古麇地出土青铜器初步研究
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摘要
2006年3～11月,在南水北调中线工程中,湖北省文物考古研究所等单位对郧县五峰乡乔家院墓群进行了考古勘探和发掘工作。该遗址发现伊始,因其所处地理位置与历史文献记载的古麇国都城“锡穴”相吻合,立刻得到考古学界、历史学界和社会大众的广泛关注。2006年12月,乔家院春秋墓群被国家文物局评为“全国重大考古新发现”。利用现代科技方法对古麇地出土青铜器进行研究,有利于拓宽对汉水中上游古文化的认识,有利于古麇文化研究的深入,有利于揭示楚文化的西进历程。
本论文最终的研究目的是,从科技角度对古麇地考古学文化进行一次较为全面、深入的探索,并希望有助于深化人们对古麇国地理地望、手工业活动、贸易往来、生产组织、社会结构等涉及当时政治、经济、文化等多方面、深层次问题的认识。此外,研究结果对阐明古麇国与楚国之间在政治互动、经济往来、文化交流、技术传播等方面的情况,也将有着较为重要的参考价值。
首先,利电感藕合等离子体发射光谱(ICP-AES)、X射线荧光(XRF)等分析方法,对考古发掘的71件青铜标本和铜器所包含的泥芯,进行了系统的检测分析。铜矿料来源研究结果表明,古麇地青铜器与左塚青铜器具有相近的矿料来源,而异于九连墩、安徽及辽西等地样品。进一步分析还发现,古麇地青铜器中微量元素特征与皖南、宁夏等地古铜锭差异比较明显,而与大冶灵乡铜锭相一致。从而推测,此批青铜器中使用了大冶矿区的铜原料。青铜器产地研究表明,此批器物所包含的泥芯原料很可能来自南方的红土区域,且与盘龙城及左塚的泥芯具有同源性。由此认为,此批青铜器应当为楚国铸造成型后再输入古麇地的。青铜合金配比及制作工艺的研究表明,古麇地出土青铜器的合金配比合理,表明制作者对合金规律有着深刻的认识,青铜合金工艺、铸造技术相当精湛和娴熟。特别指出,当地高铅青铜容器及高锡低铅铜剑,都沿袭了楚国的传统合金工艺。
显然,第二至第四章是本论文的主要部分之一,综合上述研究结果可知:此批青铜器使用了楚国的铜料、沿袭了楚国的传统合金工艺、由楚国工匠在楚国境内铸造而成。表明墓主应为楚国贵族,这里所见墓群,应是楚人入主麇地后的楚墓。
接下来,利用金相显微镜、拉曼光谱(Raman)、傅立叶红外光谱(FT-IR)和X射线衍射(XRD)等分析方法,对古麇地出土青铜器上的腐蚀产物及器物上的“附着物”进行了分析。分析结果表明,此批青铜器中普遍存在碱式氯化铜、含水氯化铜等铜的氯化锈蚀,腐蚀种类较为多样、程度较为严重。值得指出的是,分析发现白色胶结状腐蚀物中存在角铅矿,它与铜的氯化锈蚀同属有害锈。在粉状锈产生部位呈现出“铜本体—赤铜矿—副氯铜矿—孔雀石—蓝铜矿”的锈层结构。古麇地青铜器处于一种含氯的弱酸性、季节性变化环境中,器物在此环境中优先腐蚀δ相,主要发生电化学腐蚀,既有缝隙腐蚀,又有点孔状腐蚀。在此基础上,提出了简要的保护方案。
铜器上“附着物”的分析结果表明,M4:23铜剑镶嵌绿松石处的粘接材料不属于人们所熟知的动物胶、植物胶及矿物胶,其主要成分为蜂蜡。研究结果不仅丰富了我们对古代胶粘材料的认识,对古代蜂蜡研究工作的开展亦起到抛砖引玉的作用。为此指出,有必要开展我国古代蜂蜡的系统研究工作,有必要对铜器上镶嵌宝玉石、贴金银等工艺中使用的粘接(连接)材料进行深入研究。
对剑鞘上所裹的皮质材料的分析指出,早在春秋中晚期,我国先民就可能发明铁-铝盐混合鞣制的技术。考工记中未见有鞣前准备的记载,其它文献也鲜有提及。本文首次指出,最迟在春秋中晚期,我国先民已开始将纯石灰用于脱毛浸灰处理。
在合金工艺研究中,笔者发现,已有标准图谱及模拟图谱的分析材料多由铁型、砂型和失蜡法等方法铸造所得,不同于古代范铸而成的青铜器。一般说来,两者的金相组织或多或少会有一定差别。同时,不论是标准图谱或是模拟图谱中都没有提供高锡青铜的形变加工图谱。鉴于此,本论文模拟古代范铸条件,浇铸出成分不同的青铜试样,并对其进行热处理和形变加工处理,得到一系列金相图谱。不论是铸造实验还是热处理实验,这里都得到了一些新的认识,并初步显现出其具有相当的应用价值。除此之外,本实验的最大收获是,获得了含锡6%、14%、22%三种合金材料的形变加工组织。此前未见相关研究。对高锡青铜高温锤打的实验发现,材料最终显示为铸造组织,而非典型的冷加工后热处理或热锻的组织。这对探讨古代青铜兵器等高锡实用器物的制作工艺颇有参考价值。
Over the past two years, archaeologists have conducted several archaeological surveys in and around the Qiaojiayuan site, Yun County, Hubei Province, China. In the process, four tombs were discovered and excavated, all dated to the Autumn-Spring Period of ancient China (770-476 B.C., the formative period of Chinese civilization). More importantly, each tomb contained the remains of a single individual. This is the first time since the foundation of People's Republic of China that archaeologists have discovered Autumn-Spring Period tombs complete with intact burials within the boundary of Hubei province.
