Emissions of nanoparticles during friction stir welding (FSW) of aluminium alloys

Friction stir welding (FSW) is now well established as a welding process capable of joining some different types of metallic materials, as it was (1) found to be a reliable and economical way of producing high quality welds, and (2) considered a "clean" welding process that does not involve fusion of metal, as is the case with other traditional welding processes. The aim of this study was to determine whether the emission of particles during FSW in the nanorange of the most commonly used aluminum (Al) alloys, AA 5083 and AA 6082, originated from the Al alloy itself due to friction of the welding tool against the item that was being welded. Another goal was to measure Al alloys in the alveolar deposited surface area during FSW. Nanoparticles dimensions were predominantly in the 40- and 70-nm range. This study demonstrated that microparticles were also emitted during FSW but due to tool wear. However, the biological relevance and toxic manifestations of these microparticles remain to be determined.

"In-vitro" corrosion behaviour of the magnesium alloy with Al and Zn (AZ31) protected with a biodegradable polycaprolactone coating loaded with hydroxyapatite and cephalexin

Mg alloys are very susceptible to corrosion in physiological media. This behaviour limits its widespread use in biomedical applications as bioresorbable implants, but it can be controlled by applying protective coatings. On one hand, coatings must delay and control the degradation process of the bare alloy and, on the other hand, they must be functional and biocompatible. In this study a biocompatible polycaprolactone (PCL) coating was functionalised with nano hydroxyapatite (HA) particles for enhanced biocompatibility and with an antibiotic, cephalexin, for anti-bacterial purposes and applied on the AZ31 alloy. The chemical composition and the surface morphology of the coated samples, before and after the corrosion tests, were studied by scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDX) and Raman. The results showed that the presence of additives induced the formation of agglomerates and defects in the coating that resulted in the formation of pores during immersion in Hanks' solution. The corrosion resistance of the coated samples was studied in Hank's solution by electrochemical impedance spectroscopy (EIS). The results evidenced that all the coatings can provide corrosion protection of the bare alloy. However, in the presence of the additives, corrosion protection decreased. The wetting behaviour of the coating was evaluated by the static contact angle method and it was found that the presence of both hydroxyapatite and cephalexin increased the hydrophilic behaviour of the surface. The results showed that it is possible to tailor a composite coating that can store an antibiotic and nano hydroxyapatite particles, while allowing to control the in-vitro corrosion degradation of the bioresorbable Mg alloy AZ31. (C) 2015 Elsevier Ltd. All rights reserved.

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.

Biofunctional composite coating architectures based on polycaprolactone and nanohydroxyapatite for controlled corrosion activity and enhanced biocompatibility of magnesium AZ31 alloy

In this work a biofunctional composite coating architecture for controlled corrosion activity and enhanced cellular adhesion of AZ31 Mg alloys is proposed. The composite coating consists of a polycaprolactone (PCL) matrix modified with nanohydroxyapatite (HA) applied over a nanometric layer of polyetherimide (PEI). The protective properties of the coating were studied by electrochemical impedance spectroscopy (EIS), a non-disturbing technique, and the coating morphology was investigated by field emission scanning electron microscopy (FE-SEM). The results show that the composite coating protects the AZ31 substrate. The barrier properties of the coating can be optimized by changing the PCL concentration. The presence of nanohydroxyapatite particles influences the coating morphology and decreases the corrosion resistance. The biocompatibility was assessed by studying the response of osteoblastic cells on coated samples through resazurin assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The results show that the polycaprolactone to hydroxyapatite ratio affects the cell behavior and that the presence of hydroxyapatite induces high osteoblastic differentiation. (C) 2014 Elsevier B.V. All rights reserved.

Estudo do uso de hidrotalcites de Mg-Al como catalisadores heterogéneos para produção de biodiesel

