Study of the voltammetric behaviour of metam and its application to an amperometric flow system

The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MTaqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L−1. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/ Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10−1 to 1.0 mg L−1 using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min−1. Real samples were analysed via calibration curves over the concentration range 1.3×10−2 to 1.3 mg L−1. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L−1), and the value obtained was 1.5%.

Fractional dynamics and MDS visualization of earthquake phenomena

This paper analyses earthquake data in the perspective of dynamical systems and fractional calculus (FC). This new standpoint uses Multidimensional Scaling (MDS) as a powerful clustering and visualization tool. FC extends the concepts of integrals and derivatives to non-integer and complex orders. MDS is a technique that produces spatial or geometric representations of complex objects, such that those objects that are perceived to be similar in some sense are placed on the MDS maps forming clusters. In this study, over three million seismic occurrences, covering the period from January 1, 1904 up to March 14, 2012 are analysed. The events are characterized by their magnitude and spatiotemporal distributions and are divided into fifty groups, according to the Flinn–Engdahl (F–E) seismic regions of Earth. Several correlation indices are proposed to quantify the similarities among regions. MDS maps are proven as an intuitive and useful visual representation of the complex relationships that are present among seismic events, which may not be perceived on traditional geographic maps. Therefore, MDS constitutes a valid alternative to classic visualization tools for understanding the global behaviour of earthquakes.

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.

Observability of nonlinear fractional dynamical systems

We study the observability of linear and nonlinear fractional differential systems of order 0 < α < 1 by using the Mittag-Leffler matrix function and the application of Banach’s contraction mapping theorem. Several examples illustrate the concepts.

Characterizing the timing behaviour of power-line communication by means of simulation

Although power-line communication (PLC) is not a new technology, its use to support communication with timing requirements is still the focus of ongoing research. Recently, a new infrastructure was presented, intended for communication using power lines from a central location to geographically dispersed nodes using inexpensive devices. This new infrastructure uses a two-level hierarchical power-line system, together with an IP-based network. Within this infrastructure, in order to provide end-toend communication through the two levels of the powerline system, it is necessary to fully understand the behaviour of the underlying network layers. The masterslave behaviour of the PLC MAC, together with the inherent dynamic topology of power-line networks are important issues that must be fully characterised. Therefore, in this paper we present a simulation model which is being used to study and characterise the behaviour of power-line communication.

Dynamical analysis of the global warming

Global warming is a major concern nowadays. Weather conditions are changing, and it seems that human activity is one of the main causes. In fact, since the beginning of the industrial revolution, the burning of fossil fuels has increased the nonnatural emissions of carbon dioxide to the atmosphere. Carbon dioxide is a greenhouse gas that absorbs the infrared radiation produced by the reflection of the sunlight on the Earth’s surface, trapping the heat in the atmosphere. Global warming and the associated climate changes are being the subject of intensive research due to their major impact on social, economic, and health aspects of human life. This paper studies the global warming trend in the perspective of dynamical systems and fractional calculus, which is a new standpoint in this context. Worldwide distributed meteorological stations and temperature records for the last 100 years are analysed. It is shown that the application of Fourier transforms and power law trend lines leads to an assertive representation of the global warming dynamics and a simpler analysis of its characteristics.

Real-time communications over cluster-tree sensor networks with mobile sink behaviour

Modelling the fundamental performance limits of wireless sensor networks (WSNs) is of paramount importance to understand the behaviour of WSN under worst case conditions and to make the appropriate design choices. In that direction, this paper contributes with a methodology for modelling cluster tree WSNs with a mobile sink. We propose closed form recurrent expressions for computing the worst case end to end delays, buffering and bandwidth requirements across any source-destination path in the cluster tree assuming error free channel. We show how to apply our theoretical results to the specific case of IEEE 802.15.4/ZigBee WSNs. Finally, we demonstrate the validity and analyze the accuracy of our methodology through a comprehensive experimental study, therefore validating the theoretical results through experimentation.

Assessing the behaviour of RC beams subject to significant gravity loads under cyclic loads

Gravity loads can affect a reinforced concrete structure's response to seismic actions, however, traditional procedures for testing the beam behaviour do not take this effect into consideration. An experimental campaign was carried out in order to assess the influence of the gravity load on RC beam connection to the column subjected to cyclic loading. The experiments included the imposition of a conventional quasi-static test protocol based on the imposition of a reverse cyclic displacement history and of an alternative cyclic test procedure starting from the gravity load effects. The test results are presented, compared and analysed in this paper. The imposition of a cyclic test procedure that included the gravity loads effects on the RC beam ends reproduces the demands on the beams' critical zones more realistically than the traditional procedure. The consideration of the vertical load effects in the test procedure led to an accumulation of negative (hogging) deformation. This phenomenon is sustained with the behaviour of a portal frame system under cyclic loads subject to a significant level of the vertical load, leading to the formation of unidirectional plastic hinges. In addition, the hysteretic behaviour of the RC beam ends tested was simulated numerically using the nonlinear structural analysis software - OpenSees. The beam-column model simulates the global element behaviour very well, as there is a reasonable approximation to the hysteretic loops obtained experimentally. (C) 2013 Elsevier Ltd. All rights reserved.

Object transportation by multiple mobile robots controlled by attractor dynamics: theory and implementation

Dynamical systems theory is used as a theoretical language and tool to design a distributed control architecture for teams of mobile robots, that must transport a large object and simultaneously avoid collisions with (either static or dynamic) obstacles. Here we demonstrate in simulations and implementations in real robots that it is possible to simplify the architectures presented in previous work and to extend the approach to teams of n robots. The robots have no prior knowledge of the environment. The motion of each robot is controlled by a time series of asymptotical stable states. The attractor dynamics permits the integration of information from various sources in a graded manner. As a result, the robots show a strikingly smooth an stable team behaviour.

Using a cohesive damage model to predict the tensile behaviour of CFRP single-strap repairs

This work addresses both experimental and numerical analyses regarding the tensile behaviour of CFRP single-strap repairs. Two fundamental geometrical parameters were studied: overlap length and patch thickness. The numerical model used ABAQUS® software and a developed cohesive mixed-mode damage model adequate for ductile adhesives, and implemented within interface finite elements. Stress analyses and strength predictions were carried out. Experimental and numerical comparisons were performed on failure modes, failure load and equivalent stiffness of the repair. Good correlation was found between experimental and numerical results, showing that the proposed model can be successfully applied to bonded joints or repairs.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

The solvation and redox behaviour of mixed ligand COPPER(II) complexes of acetylacetonate and aromatic dimines in ionic liquids

The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.

Tensile behaviour of single and double-strap repairs on aluminium structures

In this work, an experimental study was performed on the influence of plug filling, loading rate and temperature on the tensile strength of single-strap (SS) and double-strap (DS) repairs on aluminium structures. The experimental programme includes repairs with different values of overlap length (LO=10, 20 and 30 mm), and with and without plug filling. The influence of the testing speed on the repairs strength is also addressed (considering 0.5, 5 and 25 mm/min). Accounting for the temperature effects, tests were carried out at room temperature, 50ºC and 80ºC. This will permit a comparative evaluation of the adhesive tested below and above the Glass Transition Temperature (Tg), established by the manufacturer at 67ºC. The global tendencies of the test results concerning the plug filling and overlap length analyses are interpreted from the fracture modes and typical stress distributions for bonded repairs. According to the results obtained from this work, design guidelines for repairing aluminium structures were recommended.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.