重庆余家坝遗址出土战国青铜剑腐蚀产物的无损原位分析
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摘要
余家坝遗址位于重庆市开州区(原开县)渠口镇钦云村余家坝东北部,是重庆三峡库区最重要的巴人遗存之一。自20世纪80年代该遗址被发现以后,先后进行四次发掘,出土随葬品中以青铜兵器为特色。本文利用超景深显微镜和激光拉曼光谱仪对重庆开州区余家坝遗址出土10件青铜剑的腐蚀产物进行无损形貌观察和结构分析,并探索其腐蚀原因,以期为后续开展的保护修复提供理论依据,同时为巴式青铜兵器腐蚀研究提供借鉴。分析结果显示,该批青铜剑的腐蚀可分为两类,第一类表面相对光滑、致密,其主要腐蚀产物为孔雀石、锡石和赤铜矿;第二类表面附着较多锈蚀,腐蚀产物种类较多,除孔雀石、锡石、赤铜矿外,还发现有磷铜矿、蓝磷铜矿、氯铜矿、水胆矾和磷氯铅矿等腐蚀物。在后续开展的保护工作中,应根据不同的腐蚀产物种类采取相对应的保护修复措施。
Yujiaba site is one of the most important Ba sites in the Three Gorges area.It is located at the northeast of Yujiaba,Kaizhou Disctrict,Chongqing and was discovered in 1980 s.Burial objects characterized by bronze weapons have been unearthed after four excavations.This article applies non-destructive analysis with high-fidelity optical microscope and Raman spectroscope to observe the appearance and explore the structure of corrosion products on 10 bronze swords excavated from Yujiaba site.The result shows that the bronze swords can be classified into two categories:one with category with smooth and compact surfaces,the corrosion products of which are malachite,cassiterite and cuprite,the other one contains corrosion products,namingly malachite(Cu_2CO_3(OH)_2),azurite(Cu_3(CO_3)_2(OH)_2),cuprite(Cu_2O),cerussite(PbCO_3),pyromorphite(Pb_5(PO_4)_3Cl),mimetite(Pb_5(AsO_4)_3Cl),brochantite(Cu_4SO_4(OH)_6),cassiterit e(SnO_2)and atacamite(Cu_2Cl(OH)_3).In addition,this article analyzes the cause of corrosion and tries to provide evidence for further conservation and restoration of those cultural relics and related research on corrosion of Ba bronze weapons.
Yujiaba site is one of the most important Ba sites in the Three Gorges area.It is located at the northeast of Yujiaba,Kaizhou Disctrict,Chongqing and was discovered in 1980 s.Burial objects characterized by bronze weapons have been unearthed after four excavations.This article applies non-destructive analysis with high-fidelity optical microscope and Raman spectroscope to observe the appearance and explore the structure of corrosion products on 10 bronze swords excavated from Yujiaba site.The result shows that the bronze swords can be classified into two categories:one with category with smooth and compact surfaces,the corrosion products of which are malachite,cassiterite and cuprite,the other one contains corrosion products,namingly malachite(Cu_2CO_3(OH)_2),azurite(Cu_3(CO_3)_2(OH)_2),cuprite(Cu_2O),cerussite(PbCO_3),pyromorphite(Pb_5(PO_4)_3Cl),mimetite(Pb_5(AsO_4)_3Cl),brochantite(Cu_4SO_4(OH)_6),cassiterit e(SnO_2)and atacamite(Cu_2Cl(OH)_3).In addition,this article analyzes the cause of corrosion and tries to provide evidence for further conservation and restoration of those cultural relics and related research on corrosion of Ba bronze weapons.
引文
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[7] 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.(YANG Qun,WANG Yiling,ZHANG Pengxiang,et al.A study on corrosion of ancient bronze lance by Raman microscopy[J].The Journal of Light Scattering,2001,13(1):49-53.)
[8] 贾腊江,金普军.拉曼光谱分析青铜器本体中的锈蚀产物[J].光谱学与光谱分析,2015,35(1):128-131.(JIA Lajiang,JIN Pujun.Using Raman spectrum analysis to research corrosive productions occuring in alloy of ancient bronze wares[J].Spectroscopy and spectral analysis.2015,35(1):128-131.)
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[10] HAYEZ V,GUILLAUME J,HUBIN A,et al.Micro-Raman spectroscopy for the study of corrosion products on copper alloys:setting up of a reference database and studying works of art.J Raman Spectrosc.2004,35:732-738.
[11] SHERIF KHARBISH,PETER ANDRá?,JARMILA LUPTáKOVá,et al.Raman spectra of oriented and non-oriented Cu hydroxy-phosphate minerals:Libethenite,cornetite,pseudomalachite,reichenbachiteand ludjibaite[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy.2014,130:152-163.
[12] BAJDA T,MOZGAWA W,MANECKI M,et al.Vibrational spectroscopic study of mimetite-pyromorphite solid solutions.Polyhedron.2011,30:2479-2485.
