Non-destructive analysis and appraisal of ancient Chinese porcelain by PIXE

This paper reports the results of the PIXE analysis on ancient Chinese blue and white porcelain fired at Kuan Kiln (Jingdezhen, Jiangxi province) during 13–19th century. The major, minor and trace element of porcelain body, white glaze and blue glaze were determined by PIXE. In this paper the chemical compositions of porcelain body, white glaze and blue glaze measured from Yuan (AD 1206–1368), Ming (AD 1368–1644) and Qing (AD 1616–1911) blue and white porcelain are present. The cobalt blue pigment used in Yuan, Ming and Qing are also discussed.     

龙泉窑古陶瓷年代断定的中子活化分析和Bayes判别

为实现龙泉窑古陶瓷年代的准确判定,利用中子活化分析（NAA）方法准确测定了南宋-元(AD1127—1368)和明代(AD1368—1644)龙泉窑古瓷胎中La、Sm、U、Ce等18种元素的含量。为提高实验数据的可靠性,利用马氏距离准则排除实验数据的异常值,并对实验数据进行了正态分布检验。在一定的假设前提下,应用Bayes判别法用预处理的实验数据对样品进行年代判别。结果表明：明代69个古陶瓷样品全部正确归类,南宋-元时期96个古陶瓷样品仅有3个未能正确归类,全部样品归类的正确率为98.2%,说明NAA技术和Bayes判别法可望在古陶瓷的年代断定研究中发挥重要作用。     

PIXE study on Chinese underglaze-red porcelain made in Yuan Dynasty

In China. the firing and glazed red techniques of producing underglaze-red porcelain began early in the Yuan Dynasty (AD1206-1368). This paper reports the results of the PIXE analysis of ancient Chinese underglaze-red porcelain produced at Kuan kiln (Jingdezhen, Jiangxi Province) in the Yuan Dynasty. In this work the elemental composition analysis of the obtained samples was carried out using the PIXE facility of a 3 MeV tandem accelerator at Fudan University. The major, minor and trace elements of the clay body, white and red glazes were determined,and details of the results are presented. The obtained data can be used for identification of precious Chinese Yuan underglaze-red porcelain,     

Study on ancient Chinese imitated GE ware by INAA and WDXRF

Imitated GE ware was one of the most famous products of Jingdezhen porcelain field in Ming dynasty (AD 1368-1644). The exterior features of its body and glaze are very marvelous. Black foot, purple mouth and crazing glaze are the main features of imitated GE ware. Until now, the key conditions of resulting these features are not clearly identified. In order to find the critical elements for firing these features, instrumental neutron activation analysis (INAA) and wavelength-dispersive X-ray fluorescence (WDXRF) were used to determine the element abundance patterns of imitated GE ware body and glaze. The experimental data was compared with that of imitated Longquan celadon and of Longquan celadon. The analytical results indicated that Fe, Ti and Na were the critical elements. The body of imitated GE ware which contains high Fe and Ti are the basic conditions of firing its black body, black foot and purple mouth. The glaze of imitated GE ware which contains high Na is the main condition of producing its crazing glaze. Na is the critical element which enlarges the difference in expansion coefficients between the glaze and body of imitated GE ware. Furthermore, Zijin soil was added into kaolin to make the body rich in Fe and Ti. And something which was rich in Na was used to produce crazing glaze in the manufacturing process of imitated GE ware.     

Analysis of elemental maps from glaze to body of ancient Chinese Jun and Ru porcelain by micro-X-ray fluorescence

The reasons how the middle layer of Ru and Jun porcelain between the glaze and body came into being are still not completely understood. Here, elemental maps from the glaze to the body of pieces of ancient Chinese Ru and Jun porcelain were analyzed by micro-X-ray fluorescence. The results show the middle layer was probably formed by the chemical composition of the glaze turning into glassy states and undergoing complex physical-chemical reactions with the body. However, the middle layer of Jun porcelain was formed by the chemical composition of the glaze turning into glassy states and then infiltrating the body at high temperatures during the firing process.     

