Voltammetric determination of dialifos in soils with a mercury film ultramicroelectrode

An extraction-adsorptive stripping voltammetric procedure for the determination of the pesticide dialifos in soil samples using microwave-assisted solvent extraction and a mercury film ultramicroelectrode was developed. The method is based on the use of hexane-acetone solvent (1:1, v/v) and on controlled adsorptive accumulation of the insecticide at the potential of -0.10V (versus Ag/AgCl) in the presence of Britton-Robinson buffer (pH 2.0). Soil sample extracts were analyzed directly after drying and redissolution with the supporting electrolyte, but without other pretreatment. The limit of detection obtained for a 10sec collection time was 2.0x10-8 mol L-1. Recovery experiments for the global procedure, at the 0.100µgg-1 level, gave satisfactory average and standard deviation results for the two different soils tested.

Bisphenol A migration from plastic materials: direct insight of ecotoxicity in Daphnia magna

Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1±4.3 % to 264.7±3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3±1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5±2.0 % to 118.8±1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect.

Admittance spectroscopy of Cu2ZnSnS4 based thin film solar cells

In this report, we propose an AC response equivalent circuit model to describe the admittance measurements of Cu2ZnSnS4 thin film solar cell grown by sulphurization of stacked metallic precursors. This circuit describes the contact resistances, the back contact, and the heterojunction with two trap levels. The study of the back contact resistance allowed the estimation of a back contact barrier of 246 meV. The analysis of the trap series with varying temperature revealed defect activation energies of 45 meV and 113 meV. The solar cell’s electrical parameters were obtained from the J-V curve: conversion efficiency, 1.21%; fill factor, 50%; open circuit voltage, 360 mV; and short circuit current density, 6.8 mA/cm2.

Mo bilayer for thin film photovoltaics revisited

Thin film solar cells based on Cu(In,Ga)Se2 as an absorber layer use Mo as the back contact. This metal is widely used in research and in industry but despite this, there are only a few published studies on the properties of Mo. Properties such as low resistivity and good adhesion to soda lime glass are hard to obtain at the same time. These properties are dependent on the deposition conditions and are associated with the overall stress state of the film. In this report, a study of the deposition of a Mo bilayer is carried out by analysing first single and then bilayers. The best properties of the bilayer were achieved when the bottom layer was deposited at 10 × 10−3 mbar with a thickness of 500 nm and the top layer deposited at 1 × 10−3 mbar with a thickness of 300 nm. The films deposited under these conditions showed good adhesion and a sheet resistivity lower than 0.8 .

Film thickness in a ball-on-disc contact lubricated with greases, bleed oils and base oils

Three different lubricating greases and their bleed and base oils were compared in terms of film thickness in a ball-on-disc test rig through optical interferometry. The theoretical values calculated according to Hamrock's equation are in close agreement with the base oil film thickness measurements, which validates the selected experimental methodology. The grease and bleed oil film thickness under fully flooded lubrication conditions presented quite similar behaviour and levels. Therefore, the grease film thickness under full film conditions might be predicted using their bleed oil properties, namely the viscosity and pressure-viscosity coefficient. The base and bleed oil lubricant parameter LP are proportional to the measured film thickness. A relationship between grease and the corresponding bleed oil film thickness was evidenced.

Wear resistance of TiAlSiN thin coatings

In the last decades TiAlN coatings deposited by PVD techniques have been extensively investigated but, nowadays, their potential development for tribological applications is relatively low. However, new coatings are emerging based on them, trying to improve wear behavior. TiAlSiN thin coatings are now investigated, analyzing if Si introduction increases the wear resistance of PVD films. Attending to the application, several wear test configurations has been recently used by some researchers. In this work, TiAlSiN thin coatings were produced by PVD Unbalanced Magnetron Sputtering technique and they were conveniently characterized using Scanning Electron Microscopy (SEM) provided with Energy Dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM), Electron Probe Micro-Analyzer (EPMA), Micro Hardness (MH) and Scratch Test Analysis. Properties as morphology, thickness, roughness, chemical composition and structure, hardness and film adhesion to the substrate were investigated. Concerning to wear characterization, two very different ways were chosen: micro-abrasion with ball-on-flat configuration and industrial non-standardized tests based on samples inserted in a feed channel of a selected plastic injection mould working with 30% (wt.) glass fiber reinforced polypropylene. TiAlSiN coatings with a small amount of about 5% (wt.) Si showed a similar wear behavior when compared with TiAlN reported performances, denoting that Si addition does not improve the wear performance of the TiAlN coatings in these wear test conditions.

