Temperature resolved reproduction of medieval luster

Luster is a golden metallic-like decoration produced on glazed ceramics since early Islamic times (Iraq, 9th AD). Luster is obtained by the reaction of a luster paint and the glaze surface over which it is applied. A temperature-resolved XRD experiment was designed to study the high temperature reactions in the luster paint while the luster layer is formed. The luster paint composition has been made based on the original luster paints found during the excavation of the 13th AD workshop site at Paterna (Valencia). The sulfo-reducing atmosphere created during the decomposition of cinnabar promotes the reduction of Cu²⁺ containing compounds to Cu⁺ and the presence of Hg vapours delays the precipitation of metal silver. Moreover, evidence of the formation of a melt in which the copper and silver-containing compounds dissolve has also been obtained. The thickness of the luster paint applied results in the formation of luster layers of different hues and colours. The use of a mixture of copper and silver paint results in the formation of dark-brown luster layer similar to the ones produced in early Islamic times in Iraq and showed also the characteristic blue iridescences. PACS 81.05.Pj; 81.07.-b; 78.67.-n; 82.39.Wj     

Luster decoration of ceramics: mechanisms of metallic luster formation

Luster is a metallic decoration produced since early Islamic times (9th century AD in Iraq). Different studies have shown that medieval lusters are a metal-glass nanocomposite (metal nanoparticles embodied in a silica glassy matrix) obtained from the reaction of a copper and/or silver containing paint with a glaze. The mechanisms of formation of these metallic-like layers are investigated by laboratory reproductions of Medieval luster. Copper and silver lusters are obtained based on different thermal paths and atmospheres, and by using different glaze compositions. The ionic exchange between Cu⁺ and Ag⁺ ions from the luster paint with Na⁺ and K⁺ of the glaze, is demonstrated in either oxidizing or inert atmospheres and at firing temperatures between 500 °C and 600 °C. The reduction of copper and silver to their metallic state is obtained by introducing a reducing gas afterwards. The lusters are non-metallic red ruby copper or green with brown spots silver when developed over alkaline glazes, while they appear coppery and golden metallic when developed over mixed alkaline-lead glazes. SR-XRD, optical absorption and microprobe chemical analysis of the lusters indicate that the total amount of copper and silver, and the nature and size of the nanoparticles, are similar in both cases. Further work is needed to clarify the origin of these differences. PACS 81.05.Pj; 81.07.b; 81.16.Be; 78.67.Bf; 42.50.Fx     

Zelliges from Dar‐El Beïda Palace in Meknes (Morocco): Optical Absorption and Raman Spectrometry

Samples of zelliges, from the Dar‐El Beïda Palace built in Meknes (Morocco) in the 18th century, were studied by optical absorption and Raman spectroscopies. The results obtained by the two techniques were in agreement and show that the glazes of the zelliges are lead oxide–rich in composition. Other phases were also detected, mainly the SnO₂ cassiterite opacifier for the white glaze, and heamatite (α‐Fe₂O₃) in association with magnetite Fe₃O₄ and manganese oxide (MnO₂) for the brown glaze. For the blue and green glazes, the elements responsible for the coloring are cobalt (Co²⁺) and copper (Cu²⁺), respectively.     

Characterization of pottery from Republic of Macedonia II. Raman and infrared analyses of glazed pottery finds from Skopsko Kale

Byzantine and Ottoman pottery shards from Skopsko Kale, Republic of Macedonia (27 samples) were analyzed by infrared (IR) and micro‐Raman spectroscopies. IR spectroscopy provided data for assessing the firing temperature of the ceramic body as well as the basic mineralogical composition, while micro‐Raman spectroscopy was used for studying the glazes as well as for estimating the mineralogical composition of the ceramic body. The firing temperature of the Byzantine pottery was more uniform and ranged between 700 and 800 °C. In the case of the Ottoman pottery, a clear distinction between two different firing temperatures in the samples was made, thereby dividing them into two groups (700–800 and 800–900 °C). According to the previously established relationship between glaze composition and Raman parameters, the glazes in all analyzed samples were found to be lead‐based, with firing temperature below 700 °C. A total of 25 different mineral phases was identified in the body of the ceramics. Some pigments were also identified in the pottery glazes. Oleic acid (oil) and apatite residues (protein?) were identified in one sample. Copyright © 2009 John Wiley & Sons, Ltd.     

