The Production of Lead–Tin Yellow at Merovingian Schleitheim (Switzerland)*

A Merovingian crucible fragment, with internally adhering yellow glass, and yellow glass beads of the same region and period were investigated by non‐destructive XRF, optical microscopy and SEM‐EDS. Although the microstructure and chemical composition of the yellow pigment (lead–tin yellow type II, ‘PbSnO₃’) are almost identical in both the beads and the crucible, in the latter the pigment occurs in a much higher concentration. However, the glass base in the beads and the crucible is very different, indicating that the beads were not manufactured directly from the crucible. Instead, the crucible most likely served to produce lead–tin yellow, which was subsequently mixed elsewhere with a colourless soda–lime glass to produce yellow glass beads.     

Raman Spectroscopic Analysis of Ancient Egyptian Pigments

The application of FT‐Raman spectroscopy and visible Raman microscopy to the non‐destructive analysis of pigment specimens excavated from Tell el Amarna by Flinders Petrie in the 1890s has provided information about the chemical composition of the materials used by XVIIIth Dynasty artists in the New Kingdom at the time of King Akhenaten, c. 1340 bc. Comparison of the Raman spectra of the samples labelled ‘red and yellow ochre’ with documented, archival material from geological collections provided a clear indication of the materials used in the iron(III) oxide/hydroxide system, including α‐hematite, goethite, maghemite, magnetite and lepidocrocite. The yellow–orange specimen labelled ‘realgar’ proved to be a mixture of realgar and pararealgar; since the specimen had been sheltered from light since its excavation, this could indicate that the ancient Egyptian artists recognized the colour variation and may have used this to effect in their decorations. A specimen of yellow ochre contained goethite, α‐FeO.OH, with particles of crystalline, highly ordered graphite; in contrast, the red ochre specimens contained amorphous carbon particles.     

ROMANO‐EGYPTIAN RED LEAD PIGMENT: A SUBSIDIARY COMMODITY OF SPANISH SILVER MINING AND REFINEMENT*

Samples of red pigment from a group of seven Roman‐period Egyptian mummies, known as red‐shroud mummies, are investigated. Elemental analysis by inductively coupled plasma time‐of‐flight mass spectrometry (ICP–TOFMS) shows that the samples contain mostly Pb (83–92% by weight), along with 0.2–2.0% Sn. All of the samples are found to have similar trace element distributions when normalized to the continental crust, suggesting that they share a common geological origin. Lead isotope ratios are found to match the mixed lead sources typically associated with Rio Tinto, Spain – a site extensively mined for silver during the first century ad . Raman microspectroscopy identifies the major phase of each sample to be red lead (Pb₃O₄) with a minor phase of lead tin oxide (Pb₂SnO₄). Lead tin oxide does not occur naturally, and its incidental occurrence within the sample indicates that the material was heated under oxidative conditions at temperatures in excess of 650°C. In archaeological contexts, the high‐temperature oxidative treatment of lead is typically associated with metallurgical refinement processes such as cupellation. Based on this evidence, it is argued that the pigment was produced out of litharge associated with silver cupellation at the Rio Tinto site.     

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.     

IDENTIFICATION AND DIFFERENTIATION OF OPAQUE CHINESE OVERGLAZE YELLOW ENAMELS BY RAMAN SPECTROSCOPY AND SUPPORTING TECHNIQUES*

Using Raman spectroscopy, energy-dispersive X-ray fluorescence and X-ray diffraction, the Pb–Sn–Sb triple oxide yellow and lead–tin yellow have been identified on two pieces of cloisonné enamel (Falangcai) porcelains. Lead–tin yellow and lead antimonate yellow have been identified on famille rose porcelains manufactured before and after 1911, respectively. The replacement of the Pb–Sn–Sb triple oxide yellow by lead–tin yellow and that of the lead–tin yellow by lead antimonate yellow are discussed.     

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.     

MATERIAL CHARACTERIZATION OF CERAMIC TILE MOSAIC FROM TWO 17TH‐CENTURY ISLAMIC MONUMENTS IN NORTHERN INDIA

Coloured tiles from two northern Indian monuments were analysed for their body and glaze composition. The results suggest that three different groups of tiles were used, all comprising a stonepaste body with alkali glaze. One group has strong similarities to a major Indian glass group, known as high alumina mineral natron glass, while the other two are similar to Western and Central Asian plant ash glazes, although with much lower lime content. The colorants conform with those usually employed in pre‐modern glazes, with lead‐tin yellow Type I and Type II for opaque yellow, copper blue‐turquoise, cobalt blue, manganese purple, and green through mixing of lead‐tin yellow and copper blue.     

