模拟青铜文物在乙酸气氛中的腐蚀行为
Corrosion Behavior of Simulated Bronze Relics in Acetic Acid Atmosphere
摘 要
采用电化学法制备了3种带锈青铜，以模拟青铜文物进行腐蚀试验。使用扫描电镜（SEM）、X射线衍射（XRD）和Raman光谱等方法分析了3种带锈青铜及裸青铜在乙酸气氛中腐蚀后的表面形貌和腐蚀产物。结果表明：在乙酸气氛中腐蚀后，裸青铜表面被腐蚀产物覆盖，且随腐蚀时间的延长，腐蚀产物增多，其腐蚀产物主要有Cu2O、碱式醋酸铜和醋酸铜；带Cu2O锈青铜表面的Cu2O立方晶体被破坏，转变成针状腐蚀产物，其腐蚀产物有碱式醋酸铜和醋酸铜；带CuCl锈青铜并未与乙酸发生反应，而是CuCl与空气中的水和氧气反应生成碱式氯化铜；混合锈具有三层结构，对青铜基体有一定的保护作用，其三层锈层的腐蚀是同时进行的，其腐蚀产物有碱式氯化铜、碱式醋酸铜和醋酸铜。
青铜文物
乙酸气氛
拉曼光谱
patinated bronze
bronze relic
acetic acid atmosphere
Raman spectrum
Abstract
Three kinds of bronze covered with patina were prepared by electrochemical method to simulate bronze relics for corrosion test. The surface morphology and corrosion products of three kinds of patinated bronze and bare bronze after testing in acetic acid atmosphere were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The experimental results indicate that the bare bronze surface was covered by corrosion products after corrosion in acetic acid atmosphere, the corrosion products of bare brone increased with the extension of corrosion time, and mainly included Cu2O, copper hydroxide acetate and copper acetate. The cubic crystals of Cu2O on the surface of bronze with Cu2O patina were destroyed and converted into acicular corrosion products. The corrosion products of the brone with Cu2O patina were copper hydroxide acetate and copper acetate. The CuCl patina on the surface of bronze did not react with acetic acid directly, but acted with water and oxygen in the air and generated copper chloride hydroxide. The mixed patina had three rust layers, providing protective effect on the bronze substrate to some extent. The corrosion of rust layers happened at the same time, and their corrosion products were copper chloride hydroxide, copper hydroxide acetate and copper acetate.
中图分类号 TG172 TG174 DOI 10.11973/fsyfh-201804003
所属栏目 试验研究
基金项目 国家自然科学基金项目（51671117）；上海市科委科研计划重点支撑项目（13231203000）
收稿日期 2016/9/4
修改稿日期
网络出版日期
作者单位点击查看
引用该论文: WU Xuewei,YAN Ying,ZHOU Hao,WU Laiming,SHI Bihan,ZHU Yiliang,CAI Lankun. Corrosion Behavior of Simulated Bronze Relics in Acetic Acid Atmosphere[J]. Corrosion & Protection, 2018, 39(4): 258
共有人对该论文发表了看法，其中：
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】徐群杰,潘红涛,邓先钦,等. 青铜器文物的腐蚀与防护研究进展[J]. 上海电力学院学报,2010,26(6):567-571.
【2】闫莹,张婷,周浩,等. 铜在臭氧中腐蚀初期的行为与机理[J]. 腐蚀与防护,2012,33(10):845-848.
【3】LIAO X N,CAO F H,CHEN A N,et al. In-situ investigation of atmospheric corrosion behavior of bronze under thin electrolyte layers using electrochemical technique[J]. Transactions of Nonferrous Metals Society of China,2012,22(5):1239-1249.
【4】张盼,闫莹,周浩,等. 空气环境中的臭氧对青铜文物腐蚀行为影响[J]. 腐蚀与防护,2012,33(1):163-166.
【5】PÖTZELBERGER I,MARDARE A I,HASSEL A W. Screening of catalytic effects on copper-zinc thin film combinatorial libraries for formal dehyde oxidation[J]. Physical Status Solidi (a)-Applications and Materials Science,2015,212(6):1184-1190.
【6】RYHL-SVENDSEN M,GLASTRUP J. Acetic acid and formic acid concentrations in the museum environment measured by SPME-GC/MS[J]. Atmospheric Environment,2002,36(24):3909-3916.
【7】GIBSON L T,WATT C M. Acetic and formic acids emitted from wood samples and their effect on selected materials in museum environments[J]. Corrosion Science,2010,52(1):172-178.
【8】PROSEK T,TAUBE M,DUBOIS F,et al. Application of automated electrical resistance sensors for measurement of corrosion rate of copper,bronze and iron in model indoor atmospheres containing short-chain volatile carboxylic acids[J]. Corrosion Science,2014,87(5):376-382.
