CN106245035A - 一种多胺类铜缓蚀剂 - Google Patents

一种多胺类铜缓蚀剂 Download PDF

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CN106245035A
CN106245035A CN201610655844.9A CN201610655844A CN106245035A CN 106245035 A CN106245035 A CN 106245035A CN 201610655844 A CN201610655844 A CN 201610655844A CN 106245035 A CN106245035 A CN 106245035A
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copper
triamine
corrosion
inhibition
concentration
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张大全
于印哲
王意珍
刘洁
高立新
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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Shanghai University of Electric Power
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14Nitrogen-containing compounds
    • C23F11/141Amines; Quaternary ammonium compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

本发明提供了一种多胺类铜缓蚀剂,是由(2,3‑二甲基)二亚丁基三胺和氯化钠组成的水溶液,在所述的水溶液中,(2,3‑二甲基)二亚丁基三胺的浓度为0.2mM到3.5mM,腐蚀介质氯化钠的质量百分比浓度为3%。本发明的三胺缓蚀剂能够在铜表面形成一层较致密的保护膜,对铜及其合金具有良好的缓蚀作用。通过将三胺缓蚀剂加入到模拟海水的腐蚀介质中,通过电化学测试得知该三胺类物质能够对铜及其合金产生优异的缓蚀作用,缓蚀效率达到98.6%。

