Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

Fabrication of the three-dimensional dendritic Ni-Co films by electrodeposition on stainless steel substrates

Co-deposition of nickel and cobalt was carried out on austenitic stainless steel (AISI 304) substrates by imposing a square waveform current in the cathodic region. The innovative procedure applied in this work allows creating a stable, fully developed, and open porous three-dimensional (3D) dendritic structure, which can be used as electrode for redox supercapacitors. This study investigates in detail the influence of the applied current density on the morphology, mass, and chemical composition of the deposited Ni-Co films and the resulting 3D porous network dendritic structure. The morphology and the physicochemical composition were studied by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (W). The electrochemical behavior of the materials was evaluated by cyclic voltammetry (CV). The results highlight the mechanism involved in the coelectrodeposition process and how the lower limit current density tailors the film composition and morphology, as well as its electrochemical activity.

Assessment of exposure to airborne ultrafine particles in the urban environment of Lisbon, Porugal

The aim of this study was the assessment of exposure to ultrafine in the urban environment of Lisbon, Portugal, due to automobile traffic, and consisted of the determination of deposited alveolar surface area in an avenue leading to the town center during late spring. This study revealed differentiated patterns for weekdays and weekends, which could be related with the fluxes of automobile traffic. During a typical week, ultrafine particles alveolar deposited surface area varied between 35.0 and 89.2 mu m(2)/cm(3), which is comparable with levels reported for other towns such in Germany and the United States. These measurements were also complemented by measuring the electrical mobility diameter (varying from 18.3 to 128.3 nm) and number of particles that showed higher values than those previously reported for Madrid and Brisbane. Also, electron microscopy showed that the collected particles were composed of carbonaceous agglomerates, typical of particles emitted by the exhaustion of diesel vehicles. Implications: The approach of this study considers the measurement of surface deposited alveolar area of particles in the outdoor urban environment of Lisbon, Portugal. This type of measurements has not been done so far. Only particulate matter with aerodynamic diameters <2.5 (PM2.5) and >10 (PM10) mu m have been measured in outdoor environments and the levels found cannot be found responsible for all the observed health effects. Therefore, the exposure to nano- and ultrafine particles has not been assessed systematically, and several authors consider this as a real knowledge gap and claim for data such as these that will allow for deriving better and more comprehensive epidemiologic studies. Nanoparticle surface area monitor (NSAM) equipments are recent ones and their use has been limited to indoor atmospheres. However, as this study shows, NSAM is a very powerful tool for outdoor environments also. As most lung diseases are, in fact, related to deposition of the alveolar region of the lung, the metric used in this study is the ideal one.

Modifications of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour

Desilication and a combination of alkaline followed by acid treatment were applied to MCM-22 zeolite using two different base concentrations. The samples were characterised by powder X-ray diffraction, Al-27 and Si-29 MAS-NMR spectroscopy, SEM, TEM and low temperature N-2 adsorption. The acidity of the samples was study through pyridine adsorption followed by FTIR spectroscopy and by the analyses of the hydroxyl region. The catalytic behaviour, anticipated by the effect of post-synthesis treatments on the acidity and space available inside the two internal pore systems was evaluated by using the model reaction of m-xylene transformation. The generation of mesoporosity was achieved upon alkaline treatment with 0.05 M NaOH solution and practically no additional gain was obtained when the more concentrate solution, 0.1 M, was used. Instead, Al extraction takes place along with Si, as shown by Si-29 and Al-27 MAS-NMR data, followed by Al deposition as extraframework species. Samples submitted to alkaline plus acid treatments present distinct behaviour. When the lowest NaOH solution was used no relevant effect was observed on the textural characteristics. Additionally, when the acid treatment was performed on an already fragilized MCM-22 structure, due to previous desilication with 0.1 M NaOH solution, the extraction of Al from both internal pore systems promotes their interconnection, evolving from a 2-D to a 3-D porous structure. This transformation has a marked effect in the catalytic behaviour, allowing an increase of m-xylene conversion as a consequence of an easier and faster molecular traffic in the 3-D structure. On the other hand, the continuous deposition of extraframework Al species inside the pores leads to a shape selective effect that privileges the formation of the more valuable isomer p-xylene.

