中国古代硅酸盐质文物的显微拉曼光谱研究
文献类型：学位论文
| 作者 | 赵虹霞 |
| 学位类别 | 博士 |
| 答辩日期 | 2014 |
| 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 | 便携式激光拉曼光谱仪，古代硅酸盐质文物，科技考古，无损分析，现场分析 |
| 其他题名 | Analysis of Silicate Artifacts unearthed from China by Raman Microspectroscopy |
| 中文摘要 | 文物的不可再生特性及其重要意义要求我们在提取文物信息时必须最大限度地保存文物的价值。利用显微拉曼光谱进行微区物相表征已经成为国内外众多学者的基础性工作，在与整体化学成分相结合的前提下，探索各种工艺间的区别和关联，从而为溯源研究提供参考。此外，在文物发掘现场进行原位无损分析也已成为目前科技考古领域的发展趋势之一。由于具有快速、无损、分辨率高等优势，显微拉曼光谱技术已经成为古代硅酸盐质文物（玉器、玻璃、瓷器、颜料等）研究中常用的一项物相结构分析方法，并发挥了极其重要的作用。 本论文重点采用三台显微拉曼光谱仪（包括1台实验室级别、2台便携式），以便携式X射线荧光光谱(pXRF)技术为补充，对国内外不同产地的透闪石-阳起石以及中国不同地区出土的古代硅酸盐质文物如玉器、玻璃、瓷器等分别进行了系统分析和对比研究，论文的主要内容包括以下几个方面： 1.开展LabRAM XploRA便携式激光共焦拉曼光谱仪、Renishaw inVia型显微共焦拉曼光谱仪和i-RamanTM BWS415-785S-PRB便携式近红外拉曼光谱仪之间的比较研究工作。在对大量不同材质的中国古代硅酸盐质文物进行了多次测试和精确分析后，结合多项参数对三台仪器进行了综合性能评估。 2.选取世界范围内不同产地61件透闪石-阳起石样品系统开展了拉曼光谱的半定量分析研究。在对主体物相结构进行精细拉曼光谱分析的基础上，重点探讨了高频区域OH拉伸振动与其成矿类型、阳离子分布间的关系。同时，还分析了透闪石中石墨、铬铁矿等十余种包裹体的分布规律及其与成矿类型、成矿条件之间的关系。 3.以河南淅川下寨遗址（仰韶文化晚期-石家河文化）、荥阳胡村墓地（晚商）、平顶山应国墓地（西周）和淅川下寺楚墓（春秋）四个典型遗址出土的52件玉器为代表，不仅利用拉曼光谱判定了不同时期玉器的用料特征，而且还结合石墨包裹体拉曼光谱参数的半定量分析对这批玉器进行了初步的溯源研究。 4.重点分析了新疆、河南、湖北、广西出土的公元前10世纪至公元9世纪古代玻璃中锑基、锡基乳浊剂/着色剂、原材料残余物的拉曼光谱特征，并与西方古代钠钙玻璃等制品中锑基和锡基着色剂、乳浊剂出现的时间顺序进行了比较，最后结合化学成分进一步确定了所分析古代玻璃样品的来源。此外，还选取了新疆和广西出土的西周至晋代19件不同化学成分体系的古代玻璃样品，成功利用拉曼光谱技术对它们的玻璃态结构进行系统表征和比较，讨论了风化现象对不同体系样品拉曼光谱的影响程度，并通过拟合计算在聚合指数Ip、OH拉伸振动峰的研究基础上对这批样品进行了烧成温度的判定和类群分析。 5.在聚合指数理论的基础上，本研究成功对河南巩义黄冶唐三彩窑遗址、宝丰清凉寺汝窑遗址和宝丰清凉寺窑遗址出土的唐代至元代16件古代瓷片样品进行了拉曼光谱分析，通过其聚合指数Ip、硅氧键拉伸振动峰位等拉曼光谱参数的拟合计算，不仅对这批样品的釉烧温度分别进行了推断，而且依据不同年代、不同窑口间样品的拉曼光谱差异进行了分类研究。 6.利用LabRAM XploRA便携式激光共焦拉曼光谱仪在湖北省博物馆内对著名的曾侯乙墓出土的战国早期蜻蜓眼玻璃珠成功进行了原位无损测试。首先结合化学成分、纹饰、颜色确定了样品的体系和亚类划分，进而通过拉曼光谱确定了诸如CaSb2O6、Ca2Sb2O7、Pb2Sb2O7等锑基乳浊剂、着色剂，并在与河南徐家岭墓地出土的同期蜻蜓眼样品进行对比的基础上，对曾侯乙墓出土的蜻蜓眼玻璃珠的来源和制作工艺进行了讨论。 本研究还同时对湖北省博物馆提供的9件玉器进行拉曼光谱现场原位无损检测和半定量分析。根据拉曼光谱中OH拉伸振动与阳离子分布之间的关系，确定了这批玉器的成矿类型。此外，还在与河南西周应国墓地出土的玉器样品以及新疆和田、且末玉石进行比较的基础上，利用石墨包裹体的拉曼光谱特征对这些玉器玉料的成矿温度、成矿条件等进行了讨论。 7.利用必达泰克Mini Ram型便携式光纤拉曼光谱仪在江苏盱眙大云山遗址发掘现场对玉衣片、玉棺片等18件玉器成功进行了现场原位无损测试，确定了该批玉器的多种玉料材质，并结合出土背景进行了简要讨论，为大云山遗址出土玉器的研究提供了重要的科技信息。 |
| 英文摘要 | Considering the non-reproducibility and significance of artifacts, we must do our utmost to preserve their value while extracting the information from them. The characterization of micro-area phases using Raman spectroscopy has become a basic work all over the archaeology world. Combined with chemical composition analysis, the Raman spectroscopy can provide references for the provenance study by exploring the differences and relevances among various technologies. In addition, in-situ non-destructive analysis is becoming one of the trends of archaeological science and technology. For its advantages of high-speed, non-destructivity and high resolution, the micro-Raman spectroscopy has play an important role in the structure analysis of silicate artifacts ( such as jade, glass , porcelain, pigments, etc. ). Combined with a portable X-ray fluorescence (pXRF) spectrometer, three Raman micro-spectrometers were used to systematically study the tremolite minerals, as well as silicate artifacts unearthed from China including jade, glass and porcelain. The main contents of this dissertation are listed as follows: 1. The comparative study on the LabRAM XploRA portable laser confocal Raman spectroscopy, the Renishaw inVia Raman spectroscopy and the i-RamanTM BWS415-785S-PRB portable near-infrared Raman spectroscopy were carried out. Through precise analysis of the different silicate artifact materials excavated from China, the three equipments were assessed comprehensively. 2. The semi-quantitative analysis of Raman spectra about 61 tremolite samples around the world were carried out. Based on the fine structure of the main mineral phases by Raman spectroscopy, the relations among the OH stretching vibration, mineralization types and the cation distribution were focused on. Meanwhile, we also discussed the distribution rule of a dozen of inclusions such as graphite and chromite, which are closely related to the mineralization type and conditions. 