Chemical Analyses of Potash–Lime Silicate Glass Artifacts from the Warring States Period in China

Potash–lime silicate (K₂O–CaO–SiO₂) glass dated to the Warring States Periods is one of the earliest glass types that have been found in China, but scientific research about this type of glass is scarce at home and abroad. In the present study, a total of 23 potash–lime silicate glass samples of the Warring States Period, excavated from different areas of China, were analyzed noninvasively using a portable X-ray fluorescence spectrometer (pXRF). The chemical composition of these K₂O–CaO–SiO₂ glasses was analyzed and compared with that of the potash silicate (K₂O-SiO₂) glasses of the Han Dynasties. The possible raw materials used to make the ancient K₂O–CaO–SiO₂ glasses were discussed. It appears that the ancient K₂O–CaO–SiO₂ glasses were produced in China and the potash glasses were of versatile origins. This research provides useful clues to trace the technical development of ancient Chinese glass.     

Application of a portable XRF spectrometer for classification of potash glass beads unearthed from tombs of Han Dynasty in Guangxi,China

Thirty‐seven glass beads excavated from the Han Dynasty tombs in Hepu county, Guangxi, China, were analyzed using a portable X‐ray fluorescence (PXRF) spectrometer. Reference sample Corning glass D is used to check precision and accuracy of the equipment for major and minor components. The results of inductively coupled plasma atomic emission spectroscopy and PXRF are compared to evaluate the quality of equipment for trace elements. Combined with the contents of Al₂O₃ and CaO, a new criterion of subgroup division for potash glass based on the levels of trace elements (Rb and Sr) is proposed. The correlations of Rb and K, Rb and Al, and Sr and Ca are discussed. It is thought that saltpeter was the main flux used to produce potash glasses of different groups. The positive correlation between Rb and Al, and Rb and K indicates that potassium aluminosilicate minerals may be used as raw minerals for potash glasses of group II. The results indicate that the levels of Rb and Sr can be very helpful in subgroup definition and provide useful clues to the raw materials used for glassmaking and provenance study of the potash glass found in Guangxi, China. Copyright © 2013 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.     

UV-visible and infrared absorption spectra of gamma irradiated CuO-doped lithium phosphate, lead phosphate and zinc phosphate glasses: A comparative study

Undoped and CuO-doped lithium phosphate, lead phosphate and zinc phosphate glasses were prepared. UV-visible and infrared absorption spectra of the prepared samples were measured before and after successive gamma irradiation. Experimental optical spectra of the undoped samples reveal strong UV absorption bands, which are attributed to the presence of trace iron impurities in both the lithium and zinc phosphate glasses while the lead phosphate glass exhibits broad UV bands due to combined absorption of trace iron impurities and divalent lead ions. The CuO-doped glasses reveal an extra broad visible band due to Cu²⁺ ions in octahedral coordination. The effects of gamma irradiation have been analyzed for both the sharing of all constituent components including trace iron impurities. Infrared absorption spectra of the prepared samples were investigated by the KBr disk technique. The FTIR spectra reveal main characteristic absorption bands due to different phosphate groups. The IR spectra are observed to be slightly affected by the increase of CuO in the doping level (0.2-3%) indicating the stability of the main network units.     

利用PIXE和ICP-AES 对蛇纹石原料及中国古代蛇纹石玉器的微量元素分析

以蛇纹石这一中国传统的玉材为对象,旨在通过微量元素含量分析来探索古代蛇纹石玉器原料的可能来源。采用无损的外束质子激发X射线荧光技术(PIXE)对来自中国几个典型矿区的蛇纹石样品主量元素和微量元素进行了分析。同时也采用有损的电感耦合等离子体原子发射光谱技术(ICP-AES)对这些蛇纹石样品的微量元素含量进行了比较分析。结果表明,两种分析方法所获取的蛇纹石微量元素含量趋势具有一致性,说明PIXE无损分析技术可以应用于蛇纹石的微量元素分析研究。讨论了蛇纹石的微量元素含量与地质成因之间的关系,这些蛇纹石的微量元素含量存在明显的差异,这种差异可以用来区分不同地质成因的蛇纹石。Ⅰ型地质成因的蛇纹石中微量元素中Ni含量较低,且几乎不含Cr和Co,而Ⅱ型地质成因的蛇纹石中则含有较高微量元素的Cr,Co和Ni。采用PIXE技术分析了来自浙江、江苏、河南、安徽和湖北等省出土的新石器时代至战国时期(4585 BC—221 BC)14个遗址或墓葬出土的18件蛇纹石玉器的化学成分,通过与两种地质成因类型蛇纹石的微量元素比较分析,初步推测了这些蛇纹石玉器原料的可能来源。以蛇纹石微量元素含量与地质成因类型之间的关系来探索古代蛇纹石玉器玉料可能的来源是一种有益的尝试。     

