秦早期青铜器科技考古学研究

【作者】 贾腊江；

【导师】 赵丛苍；

【作者基本信息】 西北大学 ， 考古学及博物馆学， 2010， 博士

【摘要】 秦历经弱小到强大,最后建立了中国历史上第一个统一的、多民族的中央集权制国家。在这一过程中,早期秦人所做出的贡献是不容忽视的,早期秦文化也因此成为考古界关注的热点问题之一。秦早期青铜器是早期秦文化的重要组成部分,特别是青铜兵器,不仅能够揭示秦早期青铜冶铸技术的发展情况,也可反映出秦早期军事、政治和文化交流情况。本文利用科技方法研究秦早期青铜器,从金相组织、合金配比和铅同位素比值方面,对其制作工艺特点和技术发展情况进行探讨,为早期秦文化的深入研究提供重要参考依据。秦人早期活动空间主要集中在西犬丘(西垂)、秦、汧、汧渭之会、平阳、雍等地,该区域是早期秦文化的发源和生长地。本文选择甘肃东部陇南、天水和陕西西部长陇地区和宝鸡地区出土的青铜器作为研究对象,能够相对准确地反映秦早期青铜文化的特点。青铜样品的金相和合金配比显示：1)青铜兵器含Sn量在10～18%,含Pb量在2.12-9.83%,金相组织为铸造态,与其它地区青铜器相类似。实验数据表明,早期秦人已经掌握了制作青铜兵器的关键技术；2)凤翔出土铜建筑构件含铜量在73-83%之间,含锡量在10-18%之间,含铅量在1%-10%之间,为铅锡铜三元合金,表明秦人在当时已经认识到含锡量在10～18%时的青铜,具有最佳的硬度和抗拉强度。微量元素分析显示四个地区的青铜器中的微量元素无显著差异,说明礼县、陇县、宝鸡和凤翔四地的青铜器可能使用了地质状况相同或相近的铜矿,也进一步说明秦早期青铜文化从西周到东周都可能开采着相同铜矿,具有一定的连续性。铅同位素比值关系图显示：四地的样品有一定重叠,重叠区域涵盖了宝鸡样品；陇县样品一部分分布在重叠区下方,礼县样品则一部分分布在重叠区上方,表明两者既使用相同的铅矿,也使用着异地铅矿；凤翔样品的铅同位素比值范围涵盖了其它地区样品,表明凤翔在春秋时期已经成为秦人的政治和经济中心。研究成果揭示出早期秦人的青铜冶铸业已经相当发达,很可能开发了甘肃东部秦岭山带中丰富的铅、铜矿资源,拥有独立的矿冶和青铜制造业,已经掌握了先进的青铜制作技术,尤其是青铜兵器制作技术。这个结论具有重要的考古学意义,它显示出秦人从西周到东周期间一直掌握着青铜冶铸技术,控制着所需的原料矿源,为秦人由弱变强,逐步地向东扩展势力提供了必要的资源和技术保障。拉曼光谱分析结果表明,青铜器内部的夹杂颗粒包括PbC03、PbO、Cu20和C,PbCO3和PbO是铅两种重要的碳酸盐和氧化物,揭示出铅的腐蚀过程Pb→PbO→PbC03。拉曼光谱分析证明,样品金相结构中的圆形暗灰色颗粒为Cu20,可能是铸造时或后期腐蚀的产物。此外,本文选择了秦早期青铜器作为研究对象,利用科技手段系统地研究了一大批青铜样品,在国内外尚属先例。在研究方法上,将激光剥蚀等离子体质谱仪引入青铜器微量元素无损检测之中,同时利用激光拉曼技术研究金相组织夹杂物,这些尝试有利于青铜器研究方法的发展。限于本人的水平、样品量和文献的不足,尚未能对更多的问题进行展开探讨。特别是有关秦早期矿料的矿源问题,还需进一步认真探讨。希望本文能够起到抛砖引玉的作用,吸引更多的人关注和研究早期秦文化。更多还原

