PIXE在古陶瓷、古玻璃产地中的应用研究

【作者】 张斌；

【导师】 承焕生；

【作者基本信息】 复旦大学 ， 粒子物理与原子核物理， 2004， 博士

【摘要】 古陶瓷、古玻璃的产地及矿料来源研究是目前国际科技考古的重要课题之一。它的研究成果可以为探索古代社会的生产活动、生活方式、生存状态、丧葬习俗、文化交流、商品贸易、对外往来、生产力水平和社会结构等提供相当多的有用信息，可以为研究人类历史的发展和社会的变迁及复原历史的本来面目提供部分佐证。 成分分析是古陶瓷、古玻璃的产地及矿料来源研究的基本方法之一，目前，已有多种成分分析方法应用于这一领域。质子激发X荧光分析(Proton Induced X-Ray Emission，简称PIXE)即为其中一种。它是一种高灵敏度、非破坏性、多元素同时定量分析的核技术。为了研究多种测量方法间的可比性，首次在国内对比了PIXE和ICP-AES两种方法的分析精度，结果表明本实验室使用的PIXE技术有足够的精度，可以和ICP-AES比拟，两种方法间具有互通性和互补性。本论文用PIXE技术结合数据处理的方法—多元统计分析，对古陶瓷、古玻璃的产地研究领域中的一些问题进行了研究，得到一些有价值、有意义的结果。 1、古陶的产地研究一直是国际科技考古界的难题和前沿课题。我们利用PIXE技术对微量元素具有高分析精度的特点，研究了三峡库区麻柳沱、麻柳湾和苏和坪三遗址出土的新石器时代古陶间的关系，以及麻柳沱出土的新石器时代、商代和东周时期古陶的原料来源。结果表明：微量元素含量的因子分析能将三遗址新石器时代古陶区分开；同时能将麻柳沱出土的新石器时代和商代陶器分为一组，东周陶器分为另一组。从而揭示出：大约公元前2500年，三遗址彼此间基本上没有陶器往来，他们所使用的陶器基本上是自产自用的；麻柳沱出土的新石器时代陶器的原料来源与商代相同，而与东周不同。 2、汝窑是宋代五大名窑(汝、官、哥、定和钧窑)之一。河南宝丰清凉寺窑是北宋汝官窑，但原来为民窑。2000年，在河南省汝州张公巷新发现一窑址，经初步发掘，其出土青釉瓷片中有与宝丰清凉寺窑相类似的标本，质量甚佳，我们利用PIXE技术和因子分析首次研究了张公巷窑与清凉寺汝窑出土汝瓷的原料来源和相互关系。结果表明：汝官瓷所用胎料与汝民瓷所用胎料相同，与张公巷汝瓷所用胎料不同，说明张公巷窑和清凉寺窑所用胎料均为就地取材；汝官瓷、汝民瓷和张公巷汝瓷的釉料配方不完全相同，釉的化学组分的因子分析表明三者互不相同。从而揭示出:张公巷窑与清凉寺汝官窑之间并非简单的承袭或移植关系。 3、青花瓷是我国传统瓷器中珍贵的釉下彩，具有相当高的艺术价值。对元青花微量元素均匀性的研究表明:其胎釉的微量元素含量均匀性相当好，可以为我们用微量元素鉴定元青花瓷器提供依据。青花瓷的钻料特征及来源一直是青花瓷研究的热点。对明清民窑青花钻料特征及来源研究表明:从明初洪武开始民窑青花均采用高锰低铁型的国产钻土矿作为青花料，个别样品采用了经提炼的国产钻土矿，而钻土矿的提炼技术最早可能开始于明永乐时期。 4、首次系统地开展了中国古代玻璃的研究。对中国南方出土战国至汉代的早期古玻璃研究表明:南方出土早期古玻璃至少可分为PbO一Bao一5 102和KZO一5102两个体系。聚类分析的结果表明一些玻璃有极其相同的配方和工艺。硝石或许被使用做助熔剂KZO的原料来源。KZO一5 1 02体系的古玻璃可能为中国自己制造的，但也不排除从国外进口的可能。Pbo和Bao是被单独引进玻璃的原料中的。对中国新疆出土西周至汉代的早期古玻璃研究表明:新疆出土早期古玻璃可基本上分成pbo一Bao一51仇、K20一5102、Na20一Cao一51仇和N娜o一Cao一pbo一5102四个体系。聚类分析的结果表明一些玻璃有相似的配方和工艺。Pbo一Bao一5102玻璃和KZO一51仇玻璃被认为分别来自于中国的中原地区和南方。N丙0一Cao一51仇玻璃(包括NaZQ一cao一Pbo一5102玻璃)部分样品可能来自于美索伯达米亚地区，另一部分可能在新疆当地制造。更多还原

