用NAA研究清凉寺窑和张公巷窑青瓷胎的原料特征及来源

为研究清凉寺窑汝瓷胎和张公巷窑青瓷胎的原料特征及来源, 选取37个清凉寺窑汝瓷胎样品(32个汝官瓷胎和5个汝民瓷胎)、 32个张公巷窑青瓷胎样品以及14个岩石样品, 用中子活化分析 （NAA）方法测得每个样品中的23种元素含量; 使用散布分析及主成分分析方法处理NAA数据。 结果表明: 元素Fe, Ce, Ba, Ta, Th, La, Sm和Cr可作为区分汝官瓷胎和张公巷窑青瓷胎原料产地的指纹元素; 汝官瓷胎原料产地较集中, 来源相对稳定; 清凉寺窑汝民瓷胎料产地与汝官瓷基本相同, 均为就地取材; 张公巷窑青瓷胎原料产地较为分散, 与汝官瓷不同, 但二者距离相近。 关     

PIXE analysis of Chinese Ru celadon made in the 11–12th centuries

The Ru kiln is one of the five most famous kilns (Ru, Guan, Ge, Ding and Jun kilns) in the Chinese Song Dynasty (AD 960–1279). The Ru Kuan kiln at Qingliang Temple, Henan Province, originated from the Ru folk kiln. PIXE and factor analysis were employed to study the difference between the folk celadon and the Kuan celadon. The relationship between the Ru Kuan and Ru folk celadons from the Qingliang Temple kiln site and the Ru celadon from the Zhanggongxiang kiln site, found in the last few years, was also studied. The experimental results showed that the same body raw material was used for the production of the Ru Kuan and Ru folk celadons whereas the Ru celadon from Zhanggongxiang was produced from a different body raw material. Factor analysis based on chemical components of the glaze is able to differentiate between the celadons, i.e. Ru Kuan celadon, Ru folk celadon and the Ru celadon from Zhanggongxiang. Copyright © 2005 John Wiley & Sons, Ltd.     

用主量化学组成研究汝官瓷和钧官瓷的原料来源

将84个清凉寺窑汝官瓷和钧台窑钧官瓷样品进行质子激发X射线荧光分析,得到每个样品胎和釉的7种主量化学组分。将所有样品的7种主量化学组成数据进行散布分析,以确定汝官瓷和钧官瓷原料来源是否相同。从散布分析图可以看出,汝官瓷釉和 钧官瓷釉样品的原料产地和配方明显不同,汝官瓷胎和钧官瓷胎样品的原料产地和成分接近,但有所不同。The seven main chemical components of the body and glaze samples of 84 RuGuan porcelains from Qingliangsi kiln and JunGuan porcelains from Juntai kiln are determined by the proton induced X-ray emission （ PIXE）. Then these data are analyzed by scatter analysis to confirm whether the sources of the raw materials of Ru-Guan porcelain from Qingliangsi kiln and JunGuan porcelain from Juntai kiln are the same or not. The figure of the scatter diagram shows that the sourcing area of the raw material and batch formula of RuGuan porcelain and Jun-Guan porcelain glaze are obviously different and the sources of the raw materials and components of their body samples are close but a bit different.     

Mössbauer Spectroscopy, NAA and PIXE Study on Some Archeological Problems of Ancient Chinese Ru Celadon

By Mössbauer spectroscopy, NAA and optical spectroscopy, the coloring and the firing technology of ancient Ru celadon were studied. Also, the relationship between Ru Kuan celadon from Qingliang Temple and Ru celadon from Zhanggongxiang was studied by PIXE. The glaze color of Ru celadon depends on the ratio of the structural iron ions, i.e. the Fe²⁺/Fe³⁺ ratio. Further, it depends on the firing conditions. As the Fe²⁺/Fe³⁺ ratio gradually increases, the glaze color of Ru celadon will gradually change from pea green to sky green. All the Ru celadons were fired in a reducing atmosphere. The sky green Ru celadon was fired in the most reducing atmosphere and at the highest temperature, the powder green in a more reducing atmosphere and at a lower temperature and the pea green in a lightly reducing atmosphere and at the lowest temperature. The PIXE experimental results showed that Ru Kuan celadon from Qingliang Temple and Ru celadon from Zhanggongxiang were incompletely identical in the recipe of glaze and they could be differentiated by the cluster analysis of the major element concentration of glaze.     

