A TECHNOLOGICAL EXAMINATION OF NINTH–TENTH CENTURY AD ABBASID BLUE‐AND‐WHITE WARE FROM IRAQ,AND ITS COMPARISON WITH EIGHTH CENTURY AD CHINESE BLUE‐AND‐WHITE SANCAI WARE*

Eight sherds of ninth–tenth century ad Abbaesid blue‐and‐white glazed earthenware, excavated in 1931 at Hira in western Iraq, were analysed using, variously, quantitative wavelength‐dispersive spectrometry (WDS) and energy‐dispersive spectrometry (EDS) in association with scanning electron microscopes (SEM), and semi‐quantitative X‐ray fluorescence spectrometry (XRF). In order to compare the compositions of the cobalt pigments used, the glazes of seven complete vessels of eighth century ad Chinese Tang blue‐and‐white sancai were also analysed semi‐quantitatively using XRF. The Abbasid wares were shown to have used traditional Mesopotamian alkali–lime glazes applied to calcareous clay bodies. Half the glazes examined were opacified with tin oxide. Three types of blue decoration (i.e., raised; spreading; and flat, non‐spreading) were produced using a variety of formulations, including a mixture of cobalt pigment with lead oxide. The sources of the ores used for the cobalt pigments have not been identified. However, the analytical data showed that the cobalt ore used for the Abbasid blue‐and‐white ware could be distinguished from that used for the Tang blue‐and‐white sancai by its higher iron content and by the presence of a significant amount of zinc. The use of cobalt‐blue decoration on the ninth–tenth century ad Abbasid ware was anticipated in China by eighth century ad Tang blue‐and‐white sancai wares. However, whether its introduction by the Abbasid potters should be seen as an independent invention that followed the introduction of tin‐opacified glazes in Iraq, or whether it was influenced in some way by Chinese originals, is still unresolved.     

THE CHEMICAL COMPOSITION OF BLUE PIGMENT ON CHINESE BLUE‐AND‐WHITE PORCELAIN OF THE YUAN AND MING DYNASTIES (ad 1271–1644)*

The chemical compositions of the glazes and pigments of 39 blue‐and‐white porcelains of Ming Dynasty date and three of Yuan date were examined by SR‐XRF. Both the analysis of the Fe/Mn ratio in the light blue areas of the glaze and a comparison of the Fe/Mn values between light blue, dark blue and clear glaze areas reveals that the samples can be divided into three groups. The results indicate that there are two significant changes of provenance of blue pigment during the Ming Dynasty and that some kinds of pigment were most probably imported from the Middle East. Considering literature records and other scholars’ studies, an outline picture of the pigment used on Chinese blue‐and‐white porcelain produced in Jingdezhen in the Yuan and Ming Dynasties is presented.     

Pottery technology in the Tang dynasty (ninth century ad): archaeometric analyses of a Gongyi sherd found at Siraf,Iran

In 1969–70, a single Tang dynasty blue‐spotted Gongyi sherd was found at Siraf, Iran, the main trading port on the Persian Gulf in the early Islamic period. This is the only known example of Chinese blue‐and‐white ware, whether low‐ or high‐fired, found in the Middle East from such an early date. The sherd provides direct archaeological evidence for the Indian Ocean trade between China and the Middle East in the ninth century ad . The body paste, clear glaze and blue glaze or pigment were analysed by thin‐section petrography, scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM‐EDX) and X‐ray fluorescence (XRF). The technological analysis reveals the different steps of the chaîne opératoire: clay mixing, slip and glaze application, and decoration with the cobalt blue glaze before high‐temperature firing. These steps are characteristic of Tang stoneware production at Gongyi in Henan province, China. The use of cobalt blue pigment as part of a simple spotted decoration scheme on the Gongyi sherd, and its find context within the Middle East, provides evidence for the complex interplay and influence occurring between Chinese and Middle East ceramic industries at this time. Closely comparable examples of contemporary low‐fired earthenware ceramics with cobalt blue decoration on a white tin glaze manufactured within the Middle East also occur within the same assemblage from Siraf.     

