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     

Production of gold and ruby-red lustres in Gubbio (Umbria,Italy) during the Renaissance period

The aim of this work is to gain a further insight into the knowledge of the production process of lustre-decorated ancient majolicas. Lustre is a sophisticated technique employed in the decoration of majolicas as used in central Italy during the Renaissance period. It consists of a beautiful iridescent gold or ruby-red thin metallic film, containing silver, copper and other substances and obtained in a reducing atmosphere on a previously glazed ceramic. Nowadays, it is not possible to replicate the outstanding results obtained by the ancient ceramicists, since the original recipes were lost. It is quite interesting to study lustre-production technology by means of analytical techniques now employed for advanced research on materials (XRD, ETAAS, ICP-OES, TEM-EDX-SAED and UV-Vis). In this work, we have focussed our attention on ceramic fragments decorated with both gold and ruby-red lustres, which were difficult to obtain due to complex reduction conditions required and which were a prerogative of Gubbio production. The two lustre colours differ in their chemical composition as well in their nanostructure. The presence of bismuth was disclosed and it was ascertained to be a distinctive feature of the Italian production. PACS 78.67.Bf; 81.05.Je; 68.37.Lp; 68.37.Hk; 68.90.+g     

Microchemical investigation on Renaissance coins minted at Gubbio (Central Italy)

The bulk and surface chemical composition of Renaissance coins minted at Gubbio (Central Italy) from 1508 to 1516 and from 1521 to 1538 by Francesco Maria della Rovere is investigated by means of the combined use of different analytical techniques such as scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and optical microscopy (OM). The aim of the work is to determine the bulk chemical composition of these commonly used coins at Gubbio, to ascertain their surface nature and if they were coated by a thin film of silver or other white metals similar to silver.The results indicate that the coins were produced by coating a copper core with a thin film of silver and antimony, and also with lead whose thickness is of a few microns which is now scarcely present because the original silvered surface was almost entirely removed by degradation phenomena. Furthermore, the SEM+EDS results show that the surface content of silver and antimony cannot be attributed to long-term selective corrosion phenomena leaving the coin slightly silver or antimony enriched. Therefore, the presence of silver or apparently silver-like metals i.e. antimony and lead, could be considered as a deliberate surface finishing of the coins obtained via inverse segregation or intentional selective corrosion based on pickling solutions or a combination of them. From a historical point of view the presence of a Ag or Sb film on the surface of the coins discloses the occurrence of a period of economic difficulties. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Italian Renaissance and Hispano-Moresque lustre-decorated majolicas: imitation cases of Hispano-Moresque style in central Italy

An investigation was carried out on Renaissance lustre-decorated majolica shards, found during excavations made in Umbria (central Italy) and defined by experts, on the ground of the surface decoration, as imitations of the Hispano-Moresque style. A comparison between this particular kind of samples, produced in central Italy, and some Hispano-Moresque lustre shards has been performed. The ceramic bodies as well as the lustred surfaces have been analysed by means of several techniques: inductively coupled plasma optical emission spectrometry, X-ray diffraction (XRD), atomic absorption spectrometry with electrothermal atomisation and scanning electron microscopy. By means of XRD analysis the presence of cosalite (Pb₂Bi₂S₅) has been disclosed in the Italian lustre decorations but was not observed in the Hispano-Moresque ones. A hypothesis has been made, considering bismuth as a discriminating element, between lustres produced in central Italy and the Hispano-Moresque ones. We thought that the Italian artisans were able to manage the use of bismuth. Therefore a recipe, quite similar to the one employed by the Spanish artisans, was used by the Italian ceramists if their aim was to imitate the Hispano-Moresque style. Received: 4 November 2002 / Accepted: 6 November 2002 / Published online: 28 March 2003 RID="*" ID="*"Corresponding author. Fax: +39-06/9067-2316, E-mail: pad@mlib.cnr.it     

Characterization of blue decorated Renaissance pottery fragments from Caltagirone (Sicily,Italy)