Proton induced X-ray emission (PIXE) analysis of sources of porcelain body of Ru Guan and Jun Guan porcelains

34 samples of Ru Guan porcelain body and 50 samples of Jun Guan porcelain body (both kinds being in different body colors) were selected with the purpose of finding out the source of raw materials and their classification relationship so as to search for ways of non-destructive discrimination. Proton induced X-ray emission (PIXE) has been applied to these samples to determine their chemical elements. The data of seven major chemical elements collected from these samples were further studied through fuzzy cluster analysis. Results indicate that the origin of raw materials of Jun Guan porcelain body samples is comparatively more concentrated in certain places, while that of Ru Guan porcelain body samples is scattered about. The places of origin of raw materials of the majority of Ru Guan and Jun Guan porcelain body samples have something in common, but some differences still exist. It might be an important way for non-destructive discrimination among Ru Guan and Jun Guan porcelains by combining PIXE with fuzzy cluster analysis.     

安徽繁昌柯家冲窑青白瓷釉化学组成及其制釉工艺来源研究

为了解繁昌柯家冲窑青白瓷釉化学组成特征及其演变过程,并探索我国南方早期青白釉的工艺技术来源,本文运用能量色散X射线荧光光谱法(EDXRF)分析了柯家冲窑五代至北宋中期不同阶段青白瓷釉的化学组成,并将分析结果与同时期北方定窑白瓷釉及南方越窑青瓷釉化学组成进行了综合对比研究。结果显示,繁昌柯家冲窑青白釉化学组成在北宋中期时发生了明显变化,其中尤以SiO₂含量的下降和CaO含量的上升最为明显,着色元素Fe,Mn,Ti的氧化物含量自五代时期至北宋中期变化幅度很小,繁昌柯家冲窑青白釉釉色由偏白向偏青转变的原因可能与该窑瓷器胎色的不断加深有关。此外,主成分分析及具有相似功能特性的元素组合对比分析结果显示,繁昌柯家冲窑青白瓷釉的化学组成与北方定窑白瓷釉较为接近,其釉料配方工艺可能来源于同时期我国北方地区以定窑为代表的白瓷窑场。本文研究结果对了解我国早期青白瓷釉的化学组成特征及晚唐五代时期南、北方制瓷工艺技术交流问题等有重要学术价值。     

用多元统计分析研究黄冶窑白瓷的原料特征

黄冶窑文化内涵丰富，其创烧于隋，兴盛于唐代中期，停烧于唐代晚期。为探讨不同时期黄冶窑白瓷的胎料来源和釉料配方是否相同，选取黄冶窑隋、早唐、中唐、晚唐四个时期的80个白瓷样品，利用质子激发X射线荧光分析(PIXE)测定各样品胎、釉中9种化学成分(Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、Fe₂O₃)的含量，用多元统计分析中的Fisher判别分析处理PIXE数据，并计算各样品釉的木灰釉式系数b来划分瓷釉类型。结果表明:黄冶窑四个时期的胎料取自同一或相近的地点,都是就地取材；四个时期的釉料配方比较相似，而四期白瓷的釉料配方最为稳定，且与二期釉料配方最相似，而与一期釉料配方已有明显不同；黄冶窑白瓷釉大部分为钙釉，存在少量钙碱釉和碱钙釉。     

景德镇五代瓷器组成配方的EDXRF分析

景德镇早期制瓷工艺一直是学术界所关注的焦点问题之一。采用能量色散X射线荧光法分析了景德镇五代时期湘湖窑出土白瓷和青瓷样品的胎釉元素组成,并据此探讨其原料和配方。研究表明,五代时期景德镇湘湖窑白瓷胎体所用原料为瓷石,而青瓷瓷胎应是采用瓷石配以紫金土的二元配方;白瓷和青瓷瓷釉皆使用釉果加釉灰的配方,且青瓷瓷釉配方中釉灰的用量高于白瓷瓷釉。     