PIXE analysis of ancient Chinese Changsha porcelain

In this work, proton induced X-ray emission (PIXE) method was applied for the analysis of ancient Chinese Changsha porcelain produced in the Tang dynasty (AD 618–907). A collection of glazed potsherds was obtained in the complex of the famous kiln site at Tongguan, Changsha city, Hunan province. Studies of elemental composition were carried out on ten selected Changsha potsherds. Minor and trace elements such as Ti, Mn, Fe, Co, Cu, Rb, Sr, and Zr in the material of the porcelain glaze were determined. Variation of these elements from sample to sample was investigated. Details of results are presented and discussed.     

从化学组成研究张公巷窑与清凉寺窑青瓷胎的原料产地

用质子激发X射线荧光分析（PIXE）测定宝丰清凉寺窑汝官瓷胎、民汝瓷胎和汝州张公巷窑青瓷胎的7种主量化学组分，将测得的数据进行散布分析。结果表明，清凉寺窑的汝瓷胎和张公巷窑青瓷胎的原料产地不同，但它们的关系比较接近。在清凉寺窑，汝官瓷和民汝瓷所使用的胎料基本相同。     

X-ray fluorescence in investigations of archaeological finds

X-ray fluorescence can be successfully used for analysing the elemental composition of the superficial layers of a measured object, especially for investigating surface coatings, deposits of adventitious materials on the surface, etc. An energy dispersive version of X-ray fluorescence analysis is used in our investigations for analysing various historic objects, art works and archaeological finds. Examples of the application of X-ray fluorescence to various archaeological finds from excavations in the Czech Republic are presented - shards of ancient glazed ceramics, moulds for casting metal products, the remains of a human finger with traces of brass, probably from a ring, etc.     

Chemical characterization of ancient pottery from the greater Accra region of Ghana using neutron activation analysis

Archaeology in Ghana has a long and respectable tradition. Despite this encouraging situation, significant gaps still exist in our understanding of the history of some early societies in Ghana. Accumulated evidence revealed that the Ga (Ayawaso), Dangme-Shai and the Wullf had trade and other cultural contacts with their Akan and Guan neighbours as well as the various European factors that traded and established footholds in the Accra coast. In an attempt to reconstruct the early history of the Ga, Dangme-Shai and Wullf, the archaeological material remains recovered from these communities during excavation have been studied. In all, 15 trace elements were determined in 40 pottery shards using instrumental neutron activation analysis. The elemental concentrations were processed using multivariate statistical methods, such as cluster, factor and discriminant analyses. The results revealed patterns of trade between these communities and also classified the 40 samples into two major groups based on variations in elemental compositions. The groupings suggested a clear separation between the shards from Shai and Ayawaso. The shards from Wullf scattered amongst the two groups, consistent with the archaeological findings that the Wullf community never produced their own pots.     

Chemical fingerprinting of whitewares from Nanwa site of the Chinese Erlitou state

Whitewares are among the most significant finds from Erlitou, China’s earliest state (c. 1900-1500 BC). They were primarily discovered in small numbers from elite tombs of a few sites, leading to the hypothesis that they were made at only a few places and then circulated as prestige items. Recent archaeological work indicates Nanwa may be a whiteware production site. To facilitate determining provenances, we compare the ICP-MS trace elements and TIMS Sr isotopes of Nanwa whitewares with those from Tang dynasty (618-907 AD) Gongxian kilns and Song dynasty (960-1279 AD) Ding kilns. Although all were made of white-firing kaolinic clays, each of the three groups shows a different chemical composition. Furthermore, samples from Nanwa are chemically consistent and restricted in a way analogous to those from Gongxian and Ding, implying that Nanwa whiteware was probably produced in situ. In addition, Gongxian and Ding samples define two separate linear arrays in their ⁸⁷Rb/⁸⁶Sr versus ⁸⁷Sr/⁸⁶Sr ratios, demonstrating that the clays for these samples are respectively related geochemically. Nanwa samples fall out of the linear arrays of both Gongxian and Ding, indicating that Nanwa whiteware clays were not derived from the same source rock as Gongxian clays, although the two sites are only some 25.5 km apart. In sum, beyond the general similarity of kaolinic clays used at Nanwa, Gongxian and Ding and the geographical proximity of those sites, finer distinctions of elemental and Sr isotopic contents indicate relatively unique chemical characteristics for each group. These traits provide valuable criteria to source traded ceramics of uncertain origins.     

