Flow amperometric determination of carbofuran and fenobucarb

A simple, rapid, and precise amperometric method for quantification of N-methylcarbamate pesticides in water samples and phytopharmaceuticals is presented. Carbofuran and fenobucarb are the target analytes. The method is developed in flow conditions providing the anodic oxidation of phenolic-based compounds formed after alkaline hydrolysis. Optimization of instrumental and chemical variables is presented. Under the optimal conditions, the amperometric signal is linear for carbofuran and fenobucarb concentrations over the range of 1.0*10-7 to 1.0*10-5 molL-1, with a detection limit of about 2 ngmL-1. The amperometric method is successfully applied to the analysis of spiked environmental waters and commercial formulations. The proposed method allows 90 samples to be analysed per hour, using 500 mL of sample, and producing wastewaters of low toxicity. The proposed method permits determinations at the mgL 1 level and offers advantages of simplicity, accuracy, precision, and applicability to coloured and turbid samples, and automation feasibility.

Electrochemical study of butylate: application to the analysis of water

The electroactivity of butylate (BTL) is studied by cyclic voltammetry (CV) and square wave voltammetry (SWV) at a glassy carbon electrode (GCE) and a hanging mercury drop electrode (HMDE). Britton–Robinson buffer solutions of pH 1.9–11.5 are used as supporting electrolyte. CV voltammograms using GCE show a single anodic peak regarding the oxidation of BTL at +1.7V versus AgCl/ Ag, an irreversible process controlled by diffusion. Using a HMDE, a single cathodic peak is observed, at 1.0V versus AgCl/Ag. The reduction of BTL is irreversible and controlled by adsorption. Mechanism proposals are presented for these redox transformations. Optimisation is carried out univaryingly. Linearity ranges were 0.10–0.50 mmol L-1 and 2.0–9.0 µmolL-1 for anodic and cathodic peaks, respectively. The proposed method is applied to the determination of BTL in waters. Analytical results compare well with those obtained by an HPLC method.

Determination of carbamate and urea pesticide residues in fresh vegetables using microwave-assisted extraction and liquid chromatography

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography– photodiode array (LC–PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250–403 µgkg- 1 in each pesticide. The pesticide residues were extracted using 20mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µgkg- 1 for carbaryl to 12.3 µgkg- 1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds.

Electroanalytical study of the pesticide asulam

The electrochemical behaviour of the herbicide Asulam was studied by cyclic and square wave voltammetry. Asulam may be irreversibly oxidised at a glassy carbon electrode. Maximum currents were obtained at pH=1.9 in aqueous electrolyte solution. Based on the electrochemical behaviour of Asulam, two analytical methodologies were developed for its determination in water samples, using square wave voltammetry (SWV) and flow injection analysis (FIA) coupled with an amperometric detector. Limits of detection of 7.1x10-6 mol L-1 and 1.2x10-8 mol L-1 for SWV and FIA respectively, were achieved. Repeatability was calculated by assessing the relative standard deviation (%) for 10 consecutive determinations of one sample. The found values were 2.1% for SWV and 5.0% for FIA. Validation of the results provided by SWV and FIA methodologies was performed by comparison with results from an HPLC-DAD technique. Good relative deviations were found (<5%). Recovery trials were performed to assess the accuracy of the results and the obtained values were between 84% and 107% for both methods.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in façades of historic monuments of Oporto (Portugal)

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44– 429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ΣPAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Tensile behaviour of a structural adhesive at high temperatures by the extended finite element method

