João Pedro Veiga

Magnetically recyclable magnetite–palladium (Nanocat-Fe–Pd) nanocatalyst for the Buchwald–Hartwig reaction

The immobilization of Pd on the magnetite surface afforded Nanocat-Fe–Pd using inexpensive precursors and its catalytic role in the Buchwald–Hartwig reaction for arylation of amines and amides was investigated; C–N bond formation was achieved in moderate to excellent yields and the catalyst could be separated and recycled up to five cycles by magnetic decantation without a significant loss in yield.

Monitoring the removal of soluble salts from ancient tiles by ion chromatography

The application of ion chromatography, conductometry and total carbon analysis to the study of desalination of 18th century tiles and mortars is described. Ion chromatography is shown to be a simple and adequate technique for the identification and quantitative analysis of ions which are extracted during desalination. Chloride, nitrate, sulphate, carbonate, sodium, potassium, calcium and magnesium were always found in the immersion waters, and occasionally also nitrite and oxalate.

The blue colouring of beryls from Licungo, Mozambique: an X-ray absorption spectroscopy study at the iron K-edge

Abstract The colours of natural and synthetic beryl (ideally Be3Al2Si6O18) have been attributed either to the presence of chromophore ions partially replacing Al and/or Be (Cr3+, Fe2+/3+, Mn2+) or to the occurrence of colour centres related to the presence of multi-atomic groups. However, no full explanation has been proposed for the blue colour in natural beryl gemstones (aquamarine) despite it being well established that bluish-green synthetic aquamarines containing Fe turn blue when heated for 1 h at 400°C. A X-ray absorption near-edge spectroscopy (XANES) study at the Fe K-edge was performed on blue beryl crystals from Licungo pegmatite (Mozambique) to ascertain the speciation state of this colouring element, reported in blue sapphire (ideally Al2O3) as a mixture of Fe2+ and Fe3+ in octahedral coordination. The general trend of the spectra is the same when synchrotron radiation (SR) impinges along the c axis of the hexagonal crystal, as well as along the a axis with c vertical. Conversely, a shoulder in the absorption edge is noticed when the incident beam is perpendicular to c, with this axis horizontal in the polarization plane of the SR beam, a reverse in the relative intensities of the two postedge features is simultaneously observed. Pre-edge features accounting for Fe speciation (valence plus coordination) are identical in all three situations. Considering previous approaches which account for polarization, an explanation is suggested for the special effects observed on the Fe K-edge XANES spectra of analysed blue beryl crystals. Ideas on the origin of the blue colour of this mineral are also presented.

An experimental approach for smelting tin ores from Northwestern Iberia

ABSTRACT In the present work microstructural and chemical analysis of tin and slag that resulted from three smelting experiments reconstructing prehistoric conditions are presented. Cassiterite ores were collected from northwestern (NW) Iberian deposits and were smelted in a small open pit. Results show that the loss in tin can be very high, up to 80%, mainly as a result of volatilization of Sn species. The experiments show that using handmade leather bag bellows and clay tuyeres, temperatures can easily reach >1200°C. The tin produced was a very pure (Sn) solid solution, with the presence of dispersed inclusions or phases of various composition. These included FeSn and FeSn2 intermetallics and small metallic W inclusions. Slags could be grouped into three types based on their physical characteristics, and bulk chemical analysis could relate each type as being a product from the reaction of ore material or a product from the reaction with the crucible material. Generally, it was found that in spite of very low recovery rates, the tin produced by this simple technique would have been adequate for a domestic small-scale production.

An integrated approach for assessing the bioreceptivity of glazed tiles to phototrophic microorganisms

Abstract 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.