河北三大白瓷名窑精细白瓷的SRXRF无损分析及界定标准的初步研究

选用河北邢窑、定窑、井陉窑出土的精细白瓷碎片各10片，用同步辐射X射线荧光（SRXRF）对其胎、釉＋胎中的元素进行半定量分析，并采用SPSS软件对分析数据进行聚类分析和主因子分析。统计分析结果显示上述三个窑址的白瓷的胎和釉的元素组成有显著的差异，表明用无损科技测试的手段有可能解决考古学家和陶瓷鉴定专家难以解决的问题，为建立河北白瓷的界定标准提供科学依据。     

秦陵兵马俑矿料来源及烧结方式的初步研究

岩相分析结果表明，兵马俑是夹砂陶。对这类陶器的产地分析，需做特殊处理，以去除陶胎中与粘土原料无关的沙粒。利用ICF—AES(电感耦合等离子体发射光谱法)技术测定兵马俑陶片中纯粘土部分的化学成分，并进行统计分析，其结果支持兵马俑原料取自骊山地区的看法。四块兵马俑残片的烧成温度数据高低相差260℃，不排除个别俑在开放状态下烧制的可能。     

Nuclear microscopy in Alzheimer’s disease

The elemental composition of the two types of brain lesions which characterise Alzheimer’s disease (AD) has been the subject of intense scrutiny over the last decade, ever since it was proposed that inorganic trace elements, particularly aluminium, might be implicated in the pathogenesis of the disease. The major evidence for this involvement was the detection of aluminium in the characteristic lesions of the AD brain; neuritic plaques and neurofibrillary tangles (NFTs). Using the powerful combination of Particle-Induced X-ray Emission (PIXE), Rutherford Backscattering Spectrometry (RBS) and Scanning Transmission Ion Microscopy (STIM), it is possible to image and analyse structures in brain sections without recourse to chemical staining. Previous results on elemental composition of senile plaques indicated the absence of aluminium at the 15 parts per million level. We have more recently focused on the analysis of neurofibrillary tangles (NFTs), destructive structural defects within neurons. Imaging and analysis of neurons in brain tissue presented a greater challenge due to the small dimensional size compared with the plaques. We describe the methodology and the results of imaging and analysing neurons in brain tissue sections using Nuclear Microscopy. Our results show that aluminium is not present in either neurons or surrounding tissue in unstained sections at the 20 ppm level, but can be observed in stained sections. We also report elemental concentrations showing significant elevations of phosphorus, sulphur, chlorine, iron and zinc.     

多种釉色钧官瓷胎原料来源的质子激发X射线荧光分析

为了解不同釉色钧官瓷胎的原料来源和分类关系，选取来自8种不同釉色钧官瓷的胎样品50个，对这些样品进行质子激发Χ射线荧光分析，测定每个样品的9种化学组分。对这些数据进行模糊聚类分析，所有钧官瓷胎样品被分为3大类。由此可推断，制作这批钧官瓷胎的原料不是来自于同一批料；不同类钧官瓷胎的原料来源和成分接近但又有所不同；当时的窑工采用一批胎料同时烧制各种釉色的瓷器。     

Time-of-flight detection of monoatomic ions generated by femtosecond laser ablation from large molecules

Single-shot femtosecond laser ablation (fsLA) was applied to large molecules to analyze elemental composition through out wide range of mass-to-charge ratio. Molecular samples such as Eu-DNA and cosmetic powders were atomized and ionized simultaneously by the single-shot fsLA and positive atomic ions were detected using a reflectron time-of-flight (TOF) mass spectrometer. The ratios among the signal intensity of the detected stable isotopes including ^151,153Eu and ^182-184,186W were consistent with the respective natural abundances of the isotopes. The results demonstrate the feasibility of the fsLA-TOF method as a high-throughput analytical technique for elemental microanalysis of large molecular samples in small quantities.     