Description

一种多胺类铜缓蚀剂
技术领域
本发明属于化工领域,涉及一种金属材料的防腐蚀溶液,具体来说是一种多胺类铜缓蚀剂。
背景技术
铜及其合金具有良好的热、电传导性和机械性能,在能源、信息、海洋及军事等众多行业得到广泛的应用。铜及其合金易在含Cl-、SO4 2-等腐蚀性介质中发生腐蚀,其腐蚀会造成巨大的经济损失和安全隐患。因此,铜及合金的腐蚀防护工作显得很重要。在腐蚀防护中,通常采用的方法有:合理选材、阴极保护、介质处理、添加缓蚀剂、金属表面覆盖和防腐设计及工艺改进。
而缓蚀剂作为一种常用的防腐蚀方法,具有经济有效、适应性强的特点。与其他防腐方法相比,使用缓蚀剂由于设备简单,使用方便且投资少,是一种成本少且行之有效的方法。
苯并三氮唑(BTA)被视作铜的良好缓蚀剂,其缺点在于具有一定的毒性。但是随着近年来环保力度的增强,BTA的应用受到很大限制。
发明内容
针对现有技术中的上述技术问题,本发明提供了一种多胺类铜缓蚀剂,所述的多胺类铜缓蚀剂可以解决现有技术中的苯并三氮唑铜缓蚀剂对环境造成污染的问题,满足海水淡化等新领域铜缓蚀剂应用需求。
本发明提供了一种多胺类铜缓蚀剂,是由(2,3-二甲基)二亚丁基三胺和腐蚀介质氯化钠组成的水溶液,在所述的水溶液中,(2,3-二甲基)二亚丁基三胺的浓度为0.2mM到3.5mM,腐蚀介质氯化钠的质量百分比浓度为3%。
进一步的,(2,3-二甲基)二亚丁基三胺的浓度为0.5mM。
本发明的三胺缓蚀剂能够在铜表面形成一层较致密的保护膜,对铜及其合金具有良好的缓蚀作用。本发明的这种三胺缓蚀剂常被用作饲料添加剂的合成中间体,也是食品用高档乳化剂的组分。相对于BTA,具有低毒环保的特性。由电化学可知,这种三胺对铜的缓蚀效率很高,在极化曲线的阳极区具有较宽的电流平台,能够在较宽的电位区间起到缓蚀作用,并且这种三胺最优缓蚀效率的浓度较低,能够有效地降低成本。
本发明通过将三胺缓蚀剂加入到模拟海水中,通过电化学测试得知该三胺类物质能够对铜及其合金产生优异的缓蚀作用,缓蚀效率达到98.6%。显微形貌分析可以清晰的看见该物质在铜表面形成了一层致密的缓蚀保护膜。而且,本发明实施例所述的缓蚀剂是多种生物饲料添加剂的中间体,具有绿色环保的特性,对环境造成的危害小。
本发明和已有技术相比,其技术进步是显著的。本发明的多胺经常被用来作为乳化剂和生物中间体,符合环保低毒的要求。将(2,3-二甲基)二亚丁基三胺应用在铜的腐蚀防护领域,在对铜起到缓蚀作用,减少对环境的危害,可以满足海水淡化等新型水处理领域要求。
附图说明
图1为铜电极在含有不同三胺缓蚀浓度溶液的3wt%NaCl中浸泡1h后的交流阻抗。
图2为铜电极在含有不同三胺缓蚀浓度溶液的3wt%NaCl中浸泡1h后的极化曲线。
图3为铜挂片在含有最优三胺缓蚀浓度溶液的3wt%NaCl中浸泡4天后的SEM图:(a)空白铜挂片;(b)添加三胺缓蚀剂铜挂片;(c)是图(a)的放大图;(d)是图(b)的放大图。
具体实施方式
下面通过实施例并结合附图对本发明进一步阐述,但并不限制本发明。
电化学分析
交流阻抗测试和极化曲线测试都用三电极体系完成,工作电极为铜电极,辅助电极为Pt电极和饱和甘汞电极(SCE)。工作电极用环氧树脂密封,暴露出1cm×0.5cm的工作面,测试前对工作电极进行前处理。
电化学测量在Solartron 1260和1287Electrochemical Interface测试系统上进行。极化曲线的扫描速率为1mv/s,扫描范围相对于开路电位±250mv;电化学阻抗谱测试的频率为10-2-105Hz,阻抗测量的信号幅值为5mv正弦波。
实施例1
将铜电极表面依次经不同目数金相砂纸打磨后,用无水乙醇、去离子水冲洗,以去除表面油污和油脂。
预处理好的铜电极在含有三胺浓度为0.2mM、0.5mM、1.5mM、3.5mM的3wt%NaCl中和含有BTA浓度为0.5mM的3wt%NaCl中浸泡1h。然后测试其电化学性能。
应用实施例1
本发明考察三胺缓蚀剂对铜的缓蚀性能,具体步骤如下:
铜电极浸泡在含有不同浓度缓蚀剂的3wt%NaCl中1h。
通过电化学测试铜电极在含有三胺缓蚀剂和BTA的3wt%NaCl中1h后的交流阻抗和极化曲线,结果见图1和图2,实验温度为室温。
由图1可以看出,在含有三胺缓蚀剂的3wt%NaCl中,阻抗弧的圆弧半径明显增加,保护作用明显增强。在三胺最优浓度下,对比同样浓度BTA的缓蚀效果,可以看出三胺的缓蚀效果要优于BTA的缓蚀效果。由此可知:三胺可以有效地减缓铜的腐蚀,是铜的良好缓蚀剂。由图1得出的溶液电阻Rs、膜电阻Rf、传荷电阻Rct和缓蚀效率η见表1。
表1铜电极在含有不同三胺缓蚀浓度溶液的3wt%NaCl中浸泡1h后的交流
阻抗拟合参数
浓度.(mM) Rs(Ω·cm2) Rf(Ω·cm2) Rct(Ω·cm2) η(%)
空白电极 4.43 537.5 --
BTA 0.5 5.50 559.2 10840 95.0
三胺0.2 4.48 3748 13520 96.0
三胺0.5 4.39 4657 37360 98.6
三胺1.5 4.63 3844 15980 96.6
三胺3.5 4.63 2562 9354 94.3
由图2可以看出,三胺缓蚀剂存在时,铜电极的阳极极化曲线上形成了较宽的极限电流平台(钝化区),铜电极的腐蚀电流显著降低。
实施例2
将铜挂片表面依次经过不同目数金相砂纸打磨后,用无水乙醇、去离子水冲洗,以去除表面油污和油脂。
预处理好的铜挂片在空白和含有三胺缓蚀剂的3wt%NaCl中浸泡4天。
应用实施例2
考察本发明的三胺最优缓蚀浓度对铜表面的缓蚀效果,具体步骤如下:
铜挂片在空白和含有三胺最优缓蚀浓度的3wt%NaCl中浸泡4天,然后用扫描电镜观察表面微形貌,结果见图3,实验温度为室温。
由图3可以看出,铜挂片在空白溶液中浸泡4天后,表面出现了很多点蚀坑。而在含有三胺的溶液中,铜挂片表面光亮、没有点蚀坑,并且可以看出表面形成了一层致密的保护膜。由此可知:三胺可以有效地保护铜表面,是铜的良好缓蚀剂。

Claims (2)

1.一种多胺类铜缓蚀剂,其特征在于:是由(2,3-二甲基)二亚丁基三胺和氯化钠组成的水溶液,在所述的水溶液中,(2,3-二甲基)二亚丁基三胺的浓度为0.2mM到3.5mM,氯化钠的质量百分比浓度为3%。
2.根据权利要求1所述的一种多胺类铜缓蚀剂,其特征在于:(2,3-二甲基)二亚丁基三胺的浓度为0.5mM。
CN201610655844.9A 2016-08-11 2016-08-11 一种多胺类铜缓蚀剂 Pending CN106245035A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109839348A (zh) * 2017-11-24 2019-06-04 北京蓝星清洗有限公司 一种快速筛选发动机冷却液配方的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103502300A (zh) * 2011-05-05 2014-01-08 湛新奥地利有限公司 多官能伯胺,其制备方法,及其用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103502300A (zh) * 2011-05-05 2014-01-08 湛新奥地利有限公司 多官能伯胺,其制备方法,及其用途

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* Cited by examiner, † Cited by third party
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《清洗世界》 *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109839348A (zh) * 2017-11-24 2019-06-04 北京蓝星清洗有限公司 一种快速筛选发动机冷却液配方的方法

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