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- Contribution to the Understanding of the Colour Change in Bluish-Grey LimestonesPublication . Silva, Teresa; De Oliveira, Daniel Pipa Soares; Veiga, JP; Lisboa, Jose; Carvalho, Jorge; Barreiros, M. Alexandra; Coutinho, ML; Salas-Colera, Eduardo; Vigário, RogérioABSTRACT: 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 Macico Calcario 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.
- 3DOM ceria ecoceramics from sustainable cork templates for solar thermochemical CO2 splittingPublication . Pullar, Robert C.; Novais, Rui M.; Caetano, Ana P. F.; Barreiros, M. Alexandra; Abanades, Stéphane; Almeida Costa Oliveira, Fernando
- A review of solar thermochemical CO2 splitting using ceria-based ceramics with designed morphologies and microstructuresPublication . Pullar, Robert C.; Novais, Rui M.; Caetano, Ana P. F.; Barreiros, M. Alexandra; Abanades, Stéphane; Oliveira, Fernando Almeida CostaABSTRACT: This review explores the advances in the synthesis of ceria materials with specific morphologies or porous macro- and microstructures for the solar-driven production of carbon monoxide (CO) from carbon dioxide (CO2). As the demand for renewable energy and fuels continues to grow, there is a great deal of interest in solar thermochemical fuel production (STFP), with the use of concentrated solar light to power the splitting of carbon dioxide. This can be achieved in a two-step cycle, involving the reduction of CeO2 at high temperatures, followed by oxidation at lower temperatures with CO2, splitting it to produce CO, driven by concentrated solar radiation obtained with concentrating solar technologies (CST) to provide the high reaction temperatures of typically up to 1,500 degrees C. Since cerium oxide was first explored as a solar-driven redox material in 2006, and to specifically split CO2 in 2010, there has been an increasing interest in this material. The solar-to-fuel conversion efficiency is influenced by the material composition itself, but also by the material morphology that mostly determines the available surface area for solid/gas reactions (the material oxidation mechanism is mainly governed by surface reaction). The diffusion length and specific surface area affect, respectively, the reduction and oxidation steps. They both depend on the reactive material morphology that also substantially affects the reaction kinetics and heat and mass transport in the material. Accordingly, the main relevant options for materials shaping are summarized. We explore the effects of microstructure and porosity, and the exploitation of designed structures such as fibers, 3-DOM (three-dimensionally ordered macroporous) materials, reticulated and replicated foams, and the new area of biomimetic/biomorphous porous ceria redox materials produced from natural and sustainable templates such as wood or cork, also known as ecoceramics.
- Looking into historical cracks analysing repaired silver objects by electron microscopyPublication . Tissot, Isabel; Barreiros, M. Alexandra; Lemos, Manuel; Tissot, MatthiasABSTRACT: The identification of structural alterations of silver alloy objects of cultural interest is essential to assess their state of conservation and define maintenance programmes. Alterations induced by previous repair and cleaning actions strongly affect the conservation condition, influencing the type and extension of conservation procedures. The detailed analysis of ancient repairs is a subject to be investigated. In this work, we show the potentialities of scanning electron microscopy in the characterisation of structural repairs and their influence on the conservation state of silver objects. The study of distinct silver objects dated to the 16th and 18th centuries allowed us to show, among others, the non-intentional dealloying of copper due to the use of acid solutions in surface cleanings and cracks resulting from incorrect handling. The data collected by microscopic examination contributed to the definition of preservation and maintenance methodologies applied to those silver objects.
- Sub-Bandgap Sensitization of Perovskite Semiconductors via Colloidal Quantum Dots IncorporationPublication . Ribeiro, Guilherme; Ferreira, G.; Menda, U.D.; Alexandre, Miguel; Brites, Maria João; Barreiros, M. Alexandra; Jana, S.; Águas, Hugo; Martins, Rodrigo; Fernandes, P.A.; Salomé, P.M.P.; Mendes, M.J.ABSTRACT: By taking advantage of the outstanding intrinsic optoelectronic properties of perovskite-based photovoltaic materials, together with the strong near-infrared (NIR) absorption and electronic confinement in PbS quantum dots (QDs), sub-bandgap photocurrent generation is possible, opening the way for solar cell efficiencies surpassing the classical limits. The present study shows an effective methodology for the inclusion of high densities of colloidal PbS QDs in a MAPbI3 (methylammonium lead iodide) perovskite matrix as a means to enhance the spectral window of photon absorption of the perovskite host film and allow photocurrent production below its bandgap. The QDs were introduced in the perovskite matrix in different sizes and concentrations to study the formation of quantum-confined levels within the host bandgap and the potential formation of a delocalized intermediate mini-band (IB). Pronounced sub-bandgap (in NIR) absorption was optically confirmed with the introduction of QDs in the perovskite. The consequent photocurrent generation was demonstrated via photoconductivity measurements, which indicated IB establishment in the films. Despite verifying the reduced crystallinity of the MAPbI3 matrix with a higher concentration and size of the embedded QDs, the nanostructured films showed pronounced enhancement (above 10-fold) in NIR absorption and consequent photocurrent generation at photon energies below the perovskite bandgap.
