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In this work recently produced and commercially available glazed ceramic object with metallic lustre decoration was studied by using a spectroscopic ellipsometer with rotating compensator. The thickness and metal content of the surface lustre layers are determined by ion beam analytical techniques, i.e., Rutherford backscattering spectrometry and external beam particle-induced X-ray emission and the results were utilized in the construction of multilayer optical models for the evaluation and interpretation of the spectroellipsometric measurements.

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Lusters are composite thin layers of coinage metal nanoparticles in glass displaying peculiar optical properties and obtained by a process involving ionic exchange, diffusion, and crystallization. In particular, the origin of the high reflectance (golden-shine) shown by those layers has been subject of some discussion. It has been attributed to either the presence of larger particles, thinner multiple layers or higher volume fraction of nanoparticles. The object of this paper is to clarify this for which a set of laboratory designed lusters are analysed by Rutherford backscattering spectroscopy, transmission electron microscopy, x-ray diffraction, and ultraviolet-visible spectroscopy. Model calculations and numerical simulations using the finite difference time domain method were also performed to evaluate the optical properties. Finally, the correlation between synthesis conditions, nanostructure, and optical properties is obtained for these materials.
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Astudy has been realised to elucidate the first step of lustre production in Italy. With this aim in mind, an investigation was carried out on an emblematic lustred object: Baglioni’s albarello. It is conserved at Louvre museum and it is considered as one of the very first examples of lustred object produced in Italy. The characteristics of the lustred film have been determined, identifying interesting aspects that may be used to scientifically confirm the origin of this object. This study was completed by the investigation of other objects: a not lustred albarello, still decorated with the coat of arms of Baglioni’s family and a lustred plate with the coat of arms of the Montefeltro family. The two Baglioni’s albarelli are stylistically and historically considered as produced in one of the numerous workshops of Deruta. The origin of the Montefeltro’s plate, although from central Italy, is not precisely attested. In order to acquire more information, clarifying the origin and place of production of these objects, a comparison of their physico-chemical characteristics with results obtained and already published on different well-attested productions, such as Islamic, Hispano-Moresque and Italian, was carried out. For what concerns the museum objects, the use of non-destructive investigation techniques was mandatory. For this reason, ion beam techniques as PIXE and RBS have been used at AGLAE facility, as well as a new X-ray micro-diffraction equipment, at C2RMF. Moreover, the results were compared with data obtained on shards of certain production origin, by means of chemometric techniques. Some hypothesis concerning the place of production of the examined objects have been formulated.
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This paper describes research on the technological evolution of glazed ceramics with a metallic lustre decoration starting from their emergence in the Near East until the Hispano-Moresque productions. That research covers the main known Islamic production sites and periods: Abbasid (Mesopotamia); Fatimid (Egypt); Timurid, Mongol, and Safavid (Iran); Ayyubid and Mamluk (Syria); Nasrid and Hispano-Moresque (Spain). It was allowed by the access to more than hundred full preserved objects or fragments supplied by French national museums (Mus\'ee du Louvre DAI, Mus\'ee national du Moyen Age, Mus\'ee national de C\'eramique). The characterisation of the composition and structure of the ceramics and of their decoration is mostly done through non-destructive analyses methods. The thickness and metal content of the surface lustre layers are quantified thanks to ion beam analyses performed on a particle accelerator: PIXE (particle-induced X-ray emission) for the terracotta and glazes composition and RBS (Rutherford backscattering spectrometry) for the thickness and metal content of the lustre surface layers. The preliminary results show that the features of the decorated ceramics have undergone dramatic variations when transmitted from a production to another, not only, as expected, in the composition of terracotta and glazes, but also in the thickness, the structure and the composition distribution of the lustre layers.
In ion beam analysis (IBA) the depth profiles are extracted from the experimentally determined energy profiles. The spectra, however, are subject to finite energy resolution of both extrinsic and intrinsic origin. Calculation of those effects such as instrumental beam, geometry and detection-related energy and angular spreads as well as energy straggling, multiple scattering and Doppler effects in the sample itself is not trivial, especially since it involves treatment of non-independent random processes. A proper account for energy spread is vital in IBA not only for correct extraction of elemental and isotopic depth profiles from the measured spectra, but already prior to data acquisition, in optimising experimental conditions to reach the required depth resolution at a certain depth. After a short review of the literature on the different energy spread contributions experimental examples are given from resonance, RBS, elastic BS and ERDA practice in which an account for energy spread contributions is essential. Some further examples illustrate extraction of structural information (roughness, pore size, etc.) from elaborated depth resolution calculation for such layer structures.
It is a crucial problem to obtain the number of incident particles in MeV energy ion beam techniques. To solve this problem a simple but powerful method, the transmission Faraday cup is suggested. A rotating beam chopper periodically detects the beam current. To eliminate the disturbing current of the secondary electrons it is surrounded on both sides by a Faraday cup. Additional mechanical shields as well as electrostatic and magnetic fields keep away the charged particles different from the ions of the incident beam. The (p, gamma) reaction and He RBS test measurements show that the particle number reproducibility is better than 1% and 2%, respectively. The reproducibility in the charge measurement was found to be ~ 0.6%.