【Abstract】 Provenance determination of ancient ceramics and glasses is one of the mainstreams in archaeometry research to date. This research can provide numerous available information for the study of production activity, living manner, burying custom, cultural exchange, trade of commodity, external communion, productivity standard and social structure of ancient society. It also can provide partial evidence for the study of human historical development and social evolvement and for restoring the historical truth.Composition analysis is one of the most foundational methods for study on provenance determination of ancient ceramics and glasses. Now, many methods have been applied in this field. Proton Induced X-Ray Emission (PIXE) is one of them. PIXE is a non-destructive nuclear technique with high sensitivity, and it can quantitatively analyze multi-elements at the same time. To compare the data measured by different techniques, we firstly compare the results of modern optical glass from PIXE with those from ICP-AES in China. We found that our PIXE technique has sufficient precision and can compare to ICP-AES. So the two methods can make up each other in some sense. Here, we employed PIXE combined with multivariate statistical method to study some problems of provenance determination of ancient ceramics and glasses. Some valuable and significative results can be summarized as the following:1 .The provenance determination of ancient pottery is always a difficult problem and the most preceding problem in archaeometry research. We employed PIXE with high precision for analysis of trace element to study the relationship between the Neolithic pottery unearthed from Maliutuo, Maliuwan and Suheping sites in Sanxia reservoir area. We also studied the source of raw material of pottery from Maliutuo made in the Neolithic age, the Shang Dynasty and the Eastern Zhou Dynasty. The results showed that the Neolithic pottery from the three sites could be completely divided by the factor analysis of trace element content. At the same time, the pottery from maliutuo could be divided into two groups, namely a group formed by all theNeolithic pottery and all the pottery in the Shang Dynasty and the other group formed by all the pottery in the Eastern Zhou Dynasty. It could be disclosed that in about BC 2500, no interchange of pottery occurred between the three villages. The pottery products used in daily life in the three villages were independently made. In the source of raw material, the Neolithic pottery samples from Maliutuo were identical with those in the Shang Dynasty, but different from those in the Eastern Zhou Dynasty.2. Ru kiln is one of the five most famous kilns (Ru, Guan, Ge, Ding and Jun kiln) in the Chinese Song Dynasty [AD 960-1279]. The Ru Kuan kiln at Qingliang Temple, Henan Province originated from the Ru folk kiln, hi 2000, another kiln site was found at Zhanggongxiang, Ru County of Henan Province. By the first excavation, numerous celadon shreds with high quality were unearthed. Among them, some celadon shreds were very similar to those unearthed from Qingliang Temple. So we employed PIXE and factor analysis firstly to study their source of raw material and the relationship between the two kilns. The results showed that in the raw material provenance of body, Ru Kuan celadon was identical with Ru folk celadon, while it was different from Ru celadon from Zhanggongxiang. It meant that the two kilns used local materials as the raw material of body. In the recipe of glaze, they are incompletely identical each other. By the factor analysis of the chemical composition of celadon glaze, the Ru kuan celadon, the Ru folk celadon and the Ru celadon from Zhanggongxiang could be differentiated each other, which meant that three kinds of Ru celadon were different each other. It was disclosed that Zhanggongxiang and Qingliang Temple kilns have not the simple replantable or adoptive relationship.3. The blue and white porcelain is the precious porcelain with underglaze color among the Chinese traditional porcelains. It has very更多还原