Influence of polyaniline and phthalocyanine hole-transport layers on the electrical performance of light-emitting diodes using MEH-PPV as emissive material

The influence of layer-by-layer films of polyaniline and Ni-tetrasulfonated phthalocyanine (PANI/Ni-TS-Pc) on the electrical performance of polymeric light-emitting diodes (PLED) made from (poly[2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene vinylene]) (MEH-PPV) is investigated by using current versus voltage measurements and impedance spectroscopy. The PLED is composed by a thin layer of MEH-PPV sandwiched between indium tin oxide (ITO) and aluminum electrodes, resulting in the device structure ITO/(PANI/Ni-TS-Pc)(n)/MEH-PPV/Al, where n stands for the number of PANI/Ni-TS-Pc bilayers. The deposition of PANI/Ni-TS-Pc leads to a decrease in the driving voltage of the PLEDs, which reaches a minimum when n = 5 bilayers. In addition, impedance spectroscopy data reveal that the PLED impedance decreases as more PANI/Ni-TS-Pc bilayers are deposited. The PLED structure is further described by an equivalent circuit composed by two R-C combinations, one for the bulk and other for the interface components, in series with a resistance originated in the ITO contact. From the impedance curves, the values for each circuit element is determined and it is found that both, bulk and interface resistances are decreased upon PANI/Ni-TS-Pc deposition. The results indicate that PANI/NiTS-Pc films reduce the contact resistance at ITO/MEH-PPV interface, and for that reason improve the hole-injection within the PLED structure. (c) 2007 Elsevier B.V. All rights reserved.

Curves in the Minkowski plane and their contact with pseudo-circles

We study the caustic, evolute, Minkowski symmetry set and parallels of a smooth and regular curve in the Minkowski plane.

The Effect of Contact on the Filter Paper Method for Measuring Soil Suction

The filter paper method is one of the most commonly used and critiqued techniques for measuring soil suction. However, many aspects related to its use still require some clarification. The results of a comprehensive study on the effect of the contact between the soil grains and soil water and the filter paper are presented herein. We investigated the influence of the equilibration time, the texture of the porous material and the degree of contact, or lack thereof, between the soil grains and the filter paper using Miamian #42 and three different types of porous material. To enhance the difference between the total suction and the matrix suction, osmotic suction was induced by saturating the specimens with a sodium chloride solution.

Development and Evaluation of a Pseudoreference Pt//Ag/AgCl Electrode for Electrochemical Systems

The use of standard reference electrodes, such as Ag/AgCl or saturated calomel electrodes, in potentiometric and amperometric studies involving miniaturized electrochemical systems, or those operating under positive hydraulic pressure, is often impractical. Placement of the reference electrode in the direct vicinity of the working electrode is often prohibited by the dimensions or layout of the electrochemical cell, while the alternative strategy of locating the reference electrode in a separate compartment often leads to electrolyte leakage and contamination of the system. In the present study, we have investigated the functionality of a pseudoreference electrode comprising a platinum wire, one end of which was maintained in intimate contact with the internal solution of an Ag/AgCl reference electrode while the other was connected, via a BNC connector, to a platinum probe located within the electrochemical cell. Linear and cyclic voltammetric studies, involving both aqueous and nonaqueous electrolytes, were carried out using the pseudoreference electrode and an electrochemical cup-type cell with three electrodes or an electrochemical flow reactor. In all cases, the functionality of the Pt//Ag/AgCl system was similar to that of a conventional Ag/AgCl reference electrode. Variations in the electrolyte did not alter the potential or voltammetric profile recorded when using the pseudoreference system, although peak currents were generally improved and potential values shifted by approximately +350 mV in comparison with the Ag/AgCl electrode, therefore, the system pseudoreference can be applied in any electrochemical system due to the constant potential difference. It is concluded that the pseudoreference electrode can be used with advantage to obtain potentiometric and amperometric measurements in both simple and complex electrochemical systems.

