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。     

“南澳Ⅰ号”沉船出水克拉克瓷产地的科技分析

“克拉克瓷”是我国明清时期销往欧洲的一种青花瓷器。长期以来,对于这类外销瓷器的研究始终是国际陶瓷考古学界关注的热点。2007年,“南澳Ⅰ号”明代沉船的发现和其中大批瓷器的出水,为“克拉克瓷”研究提供了新的宝贵资料。结合传统器型学方法与波长色散型X射线荧光光谱分析,探明了十件“南澳Ⅰ号”沉船出水瓷器的产地,为更深入的研究工作打好了基础。     

邛崃窑彩绘瓷彩绘工艺的SRXRF研究

邛崃窑彩绘瓷的彩绘技法,是考古学家和陶瓷专家十分关心而又长期争论、至今未有定论的问题。文章采用SRXRF方法,对邛崃窑古瓷残片剖面进行了线扫描分析,着重探讨了彩料与瓷釉的相对关系,结果发现古代邛崃窑彩绘瓷器中既有釉上彩又有釉下彩,这对我国古代瓷器彩绘工艺的发展具有一定的参考价值。     

南方各窑址原始瓷产地特征的EDXRF分析

采用能量色散X射线荧光法分析了中国南方地区各窑址出土原始瓷标本胎釉的元素组成,并通过多元统计分析,结合陶瓷工艺学,深入地分析了各窑址原始瓷的产地特征,为未知窑口原始瓷的产地判别提供了可靠依据.     

历代官窑霁蓝釉瓷的化学组成无损分析

霁蓝釉是高温钴蓝釉中的一种,创烧于元代,是景德镇四大传统名瓷之颜色釉中的优秀代表之一,具有极高的研究价值.研究采用能量色散X荧光光谱分析,较系统地测试分析了27件元、明、清时期官窑霁蓝釉瓷的胎、釉化学组成,分析探讨了不同时期霁蓝釉的组成、配方特征和演变规律,这不仅有助于探析霁蓝釉的工艺技术发展脉络,还将为研究同为钴着色的青花瓷的起源、料性特征,及技术发展脉络提供可借鉴的科学依据.     

历代景德镇青花瓷光谱特征分析研究

景德镇青花瓷是我国最具代表性的陶瓷品种之一,具有很高的学术价值和社会经济价值。不同年代的青花瓷仅靠外观难以区分,如何快速准确区分不同年代的景德镇青花瓷是文物保护界面临的一个难题。高光谱技术是一种完全无损的分析方法,并已经在壁画、字画等文物的颜料分析中得到成功应用,目前还没有关于瓷器文物的高光谱研究成果出现。选取28个历代景德镇青花瓷碎片样本,使用地面光谱仪测量样本胎釉和青花料部位反射率光谱,分析其典型光谱特征,并对历代青花料光谱特征参量变化趋势进行了分析。研究表明,青花料部位在可见近红外波段光谱特征较为显著,历代青花料光谱特征参量有较明显的差异,并有一定的变化规律。高光谱技术对于景德镇青花瓷的断代研究有很大潜力。     

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。     

明代永宣时期景德镇御窑青花瓷“铁锈斑”的显微结构研究

“铁锈斑”,是青花瓷线条色彩浓重处凝聚成的黑色、褐色或带有金属锡光的斑点。作为早期青花瓷器一种典型的鉴定特征,长久以来被认为与使用高铁低锰的进口钴料有关。多年来虽有零星报道,但受到亚微级晶体尺寸、釉熔体不均一性以及元素掺杂、晶体偏析等因素影响,其形态及结构并未得到充分研究,从而导致“铁锈斑”呈色机理不明,其作为进口钴料鉴定标准的观点也遭到质疑。结合前人研究,发现拉曼光谱与扫描电镜能谱仪在古陶瓷微晶结构解析方面极具优势,为系统阐明“铁锈斑”成分结构特征与呈色机理,使用超景深三维视频显微镜、扫描电镜与能谱仪(SEM-EDS)、拉曼光谱仪(Raman)对五件景德镇御窑永宣时期青花瓷器样品中“铁锈斑”处晶体的显微形貌与结构进行解析,并利用激光剥蚀电感耦合等离子体发射光谱(LA-ICP-AES)分别测试样品白釉区域、蓝彩区域与“铁锈斑”区域的成分。显微观察结果表明,不同样品“铁锈斑”区域析晶形态及分布的多样性是造成“铁锈斑”呈现众多视感的主要原因,且同一斑点的析晶区域内伴生有多种形态的晶体。显微结构表明,永乐时期“铁锈斑”枝晶主要以CoFe₂O₄-Fe...     