微束X射线荧光无损分析古瓷器高铅釉的方法及应用研究

研究了微会聚透镜分析高铅样品的特征,采用基于微会聚透镜的微束X射线荧光无损定量分析了一片清代彩绘瓷彩料中的元素含量,同时扫描分析了彩料中某一特定区域的元素分布。从元素分布中可推测出清代彩绘的制作工艺是先用高铅的Mn颜料绘出图案的轮廓,然后向中间填充设计好高铅的Cu颜料,或直接用高铅的Fe混合物绘画。分析结果表明,基于微会聚透镜的微束X射线荧光分析是一种较好的高铅样品的分析手段。     

锕系、镧系元素分离中新萃取剂的研究(III)——新萃取剂HMBMPPT的合成及其对铀(VI)的萃取研究

通过酰基化、氯化、硫化反应合成了新的酰代吡唑硫酮,即4-(4-甲氧基)-苯甲酰基-2,4-二氢-5-甲基-2-苯基-3H-吡唑硫酮-3(HMBMPPT)。产物的结构用红外、氢核磁共振谱、质谱、元素分析及X射线衍射进行了表征。研究了以氯仿为溶剂HMBMPPT 在硝酸介质中对铀(VI)的萃取行为,考察了稀释剂、萃取剂浓度、酸度、温度及盐析剂浓度对分配比的影响。同时,对萃取配合物的化学组成及萃取机理也进行了分析和讨论。     

古瓷中的微量元素 Ⅳ.景德镇窑场的古瓷分析之二

本文是文献[6]的续篇。对采自黄泥头和白虎湾两处窑场的瓷片进行了微最元素含量测定,还将所得结果与湖田窑场的结果作了比较。原则上看来,一个窑址产品中微量元素含量可能体现产品的特征。实验步骤如文献[2]所述。     

用中子活化分析法研究古钧瓷和古汝瓷起源关系

将50个古汝瓷、古钧瓷和仿古瓷的釉和胎等样品进行中子活化分析，测定每个样品的36种微量元素含量，将这些测量数据进行模糊聚类分析，得到动态聚类图，以确定它们的分类和材料来源。结果表明，这批样品虽然跨越几百年，釉色不同，出自不同的窑口，但古汝瓷胎和古钧瓷胎同类，古汝瓷釉和古钧瓷釉同类。胎料产地集中，釉料产地分散些，釉料产地覆盖了胎料产地。古汝瓷和古钧瓷有着基本相同的原料来源，而且这些材料来源是长期稳定的。现代钧瓷多数与古钧瓷相近；2个现代汝瓷和古汝瓷相似，1个与古汝瓷疏远；景德镇瓷与汝瓷、钧瓷无关。     

The study of chemical composition and elemental mappings of colored over-glaze porcelain fired in Qing Dynasty by micro-X-ray fluorescence

It is very difficult to measure the chemical composition of colored pigments of over-glaze porcelain by X-ray fluorescence because it contains high concentration of Pb. One of the disadvantages of our polycapillary optics is that it has low transmission efficiency to the high energy X-ray. However, it is beneficial to measure the chemical compositions of rich Pb sample. In this paper, we reported the performances of a tabletop setup of micro-X-ray fluorescence system base on slightly focusing polycapillary and its applications for analysis of rich Pb sample. A piece of Chinese ancient over-glaze porcelain was analyzed by micro-X-ray fluorescence. The experimental results showed that the Cu, Fe and Mn are the major color elements. The possibilities of the process of decorative technology were discussed in this paper, also.