DISCOVERY,PRODUCTION AND USE OF TIN‐BASED OPACIFIERS IN GLASSES,ENAMELS AND GLAZES FROM THE LATE IRON AGE ONWARDS: A REASSESSMENT*

Tin‐based opacifiers (lead stannate yellow and tin oxide white) were first used in glass production for a short period in Europe from the second to the first centuries bc , and then again throughout the Roman and Byzantine Empires from the fourth century ad onwards. Tin oxide was also used in the production of Islamic opaque glazes from the ninth century ad , and subsequently in enamels applied to Islamic and Venetian glasses from the 12th century ad onwards. A selection of published analytical data for the tin‐opacified glasses, enamels and glazes is summarized, and the methods used in their production are reassessed. The phase transformations occurring when mixtures of lead oxide, tin oxide and silica are fired are investigated with high temperature X‐ray diffraction (XRD) using a synchrotron radiation source, and these results are used to explain the observed differences in the glass, enamel and glaze compositions. Possible reasons for the use of tin‐based opacifiers in the second to first centuries bc , and for the switch from antimony‐ to tin‐based opacifiers in the fourth century ad are suggested, and the possible contexts in which tin‐based opacifiers might have been discovered are considered. The introduction of tin‐opacified glazes by Islamic potters in the ninth century ad is discussed in terms of technological transfer or independent invention.     

Studying the process of enamel powder preparation for émail champlevé by colour measurements and μ‐X‐ray mappings

Colour measurements and non‐destructive μ‐X‐ray mappings have been used for the first time in a comprehensive study of medieval émail champlevé works from different production areas in France and Germany. This approach has given a new insight into the enamel powder preparation process of the glass material used for enamelling. Colour measurements demonstrated that all production centres used glass of very similar hues, but with large differences in colour saturation. The μ‐X‐ray mapping results of blue enamels are described by a semi‐qualitative approach. Significant variations in oxide contents of lead, cobalt, manganese and antimony oxides were found. The variations suggest that more than one glass material was used to prepare the powder for enamelling. The variations in antimony and cobalt show that glass had different degrees of opacity and colour depth. The manganese and lead contents, which do not correlate with the cobalt or antimony contents, indicate that probably glass of different base compositions was used to prepare the enamel powder for one champlevé field.     

Evaluation of Quantitative XRF Analysis Applied to Determine Cobalt Sources in Chinese Blue‐and‐White Porcelain

A method using the ratios between MnO, Fe₂O₃ and CoO to differentiate the cobalt sources for Chinese blue‐and‐white porcelain was developed in Oxford in the 1950s using X‐ray fluorescence (XRF) analysis directly on the glaze. In this paper, six blue‐and‐white porcelain sherds from the Luomaqiao kiln were analysed by XRF on the glaze and by scanning electron microscopy with energy‐dispersive spectrometry (SEM‐EDS) in cross‐section. The ratios between MnO, Fe₂O₃ and CoO calculated by quantitative XRF and EDS analyses are different. The analysis depths for MnO, Fe₂O₃ and CoO are < 60 μm by XRF analysis. However, the average glaze thickness of samples is > 400 μm, and the MnO, Fe₂O₃ and CoO mainly remain in the lower layer of the glaze, which is beyond the analysis depths of XRF analysis. The limitations of major and minor quantitative analyses for differentiating cobalt sources are discussed.     

THE BLUE ENAMELS IN THE BAROQUE DECORATIONS OF THE CHURCHES OF PALERMO,SICILY: FE2+‐COLOURED GLASSES FROM LIME KILNS*

Deep blue glasses coloured by octahedral Fe²⁺ cations are often reported as textbook examples of blue pigmentation. However, despite the possibility of laboratory synthesis under reducing conditions, to date there are no well‐reported occurrences of their production and use in the past. A thorough historical, ethnographic, mineralogical, and chemico‐physical investigation of the ‘smaltini di calcara’ from several baroque churches in Palermo, Sicily, has revealed that the blue enamels widely used for altar decorations in the 17th and 18th centuries are actually a unique case of ancient blue glasses pigmented by divalent iron cations in distorted octahedral coordination. This mixed‐alkali glass was accidentally produced under severely reducing conditions in the local kilns during production of lime.     