严和店窑汝瓷和钧台窑钧官瓷的EDXRF分析

采用能量色散X射线荧光（EDXRF）技术测试了若干严和店窑汝瓷和钧台窑钧官瓷样品胎和釉的化学组成, 利用多元统计中的因子分析方法分析了两窑场胎和釉的差异。结果表明:严和店窑汝瓷和钧台窑钧官瓷能较好地加以区分。再次证明了钧瓷和汝瓷是有区别的。 The chemical components of the body and glaze samples of some Ru porcelains from Yanhedian kiln and Jun official porcelains from Juntai kiln are determined by the technology of Energy Dispersive X ray Fluorescence(EDXRF) in this work. The difference of the two kiln’s glaze and body are analyzed by factor analysis method of Multi dimensional statistical analysis. The results indicate that Yanhedian Ru porcelains can be well distinguished from Jun official porcelains from Juntai kiln. This evidence once again proves that Jun ceramics and Ru ceramics can be distinguished obviously.     

湖田窑宋代青白瓷的组成及呈色特征

景德镇宋代以生产青白瓷而闻名,其中湖田窑又是景德镇宋代窑址中最典型的一处,其生产的青白瓷精巧细致,有“假玉器”和“饶玉”之称。研究采用能量色散X荧光光谱分析仪和色差计,分析了湖田窑宋代青白瓷的胎、釉化学组成和色度值,初步探讨了不同时期青白瓷的组成、配方和呈色特征。研究表明,湖田窑北宋和南宋青白瓷胎体组成特征基本一致,均与当地瓷石原料较为接近,极有可能采用了附近的三宝瓷石原料制胎。瓷釉组成结果显示釉中含有较高的CaO和一定量的MnO和P₂O₅,表明湖田窑青白瓷釉为“钙釉”,且釉料配方中引入了一定量的草木灰。色度分析结果显示,湖田窑北宋和南宋青白瓷釉主波长分别为500和496 nm左右,均落在可见光波的绿色波段。但对比北宋和南宋瓷釉组成和色度结果发现,北宋青白瓷釉无论是组成还是色度数据结果均较南宋更为分散,且南宋青白瓷釉层呈色相较北宋样品b值更小,釉色更为偏蓝。研究认为,湖田窑青白瓷从北宋至南宋,釉料配方经历了从探索逐渐走向成熟、稳定的过程。研究结果不仅为景德镇湖田窑青白瓷的断源断代提供了数据支撑,也为湖田窑青白瓷制瓷技艺的传承和传播提供了一定的科学素材。     

后司岙匣钵工艺特征及其对青瓷釉面呈色的影响

越窑青瓷是我国最早烧制成熟的青瓷器,其中使用瓷质匣钵烧造秘色青瓷是越窑独特的烧造技术,为揭示越窑上林湖后司岙窑址出土的唐五代时期匣钵的工艺特征及其对装烧青瓷的影响,采用能量色散X荧光光谱仪（ED-XRF）、超景深显微镜、扫描电子显微镜（SEM）等现代测试分析手段,对后司岙窑址出土的唐五代时期瓷质匣钵、普通匣钵、普通青瓷、秘色青瓷进行了元素组成、显微结构、吸水率等测试分析。同时采用分光光度计,对该遗址出土的唐五代普通青瓷和秘色青瓷表面色度进行了测试分析。分析结果表明：唐五代普通匣钵的基体部分和瓷质匣钵组成相似,采用了SiO₂含量约为75%、Al₂O₃含量约为16%,且与青瓷胎体类似的当地冲积粘土类原料;而唐五代瓷质匣钵中TiO₂和Fe₂O₃的含量高于青瓷胎体且差异略大,说明青瓷胎体淘洗工艺更加严格。其中普通匣钵内存在大量平均尺寸在530 μm左右,且具有颗粒级配呈现一定规律的夹杂粗颗粒,是一类为增加普通匣钵使用寿命特意拣选添加的高硅质原料,增加了匣钵的透气性、机械强度和热稳定性从而延长匣钵的使用寿命;唐五代瓷质匣钵的气孔率为1.61%、吸水率为0.73%,低于普通匣钵8.18%和4.28%,而体积密度为2.22 g·cm-3高于普通匣钵的1.99 g·cm-3,且导热性能高于普通匣钵,有利于减少匣钵内外温差、缓解温度滞后现象。另外,上林湖后司岙窑址出土的秘色青瓷使用气孔率较低的瓷质匣钵,并进行口沿封釉,有效降低了装烧青瓷釉在冷却过程中被二次氧化的程度,提高了匣钵内气氛的稳定性和青瓷釉层中Fe2+的含量,改善了其呈色稳定性和外观效果。同时秘色青瓷釉层略厚,减少了胎体对产品外观的影响,增大了釉面折射率和明亮度,使其在CIE色度空间中相比普通青瓷处在更偏蓝绿色区域。     