“加瓷”处理绿松石的成分及谱学特征研究

近年来,市场上出现了一类利用新型无机结合剂处理的绿松石,经此类方法处理的绿松石与天然绿松石极为相似,普遍表现为结构细腻、呈现玻璃-蜡状光泽,行业上称之为“加瓷”处理绿松石（简称“加瓷”绿松石）。采取常规宝石学仪器、红外吸收光谱仪、紫外-可见分光光度计以及能谱色散型X射线荧光光谱仪对“加瓷”绿松石的宝石学性质、振动光谱特征以及化学成分组成特征进行了系统的研究和分析。研究结果显示：“加瓷”绿松石样品的密度大都小于2.200 g·cm-3,与处理前密度有关,故用于“加瓷”处理的样品以密度较低的绿松石为主;“加瓷”绿松石均表现为典型的低密度、较细腻的结构外观和蜡状-玻璃光泽的组合特征,与品质相当的天然绿松石特征不一致,可作为“加瓷”绿松石重要的辅助性鉴别特征。“加瓷”绿松石在长、短波紫外荧光下的发光性与天然绿松石近于一致;显微观察下铁线、裂隙凹陷处常出现白色融出物,孔道内可见毛发状结晶体。“加瓷”绿松石的主要化学成分与天然类似,以CuO,Al₂O₃和P₂O₅为主,并含有一定量的FeOT(铁的氧化物),ZnO、SiO₂,K₂O和CaO。其中,“加瓷”处理绿松石样品中SiO₂含量基本在6.40%以上,均高于天然绿松石中的SiO₂含量（1.96%～6.25%）,而Al₂O₃和P₂O₅含量都较天然绿松石偏低,磷铝比例基本与天然绿松石一致,为1.10左右。利用“加瓷”绿松石较高的SiO₂含量和表面特征可将其与天然绿松石进行有效鉴别。“加瓷”绿松石与天然绿松石的红外吸收光谱特征基本一致。“加瓷”绿松石的UV-Vis光谱表现为620～750 nm处的吸收峰以及425 nm附近处较为锐利的吸收峰,因颜色不同峰位稍有偏移,但总体与天然绿松石的UV-Vis光谱特征趋于一致。     

水平电极吹样法光谱分析

化探样品的光谱分析,国内应用得比较普遍的是水平电极撒样法。本文介绍采用高频火花放电雾化试样,借压缩气流通过瓷吹样管,把试样引入电弧的水平电极吹样法。十多年的生产证明,本法具有:1.元素的检出限低,一次取样、摄谱能获得三十余个易、中、难挥发元素的光谱(不包括造岩元素)。其中满足区域化探扫面样品检出限要求的有Ba、Be、B、Mn、Pb、Sn、Cr、Ni、V、Mo、Nb、La、Ti、Cu、Y、Zr、Zn、     

Heterogeneous distribution of metal nanocrystals in glazes of historical pottery

It has been recently shown that lustre decoration of medieval and renaissance pottery consists of silver and copper nanocrystals, dispersed within the glassy matrix of the ceramic glaze. Lustre surfaces show peculiar optical effects such as metallic reflection and iridescence. In many cases, lustre appears overlapped to colored drawings. Here we report the findings of a study on glazes, pigments and lustre of several shards belonging to Deruta and Gubbio pottery of XVI century. The components of glazes and pigments have been identified. Lustre is confirmed to be characterised by silver and copper metal nanocrystals inhomogeneously dispersed in the glassy matrix of the glaze. In the case of lustre overlapped to colored decorations, we found two contradictory cases. The first consists of a lustre surface successfully applied over a blue smalt geometrical drawing. The second consists of a lustre surface, unsuccessfully applied over a yellow lead-antimonate pigment. The yellow pigment hinders the formation of lustre and removes crystals of tin dioxide, normally present in the glaze as opacifier.     