【9】SCHIEWECK A,SIWINSKI B L,GENNING C,et al. Organic and inorganic pollutants in storage rooms of the Lower Saxony State Museum Hanover,Germany[J]. Atmospheric Environment,2005,39(33):6098-6108.
【10】LAFUENTE D,CANO E,MARTIN E. Indoor pollu-tion and metal corrosion by organic acids:case study of the Oteiza Museum (Spain)[M]//Science and Technology for the Conservation of Cultural Heri-tage.[S.l.]:CRC Press,2013.
【11】KOSEC T,LEGAT A. Investigation of the corrosion protection of chemically and electrochemically formed patinas on recent bronze[J]. Electrochimica Acta,2010,56(2):722-731.
【12】张桢. 氧化亚铜薄膜的电化学制备及其光催化和光电性能的研究[D]. 上海:上海交通大学,2014.
【13】BASTIDAS J M,LÍPEZ-DELGADO A,LÍPEZ F A,et al. Characterization of artificially patinated layers on artistic bronze exposed to laboratory SO2 contamination[J]. Journal of Materials Science,1997,32(1):129-133.
【14】LOPEZ-DELGADO A,CANO E,BASTIDAS J M,et al. A comparative study on copper corrosion originated by formic and acetic acid vapours[J]. Journal of Materials Science,2001,36(21):5203-5211.
【15】LÍPEZ-DELGADO A. A laboratory study of the effect of acetic acid vapor on atmospheric copper corrosion[J]. Journal of the Electrochemical Society,1998,145(12):4140-4147.
【16】雷勇,马君. 关于ppm与mg/m3的换算[J]. 中国卫生检验杂志,2008(9):1924-1924.
【17】BASTIDAS J M,LOPEZ-DELGADO A,CANO E,et al. Copper corrosion mechanism in the presence of formic acid vapor for short exposure times[J]. Journal of the Electrochemical Society,2000,147(3):999-1005.
【18】王菊琳,吕国诚,许淳淳. 青铜文物腐蚀机理研究进展[C]//第八届全国考古与文物保护(化学)学术会议论文集. 广州:中国化学会,2004.
【19】BASTIDAS D M,IGLESIA V M L. Organic acid vapours and their effect on corrosion of copper:a review[J]. Corrosion Engineering,2013,42(3):272-280.
【20】杨群,王怡林,张鹏翔,等. 拉曼光谱对古青铜矛腐蚀情形的无损研究[J]. 光散射学报,2001,13(1):49-53.
【21】李涛,秦颍,罗武干,等. 古代青铜器锈蚀产物的拉曼和红外光谱分析[J]. 有色金属工程,2008,60(2):146-152.
【22】王怡林,杨群,张鹏翔,等. 元代铜镜腐蚀情形的拉曼光谱研究[J]. 光谱学与光谱分析,2002,22(1):48-50.
【23】FROST R L. Raman spectroscopy of selected copper minerals of significance in corrosion[J]. Spectrochimica Acta Part A:Molecular & Biomolecular Spectroscopy,2003,59(6):1195-1204.
【24】刘文涵,陈丹,求海强,等. 水的514 nm激光拉曼光谱受外界环境光影响的研究[C]//浙江省第三届分析测试学术报告会论文集. 杭州:中国仪器仪表学会,2007.
【25】BELL I M,CLARK R J H,GIBBS P J. Raman spectroscopic library of natural and synthetic pigments (pre-approximately 1850 AD)[J]. Spectrochimica Acta Part A:Molecular & Biomolecular Spectroscopy,1997,53(12):2159-2179.
【26】GUO Z Y,LEI T,LI W,et al. Clean utilization of CuCl residue by microwave roasting under the atmosphere of steam and oxygen[J]. Chemical Engineering & Processing,2015,92:67-73.
【27】MONTECINOS S,SIMISON S N. Study of the corrosion products formed on a multiphase CuAlBe alloy in a sodium chloride solution by micro-Raman and in situ AFM measurements[J]. Applied Surface Science,2011,257(17):7732-7738.
【2】闫莹,张婷,周浩,等. 铜在臭氧中腐蚀初期的行为与机理[J]. 腐蚀与防护,2012,33(10):845-848.
【3】LIAO X N,CAO F H,CHEN A N,et al. In-situ investigation of atmospheric corrosion behavior of bronze under thin electrolyte layers using electrochemical technique[J]. Transactions of Nonferrous Metals Society of China,2012,22(5):1239-1249.
【4】张盼,闫莹,周浩,等. 空气环境中的臭氧对青铜文物腐蚀行为影响[J]. 腐蚀与防护,2012,33(1):163-166.
【5】PÖTZELBERGER I,MARDARE A I,HASSEL A W. Screening of catalytic effects on copper-zinc thin film combinatorial libraries for formal dehyde oxidation[J]. Physical Status Solidi (a)-Applications and Materials Science,2015,212(6):1184-1190.
