CN105780013A - 一种带碱式氯化铜锈青铜缓蚀剂及其应用 - Google Patents

一种带碱式氯化铜锈青铜缓蚀剂及其应用 Download PDF

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CN105780013A
CN105780013A CN201610139286.0A CN201610139286A CN105780013A CN 105780013 A CN105780013 A CN 105780013A CN 201610139286 A CN201610139286 A CN 201610139286A CN 105780013 A CN105780013 A CN 105780013A
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bronze
copper chloride
rust
chloride hydroxide
corrosion inhibiter
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CN105780013B (zh
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王菊琳
王天然
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting 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 inorganic inhibitors
    • C23F11/182—Sulfur, boron or silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting 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 inorganic inhibitors
    • C23F11/181—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting 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 inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors

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Abstract

本发明涉及一种稀土离子作为带碱式氯化铜锈青铜缓蚀剂及其应用，包括硫酸亚铈或硝酸亚铈。所述带锈青铜缓蚀剂为环境友好型缓蚀剂，对人和环境无危害，在模拟酸雨溶液中，当其浓度为1000mg/L时，硫酸亚铈的缓蚀效率达96.8%，硝酸亚铈的缓蚀效率达95.0%。

Description

一种带碱式氯化铜锈青铜缓蚀剂及其应用
技术领域
本发明属于金属材料腐蚀与防护技术领域，具体涉及稀土离子缓蚀剂硫酸亚铈和硝酸亚铈作为带碱式氯化铜锈青铜缓蚀剂及其应用。
背景技术
青铜器是人类文明殿堂中的瑰宝，具有极高的历史价值、文化价值和艺术价值。然而在出土和保藏过程中，许多青铜器都染上了“粉状锈”，其主要成分为碱式氯化铜。这种锈蚀产物对青铜器的保存具有致命的威胁，如果不及时进行妥善处理，青铜器便会在很短的时间内粉化、穿孔甚至完全毁坏。研究者们普遍将其归为“有害锈”。然而现在用于锈蚀青铜保护的多是有机缓蚀剂，如唑类和咪唑类化合物，这些化合物能够在锈蚀产物表面吸附成膜，从而保护锈蚀青铜。考虑到碱式氯化铜锈对青铜产生不利影响的方式，本发明经过研究发现，稀土离子缓蚀剂具备对带碱式氯化铜锈青铜进行保护的潜力，并且目前现有技术中尚未见用稀土缓蚀剂保护锈蚀青铜的报道。
发明内容
本发明的目的是克服现有带锈青铜缓蚀剂在应用中存在的上述缺点，提供一种稀土离子作为带碱式氯化铜锈青铜缓蚀剂，以及其作为带碱式氯化铜锈青铜缓蚀剂的应用。
本发明采用如下技术方案，一种带碱式氯化铜锈青铜缓蚀剂，包括硫酸亚铈和硝酸亚铈中的一种或两种。
更进一步的，所述硫酸亚铈和硝酸亚铈的浓度为1000mg/L，更具体为使用时的浓度。
本发明还保护上述带碱式氯化铜锈青铜缓蚀剂的应用，所述硫酸亚铈和硝酸亚铈在模拟酸雨溶液中的浓度为1000mg/L，其中模拟酸雨溶液的溶剂为去离子水，溶质为Na2SO4和NaHCO3。
更进一步的，所述Na2SO4为0.2g/L，所述NaHCO3为0.2g/L，用酸调节pH为5。
更进一步的，所述酸为稀硫酸。
与现有技术相比，本发明的稀土离子缓蚀剂属环境友好型缓蚀剂，使用后不会对人和环境产生不利影响。硫酸亚铈和硝酸亚铈在模拟酸雨溶液中浓度为1000mg/L时，电化学数据表明两种稀土离子缓蚀剂对带碱式氯化铜锈的青铜均具有良好的缓蚀效果。带碱式氯化铜锈的青铜在添加了1000mg/L硫酸亚铈的模拟酸雨溶液中浸泡24h，缓蚀效率达到96.8%；带碱式氯化铜锈的青铜在添加了1000mg/L硝酸亚铈的模拟酸雨溶液中浸泡24h，缓蚀效率达到95.0%。极大地提高了锈层的稳定性，优化了“粉状锈”碱式氯化铜疏松多孔的不利结构。从而证实稀土离子缓蚀剂可以用作带碱式氯化铜锈青铜的腐蚀抑制剂。