- CdTe nano-structures for photovoltaic devicesPublication . Corregidor, V.; Alves, L. C.; Franco, N.; Barreiros, M. Alexandra; Sochinskii, N. V.; Alves, E.CdTe nano-structures with diameter of ∼100 nm and variable length (200–600 nm) were fabricated on glass substrates covered with conductive buffer layers such as NiCr, ZAO (ZnO:Al2O3 + Ta2O5) or TiPd alloys. The fabrication process consisted of the starting vapour deposition of metal catalyst dropped layer followed by the isothermal catalyst-prompted vapour growth of CdTe nano-structured layer of controllable shape and surface filling. The effect of buffer layers on the crystallographic orientation and thickness of CdTe nano-structured layers is investigated by means of IBA techniques, SEM and X-ray diffraction. It was shown that the formed CdTe nano-layers have a cubic structure, mainly oriented towards the [1 1 1] crystallographic direction, except for those grown on ZAO layer where the X-ray diffraction signal is very weak to be associated to any crystallographic form. The RBS spectra recorded on different areas of each sample type showed an almost constant thickness and SEM images revealed an homogeneous and dense distribution of the structures. It was also possible to study the first stage of the nano-structures grown on the Bi2Te3 seeds.
- Biomarkers of exposure to metal dust in exhaled breath condensate: methodology optimizationPublication . Félix, P. M.; Franco, C.; Barreiros, M. Alexandra; Batista, B.; Bernardes, S.; Garcia, S. M.; Almeida, A. B.; Almeida, S. M.; Wolterbeek, H. Th.; Pinheiro, TeresaIn occupational assessments where workers are exposed to metal dust, the liquid condensate of exhaled breath (EBC) may provide unique indication of pulmonary exposure. The main goal of this study was to demonstrate the quality of EBC to biological monitoring of human exposure. A pilot study was performed in a group of metal dust–exposed workers and a group of nonexposed individuals working in offices. Only metal dust–exposed workers were followed along the working week to determine the best time of collection. Metal analyses were performed with inductively coupled plasma mass spectrometry (ICP-MS). Analytical methodology was tested using an EBC sample pool for several occupationally exposed metals: potassium, chromium, manganese, copper, zinc, strontium, cadmium, antimony, and lead. Metal contents in EBC of exposed workers were higher than controls at the beginning of the shift and remained augmented throughout the working week. The results obtained support the establishment of EBC as an indicator of pulmonary exposure to metals.
- When gold stops glittering: corrosion mechanisms of René Lalique's Art Nouveau jewelleryPublication . Tissot, Isabel; Correia, Jorge; Monteiro, Olinda C.; Barreiros, M. Alexandra; Guerra, M. F.ABSTRACT: Art Nouveau jewellery created by René Lalique is presently corroded. To identify the corrosion processes, Au-Ag-Cu alloys with compositions comparable to those used in the René Lalique’s jewellery were fabricated to be exposed to sulphide-containing environments. Using SEM-EDS, XRD, UV-Vis spectroscopy and ellipsometry, it was for the first time demon-strated that at the surface of tarnished Au alloys forms a corrosion film with a layer-by-layer structure. Considering the complex refractive indices of bulk Cu and Ag oxides and sulphides, a two-step corrosion mechanism was proposed. The formation of Cu-based compounds during the early corrosion stages is followed by the formation of Ag-based compounds. The thinness of the formed film, shown for one of the gold alloys to be of 80 nm, is due to a corrosion kinetics controlled by the presence of Au and by the formation of an Au-S self-assembled monolayer. The corrosion mechanism of gold alloys raises a new conservation challenge concerning the removal of nanometric layers.
- Scale up of microwave annealed FA0.83Cs0.17PbI1.8Br1.2 perovskite towards an industrial scale [Comunicação oral]Publication . Mascarenhas, João; Barreiros, M. Alexandra; Brites, Maria JoãoABSTRACT: Perovskite solar cells (PSCs) efficiency has rapidly increased from the initial 2009's 3.8 to recent 22.7%. This high efficiency has attracted serious attention of the researchers and industry worldwide also due to their low material cost, and simple soluction-based fabrication process.
- Charge transport and recombination of dye sensitized 1D nanostructured-TiO2 films prepared by reactive sputteringPublication . Sequeira, S.; Lobato, K.; Torres, Erica; Brites, Maria João; Barreiros, M. Alexandra; Mascarenhas, JoãoDye sensitized solar cells (DSCs) are governed by light absorption, charge injection, electron transport and recombination and electrolyte diffusion. One way to improve the efficiency of these devices is by the design of highly ordered nanostructured semiconductor materials.The advantages can be two-fold: Firstly charge transport within the metal-oxide can be enhanced and hence thicker films can be employed and secondly, the complete permeation with a solid-state hole-transport medium of the sensitized metal-oxide can be facilitated. Nanostructured materials should promote vectorial electron diffusion and have as few recombination sights as possible so as to further enhance electron lifetimes and electron collection efficiencies. These materials should also have a high surface area so as to allow for efficient dye-loading and hence light absorption. Highly ordered TiO2 nanostructured films were prepared by reactive sputtering and their charge transport characteristics evaluated in DSCs. These were compared to DSCs employing mesoporous TiO2 films prepared by doctor blade technique using commercial paste. Charge transport characteristics were evaluated by impedance spectroscopy (IS), incident photon to current conversion efficiencies (IPCE) and current-voltage (iV) curves under simulated AM1.5G irradiation. Film morphology and structural properties were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively.