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.     

INVESTIGATION ON ROMAN LEAD GLAZE FROM CANOSA: RESULTS OF CHEMICAL ANALYSES*

Five sherds of green glazed pottery excavated at Canosa (Apulia) in Italy have been analysed by scanning electron microscopy. The aim of the investigation was to determine the chemical composition of the glazes and thus obtain information on the methods used in their production. The glazes were all of the high‐lead type, coloured green by the addition of copper. Intermediate layers, observed at the interface between the glaze and body and giving the appearance of an applied white slip, were the result of the crystallization of lead feldspar from the molten glaze. Non‐calcareous clays were used in the production of the pottery bodies. Concentration profiles from the glaze exterior to the body suggested that the glazes were produced by applying a suspension consisting of lead oxide plus silica to the bodies. On the basis of the glaze and body compositions, it is suggested that the Canosa glazed pottery was produced locally.     

THE TECHNOLOGY OF GLAZED ISLAMIC CERAMICS USING DATA COLLECTED BY THE LATE ALEXANDER KACZMARCZYK

During the 1980s, the late Alexander Kaczmarczyk undertook the analysis of some 1200 glazed Islamic ceramics from Egypt, Iran, Iraq and Syria spanning the period from the eighth to the 14th centuries ad , using a combination of XRF for the glazes, and AAS or PIXE for the bodies. The aim of the present paper is, first, to bring to the attention of researchers into Islamic ceramics the fact that these analytical data are available on the Research Laboratory for Archaeology and the History of Art website, and also that some 400 of the analysed sherds are held in the Research Laboratory. Second, the paper provides a preliminary interpretation of the analytical data in terms of the choice of glaze type (i.e., alkali–lime, lead–alkali and high‐lead), tin‐opacification, body type (i.e., quartz or stonepaste, calcareous clay, and non‐calcareous clay), and colorants.     

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.     

LEAD GLAZES IN ANTIQUITY—METHODS OF PRODUCTION AND REASONS FOR USE*

Transparent high lead and tin-opacified lead-alkali glazes have been extensively used throughout Europe and the Near East from their first appearance in the Roman era and the tenth- to eleventh-century Islamic world, respectively, up until the present day. Using, to a large extent, information which is widely scattered through a diverse range of literature, the methods employed in the production of these two glaze types are first outlined and their merits are then compared with those of alkali glazes in terms of ease of preparation of the glaze mixture, ease of application of the glaze, ease of firing, cost of production, glaze-body fit and visual appearance. The principal advantages of transparent high lead glazes as compared to alkali glazes are shown to be ease of preparation and application of the glaze suspension, low susceptibility to glaze ‘crazing’ and ‘crawling’ and high, optical brilliance. Factors that influence the choice of tin-opacified lead-alkali glazes include ease of production of tin oxide by melting tin and lead metals together; a reduced risk of reduction of lead oxide to lead metal and consequent blackening of the glaze; and, again, low susceptibility to ‘crazing’ and ‘crawling’. Limits of current knowledge regarding these two glaze types and requirements for future research are outlined.     

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.     

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.     

New Data on the Soda Flux Used in the Production of Iznik Glazes and Byzantine Glasses

Previous research has shown that Iznik glazes are characterized by low potash and magnesia contents. It was therefore suggested that the flux used was either a purified plant ash or some unidentified mineral source of soda. More recently, as a result of the detection of small, but significant, amounts of boron and lithium in Byzantine glasses from western Turkey, which also exhibit low potash and magnesia contents, it has been suggested that the source of the flux used was a soda‐rich evaporite associated in some way with the extensive borax deposits in the region. LA–ICP–MS has been used to establish that Iznik glazes also contain similarly small amounts of boron and lithium. The Na/K, Na/Mg, Na/Ca and Na/B ratios for these Iznik glazes are shown to be comparable to the equivalent ratios calculated from published data for waters from a range of Na–HCO₃ type hot springs in western Turkey, with the closest match being to the hot springs around Afyon‐Gazligöl, which is consistent with documentary evidence. It is therefore proposed that the soda‐rich salts produced by evaporating water from these springs to dryness would have provided the flux required for the production of Iznik glazes and high‐boron Byzantine glasses.     