In the early 9th century AD ancient potters of Iraq discovered that after firing some copper oxides and silver salts with clay, iron oxides and some sulphur compounds applied on a ceramic glaze produced a beautiful layer with a wide range of colours, from reddish to yellowish or even greenish, and some with a characteristic metallic copper or purplish shine. Modern studies of these layers showed that they are formed by nanocrystals of copper and silver embedded in a glass matrix. Some attempts have been performed to understand ancient lustre coloration and characteristic gloss but have failed to give a clear correlation between chemical composition and colour, and generally make some assumptions on the shape and the size of the nanoparticles and the lustre nanostructure. The aim of this paper is to establish a basis for understanding lustre nanostructure linked to its optical properties from a sequence of lustre reproductions on traditional lead glazed tiles. These modern lustre decorations have been studied by means of optical microscopy, transmission electron microscopy and electron energy loss spectroscopy, UV-vis spectroscopy, low irradiation angle X-ray diffraction, synchrotron radiation X-ray diffraction and electron microprobe analysis. These results show that changes in the lustre nanostructure affect the glaze colour and shine during the lustre formation process. Lustre nanostructure showed crystal size range as a function of depth, that subsequently disappeared followed by an increase of nanoparticles mean diameter and reduction of the interparticle distances. Consequently, the dipole plasmon coupling between copper nanoparticles appeared, and seems to be responsible for the metallic shine and copper metal like coloration of the copper lustre. However, colour from the glaze surface differs when calculated for diffuse or reflected light. Diffuse coloration appears strongly affected by the copper nanocrystals, while specular coloration is not only affected by copper but also by the presence of an inhomogeneous distribution of silver nanocrystals which gives the lustre a characteristic purplish shine. (c) 2006 Elsevier Ltd. All rights reserved.
A metallized glaze, suitable for large-scale production, has been obtained starting from sepiolite-n(Cu, Fe) as a stable vector containing the metal-dispersed nanoparticles and following a conventional fast-firing fabrication route. A small fraction of black carbon (about 4 wt%) was added to the starting mixture of the glaze to avoid oxidation of Cu nanoparticles in the 500°–700°C temperature range. At higher temperature (700°–1190°C), a fraction of the oxygen dissolved in the glassy phase is consumed by the Fe°/Fe2+ and Fe2+/Fe3+ redox reaction. Based on ellipsometric and quantitative optical reflectance measurements, it has been proven that the presence of a minimum concentration of Cu nanoparticles (∼10 vol%) in the top surface glaze layer is a prerequisite to obtain an appropriate metalize glaze.
Non-destructive analysis of precious art objects is an important tool to solve provenance problems or to facilitate restoration. External beam PIXE analysis is one of the most powerful and popular methods used in this respect. The paper summarises the external beam PIXE set-up at the Accelerator Laboratory in Budapest, and two selected applications are described. Different parts of a small Cambodian metal sculpture probably made in the 11th century were analysed. It was observed that the sculpture was composed of an iron core and an outer bronze shell. This sculptural technique was well known in the Middle-East but no indication has been found about its use in the Far-East, yet. Before its restoration paint traces on a wooden relief of St. Jerome made by an unknown artist in about 1600 were analysed. Different white and red paints were distinguished at selected points and the presence of titanium on a certain part of the relief was attributed to a repainting in modern times.
Lustre ceramics, found in a workshop located in Triana (Sevilla), have been analysed to determine the composition of glazes including the metallic particle layers giving rise to the lustre effect. PIXE and RBS were used for the elemental composition and the sub-surface concentration profiles, respectively. Copper and silver at the origin of the lustre are detected by PIXE. RBS gives access to the detailed distribution of the elements in the surface layers. The simulation of RBS spectra confirms the occurrence of thin layers (less than 300 nm) containing metallic silver and/or copper. The results are compared with those obtained on other types of lustre ceramics.
In this paper we discuss the connection between the microstructure of a heterogeneous thin film and its macroscopic dielectric response ε. Effective medium theory is developed from a solution of the Clausius-Mossotti problem from basic principles. The solution is generalized to obtain the Lorentz-Lorenz. Maxwell Garnett and Bruggeman expressions. The connection between microstructure and absolute limits to the allowed values of the dielectric response of two-phase composites is reviewed. The form of these limits for two-phase composites of known composition and two- or three-dimensional isotropy can be used to derive simple expressions for ε and also for the average fields within each phase. These results are used to analyze dielectric function spectra of semiconductor films for information about density, polycrystallinity and surface roughness. Examples illustrating the detection of unwanted overlayers and the real-time determination of nucleation growth are also given.
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.
A second X-ray production database is introduced into GUPIX to complement the existing theoretical (ECPSSR–DHS) database and to provide some estimate of analytical uncertainty due to this aspect of GUPIX; it is based on published compilations and analyses of large numbers of measured K and L subshell X-ray production cross-sections. The two databases are compared through analysis of single-element standards and standard reference materials. Good agreement is observed for the case of K X-rays. In contrast, neither the theoretical nor the “reference” database appears to be entirely satisfactory in the case of L X-rays. New work is required on L subshell X-ray production cross-sections using protons. The tools in GUPIX for film thickness determination are expanded, and tested using the two alternative databases.
Since the seventies a large number of computer methods have been developed for data analysis in Rutherford backscattering spectrometry (RBS). A short review of published computer methods for ion scattering is presented. The majority of programs can be divided into two categories: the interactive spectrum synthesis and the spectrum analysis codes. In this paper recent trends and problems in the area of spectrum simulation are presented. I demonstrate the main methods and approaches on our RBX computer program. The program can use any particle-target combination and beam energy between 100 keV and 10 MeV. The calculations and fitting methods of non-Rutherford scattering cross section are included. The contributions from electronic screening, the corrected Bohr straggling and the geometrical straggling are discussed. The useful techniques for extracting an accurate depth-concentration profile directly from RBS or ERDA spectrum are discussed. Some examples of the discussed methods are also given.
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