Josep Roqué

Mass Spectrometric and Synchrotron Radiation based techniques for the identification and distribution of painting materials in samples from paints of Josep Maria Sert

BackgroundEstablishing the distribution of materials in paintings and that of their degradation products by imaging techniques is fundamental to understand the painting technique and can improve our knowledge on the conservation status of the painting. The combined use of chromatographic-mass spectrometric techniques, such as GC/MS or Py/GC/MS, and the chemical mapping of functional groups by imaging SR FTIR in transmission mode on thin sections and SR XRD line scans will be presented as a suitable approach to have a detailed characterisation of the materials in a paint sample, assuring their localisation in the sample build-up. This analytical approach has been used to study samples from Catalan paintings by Josep Maria Sert y Badía (20th century), a muralist achieving international recognition whose canvases adorned international buildings.ResultsThe pigments used by the painter as well as the organic materials used as binders and varnishes could be identified by means of conventional techniques. The distribution of these materials by means of Synchrotron Radiation based techniques allowed to establish the mixtures used by the painter depending on the purpose.ConclusionsResults show the suitability of the combined use of SR μFTIR and SR μXRD mapping and conventional techniques to unequivocally identify all the materials present in the sample and their localization in the sample build-up. This kind of approach becomes indispensable to solve the challenge of micro heterogeneous samples. The complementary interpretation of the data obtained with all the different techniques allowed the characterization of both organic and inorganic materials in the samples layer by layer as well as to establish the painting techniques used by Sert in the works-of-art under study.

Analytical study of the behaviour of some ingredients used in lustre ceramic decorations following different recipes

Ceramic lustre is a fine decoration obtained by a complex technical process. Although the general production technique is more or less known, it is much more difficult to specify the ingredients mixed in the ancient recipes used to produce lustre and their function during the process, especially components as mercury sulphide and iron oxide. To understand this point, mixtures of the components were previously characterised and tested to see which mixtures resulted in the desired lustre. Synchrotron-Radiation-Source X-ray Diffraction (SRS–XRD) of the fired mixtures was performed to check the changes produced in the ingredients. Also Voltammetry of immobilised Microparticles was applied to the raw pigment powders to obtain information about the redox behaviour. Square-wave voltammetry demonstrates the possibility of different deposits that can be formed in the first steps of the reduction process in the pigment mixture for lustre production, especially those related to solid-form reactions and pigment-electrolyte interactions. Moreover, SR–XRD shows the formation of different crystalline phases at the end of the process, in this case probably also related to gas–solid interactions and to a strong reduction atmosphere.

Islamic and Hispano-Moresque (múdejar) lead glazes in Spain: a technical approach

Abstract Islamic and Hispano-Moresque glazes from the 10th to 15th centuries found in various archaeological sites, most of them workshops, are studied to show the technical evolution of the medieval glazing process. The technology seems to show a simplification: the early Islamic glazes were applied on prefired bodies and after fritting a lead-silica mixture, whereas for the later Islamic productions the raw materials for the lead glazes were not fritted and they were applied over unfired bodies. The same simplified technology was used in the Hispano-Moresque workshops. In the Islamic workshops lead glazes were coloured by adding elements (Fe, Cu, Mn), whereas the múdejar technology simplified the process by using only one recipe to produce pots of different colour. This was achieved by applying the glaze in a different manner (on one side of the pot to obtain yellow or on both sides to obtain green), or using different pastes (already used to produce pottery for different uses). Finally, there are differences between Islamic and Hispano-Moresque tin glazes related to the crystal size of the opacifier (tin oxide crystals), which should indicate some technological differences in temperature, glaze composition and the process to obtain the frits because of the high dependence between viscosity, temperature and crystal nucleation and growth.

Nanoscale partitioning of Ru, Ir, and Pt in base-metal sulfides from the Caridad chromite deposit, Cuba

Abstract We report new results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of platinum-group elements (PGE)-rich base-metal sulfides. The Ni-Fe-Cu base-metal sulfides (BMS) studied are millerite (NiS), pentlandite [(Ni,Fe)9S8], pyrite (FeS2), and chalcopyrite (CuFeS2). These BMS were found forming composite inclusions (<60 μm across) within larger unaltered chromite from the Caridad chromite deposit, which is hosted in the mantle section of the Mayarí-Baracoa Ophiolite in eastern Cuba. Electron probe microanalysis of BMS revealed PGE values of up to 1.3 wt%, except for pentlandite grains where PGE concentrations can reach up to 12.8 wt%. Based on the amount of Ru, two types of pentlandite are defined: (1) Ru-rich pentlandite with up to 8.7 wt% of Ru and <3.5 wt% of Os, and (2) Ru-poor pentlandite with Ru <0.4 wt% and Os <0.2 wt%. Ru-rich pentlandite contains Ir-Pt nanoparticles, whereas the other sulfides do not host nanometer-sized platinum-group minerals (PGM). The Ir-Pt inclusions are found as: (1) idiomorphic, needle-shape (acicular) nanoparticles up to 500 nm occurring along the grain boundaries between Ru-rich pentlandite and millerite, and (2) nanospherical inclusions (<250 nm) dispersed through the matrix of Ru-rich pentlandite. HRTEM observations and analysis of the selected-area electron diffraction patterns revealed that nanoparticles of Ir-Pt form domains within Ru-rich pentlandite. Fast Fourier transform analyses of the HRTEM images showed epitaxy between Ir-Pt domain and PGE-poor millerite, which argues for oriented growth of the latter phase. These observations point to sub-solidus exsolution of the Ir-Pt alloy, although the presence of nanospherical Ir-Pt inclusions in some other grains suggest the possibility that Ir-Pt nanoparticles formed in the silicate melt before sulfide liquid immiscibility. These Ir-Pt nanocrystals were later collected by the sulfide melt, preceding the formation of Ru-rich pentlandite. Early crystallization of the Ru-rich pentlandite and Ir-Pt nanoparticles led to the efficient scavenging of PGE from the melt, leaving a PGE-poor sulfide residue composed of millerite, pyrite, chalcopyrite, and a second generation of PGE-poor pentlandite.