Component joining is typically performed by welding, fastening, or adhesive-bonding. For bonded aerospace applications, adhesives must withstand high-temperatures (200°C or above, depending on the application), which implies their mechanical characterization under identical conditions. The extended finite element method (XFEM) is an enhancement of the finite element method (FEM) that can be used for the strength prediction of bonded structures. This work proposes and validates damage laws for a thin layer of an epoxy adhesive at room temperature (RT), 100, 150, and 200°C using the XFEM. The fracture toughness (G Ic ) and maximum load ( ); in pure tensile loading were defined by testing double-cantilever beam (DCB) and bulk tensile specimens, respectively, which permitted building the damage laws for each temperature. The bulk test results revealed that decreased gradually with the temperature. On the other hand, the value of G Ic of the adhesive, extracted from the DCB data, was shown to be relatively insensitive to temperature up to the glass transition temperature (T g ), while above T g (at 200°C) a great reduction took place. The output of the DCB numerical simulations for the various temperatures showed a good agreement with the experimental results, which validated the obtained data for strength prediction of bonded joints in tension. By the obtained results, the XFEM proved to be an alternative for the accurate strength prediction of bonded structures.

Self-adaptive combination of global tabu search and local search for nonlinear equations

Solving systems of nonlinear equations is a very important task since the problems emerge mostly through the mathematical modelling of real problems that arise naturally in many branches of engineering and in the physical sciences. The problem can be naturally reformulated as a global optimization problem. In this paper, we show that a self-adaptive combination of a metaheuristic with a classical local search method is able to converge to some difficult problems that are not solved by Newton-type methods.

The European Project Semester at ISEP: the challenge of educating global engineers

Current engineering education challenges require approaches that promote scientific, technical, design and complementary skills while fostering autonomy, innovation and responsibility. The European Project Semester (EPS) at Instituto Superior de Engenharia do Porto (ISEP) (EPS@ISEP) is a one semester project-based learning programme (30 European Credit Transfer Units (ECTU)) for engineering students from diverse scientific backgrounds and nationalities that intends to address these goals. The students, organised in multidisciplinary and multicultural teams, are challenged to solve real multidisciplinary problems during one semester. The EPS package, although on project development (20 ECTU), includes a series of complementary seminars aimed at fostering soft, project-related and engineering transversal skills (10 ECTU). Hence, the students enrolled in this programme improve their transversal skills and learn, together and with the team of supervisors, subjects distinct from their core training. This paper presents the structure, implementation and results of the EPS@ISEP that was created in 2011 to apply the best engineering practices and promote internationalisation and engineering education innovation at ISEP.

The use of the boundary element method in the analysis of single lap joints

The most common techniques for stress analysis/strength prediction of adhesive joints involve analytical or numerical methods such as the Finite Element Method (FEM). However, the Boundary Element Method (BEM) is an alternative numerical technique that has been successfully applied for the solution of a wide variety of engineering problems. This work evaluates the applicability of the boundary elem ent code BEASY as a design tool to analyze adhesive joints. The linearity of peak shear and peel stresses with the applied displacement is studied and compared between BEASY and the analytical model of Frostig et al., considering a bonded single-lap joint under tensile loading. The BEM results are also compared with FEM in terms of stress distributions. To evaluate the mesh convergence of BEASY, the influence of the mesh refinement on peak shear and peel stress distributions is assessed. Joint stress predictions are carried out numerically in BEASY and ABAQUS®, and analytically by the models of Volkersen, Goland, and Reissner and Frostig et al. The failure loads for each model are compared with experimental results. The preparation, processing, and mesh creation times are compared for all models. BEASY results presented a good agreement with the conventional methods.

Smart Adhesive Joints: An overview of recent developments

Adhesive bonding is a viable technique for joining a wide range of materials. However, increasing the lifetime, reducing the costs, and improving the safety of structures are highly demanded nowadays. Hence, the development of new technologies and processes for easy recycle, heal, or self-heal of bonded structures are becoming of great interest for the industry. This paper provides an overview of the current developments in the use of “smart” adhesive technology and introduces the reader to early findings on the use of self-healing materials, thermally expandable particles, and nanoparticles, among others, in adhesives and their potential to increase the reliability of adhesive joints.