Renaissance blue decorated pottery fragments from the archaeological site of Caltagirone (Sicily, Italy) were analysed by scanning electron microscopy – energy dispersive X-ray spectrometry (SEM/EDS). The samples were dated back to 16th century AD on the basis of archaeological observations. The micro-chemical analyses were performed on the ceramic body and the surface decorated layer of the samples. Particularly, the investigation was addressed the characterization of the coating blue decorations. The obtained results allowed us to clearly identify smalt as pigment. Also the presence of arsenic (As) was revealed and the Co/As ratio values were calculated and related to the different process used for the pigment preparation. Further spectroscopic analyses, performed through X-ray absorbance spectroscopy (XAS), carried out at the Co K-edge, confirmed the micro-analytical results and permitted us to identify the oxidation form and the local environment of cobalt atoms. PACS  81.05.Mh; 82.80.-d; 68.37.Hk     

How the masters in Umbria,Italy, generated and used nanoparticles in art fabrication during the Renaissance period

Lustre was one of the most sophisticated techniques for the decoration of majolicas during the Renaissance period. Lustre consists of a thin metallic film containing silver, copper and other substances like iron oxide and cinnabar applied in a reducing atmosphere on a previously glazed ceramic. In this way, beautiful iridescent reflections of different colours (in particular gold and ruby-red) are obtained. The characterisation and the study of lustre-decorated majolicas is of great interest for archaeologists, but also offers possibilities for producing pottery with outstanding decoration today, following ancient examples, since nowadays Italian artisans are interested in the reproduction of the ancient recipes and procedures. Moreover, it can even suggest new procedures for obtaining uniform thin metallic films for technological applications. A study has been carried out on ancient lustre layers using numerous different analytical techniques such as XRD, SEM–EDX, TEM–EDX–SAED, ETAAS, ICP–OES, UV–vis reflectance spectroscopy and SAXS. Lustre films were shown to be formed by copper and silver clusters of nanometric dimension. The colour and the properties of the lustre films depend on the elemental composition of the impasto applied to the ceramic surface as well as on other factors like the metallic nanocluster dimension, the firing conditions, the underlying glaze composition and the procedure used. Received: 12 August 2002 / Accepted: 14 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +39-6/9067-2445, E-mail: pad@mlib.cnr.it     

Investigation of surface laser treatment of ancient calcite: the case of the grave in Torricelle (Naples, Italy)

The laser-cleaning technique has been effectively employed in many areas. Recently it has led to a huge development in art restoration. However, this technique must be optimised to remove contaminations and encrustations from surfaces without generating any physical or chemical changes of the original material.Its use has been considered to clean a 4th century B.C. chamber gravesite in Torricelle, near Nola (Naples). The wall painting could not be seen owing to bioorganic surface layer and resinous material originated from surrounding pinewood. In order to evaluate the technique effectiveness we studied the interaction of the light from a Q-switched Nd: YAG equipped with SHG to work at wavelength of 532 nm.Several characterization techniques have been employed to verify the laser effect on the cleaning of the surface versus the operating parameter configuration and to evaluate the possible damages induced by the beam. In particular, micro X-Ray fluorescence (μXRF) provided information on the chemical composition of the clean surface; X-ray microdiffraction (μXRD) was used to identify the phases and their microstructures. These techniques were effective in assessing the quality of the cleaning process and for following the changes in the microstructure of the sample.Preliminary results suggest a possible influence of the laser on the aragonite–calcite transformation. PACS 61.10.Nz; 33.20.Rm; 42.62.-b; 61.66.Fn; 81.65.Cf     

X‐ray fluorescence analysis on a group of coins from the ancient roman city of Tridentum (Trento,Italy)

A group of 83 coins, found in the archeological excavations of the ancient Roman city of Tridentum (Trento, Italy), was studied for the determination of their composition, finalized to their classification and cataloging. The coins, mainly made of copper‐based alloys, were minted between the republican period (II century BC) and the last decades of the western empire (V century AD). The X‐Ray Fluorescence archaeometric analysis has allowed a revision of the typological classification of the coins through the identification of six broad groups, each one characterized by a peculiar composition of the coins in the group. A tentative assignation of all the unreadable coins to one of the groups identified was proposed, in a way that could suggest also a possible dating of these coins. Copyright © 2014 John Wiley & Sons, Ltd.     