【6】RYHL-SVENDSEN M,GLASTRUP J. Acetic acid and formic acid concentrations in the museum environment measured by SPME-GC/MS[J]. Atmospheric Environment,2002,36(24):3909-3916.
【7】GIBSON L T,WATT C M. Acetic and formic acids emitted from wood samples and their effect on selected materials in museum environments[J]. Corrosion Science,2010,52(1):172-178.
【8】PROSEK T,TAUBE M,DUBOIS F,et al. Application of automated electrical resistance sensors for measurement of corrosion rate of copper,bronze and iron in model indoor atmospheres containing short-chain volatile carboxylic acids[J]. Corrosion Science,2014,87(5):376-382.
【9】SCHIEWECK A,SIWINSKI B L,GENNING C,et al. Organic and inorganic pollutants in storage rooms of the Lower Saxony State Museum Hanover,Germany[J]. Atmospheric Environment,2005,39(33):6098-6108.
【10】LAFUENTE D,CANO E,MARTIN E. Indoor pollu-tion and metal corrosion by organic acids:case study of the Oteiza Museum (Spain)[M]//Science and Technology for the Conservation of Cultural Heri-tage.[S.l.]:CRC Press,2013.
【11】KOSEC T,LEGAT A. Investigation of the corrosion protection of chemically and electrochemically formed patinas on recent bronze[J]. Electrochimica Acta,2010,56(2):722-731.
【12】张桢. 氧化亚铜薄膜的电化学制备及其光催化和光电性能的研究[D]. 上海:上海交通大学,2014.
【13】BASTIDAS J M,LÍPEZ-DELGADO A,LÍPEZ F A,et al. Characterization of artificially patinated layers on artistic bronze exposed to laboratory SO2 contamination[J]. Journal of Materials Science,1997,32(1):129-133.
【14】LOPEZ-DELGADO A,CANO E,BASTIDAS J M,et al. A comparative study on copper corrosion originated by formic and acetic acid vapours[J]. Journal of Materials Science,2001,36(21):5203-5211.
【15】LÍPEZ-DELGADO A. A laboratory study of the effect of acetic acid vapor on atmospheric copper corrosion[J]. Journal of the Electrochemical Society,1998,145(12):4140-4147.
【16】雷勇,马君. 关于ppm与mg/m3的换算[J]. 中国卫生检验杂志,2008(9):1924-1924.
【17】BASTIDAS J M,LOPEZ-DELGADO A,CANO E,et al. Copper corrosion mechanism in the presence of formic acid vapor for short exposure times[J]. Journal of the Electrochemical Society,2000,147(3):999-1005.
【18】王菊琳,吕国诚,许淳淳. 青铜文物腐蚀机理研究进展[C]//第八届全国考古与文物保护(化学)学术会议论文集. 广州:中国化学会,2004.
【19】BASTIDAS D M,IGLESIA V M L. Organic acid vapours and their effect on corrosion of copper:a review[J]. Corrosion Engineering,2013,42(3):272-280.
【20】杨群,王怡林,张鹏翔,等. 拉曼光谱对古青铜矛腐蚀情形的无损研究[J]. 光散射学报,2001,13(1):49-53.
【21】李涛,秦颍,罗武干,等. 古代青铜器锈蚀产物的拉曼和红外光谱分析[J]. 有色金属工程,2008,60(2):146-152.
【22】王怡林,杨群,张鹏翔,等. 元代铜镜腐蚀情形的拉曼光谱研究[J]. 光谱学与光谱分析,2002,22(1):48-50.
【23】FROST R L. Raman spectroscopy of selected copper minerals of significance in corrosion[J]. Spectrochimica Acta Part A:Molecular & Biomolecular Spectroscopy,2003,59(6):1195-1204.
【24】刘文涵,陈丹,求海强,等. 水的514 nm激光拉曼光谱受外界环境光影响的研究[C]//浙江省第三届分析测试学术报告会论文集. 杭州:中国仪器仪表学会,2007.
【25】BELL I M,CLARK R J H,GIBBS P J. Raman spectroscopic library of natural and synthetic pigments (pre-approximately 1850 AD)[J]. Spectrochimica Acta Part A:Molecular & Biomolecular Spectroscopy,1997,53(12):2159-2179.
【26】GUO Z Y,LEI T,LI W,et al. Clean utilization of CuCl residue by microwave roasting under the atmosphere of steam and oxygen[J]. Chemical Engineering & Processing,2015,92:67-73.
【27】MONTECINOS S,SIMISON S N. Study of the corrosion products formed on a multiphase CuAlBe alloy in a sodium chloride solution by micro-Raman and in situ AFM measurements[J]. Applied Surface Science,2011,257(17):7732-7738.
相关信息
