Theory of small-signal ac response of a dielectric liquid containing two groups of ions

The analysis of Macdonald for electrolytes is generalized to the case in which two groups of ions are present. We assume that the electrolyte can be considered as a dispersion of ions in a dielectric liquid, and that the ionic recombination can be neglected. We present the differential equations governing the ionic redistribution when the liquid is subjected to an external electric field, describing the simultaneous diffusion of the two groups of ions in the presence of their own space charge fields. We investigate the influence of the ions on the impedance spectroscopy of an electrolytic cell. In the analysis, we assume that each group of ions have equal mobility, the electrodes perfectly block and that the adsorption phenomena can be neglected. In this framework, it is shown that the real part of the electrical impedance of the cell has a frequency dependence presenting two plateaux, related to a type of ambipolar and free diffusion coefficients. The importance of the considered problem on the ionic characterization performed by means of the impedance spectroscopy technique was discussed. (c) 2008 American Institute of Physics.

The electrochemical behaviour of Ti-13Nb-13Zr alloy in various solutions

The electrochemical behaviour of a near-beta Ti-13Nb-13Zr alloy for the application as implants was investigated in various solutions. The electrolytes used were 0.9 wt% NaCl solution, Hanks` solution and a culture medium known as minimum essential medium (MEM) composed of salts, vitamins and amino acids, all at 37 degrees C. The electrochemical behaviour was investigated by the following electrochemical techniques: open circuit potential measurements as a function of time, electrochemical impedance spectroscopy (EIS) and determination of polarisation curves. The obtained results showed that the Ti alloy was passive in all electrolytes. The EIS results were analysed using an equivalent electrical circuit representing a duplex structure oxide layer, composed of an inner barrier layer, mainly responsible for the alloy corrosion resistance, and an outer and porous layer that has been associated to osteointegration ability. The properties of both layers were dependent on the electrolyte used. The results suggested that the thickest porous layer is formed in the MEM solution whereas the impedance of the barrier layer formed in this solution was the lowest among the electrolytes used. The polarisation curves showed a current increase at potentials around 1300 mV versus saturated calomel electrode (SCE), and this increase was also dependent on the electrolyte used. The highest increase in current density was also associated to the MEM solution suggesting that this is the most aggressive electrolyte to the Ti alloy among the three tested solutions.

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

This work investigates the influence of the addition of cerium (IV) ions on the anticorrosion properties of organic-inorganic hybrid coatings applied to passivated tin coated steel. In order to evaluate the specific effect of cerium (IV) addition on nanostructural features of the organic and inorganic phases of the hybrid coating, the hydrolytic polycondensation of silicon alkoxide and the radical polymerization of the methyl methacrylate (MMA) function were induced separately. The corrosion resistance of the coatings was evaluated by means of linear polarization, Tafel type curves and electrochemical impedance measurements. The impedance results obtained for the hybrid coatings were discussed based on an electrical equivalent circuit used to fit the experimental data. The electrochemical results clearly showed the improvement of the protective properties of the organic-inorganic hybrid coating mainly when the cerium (IV) was added to the organic phase solution precursor, which seemed to be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. (C) 2010 Elsevier Ltd. All rights reserved.

Using multidimensional projection techniques for reaching a high distinguishing ability in biosensing

Recent advances in the control of molecular engineering architectures have allowed unprecedented ability of molecular recognition in biosensing, with a promising impact for clinical diagnosis and environment control. The availability of large amounts of data from electrical, optical, or electrochemical measurements requires, however, sophisticated data treatment in order to optimize sensing performance. In this study, we show how an information visualization system based on projections, referred to as Projection Explorer (PEx), can be used to achieve high performance for biosensors made with nanostructured films containing immobilized antigens. As a proof of concept, various visualizations were obtained with impedance spectroscopy data from an array of sensors whose electrical response could be specific toward a given antibody (analyte) owing to molecular recognition processes. In addition to discussing the distinct methods for projection and normalization of the data, we demonstrate that an excellent distinction can be made between real samples tested positive for Chagas disease and Leishmaniasis, which could not be achieved with conventional statistical methods. Such high performance probably arose from the possibility of treating the data in the whole frequency range. Through a systematic analysis, it was inferred that Sammon`s mapping with standardization to normalize the data gives the best results, where distinction could be made of blood serum samples containing 10(-7) mg/mL of the antibody. The method inherent in PEx and the procedures for analyzing the impedance data are entirely generic and can be extended to optimize any type of sensor or biosensor.

