Anne Bouquillon

Alteration of lead silicate glasses due to leaching in heated acid solutions

Leaching processes were studied for lead glasses having a composition similar to that of certain archaeological materials (66 wt% PbO) to determine the mechanism of the structural evolution. The glasses were leached in two static acid media (HNO3 and CH3COOH, pH 2) at 90 °C for 35 days. Analyses were undertaken of the leaching solution (pH, inductive coupled plasma–atomic emission spectrometry) and of the bulk glass (scanning electron microscopy–energy dispersive X-ray spectrometry, Rutherford backscattering spectrometry, Raman). Results show that in both acids, up to 1 day a silicon-rich surface layer is formed via typical diffusion processes. This process continues up to 35 days in the case of acetic acid. In nitric acid, one observes a stabilisation of this layer and an increase in the metal content. In both cases, Raman data are used to interpret the structural evolutions which occur in the ‘gel’ phase.

PIXE and μ-PIXE analysis of glazes from terracotta sculptures of the della Robbia workshop

A series of PIXE analyses has been performed on glazes from terracotta sculptures of the Italian Renaissance and on reference standards. The problems related to the investigation of such heterogeneous materials are discussed and the experimental uncertainties are evaluated, for each element, from the PIXE analysis of standard glasses. Some examples from artefacts coming from Italian collections are given. This research has been conducted in the framework of the COST-G1 European action.

Gold like lustre: nanometric surface treatment for decoration of glazed ceramics in ancient Islam, Moresque Spain and Renaissance Italy

Abstract Lustre is one of the most fascinating surface decorative effects produced on glazed ceramics. This technique seems to have been born in the ninth century in factories created by the Arabs during their conquests in the Orient (Mesopotamia, Egypt and Persia). Arab potters spread their knowhow all over the Mediterranean basin, especially Spain. Italian Renaissance potters succeeded in applying it to their production. The technique is based on a specific firing of the glazed pottery in a reducing atmosphere in the presence of metallic salts. The result is a surface layer with a metallic appearance, exhibiting various colours, from gold to brown or red. This paper provides the chemical nature and the physical structure of ancient gold like lustre layers and compares them with contemporary lustres produced by a Spanish craftsman reproducing the traditional Islamic techniques. Various analytical investigations (atomic force microscopy, high resolution SEM, particle induced X-ray emission, Rutherford backscattering, TEM, X-ray induced photoelectron spectroscopy, time of flight SIMS and grazing X-ray diffraction) were carried out as well as investigations into the coloured appearance by spectrophotometry. The results show that the lustre layer consists of silver and copper particles of nanometric dimensions dispersed in a glassy matrix. A model of the lustre formation is proposed wherein the development of a new superficial glaze is described. Comparison between ancient and modern production shows how the techniques have varied through the ages.