Mass Spectrometric Methods for Colorative Mechanism Analysis of Yaozhou Porcelain GlazeSCIEI北大核心CSCD

An in-house-built femtosecond laser ionization time-of-flight mass spectrometry (fs-LI-TOFMS) has been applied to the multi-elemental analysis of porcelain glaze from Yaozhou kiln. The samples are selected representing products of different dynasties, including Tang, Five, Song, Jin, and Ming Dynasty. For exploring the colorative mechanism of Yaozhou porcelain through the elemental analysis of the glaze, the effects of all potential coloring elements, especially transition elements, were considered. There was a speculation that the typical Co-Cr-Fe-Mn recipe was used in the fabrication of Yaozhou black glaze; the low content of Fe and high content of Ni resulted in the porcelain of white glaze; an increase content of P could lead the porcelain to be yellow-glazed. Undoubtedly, this research is an important supplement to the study of the colorative mechanism of the Yaozhou porcelain system.     

耀州古瓷釉层呈色机理的质谱研究方法

采用实验室自制飞秒激光电离飞行时间质谱(fs-LI-TOFMS)对唐代、五代、宋代、金代以及明代等五个朝代的耀州窑古瓷片釉层进行多元素同时分析,研究其呈色机理,以过渡元素为重点考察陶瓷釉层中所有可能着色元素的着色效果。推测耀州黑瓷烧制采用的很可能是Co-Cr-Fe-Mn系黑色釉料;明代白釉形成的主要原因是Fe元素含量低,还有可能与Ni元素有关;釉层中P 元素含量增多会导致釉色偏黄。毫无疑问,这一系列发现是对整个耀州瓷体系釉层呈色机理的重要补充。     

黄冶窑白瓷的物相和微观结构研究

以黄冶窑四个时期的白瓷样品作为研究对象,利用X射线衍射仪（XRD）和扫描电子显微镜（SEM）对样品进行分析,结果表明:黄冶窑白瓷胎的物相基本相同,主要是莫来石、α石英和方石英、未熔石英和少量的粘土相;黄冶窑白瓷釉中有气泡存在,釉中气泡为圆形,釉中存在微米级的针状或柱状钙长石晶体,釉存在分相结构,且分相结构与析晶相伴而生;黄冶窑白瓷胎中有气孔、未熔的石英颗粒、较大的Ti颗粒、莫来石晶体和石英晶体。The white porcelain samples of the four periods of Huangye kiln were studied in this paper, and the samples were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the material phase is basically the same of the white porcelain bodies from Huangye kiln, and mainly mullite, alpha quartz and cristobalite, unmelted quartz and a small amount of clay phase; There are some round bubbles in HuangYe kiln white porcelain, glazes, so are some feldspathic crystals with micro-level needles or columnar. It is evident to observe phase separation structure, which is accompanied by the birth. Apart from some pores, unfused quartz particles, larger Ti particles, mullite crystals and quartz crystals can also be found in the embryo of Huangye kiln white porcelain.     

