Characterisation and reproduction of yellow pigments used in central Italy for decorating ceramics during Renaissance

This study presents the characterisation of prototypical yellow pigments used during the Renaissance period in Italy and the successful reproduction of homologous materials in accordance with the ancient recipes. Moreover, a large number of yellow decorative layers of Sicilian ceramic artefacts dated back from 13th to the 19th century have been selected and the main chemical, structural and minero-petrografic features have been studied by X-ray diffraction, optical microscopy and scanning electron microscopy-energy dispersive spectrometry. These results have been compared with literature data of some yellow decorations of Renaissance ceramics made in central Italy. Comparison has also been made with homologous materials that have been successfully reproduced in accordance with ancient recipes described by Cipriano Piccolpasso in the textbook: “I Tre Libri dell’Arte del Vasaio” using the same ingredients proposed by this artist. Such yellow materials reproduce the typical yellow colorants used by craftsmen of relevant sites for ceramic fabrication in central Italy, namely Città di Castello, Urbino and Castel Durante, during the 16th century.Comparative arguments have shown some intriguing differences that are indicators of both technological transfer processes between central and southern Italy as well as of some local implementations likely due to specific raw materials locally available. PACS 81.05.Je; 82.80.-d; 68.37.Hk; 68.55.-a; 61.66.Fn; 61.10.Nz     

景德镇釉上彩绘瓷器釉上彩的Raman与EDXRF分析

釉上彩绘瓷器是我国古陶瓷中重要品类之一,具有极高的艺术价值和科学价值。采用拉曼光谱和能量色散X射线荧光分析等无损技术手段,对陶瓷釉彩的元素组成和物相组成综合分析,探讨了人们广为关注的景德镇元、 明和清代釉上彩绘瓷若干典型颜料种类的组成配方及其相应的呈色机制。研究发现景德镇古代红绿彩、 五彩、 粉彩等标本中的深红釉上彩料为赤铁矿着色,黄彩为铅锡黄着色,胭脂红彩则由含量不到0.1%的金所着色,绿料皆为二价铜离子着色。研究结果也进一步说明了Raman和EDXRF这两种无损、 微区分析技术的有效结合可以在深化陶瓷类文物的分析研究,尤其是针对图案交错复杂的多种彩绘颜料研究方面起到重要的作用。     

Pre-columbian nanotechnology: reconciling the mysteries of the maya blue pigment

The ancient Maya combined skills in organic chemistry and mineralogy to create an important technology – the first permanent organic pigment. The unique color and stability of Maya Blue can be explained by a new model where indigo dye fills the grooves present at the surface of palygorskite clay, forming a hydrogen bonded organic/inorganic complex. Existing theory assumes the dye is dispersed inside the channels of an opaque mineral. Based on data from thermal analysis, synchrotron and neutron diffraction, ESEM and chemical modelling calculations, our new concept of Maya Blue structure resolves this contradiction and suggests some novel possibilities for more durable, environmentally benign pigments. PACS 61.66-f; 62.23.St; 61.66.Fn; 61.66.Hq     

Minero-petrographic, thermal and microchemical investigation of historical mortars used in Catania (Sicily) during the XVII century A.D.

The combination of X-Ray Diffraction (XRD), Scanning Electron Microscopy-Energy Dispersive Spectrometry (SEM-EDS), Differential Thermal Analysis-Thermogravimetry (DTA-TG) and Optical Microscopy (OM) has been used to study several different ancient mortars recovered in the S. Nicola Church (built after the devasting earthquake of the 1693) and other historic buildings located in the historical center of Catania (Eastern Sicily). Investigations have been focused on the identification of raw materials mixed in the different mortars and their provenance as well as on the study of the relevant technological aspects of manufacturing processes. Minero-petrographic data have often shown that local volcanic raw materials have been used as aggregate fractions and, in particular, a new volcanic material, the so-called ghiara, has been largely adopted for the construction of the walls of the monuments after the earthquake. It is worthy to note that ghiara is a by-product of erupted magma during the impressive Etna eruption of 1669, which almost completely covered the centre of Catania. The following reaction with the soil gave rise to the formation of a layer of this typical ochre-coloured material. Moreover, the precise provenance of the ghiara has been determined trough geological surveys of the most important historic quarries. Results have allowed the identification of exploited sources of ghiara.Furthermore, combination of SEM-EDS results and thermal information have indicated the hydraulic nature of the mortars due to the formation of hydraulic phases at the binder-aggregate interface. It, therefore, is due to the fact that the ghiara has slight pozzolanic properties.Present data have an important role for any satisfactory reproduction of the ancient manufacturing techniques to be used for the restoration of the S. Nicola Church. PACS 81.70.Pg; 82.80.d; 61.10.Nz; 61.66.Fn     