X‐ray Diffraction and SEM Investigation of Wall Paintings Found in the Roman Temple Complex at Horvat Omrit,Israel

In the present study, the fragments of wall painting found in the Roman Temple Complex at Horvat Omrit were analysed for the first time using the non‐destructive techniques of X‐ray diffraction (XRD) and scanning electron microscopy (ESEM) equipped with energy‐dispersive X‐ray spectroscopy (EDS). The application of these methods enabled unambiguous identifications of the pigments and plaster components of the samples. Quantitative information on mineral composition, crystallite size and elemental composition of each studied paint layer and plaster was collected. Based on the results of the XRD and EDS analyses, the green pigment was identified as celadonite. It was revealed that the Egyptian blue pigment does not contain impurities of tin and lead, and this excludes the use of bronze scrap in its synthesis. Comparison of the mineral composition of the paint layers indicates that a wider palette of colours was obtained by mixing the available mineral pigments. The study of cross‐sections of painted specimens revealed the usage of slaked lime for plastering. The obtained results give a new insight into the wall painting technique employed by ancient artists at Horvat Omrit, in northern Israel.     

The production technology of Iznik pottery—a reassessment*

Previous research has established that Iznik pottery differs from other Islamic stonepaste pottery in that its stonepaste bodies contain lead oxide as well as soda and lime, and that a significant proportion of the tin oxide in its glaze is present in solution rather than as tin oxide particles. In order to better understand these distinguishing features, the chemical compositions and microstructures of Iznik pottery and tile samples, together with those of lumps of glass found in association, were investigated using both scanning electron and optical microscopy. These data have been supplemented by the study of replicate lead–alkali glazes produced in the laboratory with a range of different compositions. The results demonstrate that separate soda–lime and high‐lead glasses were used in the production of Iznik stonepaste bodies, and that the total glass contents of the bodies were significantly higher than those quoted by Abū’l‐Qāsim, who was writing in about ad 1300. The very high purity of the lead–soda Iznik glazes indicated that the alkali flux used was either a purified plant ash or an as yet unidentified mineral source of soda. Replication experiments established that the high solubility of tin oxide in the glaze was due to the high purity of the glaze constituents. Furthermore, it is suggested that tin oxide was added to the glaze in order to give it a very slight opacity and thus obscure any blemishes in the underlying body.     

MOSAIC GLASS FROM ST PETER'S,ROME: MANUFACTURING TECHNIQUES AND RAW MATERIALS EMPLOYED IN LATE 16TH‐CENTURY ITALIAN OPAQUE GLASS

A recent restoration of late 16th‐century mosaics in one of the vaults beneath the dome of St Peter's Basilica in Rome allowed sampling and analysis of a group of glass tesserae. The aim of this work is the characterization of opaque coloured glasses possibly produced in Rome. The characteristics of the glass from St Peter's were compared with those of Venetian and Tuscan production, in order to assess possible common origins. Chemical analysis of 30 samples was carried out by electron microprobe, while the nature and morphology of opacifiers were determined by X‐ray diffraction and scanning electron microscopy. Almost all the opaque samples were characterized by the presence of SnO₂ crystals. In addition, depending on the colour of the glass, other crystalline phases were identified: lead‐tin oxide (PbSnO₃) in yellow glass, cuprite (Cu₂O) in orange glass and two calcium‐tin silicates with different stoichiometry (CaSnSiO₅ and Ca₃SnSi₂O₉) in the green‐yellow variety. A frame of reference for identifying raw materials and glass‐making techniques is provided by textual sources, here examined in comparison with the compositional characteristics of the tesserae from St Peter's.     

Early Renaissance Production Recipes for Naples Yellow Pigment: A Mineralogical and Lead Isotope Study of Italian Majolica from Montelupo (Florence)

The Naples Yellow pigment was apparently used for the first time by the Egyptians, as a glass‐colouring agent. Also known in the Mesopotamian and Roman cultures, the recipe was lost in Western Europe between the fourth and the 16th centuries ad . The recipe for the production of lead antimonate recently discovered in the ‘Codice Calabranci’ (second half of the 15th century) at Montelupo, a small town near Florence (Italy) known for its large‐scale ceramic production, possibly represents the very first evidence of the reintroduction of Naples Yellow in Western Europe after a long period of absence. The major‐element composition of the lead antimonate pigment in the Montelupo ceramics of the 15th and 16th centuries is in accordance with the ‘Codice Calabranci’ recipes. Lead isotope analyses indicate that the lead used to produce the yellow pigments and the underlying glaze of the Montelupo majolica did not come from the Tuscan mining districts, but was possibly imported via Venice from more distant lead sources in Turkey.     

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.     