According to historical documents, the Qiaojiayuan site is geographically located within the boundary of the ancient Jun state. During this time period, tombs were reserved for the powerful and elite members of society.
The archaeological excavations unearthed a total of 132 artifacts, of which the bronzes played the main part (around 71 pieces). The typical bronzes of the period consist of elaborate vessels of interlaced designs known as Ding, Pan, Yi, Fou, Gui, and Ge. Swords and other articles were also made of bronze. For its significance to the study of the culture of ancient Jun, the Qiaojiayuan site was awarded "The National Significant Archaeological New Findings" in 2006.
According to historical records, ancient Jun had a very long-time history. Through the periods of the Xia, Shang, and Zhou dynasties, Jun maintained a very close relationship with each of these dynasties as they were represented in the Zhongyuan district. By the Spring-Autumn Period, ancient Jun had established a close association with the Chu state. What remained unknown are the details of these relationships, associations and alliances. Through the systematic examination of excavated bronzes from ancient Jun, we should be able to: 1) trace the background of relationships between ancient Jun and dynasties in Zhongyuan district, as well as the relationship between Jun and Chu; and 2) broaden our knowledge about ancient Jun civilization and culture.
The main research in this dissertation is divided into five parts:
1) The Provenance Study of Ores for Bronze Casting.
With a combined use of ICP-AES, XRF, and other analytical methods, we will complete a trace-element analysis on the excavated bronzes from the Qiaojiayuan site. Through a carefully selection of trace elements for cluster analysis, we expect to identify the provenance of the ores that were used for bronzes casting by the craftsman of ancient Jun.
To this end, the archaeological surveys located a very large ancient mining site, the An Cheng East Zhou copper mining site, nearby. We have carefully and systematically surveyed this site and its surroundings, and sampled the ores. For the sake of comparison, we also sampled the ores from the Zhaobishan copper mining sites within Ningxia Province and from the Tonglvshan copper mining sites within Hubei Province. The former is traditionally believed to be under the control of the Zhongyuan dynasties, while the latter belonged to the ancient Chu state.
