João Pedro Veiga

© 2016, Springer-Verlag Berlin Heidelberg.The glaze and in-glaze pigments of the historical nineteenth-century glazed tiles from the Pena National Palace (Sintra, Portugal) were characterized using a multi-analytical approach. Chemical composition and microstructural characterization were ascertained by µ-PIXE, µ-Raman, optical microscopy and VP-SEM–EDS. The manufacturing technique and colour palette in these tiles were found to be close to the ceramic pigments used in traditional majolica. The blue and purple colours derive from cobalt oxide and manganese oxide, respectively. A mixture of Pb–Sn–Sb yellow with cobalt oxide and iron oxide was used for green and dark yellow, respectively, while grey tonalities consist of a complex mixture of cobalt oxide, manganese oxide and Pb–Sn–Sb yellow in different proportions. Results obtained allowed the determination of the oxides and elements used in pigments as well as production techniques, resorting to traditional majolica manufacture, although the tiles were produced by the end of the nineteenth century.

Bluish-grey limestones have been extensively used as ornamental stones for decoration purposes in buildings, as well as in works of art, and accordingly, have been the target of intense exploration. In Portugal, the Jurassic limestone massif known as the Maciço Calcário Estremenho (MCE), has been the source of grey-coloured ornamental stones, namely the Azul Valverde (one of the most well-known bluish-grey limestones) and Atlantic Blue varieties, both of which may undergo colour changes in outdoor environments. In this sense, it is important to understand the sudden colour change from bluish-grey to yellow/beige in the same limestone block in a quarry, or even, what happens to the colour when polished limestone is placed outdoors. This study was undertaken using various techniques, namely XRF (X-ray fluorescence spectrometry), XRD (X-ray diffraction), SEM (scanning electron microscopy), DTA–TG (differential thermal analysis/thermogravimetry) and colourimetry. Synchrotron radiation was also used at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) where XANES (X-ray Absorption Near Edge Structure) spectra at Fe K-edge were collected to ascertain the speciation state of Fe in different coloured zones of the limestone, previously checked by EDXRF (energy dispersive X-ray fluorescence). The presence of Fe2+ and Fe3+ are responsible for the greyish and yellow/brown colour, respectively. On the other hand, the UV radiation from the sun causes a quickened and severe bleaching/fading on the dark blue/grey polished limestone.

Glass samples with a molar composition (64+x)ZnO-(16-x)B2O3-20SiO2, where x=0 or 1, were successfully synthesized using a melt-quenching technique. Based on differential thermal analysis data, the produced glass samples were submitted to controlled heat-treatments at selected temperatures (610, 615 and 620{\{}$\backslash$textdegree{\}}C) during various times ranging from 8 to 30h. The crystallization of willemite (Zn2SiO4) within the glass matrix was confirmed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Under specific heat-treatment conditions, transparent nanocomposite glass-ceramics were obtained, as confirmed by UV-vis spectroscopy. The influence of temperature, holding time and glass composition on crystal growth was investigated. The mean crystallite size was determined by image analysis on SEM micrographs. The results indicated an increase on the crystallite size and density with time and temperature. The change of crystallite size with time for the heat-treatments at 615 and 620{\{}$\backslash$textdegree{\}}C depended on the glass composition. Under fixed heat-treatment conditions, the crystallite density was comparatively higher for the glass composition with higher ZnO content. {\{}©{\}} 2016.

© 2016 Elsevier B.V. All rights reserved.Different glasses based on the ZnO-B2O3-SiO2 system, with a ZnO content ≥ 60 mol{%} and a fixed SiO2 content (20 mol{%}), were synthesised using a melt-quenching method. Glass samples with zinc oxide concentrations as high as 65 mol{%} were prepared successfully without deteriorating the glass-forming ability. The glass samples were submitted to controlled heat-treatments, and the effect of the ZnO/B2O3 molar ratio on the formation of crystalline phases within the glass matrix was investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). DTA results indicated that the glass transition and the onset crystallization temperatures of the studied glasses tended to increase with the increment on the ZnO/B2O3 ratio. XRD data showed that the zinc binary crystalline phases, willemite (Zn2SiO4), a zinc orthosilicate, and zinc borate (Zn3B2O6) could be present in the crystallized glasses, depending on the heat-treatment conditions. The formation of willemite was promoted by an increasing ZnO/B2O3 ratio. Microstructural observations performed by SEM indicated that under controlled experimental parameters (glass composition, heat-treatment temperature and time) the precipitation of nanocrystals within the glass matrix can be achieved, resulting in transparent and translucent willemite glass-ceramics.

© 2016 Taylor {&} Francis.A laboratory-based methodology was designed to assess the bioreceptivity of glazed tiles. The experimental set-up consisted of multiple steps: manufacturing of pristine and artificially aged glazed tiles, enrichment of phototrophic microorganisms, inoculation of phototrophs on glazed tiles, incubation under optimal conditions and quantification of biomass. In addition, tile intrinsic properties were assessed to determine which material properties contributed to tile bioreceptivity. Biofilm growth and biomass were appraised by digital image analysis, colorimetry and chlorophyll a analysis. SEM, micro-Raman and micro-particle induced X-ray emission analyses were carried out to investigate the biodeteriorating potential of phototrophic microorganisms on the glazed tiles. This practical and multidisciplinary approach showed that the accelerated colonization conditions allowed different types of tile bioreceptivity to be distinguished and to be related to precise characteristics of the material. Aged tiles showed higher bioreceptivity than pristine tiles due to their higher capillarity and permeability. Moreover, biophysical deterioration caused by chasmoendolithic growth was observed on colonized tile surfaces.

This paper presents a comprehensive study of the evidence for ancient tin mining at the Ervedosa mine (Vinhais, Portugal). The geological context of the site indicates a rich cassiterite (SnO2) deposit, which was subject to mining in the twentieth century. Some ancient mining and ore processing stone tools were recovered during the twentieth century mining operations, namely one hammer, one pounder, one flat anvil and five small tools used both as pounders and crushing anvils, evidencing prehistoric mining activities. XRF and SEM–EDS chemical analyses were performed on primary and secondary cassiterite samples from the mining site, demonstrating the abundance and chemical heterogeneity of the tin (Sn) ores. The stone tools can be ascribed to Bronze Age or, at the latest, Early Iron Age (2nd millennium to the first half of 1st millennium BCE) by comparison with similar tools from other Iberian and European archaeological contexts. High-resolution photogrammetric 3D models of the tools are made available in this study. The historical descriptions of the findings and the research made on the technical archives about the mine allowed correlating the tools to mining in a primary context, focused on rich quartz veins in granitic or greisen bedrock, rather than mining in a secondary context. XRF and SEM–EDS analyses performed on the stone material and on surface adherences support their identification as specific types of hard rocks, such as granite, amphibolite and quartzite, and allowed the detection of Sn-rich adherent particles, confirming their use for Sn-material processing. The potential relation between the cassiterite resources and the local later prehistoric (Bronze Age to Early Iron Age) settlement pattern is also discussed. The results raise awareness and provide relevant data about the existence of tin mining in primary contexts during later prehistoric times in the NW Iberian Peninsula.