新郑西亚斯东周玉器材料属性与加工工艺的科技分析

中国玉文化源远流长，治玉工艺经过各个时代的不断发展和完善，在一定程度上能反映古代社会生产力发展水平及文化、贸易、技术交流等信息。利用能量色散型X射线荧光光谱（EDXRF）、激光拉曼光谱（LRS）、超景深光学显微系统（OM）等分析技术，结合硅胶覆膜微痕复制技术，对河南省新郑西亚斯东周墓地出土的一批玉器进行科技分析。首先利用化学成分和物相结构分析技术确定了玉器材质的矿物属性，其次利用显微分析技术表征了玉器表面及穿孔内部和印模的加工痕迹，特别是阴刻纹饰和穿孔微痕特征，最后探讨了玉器样品的材料属性和加工工艺两者之间的联系。化学成分和物相结构分析结果表明，所分析的西亚斯东周玉器材质丰富，主要矿物组成有滑石、透闪石、水晶、云母等。玉器表面纹饰微痕特征分析表明，所分析玉器阴刻工艺采用了两种加工工具，分别是砣具和手持硬质工具。穿孔微痕分析特征表明，钻孔包括单面钻孔和双面/多面钻孔两种方式，钻孔工艺则有实心钻、管钻等。部分玉器钻孔形状和内部微痕特征表明，尽管均采用了实心钻工艺，但所采用的实心钻头在形状上存在差异，同时，也存在是否配合解玉砂进行钻孔的差异。不同材料属性的玉器采用了不同的加工工艺。滑石质玉器，莫氏硬度1，器型主要为玉片饰，其表面阴刻纹饰主要采用手持硬质工具进行刻画，钻孔主要采用了双面钻孔方式，并使用了实心钻头未添加解玉砂进行加工，钻头形状可能为圆锥状；云母质玉器，莫氏硬度2~3，器型主要为玉玦片饰，纹饰采用了砣具添加解玉砂的加工工艺，钻孔方式为单面钻孔，采用了管钻工艺。透闪石型玉器，莫氏硬度5~6，器型主要为玉片饰，表面纹饰采用砣具配合解玉砂砣刻，以双面钻孔的方式为主，钻孔工艺为实心钻头配合解玉砂工艺，钻头形状与滑石类样品一致，为圆锥状。水晶质玉器，莫氏硬度7，均为珠饰，表面无纹饰，钻孔方式为双面/多面钻孔，钻孔工艺为实心钻配合解玉砂工艺，且钻头可能为圆柱形。研究结果表明，玉器表面纹饰所采用的阴刻工艺和钻孔工艺，与玉器本身的材料属性、器型等存在密切关系。     

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.     

The use of atmospheric pressure laser desorption mass spectrometry for the study of iron-gall ink

The study of ancient works of art is a very challenging task, mainly due to the impossibility of applying experimental approaches that could damage anyhow the object from which analytical information has to be obtained. Spatially resolved analytical methods have significantly enhanced our capacity to study ancient material since they cause minimal and at times no damage to the studied object. Unfortunately, only a few analytical techniques operating within the requested spatial resolution are applicable for the investigation of the organic components of artistic and archaeological objects. In this work, iron-gall ink was prepared according to ancient recipes and its composition was evaluated by AP/MALDI-MS. The latter is demonstrated to be a very valuable tool for the study of the organic components of ancient works of art as it combines the advantages of the vacuum MALDI-MS analytical approach to the possibility of analysing samples in air. In situ analyses were also carried out by analysing strokes of ink directly from paper and parchment. PACS 82.80.Ms; 61.66.Hq; 87.14.-g     

Polychrome glass from Etruscan sites: first non-destructive characterization with synchrotron μ-XRF, μ-XANES and XRPD