Viability of the use of thin-film A-SiC:H photodiodes for protein identification

In this paper, we present a multilayer device based on a-Si:H/a-SiC:H that operates as photodetector and optical filter. The use of such device in protein detection applications is relevant in Fluorescence Resonance Energy Transfer (FRET) measurements. This method demands the detection of fluorescent signals located at specific wavelengths bands in the visible part of the electromagnetic spectrum. The device operates in the visible range with a selective sensitivity dependent on electrical and optical bias. Several nanosensors were tested with a commercial spectrophotometer to assess the performance of FRET signals using glucose solutions of different concentrations. The proposed device was used to demonstrate the possibility of FRET signals detection, using visible signals of similar wavelength and intensity. The device sensitivity was tuned to enhance the wavelength band of interest using steady state optical bias at 400 nm. Results show the ability of the device to detect signals in this range. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Drilling of fibre reinforced plastic laminates

The use of fibre reinforced plastics – FRP’s – in structures is under a considerable increase. Advantages of their use are related with their low weight, high strength and stiffness. The improvement of the dynamic characteristics has been profitable for aeronautics, automobile, railway, naval and sporting goods industries. Drilling is a widely used machining technique as it is needed to assemble parts in a structure. This is a unique machining process, characterized by the existence of two different mechanisms: extrusion by the drill chisel edge and cutting by the rotating cutting lips. Drilling raises particular problems that can reduce mechanical and fatigue strength of the parts. In this work, quasi-isotropic hybrid laminates with 25% of carbon fibre reinforced plies and 4 mm thickness are produced, tested and drilled. Three different drill geometries are compared. Results considered are the interlaminar fracture toughness in Mode I – GIc –, thrust force during drilling and delamination extent after drilling. A bearing test is performed to evaluate tool influence on the load carrying capacity of the plate. Results consider the influence of drill geometry on delamination. A correlation linking plate damage to bearing test results is presented.

Taper angle optimization of scarf repairs in carbon-epoxy laminates

The increasing use of Carbon-Fibre Reinforced Plastic (CFRP) laminates in high responsibility applications introduces an issue regarding their handling after damage. The availability of efficient repair methods is essential to restore the strength of the structure. The availability of accurate predictive tools for the repairs behaviour is also essential for the reduction of costs and time associated to extensive tests. This work reports on a numerical study of the tensile behaviour of three-dimensional (3D) adhesively-bonded scarf repairs in CFRP structures, using a ductile adhesive. The Finite Element (FE) analysis was performed in ABAQUS® and Cohesive Zone Models (CZM’s) was used for the simulation of damage in the adhesive layer. A parametric study was performed on two geometric parameters. The use of overlaminating plies covering the repaired region at the outer or both repair surfaces was also tested as an attempt to increase the repairs efficiency. The results allowed the proposal of design principles for repairing CFRP structures.

TiB2 nanostructured coating for GFRP injection moulds

In the injection moulding of polypropylene reinforced with hard glass fibres, die materials are commonly subjected to severe abrasive wear. In order to improve its wear resistance, an unbalanced magnetron sputtering PVD compositional monolayered coating has been produced. The film was composed by a nanostructured TiB2 monolayer. Microstructure characterization and thickness evaluation were conducted by scanning electron microscopy (SEM). Film topography and roughness were accessed by SEM and Atomic Force Microscopy (AFM). The phase analyse was investigated by X-ray diffraction (XRD), using Cu Kalpha radiation. Scratch tests were conducted in order to study the film adhesion to the substrate. Load-Displacement curves (nanoindentation analysis) allowed measuring the film hardness and Young's modulus. A ball-cratering tribometer was used to determine the micro-abrasion laboratorial wear resistance, under different tests conditions, using SiC particles in distilled water slurry. At the end of these tests, the worn surfaces were analyzed by SEM and Energy Dispersive X-ray Spectroscopy (EDS) in order to compare these results with some other coatings already tested in the same conditions. To test the practical wear resistance, 135000 injection cycles were done in a plastic injection industrial mould. Coated samples were put on the plastic feed canal, after a turbulent zone. In these tests, a 30% (wt) glass fibres reinforced polypropylene was used. Worn sample surfaces were analyzed by SEM after 45.000 and 90.000 cycles. Image analyses were made in order to evaluate the damage increases and to observe the wear mechanisms involved.

