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.     

THE COMPOSITION AND MANUFACTURE OF EARLY MEDIEVAL COLOURED WINDOW GLASS FROM SION (VALAIS,SWITZERLAND)—A ROMAN GLASS‐MAKING TRADITION OR INNOVATIVE CRAFTSMANSHIP?*

Archaeological excavations between 1984 and 2001 at the early Christian cemetery church in Sion, Sous‐le‐Scex (Rhône Valley, Switzerland), brought to light more than 400 pieces of coloured window glass dating from the fifth or sixth centuries ad . The aims of this paper are threefold: first, to characterize the shape, colour and chemical composition of the glass; secondly, to understand whether the production of the coloured window panes followed traditional Roman glazing techniques or was of a more innovative nature; and, thirdly, to provide some indications as to the overall design of these early ornamental glass windows. Forty samples of coloured glass have been analysed by wavelength‐dispersive X‐ray fluorescence. The results of the chemical and the technological studies showed that most of the glass was produced using recycled glass, particularly as a colouring agent. Some of the glass was made of essentially unmodified glass of the Levantine I type. The results taken together seem to confirm that raw glass from this region was widely traded and used between the fourth and seventh centuries ad . The artisans at Sion were apparently still making use of the highly developed techniques of Roman glass production. The colour spectrum, manufacture and design of the windows, however, suggest that they represent early examples of ornamental coloured glass windows.     

COLOURED OPAQUE GLASS BEADS OF THE MEROVINGIANS*

Monochrome coloured opaque glass beads of the Merovingians have been examined by different analytical methods. A large number of mostly unprepared beads have been measured by X‐ray fluorescence analysis. X‐ray diffraction was used for the identification of the crystalline colouring and opacifying pigments, and electron probe micro‐analysis as well as scanning electron microscopy were applied to study the composition and the microstructure of a white, brown, green, orange and yellow glass bead. After subtracting the content of colouring oxides of the glass beads and normalizing the residual values to 100% an identical soda‐lime‐glass matrix was obtained. The origin of the colouring metal oxides is discussed.     

ROMAN GLASS‐MAKING AT COPPERGATE,YORK? ANALYTICAL EVIDENCE FOR THE NATURE OF PRODUCTION*

Ceramic vessels and associated vitreous debris, excavated at Coppergate, York, UK, have been interpreted as the remains of Roman glass‐making from the raw materials. This paper reports the results of analysis of this assemblage by XRF, ICPS, XRD, SEM– EDAX and thin‐section petrography. These findings suggest that some ceramic vessels, used as crucibles, have been subjected to temperatures up to 1200°C, well above the firing temperatures of the local domestic assemblage from which they were selected. Analysis of quartz‐rich debris, intimately mixed with glass in some samples and in others interleaved with glassy phases, indicates partially reacted glass‐making raw materials, with α‐quartz, tridymite and cristoballite phases represented. This could represent evidence either of a failed attempt to frit the raw materials, or a batch that had not fully fused. Variability in the composition of glass at the site is viewed in the light of glass‐making technology, and possible interpretations concerning this episode are discussed in the light of the archaeological evidence.     

OPTICAL PROPERTIES OF TIN‐OPACIFIED GLAZES*

Tin glazes contain SnO2 particles, with a diameter similar to the wavelength of visible light, which are responsible for glaze opacification. In this paper a theoretical model to explain the optical behaviour of these glazes is developed. This model is tested by measurement of the reflectance and transmittance spectra for different optical paths in Spanish Islamic and mudejar glazed ceramics and it is shown to be valid by total reflectance non‐destructive measurements on a wide range of other Islamic and related glazed ceramics.     

NEUTRON ACTIVATION ANALYSIS AT THE BRITISH MUSEUM,LONDON

Neutron activation analysis was used at the British Museum from 1978 until 2002 for provenance studies on ceramics and marble. Significant numbers of the items analysed were of high quality and value, and careful sampling was necessary to avoid damage to the object. An in‐house British Museum Standard Pottery was established and inter‐calibrated with a number of standards used by other archaeometry laboratories. The results of the projects have been published in many papers, and the databases established will be of use to future scholars interested in the ceramic groups represented. Projects on Greek and Near Eastern pottery have been undertaken. Relatively large numbers of north European medieval and post‐medieval pottery samples were analysed, as well as the tin‐glazed ceramics of Spain and Italy. Classical marble has also formed the subject of another project and a database of quarry material has been established.     

Wavelength‐dispersive X‐ray fluorescence analysis of ancient glasses*

The application of X‐ray fluorescence to the study of the composition of ancient glasses has been limited by the large amount of material required for samples. In this paper the setting of a reduced sampling XRF method for the analysis of ancient glasses is described. The method involves the preparation of glass beads by melting the sample with lithium tetraborate flux. By means of reference and synthetic samples, the method allows regression curves to be set, covering broad ranges from ppm to high concentrations. By means of a single program, up to 31 elements of interest in the study of ancient glass are analysed. The reproducibility, sensitivity and reliability of the method are discussed. The results demonstrate that 0.2 g of glass is sufficient to obtain accurate and sensitive analyses for most of the elements of interest.     

