FAIENCE: AN INVESTIGATION OF THE MICROSTRUCTURES ASSOCIATED WITH THE DIFFERENT METHODS OF GLAZING

The microstructures of faience, produced in the laboratory by the direct application of the glazing mixture (both in the raw state and in the form of prefired and ground frit) and by the efflorescence and cementation glazing methods, have been studied in polished sections in the scanning electron microscope (SEM). The microstructures observed were defined in terms of (1) thickness of the surface glaze layer, (2) thickness of the glaze-core interaction layer, (3) nature of the boundary between the interaction layer and the core and (4) extent of any interstitial glass phase within the quartz core. These parameters provide the basis for distinguishing between faience made by the three principal methods of glazing used in antiquity. Hence the method used to glaze an ancient faience object can be inferred from its microstructure as observed in polished section in the SEM.     

Production Technology for Copper‐ and Cobalt‐Blue Vitreous Materials from the New Kingdom Site of Amarna—A Reappraisal*

Previously published data on the chemical compositions and microstructures of copper‐ and cobalt‐blue frit, glass and faience from the New Kingdom site of Amarna in Egypt ( Shortland 2000 ) are summarized. The data are then used to infer the raw materials and processes employed in the production of these vitreous materials. The results suggest that crushed quartz pebbles were the source of the quartz for all the materials, but that different sources of alkali, both natron and a range of plant ashes, were used in the production of each material. It seems probable that the cobalt‐rich alum colorant was pre‐treated before use by precipitating cobalt hydroxide from a solution of the alum by the addition of natron. It is further hypothesized that cobalt‐blue glass was produced by melting the cobalt‐blue frit together with additional plant ash and possibly quartz. Finally, it is suggested that, in glazing the cobalt‐blue Variant D faience first produced in the 18th Dynasty, the efflorescence or application method was selected according to object type.     

The production technology of Egyptian blue and green frits from second millennium BC Egypt and Mesopotamia

The microstructures and chemical compositions of some 55 Egyptian blue and green frit samples from New Kingdom Egypt and 15th century BC Mesopotamia are determined using analytical scanning electron microscopy, the main focus being on frit cakes, powder residues, and frit vessel and bead fragments from one of the “factory areas” at Amarna in Middle Egypt. Replicate Egyptian blue frits produced in the laboratory are similarly investigated. Comparison of the microstructures of the ancient and replicate samples suggest that frit cakes are the primary product, and that these were ground to produce the powder, and then moulded to shape and refired to produce the vessels and beads. Egyptian blue and green frits are shown to be distinct pigments, the pigment produced depending on the relative proportions of copper oxide and lime in the mixtures. The bulk and glass phase compositions are used to try to infer the different sources of the quartz, lime, copper and alkali flux used in the production of frits from Egypt and Mesopotamia. An estimate is made of the scale of production of Egyptian blue frit in New Kingdom Egypt.     

A technological study of ancient faience from Egypt

The chemical compositions and microstructures of some 35 faience objects from Egypt spanning the period from the Middle Kingdom through to the 22nd dynasty are determined using analytical scanning electron microscopy. Replicate faience beads glazed in the laboratory using the efflorescence and cementation methods are similarly investigated. In efflorescence glazing, there appears to be preferential efflorescence of soda over potash, and in cementation glazing, preferential take up of potash over soda into the glaze. These data are then used to try to infer the raw materials and methods of glazing employed in the production of the ancient faience. The glaze/glass phases present in the faience differ significantly in composition from that of New Kingdom glass. This could be due either to the use of different plant ashes or to changes in the composition of the plant ashes during the production of faience and/or glass. Although it is only rarely possible to determine with certainty whether ancient faience was glazed by efflorescence, cementation or application, the observed microstructures provide an indication of the approach adopted to achieve desired performance characteristics such as strength.     

Egyptian faience glazing by the cementation method part 1: an investigation of the glazing powder composition and glazing mechanism

In cementation glazing, for various reasons, there are significant differences between the composition of the glass phases present in the faience microstructure and the glazing powder composition. Furthermore, in this glazing method, the glazing powder should perform more functions, which are: producing a shiny and smooth glaze coating, producing a firm capsule surrounding objects entirely (to prevent adhesion between sintered glazing mixture and the melting glaze coating), and, finally, producing a porous and friable sintered glazing mixture for safe and easy removal of buried objects. It is obvious that these functions also have significant effects on the glazing powder composition and constitution. Therefore, analytical data on faience glass phases are very unlikely to reflect the strict composition and constitution of the original glazing powder properly. Accordingly, the composition and constitution of cementation glazing powder have remained obscure for a long time. These data are particularly crucial factors for cementation replication experiments and, consequently, for our awareness of the ancient faience production. In this paper, a series of cementation replication experiments have been conducted in an attempt to provide further clarification of these issues. In addition, as a comparative indicator for alkali and copper vaporisation, a small piece of rock quartz was placed separately above the glazing powder. After firing, the appearance of the faience objects and quartz pieces and the microstructures and chemical compositions of a select group of samples, obtained using Scanning Electron Microscopy – Energy Dispersive Spectroscopy (SEM-EDS), were investigated. The discussion has focused mainly on issues such as the raw materials and their contribution in the glazing process, the criteria for determining the faience glazing methods, the necessary quantity of alkalis for a successful cementation glazing, and, particularly, the glazing mechanism.     

