LA-ICP-AES分析丝绸之路且末出土玻璃器成分特点

位于丝绸之路南道上的新疆且末古国扎滚鲁克墓地M133墓和M49墓分别出土了一批珍贵的玻璃料珠和一件玻璃杯,时代为东汉-南北朝时期(公元1～6世纪)。利用激光刻蚀电感耦合等离子体发射光谱(LA-ICP-AES)对这批样品进行化学成分分析,并讨论了这一方法的优势与准确性。分析数据显示,这批样品具有典型的西方钠钙玻璃的成分特点。根据现代西方古代玻璃研究体系中助熔剂的不同,这批玻璃又划分为泡碱玻璃和植物灰玻璃两类,并对玻璃成分的相似性与差异进行探讨。该研究以玻璃为载体反映了且末古国与西方的贸易与文化交流的历史,而且为玻璃的产地来源与制作工艺研究提供了重要的参考。     

甘肃马家塬战国墓地M4出土硅酸盐珠饰的科学分析研究

结合X射线荧光光谱、拉曼光谱和X射线衍射分析,对甘肃马家塬战国墓地M4出土的11件装饰性硅酸盐珠饰进行了无损分析研究。依据分析结果将这些样品划分为钠钙硅酸盐玻璃、铅钡硅酸盐玻璃和釉砂三种类型。化学成分分析结果表明：钠钙硅酸盐蜻蜓眼玻璃珠的蓝色眼珠部分采用Co2+着色。拉曼光谱分析在铅钡体系硅酸盐样品中检测到了人工合成的硅酸钡铜系中国蓝和中国紫颜料,在钠钙蜻蜓眼玻璃的白色区域检测到了锑酸钙(CaSb₂O₆)乳浊剂/着色剂。结合已有的研究结果,探讨了所分析样品的可能来源及其反映的早期文化和技术交流状况。含有中国蓝、中国紫的装饰性珠子的制作材料和工艺应当是受到当时秦人的影响。而钠钙蜻蜓眼珠的成分特点,又与新疆等西北地区出土的同类珠子有相似之处。可见西戎人在玻璃制作技术方面同时受到北方草原民族文化和秦文化的共同影响。这批样品中以泥芯和玻璃化材料共同组成的装饰珠子,可能是从釉砂珠向玻璃珠的过渡类型,这对于研究我国玻璃的起源问题提供了新的参考资料。     

湖北襄樊出土有色玻璃串饰的检测分析

运用X射线衍射(XRD)和X射线荧光光谱(XRF)等手段,对湖北襄樊一处时代在东汉末年至魏晋初年之间贵族墓出土的不同颜色玻璃珠串饰进行了物相和成分分析.结果表明,这些玻璃珠属于低铅的PbO-SiO2系统配方,各种助熔剂的含量都很低,且矿物原料比较纯,杂质含量低;古代玻璃中常见的铜、铁等致色元素含量很低,而铋的氧化物含量...     

一批金元时期古玻璃的EDXRF探针无损分析

利用EDXRF探针无损分析技术,分析了河南禹县阳翟遗址出土的一批金元时期的玻璃样品,以研究这批古玻璃的工艺技术特点.分析显示,所有蓝色玻璃样品的呈色剂均为CuO,而非CoO.从化学组成来看,这批古玻璃的种类较为复杂,主要包括钾钙玻璃、钠钙玻璃和铅钾钙玻璃等.     

陕西临潼新丰墓地出土战国秦汉时期玻璃器分析研究

陕西临潼新丰墓地的年代分两个阶段,第一阶段是战国中期偏晚至秦代,第二个阶段是西汉中期至东汉时期。该墓地有700余墓葬,其中12座墓葬出土玻璃制品100余件,包括蜻蜓眼珠,玻璃珠、耳珰。选取5件样品,涵盖上述三种器形。采用光学显微镜和扫描电子显微镜观察玻璃的结构特征,能谱仪分析其成分。采用激光拉曼光谱分析玻璃相中的晶体。结果显示5件玻璃样品中有4件铅钡玻璃,蓝色玻璃主要为铜离子着色,红色玻璃为Fe2O3晶体着色,白色乳浊玻璃为析晶造成的乳浊效果。1件为钾钙钠釉层的费昂斯制品,着色元素为铜和铁。同时讨论了铅钡玻璃和钾钙釉费昂斯的技术问题。     

古代玻璃样品表面因素对便携式X射线荧光定量分析的影响

便携式X射线荧光光谱分析技术(PXRF)是一种表面分析技术,样品表面状况对定量分析结果有很大的影响.本文采用PXRF对新疆、广西、江苏等地出土的Na2O-CaO-SiO2,K2O-SiO2和PbO-BaO-SiO2体系古代玻璃的风化表面与内部进行了定量分析,指出了主要助熔剂的含量在不同部位的变化.另外,还研究了样品与参...     