MICRO‐RAMAN SPECTROSCOPY CHARACTERIZATION OF DELLA ROBBIA GLAZES*

Micro‐Raman spectroscopy and the laser‐induced transformation technique were used for systematic study of five coloured glazes on Saint John the Baptist (29 inch tondo), a majolica terracotta relief attributed to Luca Della Robbia and on permanent exhibit in The John and Mable Ringling Museum of Art. We suggest that ions in a lead silicate matrix, called ‘lead ultramarine’, could contribute to the famous Della Robbia blue colour, in addition to the effect of Co atoms as suggested previously by Pappalardo et al. (2004 ). The original yellow glaze contains lead(II) antimonate. The green is a mixture of the yellow and blue pigments, the brown contains hematite, and the white glaze contains tin dioxide as an opacifier. The use of lead oxide as a main fluxing agent is confirmed by laser‐induced micro‐crystallization.     

Portuguese Blue‐on‐Blue 16th–17th Century Pottery

Blue‐on‐blue (‘berettino’) sherds have appeared in numerous production and consumption archaeological excavations in Lisbon and other archaeological sites in Portugal (dated from the mid‐16th century to the beginning of the 17th century). The abundance of this interesting faience led us to compare it with similar pottery from other well‐known production centres in Italy, namely Liguria (Savona and Albisola), Spain (the Triana kilns) and the Low Countries. Differences in the diffraction patterns of the sherds' pastes from the four countries were observed. In most samples, cobalt blue silicate (cobalt olivine) was identified in the dark blue or light blue glazes through the use of micro‐Raman spectroscopy and diffuse reflectance spectra. A remarkable difference in the calcite contents of the Lisbon and Seville pottery sherds was observed, in accordance with previous observations of high calcite contents of Seville ceramics. A comparison was also made for all of the blue‐on‐blue sherds studied here with many other 16th–17th century sherds from Lisbon using bivariate plots of K/Si versus Ca/Si. Lisbon and Seville pottery behave very differently, whereas sherds from Italy and the Low Countries occupy intermediate positions.     

CHARACTERIZATION OF 18TH‐CENTURY MEISSEN PORCELAIN USING SEM–EDS*

Analytical investigations of fragmented Meissen porcelains well dated to between 1725 and 1763 have been carried out using SEM–EDS. The aim of the analysis was to characterize elements in bodies, glazes and overglaze enamels in order to create a baseline data set of materials used in the manufacture of porcelain at the Meissen factory, Saxony, during the 18th century. Analyses indicate body and glaze compositions to be consistent with a post c.1720–30 date, when a change from a lime‐rich flux to a potassium‐rich flux is documented to have occurred. Overglaze enamel compositions are shown to be consistent with contemporary accounts of enamel preparations at Meissen. Overglaze enamel compositions show that mixtures of pigments, in addition to documented enamel 18th‐century preparations, were in use at Meissen between c. 1725 and 1763.     

Vietnamese (15th Century) Blue‐And‐White,Tam Thai and Lustre Porcelains/Stonewares: Glaze Composition and Decoration Techniques*

EDS, X‐ray fluorescence, Raman spectroscopy, thermal expansion–shrinkage measurement and scanning electron microscopy were applied to determine the elemental components, structural phases and glazing temperatures of the transparent glazes, blue underglaze and overglaze tam thai (including gold‐like lustre) decorations from the 15th‐century Vietnamese porcelains/stonewares found at the Chu Ðâu–My Xa kiln site and in the Cù Lao Chàm (Hôi An) cargo. The ancient technology for colouring the glazes is discussed. The various blue tones in the underglazed décor result from cobalt‐containing manganese ore, with the intentional addition of iron oxide. The overglaze copper‐green and the gold‐like lustre were obtained by dispersing copper in lead‐based glass. The red colour was made using hematite dispersed in lead‐rich flux.     