Adhesion and wear behaviour of NCD coatings on Si3N4 by micro-abrasion tests

Nanocrystalline diamond (NCD) coatings offer an excellent alternative for tribological applications, preserving most of the intrinsic mechanical properties of polycrystalline CVD diamond and adding to it an extreme surface smoothness. Silicon nitride (Si3N4) ceramics are reported to guarantee high adhesion levels to CVD microcrystalline diamond coatings, but the NCD adhesion to Si3N4 is not yet well established. Micro-abrasion tests are appropriate for evaluating the abrasive wear resistance of a given surface, but they also provide information on thin film/substrate interfacial resistance, i.e., film adhesion. In this study, a comparison is made between the behaviour of NCD films deposited by hot-filament chemical vapour deposition (HFCVD) and microwave plasma assisted chemical vapour deposition (MPCVD) techniques. Silicon nitride (Si3N4) ceramic discs were selected as substrates. The NCD depositions by HFCVD and MPCVD were carried out using H2–CH4 and H2–CH4–N2 gas mixtures, respectively. An adequate set of growth parameters was chosen for each CVD technique, resulting in NCD films having a final thickness of 5 m. A micro-abrasion tribometer was used, with 3 m diamond grit as the abrasive slurry element. Experiments were carried out at a constant rotational speed (80 r.p.m.) and by varying the applied load in the range of 0.25–0.75 N. The wear rate for MPCVD NCD (3.7±0.8 × 10−5 m3N−1m−1) is compatible with those reported for microcrystalline CVD diamond. The HFCVD films displayed poorer adhesion to the Si3N4 ceramic substrates than the MPCVD ones. However, the HFCVD films show better wear resistance as a result of their higher crystallinity according to the UV Raman data, despite evidencing premature adhesion failure.

Gestão de resíduos produzidos num sistema de drenagem e tratamento de águas residuais

O presente trabalho centra-se na gestão de resíduos produzidos no sistema de drenagem e tratamento de águas residuais do município de Vila Nova de Gaia. A entidade onde decorreu o trabalho é uma empresa responsável pela distribuição de água e pela drenagem e tratamento de águas residuais. A empresa está certificada pela norma NP EN ISO 14001, desde 2001, sendo então um dos objectivos o enquadramento da gestão dos resíduos em estudo na referida norma, acompanhando os requisitos da mesma com vista ao seu total cumprimento. Outros dos objectivos foi estudar qual a opção de tratamento mais adequada a aplicar ao resíduo no seu local de armazenamento temporário com vista a minorar os seus impactes ambientais. De acordo com a caracterização analítica do resíduo e com os aspetos legais aplicáveis, foram também analisados os destinos finais possíveis e ambientalmente adequados ao resíduo. A medida proposta para a minimização de impactes no local de armazenamento temporário do resíduo foi a estabilização com cal nos leitos de secagem, disponíveis numa antiga ETAR de loteamento. O doseamento de cal a aplicar ao resíduo será de 10 kg de cal apagada comercial (Ca (OH)2) por uma tonelada de resíduo fresco com um período mínimo de secagem de 2 meses. Outra das medidas de minimização de impactes selecionada foi a implantação de uma cortina arbórea ao redor da instalação. Sendo o resíduo em estudo muito heterogéneo, constituído principalmente por areias, terras e gradados, a valorização foi equacionada mas não foram encontrados alternativas viáveis. O destino final considerado como mais adequado tendo em conta todas as características do resíduo e eluato, analisadas de acordo com o previsto no Decreto-Lei n.º 183/2009 de 10 de Agosto, foi o aterro para resíduos não perigosos. Foi também objecto do estudo a identificação e análise de todos os aspectos ambientais relacionados com a gestão de resíduos e a avaliação da sua significância. Dos aspectos ambientais identificados como significativos, destacam-se aqueles que ocorrem presentemente, os resíduos armazenados (gradados/limpeza de redes), e os que podem ocorrer em situações de emergência, fuga/derrame de óleos/combustíveis e cheiros/odores. De forma a minimizar os aspectos ambientais identificados, e de acordo com a norma NP EN ISO 14001, foram propostas ações que constam de um programa de gestão elaborado para este trabalho, onde se definem os objectivos, metas e prazos. As principais medidas propostas no programa de gestão foram: Estabilização com cal (inicial e reforço se necessário); melhoria do espaço envolvente; análise de questões de saúde ocupacional/segurança; adjudicação de prestação de serviços da recolha por operador licenciado; implantação da cortina arbórea; registo no SIRAPA; criação de planos de emergência ambiental e de segurança.

