便携式X射线荧光光谱仪在科技考古领域中的发展及应用
文献类型：学位论文
| 作者 | 刘松 |
| 学位类别 | 博士 |
| 答辩日期 | 2012 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 干福熹 |
| 关键词 | 便携式X射线荧光光谱仪 科技考古 无损分析 现场分析 古代玻璃 |
| 其他题名 | The development of portable X-Ray fluorescence analysis and its application in scientific and technological archaeology |
| 中文摘要 | 由于文物的不可再生性及其蕴含的丰富的科技、历史、艺术价值，世界不同国家都制定了相应的法律或法规对文物的移动、保护、科技研究的技术手段进行规范和限制。在文物发掘现场或保管地进行无损分析是目前科技考古领域的一个趋势。能量色散型X射线荧光分析技术是一种常用的化学成分分析技术，具有快速、无损等技术优点，在古代硅酸盐质文物（玻璃、颜料、陶瓷、玉器等）的研究中发挥了重要作用，但现有的便携式X射线荧光设备普遍存在对轻元素Na、Mg的探测灵敏度较低或无法检测的弱点，严重制约了其在文物研究中的应用。 本论文重点发展了从日本OURSTEX公司引进的便携式OURSTEX 100FA型能量色散型X射线荧光光谱仪（pXRF），成功实现了对新疆、广西、江苏、陕西等地出土的不同历史时期古代玻璃的化学成分、着色特征、制作工艺等的系统研究，并结合配备能谱分析仪的扫描电镜系统（SEM-EDS）、激光拉曼光谱分析（LRS）、X射线衍射分析（XRD）等技术，对新疆出土的古代玻璃样品中化合物着色技术进行了研究。同时，结合国内外已有的关于古代玻璃的研究结果，探讨了所分析古代玻璃的可能产地，以及与此相关的中西方和国内各地区间与古代玻璃相关的技术、文化交流。本论文成功地对陕西西安法门寺地宫出土的唐代玻璃器皿、江苏无锡鸿山越墓出土的琉璃盘蛇玲珑球形釉陶器进行了现场分析。最后， 本论文建立了软玉主量次量及个别微量元素定量分析的工作曲线。 论文的主要内容包括以下七个方面： （一） 根据所研究不同体系的古代玻璃，从德国Breitlander Eichproben und Labomaterial GmbH公司、美国国家标准与技术研究院（NIST，National Institute of Standards and Technology）、美国康宁玻璃博物馆（Corning Musuem of Glass）等处选取了玻璃标准参考样品29件，以及国内光学玻璃参考样品6件，制作了针对钠钙硅酸盐玻璃、铅钡硅酸盐玻璃、钾硅酸盐玻璃的定量分析工作曲线，实现了对不同体系古代玻璃中包括轻元素Na、Mg在内的主量、次量和部分微量元素的定量分析。利用建立好的工作曲线，对仪器的的精确度、准确度和元素检测限等进行了测试和计算。 （二） 针对不同成分体系的古代玻璃样品，重点探讨了表面风化对定量分析的影响程度。将pXRF所得分析结果与电感耦合等离子体原子发射光谱分析（ICP-AES）、SEM-EDS所得结果进行了比较研究，探讨了不同技术方法所得结果之间差异的原因。 （三） 尽管本中心对新疆出土的古代玻璃样品已经做过研究，但以前的测试分析结果没有对Na、Mg等轻元素进行定量分析。本论文利用pXRF技术对新疆出土的西周至宋元时期的玻璃器皿和珠饰进行了系统研究，对Na、Mg进行了定量分析。研究结果表明，不同历史时期新疆出土的古代玻璃样品是多源的，制作方法是多样的。除采用过渡金属离子Fe、Co、Cu、Mn等着色外，一些从西方传入的古代玻璃采用化合物着色或者作为乳浊剂，如锡酸铅（PbSnO3）、锑酸铅（Pb2Sb2O7）、锡石（SnO2）等。锡酸铅和锑酸铅出现的历史时间段有明显差异。 （四） 利用pXRF技术对广西合浦、江苏无锡鸿山越墓遗址两地出土的钾硅酸盐玻璃进行了系统研究。鸿山越墓出土的钾玻璃为公元前5世纪，年代远早于广西汉代出土的钾玻璃，为中国出现较早的钾硅酸盐玻璃，对研究中国古代钾硅酸盐玻璃的起源具有较大的指导意义。 （五） 现场分析已成为科技考古领域的一大趋势。本论文利用pXRF技术成功对陕西法门寺地宫出土的唐代玻璃器皿进行了测试分析。法门寺地宫出土的唐代玻璃器皿保存状态完好，具有极高的研究价值，而且以前从未进行任何分析。本论文首次对其进行了化学成分分析，明确了这些器物的化学成分体系、着色特征，并对可能的产地进行了简单的讨论。研究结果极大改变和丰富了对这些器物的认识。研究为国内首次。 （六） 本论文还对鸿山越墓出土的琉璃盘蛇玲珑球形釉陶器进行了现场分析测试。测试结果表明，此釉陶器采用的是铅釉。一般认为，低温铅釉出现的时间是在东汉，而本文的测试结果将低温釉技术出现时间向前推进了至少500年。 （七） 本论文利用质子激发X射线荧光分析技术对国内新疆、青海等地的软玉矿石的测试结果作为参考值，建立了相应的工作曲线。利用工作曲线对国内外软玉样品进行了测试，并将测试结果与质子激发X射线荧光技术的测试结果进行了对比，为今后的工作打好基础。 |
| 英文摘要 | Considering the non-reproducibility and great technical, historic and artistic values, laws and rules have been made to confine the transfer of cultural relics and the analytical techniques used. At present, the nondestructive analysis on site has been become a trend in the filed of archeometry. As one of common chemical composition analysis techniques, energy dispersived X-Ray fluorescence techniques with characteristics of fastness, nodestructiveness has taken an important role in the studies of ancient materials including ancient silicate glasses, pigments, ceramics and jades. The low sensitivity of portable equipments for light elements, such as Na and Mg, restricts its application in ancient artifacts studies. OURSTEX 100FA type portable X-Ray fluorescence spectrmeter (pXRF) introduced from Japan has been developed in this dissertation and applied to the systemic studies of chemical compositions, characteristics of coloring, glassmaking techniques for ancient glass excavated from Xinjiang, Guangxi, Jiangsu and Shanxi in different historcal periods successfully combined with scanning electron microscopy /energy-dispersive X-ray spectroscopy (SEM-EDS), Laser Raman spectroscopy (LRS) and X-Ray diffraction techniques (XRD). Refered to results reported by scholars from China and abroad, the possible origins, technical and cultural exchange of relative between the West and East in ancient time has been discussed. On site analysis has been applied successfully to the glasses excavated from Famen Temple in Shanxi province and to glazed pottery excavated from burials of the Yue State at Hongshan, Wuxi city, Jiangsu province. Calibration