用指纹元素散布分析研究古耀州瓷胎的起源

选取耀州窑瓷胎样品25个，唐三彩的胎3个，作坊匣钵料样品1个，耀州博物馆附近粘土矿样品4个．用中子活化分析测量样品中29种元素的含量，从这29种元素中挑选出8种指纹元素，将指纹元素的含量进行散布分析．结果表明，出自不同窑口的古耀州瓷的胎，有着长期稳定的、集中的原料产地．耀州窑唐三彩的胎料产地和耀州瓷胎的原料产地相同．25 samples of Yaozhou porcelain bodies, 3 samples of the tri-color pottery bodies during the Tang Dynasty, 1 samples of Saggar material during Song Dynasty and 4 samples of clay mineral taken from the place near Yaozhou Kiln Museum was selected . The technique of neutron activation analysis (NAA) has been employed to measure the content of 29 kinds of elements in the samples. 8 elements of them were selected as fingerprint elements to make scatter analysis.The conclusion is that the ancient Yaozhou por...     

便携式能量色散型X射线荧光光谱仪在中国古代玻璃化学成分分析中的应用

中国古玻璃研究的一个重要方面是古玻璃的化学成分分析,它为中国古玻璃的起源和技术发展提供了科学依据,因此,发展新的化学成分分析方法是非常有必要的.便携式能量色散型X射线荧光分析(portable energy-dispersive X-ray fluorescence annlysis,PXRE)技术的最大特点就是其便携性,可以对不可移动或难以移出博物馆的文物进行科技分析.文章详细介绍了中国科学院上海光学精密机械研究所科技考古中心与日本OURSTEX公司合作改进的便携式能量色散型X射线荧光分析仪的组成、工作原理及分析过程等,列举了将其应用于新疆出土古玻璃样品的测试结果,并与质子激发X射线荧光分析技术所获结果进行了比较.便携式能量色散型X射线荧光分析技术在现场分析方面具有极为广阔的应用前景.     

Comparison of trace elements analysis of nephrite samples from different deposits by PIXE and ICP‐AES

Comparing values of trace elements determined by external‐beam proton‐induced X‐ray emission (PIXE) and inductively coupled plasma atomic emission spectrometry (ICP‐AES) is important to find the provenience of raw materials of ancient nephrite artifacts, because most previous elemental characterizations of nephrite minerals were obtained by ICP‐AES, but PIXE presents the possibility of nondestructive analysis for largely and integrally ancient nephrite artifacts. In this work based on 12 nephrite minerals, it shows that the distribution of trace elements of nephrite samples both in PIXE and ICP‐AES data are generally consistent, although large differences exist in some elements. According to the trace elements, the two types of nephrite mineralization origins can be distinguished, determined by PIXE and ICP‐AES, respectively. Moreover, depending on the PIXE and ICP‐AES data, Sr can be regarded as fingerprint element of Xiaomeiling nephrite minerals, and the differentiation of Sr content between Xiaomeiling nephrite minerals and ancient nephrite artifacts from Liangzhu culture (3300–2300 bc ) is clear evidence that the raw materials of the artifacts are not from Xiaomeiling deposit. The nephrite minerals from Wenchuan deposit can be distinguished from other samples because of their high values of Mn/Fe. Therefore, the PIXE can be used with ICP‐AES to judge mineralization mechanism and find fingerprint elements of raw materials of ancient nephrite artifacts. Copyright © 2012 John Wiley & Sons, Ltd.     

