清代红绿彩瓷器无损分析研究  

Non-Destructive Analysis of Red and Green Porcelain in Qing Dynasty

作　　者：潘秋丽[1] 邵金发 李融武[2] 程琳[1] 王荣[1] PAN Qiu-li;SHAO Jin-fa;LI Rong-wu;CHENG Lin;WANG Rong(Key Laboratory of Beam Technology of Ministry of Education,College of Nuclear Science and Technology,Beijing Normal University,Beijing 100875,China;Department of Physics,Beijing Normal University,Beijing 100875,China)

机构地区：[1]射线束技术教育部重点实验室,北京师范大学核科学与技术学院,北京100875 [2]北京师范大学物理系,北京100875

出　　处：《光谱学与光谱分析》2022年第3期732-736,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(12075028)资助。

摘　　要：红绿彩瓷器是我国陶瓷史上一种重要的釉上彩瓷器,分析其彩料的化学组成和物相结构对其烧制工艺的研究有很重要的意义。但由于瓷器表面的不平整和彩料分布的不均匀性,导致其不满足传统的1 mm×10 mm线光源的X射线衍射仪对样品的测试要求。而毛细管聚焦的X射线衍射仪采用点光源的方式照射样品,毛细管X光透镜对Cu-K_(α)的能量有高达3个数量级的放大倍数,同时具有低的发散度,能实现样品直径100μm的微区和直径3 mm的常规X射线衍射分析,非常适合古陶瓷类样品矿物结构的无损分析的研究。因此,应用毛细管聚焦的微束X射线荧光谱仪和毛细管聚焦的X射线衍射谱仪对江西景德镇出土的清代红绿彩瓷的白釉和釉上彩料的化学成分和物相结构进行分析,并对红绿彩瓷彩料中2 mm×2 mm感兴趣区域内多元素分布和矿物相的分布进行了二维扫描分析。结果表明,Cu为绿彩的主要着色元素,在绿彩中的含量为0.02%,部分以Pb_(8)Cu(Si_(2)O_(7))_(3)(PDF 31-0464)晶相形式存在;Fe为红彩的主要着色元素,Fe含量为1.63%,部分Fe元素以Fe_(2)O_(3)(PDF 47-1409)的晶相形式存在;其中Pb在绿彩和红彩中的含量分别为41.49%和6.29%,其主要作用是使彩料的熔点降低,部分Pb在700~800℃的烧制过程中与Cu元素和Si元素相结合以Pb_(8)Cu(Si_(2)O_(7))_(3)(PDF 31-0464)晶相形式存在。从扫描区域内的元素分布图和晶相分布图可以看出,彩料原料中着色元素Cu和Fe的矿物晶相与Cu和Fe的元素分布不一致,表明原料中原有的Cu和Fe的矿物晶相在烧制过程中基本上都消失了,仅剩余或生成部分Fe_(2)O_(3)晶相;白釉中存在莫来石晶相,说明白釉是在高温下烧制而成;其中Pb_(8)Cu(Si_(2)O_(7))_(3)晶相的形成温度在750℃左右,因此可以进一步说明清代红绿彩的绿彩料是在低温下烧制而成。以上结果说明,毛细管聚焦的微束X射线荧光和毛细管聚焦的�The red and green colored porcelain is an important overglaze colored porcelain in the history of Chinese ceramics.It is significant to analyze the chemical composition and phase structure of the colored pigments to study the process of fired technologies.However,the traditional X-ray diffractometer with a 1 mm×10 mm line source is not easy to measure the porcelain sample of uneven surface and unevenly distributed color material.The capillary-focused X-ray diffractometer has a point X-ray beam to irradiate the sample.The capillary X-ray lens has a magnification of up to 3 orders of magnitude to the energy of Cu-K_(α) and has a low divergence of the X-ray beam.Therefore,it can measure the sample with a diameter of 100 micrometers and the conventional X-ray diffraction analysis of a sample with diameter of 3 mm,which is very suitable for the non-destructive analysis of the mineral structure of ancient ceramic samples.This article reports the results of the chemical composition and phase structure of the white glaze and red and green-colored pigments in the Qing Dynasty unearthed in Jingdezhen,Jiangxi province by the capillary focused microbeam X-ray fluorescence spectrometer,and the capillary focused X-ray diffraction spectrometer developed by our laboratory.It carried out the two-dimensional scanning analysis of the distribution of multi-element and mineral phases in the interest region(2 mm×2 mm)of the red and green colored porcelain.The results show that at first,Cu is the main coloring element of green colored pigments and the concentration of Cu in green colored pigments is 0.02%.Moreover,parts of Cu exist in the form of the Pb_(8)Cu(Si_(2)O_(7))_(3) crystal phase.Secondly,Fe is the main coloring element of red-colored pigments,and the contractions of Fe in red-colored pigments is 1.63%,and parts of Fe exist in the form of the Fe_(2)O_(3) crystal phase;Thirdly,the concentrations of Pb in green and red-colored pigments is 41.49%and 6.29%,respectively.The main function of Pb is to lower the melting point of t

关 键 词：红绿彩瓷 毛细管X光透镜 X射线衍射分析 微束X射线荧光分析 釉上彩瓷器 

分 类 号：O434.19[机械工程—光学工程]