curves for nephrite and serpentine were also created. The main contens of this dissertation include six parts, which are listed as follows: (1) In order to realize quantitative analysis of different anceint glass systems including Na2O-CaO-SiO2, K2O-SiO, PbO-BaO-SiO2, 29 glass standard reference materials chosed from Breitlander Eichproben und Labomaterial GmbH, National Institute of Standards and Technology and Corning Museum of Glass, and 6 Optical glasses produced in China, were chosen to create elements calibration curves. Quantitative analysis for most elements, including Na and Mg, can be done by the calibration curves created. The precision and accuracy of the equipment were measured and the detection limits were also calculated based on the calibrations. (2) The effects of weathering for different glass systems measured by the quantitative analysis were discussed. The results obtained by pXRF were compared to that of inductively coupled plasma atomic emission spectroscopy (ICP-AES), proton induced X-Ray emission (PIXE) technique and SEM-EDS. The reasons for differences among the results obtained by these techniques were also discussed. (3) The pXRF were used to chemical analysis of ancient glass vessels and beads founded from Xinjiang, which dates from Western Zhou dynasty to Song-Yuan periods. The excavated historical sites are mainly along the ancient Silk Road. The results indicate that the ancient glasses dated to different periods found in Xinjiang are of multi-origins and the techniques used in making them are also various. The results show that the colorants used in the ancient glass include not only the transition metal ions, such as Fe2+, Fe3+, Co2+, Cu2+ , Mn3+, but also compounds, such as PbSnO3, Pb2Sb2O7, SnO2. The application time of PbSnO3 and Pb2Sb2O7 has obvious difference. (4) The pXRF were also used to study ancient potassium silicate glass dated to West Han Dynasty excavated from Hepu county, Guangxi province and the burials of the Yue State at Hongshan, Wuxi city, Jiangsu province which dated to the Warring States. The study of potassium silicate glass unearthed from the burials of the Yue State at Hongshan has great guiding significance to the origins of ancient Chinese potassium silicate glass for its early times. (5) On site analysis has been applied successfully to the glass vessels unearthed from Famen temple which dated to Tang Dynasty. The vessels have important research values for its integrity. No analysis has been performed on them and this is the first time for chenmical analysis. The results clarified the chemical compositions, coloring characteristics. The possuble origins of these samples were also discussed. These results provided further understanding and changed some previous opinions on these artifacts. On site analysis has been performed for the first time in China. (6) On site analysis has also been applied successfully to the glazed pottery unerarthed from burials of the Yue State at Hongshan, Wuxi city, Jiangsu province. The results indicate that the glaze is rich in lead and belongs to low temperature glaze. According to literatures, the time of low temperature glaze first appeared in East Han Dynasty, and our results proved that the time of first appearance for low temperature glaze is at least 500 years earlier than that mentioned in the literatures. (7) Calibration curves for nephrite and serpentine were created based on the results obtained by proton induced X-Ray emission techniques (PIXE). The results obtained by pXRF were compared to that of PIXE. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15678]  |
| 专题 | 上海光学精密机械研究所_学位论文 |
| 推荐引用方式 GB/T 7714 | 刘松. 便携式X射线荧光光谱仪在科技考古领域中的发展及应用[D]. 中国科学院上海光学精密机械研究所. 2012. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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