Numerical and Experimental Analysis of Balanced and Unbalanced Adhesive Single-Lap Joints between Aluminium Adherends

The single-lap joint is the most commonly used, although it endures significant bending due to the non-collinear load path, which negatively affects its load bearing capabilities. The use of material or geometric changes is widely documented in the literature to reduce this handicap, acting by reduction of peel and shear peak stresses or alterations of the failure mechanism emerging from local modifications. In this work, the effect of using different thickness adherends on the tensile strength of single-lap joints, bonded with a ductile and brittle adhesive, was numerically and experimentally evaluated. The joints were tested under tension for different combinations of adherend thickness. The effect of the adherends thickness mismatch on the stress distributions was also investigated by Finite Elements (FE), which explained the experimental results and the strength prediction of the joints. The numerical study was made by FE and Cohesive Zone Modelling (CZM), which allowed characterizing the entire fracture process. For this purpose, a FE analysis was performed in ABAQUS® considering geometric non-linearities. In the end, a detailed comparative evaluation of unbalanced joints, commonly used in engineering applications, is presented to give an understanding on how modifications in the bonded structures thickness can influence the joint performance.

Effect of Adherend Recessing on the Tensile Strength of Single Lap Joints

Bonded joints are gaining importance in many fields of manufacturing owing to a significant number of advantages to the traditional methods. The single lap joint (SLJ) is the most commonly used method. The use of material or geometric changes in SLJ reduces peel and shear peak stresses at the damage initiation sites. In this work, the effect of adherend recessing at the overlap edges on the tensile strength of SLJ, bonded with a brittle adhesive, was experimentally and numerically studied. The recess dimensions (length and depth) were optimized for different values of overlap length (LO), thus allowing the maximization of the joint’s strength by the reduction of peak stresses at the overlap edges. The effect of recessing was also investigated by a finite element (FE) analysis and cohesive zone modelling (CZM), which allowed characterizing the entire fracture process and provided joint strength predictions. For this purpose, a static FE analysis was performed in ABAQUS1 considering geometric nonlinearities. In the end, the experimental and FE results revealed the accuracy of the FE analysis in predicting the strength and also provided some design principles for the strength improvement of SLJ using a relatively simple and straightforward technique.

Condition-Based Diagnosis of Mechatronic Systems Using a Fractional Calculus Approach

While fractional calculus (FC) is as old as integer calculus, its application has been mainly restricted to mathematics. However, many real systems are better described using FC equations than with integer models. FC is a suitable tool for describing systems characterised by their fractal nature, long-term memory and chaotic behaviour. It is a promising methodology for failure analysis and modelling, since the behaviour of a failing system depends on factors that increase the model’s complexity. This paper explores the proficiency of FC in modelling complex behaviour by tuning only a few parameters. This work proposes a novel two-step strategy for diagnosis, first modelling common failure conditions and, second, by comparing these models with real machine signals and using the difference to feed a computational classifier. Our proposal is validated using an electrical motor coupled with a mechanical gear reducer.

The effect of adhesive thickness on the mechanical behavior of a structural polyurethane adhesive

One parameter that influences the adhesively bonded joints performance is the adhesive layer thickness. Hence, its effect has to be investigated experimentally and should be taken into consideration in the design of adhesive joints. Most of the results from literature are for typical structural epoxy adhesives which are generally formulated to perform in thin sections. However, polyurethane adhesives are designed to perform in thicker sections and might have a different behavior as a function of adhesive thickness. In this study, the effect of adhesive thickness on the mechanical behavior of a structural polyurethane adhesive was investigated. The mode I fracture toughness of the adhesive was measured using double-cantilever beam (DCB) tests with various thicknesses of the adhesive layer ranging from 0.2 to 2 mm. In addition, single lap joints (SLJs) were fabricated and tested to assess the influence of adhesive thickness on the lap-shear strength of the adhesive. An increasing fracture toughness with increasing adhesive thickness was found. The lap-shear strength decreases as the adhesive layer gets thicker, but in contrast to joints with brittle adhesives the decrease trend was less pronounced.