A transesterificação de óleos vegetais ou gorduras animais com um álcool de baixo peso molecular é o principal processo utilizado na produção de biodiesel. Actualmente os processos industriais utilizam catalisadores homogéneos para acelerar a reacção. No entanto a utilização de catalisadores heterogéneos, no processo de transesterificação, tem sido sugerido por vários investigadores pois, são amigos do ambiente e podem ser regenerados e reutilizados portanto possibilitam a utilização de processos contínuos. Neste contexto, a utilização de hidrotalcites Mg-Al, como catalisadores heterogéneos para produção de biodiesel foi investigada neste trabalho experimental. As hidrotalcites com diferentes razões molares Mg/Al (Mg/Al=1, 2, 3 e 4) foram preparadas pelo método de co-precipitação. As diversas matrizes catalíticas obtidas, calcinadas a diferentes temperaturas, foram caracterizadas por difracção de raios X (DRX), análise térmica (TG-DSC), espectroscopia de infravermelhos (MIR), microscopia electrónica de varrimento (SEM) e isotérmicas de adsorção com azoto (BET). Estes catalisadores foram testados na metanólise de óleos vegetais para produzir biodiesel. As hidrotalcites Mg/Al=2, HT2A e HT2B (preparada com metade da quantidade de NaOH) calcinadas a 507 ºC e 700 ºC, respectivamente, foram as que apresentaram melhores resultados ao catalisar a reacção com um rendimento em éster superior a 97%, utilizando 2.5% da massa de catalisador, em relação à massa do óleo, razão molar metanol/óleo igual a 12, temperatura reaccional de 65 ºC durante 4h. Foi também investigada a reutilização do catalisador e o efeito da temperatura de calcinação. Constatou-se que o catalisador hidrotalcite HT2B apresentou melhor comportamento catalítico pois permitiu catalisar a reacção de transesterificação até três ciclos reaccionais, convertendo em ésteres 97%, 92% e 34% no primeiro, segundo e terceiro ciclos reaccionais, respectivamente. A análise de, algumas propriedades do biodiesel obtido como, o índice de acidez, a viscosidade e o índice de iodo mostraram que os resultados obtidos estão dentro dos valores limite recomendados pela norma EN 14214. Em anexo apresenta-se uma comunicação à First International Conference on Materials for Energy, Karlsruhe, 2010.

Prensa electromagnética com recuperação de energia para corte e moldagem de chapas e tubos de AL

Foi desenvolvido um conversor de potência e atuador mecânico para a moldagem e corte, por ação de pressão magnética, de chapas e tubos de Al, com uma energia máxima de descarga de 10kJ. O conversor é composto por duas malhas de descarga em paralelo e duas malhas de recuperação de energia. O circuito é capaz de gerar uma corrente de pico de 50kA com uma taxa de variação máxima de 2kA/s através de um atuador, recuperar até 32% da sua energia inicial e diminuir o tempo de carga dos bancos de condensadores no mesmo valor, reduzindo assim a potência da fonte de alimentação primária Foram construídos vários atuadores de forma a otimizar o processo, considerando as várias funções pretendidas, como a deformação ou corte de chapas e compressão de tubos. O circuito elétrico aproximado desenvolvido em Matlab/Simulink foi validado, considerando apenas o funcionamento da malha primária sem o atuador e a dinâmica associada, sendo capaz de simular as respostas do sistema para várias situações específicas, tornando-se numa ferramenta para otimização do mesmo. Experimentalmente, os resultados obtidos provam ser possível cortar chapas Al de 0,5 e 0,8mm, com apenas 13% da energia total do circuito, e comprimir tubos de Al com 2mm de espessura e 50mm de diâmetro com apenas 2,4kJ. A topologia do circuito e a construção da máquina tiveram em conta vários aspetos que melhoram a proteção de pessoas e equipamentos e devida à sua configuração este é capaz de suportar variações de capacidade nos bancos de condensadores e variações de indutância nas bobinas de recuperação de energia sem se danificar.

Hacia una introducción selectiva al teatro en Portugal: breve encuadramiento

Texto dividido em duas partes, na primeira aborda-se a evolução do teatro em Portugal do pós segunda grande guerra à contemporaneidade, focando particularmente o experimentalismo do final dos anos quarenta, um período que se pode caracterizar por uma ânsia de renovação e modernização; a constituição de um teatro independente fortemente politizado nos anos setenta; e a pluralidade da cena contemporânea. Na segunda parte aborda-se a alegada incapacidade atávica dos escritores portugueses para a escrita dramática, mapeando os nomes mais significativos do pós-25 de Abril de 1974 até à contemporaneidade.

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.

Electrochemical response of 70Co-30Ni highly branched 3D-dendritic structures for charge storage electrodes

A 70Co-30Ni dendritic alloy was produced on stainless steel by pulse electrodeposition in the cathodic domain, and oxidized by potential cycling. X-ray diffraction (XRD) identified the presence of two phases and scanning electron microscopy (SEM) evidenced an open 3D highly branched dendritic morphology. After potential cycling in 1 M KOH, SEM and X-ray photoelectron spectroscopy (XPS) revealed, respectively, the presence of thin nanoplates, composed of Co and Ni oxi-hydroxides and hydroxides over the original dendritic film. Cyclic voltammetry tests showd the presence of redox peaks assigned to the oxidation and reduction of Ni and Co centres in the surface film. Charge/discharge measurements revealed capacity values of 121 mAh g(1) at 1 mA cm(2). The capacity retention under 8000 cycles was above 70%, stating the good reversibility of these redox materials and its suitability to be used as charge storage electrodes. Electrochemical impedance spectroscopy (EIS) spectra, taken under different applied bias, showed that the capacitance increased when the electrode was fully oxidized and decreased when the electrode was reduced, reflecting different states-of-charge of the electrode. (C) 2015 Elsevier Ltd. All rights reserved.