By use of ICP-AES analysis, we want to find out whether the ores chosen for bronze casting in ancient Jun are from the An Cheng East Zhou copper mining site or some other site. If the results indicate the ores are not from An Cheng East Zhou mining site, then we will have to do some additional revisit our work and address a new question: is there a close relationship between the bronzes excavated from ancient Jun and the copper mining sites somewhere else, e.g., the Zhaobishan copper mining site or the Tonglvshan copper mining site?
2) The Search for the Original Casting Place for the Jun Bronzes.
Our previous research made use of both ICP-AES and XRF methods to analyze the finely-ground clay found in bronzes as well as the soils from excavation sites and clay moulds found nearby. Using a cluster analysis, we were able to identify what seemed to be a very close relationship between the trace-elements both in the finely-ground clay and the soils from the original casting places for bronzes. This relationship was also observed and reaffirmed in the archaeological evidence. So, in our current research, we will be using this method to determine if the Jun bronzes were cast nearby or in some other place.
3) The Aim to Better Understand Bronze Production Technology.
The production technology of ancient bronzes is a very important topic in the discussion about bronze cultural civilization. In the research, we are using XRF analysis and metallurgical information to examine the composition of alloys and their microstructure. In order to better understand the microstructure of ancient bronzes, we also did casting experiments.
4) Corrosion Studies and Studies for Conservation Work.
By combining the analyses of corrosion products through XRD, RM, and XRF with analyses of soil, marine environments, etc., we can better understand how some corroded bronzes were so well preserved, while others were not. This study can also provide meaningful information for conservation and restoration work.
5) The aim to Better Understand Remnant Substance on Bronzes.
By use of FT-IR, RM, and XRF analysis, we want to find out whether the remnant substance on bronzes belongs to organic material or inorganic material. If the results indicate the remnant substance belongs to organic material, then we will have to do more research and find out what kind of material may it be? From this study, we can better understand the adhering material on ancient bronzes, and the tanbark technology of ancient China.
From a larger perspective, the overall goal of this research is to develop a comprehensive and in-depth understanding of Jun culture. Most importantly, we are treating the bronzes as proxy for the human actions of this ancient state. We believe that integrating these four technical components of archaeological analysis within a broader context focused on the interaction between Jun culture and the materials it produced, we should be able to develop a more complete picture of the history of ancient Jun.