【Abstract】 After a long time of development, the kingdom of Qin gradually grew powerful and became formidable. Finally it established the first centralized authority empire after unifying six kingdoms into one united state by war in Chinese history. During such a process, the effort and contribution of early Qin people can never be overstated, accordingly, the research and study of early Qin culture stands out as one of the focal issues in the field of archeological and historical study.The bronze, especially the bronze weapons in early Qin period are indispensable elements of Qin people, they not only reveal the achievement of bronze casting technology, but also reflect problems of the military affairs, politics, economy and culture in early Qin period. This dissertation focuses on the study of a group of weapons in early Qin period with some technological approaches. It tries to explore the characteristics of their manufacture technology and raw mineral materials by studying their metallographic structures, ratios of alloy elements and lead isotope ratios, thus to provide important reference to the study of early Qin culture.The range of action of early Qin people mainly locates in areas as West Dog Hill (Xichui), Qin, Qian, the confluence of Qian and Wei, Pingyang, Yong, and so on. where is the place the early Qin culture originated and developed. This dissertation is based on the study of bronzes evacuated from places of Longnan area in east Gansu Province, Tianshui, Changlong area and Baoji area in the west part of Shaanxi Province. By studying bronze wares from these areas, it can adequately reveal the characteristics contained in them about the early Qin bronze culture.The ratios of the bronze alloy elements reveal:1) The Sn content in the bronze weapons is 10～18%, the Pb content is 2.12～9.83%. The metallographic structure is of casting state, and it is similar to that of other kingdoms. The results show that the early Qin people have already mastered the key casting technology to make bronze weapon; 2) The bronze architectural components evacuated in Fengxiang have a bronze content of 73～83%, the Sn content of 10～18%, the Pb content of 1～10%, which are alloys of lead, tin and copper. This shows that the early Qin people have already realized that the bronze with 10～18% Sn content has the best hardness and tensile strength.Trace element analyses to the bronzes evacuated in the four areas show that there are no significant differences regarding the trace elements, which means the bronzes excavated from Longxian, Lixian, Fengxiang and Baoji are made out of the same copper mines. Above of all, it further illustrates that the early Qin bronze culture exploited the same copper mines from West Zhou Dynasty to East Zhou Dynasty. That is say, there is continuity in them.Lead isotope ratio relationship charts show:the samples of the four areas have overlapping area, which covers samples from Baoji. Some Longxian samples distribute under the overlapping area, and some samples from Lixian extend above the overlapping area, which shows that the two share not only the same lead mines, but also use lead mines from different areas. Especially, lead isotope ratio ranges of Fengxiang samples cover that of the samples from the other areas which indicates that Fengxiang was already the political and economic center of Qin people as early as the Spring and Autumn Period.The result of the research reveals that the bronze smelting and casting profession of early Qin people has already been quite advanced, it is pretty likely that they had exploited the rich lead mine and copper mine resources in east Gansu Province of Qinling Mountain. They might have had independent mining, metallurgy and bronze manufacturing profession, and also had mastered the advanced bronze smelting and casting technology, especially including bronze weapons. This conclusion shows that the Qin people master the bronze casting technique during West Zhou and East Zhou period. It has great archeological significance, because the potential information post out that the early Qin people could expand gradually from west to east just depending on the guarantee of mineral resource and advanced techniques.The Raman spectrum analysis shows that the inclusion in the bronze are lead carbonate (PbCO3), Lead (Ⅱ) oxide (PbO), Cuprite(Cu2O) and Carbon(C). PbCO3 and PbO are important carbonate and oxide of lead, which indicates the corrosive process of lead as Pb→PbO→PbCO3. The Raman Analysis demonstrates that the round dark grey inclusion in the metallographic structures is Cu2O, possibly the result of casting or later corrosion.In addition, the dissertation chooses the early Qin bronze as research object through modern Instrumental Analysis to give them a systematical study, which is a new research at home and abroad. On the other hand, it introduces the laser ablation plasma mass spectrometer to study bronzes about their trace elements in situ with non-destructiveness. Meanwhile, Micro-Raman spectroscopy is employed to study the inclusion in metallographic texture. These attempts can be beneficial to promote the researching methods about ancient bronze explore.Finally, due to the limitation of my personal ability, the limited amount of samples and the inadequacy of literature, some of the relevant issues are short of sufficient further probe, especially about the mining sources of the mine materials in early Qin period, this would be the focus of further study for the next step. It is of my hope that the dissertation can draw more people to provide valuable suggestions, and attract more people to the study of early Qin culture.更多还原