一种新型的微束X射线荧光谱仪及其在考古学中的应用

介绍了一种新型的基于X光透镜的微束X射线荧光分析系统的结构、性能和特点及其在考古学中的应用.X光透镜将旋转阳极X射线发生器产生的X射线束聚成直径为几十微米的光束，实现了对考古样品的无损、原位、微区的分析.为了检验微束分析系统的可行性，分析了一片明代青花瓷残片中青花部位的元素分布，结果表明青花中Mn和Co元素的含量与青花颜色的深浅相一致；相关性分析表明Mn和Co呈现非常好的线性相关；Mn和Co的含量或比值对青花的产地和真伪的辨别有着重要的意义. 关键词： X光透镜 微束X射线荧光 青花     

安徽枞阳出土西周至战国时期青铜器的矿料来源研究

采用激光剥蚀电感耦合等离子体质谱(LA-ICP-MS),对枞阳境内出土西周至战国时期青铜器和汤家墩遗址出土炼渣中的铜颗粒进行微量元素原位无损分析,以探讨枞阳县境内出土青铜器的铜矿来源。结果表明,枞阳汤家墩遗址冶炼铜金属颗粒中的Co,As,Sb,Ag和Bi等元素含量较高,其微量元素特征不同于铜陵和铜绿山的冶炼金属铜;从西周至战国时期,枞阳青铜器所用铜矿来源比较稳定,主要来自汤家墩遗址周边的枞阳县境内,有少量器物的铜矿可能来自长江以南的铜陵地区;LA-ICP-MS可用于青铜器和古铜矿冶遗址炼渣中所夹杂铜颗粒的微量元素原位无损分析,从而为利用炼渣探讨古矿冶遗址冶炼金属产品的微量元素特征奠定了基础,对探讨三代青铜器的矿料来源研究具有重要的应用价值。     

景德镇釉上彩绘瓷器釉上彩的Raman与EDXRF分析

釉上彩绘瓷器是我国古陶瓷中重要品类之一,具有极高的艺术价值和科学价值。采用拉曼光谱和能量色散X射线荧光分析等无损技术手段,对陶瓷釉彩的元素组成和物相组成综合分析,探讨了人们广为关注的景德镇元、 明和清代釉上彩绘瓷若干典型颜料种类的组成配方及其相应的呈色机制。研究发现景德镇古代红绿彩、 五彩、 粉彩等标本中的深红釉上彩料为赤铁矿着色,黄彩为铅锡黄着色,胭脂红彩则由含量不到0.1%的金所着色,绿料皆为二价铜离子着色。研究结果也进一步说明了Raman和EDXRF这两种无损、 微区分析技术的有效结合可以在深化陶瓷类文物的分析研究,尤其是针对图案交错复杂的多种彩绘颜料研究方面起到重要的作用。     

On‐site analysis of Chinese Cloisonné enamels from fifteenth to nineteenth centuries

A selection of 22 rare Chinese cloisonné enamels, from fifteenth century to nineteenth century A.D ., has been studied on‐site in the storage rooms of the musée des Arts décoratifs in Paris. The Raman signatures of the transparent and/or opacified glass matrix are discussed and compared with those that were previously recorded on glazed pottery, enameled and stained glasses. Enamels mostly belong to lead‐based potash‐lime glasses. Three different compositions, lead‐potash‐lime (fifteenth, sixteenth, eighteenth and nineteenth century), soda‐rich (sixteenth–seventeenth century) and soda‐lime (seventeenth century) are identified according to the wavenumber maxima of the Si O stretching and bending multiplets. Most of the pigment signatures are similar to those recorded on ceramic glazes and glass enamels, which proves the link between the technologies but a specific opacifier is observed: fluorite (CaF₂). Naples Yellow pigment variations give characteristic signatures. Additionally, a comparison is made with Limoges enamels (sixteenth–nineteenth century A.D. ). Copyright © 2009 John Wiley & Sons, Ltd.     