ANALYSIS OF LATE BRONZE AGE GLASS AXES FROM NIPPUR—A NEW COBALT COLOURANT

A multidisciplinary study of a unique group of Late Bronze Age (LBA) ceremonial glass axe heads and other artefacts shows that these are the first significant group of glasses coloured with cobalt to be identified from the Near East. The axes were excavated from the site of Nippur, in present‐day Iraq. Several are incised with the names of three kings, which dates the material to the 14th–13th centuries bc . Analysis by laser ablation inductively coupled plasma mass spectrometry (LA–ICPMS) indicates that the glass had high magnesia (MgO) and potash (K₂O) associated with a plant‐ash flux and was coloured blue by copper or a combination of copper and cobalt. These glasses are similar, but not identical, in major element composition to blue‐coloured glasses manufactured in ancient Egypt and elsewhere in Mesopotamia in the same period. However, the Nippur cobalt‐ and copper‐coloured glasses exhibit significantly different trace elemental compositions compared to Egyptian glass coloured with cobalt, showing that the ancient Near Eastern glassmakers had clearly identified and utilized a distinctive cobalt ore source for the colouring of this glass. Since it was previously thought that the only cobalt ores exploited in the LBA were exclusively of Egyptian origin, this new finding provides new insights on the origins of glass and how it was traded during the Bronze Age period.     

关于青花起源的思考

关于青花的起源,长期来一直有中国起源说和外来技术影响说两种意见。本文着重从低温釉陶生产技术源流和对青料的使用出发,论证了最早出现在巩县窑的唐青花瓷器,只是北魏以来低温釉陶生产技术在新条件下的新产物。认定唐青花的出现是外来绘画理论和绘画技术影响中国艺坛的结果。     

Comparison of the Different Types of Qinghua Porcelain from Jingdezhen in the Yuan Dynasty of China (ad 1271–1368) by Micro X‐ray Fluorescence Spectroscopy (μ‐XRF) and Microscopy

The Yuan Qinghua porcelain produced in the city of Jingdezhen, in China, mainly includes the gaudy blue type, a blue–grey or grey‐coloured type and the type featuring a blue colour with a slight amount of grey. For a long time, only the gaudy blue type was focused on and discussed, while the other two types, which contain equally important information with regard to recovering the manufacturing technology of Yuan Qinghua, were always ignored by scientific researchers. In this paper, by using micro X‐ray fluorescence spectroscopy (μ‐XRF), spectrophotometry and optical microscopy, all three different types of Yuan Qinghua porcelain are analysed systemically and, based on the analyses of the body, the glaze and the blue decoration, the differences in the materials and the manufacturing technologies of the three different types are discussed. This not only provides a good basis for the reconstruction of the whole picture of the manufacturing process of Yuan Qinghua porcelains in Jingdezhen, but also contributes to database‐building for the identification of Qinghua porcelain.     

故宫宁寿宫装饰彩瓷嵌片釉彩料的分析研究

故宫宁寿宫花园延趣楼、萃赏楼内檐装修釉上彩瓷装饰嵌片,是研究乾隆时期釉上彩瓷的珍贵标本。本研究采用X射线荧光能谱仪、显微激光拉曼光谱仪和实体显微镜,对乾隆时期釉上彩瓷样品进行无损分析。结果表明,蓝色、胭脂红色釉彩的基底釉为铅钾玻璃,白色、黄色、黄绿色、绿色釉彩的基底釉为铅玻璃。白彩的乳浊剂和着色剂为砷酸铅;蓝彩的乳浊剂为砷酸铅,着色元素为Co;黄彩为铅锡黄Ⅱ型乳浊及着色;黄绿彩为铅锡黄Ⅱ型和Cu共同作用;胭脂红彩为Au着色;绿彩为Cu着色;黑彩需覆盖透明绿彩于珠明料上才能完全发色;橘红彩为赤铁矿着色和乳浊;棕彩则为赤铁矿和Mn、Co共同着色。本研究成果可为乾隆时期釉上彩瓷的原料与工艺研究提供基础数据。     

ANALYSIS OF NASRID POLYCHROME CARPENTRY AT THE HALL OF THE MEXUAR PALACE,ALHAMBRA COMPLEX (GRANADA,SPAIN), COMBINING MICROSCOPIC,CHROMATOGRAPHIC AND SPECTROSCOPIC METHODS*†

