R.J.C. Silva

An efficient non-mediated amperometric biosensor for nitrite determination

In this paper we propose the construction of a new non-mediated electrochemical biosensor for nitrite determination in complex samples. The device is based on the stable and selective cytochrome c nitrite reductase (ccNiR) from Desulfovibrio desulfuricans, which has both high turnover and heterogeneous electron transfer rates. In opposition to previous efforts making use of several redox mediators, in this work we exploited the capacity of ccNiR to display a direct electrochemical response when interacting with pyrolytic graphite (PG) surfaces. To enable the analytical application of such bioelectrode the protein was successfully incorporated within a porous silica glass made by the sol-gel process. In the presence of nitrite, the ccNiR/sol-gel/PG electrode promptly displays catalytic currents indicating that the entrapped ccNiR molecules are reduced via direct electron transfer. This result is noteworthy since the protein molecules are caged inside a non-conductive silica network, in the absence of any mediator species or electron relay. At optimal conditions, the minimum detectable concentration is 120 nM. The biosensor sensitivity is 430 mA M(-1) cm(-2) within a linear range of 0.25-50 microM, keeping a stable response up to two weeks. The analysis of nitrites in freshwaters using the method of standard addition was highly accurated.

Characterisation of Late Bronze Age large size shield nails by EDXRF, micro-EDXRF and X-ray digital radiography

In the present study six exceptional large size metallic nails, a dagger and a sickle from the Late Bronze Age archaeological site of Figueiredo das Donas (Central Portugal) have been analysed by EDXRF, micro-EDXRF and X-ray digital radiography for the study of material composition and technology of fabrication. The combination of these analytical and examination techniques showed that all artefacts are made of bronze with As, Sb and Pb impurities, and that the nails were most likely manufactured using the casting-on technique. These results reinforce the use of binary bronze by Late Bronze Age in the region, and the incorporation of new fabrication technologies that resulted from ancient spheres of interaction.

First Results from the ESCA Microscopy Beamline on ELETTRA

The results of the first experiments with test samples, tool steel and polycrystalline Sn carried out with the scanning photoemission microscope built on the ELETTRA storage ring in Trieste are presented and discussed. The scanning photoemission microscope uses a zone plate optical system for demagnification of the photon beam to submicron dimensions. The present performance of the microscope in photoemission allows elemental and chemical mapping and small-spot photoelectron spectroscopy with lateral resolution better than 200 nm. The reported results show how photoemission microscopy can distinguish the spatial distribution of carbide phases with different Fe content at the surface of a tool steel and the correlation between inhomogeneous oxidation of a polycrystalline Sn sample and its grain structure

Multifocus Optical Microscopy Applied to the Study of Archaeological Metals

Studies on cultural metal artifacts can benefit greatly from microscopy techniques. The examination of microstructural features can provide relevant information about ancient manufacturing techniques, as well as about corrosion/degradation processes. In the present work, advantages of the use of multifocus imaging techniques in optical microscopy for the study of archaeological metals are presented. An archaeometallurgical study of a large collection of bronzes demonstrates the possibility of a microstructural study with no need for sample removal, which is a great advantage in the study of cultural objects. In addition, the study of mounted samples illustrates the advantages of the multifocus technique in the examination of particular corrosion features, with the possibility of three-dimensional reconstructions.

Orientalizing Artifacts from Fraga dos Corvos Rock Shelter in North Portugal

An unusual set of metallic artifacts with orientalizing character, attributed to a late period of the Late Bronze Age (LBA), was found in a shelter in Northern Portugal. Conventional and micro-energy dispersive X-ray fluorescence (XRF) analyses have been performed to determine the metal composition. The microstructures of some artifacts have also been studied under optical and scanning electron microscope (SEM). The results show that most of the items are made of a copper–tin alloy with low lead content and show a recrystallized grained microstructure.