Dielectric Dispersion of Water in the Frequency Range from 10 mHz to 30 MHz

We investigate the dielectric dispersion of water, specially in the low-frequency range, by using the impedance spectroscopy technique. The frequency dependencies of the real R and imaginary Z parts of the impedance Could not be explained by means of the Usual description of the dielectric properties of the water as all insulating liquid containing ions. This is due to the incomplete knowledge of the parameters entering in the fundamental equations describing the evolution of the system, and oil the mechanisms regulating the exchange of charge of the cell with the external circuit. We propose a simple description of our experimental data based on the model of Debye, by invoking a dc conductivity of the cell, related to the nonblocking character of the electrodes. A discussion on the electric Circuits able to simulate the cell under investigation, based oil bulk and Surface elements, is also reported. We find that the simple circuit formed by a series of two parallels of resistance and capacitance is able to reproduce the experimental data concerning the real and imaginary part of the electrical impedance of the cell for frequency larger than 1 Hz. According to this description, one of the parallels takes into account the electrical properties of interface between the electrode and water, and the other of the bulk. For frequency lower than 1 Hz, a good agreement with the experimental data is obtained by simulating the electrical properties of the interface by means of the constant phase element.

Ac and dc magnetotransport properties of the phase-separated La(0.6)Y(0.1)Ca(0.3)MnO(3) manganite

The physical properties of the La(0.6)Y(0.1)Ca(0.3)MnO(3) compound have been investigated, focusing on the magnetoresistance phenomenon studied by both dc and ac electrical transport measurements. X-ray diffraction and scanning electron microscopy analysis of ceramic samples prepared by the sol-gel method revealed that specimens are single phase and have average grain size of similar to 0.5 mu m. Magnetization and 4-probe dc electrical resistivity rho(T,H) experiments showed that a ferromagnetic transition at T(C) similar to 170 K is closely related to a metal-insulator (MI) transition occurring at essentially the same temperature T(MI). The magnetoresistance effect was found to be more pronounced at low applied fields (H <= 2.5 T) and temperatures close to the MI transition. The ac electrical transport was investigated by impedance spectroscopy Z(f,T,H) under applied magnetic field H up to 1 T. The Z(f,T,H) data exhibited two well-defined relaxation processes that exhibit different behaviors depending on the temperature and applied magnetic field. Pronounced effects were observed close to T (C) and were associated with the coexistence of clusters with different electronic and magnetic properties. In addition, the appreciable decrease of the electrical permittivity epsilon`(T,H) is consistent with changes in the concentration of e(g) mobile holes, a feature much more pronounced close to T (C).

Dendrimer-assisted immobilization of alcohol dehydrogenase in nanostructured films for biosensing: Ethanol detection using electrical capacitance measurements

The selective determination of alcohol molecules either in aqueous solutions or in vapor phase is of great importance for several technological areas. In the last years, a number of researchers have reported the fabrication of highly sensitive sensors for ethanol detection, based upon specific enzymatic reactions occurring at the surface of enzyme-containing electrodes. In this study, the enzyme alcohol dehydrogenase (ADH) was immobilized in a layer-by-layer fashion onto Au-interdigitated electrodes (IDEs), in conjunction with layers of PAMAM dendrimers. The immobilization process was followed in Teal time using quartz crystal microbalance (QCM), indicating that an average mass of 52.1 ng of ADH was adsorbed at each deposition step. Detection was carried out using a novel strategy entirely based upon electrical capacitance measurements, through which ethanol could be detected at concentrations of 1 part per million by volume (ppmv). (C) 2007 Elsevier B.V. All rights reserved.

How grain boundaries modify the high-temperature dielectric response of ferroelectric electroceramics like BaTiO(3)?

Dielectric properties of BaTiO(3) ferroelectric ceramics were studied over wide frequency and temperature ranges. The materials showed complex dielectric behaviors, which included an anomalous increase of permittivity towards higher temperatures. Important, this property tended however to saturate to values that varied with grain-boundary density. Application of impedance spectroscopy and consideration of the series-layer model allowed a coherent discussion of these and other interesting observations from this work. In particular, analysis of the relationship existing in this model between macroscopic and microscopic dielectric properties rendered possible to account for grain vs. grain-boundary dielectric behaviors, in harmony with microstructure features, and to know the dielectric anomaly strength to be in fact expected from grain boundaries in such polycrystalline materials. (C) 2010 Elsevier Ltd. All rights reserved.