This work is devoted to the characterization of a suite of very rare, highly decorated and coloured glass vessels and beads from the VII to the IV century BC. The most serious difficulty in developing this study was that any sampling – even micro-sampling – was absolutely forbidden. As a consequence, the mineralogical and chemical nature of chromophores and opacifiers present in these Iron Age finds were identified by means of the following synchrotron-based, strictly non-destructive, techniques: micro X-ray fluorescence (μ-XRF), Fe K-edge micro X-ray absorption near edge spectroscopy (μ-XANES) and X-ray powder diffraction (XRPD). The μ-XRF mapping evidenced high levels of Pb and Sb in the yellow decorations and the presence of only Sb in the white and light-blue ones. Purple and black glass show high amounts of Mn and Fe, respectively. The XRPD analyses confirmed the presence of lead and calcium antimonates in yellow, turquoise and white decorations. Fe K-edge μ-XANES spectra were collected in different coloured parts of the finds, thus enabling the mapping of the oxidation state of these elements across the samples. In most of the samples iron is present in the reduced form Fe²⁺ in the bulk glass of the vessels, and in the oxidized form Fe³⁺ in the decorations, indicating that these glass artefacts were produced in at least two distinct processing steps under different furnace conditions. PACS  29.20.Lq; 81.80.Kf; 61.10.Ht     

A multi-analytical approach for the study of the pigments used in the wall paintings from a building complex on the Caelian Hill (Rome)

In the present study, shards from Roman wall paintings (from the end of the first century to the fourth century A.D.) decorating the domus below the Basilica of SS. John and Paul on the Caelian Hill (Rome), were analyzed in order to identify the pigments used. The analytical techniques employed for the characterization of the pigments were the scanning electron microscope coupled with an energy dispersive spectrometer (SEM-EDS) and infrared spectroscopy (ATR and micro ATR). While SEM-EDS allowed to perform a qualitative analysis of the material, by FT-IR chemical species have been identified. The pigments identified were those mentioned in the literature for the Imperial Roman fresco painting: different types of ochre (yellow and red), mixtures containing lead, green earths and precious pigments such as cinnabar and Egyptian blue. They were often used as mixtures and the use of the most valuable pigments (cinnabar and Egyptian blue) were found in the most ancient rooms.     

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.     

On the comparative study of three silver coins of the IIIrd century B.C. minted in Korkyra, Dyrrachion and by the Illyrian king Monounios

The microstructure of three silver coins dating back to the IIIrdcentury B.C. from the Illyrian King Monounios, the ancient Greek city of Dyrrachion and the ancient Greek city of Korkyra was studied with XRF, PIXE, microhardness measurements, and light and electron microscopy. From this investigation it turned out that these coins have different chemical compositions and different microstructures. The as-collected data allow the determination of a possible minting method. The Korkyra coin was probably hot-worked or cold-worked and annealed, while after cooling, it was cold-worked again. The coin of King Monounios is composed by equi-axed grains which are overrun by slip lines. Consequently it is likely that this coin was casted and then cold-struck. Finally the coin from Dyrrachion is characterized by small-sized grains and strain lines and as a result this coin was probably cold-struck. PACS 07.60.Pb; 78.70.En; 68.37.Ef; Hk; Lp; Nq; 61.66.Bi; 61.72.Mm     

Evolution of past enamel technology and metal conservation issues: the case of two Byzantine style bindings

The results of a Raman spectroscopic study of the cloisonne’ and basse‐taille enamels, which beautify two Byzantine style bindings from the Marciana Library (Venice), namely the Lat. III,111 and the MsGR.I.53 codexes, are presented in this work. The first binding dates back to the 13th century and was subject to an early restoration work in the 14th century, when new enamels substituted four originals. The second binding, from the 15th century, shows a lower number of enamels, all originals, and with a larger color palette. The white and yellow enamels of both codexes were successfully characterized and the red ones, where hematite was not used. Interestingly the white and yellow color of the 13th century enamels of the Lat. III,111 codex has been obtained by an ancient technique of the glass technology, which was already obsolete in the 13th century, and is based on the use of calcium antimonate and Naples yellow. The white color in the other binding's enamels have been instead obtained by using cassiterite, according to the tradition of the time. Cassiterite was also mixed to Naples yellow in the enamels of the MsGR.I.53 codex, to change the yellow hue. The identification of agents determining some colors is instead uncertain or not feasible by Raman spectroscopy. The transparency of the 14th century enamels of the Lat. III,111 codex has allowed the comparison of metal degradation below the enamels and in regions exposed to the atmosphere. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman spectroscopy (SERS) on silver colloids for the identification of ancient textile dyes. Part II: pomegranate and sumac