THE PROVENANCE AND TECHNOLOGY OF NEAR EASTERN GLASS: OXYGEN ISOTOPES BY LASER FLUORINATION AS A COMPLEMENT TO STRONTIUM*

The ability to make rapid measurements on small samples using laser fluorination enhances the potential of oxygen isotopes in the investigation of early inorganic materials and technologies. δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values are presented for glass from two primary production sites, four secondary production sites and a consumer site in the Near East, dating from Late Antiquity to the medieval period. δ¹⁸O is in general slightly less effective than ⁸⁷Sr/⁸⁶Sr in discriminating between sources, as the spread of measured values from a single source is somewhat broader relative to the available range. However, while ⁸⁷Sr/⁸⁶Sr is derived predominantly from either the lime‐bearing fraction of the glass‐making sand or the plant ash used as a source of alkali, δ¹⁸O derives mainly from the silica. Thus the two measurements can provide complementary information. A comparison of δ¹⁸O for late Roman – Islamic glasses made on the coast of Syria–Palestine with those of previously analysed glasses from Roman Europe suggests that the European glasses are relatively enriched in ¹⁸O. This appears to contradict the view that most Roman glass was made using Levantine sand and possible interpretations are discussed.     

ARCHAEOMETRIC INVESTIGATIONS OF SGRAFFITO CERAMIC TILES (FIFTEENTH‐SIXTEENTH CENTURIES) RECOVERED FROM EXCAVATIONS IN UDINE (NORTH‐EAST ITALY)*

Most of the Renaissance sgraffito tiles excavated in Udine (Italy) constitute a homogeous group, the tile body having a CaO/MgO molar ratio ?= 3:2. They were produced using a dolomite‐ and calcite‐containing clay fired at 900–950°C. A small group of samples, with a lower firing temperature and a CaO/MgO ratio ?= 2:3, was probably produced in a different factory. Slip and transparent glaze, characterized by optical microscopy and inductively coupled plasma atomic emission spectrometry, are an illite‐rich clay and a lead silicate, respectively.     

THE COMPLEMENTARY USE OF NEUTRONS AND X‐RAYS FOR THE NON‐DESTRUCTIVE INVESTIGATION OF ARCHAEOLOGICAL OBJECTS FROM SWISS COLLECTIONS*

This paper shows the possibilities offered by the combined use of non‐destructive neutron and X‐ray beams in archaeological research on metallic finds. The following five artefacts from Swiss excavations were submitted to investigation, each with dedicated aims: a Roman sword, a Roman dagger, an Iron Age bucket, Iron Age spearheads and a Roman finger ring. The images obtained with both methods—neutrons and X‐rays—are discussed in length in this paper. The investigations took place at the Paul Scherrer Institute and the archaeologists who studied the objects come from the Universities of Lausanne and Zurich.     

CYPRIOT BYZANTINE GLAZED POTTERY: A STUDY OF THE PAPHOS WORKSHOPS

Twenty‐five samples of Byzantine glazed pottery from two archaeological sites between Limassol and Paphos region (Cyprus), dated between the 12th and 15th century ad were studied using micro X‐ray fluorescence spectroscopy, scanning electron microscopy and X‐ray diffraction analysis. It was found that all the glazes contain lead, following the main manufacturing process of medieval pottery in the Mediterranean territory, while some of them contain tin, possibly for better opacity. Furthermore, it is shown that copper, iron and cobalt with nickel are responsible for the decoration colours. Finally, the application of principal component analysis revealed significant differentiation for some of the samples.     

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.     

MINERALOGICAL INVESTIGATIONS OF MEDIEVAL BRICK SAMPLES FROM BÉKÉS COUNTY (SE HUNGARY)

Brick samples from nine archaeological sites representing seven contemporary medieval settlements in Békés County (SE Hungary) were analysed by quantitative X‐ray powder diffraction, optical microscopic, scanning electron microscopic and coupled thermal analytical – evolved gas analytical methods. The aims of this study were to give a mineralogical–petrographical characterization of the brick samples, to gain possible information on the raw clay and the admixed materials, and to determine the firing techniques applied in medieval southeastern Hungary. The mineralogical composition of the samples suggests that the locally extracted clay was mixed with fluvial sand and wheat (Triticum monococcum L.) chaff. The moulded bricks were fired in clamps. The different degrees of calcite consumption suggest that the firing temperature ranged from ～750°C to ～950°C. Moreover, the well‐developed reaction coronas on calcite grains indicate long firing times, lasting perhaps several days.     

SCIENTIFIC ANALYSIS OF SEVENTH‐CENTURY GLASS FRAGMENTS FROM THE CRYPTA BALBI IN ROME*

Inductively coupled plasma emission spectroscopy, reflectance spectroscopy and X‐ray diffraction were used to study seventh‐century AD glass fragments from the Crypta Balbi in Rome. All the samples were found to be silica‐soda‐lime glasses. Iron determines the colour of blue‐green, green and yellow‐green transparent glasses; chemical composition suggests deliberate addition of iron and/or manganese in about half the samples. Copper was found as the main colourant in red, pale blue and blue‐green opaque fragments; elemental copper acts as an opacifier in red glass, and calcium antimonate in white, pale blue and blue‐green glasses. Detection of antimony in transparent fragments suggests recycling of opaque mosaic tesserae.