Corrosion Situation of Copper Coins from Shipwreck Huaguang Reef No. Ⅰ
摘 要
“华光礁Ⅰ号”沉船中发现了6枚古代铜钱,利用X射线衍射(XRD)、X射线荧光(XRF)、扫描电镜与能谱仪(SEM-EDS)、X射线探伤仪等对这6枚古代铜钱表面的腐蚀产物进行分析。结果表明:腐蚀产物的主要组成元素是Cu、Sn、Pb、Fe;铜钱表面文字“开元通宝”清晰可见,6号铜钱内部有一条裂隙,大多铜钱局部因腐蚀疏松变薄,厚度不一,应为铜钱基体腐蚀流失的结果。铜钱表明黑色腐蚀产物主要由铜蓝、久辉铜矿组成,部分含方铅矿、白铅矿和铅矾;白色腐蚀产物主要含文石、方解石,有少量黄铁矿;白色锈层为锡石;黄褐色锈层应含针铁矿、磁铁矿、赤铁矿、菱铁矿;灰色锈蚀物为久辉铜矿、白铅矿、辉铜矿、羟锡铜石和石英。腐蚀产物中并未发现诱发“青铜病”的有害锈氯铜矿。
Abstract
Six ancient copper coins were found in the wreck of Huaguang Jiao "Ⅰ". The corrosion products on the surface of the six ancient copper coins were analyzed by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope and energy dispersive spectrometer (SEM-EDS), and X-ray flaw detector. The results showed that the main constituent elements of the corrosion products were Cu, Sn, Pb and Fe; the Chinese characters "Kaiyuan Tongbao (开元通宝)" on the surface of the copper coins were clearly visible, and there was a crack inside the No. 6 copper coin. Most of the copper coins were partially thinned due to corrosion, and the thickness was different, which should be the result of the corrosion and loss of the copper coin matrix. The black corrosion products on the surface of copper coins were mainly composed of copper blue and chalcocite, and some of them contained galena, galena and leadite; the white corrosion products mainly contained aragonite, calcite, and a small amount of pyrite. The white rust layer was cassiterite; the yellow-brown rust layer should contain goethite, magnetite, hematite and siderite. The grey rust was chalcocite, cuprite, chalcocite, cassiterite and quartz. In the corrosion products, no harmful patacalite inducing "bronze disease" was not found.
中图分类号 TG174 DOI 10.11973/fsyfh-202204008
所属栏目 应用技术
基金项目 2019年海南省基础与应用基础研究计划(2019RC362)
收稿日期 2020/3/23
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引用该论文: BAO Chunlei. Corrosion Situation of Copper Coins from Shipwreck Huaguang Reef No. Ⅰ[J]. Corrosion & Protection, 2022, 43(4): 40
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参考文献
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【3】Gettens R J. The corrosion products of metal antiquities[M]. Washington DC. Smithsonian Institution,1964:550-557.
【4】ODDY W A,HUGHES M J. The stabilization of 'active' bronze and iron antiquities by the use of sodium sesquicarbonate[J]. Studies in Conservation,1970,15(3):183-189.
【5】GETTENS R J. The corrosion products of metal antiquities[M]. Washington DC:Smithsonian Institution,1964:555-556.
【6】NORTH N A,MACLEOD I D. Corrosion of metals[M]. Amsterdam:Elsevier,1987:68-98.
【7】DONNY L H. Methods of conserving archaeological material from underwater sites[M]. Texas:Texas A&M University Press,1999:74.
【8】祝鸿范,周庚余,陈萍. 处理青铜器有害锈的一种新方法[J]. 文物保护与考古科学,1989,1(1):1-5.
【9】高英. 古代青铜器的腐蚀性破坏[J]. 中国历史博物馆馆刊,1979(1):121-134.
【10】包春磊,贾世杰,符燕,等. 海南省博物馆馆藏出水古铁炮腐蚀产物分析[J]. 腐蚀与防护,2014,35(1):83-86,90.
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【13】MCNEIL M B,MOHR D W. Sulfate formation during corrosion of copper alloy objects[J]. MRS Proceedings,1992,267:1047.
【14】杨恒,田兴玲,李乃胜,等. 广东"南澳Ⅰ号"明代沉船出水铜器腐蚀产物分析[J]. 中国文物科学研究,2012(3):87-91.
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