Two versions of the threshold contact model in two dimensions

Two versions of the threshold contact process ordinary and conservative - are studied on a square lattice. In the first, particles are created on active sites, those having at least two nearest neighbor sites occupied, and are annihilated spontaneously. In the conservative version, a particle jumps from its site to an active site. Mean-field analysis suggests the existence of a first-order phase transition, which is confirmed by Monte Carlo simulations. In the thermodynamic limit, the two versions are found to give the same results. (C) 2012 Elsevier B.V. All rights reserved.

Mechanistic changes observed in heavy water for nitrate reduction reaction on palladium-modified Pt(hkl) electrodes

Reduction of nitrate on palladium-modified platinum single-crystal electrodes has been investigated both voltammetrically and spectroscopically in acidic media (pH = 1). Results obtained in H2O and D2O solvents are compared for the three crystallographic orientations. FTIR and differential electrochemical mass spectrometry (DEMS) results clearly indicate that the isotopic substitution of the solvent has a large effect in the mechanism of the reaction, changing the nature of the detected products. For Pt(111)/Pd and Pt(100)/Pd, N2O is detected as the main product of nitrate reduction when D2O is used as solvent, while no N2O is detected when the reaction is performed in H2O. For Pt(110)/Pd, N2O is detected in both solvents, although the use of D2O clearly favours the preferential formation of this product. The magnitude of voltammetric currents is also affected by the nature of the solvent. This has been analysed considering, in addition to the different product distribution, the existence of different transport numbers and optical constants of the solvent.

STRATEGIES FOR PREPARATION OF MOLECULARLY IMPRINTED POLYMERS MODIFIED ELECTRODES AND THEIR APPLICATION IN ELECTROANALYSIS: A REVIEW

Molecularly imprinted polymers (MIP's) have been applied in several areas of analytical chemistry, including the modification of electrodes. The main purpose of such modification is improving selectivity; however, a gain in sensitivity was also observed in many cases. The most frequent approaches for these modifications are the electrodeposition of polymer films and sol gel deposits, spin and drop coating and self-assembling of films on metal nanoparticles. The preparation of bulk (body) modified composites as carbon pastes and polymer agglutinated graphite have also been investigated. In all cases several analytes including pharmaceuticals, pesticides, and inorganic species, as well as molecules with biological relevance have been successfully used as templates and analyzed with such devices in electroanalytical procedures. Herein, 65 references are presented concerning the general characteristics and some details related to the preparation of MIP's including a description of electrodes modified with MIP's by different approaches. The results using voltammetric and amperometric detection are described.

Borohydride electrooxidation on Au and Pt electrodes

Direct borohydride fuel cells (DBFCs) are attractive energy generators for powering portable electronic devices, mainly due to their high energy density and number of electrons per borohydride ion. However, the lack of a highly efficient electrocatalyst for the borohydride oxidation reaction limits the performance of these devices. The most commonly studied electrocatalysts for this reaction are composed of gold and platinum. Nevertheless, for these metals, the borohydride electrooxidation reaction mechanism (BOR) is not completely understood, and the total oxidation reaction, involving eight electrons per BH4- species, competes with parallel reactions, with a lower number of exchanged electrons and/or with heterogeneous chemical hydrolysis. Considering the above-mentioned issues, this work presents recent advances in the knowledge of the BOR pathways on polycrystalline (bulk) Au and Pt electrocatalysts. It presents the studies of the BOR reaction on Au and Pt electrodes using in situ Fourier Transform Infrared Spectroscopy (FUR), and on-line Differential Electrochemical Mass Spectrometry (DEMS). The spectroscopic and spectrometric data provided physical evidence of intermediate species and the formation of H-2 in the course of the BOR as a function of the electrode potential. These results enabled to advance in the knowledge about the BOR pathways on Au and Pt electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 mu M; dynamic range: 2-200 mu M, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: +/- 7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.