The effectiveness of surface‐enhanced Raman spectroscopy (SERS) spectrocsopy on Ag colloids has been successfully demonstrated for the identification of a yellow dye in two ancient wool threads found in the Royal Tumulus of In Aghelachem, Libyan Sahara, belonging to the Garamantian period (2nd–3rd century A.D.). High‐performance liquid chromatography (HPLC) highlighted the presence of ellagic acid in the extracts from the threads, excluding other chromophores. This result, together with the abundance of malic acid detected by gas chromatography‐mass spectrometry (GC‐MS), suggested the possible use of pomegranate rind or sumac berries as source of the yellow dye, both plants being documented in the Fezzan area during the Garamantian period. HPLC analyses and SERS spectra acquired on the extracts of the ancient threads were therefore compared with those obtained from pomegranate and sumac extracts of the corresponding fruits and reference dyed wool samples, allowing us to identify the yellow dye as deriving from pomegranate (Punica granatum L.). SERS spectra of ellagic acid and dyes extracted from pomegranate rind and sumac berries are reported here for the first time. A methodological improvement is also presented, based on the use of NaClO₄ as aggregating agent, that leads to a significant increase of the signal‐to‐noise ratio in the SERS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

The cleaning of early glasses: investigation about the reactivity of different chemical treatments on the surface of ancient glasses

X-ray photoelectron spectroscopy (XPS) has been used to evaluate the reactivity of different chemical cleaning procedures on the surface of archaeological glasses. Investigations were performed on a series of Roman glass samples coming from Sicilian excavations. The ancient freshly fractured glass samples were subjected to different cleaning protocols such as piranha solution (solution of sulphuric acid and hydrogen peroxide) and EDTA/ammonia and citric acid/ammonia solutions at different pH values. The atomic concentrations of alkaline and alkaline-earth ions, measured using XPS spectra acquired at the surface of all the samples, revealed that, in acid solution, the reactivities of the EDTA and citric acid solutions were higher than that of the piranha solution. Moreover, in alkaline conditions, the reactivities of the chelating agent/ammonia solutions seem to be very high and effective in taking out alkaline and alkaline-earth ions and in destroying the external glassy structure with the formation of a silica gel thin film. PACS  61.43.Fs; 81.65.Cf; 61.66.Fn; 82.80.Pv     

Crocoite PbCrO4 and mimetite Pb5(AsO4)3Cl: rare minerals in highly degraded mediaeval murals in Northern Bohemia

Mural paintings of exceptional quality, which can be discerned in spite of their extensive mechanical damage and colour fading, have been uncovered in the church of St. Gallus in Kuřívody, Northern Bohemia, dated to the second half of the 13th century. Materials research with particular use of portable X‐ray fluorescence, Raman micro‐spectroscopy and powder X‐ray micro‐diffraction revealed the presence of rare pigments. In Kuřívody, it is only a second identification of intentionally used yellow mineral crocoite (PbCrO₄) in European art. Its identification is facilitated by providing a very good Raman scattering, even when present in small amounts in fragmentarily preserved colour layers. Light yellow mimetite (Pb₅(AsO₄)₃Cl) was never before mentioned as intentionally used pigment in Europe. Its finding in Kuřívody, however, corresponds more likely with undesirable physical–chemical conditions causing its formation by alteration of orpiment (As₂S₃) and minium (Pb₃O₄). Obtained results highlight the importance of Raman spectroscopy for direct identification of mineral pigments in low concentrations, which may be crucial for interpreting cultural heritage objects in historical context. By materials, the almost forgotten paintings in Kuřívody can be seen as outstanding and rare example of ancient artistic tradition that has spread to Europe from Mediterranean in early Middle Ages. After all, mineral crocoite was already used by ancient Egyptians to paint sarcophagi and degraded orpiment decorates the walls of the Nefertari's tomb in Thebes. Copyright © 2014 John Wiley & Sons, Ltd.     