AN ANALYSIS OF THE GEM‐BLUE GLAZE OF YE WANG'S KOJI POTTERY*

Koji pottery is a glazed ceramic art used widely for figurines. In early Taiwan, it was employed in temple construction for decorative purposes. Ye Wang (1826–87) is the first historically documented Koji artist of Taiwan and also the most prominent Koji pottery artist, noted for his modelling and glazing skills. Unfortunately, his unique technique was lost following his death in 1887. In order to provide vital information for ongoing conservation work on Koji pottery, this study analysed the physical and chemical characteristics of Ye Wang's gem‐blue glaze, to discover the glaze formula. DSC combined with the two‐thirds rule revealed that the firing temperature of Ye Wang's works of art was most probably around 878–923°C. EPMA revealed that the gem‐blue glaze has high alkali levels, and belongs to the PbO–K₂O–B₂O₃–Na₂O–SiO₂ system, deriving its unique colour from copper, iron, manganese and cobalt. This study found high potassium levels in the gem‐blue glaze, which are generally a characteristic of traditional Chinese glazes. In addition, a unique discovery of boron, commonly used in famille rose, was also identified in the glaze. By comparing spectra of historical and reconstructed glazes and adjusting the proportion of chromophoric elements, this study found a glazing formula with colours close to those of Ye Wang's gem‐blue glaze.     

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.     

TECHNOLOGY AND COLOUR DEVELOPMENT OF HISPANO-MORESQUE LEAD-GLAZED POTTERY

Lead-glazed pottery from the medieval workshop of Les Olleries Majors (Paterna, Spain) has been studied by Mössbauer spectroscopy, X-ray diffraction, X-ray fluorescence and optical spectroscopy. Yellow, brown and honey-coloured glazes occur on pots glazed on only one surface. They have virtually identical compositions and transmittance spectra, their apparent differences in colour are due to the colours of the underlying pastes. Yellow glazes occur on cream-coloured calcareous bodies, honey-coloured glazes occur on less calcareous bodies with some development of hematite, while brown glazes occur on red siliceous cooking-pots. Green glazes are found on pots glazed on both surfaces; the glazes trapped CO₂ evolved by decomposing carbonates, resulting in an internal reducing environment. This caused the reduction of iron to the ferrous state which coloured the glaze green by diffusion.     

The earliest high-fired glazed ceramics in China: the composition of the proto-porcelain from Zhejiang during the Shang and Zhou periods (c. 1700–221 BC)

Bodies and glazes of 54 proto-porcelain sherds and 18 non proto-porcelain samples from Shang and Zhou periods production sites in Deqing, Zhejiang province were analysed by EPMA-WDS. The results indicate that the bodies of all samples were made from local raw material – porcelain stone, with the proto-porcelain samples being made from clay of higher quality. Wood ashes, high in lime and low in potash, were intentionally applied to the proto-porcelain samples, resulting in the formation of lime-rich glazes whose compositions were determined by a temperature-controlled mechanism. In contrast, kiln fragments and furniture show a potash-rich fuel vapour glaze, which formed unintentionally during use of the kiln. The firing temperature for most of the proto-porcelain glazes is around the maturing temperature for typical more recent lime glazes, showing that the potters were already at such an early time able to attain sufficiently high temperature in their kilns.     

The production and technology of glazed ceramics from the middle ages,found in the saepinum territory (Italy): a multimethodic approach*

A collection of ceramics from the Middle Ages found in Altilia and Terravecchia (the Saepinum area, Campobasso, Italy) were characterized by using different mineralogical analyses to investigate their provenance and production techniques. The body ceramic was investigated using Rietveld phase analysis of X‐ray powder diffraction patterns, X‐ray fluorescence spectrometry and scanning electron microscopy. The chemical compositions of the coatings were measured by scanning electron microscopy and their mineralogical compositions were determined using a particular technique of X‐ray small‐angle scattering (SAS) optimized for studies of thin films. Moreover, the material used for decoration was studied using micro‐Raman spectroscopy. The archaeometric results confirmed the distinction into two different ceramic classes, already individuated from archaeological analysis: the Altilia objects belong to the protomajolica class, whereas the objects from Terravecchia are RMR (ramina‐manganese‐red) ceramics. A comparison between the chemical and mineralogical compositions of good‐quality ceramic objects and those of waste products indicated local production of the ceramics. A sharp distinction was found in the chemical composition of the coatings: the Altilia products have tin‐opacified lead glazes, while the Terravecchia ones have transparent high‐lead glazes. Among the Altilia products, the unsuccessful process that produced a large quantity of discarded materials was attributed to the high lead content of the glazes. In fact, the principal advantage of the high lead content was to make the preparation and application of the glaze suspension easier, but the risk of reduction of lead oxide to metallic lead was greatly increased. Using micro‐Raman spectroscopy, the following minerals were identified as pigments: pyrolusite for the dark colour, malachite for green, lepidocrocite for yellow and hematite for red.     

