[J].Surface&coatings technology, 2010, 204(9):1646-1650.
[20]KASHKOVSKIY R V, KUZNETSOV Y I, KAZANSKY LP.Inhibitionofhydrogensulfidecorrosionofsteelin gasphasebytributylamine[J].Corrosionscience,2012,64:126-136.