同步辐射在古陶瓷研究中的初步应用
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摘要
中华文明,源远流长。早在万年以前,中国就出现了陶器,而中国还是瓷器的故乡。瓷器的发明及其工艺和技术上的辉煌成就,是我国对人类文明所作的巨大贡献。古陶瓷是科学和艺术的结晶,是民族文化和中外文化交流的见证。古陶瓷的研究,可从一个侧面揭示当时的社会生活、文化交流乃至政治和经济。
我国对古陶瓷的科技分析研究始于上世纪二十年代,而近些年得以迅速发展。古陶瓷的分析方法主要有两类,即成分分析方法和结构分析方法。一般说来,分析仪器都离不开光源,而同步辐射光源是有史以来人类制造的质量、性能皆最佳的光源。基于同步辐射光源发展起来的各种实验分析技术,较之常规试验方法,具有很多十分突出的优势,现已广泛应用于物理、化学、生物、医学、地矿、催化、材料等领域。然而,同步辐射技术在古陶瓷研究领域的应用却刚刚起步,因此,利用同步辐射技术研究古陶瓷,无论方法的建立,抑或古陶瓷研究本身,都具有非常重要的意义,特别是前者,其可望对同步辐射应用于其它考古材料提供有益的借鉴。
本博士论文聚焦同步辐射技术应用于古陶瓷研究的领域。论文第一章,概括介绍了古陶瓷科技分析常用的一些成分和结构分析方法,总结评价了它们的一些优点和缺点,并对同步辐射在古陶瓷研究中的应用作了初步的总结。
同步辐射X射线荧光(SRXRF)是一种重要的成分分析方法,具有无损、微区、准确、快速的特点。第二章对同步辐射光源、同步辐射X射线荧光和X射线吸收精细结构的原理和试验方法作了简要介绍。
论文第三章介绍了SRXRF法在青白瓷产地探索领域的应用。具体说来,即利用SRXRF法,分析不同窑口青白瓷胎的成分,并以陶瓷参考样校正所测数据。经多元统计分析,发现Rb、Sr、Zn、Mn、Cu、TFe_2O_3、K_2O、Na_2O等元素含量具有明显的产地特征,这一结果表明,SRXRF在古青白瓷鉴定中,有着较为理想的应用前景。
中国的青花瓷名扬中外,是中西方文化交流的重要载体。论文第四章介绍了斯里兰卡曼泰遗址出土青花瓷产地的探索。利用同步辐射X射线荧光、中子活化等多种技术手段分析了斯里兰卡曼泰遗址出土的7枚青花瓷残片的结构和成分,并根据多元统计分析,初步判断其中的4枚青花瓷残片产自中国景德镇,而其余3枚样品的出处尚不能确定,需作进一步研究。
X射线吸收精细结构(X-ray absorption fine structure,XAFS)是一种强有力的结构分析手段,可给出某一种原子周围几个邻近配位壳层的结构信息。与其它结构分析方法相比,XAFS不要求样品具有长程有序结构,不需要破坏样品,因此,XAFS非常适合用于非晶态的古陶瓷结构分析。为此,论文第五章主要阐述了这一方面的工作,即利用XAFS谱结合线性叠加拟合法,分析了古汝瓷釉中Fe的价态,利用色差计分析了样品的主波长,结果表明,瓷釉中Fe~(2+)/Fe~(3+)大,则釉色偏青,反之则偏黄。也说明了XAFS可成功应用于古陶瓷的结构分析研究领域。论文最后一章则对同步辐射在古陶瓷研究领域的应用作了简单的总结和展望。
China has a long history and culture. As early as ten thousand years ago, China has emerged pottery. China is also the hometown of porcelain. The technology and the invention of porcelain and brilliant technically achievements have made a tremendous contribution for human life and culture. Ancient ceramics is the crystallization of science and the arts, also is the witnesses of ethnic and cultural exchanges between Chinese and foreign country. The research of ancient ceramics can be used as a reflection of the social life and cultural exchanges as well as the political and economic.