Chemical and Textural Characterization of Tin Glazes in Islamic Ceramics from Eastern Spain

Several productions of Islamic tin glazed pottery from eastern Spain have been studied under the chemical and microstructural points of view by means of WDS, SEM/EDX, XRD and XRF analyses. Samples of Islamic pottery from the workshops of Murcia 10th, Zaragoza 11th, Mallorca 11th, Denia 13th, Granada 14th and Córdoba 10th, which represent a wide range of local productions from medieval eastern Spain, have been studied in order to obtain the trends of the technical and compositional evolution. From the experimental data, some common features can be established, as well as some differences. All the Islamic Spanish opaque glazes are lead glazes with PbO contents from 37 to 56%, opacified with tin oxide in the range 4–15%. In all the cases, they were applied on a previously biscuited body made with a Ca-rich clay, probably to produce a buff colour less apparent through the glaze. The thicknesses range from 100 to 150 microns and the opacification is achieved by small crystals of SnO₂(under a micron of size). The main differences are the size and distribution of such small crystals, being smaller in the early Islamic productions (Zaragoza and Murcia) and bigger in the late productions.     

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.     

Compositional and Microstructural Study of KoryŎ Celadon and Whiteware Excavated from SŎRi Kiln in Kyŏnggi Province

An extensive study of the composition and microstructure of celadon and whiteware sherds excavated at Sori, one of the most important sites that were active during the founding stage of the stoneware and porcelain industry in Korea, was carried out. The analysed sherds were organized according to four different levels of the excavation and four different styles of haemurigup foot rim. Principal component analysis of the chemical compositions of the sherds revealed slight differences in their body and glaze compositions between the levels of excavation. Porcelain stone with high silica and low aluminium contents was generally used as the body material and wood ash as the chief flux in the glaze. Over the period of operation, the aluminium content in the bodies of the ceramics decreased and the P₂O₅ content in the glazes increased. Glazed bodies were fired in a single step, in contrast to the two‐step method used in later ceramic production. Firing conditions were adjusted to produce vitrification of the glazes, which meant that vitrification of the ceramic bodies occurred to varying extents, mostly determined by the relative contents of flux in the body and the glaze.     

TECHNOLOGY OF PRODUCTION OF GHAZNAVID GLAZED POTTERY FROM BUST AND LASHKAR‐I BAZAR (AFGHANISTAN)

Fifteen fragments of glazed pottery were studied by scanning electron microscopy coupled with energy‐dispersive X‐ray analysis (SEM–EDS). The fragments, dated from between the 11th and the 12th centuries, are part of a group excavated at ancient Bust and Lashkar‐i Bazar (southern Afghanistan) and belonging to the International Museum of Ceramics in Faenza. All the samples are characterized by highly calcareous bodies, and all of them but one is coated with a transparent lead glaze; the last fragment is, instead, coated with a turquoise opaque lead–alkali glaze. With three exceptions, the studied fragments show underglaze decorations featuring white, red, green or black motifs applied on to a white, red or black engobe; one of the remaining glazes is applied on to a monochrome white slip and the other two directly on to the ceramic body. Optical microscopy and SEM images show that engobes and decorations were obtained by deposition of differently coloured clayey slips, the composition of which was characterized by EDS analyses. In particular, black engobes and decorative motifs were obtained by recourse to manganese and iron compounds or to chromium, magnesium and iron compounds; it appears that both possibilities could be exploited for obtaining different decorative motifs on the same object.     

LEAD ISOTOPE ANALYSIS OF TANG SANCAI POTTERY GLAZES FROM GONGYI KILN,HENAN PROVINCE AND HUANGBAO KILN,SHAANXI PROVINCE

Through the use of MC–ICP–MS, this study analyses the lead isotope ratios of 19 Tang Sancai pottery glazes unearthed from the Gongyi and Huangbao kiln sites. According to their different lead isotope ratios, the two kilns can be grouped separately. The research also suggests that the Gongyi and Huangbao kilns are independent production centres of Tang Sancai in the Tang Dynasty. The data from the Huangbao kiln indicates that the lead in the glazes originates from the Northern China geochemical province, while the data from Gongyi kiln suggests its source as the Yangtze geochemical province. Furthermore, the results obtained for the Tang Sancai pottery indicate that the lead sources for glaze making of these two kilns were very consistent, which suggests that lead isotope analysis could be a helpful method to identify the kilns producing Tang Sancai artefacts.     

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.     

Chemical Composition and Manufacturing Technology of a Collection of Various Types of Islamic Glazes Excavated from Jordan

A collection of Islamic glazed pottery shards that were excavated from the archaeological site of Dohaleh/Northern Jordan were chemically analysed. The glazes belong to three different decorative styles. The chemical analysis of the glazes was carried out using energy dispersive x-ray fluorescence. The chemical analysis results enable the classification of the glazes into the three distinct compositional groups with reference to their principal modifier, these are: the alkaline glazes, the high lead glazes and the lead–alkali glazes. In some cases the body fabric was analysed by a combination of petrographic and chemical analysis techniques. The study show that inherited traditional techniques were combined with innovative Islamic techniques were used for the production of the glazes.