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.     

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     

Main chemical ingredients of the celadon glaze from Qingliangsi kiln and Zhanggongxiang kiln

The proton induced X-ray emission (PIXE) is used to determine the chemical ingredients of seven main elements in the samples of Ru Guan porcelain glazes and Ru Civil porcelain from Qingliangsi kiln in Baofeng County and the samples of celadon glaze from Zhanggongxiang kiln in Ruzhou City. The PIXE data are then analyzed by scatter analysis and fuzzy cluster method for determining their classification and provenance. The results show that there are obvious differences between the ingredients of glaze material of Ru Guan porcelain and Ru Civil porcelain from Qingliangsi kiln, of which the former ingredients are stable and its source is localized, and that the sources and ingredients of the glaze of Ru Guan porcelain and those of celadon glaze from Zhanggongxiang kiln are not wholly the same, of which the latter sources are much scattering.     

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。     

东门渡窑古陶瓷化学成分与烧制工艺研究

芜湖东门渡窑是古代宣州窑场的早期窑口之一,属古越窑系青瓷;该窑口出产的陶瓷产品器型别具一格,具有鲜明的地域特色.但长期以来,对于东门渡窑瓷器仅仅从其外观推测其工艺特征,对该类瓷器的微观结构特征和配方工艺特点缺乏必要的分析证据.为系统解析东门渡窑古陶瓷的胎、釉化学组成和烧制工艺,运用波长色散X射线荧光光谱法(EDXRF)...     

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。     

南海一号出水景德镇窑与龙泉窑青瓷特征的无损分析研究

古代陶瓷产地研究是陶瓷考古的重要内容,也是科技考古工作者研究的重点。目前国内古代陶瓷产地研究主要依赖化学成分分析技术,对陶瓷釉层结构特征的无损分析研究却相对缺乏,难以对古代陶瓷进行全方位的认知。该研究首次将光学相干层析(OCT)与X射线荧光(XRF)光谱分析技术相结合,对南海一号沉船出水的南宋初期景德镇窑和龙泉窑青瓷瓷釉的断层结构特征和化学成分特征进行综合无损分析研究。首先采用扫频OCT成像系统对两个窑址青瓷瓷釉断层结构及装饰工艺特征进行了研究,分析了青瓷瓷釉类型、釉层厚度、釉层内气泡、包裹体、表面裂纹等特征及分布状况,对比了两窑址青瓷瓷釉断层结构特征,确定了可能采用的装饰工艺。其次,利用X射线荧光(XRF)光谱分析获得了两窑址青瓷胎釉的化学成分,对比研究了两个窑址青瓷胎釉化学成分差异,进而探讨了瓷釉断层OCT图像特征与釉层化学成分之间存在的联系。实验结果表明,景德镇青瓷和龙泉青瓷样品在釉层厚度、气泡、裂纹、包裹体等瓷釉断层结构特征上差异明显,在胎釉化学成分方面,两类青瓷在胎釉着色相关元素、釉层碱性氧化物等成分含量上也存在差异。同时,瓷釉断面结构特征差异与釉层化学成分差异存在紧密联系。实验证明,将OCT与XRF相结合是一种有效的辨别瓷器窑口的科学技术方法。     

陕西西岳庙古琉璃胎料来源的INAA研究及多元统计分析

用仪器中子活化分析研究了陕西立地坡明代地层和陕西西岳庙宋、元、明、清早期、清晚期4个地层出土的古琉璃胎中的主量和微量元素, 并对实验数据进行多元统计分析. 结果表明, 陕西西岳庙从宋到清早期古琉璃胎料很稳定, 其原料可能来自本地； 清晚期古琉璃胎料与宋到清早期的古琉璃之间存在明显的区别, 明代3个样品和清晚期的古琉璃制造原料与立地坡出土的古琉璃其成分相近, 西岳庙清晚期的古琉璃可能来自陕西立地坡窑烧制.     

