ANTIMONATE OPAQUE GLAZE COLOURS FROM THE FAIENCE MANUFACTURE OF LE BOIS D’ÉPENSE (19TH CENTURY,NORTHEASTERN FRANCE)*

Three types of antimony‐based, opaque ceramic colours were used in the faience workshop of Le Bois d’Épense during the first decades of the 19th century; that is, yellow, tawny and green. Yellow is generated by lead antimonate crystals (Naples Yellow), which are incorporated into an uncoloured glass matrix. According to SEM–EDS measurements, these pigments contain iron. The tawny colour is the optical result of the combined presence of similar yellow, iron‐bearing lead antimonate particles in a Fe‐rich, brownish glass matrix. The green opaque colour is produced by the combination of a blue cobalt glass and yellow Pb–Sn–Fe‐antimonate crystals. Cores of zoned pigments lighten the recipes, according to which the pigments were produced. First, they were synthesized by calcination, ground and then mixed with a colourless, brown or blue glass powder. The resulting powder mixture was added to a liquid agent and used as high‐temperature ceramic colour.     

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.     

Glass from the Archaeological Museum of Adria (North-East Italy): new insights into Early Roman production technologies

In the present study, the first archaeometric data on an ample selection of intentionally coloured (or decoloured) Early Roman glass (1st–2nd centuries AD) from the Archaeological Museum of Adria (Rovigo, Italy) are reported. The analysed samples are 61 in total, both transparent and opaque, and were characterised from the textural (SEM-EDS), mineralogical (XRPD) and chemical (XRF, EPMA, LA-ICP-MS) points of view. This combined approach allowed us to identify the raw materials and production technologies employed in the manufacture of glassware. Results for the transparent samples show that they are all silica-soda-lime glasses. Most of them, independently of colour, have compositions close to those of typical Roman glass, produced with natron as flux. No relationships were identified among chemical compositions, types or production techniques, but a dependence on bulk composition was identified for some particular colours, revealing the careful and intentional selection of raw materials. This is the case of Sb-colourless glass, produced with sand of high purity, a group of intensely coloured objects, mainly emerald green and black, produced with soda ash as flux, and some blue examples produced with various sources of sand or soda ash as flux. Two main types of opacifiers were identified for the opaque samples: calcium antimonate for white, mauve and blue glasses, and lead antimonate for the yellow ones; in one case, a yellow lead-tin antimonate was also identified. As regards the opaque glasses, most of the samples opacified with calcium antimonate are silica-soda-lime in composition, similar to the typical Roman glass. Instead, samples opacified with lead and/or lead-tin antimonates are lead glasses, suggesting different production technologies.     

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.     

Tracing the origins of Eastern European enamelling: Chemical composition of glass and enamels from the Bryansk hoard (south‐western Russia)

The chemical composition of a series of Eastern European enamels from the Bryansk hoard from the third century ad and other sites was studied using scanning electron microscopy with energy‐dispersive spectroscopy (SEM‐EDS) and electron microprobe analysis (EPMA) techniques. Red opaque glass is homogeneous compositionally, suggesting not only common manufacturing traditions but also identical types and sources of raw materials and, consequently, a single origin. The glass is made in the Roman tradition of enamelling, which appeared in the mid‐first century ad , as was the case with orange glass. The difference in the lead content in glass of different colours, which determines the melting temperature, allows the reconstruction of polychrome enamelling techniques.     

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.     

Glass Fragments from the Crypta Balbi in Rome: the Composition of Eighth‐century Fragments

Eighth‐century glass fragments from the Crypta Balbi in Rome were analysed by inductively coupled plasma emission spectroscopy. The samples included fragments of artefacts as well as ingots of raw glass and wasters. All the fragments proved to be soda–lime glasses. Manganese‐to‐iron atomic ratios are highly variable and determine the colour of a large number of samples. Fairly high copper contents, generally associated with relatively high amounts of antimony and lead, were detected in some green and blue–green samples: this suggests recycling of glass in the form of opaque mosaic tesserae. All three elements are higher in eighth‐century than in previously analysed seventh‐century fragments. This may indicate greater recourse to recycled glass, related to a reduction in trade exchanges in the Mediterranean.     

Between east and west: Glass beads from the eighth to third centuries bce from Poland

The study analyses the chemical composition of 57 glass samples from 40 beads discovered at 20 archaeological sites in Poland. The beads are dated to Hallstatt C–Early La Tène periods (c.800/750–260/250 bce ). Analyses were carried out using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Two groups were distinguished among the glasses based on the MgO/K₂O ratio: high-magnesium glass (HMG), five samples; and low-magnesium glass (LMG), 52 samples. The former were melted with halophyte plant ash, the second with mineral soda. These glasses were produced in the Eastern Mediterranean (more likely in Mesopotamia or Syro-Palestine than in Egypt) and transported in the form of semi-products to secondary glass workshops in Europe. Some of the white opaque glass was coloured and opacified in Europe.     

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.     