An assessment study of tiles from Topkapı Palace Museum with energy‐dispersive X‐ray and Raman spectrometers

A limited number of studies concerning Ottoman ceramic technology have been performed using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. The discovery of the ceramics, which were described as ‘Iznik’, at excavation sites outside of the city of Iznik, caused disagreements over the exact origin of Iznik products. In this study, bodies, glazes, and pigments of 46 tile/ceramic shards of unknown origin, which were supplied from the vaults of Topkapı Palace Museum, and two reference tile fragments, known as Kütahya products, supplied from the demolished Surp Krikor Lusavoriç church and, additionally, two Iznik reference tiles were examined using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. Results of both techniques were evaluated together for the first time to determine the power of nondestructive Raman spectroscopy technique in differentiation of Ottoman tiles. In this work, bodies of the Kütahya tiles were found to be different than Iznik and Tekfur stone‐paste bodies, which are rich in clay rather than quartz. Two different lead‐alkali glaze compositions were found for Kütahya tiles; one was rich in PbO (over 35%) and the other one was rich in alkali (PbO less than 25%). Barite inclusions were detected in the bodies and in the glazes of some Ottoman tiles, which could be the fingerprint for the Kütahya products. It was found that the under glaze red decoration is essentially a mixture of hematite and quartz in different proportions. Shades of red decoration mainly depend on the amount of hematite in the mixture. Sixteenth century tomato red decoration contains more quartz compared with 17th century dark red decoration. This study showed that a similar technology was also applied at Kütahya in the 16th century. A linear correlation was found between the position of the Raman intense stretching peak Q₃ and lead oxide content of lead‐alkali glazes, which could allow for the differentiation of Ottoman tiles based on the nondestructive Raman analysis. This study provides an important additional reference data and discussion for the Ottoman tiles. Copyright © 2011 John Wiley & Sons, Ltd.     

Heterogeneous distribution of metal nanocrystals in glazes of historical pottery

It has been recently shown that lustre decoration of medieval and renaissance pottery consists of silver and copper nanocrystals, dispersed within the glassy matrix of the ceramic glaze. Lustre surfaces show peculiar optical effects such as metallic reflection and iridescence. In many cases, lustre appears overlapped to colored drawings. Here we report the findings of a study on glazes, pigments and lustre of several shards belonging to Deruta and Gubbio pottery of XVI century. The components of glazes and pigments have been identified. Lustre is confirmed to be characterised by silver and copper metal nanocrystals inhomogeneously dispersed in the glassy matrix of the glaze. In the case of lustre overlapped to colored decorations, we found two contradictory cases. The first consists of a lustre surface successfully applied over a blue smalt geometrical drawing. The second consists of a lustre surface, unsuccessfully applied over a yellow lead-antimonate pigment. The yellow pigment hinders the formation of lustre and removes crystals of tin dioxide, normally present in the glaze as opacifier.     

Applications of a synergic analytical strategy to figure out technologies in medieval glazed pottery with “negative decoration” from Italy

Glazed pottery with “negative decoration” samples, dating back to the twelfth to thirteenth century ad and coming from three sites along the Adriatic coast, Siponto, Egnatia and Trani (Southern Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Optical microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy, X-ray diffraction and micro-Raman spectroscopy investigations were carried out on ceramic bodies, pigments and glazes of the fragments. We aimed to outline the technological features, define the nature of decorations and coatings—glazes and engobes—and look for clues to hypothesize provenance. Results obtained show clear differences in raw materials and production technology between the impressed ceramic of Islamic tradition and the incised one of Byzantine tradition. Regarding the latter, evidences of a non-local origin can be found in the compositional diversity of raw materials used for the ceramic bodies of fragments decorated with spiral and pseudo-kufic motifs, which stressed the use of clays so far not recorded in Apulia. At the same time, at least in the case of Siponto, the compositional similarity of both ceramic bodies and materials used under the glaze for impressed ceramic and painted polychrome ceramics (RMR and protomaiolica), more likely local production, could suggest that both were produced in the same workshops.     

XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th–13th century)

It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag⁺, Cu⁺ and Cu²⁺ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag⁺ and Cu⁺ ions can be present. The achievement of metallic Cu and the absence of Cu²⁺ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.     

Some aspects of the characterization of decorations on ceramic glazes

From antiquity, glazes have been one of the techniques used for decorating ceramics. Potters took advantage of the optical properties of these glazes to improve the quality of the object, especially to obtain an appearance or some characteristics that had commercial success. This is why it is important to know the reasons of the visual appearance of glazes. In this paper we present some aspects of the characterization of lustre, one of the on-glaze decorations that results in a more spectacular visual effect, as a microstructure, its composition, its raw materials and some technological aspects of its production. Lustre is a three-dimensional heterogeneous structure, where copper and silver nanoparticles play the most important role, but also alkali elements in the glaze and other components of raw lustre pigments. Lustre properties are determined by copper and silver composition and by distribution and dimension of these metallic nanocrystals in the decoration layer. PACS 61.46.+w; 68.37.Hk; 68.37.Lp; 81.05.-t; 79.60.-i; 81.07.-b ; 78.67.Bf; 81.05.Kf; 81.05.Je     

Characterisation of decorations on Iranian (10th–13th century) lustreware

It has been recently shown that lustre decoration of Medieval and Renaissance pottery consists of silver and copper nanoparticles, dispersed within the glassy matrix of the ceramic glaze. Lustre surfaces show peculiar optical effects, such as metallic reflection and iridescence. Here we report the findings of a study on lustred glazes of several shards belonging to Iranian pottery of the 10th and 13th centuries, decorated on both sides. Two different glazes, depending on the side of the sample, have been identified. Different lustre chromatic effects are characterised by the relative presence of silver- and copper-metal nanoparticles dispersed in the glassy matrix. PACS 61.46.+w     

Composition analysis of medieval ceramics by laser-induced breakdown spectroscopy (LIBS)

Laser-induced breakdown spectroscopy (LIBS) technique is expected to be one of the most preferred techniques in archaeology research since it does not disrupt the structural and chemical form of archaeological samples, and it is considered virtually nondestructive analysis method. In this work, LIBS is used for analyses of glaze, paint, and clay of medieval ceramics collected from East Plain Cilicia, Osmaniye Province during archaeological survey. Transparent glazed and colour-painted ceramics of the Islam and Byzantine pottery traditions are analysed to detect distinctive and common features of the chemical compositions of their glazes. The spectral lines of Islamic and Byzantine glazes indicate that their structures are same. However, strontium (Sr) is determined in the transparent glaze of Islamic ceramics. Elemental composition and homogeneity of paint on one of the sample are determined by LIBS analysis. Colour changes are related with composition differences of the paint content in the archaeological ceramic. In addition, the clay classification of archaeological ceramics taken from the Yap?l?p?nar mounds, Ta?l?höyük mounds, and Ören?ehir ancient sites is done using PCA and PLS-DA chemometric techniques. According to the results of the classification, Yap?l?p?nar mounds terracotta ceramics differ from those of Ta?l?höyük and Ören?ehir ancient sites.     