EDXRF微量元素分析在文物断源断代中的研究

能量色散X荧光分析（EDXRF）是重要的元素成分析方法之一,现已成为一种强有力的定性和精确定量的无损分析测试技术。能量色散X荧光分析（EDXRF）技术具有不破坏分析样品,并能快速进行钠（Z11）至铀（Z92）的多元素的同时分析,以及分析的浓度范围宽广,精度高等特点,因此,特别适合于进行文物材料的成分分析研究,尤其适合测试极其珍贵的古陶瓷完整文物样品分析与鉴定。文章运用该方法对选自杭州南宋官窑窑址、龙泉古窑址出土的14个样品的南宋官窑青瓷、南宋龙泉窑青瓷和现代仿古青瓷等进行了元素分析的对比研究,分析测定古陶瓷样品中胎、釉的主、次量及微量元素组成,寻找组成中的“指纹”特征元素,试图为古陶瓷文物的断源、断代研究和真伪鉴定提供科学依据。研究结果表明能量色散X荧光分析（EDXRF）是一种较理想的文物研究和鉴定的科学分析手段。     

Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

Yellow and colorless ancient glasses, which were once used to decorate the Temple of the Emerald Buddha, Bangkok, Thailand, around 150 years ago, are studied to unravel the long-lost glass-making recipes and manufacturing techniques. Analyses of chemical compositions, using synchrotron x-ray fluorescence (SRXRF), indicate that the Thai ancient glasses are soda lime silica glasses (60 % SiO₂; 10 % Na₂O; 10 % CaO) bearing lead oxide between 2–16 %. Iron (1.5–9.4 % Fe₂O₃) and manganese (1.7 % MnO) are present in larger abundance than the other 3d transition metals detected (0.04–0.2 %). K-edge x-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure spectroscopy (EXAFS) provide conclusive evidence on the oxidation states of Fe being 3+ and Mn being 2+ and on short-length tetrahedral structures around the cations. This suggests that iron is used as a yellow colorant with manganese as a decolorant. L ₃-edge XANES results reveal the oxidation states of lead as 2+. The results from this work provide information crucial for replicating these decorative glasses for the future restoration of the Temple of the Emerald Buddha.     

Scientific analysis of some glazed pottery unearthed from Warring States Chu tombs in Jiangling,Hubei Province: Indication for the origin of the low-fired glazed pottery in China

A portable energy dispersive X-ray fluorescence spectrometer and a micro-Raman spectrometer are used for the nondestructive analysis of a batch of glazed pottery ornaments unearthed from Warring States Chu (楚) tombs (B.C.475–B.C.221) in Jiangling, Hubei Province, China. According to the chemical compositions obtained, all of the glazes belong to the lead–barium–silicate (PbO–BaO–SiO₂) system and contain certain levels of copper. The man-made barium copper silicate pigment crystals, such as Chinese blue (BaCuSi₄O₁₀) and Chinese purple (BaCuSi₂O₆), are identified from several samples by micro-Raman spectrometer. Besides, gypsum and hematite are found in the white and brown regions of two eye beads. Combined with other glazed pottery and the related silicate artifacts (e.g., lead–barium glass and faience, potash–lime glass and glazed pottery, high-lead glazed pottery, etc.), the origin, development, and affected factors of ancient Chinese low-fired glazed pottery have been discussed preliminarily. The present study provides principal evidences for the technological provenance, raw material recipes, and the relationship between low-fired glazed pottery and related vitreous materials of ancient China. It also provides some significant clues for the origin and the development of ancient Chinese lead–barium glass.     

Effects of Mg and Zn on the surface of doped melt-derived glass for biomaterials applications

Bioactive glasses in the system SiO₂-CaO-Na₂O-P₂O₅ were synthesized pure and doped with magnesium or zinc by melt-derived method. The bioactivity was studied during in vitro assays: the ability of hydroxycarbonate apatite (HCA) layer to form on the glass surface was examined after contact with simulated body fluid (SBF). The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) studies were performed before and after immersion in vitro assays. The SBF solutions were also analyzed using inductively coupled plasma-optical emission spectroscopy (ICP-OES).Introduction of magnesium and zinc as trace element induces several modifications on the observed phenomena at the glass surface and in SBF solution after immersion of the samples. The chemical durability of the glasses, the formation of the silica-rich layer and the crystallization of the HCA layer were affected, but not present the same modifications as the introduced doping element.     