Immunopathologic studies in myocardial biopsies of patients with Chagas' disease and idiopathic cardiomyopathy

Right ventricular endomyocardial biopsies were studied in 30 patients, 15 with myocardiopathy from chronic Chagas'disease and 15 with idiopathic congestive myocardiopathy; five other myocardial samples were taken at necropsies of patients with chronic Chagas' disease. The authors tried to establish by means of direct immunofluorescence techniques whether there were immunoglobulins G, A and M, fibrinogen and C3 complement deposition in the myocardium; only one of these 30 patients exhibited a positive reaction to IgG, it was a patient with idiopathic congestive myocardiopathy. All fragments from patients with Chagas' disease showed no response to any of the fluorescent conjugates. These findings do not support the idea that anti-myoeardial antibodies have pathogenic importance in the evolution of dilated or chagasic myocardiopathies.

High-performance flexible hybrid field-effect transistors based on cellulose fiber paper

IEEE Electron Device Letters, VOL. 29, NO. 9,

The Neogene of the Lower Tagus Basin (Portugal)

Revista Española de Paleontologia 19 (2), 229-242

Conditional probability applied to the definition of limestone geochemical facies: A new Methodological Approach

A new method, based on linear correlation and phase diagrams was successfully developed for processes like the sedimentary process, where the deposition phase can have different time duration - represented by repeated values in a series - and where the erosion can play an important rule deleting values of a series. The sampling process itself can be the cause of repeated values - large strata twice sampled - or deleted values: tiny strata fitted between two consecutive samples. What we developed was a mathematical procedure which, based upon the depth chemical composition evolution, allows the establishment of frontiers as well as the periodicity of different sedimentary environments. The basic tool isn't more than a linear correlation analysis which allow us to detect the existence of eventual evolution rules, connected with cyclical phenomena within time series (considering the space assimilated to time), with the final objective of prevision. A very interesting discovery was the phenomenon of repeated sliding windows that represent quasi-cycles of a series of quasi-periods. An accurate forecast can be obtained if we are inside a quasi-cycle (it is possible to predict the other elements of the cycle with the probability related with the number of repeated and deleted points). We deal with an innovator methodology, reason why it's efficiency is being tested in some case studies, with remarkable results that shows it's efficacy. Keywords: sedimentary environments, sequence stratigraphy, data analysis, time-series, conditional probability.

Impact of the Meteorology Conditions on the Particulate Matter Dispersion from an Industrial Complex into Urban and Suburban Areas

The aim of this work was to assess the influence of meteorological conditions on the dispersion of particulate matter from an industrial zone into urban and suburban areas. The particulate matter concentration was related to the most important meteorological variables such as wind direction, velocity and frequency. A coal-fired power plant was considered to be the main emission source with two stacks of 225 m height. A middle point between the two stacks was taken as the centre of two concentric circles with 6 and 20 km radius delimiting the sampling area. About 40 sampling collectors were placed within this area. Meteorological data was obtained from a portable meteorological station placed at approximately 1.7 km to SE from the stacks. Additional data was obtained from the electrical company that runs the coal power plant. These data covers the years from 2006 to the present. A detailed statistical analysis was performed to identify the most frequent meteorological conditions concerning mainly wind speed and direction. This analysis revealed that the most frequent wind blows from Northwest and North and the strongest winds blow from Northwest. Particulate matter deposition was obtained in two sampling campaigns carried out in summer and in spring. For the first campaign the monthly average flux deposition was 1.90 g/m2 and for the second campaign this value was 0.79 g/m2. Wind dispersion occurred predominantly from North to South, away from the nearest residential area, located at about 6 km to Northwest from the stacks. Nevertheless, the higher deposition fluxes occurred in the NW/N and NE/E quadrants. This study was conducted considering only the contribution of particulate matter from coal combustion, however, others sources may be present as well, such as road traffic. Additional chemical analyses and microanalysis are needed to identify the source linkage to flux deposition levels.