Copper red glazes: a coating with two families of particles

In order to explain the origin of the deep red color of copper glazes on ceramics, a ceramist has elaborated, by firing under reducing atmosphere, a significant number of tiles. The analysis of the structure and composition of a representative sample by transmission electron microscopy and electron energy loss spectroscopy, followed by an optical characterization and an optical modeling using the radiative transfer approach (four-flux model), have enabled a comprehensive explanation of the origin of the color in these glazes: the presence of two families of copper nanoparticles in the vitreous matrix. The first, purely absorbing, of diameter 10–50 nm, essentially creates color by a subtractive process. The second, due to its larger diameter, 100 nm or more, mainly acts on color by scattering of the visible light. Both act competitively in the layer. A color chart of all the hues which can be reached by this technique has eventually been theoretically calculated.     

The use of micro-XRD for the study of glaze color decorations

The compounds responsible for the colors and decorations in glass and glazed ceramics include: coloring agents (transition-metal ions), pigments (micro- and nanoprecipitates of compounds that either do not dissolve or recrystallize in the glassy matrix) and opacifiers (microcrystalline compounds with high light scattering capability). Their composition, structure and range of stability are highly dependent not only on the composition but also on the procedures followed to obtain them. Chemical composition of the colorants and crystallites may be obtained by means of SEM-EDX and WDX. Synchrotron radiation micro-X-ray diffraction (SR-micro-XRD) has a small beam size adequate (10 to 50 microns footprint size) to obtain the structural information of crystalline compounds and high brilliance, optimal for determining the crystallites even when present in low amounts. In addition, in glass decorations the crystallites often appear forming thin layers (from 10 to 100 micrometers thick) and they show a depth-dependent composition and crystal structure. Their nature and distribution across the glass/glaze decorations gives direct information on the technology of production and stability and may be related to the color and appearance. A selection of glass and glaze coloring agents and decorations are studied by means of SR-micro-XRD and SEM-EDX including: manganese brown, antimony yellow, red copper lusters and cobalt blue. The selection includes Medieval (Islamic, and Hispano Moresque) and Renaissance tin-glazed ceramics from the 10th to the 17th century AD.     

历代定窑白瓷的EDXRF和XAFS分析

定窑是我国宋代五大名窑中唯一以生产白瓷而闻名于世的窑厂,其高超的刻印花纹技术及首创的支圈覆烧工艺,对国内外许多窑场产生了深远的影响。采用(energy dispersive X-ray fluorescence, EDXRF)探索了历代定窑白瓷的组成配方,并采用X射线吸收精细结构(XAFS)法分析了瓷釉中Fe元素的价态,以探讨定窑白瓷的相关烧制工艺。研究发现,定窑白瓷瓷胎具有典型北方瓷器“高铝低硅”的特征,并在瓷胎中特意添加了富含CaO的矿物原料,对瓷胎的烧结有一定的促进作用。瓷胎中的TiO₂应主要是高岭土原料中的杂质。定窑白瓷瓷釉具有“高钙高镁”特征,基本属于钙镁釉或钙镁碱釉。其瓷釉配方中应含有一定量的白云石或滑石。瓷釉中K₂O的含量逐步增加,反映了定窑瓷釉由钙镁釉向钙碱釉发展演变的过程。此外,根据瓷釉中的Al₂O₃,MnO和P₂O₅等含量的特征,可以推测釉料配方中应添加了草木灰和高岭土。由XAFS分析结果可知,晚唐五代时期定窑白瓷釉中Fe3+比例最高,金代次之,宋代最低,不同时期定窑白瓷皆是在还原气氛中烧成。宋金时期定窑白瓷白中泛黄可能由于燃料煤中富含的硫在燃烧过程中与瓷釉反应,生成Fe-S化合物所致。     

Micro‐Raman and infrared analysis of medieval pottery findings from Braničevo,Serbia

