基于同步辐射X射线粉末衍射定量分析方法研究早期瓷器的发展演变

During the early development of traditional ceramic in China, the pottery technology made great progress in the selection of raw materials, firing and glazing. The quality of ceramic product has been gradually improved, and the technology accumulation has laid a foundation for the emergence of mature celadon. However, there are still many controversies in the process of evolution, especially how to scientifically evaluate the quality of ceramic products, which is of great significance to how to understand the early development history of ceramics in China. In this project, the quality of the early ceramic body was evaluated by using the phase composition as the primary indicator. We aim to systematically collect the pottery, stamped stoneware, proto porcelain and mature celadon from Zhejiang Province as analysis object of this project, and discuss distinction and contact in phase composition between them. On the experimental method, the high resolution X-ray powder diffraction method will be used to analyze the phase composition of the bodies. Considering the operability of the experiment and the accuracy of the analysis, we want to take full advantage of the synchrotron radiation X-ray source. We apply the Rietveld method as a tool to obtain the phase structure information of sample and quantify the proportion of amorphous state and mullite. Comprehensively considering phase structure, chemical composition, firing temperature, porosity and microstructure, we expect to establish a scientific method to evaluate the quality of ceramic body. We hope it would provide new research perspectives for study of early development history of Chinese ceramic.

我国传统瓷器早期发展过程中，烧制工艺在原料选择、烧成温度和施釉技术等方面取得巨大进步，产品质量逐步提高，技术的不断积累为成熟青瓷的出现奠定了基础。但目前人们对这一演进过程中的许多问题仍存在争议，特别是如何科学评价陶瓷产品质量问题，它对客观认识我国陶瓷早期发展历史具有重要意义。本项目以胎体物相构成为主要指标评估早期陶瓷器胎体质量，计划系统性地收集浙江地区陶器、印纹硬陶、原始瓷和成熟瓷器作为研究对象，讨论它们在胎体物相构成方面的区别与联系。实验方法上，采用高分辨率X射线粉末衍射方法分析胎体物相构成信息，考虑到实验的操作性及数据的准确性，利用同步辐射X射线光源的独特优势，通过Rietveld全谱拟合方法深入挖掘样品结构信息，定量分析非晶态石英和莫来石等结构，综合物相结构、化学组成、烧成温度、孔隙率和显微结构等信息，建立科学的胎体质量评价体系，为我国陶瓷早期发展历史研究提供新的思路和观点。

商周时期原始青瓷的出现及演变为之后陶瓷生产的蓬勃发展奠定了技术基础，这一阶段内烧造工艺不断改进，产品质量逐步提高，全面认识这一发展过程对理解我国传统陶瓷的历史具有重要意义。但目前人们对这一演进过程中的许多问题仍存在争议，特别是如何科学评价陶瓷产品质量问题。浙江地区在此过程中扮演了重要的角色，因此项目以该地区商周时期典型陶瓷产品作为研究对象，梳理其发展演变的历史。项目组系统地收集了浙江地区近些年不同窑址出土的商周时期陶瓷标本，样品类型包括陶器、印纹硬陶、原始青瓷和成熟青瓷。利用多种实验手段对物相结构、化学组成、烧成温度、孔隙率和显微结构等进行了分析表征，重点是利用X射线粉末衍射方法挖掘胎体物相构成信息，以此为参考依据科学评价胎体质量，为我国陶瓷早期发展历史研究提供新的思路和观点。分析结果表明早期陶器和部分原始青瓷胎体中含铁量较高，而商周时期大部原始青瓷和成熟青瓷产品在原料使用、烧成温度和物相转化等方面并没有明显的差别。不同时期青瓷产品应都是以瓷石为制胎原料，釉为高钙釉，它们之间的差异主要是在外观方面，不同来源样品釉的颜色和均匀性不同。光管X射线衍射分析结果表明早期陶器中几乎没有莫来石等高温相，而印纹硬陶、原始青瓷和成熟青瓷内部物相构成相近，都是由石英、莫来石组成，部分样品含有方石英相，不同类型样品之间的差别是各类物相的相对比例不同。高温相的普遍存在表明它们都经过高温烧造的过程。利用同步辐射X射线对部分典型样品进行了粉末衍射分析，获取了高分辨率的衍射图谱，利用Rietveld全谱拟合和RIR方法对谱图进行物相半定量分析，建立了适合于陶瓷胎体物相研究的实验方法。