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。     

元代都城琉璃瓦釉层的EDXRF和SEM-EDS分析

元代的琉璃瓦制作技术承自宋辽,对明清产生重要影响,是中国琉璃瓦制作技术发展的过渡时期。元上都与元中都所使用的琉璃瓦,代表了元代早期和中期琉璃瓦制作技术的最高水平。为探索元代不同时期琉璃瓦的制作技术和工艺特点,结合考古资料与相关文献,以X射线荧光光谱法（EDXRF）为基础,结合扫描电镜与能谱仪（SEM-EDS）,对元上都遗址、元中都遗址出土琉璃瓦样品釉层组成进行了测定。分析结果显示,元上都与元中都釉层包括釉与化妆土,化妆土厚度在122~260 μm之间。元上都孔雀蓝釉琉璃瓦釉料属于PbO-K₂O-SiO₂体系,和元大都孔雀蓝釉组成相似,原料组成为石英、硝、铅末、铜末;蓝釉琉璃瓦化妆土结构致密,CaO与SiO₂含量大于20%,原料可能是钙长石与黏土,应是釉料的一部分。元上都绿釉与元中都绿釉黄釉琉璃瓦釉同为PbO-SiO₂体系,基本原料组成都为石英,铅末,着色剂分别为铜与铁。元上都绿釉配方与北宋时期的接近,釉料配方也符合《营造法式》记载,但逐渐减少铅的比例为获得更浅的釉色,在元中期逐渐稳定;元中都黄釉琉璃瓦釉料铅硅比与元大都相近,配方在元中期探索中逐渐固定,沿用至明代早期,是提升明中期釉料的基础;两处遗址绿釉琉璃瓦与元中都黄釉琉璃瓦化妆土与胎釉结合紧密,Ca含量很高,厚度较薄,很可能是石灰浆[Ca(OH)₂],工匠在施加化妆土时既节约成本又能提高产品质量。三种釉色分别属于PbO-K₂O-SiO₂与PbO-SiO₂两种体系,组成原料差异明显,都用于建筑装饰,极大丰富了琉璃釉色,化妆土的应用在琉璃技术中也是一项创新。能量色散X射线荧光光谱具有分析快速、状态稳定的特点,已在琉璃瓦测试研究中得到普及,而元上都元中都琉璃瓦釉层的研究结果,补充了元代琉璃瓦的研究资料,并对探索中国琉璃瓦工艺发展历程提供一定科学依据。     

Raman scattering features of lead pyroantimonate compounds: implication for the non‐invasive identification of yellow pigments on ancient ceramics. Part II. In situ characterisation of Renaissance plates by portable micro‐Raman and XRF studies

The effectiveness of Raman spectroscopy (using a bench‐top system on standard pigments) for the characterisation of modified lead antimonate yellows was demonstrated in the already published Part I. The knowledge gained is employed here for the study of yellow glazes on genuine Renaissance plates with the aim of identifying non‐invasively lead pyroantimonate compounds by portable micro‐Raman equipment. The investigation was carried out directly on site, at the Victoria and Albert Museum (London, UK) and at the Museo Statale d'Arte Medievale di Arezzo (Arezzo, Italy), combining Raman and X‐ray fluorescence analyses. In addition to the spectral features of both unmodified Naples yellow and Sn‐ and Zn‐modified lead antimonate compounds, the Raman patterns related to partially modified pyrochlore structures were observed. For this reason, the possible Sn‐induced modification of Naples yellow by cassiterite (SnO₂), present within the glaze as opacifier was explored on lead antimonate yellow glaze mock‐ups fired at different temperatures. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Mössbauer analysis of the firing process of the sky-green glaze of the imitative ancient Chinese Ru porcelain

The variation of the Mössbauer parameters of the imitative ancient Ru porcelain skygreen glaze with the firing conditions is studied in detail in the present paper. The Mössbauer spectra show that the sky-green glaze contains three kinds of iron minerals, i.e. the structural iron (Fe²⁺ and Fe³⁺); Fe₂O₃ and Fe₃O₄. The relative intensity of the paramagnetic peak Fe²⁺ increases and the magnetic ratio of the magnetic peak decreases with increasing temperature. Based on the variation of the quadrupole splitting (QS) of the paramagnetic peak Fe²⁺, the phase transformation characteristics of the sky-green glaze in the firing process is discussed. The coloring mechanism of the sky-green glaze and the variation of its magnetism in the firing process are also investigated in the present paper.     

晚清彩瓷釉料的拉曼光谱研究

本文利用便携式拉曼光谱仪并结合显微拉曼光谱仪对几件清末彩瓷的拉曼光谱进行了研究。根据谱峰分析, 这几件晚清彩瓷中暗红色釉料均为Fe2O3; 浅红色和绿色彩釉的主要原料是碱式碳酸铜, 是由于工艺不同而导致铜化合物显色不同; 青黄色颜料的主要原料则是复合铅锡锑黄釉料。     

Synchrotron radiation micro-XRD in the study of glaze technology

The production of glass represented an important technological achievement, and it was the starting point for the invention of a large variety of materials, produced by processes involving melting, partial or total, and precipitation of new crystalline compounds during cooling. In particular, those crystallites built-in the glaze due to partial or total insolubility of some elements originally present in the melt (for instance some colourants and opacifiers), as well as those crystallites formed in the glazes resulting from the interaction of the melt and the ceramic surface are subject of the highest interest in the study of glaze technology. Finally, devitrification and weathering gives rise to precipitation of new crystalline compounds closer to the surfaces and interfaces.