A selection of Byzantine table pottery (17 samples) dating from the period between the beginning of the 12th century and the first half of the 13th century, discovered at Braničevo in Serbia, were analysed by Fourier transform infrared, micro‐Raman and scanning electron microscopy with energy dispersive spectroscopy and petrography analysis. The aim of the investigation was to determine the chemical and mineralogical composition of the body and of the glaze and thus to determine the production technology. Fourier transform infrared spectroscopy provided data for estimating the firing temperature and the basic mineralogical composition, and micro‐Raman spectroscopy was applied to study and characterise both the glaze and the body of the analysed sherds. It was found that noncalcareous clays, characterised by a rich mineral assemblage, were fired at temperatures between 700 and 900 °C. Oxidizing atmosphere was applied in the production of the red colour pottery. The dark and grey coloured paste of one group of sherds was produced by firing organic matter‐rich clays in a reducing environment. The main type of transparent glaze was identified as lead‐rich, and two samples were alkali–lime glazed. Copyright © 2011 John Wiley & Sons, Ltd.     

富铁原料对铁系析晶釉的影响机制初探

黑釉瓷是我国古代最普遍的色釉瓷品种之一,由于原料易得,故各地都有烧造,尤其在宋代得到迅猛发展.目前,在古代黑釉中已发现α-Fe2 O3,ε-Fe2 O3,Fe3 O4等多种铁的氧化物析晶,但关于富铁原料对晶体种类的影响机制却鲜有报道.因此,本研究以汝州大峪青石头、红石头和杭州紫金土作为研究对象,采用超景深显微镜、X射线...     

Tentative differentiation between Iznik tiles and copies with Raman spectroscopy using both laboratory and portable instruments

Iznik tiles dated from the 16th century, copies of tiles and pottery of Théodore Deck from the 19th century and also tiles without any information on their origin were analyzed with both laboratory and portable Raman instruments. As the original tiles are generally fixed on the walls of historical buildings, the portable Raman spectrometer is more convenient for the analysis but the information obtained from the spectra is not very useful because of the medium resolution and complex baseline of the instrument in spite of its speed and ease of use. The Raman signature of the glazes is the most pertinent and easily accessible fingerprint of the artifacts. The differentiation between Iznik ceramics and other samples could be made with Raman spectrometers, according to the specific signature of Si O stretching and bending bands of Iznik glazes. Copyright © 2009 John Wiley & Sons, Ltd.     

Nondestructive on‐site identification of ancient glasses: genuine artefacts,embellished pieces or forgeries?

A selection of 23 rare glass objects, mostly enameled, of various provenance and age, from the 5th century BC to the 19th century AD including the Western and Islamic Middle Ages but with a focus on 16th–18th century Venetian and French ‘façon de Venise’ artefacts, have been studied on‐site at the Sèvres museum or at the laboratory. The Raman signatures of the transparent or opacified glass matrix and of enameled decorations are discussed and compared to those previously recorded on ceramics and stained glasses. The Raman parameters allow discrimination between 2 groups (with some variations) of glass bodies, belonging to mixed Ca–Na and Ca‐containing Na‐rich silicates, with some exceptions. Most enamels are instead lead‐based glasses, but we also found enamels having a composition close to that of the glass body. Most of the pigment signatures are similar to those recorded on ceramic glazes, which proves the link between the two technologies. A particular emphasis was given to the identification of white opacification techniques. Very specific signatures could question the authenticity of some artefacts, and at least in two cases, arguments have been found to identify a fake or embellished artefact. Copyright © 2008 John Wiley & Sons, Ltd.     

Reactivity of chromium-based pigments in a porcelain glaze

This paper presents a comprehensive investigation at the microscopic scale of various pigments composed of chromium from the French ‘Manufacture de Sèvres’ to establish the origin of color in glazes. Electron microscopy coupled with X-ray diffraction allows the determination of the microstructure and composition of the crystalline phases after firing. X-ray absorption spectroscopy reveals subtle changes in the medium-range ordering around Cr with high spatial resolution, in the pigment grain or at the pigment/glass interface. Principal results indicate systematic and common changes whatever the pigment types: (i) Cr-enrichment for the final crystals, that controls the coloration of the glaze, (ii) migration of specific elements such as Al or Zn from the pigments to the amorphous part of the glaze, and (iii) crystallization of anorthite in the near proximity of the altered Cr-bearing crystalline pigments.