新疆两处遗址出土绿松石文物的成分分析和产源判别

绿松石是一种产地有限,却在世界范围内被广泛使用的珍稀宝石资源,研究绿松石文物的矿料来源可为了解古代不同地区间珍稀资源的获取与交流模式、文化传播途径、早期贸易网络等学术问题提供帮助。新疆绿松石文物的矿料来源是近年来科技考古关注的热点问题之一,目前存在中原说、波斯说、新疆说和多元说等观点。研究新疆绿松石文物的产源,其难点在于既要保证文物的安全,又要确保分析数据的准确性,同时要避免样品表面污染对数据结果带来的干扰。鉴于此,采用等离子体原子发射光谱LA-ICP-AES对新疆加依、西沟两处墓地出土的绿松石进行化学成分分析,并结合秦岭东部五处产地的绿松石成分数据,经主成分分析绘制散点图——建立产地区分模型。主成分分析结果显示加依墓地样品中有五枚是罕见的锌绿松石,其余同西沟墓地绿松石的成分相近,均含有相对较高比例的Fe和Sr。结合中原地区的绿松石成分数据对比分析,发现新疆两遗址绿松石的微量元素特征相近,以高B2O低BaO为特征区别于中原地区的绿松石样品。在产地区分模型中,代表加依墓地和西沟墓地出土绿松石的散点聚集成团,且明显区分于白河、郧县、洛南、竹山、淅川五地的散点分布区域。综上结果表明新疆东部两处遗址的绿松石制品与中原东秦岭五处绿松石矿区所产矿料的成分差异较大,鉴于近年来新疆哈密发现与两处遗址同时代的绿松石采矿遗址,推测加依墓地、西沟墓地的绿松石制品其矿料来自中原地区的可能性较小。     

陕西战国秦墓出土玻璃和汉紫六博棋子分析研究

利用超景深显微镜（OM）、激光拉曼光谱仪(Raman)、X射线荧光光谱仪(XRF)、扫描电子显微镜能谱(SEM-EDS)、色度仪等多种手段,对陕西战国秦墓出土的两种质地、颜色不同的六博棋子进行了综合分析检测。鉴定出蓝色样品为铅钡玻璃,紫色样品为中国紫制品,发现了中国紫在战国时期的新用途。并对比陕西出土的铅钡玻璃制品与两湖、四川地区出土的同时代的铅钡玻璃制品在成分组成上的差异,推测战国时期铅钡玻璃的制作工艺已成熟,可根据器物形制的需求进行不同的成分配比。同时,还发现当时的玻璃制作已有旧料重熔制作新器的现象。在确定中国紫成分的基础上,利用色度计进行色度测试,根据光谱数据,首次为人造硅酸铜钡颜料确定了特征光谱峰,使快速、无损的对人造硅酸铜钡颜料的鉴定识别成为可能。     

拉曼光谱技术在中国古玉、古玉器鉴定和研究中的应用

激光拉曼光谱技术是应用于科技考古研究中的高技术之一,属于无损分析研究,但作为一种很好的无损分析方法它在中国古代玉器研究中的应用并不非常广泛。文章首先介绍了激光拉曼光谱技术的基本原理及近几年来国内外的最新进展,然后从矿物结构与拉曼特征峰之间的关系入手比较了目前国内外5种常见玉石的激光拉曼研究结果。然后分别通过对浙江良渚遗址和河南安阳殷墟遗址出土的4件中国古代玉器与新疆和田地区出产的软玉样品进行对比研究,成功地利用激光拉曼光谱技术对一批中国古代玉器进行了无损鉴定,从而阐明该项技术在中国古代玉器结构测试和材质鉴定中是一种很好的无损分析研究方法。最后,讨论了目前激光拉曼光谱技术在中国古玉和古代玉器研究中存在的局限性并对其发展前景进行了展望。     

河南宝丰和新郑出土硅酸盐制品的无损分析研究

无损分析是文物样品研究的重要内容,研究中采用便携式能量色散型X射线荧光光谱仪(pXRF)和激光拉曼光谱仪(LRS),对河南宝丰和新郑出土的21件战国晚期到汉代的硅酸盐制品进行了化学成分分析和微区物相分析。依据化学成分分析结果,将样品划分为铅钡硅酸盐玻璃、钾硅酸盐玻璃、釉砂和铅钡釉砂四类分别进行讨论,并对样品的着色机理进行了初步探讨;利用激光拉曼光谱在部分蜻蜓眼和圆环珠蓝色颜料中检测到了中国蓝(BaCuSi₄O₁₀)、中国紫(BaCuSi₂O₆)和中国深蓝(BaCu₂Si₂O₇),同时成功确定了部分样品中存在石英、方解石、碳酸铅、煅棕土、绿土等多种物相;结合考古研究资料,对这些样品的来源进行了简要讨论,其中本实验铅钡硅酸盐玻璃、钾硅酸盐玻璃耳珰和铅钡釉砂为我国自制,而另外1件釉砂可能属于舶来品,反映了我国古代中原各地区间,以及中原与西域间有着广泛的文化技术交流。便携式能量色散型X射线荧光光谱仪和激光拉曼光谱仪的相互结合,能够提供硅酸盐制品的有效化学成分和结构信息,在文物科学分析中显示出特有的优势,为其考古研究提供有益的信息。     