[13] FRANCESCA OSPITALI,CRISTINA CHIAVARI,CARLA MARTINI,et al.The characterization of Sn-based corrosion products in ancient bronzes:a Raman approach,J Raman Spectrosc.2012,43:1596-1603.
[14] 杨小刚,三峡地区春秋战国至汉代青铜器科技研究[M].北京:科学出版社,2013.(YANG Xiaogang,Scientific Study on the Bronze Dating from Spring & Autumn Period to Han Dynasty[M].Science Press,Beijing.2013.)
[15] XIAOPAN FAN,IAN C.Freestone,Occurrence of phosphatic corrosion products on bronze swords of the Warring States period buried at Lijiaba site in Chongqing,China[J].Heritage Science.2017(5):48-56.
[2] 重庆市文物局,重庆市移民局.重庆库区考古报告集(2000卷)[M].北京:科学出版,2007.(Cultural Relics Heritage Bureau of Chongqing,Resettlement Bureau of Chongqing.Collections of reports on the archaeological excavation in the Three Gorges Dam,Chongqing in 2000[M].Sciences Press,Beijing,2007.)
[3] 重庆市文物局,重庆市移民局,重庆库区考古报告集(2001卷)[M].北京:科学出版社,2007.(Cultural Relics Heritage Bureau of Chongqing,Resettlement Bureau of Chongqing.Collections of reports on the archaeological excavation in the Three Gorges Dam,Chongqing in 2001[M].Sciences Press,Beijing,2007.)
[4] 山东大学东方考古研究中心,重庆市文化局,开县文物管理所,重庆开县余家坝墓地2002年发掘简报[J].江汉考古,2004(3):38-48.(Research Center of Oriental Archaeology,Shandong University,et al.Brief report on excavation of Yujiaba cemetery at Kaixian,Chongqing[J].Jianghan Archaeology,2004(3):38-48.)
[5] 陈淑卿,王芬,重庆余家坝巴人墓地的发掘收货[J].山东大学学报(哲学社会科学版),2004(1):19-24.(CHEN Shuqing,WANG Fen,The excavation of Ba’s tombs at Yujiaba site in Chongqing[J].Journal of Shandong University(Philosophy and Social Sciences),2004(1):19-24.)
[6] 重庆市文化遗产研究院,重庆文化遗产保护中心,开州博物馆,重庆市开县馆藏青铜文物保护与研究[M].北京:科学出版社,2016.(Chongqing Cultural Heritage Research Institute,Chongqing Cultural Heritage Protection Center,Kaizhou Museum.Conservation and Research on the bronze relics collected in Kaizhou Museum[M].Sciences Press,Beijing,2016.)
[7] 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.(YANG Qun,WANG Yiling,ZHANG Pengxiang,et al.A study on corrosion of ancient bronze lance by Raman microscopy[J].The Journal of Light Scattering,2001,13(1):49-53.)
[8] 贾腊江,金普军.拉曼光谱分析青铜器本体中的锈蚀产物[J].光谱学与光谱分析,2015,35(1):128-131.(JIA Lajiang,JIN Pujun.Using Raman spectrum analysis to research corrosive productions occuring in alloy of ancient bronze wares[J].Spectroscopy and spectral analysis.2015,35(1):128-131.)
[9] BOUCHARD M,SMITH D C.Catalogue of 45 reference Raman spectra of minerals concerning research in art history or archaeology,especially on corroded metals and coloured glass[J].Spectrochimica Acta Part A.2003,59:2247-2266.
[10] HAYEZ V,GUILLAUME J,HUBIN A,et al.Micro-Raman spectroscopy for the study of corrosion products on copper alloys:setting up of a reference database and studying works of art.J Raman Spectrosc.2004,35:732-738.
[11] SHERIF KHARBISH,PETER ANDRá?,JARMILA LUPTáKOVá,et al.Raman spectra of oriented and non-oriented Cu hydroxy-phosphate minerals:Libethenite,cornetite,pseudomalachite,reichenbachiteand ludjibaite[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy.2014,130:152-163.
[12] BAJDA T,MOZGAWA W,MANECKI M,et al.Vibrational spectroscopic study of mimetite-pyromorphite solid solutions.Polyhedron.2011,30:2479-2485.
[13] FRANCESCA OSPITALI,CRISTINA CHIAVARI,CARLA MARTINI,et al.The characterization of Sn-based corrosion products in ancient bronzes:a Raman approach,J Raman Spectrosc.2012,43:1596-1603.
[14] 杨小刚,三峡地区春秋战国至汉代青铜器科技研究[M].北京:科学出版社,2013.(YANG Xiaogang,Scientific Study on the Bronze Dating from Spring & Autumn Period to Han Dynasty[M].Science Press,Beijing.2013.)
[15] XIAOPAN FAN,IAN C.Freestone,Occurrence of phosphatic corrosion products on bronze swords of the Warring States period buried at Lijiaba site in Chongqing,China[J].Heritage Science.2017(5):48-56.