Influence of the deposition pressure on the properties of transparent and conductive ZnO: Ga thin-film produced by r.f. sputtering at room temperature

Thin Solid Films, vol. 427, nº 1-2

New recycling approaches for thermoset polymeric composite wastes – an experimental study on polyester based concrete materials filled with fibre reinforced plastic recyclates

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

Kinetic measurements during transient film growth on zinc

Quimica Nova, Vol. 32, Nº2

Experimental study on polyester based concretes filled with glass fibre reinforced plastic recyclates – a contribution to composite materials sustainability

The development and applications of thermoset polymeric composites, namely fibre reinforced plastics (FRP), have shifted in the last decades more and more into the mass market [1]. Despite of all advantages associated to FRP based products, the increasing production and consume also lead to an increasing amount of FRP wastes, either end-of-lifecycle products, or scrap and by-products generated by the manufacturing process itself. Whereas thermoplastic FRPs can be easily recycled, by remelting and remoulding, recyclability of thermosetting FRPs constitutes a more difficult task due to cross-linked nature of resin matrix. To date, most of the thermoset based FRP waste is being incinerated or landfilled, leading to negative environmental impacts and supplementary added costs to FRP producers and suppliers. This actual framework is putting increasing pressure on the industry to address the options available for FRP waste management, being an important driver for applied research undertaken cost efficient recycling methods. [1-2]. In spite of this, research on recycling solutions for thermoset composites is still at an elementary stage. Thermal and/or chemical recycling processes, with partial fibre recovering, have been investigated mostly for carbon fibre reinforced plastics (CFRP) due to inherent value of carbon fibre reinforcement; whereas for glass fibre reinforced plastics (GFRP), mechanical recycling, by means of milling and grinding processes, has been considered a more viable recycling method [1-2]. Though, at the moment, few solutions in the reuse of mechanically-recycled GFRP composites into valueadded products are being explored. Aiming filling this gap, in this study, a new waste management solution for thermoset GFRP based products was assessed. The mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the potential added value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. The use of a cementless concrete as host material for GFRP recyclates, instead of a conventional Portland cement based concrete, presents an important asset in avoiding the eventual incompatibility problems arisen from alkalis silica reaction between glass fibres and cementious binder matrix. Additionally, due to hermetic nature of resin binder, polymer based concretes present greater ability for incorporating recycled waste products [3]. Under this scope, different GFRP waste admixed polymer mortar (PM) formulations were analyzed varying the size grading and content of GFRP powder and fibre mix waste. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacities of modified mortars with regard to waste-free polymer mortars.

Wuthering heights on the screen: exploring the relations between film adaptation and subtitling

This essay aims to confront the literary text Wuthering Heights by Emily Brontë with five of its screen adaptations and Portuguese subtitles. Owing to the scope of the study, it will necessarily afford merely a bird‘s eye view of the issues and serve as a starting point for further research. Accordingly, the following questions are used as guidelines: What transformations occur in the process of adapting the original text to the screen? Do subtitles update the film dialogues to the target audience‘s cultural and linguistic context? Are subtitles influenced more by oral speech than by written literary discourse? Shouldn‘t subtitles in fact reflect the poetic function prevalent in screen adaptations of literary texts? Rather than attempt to answer these questions, we focus on the objects as phenomena. Our interdisciplinary undertaking clearly involves a semio-pragmatic stance, at this stage trying to avoid theoretical backdrops that may affect our apprehension of the objects as to their qualities, singularities, and conventional traits, based on Lucia Santaella‘s interpretation of Charles S. Peirce‘s phaneroscopy. From an empirical standpoint, we gather features and describe peculiarities, under the presumption that there are substrata in subtitling that point or should point to the literary source text, albeit through the mediation of a film script and a particular cinematic style. Therefore, we consider how the subtitling process may be influenced by the literary intertext, the idiosyncrasies of a particular film adaptation, as well as the socio-cultural context of the subtitler and target audience. First, we isolate one of the novel‘s most poignant scenes – ‗I am Heathcliff‘ – taking into account its symbolic play and significance in relation to character and plot construction. Secondly, we study American, English, French, and Mexican adaptations of the excerpt into film in terms of intersemiotic transformations. Then we analyze differences between the film dialogues and their Portuguese subtitles.