本论文最终的研究目的是,从科技角度对古麇地考古学文化进行一次较为全面、深入的探索,并希望有助于深化人们对古麇国地理地望、手工业活动、贸易往来、生产组织、社会结构等涉及当时政治、经济、文化等多方面、深层次问题的认识。此外,研究结果对阐明古麇国与楚国之间在政治互动、经济往来、文化交流、技术传播等方面的情况,也将有着较为重要的参考价值。
首先,利电感藕合等离子体发射光谱(ICP-AES)、X射线荧光(XRF)等分析方法,对考古发掘的71件青铜标本和铜器所包含的泥芯,进行了系统的检测分析。铜矿料来源研究结果表明,古麇地青铜器与左塚青铜器具有相近的矿料来源,而异于九连墩、安徽及辽西等地样品。进一步分析还发现,古麇地青铜器中微量元素特征与皖南、宁夏等地古铜锭差异比较明显,而与大冶灵乡铜锭相一致。从而推测,此批青铜器中使用了大冶矿区的铜原料。青铜器产地研究表明,此批器物所包含的泥芯原料很可能来自南方的红土区域,且与盘龙城及左塚的泥芯具有同源性。由此认为,此批青铜器应当为楚国铸造成型后再输入古麇地的。青铜合金配比及制作工艺的研究表明,古麇地出土青铜器的合金配比合理,表明制作者对合金规律有着深刻的认识,青铜合金工艺、铸造技术相当精湛和娴熟。特别指出,当地高铅青铜容器及高锡低铅铜剑,都沿袭了楚国的传统合金工艺。
显然,第二至第四章是本论文的主要部分之一,综合上述研究结果可知:此批青铜器使用了楚国的铜料、沿袭了楚国的传统合金工艺、由楚国工匠在楚国境内铸造而成。表明墓主应为楚国贵族,这里所见墓群,应是楚人入主麇地后的楚墓。
接下来,利用金相显微镜、拉曼光谱(Raman)、傅立叶红外光谱(FT-IR)和X射线衍射(XRD)等分析方法,对古麇地出土青铜器上的腐蚀产物及器物上的“附着物”进行了分析。分析结果表明,此批青铜器中普遍存在碱式氯化铜、含水氯化铜等铜的氯化锈蚀,腐蚀种类较为多样、程度较为严重。值得指出的是,分析发现白色胶结状腐蚀物中存在角铅矿,它与铜的氯化锈蚀同属有害锈。在粉状锈产生部位呈现出“铜本体—赤铜矿—副氯铜矿—孔雀石—蓝铜矿”的锈层结构。古麇地青铜器处于一种含氯的弱酸性、季节性变化环境中,器物在此环境中优先腐蚀δ相,主要发生电化学腐蚀,既有缝隙腐蚀,又有点孔状腐蚀。在此基础上,提出了简要的保护方案。
铜器上“附着物”的分析结果表明,M4:23铜剑镶嵌绿松石处的粘接材料不属于人们所熟知的动物胶、植物胶及矿物胶,其主要成分为蜂蜡。研究结果不仅丰富了我们对古代胶粘材料的认识,对古代蜂蜡研究工作的开展亦起到抛砖引玉的作用。为此指出,有必要开展我国古代蜂蜡的系统研究工作,有必要对铜器上镶嵌宝玉石、贴金银等工艺中使用的粘接(连接)材料进行深入研究。
对剑鞘上所裹的皮质材料的分析指出,早在春秋中晚期,我国先民就可能发明铁-铝盐混合鞣制的技术。考工记中未见有鞣前准备的记载,其它文献也鲜有提及。本文首次指出,最迟在春秋中晚期,我国先民已开始将纯石灰用于脱毛浸灰处理。
在合金工艺研究中,笔者发现,已有标准图谱及模拟图谱的分析材料多由铁型、砂型和失蜡法等方法铸造所得,不同于古代范铸而成的青铜器。一般说来,两者的金相组织或多或少会有一定差别。同时,不论是标准图谱或是模拟图谱中都没有提供高锡青铜的形变加工图谱。鉴于此,本论文模拟古代范铸条件,浇铸出成分不同的青铜试样,并对其进行热处理和形变加工处理,得到一系列金相图谱。不论是铸造实验还是热处理实验,这里都得到了一些新的认识,并初步显现出其具有相当的应用价值。除此之外,本实验的最大收获是,获得了含锡6%、14%、22%三种合金材料的形变加工组织。此前未见相关研究。对高锡青铜高温锤打的实验发现,材料最终显示为铸造组织,而非典型的冷加工后热处理或热锻的组织。这对探讨古代青铜兵器等高锡实用器物的制作工艺颇有参考价值。
Over the past two years, archaeologists have conducted several archaeological surveys in and around the Qiaojiayuan site, Yun County, Hubei Province, China. In the process, four tombs were discovered and excavated, all dated to the Autumn-Spring Period of ancient China (770-476 B.C., the formative period of Chinese civilization). More importantly, each tomb contained the remains of a single individual. This is the first time since the foundation of People's Republic of China that archaeologists have discovered Autumn-Spring Period tombs complete with intact burials within the boundary of Hubei province.
According to historical documents, the Qiaojiayuan site is geographically located within the boundary of the ancient Jun state. During this time period, tombs were reserved for the powerful and elite members of society.
The archaeological excavations unearthed a total of 132 artifacts, of which the bronzes played the main part (around 71 pieces). The typical bronzes of the period consist of elaborate vessels of interlaced designs known as Ding, Pan, Yi, Fou, Gui, and Ge. Swords and other articles were also made of bronze. For its significance to the study of the culture of ancient Jun, the Qiaojiayuan site was awarded "The National Significant Archaeological New Findings" in 2006.