Using Raman spectroscopy as a tool for the detection of iron in glass

Raman spectroscopy has been used to identify iron‐containing glasses. This nondestructive technique offers a fast method to obtain qualitative information about the presence of iron oxides in glass. The effect of the iron content in glass samples is reflected on the topology of the Raman spectra: A strong link between the ratio of the Q₂/Q₃ vibration units of the silica tetrahedral structure is seen. If matrix effects are taken into account, also (semi)quantitative results can be obtained from the calibration lines. The linear calibration is based on the normalized band intensity at 980 cm⁻¹ (I₉₈₀/I₁₀₉₀) and the iron oxide concentration for similar glasses. In amber and dark colored glasses, an extra peak in the spectrum indicates the presence of a FeS chromophore. Different series of glasses of various origins (ancient and modern/industrial glass) have been considered. Copyright © 2011 John Wiley & Sons, Ltd.     

ICP-AES法测定古代车师人肋骨中的痕量元素

近几十年来 ,古代人群的食谱研究已经成为现代科技考古学的一个重要组成部分 ,也是当前国际科技考古学研究领域的一项前沿性课题。人类骨骼的微量元素分析为重建古代居民的食谱提供了大量信息。本文用硝酸 盐酸消解样品 ,采用电感耦合等离子发射光谱仪 (ICP AES) ,在选定的最佳条件下 ,对新疆地区古代车师人肋骨中的Sr,Zn ,Ca ,Cu ,Mg,Fe ,Ba ,Mn等 8种痕量元素进行了测定 ,该方法采用一次溶样 ,多元素同时测定 ,回收率为 87 4 %～ 1 0 6 6 %之间。相对标准偏差为 0 5 %～ 3 3%。该方法简单 ,快捷可靠 ,适用于古代骨样品的测定 ,结果令人满意。其结果为考古学和人类学的研究提供了科学的依据。同时考察了不同酸度对分析结果的影响和共存元素间的相互干扰 ,此外还进行了精密度实验。     

Calibrated U-TH glasses for neutron dosimetry and determination of uranium and thorium concentration by the fission track method

We have prepared a series of standard uranium glasses. A primary standard containing 41 ppm of added U had its concentration and isotope ratio verified by mass spectrometry and by fission track techniques. Secondary standards were compared to the primary standard using the fission track technique. These glasses are useful for measuring both Th and U in solids. The U concentration in an unknown is determined by comparing the fission track density induced by thermal neutron irradiation with the corresponding density in the standard. Th is measured by a cyclotron irradiation using the same U standards. The glasses are also useful for neutron dosimetry. Investigators may obtain small samples of most of these standards from R. H. Brill of the Corning Museum of Glass. Although most of the glasses were fabricated from depleted uranium, one standard containing natural uranium is available. A standard Th glass with concentration of 41 ppm was also made.     

Bismuth silicate glass as host media for some selected rare-earth ions and effects of gamma irradiation

Ultraviolet, visible and infrared spectral measurements were used to investigate prepared undoped and rare-earth doped (2.5%) bismuth silicate glasses (80% Bi₂O₃–20%SiO₂) before and after being subjected to gamma irradiation (8?Mrad). The base bismuth silicate glass reveals strong extended UV–near visible absorption bands which are attributed to the presence of trace iron impurities in the raw materials together with absorption due to sharing of Bi³⁺ ions. The RE-doped samples show the same strong UV–near visible bands as the undoped glasses beside extra narrow characteristic bands mostly in the visible and near-infrared regions due to the respective studied rare-earth ions. The base undoped and all RE-doped samples except CeO₂ sample reveal quite resistance to the effect of gamma irradiation due to heavy atomic mass Bi³⁺ ions present in high content (80%) and the rare-earth ions are known to be weakly affected due to the known 5s, 5p shielding. The exceptional effect of CeO₂-doped sample is related to the ability of Ce³⁺ ions to change its oxidation state through photochemical reaction by irradiation or exchange with Fe³⁺ present as trace iron impurities. The FT infrared spectra of the prepared glasses reveal characteristic absorption bands which are related to the silicate groups together with the sharing of vibrational modes due to Bi–O groups. The IR spectra are slightly affected by gamma irradiation indicating the stability of the structural network groups consisting of SiO₄ and BiO₆ units.