安徽繁昌窑青白瓷化学组成的WDXRF分析研究

安徽繁昌窑五代时期(AD907-960)创烧青白瓷,是目前已知的我国最早烧造青白瓷的窑场。北宋中期(AD1023-1085)后,繁昌窑迅速衰落,对其衰落原因,目前尚不清楚。文章运用波长色散X射线荧光光谱法(WDXRF)分析了繁昌窑青白瓷胎的化学组成,结果显示北宋中期时繁昌窑瓷胎的主微元素化学组成均发生了较为明显的改变。结合中子活化分析及瓷釉研究的结果来看,这种改变应是因其制瓷原料或胎料配方发生变化引起的。同时,这种瓷胎化学组成的变化也是导致繁昌窑北宋中期产品质量下降并最终迅速衰落的主要原因。     

中国古代南方白瓷的组成特征研究

景德镇窑和德化窑是南方白釉瓷窑口中最具有代表性的两个窑口。该文利用能量色散X射线荧光光谱分析仪,对30件宋、元、明时期的德化白瓷以及元代景德镇枢府白瓷样品进行了测试,并从时空角度对比分析了不同白瓷样品胎釉的组成特征。结果表明,景德镇枢府白瓷胎釉组成铁含量均明显偏高,而德化白瓷胎釉组成中的钾含量均明显偏高,且随着时间发展具有上升趋势,这应是德化雕塑白瓷异军突起的主要原因。     

河南省清凉寺窑址出土富铁釉瓷的无损分析研究

富铁釉瓷在中国古陶瓷史上具有重要地位，综合利用光学相干层析成像技术(OCT)、光学显微镜(OM)、激光拉曼光谱技术(LRS)和X射线荧光光谱分析技术(XRF) 对河南省宝丰清凉寺窑址出土宋金时期富铁釉瓷样品进行无损分析研究，获取了富铁釉瓷的釉层结构、釉面析晶的物相信息及胎釉化学成分等信息，探讨了釉层断面OCT灰度图像特征与其显微结构之间的关系以及富铁釉瓷的烧制工艺。结果表明，酱釉瓷和柿叶红釉瓷表面及黑釉红斑区存在富铁析晶层，黑釉瓷釉层表面未发现富铁析晶层的存在。酱釉瓷釉层富铁析晶层中铁的氧化物以ε-Fe₂O₃晶体为主，而柿叶红釉层则主要是α-Fe₂O₃晶体，黑釉红斑层同时存在ε-Fe₂O₃，α-Fe₂O₃晶体以及磁铁矿。上述差异形成的原因与釉层化学成和烧制工艺存在联系。釉层中高含量碱土金属氧化物及氧化铁区域更容易析出氧化铁晶体。黑釉瓷烧成气氛以还原气氛为主，而酱釉瓷和柿叶红釉瓷则倾向于氧化烧成气氛，且柿叶红釉瓷的烧成温度高于酱釉瓷。该研究将OCT，OM，LRS与XRF相结合，有助于加强对富铁釉瓷的整体认知，为富铁釉瓷的断源断代提供更为丰富的线索。     

景德镇仿龙泉青瓷与龙泉青瓷组成特征研究

龙泉青瓷不仅受到了国内外陶瓷爱好者的热捧,还被不同地区广大窑工争相效仿,其中以景德镇明清时期仿制最具代表性。利用能量色散X荧光光谱分析仪对38 件宋、元、明时期的龙泉青瓷以及明代景德镇仿龙泉青瓷进行了测试,并结合烧成温度分析结果,从时空角度对比分析了两地青瓷胎釉组成特征、演变规律和形成原因,有助于了解我国南方青釉瓷的演变发展、相互交流和影响,为不同产地青瓷的断源断代提供了一定的科学依据。     

明清官窑霁蓝釉的组成和色度特征

明清时期官窑颜色釉瓷是我国古代名瓷的优秀代表,然而由于官窑霁蓝釉瓷生产、使用制度严格,样品极为珍稀,故研究内容较少。研究采用能量色散X荧光光谱分析和色差计,较系统地测试了17件明清官窑霁蓝釉瓷的化学组成和色度值,初步揭示了不同时期官窑霁蓝釉的组成、配方和色度特征。结果表明,明代霁蓝釉所用着色矿物锰含量高于清代,釉灰用量、明度值均低于清代,发色更为沉稳、凝重;明代瓷胎配方组成中所用瓷石含量高于清代。