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。     

陕西咸阳出土东汉陶器表面彩绘成分研究

为掌握陕西省咸阳市渭城区周陵镇费家村南两座东汉墓葬M17和M19出土15件陶器表面彩绘成分及保存现状,通过XRF,XRD,FTIR和SEM-EDS等分析仪器进行检测。经分析检测发现:M17出土6件陶器表面使用铅丹作为颜料,部分铅丹已转化为白色碳酸铅(PbCO_3)。M19出土陶器表面分别使用朱砂和铁红颜料,同时确定在部分器物表面使用了髹漆工艺。在M19出土的3件器物口沿处发现二氧化锡层,通过扫描电镜能谱分析和文献研究,确定其应为单质锡氧化而来,且使用锡汞齐方法镀锡,为进一步认识和理解这批器物提供了基础。     

Malkata and Lisht Glassmaking Technologies: Towards a Specific Link between Second Millennium BC

Elemental analyses have been conducted on 61 coloured opaque glasses from the Malkata and Lisht New Kingdom glass factories. The presence of tin in several of the blue glasses suggests that a bronze casting byproduct or corrosion product was the source of the copper colorant for these glasses. A positive correlation between the lead and antimony concentrations of the yellow and green opaque glasses, plus a consistent excess of lead oxide in these glasses, suggests the use of antimony‐rich cupellation litharge as the source for the Pb₂Sb₂O₇ , colorant in these glasses. The metallurgical byproducts used to colour the Malkata and Lisht glasses provide an explicit mechanism for Peltenburg's theory of interaction between second millennium BC glassmakers and contemporary metalworkers.     

Colouring Agents in the Pottery Glazes of Western Anatolia: New Evidence for the Use of Naples Yellow Pigment Variations During The Late Byzantine Period

A group of the late 12th–13th century Byzantine pottery glazes, mostly related to Zeuxippus Ware Type pottery from the Ku?adas? Kad?kalesi/Anaia site in western Anatolia, was characterized non‐destructively using Raman spectrometry. SEM–EDX was also used complementarily for the glaze characterization. The nature and composition of the glazes, firing conditions, aspects of colour formation and pigments used were discussed. The glazes were found to be lead‐rich silicates, fired close to 700°C on the basis of the Si–O stretching peak maxima of the Raman spectra recorded at ～920–980 cm^–1, as also confirmed by SEM–EDX analysis. The polymerization index values calculated are between approximately 0.05 and 0.1. The use of biscuit‐fired bodies prior to glaze application was suggested based on the results of SEM–EDX analysis. In particular, the detection of Naples yellow pigment variations on a locally produced pottery sample is quite significant, since the use of this type of pigment has hardly ever been reported between the Roman period and the Renaissance.     

THE COLOURED TESSERAE DECORATING THE VAULTS OF THE FARAGOLA BALNEUM (ASCOLI SATRIANO,FOGGIA, SOUTHERN ITALY)

Twenty‐six tesserae (red, orange, yellow, light amber, green, blue and white) from the balneum of the villa at Faragola (Ascoli Satriano, Foggia) have been examined by colorimetry, ICP–MS, ICP–OES and SEM–EDS. Different types of calcareous sands have been used as the source of silica (network former), also providing the stabilizing agent. A natron‐type soda source served as the network modifier; however, the use of a sodium‐rich plant ash and the recycling process have been hypothesized for the production of two tesserae (FT 1 red and FT 3 orange). The colouring and opacifying agents were Cu oxide (cuprite, orange), metallic copper (red), Pb antimonates (yellow), Ca antimonates (white), a mixture of copper (Cu²⁺) and Pb antimonates (green), a mixture of cobalt (Co²⁺) or copper (Cu²⁺) and Ca antimonates (blue). The light amber tesserae should owe their colour to iron (Fe³⁺) alone or associated with sulphide (S^2?) and Ca antimonates. It is likely that the Faragola tesserae were locally produced in a secondary glass workshop.     

The Tomb of the Three Brothers in Palmyra: The Use of Mimetite,A Rare Yellow Pigment,in A Rich Decoration

The wall paintings of the Tomb of the Three Brothers in Palmyra display a very rich Greco‐Roman iconography. The study of the painting reveals the use of a great variety of pigments, including Egyptian blue and an extremely rare bright yellow pigment, mimetite, of which no other traces are known for this period. This pigment was identified through the combined use of two methods of analysis, scanning electron microscopy associated with X‐ray microanalysis (SEM–EDS) and X‐ray micro‐diffraction (XRD). The varied chromatic palette used underlines the refinement and the particular care given to these decorations. Notable differences have been found between the pigments of the decorations of the arch and those used for the rest of the chamber.