Corrosion behaviour of aluminium syntactic functionally graded composites

Syntactic Functionally Graded Metal Matrix Composites (SFGMMC) are a type of composites reinforced by microballoons exhibiting a graded reinforcement distribution. These materials constitute a promising new generation of lightweight structural materials for aerospace, marine and shielding/insulation applications. In this work, A356 alloy reinforced with silica-alumina microballoons (SiO2-Al2O3) was processed by casting techniques. The influence of the microballoon distribution gradient on the corrosion behaviour of the composite was investigated by potentiodynamic polarisation and Electrochemical Impedance Spectroscopy (EIS). Composite surfaces were analysed before and after testing by Optical Microscopy (OM) and Scanning Electron Microscopy (SEM) to determine the influence of microstructural changes.

Structural characterisation of NiTi thin film shape memory alloys

Currently, microactuators are being developed using shape memory alloys (SMAs), which allow simple design geometries and provide large work outputs in restricted space. Several techniques have been used to produce NiTi shape memory alloy thin films, but from the practical point of view, only the sputter deposition method has succeeded so far. Vacuum evaporation of NiTi binary alloy entails the potential problem of the evaporation rates of each component not being the same due to differences in vapour pressure. Aiming to study the possible applications of SMAs to microfabrication, NiTi thin films were produced at CENIMAT by sputter and vacuum evaporation using raw materials from different sources. The films were analysed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) at room temperature, as well as in situ high temperature, in order to characterise the temperature ranges at which the different structural transformations occur.

Spectroscopic ellipsometry study of amorphous silicon anodically oxidised

In this work, spectroscopic ellipsometry was used to characterise oxide films produced by anodic oxidation of amorphous silicon using an ethylene glycol (0.04 M KNO3) solution. The data obtained show that the growth of the oxide is not only a function of the voltage applied, but also of the current density and of the time process. An empiric model based on a power law is proposed for the growth of the oxide using, as parameters, the voltages and the time process. The oxide produced shows porosity of approximately 12%, which can be reduced down to 6% under well-controlled growth conditions.

Primary bioreceptivity of limestones used in southern European monuments

Abstract Different Mediterranean Basin limestones, like Calcário Ançã (Portugal), Calcário Lioz (Portugal), Piedra San Cristobal (Spain), Piedra Escúzar (Spain) and Pietra di Lecce (Italy), have been widely used as building materials in the European architecture. The aim of this study was focused on biodeterioration, mainly on evaluation of the primary bioreceptivity of those materials. A set of samples was inoculated with a cultured photosynthetic biofilm under laboratory conditions. Several assessment tools were applied to monitor the colonization overtime of the different lithotypes. After 3 months of incubation the colonization occurred endolithically in some lithotypes, namely Piedra San Cristobal and Piedra Escúzar. Spectrophotometric determination of chlorophyll a was a useful analytical technique to achieve the total amount of photosynthetic biomass on rock substrates, demonstrating that Piedra Escúzar and Calcário Lioz were the highest and lowest bioreceptive lithotypes, respectively. Microscopic and image analyses were essential to understand the stone colonization process and its pattern of distribution. Physical stone parameters and exposure conditions were shown to play an important role in the establishment and development of photosynthetic colonization.

Microstructure Interpretation of Copper and Bronze Archaeological Artefacts from Portugal

In the present paper, a selection of micrographs showing some typical microstructures and corrosion layers developed in copper and bronze alloys from different archaeological contexts will be discussed. Metallurgic interpretation of the microstructures observed, based in the proper binary equilibrium phase diagrams is presented. Micro-EDXRF and SEM-EDS analysis were carried out to assess the alloy composition and to contribute to the understanding of the corrosion processes occurred during the long periods of burial of the archaeological metals. Examples of surface decuprification, strong intergranular corrosion, cuprite under green corrosion layers and copper redeposition indicate particular corrosion processes. The presence of copper oxides, sulphides inclusions, lead globules and porosities is also documented.