Effect of contact and systemic insecticides on the sharpshooter Bucephalogonia xanthophis (Hemiptera: cicadellidae), a vector of Xylella fastidiosa in citrus

The knockdown and toxic effects of insecticides of different chemical groups and modes of action registered for citrus in Brazil were investigated for effective control of Bucephalogonia xanthophis, a sharpshooter vector of Xylella fastidiosa in citrus. The active ingredients dimethoate (1.2 mL/1.2L), imidacloprid (0.24 mL/1.2L) and lambda-cyhalothrin (0.24 mL/1.2L), as well as a control (water), were sprayed onto branches of potted-citrus nursery trees to evaluate the effect of residual contact. The insects were confined on sprayed branches by using sleeve cages, in groups of 10 per branch (5 branches/treatment). Lambdacyhalothrin showed a knockdown effect on B. xanthophis (>70% mortality within 2 h of exposure), and the residues were effective for approximately one wk. Imidacloprid, lambdacyhalothrin and dimethoate suppressed the vector populations for up to 3 wk after application, when the insects were exposed to sprayed plants for at least 24 h. In another experiment, 2 neonicotinoid insecticides (thiamethoxam and imidacloprid) were applied by soil drench to potted nursery trees, in order to study their systemic effect, i.e., mortality by ingestion on sharpshooter adults. Thiamethoxam and imidacloprid effectively controlled the vectors at all concentrations tested, when the insects were exposed to treated plants for 24 h (>80% mortality) or 48 h (near 100% mortality). The knockdown effect of thiamethoxam and lambda-cyhalothrin might be particularly important to prevent vector transmission of X. fastidiosa in citrus groves.

Development of paper based electrodes: From air-breathing to paintable enzymatic cathodes

This work presents the results from the development of bio-cathodes for the application on paper-based biofuel cells. Our main goal here is to demonstrate the possibility of using different designs of air-breathing bio-cathodes and ink-based bio-cathodes for this new type of paper based electrochemical cell. The electrochemical performance for the bio-electrocatalytic oxygen reduction reaction was studied by using open circuit voltage and amperometry measurements, as well as polarization curves to probe the four-electron reduction reaction of ambient oxygen catalyzed by bilirubin oxidase (BOx). The electrochemical measurements showed that all procedures allowed the direct electron transfer from the active site of the bilirubin oxidase to the electrode surface with a limiting current density of almost 500 mu A cm(-2) for an air-breathing BOx cathode and 150 mu A cm(-2) for an ink based BOx cathode. Under a load of 300 mV a stable current density was obtained for 12 h of continuous operation. (C) 2012 Elsevier Ltd. All rights reserved.

Experimental and numerical analysis of dry contact in the pin on disc test

The reduction of friction and wear in systems presenting metal-to-metal contacts, as in several mechanical components, represents a traditional challenge in tribology. In this context, this work presents a computational study based on the linear Archard's wear law and finite element modeling (FEM), in order to analyze unlubricated sliding wear observed in typical pin on disc tests. Such modeling was developed using finite element software Abaqus® with 3-D deformable geometries and elastic–plastic material behavior for the contact surfaces. Archard's wear model was implemented into a FORTRAN user subroutine (UMESHMOTION) in order to describe sliding wear. Modeling of debris and oxide formation mechanisms was taken into account by the use of a global wear coefficient obtained from experimental measurements. Such implementation considers an incremental computation for surface wear based on the nodal displacements by means of adaptive mesh tools that rearrange local nodal positions. In this way, the worn track was obtained and new surface profile is integrated for mass loss assessments. This work also presents experimental pin on disc tests with AISI 4140 pins on rotating AISI H13 discs with normal loads of 10, 35, 70 and 140 N, which represent, respectively, mild, transition and severe wear regimes, at sliding speed of 0.1 m/s. Numerical and experimental results were compared in terms of wear rate and friction coefficient. Furthermore, in the numerical simulation the stress field distribution and changes in the surface profile across the worn track of the disc were analyzed. The applied numerical formulation has shown to be more appropriate to predict mild wear regime than severe regime, especially due to the shorter running-in period observed in lower loads that characterizes this kind of regime.