In situ analysis of stratified glass eye beads from the tomb of Marquis Yi of the Zeng State in Hubei Province,China using XRF and micro‐Raman spectrometry

A total of 46 stratified glass eye beads in Hubei Provincial Museum, Wuhan, China were analyzed in situ by means of portable X‐ray fluorescence and Raman 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 late), in Hubei Province. It is determined that most of these elegant glass beads belong to the typical soda‐lime‐silicate glasses with low contents of MgO and K₂O. The colorants used within these beads are attributed to two types: antimony‐based compound opacifiers/colorants and the transition metals in their oxidized state such as Co, Cu, and Fe ions. 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 unearthed from Xu Jialing Tomb (5th–4th century bc ) in Henan Province, we discussed the provenance of these stratified glass eye beads and relative issues briefly. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman classification of glass beads excavated on Mapungubwe hill and K2, two archaeological sites in South Africa

About 200 coloured glass beads (red, yellow, green, blue, white, black, pink, plum) excavated on Mapungubwe hill and at K2, archaeological sites in the Limpopo valley South Africa, were studied with Raman scattering. This is also the most southern site in Africa where evidence for glass reworking has been found. The glass matrix of the beads was classified according to its Raman signature into three main subgroups and corroded glass could also be identified. At least seven different chromophores or pigments (lazurite, lead tin yellow type II, Ca/Pb arsenate, chromate, calcium antimonate, Fe–S ‘amber’ and a spinel) were identified. Many of the pigments were manufactured after the 13th century, confirming the presence of modern beads in the archaeological record. This calls for further research to find a way to reconcile the carbon dating of the hill, which currently gives the last occupation date on the hill as 1290 AD with the physical evidence of the modern beads excavated on the hill. The results are discussed in terms of the glass production origin of the beads (Europe, Mediterranean area, India, China). Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of some ancient glass vessels fragments found in Xinjiang,China, using a portable energy dispersive XRF spectrometer

In this article, a portable energy dispersive X‐ray fluorescence spectrometer having determination capability for elements of Na and Mg is applied to characterization of the 58 ancient glass vessels fragments found in Xinjiang, China, successfully. These ancient glass samples were found in different historical sites dated from the Han Dynasty (202 B.C.–220 A.D.) to early Yuan Dynasty (1271–1368 A.D.). The chemical composition difference between the original weathered and inner fresh surfaces is distinguished. Using Mg, Ca, Al and K as the diagnostic elements, the glass samples analyzed are mainly classified into three types through cluster analysis. Each type of glass seems to be produced under different recipes. The techniques used to make these glasses and their possible provenances are discussed briefly. The obtained results provide new useful information for further understanding of the exchange and trade networks related to early glasses found in Xinjiang, China. Copyright © 2011 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the Mapungubwe oblates: glass trade beads excavated at an Iron Age archaeological site in South Africa

Oblate seed beads (2–4 mm) excavated on Mapungubwe hill, an Iron Age site in South Africa, were analysed with Raman microscopy and supportive techniques to determine the glass technology and pigments used to produce the beads. The Raman spectra and XRF analysis of the beads classify the glass as a typical soda/lime/potash glass similar to Islamic glass from the 8th century (Ommayad), but with higher levels of aluminium, iron and magnesium. The turquoise, bright green, bright yellow and orange colours were obtained by utilizing a combination of cassiterite (SnO₂) and lead tin yellow type II (PbSn_1−xSi_xO₃). Doping with cobalt and manganese produced dark blue and plum‐coloured beads. The Fe‐S chromophore was detected through its resonance‐enhanced spectrum in the black beads. Corrosion of the black beads was investigated and an organic phase detected on the beads, which might have influenced the corrosion process. This detailed profile of the glass technology used to produce the Mapungubwe oblates might eventually help to determine their provenance. Copyright © 2007 John Wiley & Sons, Ltd.     

Nondestructive on‐site identification of ancient glasses: genuine artefacts,embellished pieces or forgeries?

A selection of 23 rare glass objects, mostly enameled, of various provenance and age, from the 5th century BC to the 19th century AD including the Western and Islamic Middle Ages but with a focus on 16th–18th century Venetian and French ‘façon de Venise’ artefacts, have been studied on‐site at the Sèvres museum or at the laboratory. The Raman signatures of the transparent or opacified glass matrix and of enameled decorations are discussed and compared to those previously recorded on ceramics and stained glasses. The Raman parameters allow discrimination between 2 groups (with some variations) of glass bodies, belonging to mixed Ca–Na and Ca‐containing Na‐rich silicates, with some exceptions. Most enamels are instead lead‐based glasses, but we also found enamels having a composition close to that of the glass body. Most of the pigment signatures are similar to those recorded on ceramic glazes, which proves the link between the two technologies. A particular emphasis was given to the identification of white opacification techniques. Very specific signatures could question the authenticity of some artefacts, and at least in two cases, arguments have been found to identify a fake or embellished artefact. Copyright © 2008 John Wiley & Sons, Ltd.