Development of zirconia-magnesia/zirconia-yttria composite solid electrolytes

Composite solid electrolytes were prepared by thoroughly mixing ZrO2:8 mol% MgO (Z8Mg) and ZrO(2):3 mol% Y(2)O(3) (Z3Y) ceramic powders followed by pressing and sintering at 1500 degrees C/1 h. The properties of the sintered pellets were studied by X-ray diffraction for evaluation of the structural phases by the Rietveld method, by high-temperature dilatometry for analysis of the thermal shrinkage/expansion behavior, and by impedance spectroscopy for determination of the oxide ion conductivity. The x(Z8Mg)+(1-x)(Z3Y) specimens, x= 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0, are partially stabilized (monoclinic, cubic and tetragonal phases) with density >94% of the theoretical density and show thermal shock resistance and electrical conductivity values suitable for high-temperature oxygen gas detection. One-end closed tube samples of the composite solid electrolytes were assembled in Pt/Z8Mg+Z3Y/Cr+Cr(2)O(3)/Pt electrochemical cells for exposure to different levels of oxygen in the 1-850 ppm range. The total electrical conductivity increases for increasing the relative Z3Y content. Addition of Z3Y to Z8Mg (80 wt.%-20 wt.%) suppresses the electronic contribution to the electrical conductivity at 620 degrees C. (c) 2008 Elsevier B.V. All rights reserved.

Role of Polyelectrolyte for Layer-by-Layer Compact TiO(2) Films in Efficiency Enhanced Dye-Sensitized Solar Cells

Efficient compact TiO(2) films using different polyeleetrolytes are prepared by the layer-by-layer technique (LbL) and applied as an effective contact and blocking film in dye-sensitized solar cells (DSCs). The polyanion thermal stability plays a major role on the compact layers, which decreases back electron transfer processes and current losses at the FTO/TiO(2) interface. FESEM images show that polyelectrolytes such is sodium sullonated polystyrene (PSS) and sulfonated lignin (SE), in comparison to poly(acrylic acid) (FAA), ensure an adequate morphology for the LbL TiO(2) layer deposited before the mesoporous film, even triter the sintering step at 450 degrees C. The so treated photoanode in DSCs leads to a 30% improvement On the overall conversion efficiency. Electrochemical impedance spectroscopy (EIS) is employed to ascertain the role of die compact films with such polyelectrolytes. The significant increase in V(oc) of the solar cells with adequate polyelectrolytes in the LbL TiO(2) films shows their pivotal role in decreasing the electron recombination at the FTO surface and enhancing the electrical contact of FTO with the mesoporous TiO(2) layer.

Evidence of redox interactions between polypyrrole and Fe(3)O(4) in polypyrrole-Fe(3)O(4) composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe(3)O(4) incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation. (C) 2009 Elsevier Ltd. All rights reserved.

Effect of adding CaO to ZrO(2) support on nickel catalyst activity in dry reforming of methane

Nickel catalysts with a load of 5 wt% Ni, supported on pure ZrO(2) and ZrO(2) stabilized with 4, 8 and 14 mol% CaO, were prepared by the polymerization method. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction with hydrogen (TPR-H(2)), specific surface area (BET) and impedance spectroscopy (IS) and tested in the carbon dioxide reforming of methane. The XRD patterns showed the presence of the oxide precursor (NiO) and the tetragonal phase of CaO-ZrO(2) solid solutions. According to the TPR-H(2) analysis, the reduction of various NiO species was influenced by the support composition. The electrical properties of the support have a proportional effect on the catalytic activities. Catalytic tests were done at 800 degrees C for 6 h and the composition of the gaseous products and the catalytic conversion depended on the CaO-ZrO(2) solid solution composition and its influence on supported NiO species. A direct relation was found between the variation in the electrical conductivity of the support, the nickel species supported on it and the performance in the catalytic tests. (C) 2009 Elsevier B.V. All rights reserved.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This À-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable À-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.

Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

DFT and electrochemical studies on nortriptyline oxidation sites

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule`s activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.