According to historical records, ancient Jun had a very long-time history. Through the periods of the Xia, Shang, and Zhou dynasties, Jun maintained a very close relationship with each of these dynasties as they were represented in the Zhongyuan district. By the Spring-Autumn Period, ancient Jun had established a close association with the Chu state. What remained unknown are the details of these relationships, associations and alliances. Through the systematic examination of excavated bronzes from ancient Jun, we should be able to: 1) trace the background of relationships between ancient Jun and dynasties in Zhongyuan district, as well as the relationship between Jun and Chu; and 2) broaden our knowledge about ancient Jun civilization and culture.
The main research in this dissertation is divided into five parts:
1) The Provenance Study of Ores for Bronze Casting.
With a combined use of ICP-AES, XRF, and other analytical methods, we will complete a trace-element analysis on the excavated bronzes from the Qiaojiayuan site. Through a carefully selection of trace elements for cluster analysis, we expect to identify the provenance of the ores that were used for bronzes casting by the craftsman of ancient Jun.
To this end, the archaeological surveys located a very large ancient mining site, the An Cheng East Zhou copper mining site, nearby. We have carefully and systematically surveyed this site and its surroundings, and sampled the ores. For the sake of comparison, we also sampled the ores from the Zhaobishan copper mining sites within Ningxia Province and from the Tonglvshan copper mining sites within Hubei Province. The former is traditionally believed to be under the control of the Zhongyuan dynasties, while the latter belonged to the ancient Chu state.
By use of ICP-AES analysis, we want to find out whether the ores chosen for bronze casting in ancient Jun are from the An Cheng East Zhou copper mining site or some other site. If the results indicate the ores are not from An Cheng East Zhou mining site, then we will have to do some additional revisit our work and address a new question: is there a close relationship between the bronzes excavated from ancient Jun and the copper mining sites somewhere else, e.g., the Zhaobishan copper mining site or the Tonglvshan copper mining site?
2) The Search for the Original Casting Place for the Jun Bronzes.
Our previous research made use of both ICP-AES and XRF methods to analyze the finely-ground clay found in bronzes as well as the soils from excavation sites and clay moulds found nearby. Using a cluster analysis, we were able to identify what seemed to be a very close relationship between the trace-elements both in the finely-ground clay and the soils from the original casting places for bronzes. This relationship was also observed and reaffirmed in the archaeological evidence. So, in our current research, we will be using this method to determine if the Jun bronzes were cast nearby or in some other place.
3) The Aim to Better Understand Bronze Production Technology.
The production technology of ancient bronzes is a very important topic in the discussion about bronze cultural civilization. In the research, we are using XRF analysis and metallurgical information to examine the composition of alloys and their microstructure. In order to better understand the microstructure of ancient bronzes, we also did casting experiments.
4) Corrosion Studies and Studies for Conservation Work.
By combining the analyses of corrosion products through XRD, RM, and XRF with analyses of soil, marine environments, etc., we can better understand how some corroded bronzes were so well preserved, while others were not. This study can also provide meaningful information for conservation and restoration work.
5) The aim to Better Understand Remnant Substance on Bronzes.
By use of FT-IR, RM, and XRF analysis, we want to find out whether the remnant substance on bronzes belongs to organic material or inorganic material. If the results indicate the remnant substance belongs to organic material, then we will have to do more research and find out what kind of material may it be? From this study, we can better understand the adhering material on ancient bronzes, and the tanbark technology of ancient China.
From a larger perspective, the overall goal of this research is to develop a comprehensive and in-depth understanding of Jun culture. Most importantly, we are treating the bronzes as proxy for the human actions of this ancient state. We believe that integrating these four technical components of archaeological analysis within a broader context focused on the interaction between Jun culture and the materials it produced, we should be able to develop a more complete picture of the history of ancient Jun.
引文
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