The pigments, binders and execution techniques used by the Nasrids (1238–1492) to polychrome carpentry in the Hall of the Mexuar Palace at the Alhambra (Granada, Spain) were studied using optical microscopy, scanning electron microscopy with EDX analysis, selective staining techniques and gas chromatography – mass spectrometry. This pioneering investigation presents the first results of a research project devoted to filling gaps in the knowledge of Nasrid art, traditionally approached by stylistic studies. Moreover, it is essential for the polychromy conservation of the studied artworks, and will help to clarify historical and painting uncertainties in the Alhambra monument. The palette consists of a limited range of colours: white (lead‐base pigment), red (cinnabar and red lead), blue (lapis lazuli), black (carbon‐based) and false gold (golden tin). Tempera grassa was the painting technique identified. Two types of grounds were used: (i) gypsum in calligraphy decoration for the false gold technique, and (ii) synthetic minium in geometric drawings in carpentry. Organic insulating layers of linseed oil were used between paint strata. Artists applied synthetic minium to protect the wood (Juglans regia and conifer) against attack by xylophages. To lighten the surface darkened by this ground layer, powdered tin was added to achieve a metallic lustre.     

A STUDY ON LATE MEDIEVAL TRANSPARENT‐GLAZED POTTERY AND ARCHAIC MAJOLICA FROM ORVIETO (CENTRAL ITALY)*

Nineteen samples of medieval transparent‐glazed pottery and archaic majolica from Orvieto (central Italy) were studied. They were classified by archaeological criterion as follows: five transparent‐glazed fragments with green and brown decorations (first half of the 13th century), eight green transparent‐glazed fragments (13th century) and six tin‐glazed fragments with green and brown decorations (second half of the 13th century). SEM–EDX, XRD (the Rietveld method) and XRF were used to characterize the chemical and mineralogical compositions both of the bodies and the coatings. In all of the samples, the paste is Ca‐rich with CaO contents as high as 13–20 wt%. The mineralogical composition is compatible with a firing temperature of about 950°C, which is the typical temperature reached in a wood kiln. No difference was observed between the bodies of transparent‐ and tin‐glazed pottery. In the case of transparent glazes, the burial conditions lead to heavy weathering of the samples. However, on the basis of the analyses carried out in non‐weathered areas, the typical composition is PbO 55–65 wt%, SiO₂31–35 wt%. In tin glazes, the tin is scattered on the mass of the glaze as SnO₂crystals with a concentration of 7–14 wt%. Concerning the decorations, it is established that the green colour is due to the presence of copper, while manganese is responsible for the brown colour. These pigments, which represent the typical colours of ‘archaic majolica’, are spread through the glaze homogeneously, apart from one case in which there is clear evidence of manganese oxide crystals.     

The Intentional Use of Lead–tin Orange in Indian Islamic Glazes and Its Preliminary Characterization

We describe the historical appearance, composition and texture of a little‐known orange pigment in 17th‐century northern India. The pigment shares similarities with lead–tin yellow type II, but has between 6 and 7 wt% zinc oxide instead of silica as a minor element in its structure, in addition to the dominant lead and tin oxide. The consistency of its occurrence and composition across several important and highly decorated monuments and relatively wide chronological and geographical ranges of use indicate the controlled and intentional production of this pigment. We propose to use the name lead–tin orange for this material, indicating its similarity to lead–tin yellow but highlighting its independent character and distinct colour.     

山东临淄山王村俑坑出土陶质彩绘颜料初步分析

2008年5月山东临淄山王村俑坑出土了数量较多的彩绘陶质文物,为了了解彩绘颜料结构和成分,采用粉末偏光显微法、剖面观察结合拉曼光谱分析对彩绘文物表面颜料样品进行分析。结果表明,这批陶质文物表面彩绘是以白灰做地仗层,由碳酸钙、白土、铁黑（Fe₃O₄）、铁红（Fe₂O₃）、朱砂等颜料调和而成,且厚度不均。在个别样品中发现了少量的中国蓝颗粒(BaCuSi₄O₁₀),这是这次分析中较为重要的发现,此分析结果也可为考古研究提供科学信息。