古代青铜器锡腐蚀产物研究回顾——特点、表征方法、腐蚀模型  

Review of the research on tin corrosion products of ancient bronze:properties,characterization methods and corrosion models

作　　者：邹非池 刘建宇[1,2] 刘瀚文 曲亮 ZOU Feichi;LIU Jianyu;LIU Hanwen;QU Liang(Conservation Standards Research Institute,the Palace Museum,Beijing 100009,China;China-Greece Cultural Relics Protection Technology“the Belt and Road”Joint Laboratory,Beijing 100009,China)

机构地区：[1]故宫博物院文物保护标准化研究所,北京100009 [2]中国-希腊文物保护技术“一带一路”联合实验室,北京100009

出　　处：《文物保护与考古科学》2024年第4期128-142,共15页Sciences of Conservation and Archaeology

基　　金：中国-希腊文物保护技术“一带一路”联合实验室建设与联合研究(2020YFE0204600)。

摘　　要：对青铜器腐蚀机理的研究是对其进行保护修复的重要前提,在过去的数十年间,与铜和铅的腐蚀产物相比,文物保护领域对于锡腐蚀产物的认识和研究是相对缺乏且零散的。本文回顾了不同领域在锡腐蚀产物发展过程、特点以及表征方法等方面的研究成果。青铜器中锡腐蚀后一般首先形成复杂的水合氧化物(SnO_(x)·nH_(2)O),随后在氧化性条件下进一步氧化脱水,向锡石(SnO_(2))转变,但由于此转变过程漫长而复杂,导致了锡腐蚀产物具有低结晶度、高电阻率、离子交换等特殊性质。通过梳理X射线衍射分析技术、拉曼光谱以及X射线光电子能谱以及其他分析方法在青铜器锡腐蚀产物表征中的应用进一步探讨了锡腐蚀产物的性质。最后,本文在回顾不同环境下的锡腐蚀产物的研究成果的基础上,介绍并比较了不同环境下青铜器的腐蚀模型。The study of the mechanism of corrosion of ancient bronze is an important prerequisite for its conservation and restoration.Over the past few decades,compared with the corrosion products of copper and lead,the understanding and research on tin corrosion products in the field of cultural relic conservation have been relatively insufficient and unsystematic.This article reviews research achievements in the formation process,as well as characteristics and characterization methods for tin corrosion products in different fields.We first summarize the transformation process of tin-formed corrosion products.Generally,the bivalent hydrated oxide SnO·nH_(2)O is formed first after the corrosion of tin in bronze,and the tetravalent oxide SnO_(2)·nH_(2)O is partially formed under oxidizing conditions,resulting in a complex hydrated oxide—SnO_(x)·nH_(2)O.Then cassiterite(SnO_(2))is formed after further oxidization and dehydration.Due to the long and complex dehydration process in the natural environment,the tin corrosion products show an amorphous-nanocrystalline gel state externally.We then review some special properties of tin corrosion products.The first property is that the crystallinity is low—it is often difficult for the methods commonly used for cultural relic analysis(such as XRD and Raman spectrometry)to collect signals of tin corrosion products in bronze,or the signals are weak,mainly because they are in the transition stage from being amorphous to crystalline.The second property is in-situ deposition—copper and lead in bronze often migrate outwards after corrosion,while tin is corroded and deposits in situ,which is also the reason why some bronze objects suffer from severe corrosion,but the“tin rich patina”can retain the original state of the objects.The third property is high electrical resistivity—the formation and deposition of tin corrosion products can polarize the original anode and inhibit the corrosion of the anode metal matrix;however,the corrosion product film on bronze is not uniform and

关 键 词：锡腐蚀产物 非晶 表征方法 腐蚀模型 

分 类 号：K876.41[历史地理—考古学及博物馆学]