附图说明
下面通过附图对本发明做进一步的描述：
图1、带碱式氯化铜锈青铜试样在未添加缓蚀剂的模拟酸雨溶液中不同浸泡时间（共24h）的EIS曲线；
图2、带碱式氯化铜锈青铜试样在添加1000mg/L硫酸亚铈的模拟酸雨溶液中不同浸泡时间（共24h）的EIS曲线；
图3、带碱式氯化铜锈青铜试样在添加1000mg/L硝酸亚铈的模拟酸雨溶液中不同浸泡时间（共24h）的EIS曲线。
具体实施方式
下面通过实施例对本发明做进一步的描述：
实施例1
（1）溶液配制
模拟酸雨溶液的配制：[Na2SO4]=0.2g/L，[NaHCO3]=0.2g/L，用稀硫酸调pH到5。实验中所用器皿均用去离子水洗净，所用溶液均用去离子水配制。
（2）青铜电极
在青铜试样背部焊接铜导线，而后将试样用环氧树脂密封，后经打磨露出工作面，工作面面积为1.0cm2，测试前依次用200#、400#、600#、800#和1000#砂纸打磨工作面，用去离子冲洗工作面，最后用丙酮清洁工作面，放入干燥器中干燥备用。
（3）青铜电极表面碱式氯化铜锈的制备
首先通过电化学法制备CuCl锈，将裸青铜在除氧的pH为7.00的0.028mol/LNaCl+0.01mol/LNa2SO4+0.016mol/LNaHCO3中，+0.40V（vs.SCE）下恒电位极化30min，去离子水冲洗干净，干燥备用。而后每隔8h喷一次水，持续20天得到长有碱式氯化铜锈的青铜试样。
（4）测试方法
测试采用电化学阻抗法，采用经典的三电极体系，工作电极为带碱式氯化铜锈的青铜电极，参比电极为饱和甘汞电极，辅助电极为铂电极。测量设备为科斯特CS350电化学工作站，EIS测试频率范围为100kHz—10mHz，扰动信号为10mV。
图1为带碱式氯化铜锈青铜电极在未添加缓蚀剂的模拟酸雨溶液中浸泡24h过程中不同浸泡阶段的EIS曲线，各条曲线均包含3个容抗弧，从左到右依次称为高频容抗弧，中频容抗弧和低频容抗弧，内嵌图为最左端高频区的放大。高频容抗弧的大小代表反应物或反应产物穿过青铜电极表面氧化膜层的阻力，中频容抗弧的大小代表未腐蚀的青铜基体发生电化学反应的阻力，低频容抗弧的大小代表了锈层发生氧化还原反应的阻力。三个容抗弧中，中频弧和低频弧是研究的重点。从6h起曲线的低频端（最右侧）出现一条45°的直线，此直线代表电极反应由扩散控制。在整个浸泡过程中中频容抗弧和低频容抗弧均持续减小，表明随浸泡时间的延长，基体变得更容易被腐蚀，且锈层中的活性腐蚀产物增多，锈层的稳定性下降。
图2为带碱式氯化铜锈青铜电极在添加1000mg/L硫酸亚铈的模拟酸雨溶液中浸泡24h过程中不同浸泡阶段的EIS曲线，各条曲线均包含3个容抗弧，随浸泡时间的延长，中频容抗弧和低频容抗弧均增大，表明缓蚀剂的加入不仅增强了基体的耐蚀性，也提高了锈层的稳定性。
图3为带碱式氯化铜锈青铜电极在添加1000mg/L硝酸亚铈的模拟酸雨溶液中浸泡24h过程中不同浸泡阶段的EIS曲线，各条曲线均包含3个容抗弧，随浸泡时间的延长，中频容抗弧和低频容抗弧均增大，表明缓蚀剂的加入不仅增强了基体的耐蚀性，也提高了锈层的稳定性。
两种稀土离子缓蚀剂的缓蚀效率通过EIS计算得到的极化电阻Rp值按照如下公式进行计算：
式中Rp(0)为未添加缓蚀剂情况下的极化电阻，而Rp(i)为添加缓蚀剂情况下的极化电阻，即3个容抗弧阻抗值之和。
表1硫酸亚铈和硝酸亚铈对带碱式氯化铜锈青铜在模拟酸雨溶液中的缓蚀效率
由上表1可以看出，两种稀土离子缓蚀剂的缓蚀效率均随浸泡时间的延长而增大，浸泡24h，硫酸亚铈的缓蚀效率可达96.8%，硝酸亚铈的缓蚀效率可达95.0%。以上结果说明硫酸亚铈和硝酸亚铈对带碱式氯化铜锈青铜电极具有优异的保护效果，既可以保护未被腐蚀的青铜基体，又可以稳定碱式氯化铜锈。
上面结合实施例对本发明进行了示例性的描述，显然本发明的实现并不受上述实施例的限制，只要采用了本发明的方法构思和技术方案进行的各种改进，或未经改进将本发明的构思和技术方案直接应用于其它场合的，均在本发明的保护范围内。

Claims (5)

1.一种带碱式氯化铜锈青铜缓蚀剂，其特征在于，包括硫酸亚铈和硝酸亚铈中的一种或两种。
2.根据权利要求1所述的带碱式氯化铜锈青铜缓蚀剂，其特征在于，所述硫酸亚铈和硝酸亚铈的浓度为1000mg/L。
3.权利要求1或2所述的带碱式氯化铜锈青铜缓蚀剂的应用，其特征在于，所述硫酸亚铈和硝酸亚铈在模拟酸雨溶液中的浓度为1000mg/L，其中模拟酸雨溶液的溶剂为去离子水，溶质为Na2SO4和NaHCO3。
4.根据权利要求3所述的应用，其特征在于，所述Na2SO4为0.2g/L，所述NaHCO3为0.2g/L，用酸调节pH为5。
5.根据权利要求4所述的应用，其特征在于，所述酸为稀硫酸。
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