Palinomorfos ante-cenomanianos do «Grés do Buçaco» (Lousã, Portugal) *

The palynological study of sediments from lower levels of Lousã basin (Lomba do Alveite Arkoses). is presented. The palynological association includes several species of Appendicisporites and Cicatricosisporites, Costatoperforosporites sp., Ischyosporites teixeirae, Pattelasporites tavaredensis, Echinatisporis sp., Spheripollenites perinatus, Tricolpopollenites sp. and Retitricolpites maximus. The presence of the last two forms, and the absence of Normapolles, suggest an ante-Cenomanian, most probably Albian age for the assemblage. From these results, the begining of the infilling of the Lousã basin, is, at least in part, synchronous with the deposition of the «Grés Grosseiro Inferior» from the Occidental portuguese Basin. The presence of Lower Cretaceous sediments directly overlying the Paleozoic basement, hence outside of the Occidental Portuguese Basin,is shown for the first time.

Pliocene-quaternary upwelling in the SoutheasternAtlantic may reflect changes in water mass production

Proceedings of tile 1" R.C.A.N.S. Congress, Lisboa, October 1992

Characterisation and electrochemical behaviour of electrodeposited Cu-Fe foams applied as pseudocapacitor electrodes

Copper iron (Cu-Fe) 3D porous foams for supercapacitor electrodes were electrodeposited in the cathodic regime, on stainless steel current collectors, using hydrogen bubbling dynamic template. The foams were prepared at different current densities and deposition times. The foams were submitted to thermal conditioning at temperatures of 150 and 250 degrees C. The morphology, composition and structure of the formed films were studied by SEM, EDS and XRD, respectively. The electrochemical behaviour was studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronopotentiometry. The morphology of the 3D Cu-Fe foams is sensitive to the electrodeposition current and time. The increase of the current density produces a denser, larger and more ramified dendritic structure. Thermal conditioning at high temperature induces a coarser grain structure and the formation of copper oxides, which affect the electrochemical behaviour. The electrochemical response reveals the presence of various redox peaks assigned to the oxidation and reduction of Cu and Fe oxides and hydroxides in the foams. The specific capacitance of the 3D Cu Fe foams was significantly enhanced by thermal conditioning at 150 degrees C. The highest specific capacitance values attained 297 Fg(-1) which are much above the ones typically observed for single Cu or Fe Oxides and hydroxides. These values highlight a synergistic behaviour resulting from the combination of Cu and Fe in the form of nanostructured metallic foams. Moreover, the capacitance retention observed in an 8000 charge/discharge cycling test was above 66%, stating the good performance of these materials and its enhanced electrochemical response as supercapacitor negative electrodes. (C) 2014 Elsevier B.V. All rights reserved.

Paleoambiental reconstruction based on mineralogical data of quaternary littoral deposits occuring at Cortegaça and Maceda beaches (Ovar, Portugal)

The main goal of the present work is the use of mineralogical data corresponding to sediment fine fractions (silt and clay) of Quaternary littoral deposits for the definition of a more detailed vertical zonography and to discriminate the most significant morphoclimatic changes concerned with sediment source areas and sediment deposition areas. The analysis of the available mineralogical data reveals a vertical evolution of the mineral composition. The following aspects deserve particular reference: 1) fine fractions (<38 nm) are composed of quartz and phyllosilicates associated to feldspars, prevailing over other minerals; however in certain sections iron hydroxides and evaporitic minerals occur in significant amounts; 2) clay fractions (<2 nm) show a general prevalence of illite associated with kaolinite and oscillations, in relative terms, of kaolinite and illite contents. Qualitative and quantitative lateral and vertical variations of clay and non clay minerals allow the discrimination of sedimentary sequences and the establishment of the ritmicity and periodicity of the morphoclimatic Quaternary episodes that occurred in the Cortegaça and Maceda beaches. To each one of the sedimentary sequences corresponds, in a first stage, a littoral environment that increasingly became more continental. Climate would be mild to cold, sometimes with humidity - aridity oscillations. Warmer and moister episodes alternated with cooler and dryer ones.