A Mössbauer study of an ancient pottery figure (Western-Han dynasty)

The grey pottery figure manufactured in the Western-Han Dynasty (175-118 B.C.) and the clay gathered from the same site of Beidongshan in Xuzhou have been studied by X-ray Diffraction(XRD). X-ray Fluorescence (XRF), and Mössbauer spectroscopy. They were simultaneously fired under the same conditions in different atmospheres at various temperature up to 1100°C. This study deals with the original firing atmosphere, original firing temperature and its provenance. The information mentioned above can be inferred from the method of the refiring pottery and the firing clay. The results of the original firing temperature deduced from both of them are in goodself agreement. It is found that the values of the Mössbauer parameters for the unrefired pottery figure are approximately the same as those for the clay fired at 950°C for five hours in a reduced atmosphere. The XRF analysis confirmed the locality of this pottery figure.     

Determination of the debris produced from poly(ethylene terephthalate) during KrF excimer laser ablation

Pulsed UV laser beams, which are widely used in the processing of polymers, have many advantages because their photon energy is higher than the binding energy of polymers. Fabricating polymers with a UV laser process is faster, cleaner, and more convenient than with other processes. Nevertheless, some problems occur in the precision microprocessing of polymers. For example, the formation and deposition of surface debris, which is produced from the breakdown of either polymer chains or radical bonds.To determine the formation and origin of surface debris, a KrF excimer laser beam (248 nm) was used in the processing of poly(ethylene terephthalate) (PET). The investigation of the debris formation was facilitated by UV-vis spectroscopy, ATR FT-IR spectroscopy, and NMR spectroscopy. The UV-vis absorption peak indicates that the primary chromophore in the PET is benzoate. Furthermore, because benzoate causes the primary absorption, the absorbed energy is transferred by heat generation to an unsaturated ester. The ATR FT-IR spectrometer measurements show that the phenyl systems in the benzoate are demolished by ablation. This phenomenon indicates that the photochemical reaction causes the benzoate bonds to break down, and this breakdown in turn causes the carbonization to leave debris on the PET.     

Transverse-momentum spectra of hadrons produced in central heavy-ion collisions

In-medium effects of transverse-mass distributions of quarks and gluons are considered assuming a possible local equilibrium for colorless quark objects like mesons and baryons created in central AA collisions. It is shown that the average square of the transverse momentum for these partons grows and then saturates when the initial energy increases. Within the quark-gluon string model, it leads to an energy dependence of hadron transverse-mass spectra which is similar to that observed in heavy-ion collisions. A comparison with other scenarios is given. The text was submitted by the authors in English.     

Further study of theE/f 1 (1420) meson in central production

We have studied the reactions \(({{\pi ^ + } \mathord{\left/ {\vphantom {{\pi ^ + } p}} \right. \kern-0em} p})p \to ({{\pi ^ + } \mathord{\left/ {\vphantom {{\pi ^ + } p}} \right. \kern-0em} p})(K\bar K\pi )p\) where the \(K\bar K\pi \) system is centrally produced, at 85 GeV/c and 300 GeV/c using the CERN Omega spectrometer. A spin-parity analysis of theK _S ⁰ K ^± π ^? system shows the presence of a strongJ ^PC=1⁺⁺ signal which we identify as theE/f ₁ (1420) meson. We also find evidence for the decayE/f ₁(1420)→K _S ⁰ K _S ⁰ π ⁰ which determines theC-parity of this state to be positive. Alternative explanations of the data have been tested and ruled out. Hence we obtain the quantum numbers of theE/f ₁ (1420) to beI ^G(J^PC)=0⁺(1⁺).     

Ancient silver extraction in the Montevecchio mine basin (Sardinia, Italy): micro-chemical study of pyrometallurgical materials

Different pyrometallurgical materials such as slags, refractory materials and thermally treated lead ores likely related to smelting and extractive processes and chronologically related to Punic and Roman periods (IV–III BC) have been found at Bocche di Sciria and Conca e Mosu in the Montevecchio mine basin (south western Sardinia, Italy), where archaeological findings and classical authors locate extractive metallurgy activities since pre-Roman times. By means of the combined use of X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectrometry (EDS), selected-area X-ray photoelectron spectroscopy (XPS) and optical microscopy (OM), micro-chemical and micro-structural investigations have been carried out in order to identify the nature of the pyrometallurgical materials, to decipher the processes carried out there and their technological steps and to determine the technological level of competence reached by the ancient metallurgists. The results confirm that the findings can be associated with smelting and extractive processes carried out close to the metal ore deposits first for the argentiferous lead production and, then, for the silver recovery via a cupellation process. Finally, the results disclose the high level of technological competence of the ancient metallurgists able to carry out complex high-temperature processes to treat the argentiferous lead ores and to recover low amounts of silver via high-temperature lead-selective oxidation.     

Mössbauer study of archaeological ceramics from Valle del Alto Sinu (Colombia)

A physico-chemical characterization of ceramic samples from the arachaeological sites of El Cabrero, El Gallo, and El Frasquillo (Valle del Alto Sinú) is presented. Extensive use of Mössbauer spectroscopy data reveals that the currently used typological classification scheme of Dolmatoff is related to the production technology of the different artifacts. In addition, a model for firing conditions for “Rojo Sencillo”, “Tierra Impresa”, “Tierra Incisa”, and “Blanco” types of ceramics is proposed.     

Radioactivity in waters of Mt. Etna (Italy)

Radioactivity in underground waters from Mt. Etna was investigated on the basis of 13 samples. The samples were collected from springs, wells and galleries around the volcano. Water from nine out of thirteen intakes is used for consumption. Activity concentration of uranium isotopes ^234,238U, radium isotopes ^226,228Ra and radon ²²²Rn were determined with the use different nuclear spectrometry techniques. The measurements of radium and radon activity concentration were performed with the use of a liquid scintillation counter. The determination of uranium isotopes was carried out with the use of alpha spectrometry. All samples show uranium concentration above Minimum Detectable Activity (MDA), with the highest total uranium (²³⁴U + ²³⁸U) activity concentration equal to 130 mBq/l. For radium isotopes, all samples except one showed the activity concentration below MDA. Radon activity concentration was within the range from 1 to 13 Bq/l, hence these waters can be classified as low-radon waters.     

Bismuth knowledge during the Renaissance strengthened by its use in Italian lustres production

The knowledge of bismuth during the XV and XVI centuries represents an open question since, according to some authors, this element was confused with lead, tin and silver. On the contrary, G. Agricola (1494–1555), the pioneer of mineralogical science in Europe, in his two works (De Natura Fossilium, Lib X, 1546 and Bermannus Sive De Re Metallica Dialogus, 1528) asserts that bismuth was considered as an element distinct from the other metals at that time. This question gave rise to some interest, and von Lippmann in 1930 wrote a treatise dealing with the history of bismuth between 1400 and 1800. In this work we present the results obtained on Italian and Hispano–Moresque shards studied by means of X-ray diffraction, atomic absorption spectrometry with electrothermal atomisation, inductively coupled plasma optical emission spectrometry and scanning electron microscopy. It seems that our work could provide a new and important contribution to this debate, because we found bismuth in lustre composition of Renaissance shards produced in central Italy. Furthermore, we found that it could also be considered as a discriminating element between Italian and Hispano–Moresque productions, useful to assess their origin. PACS 81.05.Je; 82.80.-d; 61.10.Nz     

Automated SEM-EDS pottery classification based on minero-chemical quantitative parameters: An application on ancient Greek pottery from Adrano (NE Sicily,Italy)

A new SEM-EDS procedure for ancient ceramic classification, based on the automated acquisition and the semiautomated processing of multi-elemental X-ray maps, is described. Based on the detection of each aplastic inclusion, the procedure allows to simultaneously obtain a quantitative evaluation of both the inclusion mineral–chemical composition and the ceramic matrix chemical composition. The two data sets can individually or jointly be subjected to statistical methods. The proposed protocol was applied on a set of 22 samples of black glaze pottery from Adrano (north-eastern Sicily), Hellenistic age (4th to 2nd centuries B.C.). Two main groups emerged from the application of the procedure, mainly distinguished for their quartz–feldspars versus calcium–aluminosilicate relative abundance as the inclusion mineral–chemical composition is concerned and for their matrix SiO₂ versus CaO. The classification based on the inclusion mineral–chemical data obtained with the proposed method mirrors the results from the traditional OM observation, but when the two data sets are simultaneously considered, a subtler differentiation is observed with the separation of one of the groups in two subgroups, allowing to refine the partition.