Micro‐structural characterization of red decorations of red and green color porcelain (Honglvcai) in China

Red and green color porcelain (Honglvcai) is an important type of polychrome porcelains invented in North China during Song and Jin Dynasties. One of its great successes is its red decoration painted on the surface of glaze and fired at low temperature. Raman spectroscopy and X‐ray absorption fine structure (XAFS) at Fe K‐edge, were used to characterize the microstructure of red decorations from Song and Jin Dynasties to Ming Dynasty. The analyzing results on eight samples showed that hematite (α‐Fe₂O₃) was the main chromogenic substance in red decorations from different dynasties, which indicated a similar technological skill among the investigated samples. The oxidation state of iron in red decorations was determined to be mainly trivalent, indicating that red decorations were fired under oxidizing atmosphere. Besides, it was found that the hematite (α‐Fe₂O₃) in red decorations had a distorted structure, which was presumed to be an important factor influencing the color of red decorations. Copyright © 2009 John Wiley & Sons, Ltd.     

NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying ¹H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k     

Weathering of gilding decorations investigated by SR: development and distribution of calcium oxalates in the case of Sant Benet de Bages (Barcelona,Spain)

In this paper seventeenth century gilded paintings from the crypt of Sant Benet de Bages, a medieval monastery in the Catalonia region of Spain, near Barcelona, have been studied. Cross sections from two different gilded decorations were studied by means of optical microscopy and electron microscopy and EDS to determine the statigraphy and elemental composition, and by means of FTIR coupled to a microscope to determine the binding media associated to each layer. These preliminary results demonstrated that gilded decorations were made by the application of a gold foil on a mordant substrate on a gypsum base, while the mouldings of the vaults seem to be gilded on a bol with a glaze on top of the gold leaf. It is interesting to notice that the first remained unaltered, while the gilded vault mouldings look almost black, due to the darkening of the organic material. To elucidate the causes involved in the darkening of the sample from the vaults a set of synchrotron μXRD and μFTIR experiments have been carried out on these samples at the ESRF (ID18F and ID21, respectively). High brightness and small spot working conditions revealed the development and distribution of calcium oxalates in the binding media, which seem to be responsible for the darkening. Results point out the fact that weddellite (CaC₂O₄·2H₂O) is the phase formed in those layers where organic material has also been identified or at least it would be supposed to be by bibliographic sources and not necessarily those superficial as it would have been suggested due to the similarities with patinas formation. PACS 78.30-j; 68.37.Hk; 61.10.Nz     

Pair correlations and interaction energies in FePd single crystal

Diffuse neutron scattering measurements were carried out in a FePd single crystal at 1020 K in the (100) and (110) reciprocal planes. The diffuse intensity is nearly symmetric, showing that the static displacements are small. A set of displacement and short-range order parameters have been fitted to the measured data using a least square procedure. The short-range order parameters have been used in conjunction with an inverse cluster variation method to deduce the pair interaction energies. A strong attractive interaction between second nearest-neighbour like atoms is found.Received: 11 August 2004, Published online: 12 October 2004PACS: 61.12.Ex Neutron scattering - 64.60.Cn Order-disorder transformations - 61.66.Dk Alloys     

Technological features of ‘gnathia’ pottery

‘Gnathia’ pottery samples, dating back to the mid‐fourth and third century BC, from the archaeological site of Egnazia (Fasano, Brindisi, Italy) have been characterised from the physical‐chemical, mineralogical and morphological points of view. Optical and scanning electron microscopy, X‐ray energy‐dispersive spectroscopy and X‐ray diffraction analyses have been carried out on the ceramic body, black gloss, white, yellow and red over‐paintings of fragments, with the aim of outlining technological features and defining the nature of coatings and decorations. Analytical results confirm from both a technological and morphological/decorative point of view the close relationship between ‘Gnathia’ pottery and red figured pottery, particularly with the Apulian red figured from which it takes its inspiration. At the same time the experimental results highlight shared characteristics and differences with both Attic and Apulian red figured productions. The biggest difference is in the utilisation of the ‘ingobbio rosso’ layer that covers the ceramic body. This does not seem to be based on aesthetic grounds, as in the case of Apulian red figured pottery, but on application of acquired production processes, since ‘Gnathia’ pottery was made in the same workshops as red figured pottery. Copyright © 2009 John Wiley & Sons, Ltd.