不同窑口古代青瓷的产地特征的中子活化分析

产地属性是科学鉴别遗址和墓葬中出土的古陶瓷烧制产地的重要依据.用仪器中子活化（INAA）有损分析了浙江寺龙口越窑、江西洪州窑和陕西耀州窑出土的古瓷碎片样品,通过实验数据的统计分析,结果表明3个窑口古瓷的元素组成具有各自的特征,它们之间具有可以区分的依据,寺龙口越窑与南方江西洪州窑的制胎原料关系较近,与北方陕西耀州窑的关系较远.这些试验结果将为古陶瓷地研究提供重要参数.Provenance characteristic is an important scientific parameter to identify ancient porcelain wares unearthed from sites and graves.The porcelain samples of Si Long Kou kiln of Zhejiang Province,Hong Zhou kiln of Jiangxi Province and Yao Zhou kiln of Shanxi Province have been analyzed with neutron activation analysis(NAA) in this paper.The experimental data were studied with statistic methods.The results show that the chemical compositions of porcelain body samples for three kilns were different. The difference was been able identified. The body materials of both Si Long Kou Yue kiln and Hong Zhou kiln of Jiangxi were similar. The samples of Yao Zhou kiln in north of China existed obvious difference.     

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.     

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.     

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...     

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.     

巩窑唐代早期白瓷的EDXRF线扫描分析

具有悠久瓷器生产历史的巩窑,是我国古代北方烧制白瓷的3个代表性窑口之一。在唐代早期,为了掩盖瓷胎表面的粗糙状态和较深的胎体颜色,提高瓷器的质量和白度,巩窑白瓷在胎的表面施加了一层装饰层——化妆土。用能量色散X射线探针技术对这些白瓷碎片的剖面进行了主要化学成分的线扫描分析,结果表明： 巩窑唐代早期白瓷的化妆土使用了不同的原料,与光学显微镜下观察到的现象相符合。另外,白瓷釉可能是加有草木灰的钙釉。     

综合流动和传热的废轮胎回转窑热解模型

废轮胎在回转窑内的热解主要受到气-固相流动、传质和传热及化学反应动力参数等因素的影响。在对回转窑 内固体颗粒运动、传热传质进行分析的基础上,结合对轮胎热解反应动力学的研究,发展了综合流动、传热的废轮胎回转 窑热解模型,可计算得到回转窑内热解的温度分布、物料转化率、产物得率等。模型计算结果与试验结果吻合较好。     

巴中水宁寺摩岩石刻的彩绘颜料分析

巴中水宁寺摩崖造像以题材广泛、形式多样、雕刻精致著称于世,但潮湿的环境,不稳定的崖体,半露天的保存环境使水宁寺石刻遭到了严重的破坏,影响了石刻的艺术性,因此水宁寺摩崖造像保护修复工作迫在眉睫.通过对水宁寺石刻颜料的分析,获取彩绘颜料的信息,一方面为颜料复原提供科学依据,另一方面也有利于文物工作者展开针对性保护工作,具有...     

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。     

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。     

历代定窑白瓷的EDXRF和XAFS分析

定窑是我国宋代五大名窑中唯一以生产白瓷而闻名于世的窑厂,其高超的刻印花纹技术及首创的支圈覆烧工艺,对国内外许多窑场产生了深远的影响。采用(energy dispersive X-ray fluorescence, EDXRF)探索了历代定窑白瓷的组成配方,并采用X射线吸收精细结构(XAFS)法分析了瓷釉中Fe元素的价态,以探讨定窑白瓷的相关烧制工艺。研究发现,定窑白瓷瓷胎具有典型北方瓷器“高铝低硅”的特征,并在瓷胎中特意添加了富含CaO的矿物原料,对瓷胎的烧结有一定的促进作用。瓷胎中的TiO₂应主要是高岭土原料中的杂质。定窑白瓷瓷釉具有“高钙高镁”特征,基本属于钙镁釉或钙镁碱釉。其瓷釉配方中应含有一定量的白云石或滑石。瓷釉中K₂O的含量逐步增加,反映了定窑瓷釉由钙镁釉向钙碱釉发展演变的过程。此外,根据瓷釉中的Al₂O₃,MnO和P₂O₅等含量的特征,可以推测釉料配方中应添加了草木灰和高岭土。由XAFS分析结果可知,晚唐五代时期定窑白瓷釉中Fe3+比例最高,金代次之,宋代最低,不同时期定窑白瓷皆是在还原气氛中烧成。宋金时期定窑白瓷白中泛黄可能由于燃料煤中富含的硫在燃烧过程中与瓷釉反应,生成Fe-S化合物所致。     

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。