BYZANTINE OPAQUE RED GLASS TESSERAE FROM BEIT SHEAN,ISRAEL*

This paper presents the results of analysis of Byzantine opaque red glass tesserae derived from three separate locations in the ancient city of Beit Shean, Israel. Investigation proceeded using reflective light microscopy, energy dispersive X‐ray fluorescence and energy dispersive scanning electron microscopy. The glass matrix of the tesserae was found to be heterogeneous, with many inclusions. Similarities and differences between tesserae from the two mosaics are examined and discussed. Implications for locale of manufacture and production techniques are considered. Comparisons between the three locations led to conclusions about the use of the tunnel as a storage site and the implications of this for future research on mosaics.     

The first archaeometric data on polychrome Iron Age glass from sites located in northern Italy

A large sample set of transparent and opaque glass artefacts recovered from Etruscan contexts in northern Italy (Bologna and Spina (FE) necropoleis) and dated to a period between the 6th and 4th century BC are analysed in this paper. Samples of highly decorated beads, spindle whorls and vessels of the ‘Mediterranean Group I’ (Alabastron, Oinochoes, Amphoriskos) were selected in order to determine whether these different glass artefacts were produced at the same manufacturing site. While the vessels almost certainly originate from Greece, the beads could derive from a more ancient local production ascertained at the site of Frattesina (Rovigo, Italy) and dated to the Bronze Age.     

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.     

Pre-Roman glass from Mozia (Sicily-Italy): the first archaeometrical data

This study present the results of an archaeometrical investigation performed on a series of opaque pre-Roman glass (vessels and ornaments) dated from the 6th to 4th century BC coming from Sicily. Sixteen core formed vessels, twelve beads, three pendants and one spindle-whorl recovered in the Phoenician-Punic sites of Mozia and Birgi were analysed thought a micro destructive approach. The complete chemical analyses and X-Ray diffraction analyses were performed on small fragments of glass. The aims of this work are: 1) to obtain a chemical characterization of these samples in order to understand the raw materials employed for their production; 2) to obtain information regarding the opacifying phases dispersed in the glass; 3) to make a comparison with the results recently obtained on coeval and similar finds recovered in other cultural context, in particular in Northern Italian Etruscan contexts in order to understand whether they could belong to the same Greek-Eastern production.     

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara-a-Velha,Portugal: comparison with Venetian and façon-de-Venise production

A set of ten Millefiori glass fragments dating from the 17th century, originated from archaeological excavations carried out at the Monastery of Sta. Clara-a-Velha (Coimbra, Portugal), were characterized by X-ray electron probe microanalysis (EPMA), Raman microscopy and UV–Visible absorption spectroscopy. All glasses are of soda-lime-silica type. The use of coastal plant ash is suggested by the relatively high content of MgO, K₂O and P₂O₅, as well as by the presence of chlorine. Tin oxide or calcium antimonate were the opacifiers used in the opaque glasses, cobalt in the blue glasses, copper in the turquoise glasses, iron in the yellow and greenish glasses, and iron and copper were found in the opaque red and aventurine glasses. Based on the concentrations of alumina and silica four different sources of silica were identified, allowing the classification of the glasses into the following compositional groups: low alumina (<2 wt%), which includes a sub-group of cristallo samples with SiO₂ > 70 wt%, medium alumina (2–3 wt%), high alumina (3–6 wt%) and very high alumina (>6 wt%). Comparison with genuine Venetian and façon-de-Venise compositions showed that two fragments are of Venetian production, one of Venetian or Spanish production and the remaining are of unknown provenance. In two fragments the glass of the decoration is probably Venetian or Spanish but the glass used in the body is also of unknown provenance.     

Chemical Analysis of 17th‐century Red Glass Trade Beads from Northeastern North America and Amsterdam

Seventeenth‐century opaque red (redwood) glass trade beads of different shapes and sizes were made of mixed alkali (mainly soda)–lime glasses and were coloured with Cu, presumably as cuprous oxide or as finely dispersed elemental Cu. During the early 17th century, beads of all shapes were opacified with Sn; cored beads, with uncoloured cores and hence lower Cu levels, also tended to have slightly lower Sn contents than uncored beads. By the mid‐17th century, cored tubular beads were being opacified with a combination of Sn and Sb, a technological change similar to that observed in white glass trade beads, while uncored redwood beads appear not to have been opacified with either Sn or Sb. Bead chemistries are sufficiently different to allow them to be sorted into subgroups, which may then be tracked in various archaeological sites and regions.     

The palaeo-Christian glass mosaic of St. Prosdocimus (Padova,Italy): archaeometric characterisation of tesserae with antimony- or phosphorus-based opacifiers