Optical Coherence Tomography for the non-invasive investigation of the microstructure of ancient Egyptian faience

Optical Coherence Tomography (OCT) is a non-invasive subsurface 3D imaging technique based on the Michelson interferometer. The non-invasive nature of OCT and its speed of acquisition makes it possible to image large volumes of intact objects to yield a complete overview of the microstructure. The production methods for ancient Egyptian faience were first investigated using scanning electron microscopy (SEM) imaging of the microstructure in polished sections and microprobe analysis of the composition of the glass phases. These studies were based on original Egyptian faience objects and laboratory reproductions of faience beads made using three different production methods. The microstructure of the same laboratory samples and the Egyptian faience objects from the British Museum Research Laboratory Collection are re-examined using OCT. It is found that OCT virtual cross-section images can be used to group ancient faience objects into three categories on the basis of the morphology of the surface glaze layer and the glaze/core interaction layer. The OCT images correspond well with SEM images of polished sections of ancient faience objects and laboratory reproductions. The virtual cross-sections produced by OCT are somewhat limited by the penetration depth, which is affected by the high absorption coefficient of the material and, therefore, cannot always provide information on the presence or absence of interparticle glass that binds together the quartz particles in the core. Nevertheless, the top two layers are well imaged and since OCT images can be obtained rapidly and without the necessity of removing a sample, the method can be applied to a very much wider range of ancient faience objects than is possible by SEM examination of polished cross-sections. In summary, this paper examines to what extent OCT can assist the investigation of the production techniques of ancient Egyptian faience.     

THE TECHNOLOGY OF PRODUCTION OF SASANIAN GLAZED POTTERY FROM VEH ARDAŠ?R (CENTRAL IRAQ)

Scanning electron microscopy coupled with an energy dispersive X‐ray detector (SEM‐EDS) has been used to study samples of Sasanian glazed pottery. Analysis of ceramic bodies revealed a general homogeneity in composition among the studied samples and the use of calcareous clay for their manufacture. Glazes are typically alkaline in composition, with sodium and potassium oxide contents between 8 and 13%, and between 3 and 5%, respectively; calcium and magnesium oxide contents are between 7 and 10%, and between 3 and 5%, respectively. These data suggest the use of plant ash together with a silica source for glaze production. Coating thickness is highly variable among different samples, from some 400 up to 1200 µm, but it is generally uniform when a single sample is concerned. Glazes are mostly coloured blue or blue‐green; copper and iron are the colouring agents detected; abundance of bubbles, silicate crystals and relics of unmelted material are responsible for their generally opaque appearance, together with the presence of weathering products. The characteristics of the body to glaze contact zone, together with the widespread presence of bubbles, would not rule out production by a single firing process. A few samples feature a peculiar gritty coating on one side of their surface; SEM images show that they are actually partially vitrified, and EDS data denote a rather heterogeneous composition. It seems possible that they result from mixing clay together with the frit used for glaze development.     

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.     

DARK AND SHINY: THE DISCOVERY OF CHROMITE IN BRONZE AGE FAIENCE*

The Late Bronze Age (1550–1200 bc ) in the Near East was a period of cultural development, international trade and technological innovation, notably in metallurgy and silicate technology. As a spin‐off of the new glass technology, new colorants were also applied to faience glazes presumably to increase their aesthetic value. Here, we report on the presence of chromite minerals in the glaze of a faience vessel from Deir ‘Alla, Jordan, 1200 years earlier than reported so far. Importantly, chromite was not only used as a greyish pigment, but also as a nucleating agent for spherulitic crystallization of augite in the amorphous glaze. These synthetic augite formations give a unique, sparkly appearance to the faience vessel, apparently imitating a metallic look. The making of such an intricate glaze and its contemporary significance reflect not only the high level but also the appreciation of innovation in that region at that time.     

Colour in Minoan faience

The microstructures and chemical compositions of some 15 faience objects from Crete spanning the period from Middle Minoan IIIA through to Late Minoan IA are determined using analytical scanning electron microscopy. The Minoan faience is compared with replicate faience beads produced in the laboratory using various combinations of manganese, copper and iron as colorants. The alkali contents of the replicate beads are varied so that the colorants are present both as ions in a glass phase and as particulate oxides. These data are then used to try to infer the original colour of the Minoan faience, the great majority of which has suffered severe weathering during burial. The results suggest that instead of the present day “hallmark greys and browns” and “subtle greens and blues”, Minoan faience originally exhibited a wide range of colours, including bright turquoise blue, purple and violet, and pale yellow-green and greenish turquoise.     

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.     