3. Fifty-two typical jade artifacts were selected for the micro-Raman analysis. All these samples were excavated from Xiazhai in Xichuan, Hu village in Xingyang, the Cemetery of the Ying State in Pingdingshan and Chu Tomb of Xiasi in Xichuan. The characteristics of the raw materials of these samples in different periods were identified. Moreover, provenance study about them was also carried out with graphite inclusions analysis by Raman spectrometers . 4. The characteristics of Raman spectra of the antimony-based, tin-based opacifiers/colorants and raw material residues used in ancient glass unearthed from Xinjiang, Henan, Hubei and Guangxi were studied, which were dated mainly from the 10th century BC to the 9th century AD. They were compared with the chronology of soda-lime silicate ancient glass from the West. With the chemical composition analysis, the origin of these ancient glass were identified. Meanwhile, 19 ancient glass samples with different chemical composition unearthed from Xinjiang and Guangxi dating from the Western Zhou Dynasty to the Jin Dynasty were systematically characterized and compared using Raman microspectroscopy. The loss of flux by weathering on the surface of samples can affect their Raman spectra in different degrees. Finally, the firing temperature and group analysis about these samples were successfully deduced according to the polymerisation index Ip and Si-O stretching vibrations analyzed by peak fitting and calculating. 5. On the basis of the polymerisation index theory, 16 ancient ceramic samples were analyzed by Raman microspectroscopy. All these samples were excavated from the Kilns of Huangye in Gongyi, Ru Kiln of Qingliang Temple in Baofeng and Qingliang Temple in Baofeng from the Tang Dynasty to the Yuan Dynasty. Through fitting calculation of polymerization index Ip and Si-O stretching vibrations, the firing temperatures and the distributions of Raman spectral parameters for these samples from different period and different kilns were discussed respectively. 6. 46 stratified glass eye beads in Hubei Provincial Museum, Wuhan, China were analyzed in situ by portable Raman micro-spectrometers and X-ray fluorescence spectrometers. These beads were excavated from the famous tomb of Marquis Yi of the Zeng State, which was dated back to the early Warring States Period (433 BC or little later), in Hubei Province. According to their characteristics of typology, chemical composition and micro-crystals within samples, we classified them into three subtypes and evaluated the possible relations among them. In addition, through comparing with the similar contemporary samples, we discussed the provenance of these stratified glass eye beads and related issues briefly. Nine jade artifacts were also measured in situ by Raman spectrometers. According to the relationship between the OH stretching vibration and distribution of cations, their mineralization types were determined. Compared with jade artifacts from the Ying State and tremolite minerals from Xinjiang, both the mineralization temperature and conditions were discussed with the Raman spectra of graphite inclusions. 7. Eighteen jade artifacts including jade garment and jade coffin pieces were selected for in situ analysis by i-RamanTM BWS415-785S-PRB portable near-infrared Raman spectrometer in Jiangdu King’s Tomb of the Western Han Dynasty in Xuyi, Jiangsu Province. The raw materials of these samples were identified, and some related issues were discussed briefly combined with its unearthing background. These results provide important scientific information for the archaeological research. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15855]  |
| 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 | 赵虹霞. 中国古代硅酸盐质文物的显微拉曼光谱研究[D]. 中国科学院上海光学精密机械研究所. 2014. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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