The present paper reports the results of archaeometric characterisation of the opaque tesserae, intentionally coloured with antimony- or phosphorus-based opacifiers, coming from one of the two only palaeo-Christian glass mosaics known in the Veneto region (Italy), i.e., the mosaic which decorated the votive chapel of St. Prosdocimus in Padova. In particular, 55 tesserae belonging to glass types “White”, “Blue”, “Yellow”, “Green” and “Brown” are examined here. The multi-methodological approach (SEM-EDS, EMPA, XRPD, imaging spectroscopy coupled, in some cases, with XAS) gave valuable insights into the complexities of palaeo-Christian glass mosaic production technologies. Two main groups are identified, one characterised by glassy matrixes and opacifiers (calcium or lead antimonate) typical of the Roman period and comprising all “White”, “Blue”, and “Yellow” tesserae and some “Green” ones, and the other characterised by glassy matrixes and an opacifier (calcium phosphate) typical of the 6th century AD, composed of “Green” and “Brown” tesserae. This suggests that, during that century there was a gradual change from older to “new” production technologies: although new opacifiers such as calcium phosphate started to be used, the frequent use of antimony-based ones (43/55 samples) supports the hypothesis that their systematic use was extended until the 6th century, although re-using old tesserae cannot be completely excluded. In addition, comparisons with compositional groups already identified in the “gold” tesserae of the same mosaic and tesserae from Ravenna demonstrate that both the same “base compositions” of the glass were used to produce transparent and opaque glass. This evidence, coupled with the results of the historical-artistic study, suggests technological connections between Padova and Ravenna, the capital of Byzantine mosaics in Italy. Micro-structural observations and chemical analyses of the Paduan antimony-based opacified glass demonstrate that different processes and raw materials were used in their production. Both in situ and ex situ crystallisation can be identified for calcium and lead antimonate in Paduan tesserae, whereas the production of tesserae opacified with calcium phosphate generally appears to be highly standardised. Although the opacifiers used in the Paduan tesserae support technological transitions, the colouring elements identified here, i.e., iron and manganese for white, yellow, brown and some green tesserae, cobalt for blue, and copper for blue and green, suggest continuity, because their use is widely testified in the production of both transparent and opaque glass artefacts dating from the Bronze Age until Medieval times, from whichever archaeological site the samples come. Peculiar relationships among the oxidation states of colouring elements, their contents in the glassy matrix, the types of opacifiers used, and the final colour of tesserae were identified. In addition, the correlations of cobalt and/or copper with other elements, together with identification of relics of colouring and “metallic” droplets, allow us to speculate on possible sources and production technologies. Lastly, identification of newly formed crystalline inclusions in tesserae also yields information on kiln temperatures, which ranged between 900 and 1150 °C, a range easily reached in the furnaces of the 6th century AD.     

Archaeometric investigation of Roman tesserae from Herculaneum (Italy) by the combined use of complementary micro-destructive analytical techniques

Vitreous tesserae from two mosaics in Herculaneum (Italy) dating from the 1st century AD have been investigated in order to gather information on Imperial Age opaque glass. The combined use of complementary micro-destructive analytical techniques, namely optical microscopy (OM), scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), inductively coupled plasma-mass spectrometry (ICP-MS), transmission electron microscopy (TEM), and X-ray powder diffraction (XRPD) allowed to define the nature of formers, fluxes, chromophores and opacifying compounds and to determine the type of raw materials employed for their introduction. The results confirmed the high technological level of Imperial Age glassmakers and clarified some details of the production processes. Experimental data have been obtained concerning formation of antimony-based opacifiers. The presence of tin-containing Ca- and Pb-antimonates has been ascertained in various green, yellow and turquoise tesserae. Moreover, unusual divergences from the established Roman age ‘low magnesia–low potash’ (LMLK) glass composition have been found for some red and green samples.     

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.     

THE APPLICATION OF TIME‐OF‐FLIGHT SECONDARY ION MASS SPECTROMETRY (ToF‐SIMS) TO THE CHARACTERIZATION OF OPAQUE ANCIENT GLASSES*

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) has been used, for the first time, for the characterization of opaque ancient glasses. Isotope‐specific chemical imaging with sub‐micron resolution enabled the separate analysis of opacifiying inclusions and the surrounding glass matrix. Phase identification has been demonstrated and quantification of the matrix composition has been investigated by use of Corning Glass Standard B as a model. Trace element detection limits are typically in the range 0.5–5.0 ppm atomic—in favourable cases down to 0.01 ppm. For the analysis of inclusions in particular, this has the potential to provide new information of use in establishing provenance and trade routes by ‘fingerprinting’ as well as the investigation of manufacturing techniques, as demonstrated by comparisons between glasses and with EDX data from the same samples.     

长沙窑乳浊釉制瓷技术的科技研究

长沙窑是中国唐代著名外销窑口,早期烧制青釉产品、后期发展到烧制青釉彩瓷和乳浊釉彩瓷,成为当时中外文化交流阶段性总结的集大成者。而长沙窑广泛使用的乳浊釉,特别是乳浊白釉为其彩绘提供了重要的釉层,是长沙窑彩瓷能够大放光彩的基础之一。鉴于此,为研究长沙窑乳浊釉制瓷技术,以铜官窑遗址和黄泗浦遗址出土的长沙窑瓷片为研究对象,利用光学显微镜、能量色散X射线荧光光谱仪、扫描电子显微镜和分光光度计等多种仪器,对长沙窑胎体和釉层进行了测试,着重探讨和揭示了长沙窑乳浊釉瓷的胎体原料、釉层乳浊机理、釉层原料以及兴起原因,为全面认识长沙窑乳浊釉瓷的制釉技术来源和科技内涵提供科学依据。