河南三门峡虢国墓出土西周——春秋时期费昂斯珠的分析研究

河南三门峡虢国墓是西周晚期至春秋初期的大型邦国墓地,其中M2009的六璜组玉佩上使用了费昂斯珠,作为人工制品的费昂斯珠,其材料组成和工艺特点显示了古代科技水平,利用科学分析揭示其科学价值很有意义。本研究运用扫描电子显微镜(SEM-EDX)、激光拉曼光谱(Raman)分析了四件三门峡虢国墓M2009出土的费昂斯珠的微观结构和成分。研究发现,四件费昂斯珠采用直接施釉法,釉层使用了铜离子着色,可能使用了含氯和铜的矿物。费昂斯珠的内外表层还发现了羟基磷灰石和朱砂,来自于墓主遗骸和墓葬环境。     

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.     

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.     

An early Iron Age assemblage of faience beads from Ashkelon,Israel: chemical composition and manufacturing process

The microstructure and chemical composition of eight faience beads from an early Iron Age (12th century BCE) assemblage found in the ancient city port of Ashkelon (Israel) are determined by means of FTIR spectrometry, pXRF, microRaman and SEM-EDS analysis. The results are compared with published data of Egyptian and Near Eastern artifacts. Each sample exhibits a hue which is obtained by adding a specific colorant to the glazing mixture. A new gray chalcopyrite-manganese-based colorant was identified. Cementation glazing was most likely used in the manufacturing process of the specimens analyzed, except for the blue bead, which is an Egyptian blue frit. The results suggest that these objects represent a unique assemblage, quite different from contemporary Egyptian and Near Eastern materials, and provide new information regarding the Iron Age faience evidence in the southern Levant.     

湖北宜昌万福垴遗址出土费昂斯珠科技分析与研究

湖北宜昌万福垴遗址是西周中晚期至春秋时期的以楚文化为主的遗存,以该遗址M8出土的费昂斯(faience)珠为研究对象,以期通过分析其成分和结构特征并讨论其工艺特征,丰富对长江中下游地区该时期费昂斯的相关认识。本研究使用扫描电子显微镜,分析结果显示费昂斯制品以富钾费昂斯及混合碱费昂斯为主。再依据以往发表的西周时期费昂斯制品的科技研究,结合考古发掘相关材料,试图从费昂斯器物使用方式的角度,窥视其在古人精神文明进程中的角色,反观费昂斯在中原地区的发展脉络。     

甘肃张家川马家塬战国墓地M4出土料珠研究

甘肃马家塬墓地是战国晚期至秦初的西戎墓地,本研究以该墓地M4出土的料珠为研究对象,以期通过分析其成分和结构特征,讨论其工艺特征,以丰富对战国时期费昂斯的相关认识。研究使用扫描电子显微镜-能谱和激光拉曼光谱仪,分析结果显示料珠为费昂斯制品,其釉层玻璃化程度很高,经历腐蚀后熔剂流失严重,明显区别于西周时期的费昂斯制品。同时确定釉层中的一些高锡颗粒物为SnO_2,表明当时在釉层制作中加入锡石或锡粉末。该费昂斯制品应采取了直接施釉或包埋施釉工艺。研究结果可为我国费昂斯发展历程演变提供信息。     

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.     

LEAD ISOTOPIC ANALYSIS OF EIGHTEENTH‐DYNASTY EGYPTIAN EYEPAINTS AND LEAD ANTIMONATE COLOURANTS*

New lead isotopic analyses are presented for lead antimonate coloured glass and faience from Amarna in Middle Egypt and dated to around 1350 BC. When compared to existing data, these suggest that Gebel Zeit on the Red Sea coast of Egypt may be the source for some of the lead antimonate colourants used in Egypt and possibly for the galena kohls of Eighteenth‐Dynasty date as well.     

LUSTRE COLOUR AND SHINE FROM THE OLLERIES XIQUES WORKSHOP IN PATERNA (SPAIN), 13TH CENTURY AD: NANOSTRUCTURE,CHEMICAL COMPOSITION AND ANNEALING CONDITIONS*

Lustre is a medieval ceramic decoration, corresponding to a nanostructured thin layer formed by metallic copper and silver nanocrystals embedded in a glass matrix, which required deep knowledge on the part of the artisans with regard to the raw materials used and the kiln conditions. Their empirical knowledge led to the achievement of colourful lustre decorations ranging from reddish to yellowish or even greenish, some of them with a metallic shine with an associated purplish iridescence. Lustre ceramics dating from the 13th century from the Olleries Xiques workshop in Paterna (Spain) have been studied, linking their chemical composition and nanostructure with their colours and shine. Two kinds of nanostructures are found, yellowish lustre decoration constituted by a silver metal–glass nanocomposite, and reddish lustre decoration constituted by metallic copper nanocrystals and copper oxide nanocrystals; in some cases, metallic copper nanocrystals covered with an oxidized shell of CuO and partly Cu₂O have been found. However, even with significant amounts of copper oxide, the lustre still exhibits a copper metal‐like shine. The bluish iridescence observed at a specular angle in the lustre could not be explained completely by means of the chemical composition, and metallic silver nanoparticle light scattering is proposed as a possible explanation.