The scientific and technological analysis for ancient ceramics in China began in the 1920s, also had a rapid development in recent years. The main analytical methods are component analysis and structure analysis methods. Synchrotron radiation light source is the most outstanding source created by the mankind. Compared with other ordinary methods, the experimental analysis technologies on the basis of synchrotron radiation light source have many advantages, also be widely applied in physics, chemistry, biology, medical, and mining, catalysis, materials, and other fields. The applies of synchrotron radiation technology in the ancient ceramics research has just started, therefore, the use of synchrotron radiation technology on the research of ancient ceramics, both in the establishment of methods, or in the ancient ceramics study itself, all of which have very important significance. Which also can be an example for applies of the synchrotron radiation technology in other archaeological materials.
In the first chapter the ordinary composition and structure analysis methods used in the ancient ceramic analysis were outlined as well as their advantages and disadvantages. The preliminary application of synchrotron radiation in the ancient ceramics was summarized. The second chapter briefly introduced the principle and the test methods of the synchrotron radiation light source, synchrotron radiation X-ray fluorescence and X-ray absorption fine structure.
Synchrotron radiation X-ray fluorescence (SRXRF) was an important non-destructive component analysis method. Chinese ancient bluish-white porcelains from different kilns were analyzed by using SRXRF in chapter 3. The statistical analysis results of the experiment data indicated that the content of elements including Rb、Sr、Zn、Mn、Cu、TFe_2O_3、K_2O、Na_2O could reflect the local feature of the form porcelain clay, which could offer a certain parameter for the kiln identification of ancient bluish-white porcelains. The result also proved that SRXRF was a promising method for the kiln identification of ancient porcelains.
In the fourth chapter, the structure and concentration of seven pieces of blue and white porcelains excavated in Mantai site of Sri Lanka were studied by different technique means, such as synchrotron radiation X-ray fluorescence, neutron activation analysis and so on. According to the Multi-statistical analysis, four pieces of blue and white porcelains were made in Jingdezhen, China. The provenance of the other three samples needed further study.
X-ray absorption fine structure is a powerful means of structural analysis, by which the structure information of neighboring atoms around a certain atom can be obtained. Compared with other structural analysis method, XAFS does not require long-range order structure and destruction of samples. Therefore, it is very suitable for XAFS to analysis amorphous structure of the ancient ceramics. In the fifth chapter, the Fe element's valence state in the Ru porcelain was studied using X-ray absorption fine structure spectrum along with linear combination Fitting method. The main wavelength of the samples was also obtained by colorimeter. The results showed that the bigger Fe~(2+) / Fe~(3+) in glaze caused Glaze color to be cyan, otherwise partial to yellow. The simple summarization and prospects of the application of Synchrotron radiation in ancient ceramics were showed out in the last chapter.
我国对古陶瓷的科技分析研究始于上世纪二十年代,而近些年得以迅速发展。古陶瓷的分析方法主要有两类,即成分分析方法和结构分析方法。一般说来,分析仪器都离不开光源,而同步辐射光源是有史以来人类制造的质量、性能皆最佳的光源。基于同步辐射光源发展起来的各种实验分析技术,较之常规试验方法,具有很多十分突出的优势,现已广泛应用于物理、化学、生物、医学、地矿、催化、材料等领域。然而,同步辐射技术在古陶瓷研究领域的应用却刚刚起步,因此,利用同步辐射技术研究古陶瓷,无论方法的建立,抑或古陶瓷研究本身,都具有非常重要的意义,特别是前者,其可望对同步辐射应用于其它考古材料提供有益的借鉴。
本博士论文聚焦同步辐射技术应用于古陶瓷研究的领域。论文第一章,概括介绍了古陶瓷科技分析常用的一些成分和结构分析方法,总结评价了它们的一些优点和缺点,并对同步辐射在古陶瓷研究中的应用作了初步的总结。
同步辐射X射线荧光(SRXRF)是一种重要的成分分析方法,具有无损、微区、准确、快速的特点。第二章对同步辐射光源、同步辐射X射线荧光和X射线吸收精细结构的原理和试验方法作了简要介绍。
论文第三章介绍了SRXRF法在青白瓷产地探索领域的应用。具体说来,即利用SRXRF法,分析不同窑口青白瓷胎的成分,并以陶瓷参考样校正所测数据。经多元统计分析,发现Rb、Sr、Zn、Mn、Cu、TFe_2O_3、K_2O、Na_2O等元素含量具有明显的产地特征,这一结果表明,SRXRF在古青白瓷鉴定中,有着较为理想的应用前景。
中国的青花瓷名扬中外,是中西方文化交流的重要载体。论文第四章介绍了斯里兰卡曼泰遗址出土青花瓷产地的探索。利用同步辐射X射线荧光、中子活化等多种技术手段分析了斯里兰卡曼泰遗址出土的7枚青花瓷残片的结构和成分,并根据多元统计分析,初步判断其中的4枚青花瓷残片产自中国景德镇,而其余3枚样品的出处尚不能确定,需作进一步研究。
X射线吸收精细结构(X-ray absorption fine structure,XAFS)是一种强有力的结构分析手段,可给出某一种原子周围几个邻近配位壳层的结构信息。与其它结构分析方法相比,XAFS不要求样品具有长程有序结构,不需要破坏样品,因此,XAFS非常适合用于非晶态的古陶瓷结构分析。为此,论文第五章主要阐述了这一方面的工作,即利用XAFS谱结合线性叠加拟合法,分析了古汝瓷釉中Fe的价态,利用色差计分析了样品的主波长,结果表明,瓷釉中Fe~(2+)/Fe~(3+)大,则釉色偏青,反之则偏黄。也说明了XAFS可成功应用于古陶瓷的结构分析研究领域。论文最后一章则对同步辐射在古陶瓷研究领域的应用作了简单的总结和展望。
China has a long history and culture. As early as ten thousand years ago, China has emerged pottery. China is also the hometown of porcelain. The technology and the invention of porcelain and brilliant technically achievements have made a tremendous contribution for human life and culture. Ancient ceramics is the crystallization of science and the arts, also is the witnesses of ethnic and cultural exchanges between Chinese and foreign country. The research of ancient ceramics can be used as a reflection of the social life and cultural exchanges as well as the political and economic.
The scientific and technological analysis for ancient ceramics in China began in the 1920s, also had a rapid development in recent years. The main analytical methods are component analysis and structure analysis methods. Synchrotron radiation light source is the most outstanding source created by the mankind. Compared with other ordinary methods, the experimental analysis technologies on the basis of synchrotron radiation light source have many advantages, also be widely applied in physics, chemistry, biology, medical, and mining, catalysis, materials, and other fields. The applies of synchrotron radiation technology in the ancient ceramics research has just started, therefore, the use of synchrotron radiation technology on the research of ancient ceramics, both in the establishment of methods, or in the ancient ceramics study itself, all of which have very important significance. Which also can be an example for applies of the synchrotron radiation technology in other archaeological materials.
In the first chapter the ordinary composition and structure analysis methods used in the ancient ceramic analysis were outlined as well as their advantages and disadvantages. The preliminary application of synchrotron radiation in the ancient ceramics was summarized. The second chapter briefly introduced the principle and the test methods of the synchrotron radiation light source, synchrotron radiation X-ray fluorescence and X-ray absorption fine structure.
Synchrotron radiation X-ray fluorescence (SRXRF) was an important non-destructive component analysis method. Chinese ancient bluish-white porcelains from different kilns were analyzed by using SRXRF in chapter 3. The statistical analysis results of the experiment data indicated that the content of elements including Rb、Sr、Zn、Mn、Cu、TFe_2O_3、K_2O、Na_2O could reflect the local feature of the form porcelain clay, which could offer a certain parameter for the kiln identification of ancient bluish-white porcelains. The result also proved that SRXRF was a promising method for the kiln identification of ancient porcelains.
In the fourth chapter, the structure and concentration of seven pieces of blue and white porcelains excavated in Mantai site of Sri Lanka were studied by different technique means, such as synchrotron radiation X-ray fluorescence, neutron activation analysis and so on. According to the Multi-statistical analysis, four pieces of blue and white porcelains were made in Jingdezhen, China. The provenance of the other three samples needed further study.
X-ray absorption fine structure is a powerful means of structural analysis, by which the structure information of neighboring atoms around a certain atom can be obtained. Compared with other structural analysis method, XAFS does not require long-range order structure and destruction of samples. Therefore, it is very suitable for XAFS to analysis amorphous structure of the ancient ceramics. In the fifth chapter, the Fe element's valence state in the Ru porcelain was studied using X-ray absorption fine structure spectrum along with linear combination Fitting method. The main wavelength of the samples was also obtained by colorimeter. The results showed that the bigger Fe~(2+) / Fe~(3+) in glaze caused Glaze color to be cyan, otherwise partial to yellow. The simple summarization and prospects of the application of Synchrotron radiation in ancient ceramics were showed out in the last chapter.
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