Separation of dielectric and space charge polarizations in CaCu3Ti4O12/CaTiO3 composite polycrystalline systems

The complex analysis of dielectric/capacitance is a very useful approach to separate different polarization contributions existing in polycrystalline ceramics. In this letter, the authors use this type of spectroscopic analysis to separate the bulk's dielectric dipolar relaxation contributions from the polarization contribution due to space charge in the grain boundaries of a CaCu3Ti4O12/CaTiO3 polycrystalline composite system. The bulk dielectric dipolar relaxation was attributed to the self-intertwined domain structures from the CaCu3Ti4O12 phase coupled to the dipole relaxation from the CaTiO3 phase, while the space charge relaxation was attributed to the Schottky-type potential barrier responsible for the highly non-Ohmic properties observed in this composite polycrystalline system.

Preparation, microstructural and electrical characterization of SrTiO3 thin films prepared by chemical route

Polycrystalline SrTiO3 thin films having a cubic perovskite structure were prepared at different temperatures by the polymeric precursor method on platinum-coated silicon substrate. Crystalline films with uniform composition and thickness were prepared by spin-coating and the post-deposition heat treatment was carried out at different temperatures. The film showed good structural, dielectric, and insulating properties, Scanning electron microscopy (SEM) micrographs showed no occurrence of interdiffusion between the bottom electrode (platinum) and the film during post-annealing, indicating a stable interface between the SrTiO3 and the bottom electrode. The dielectric constant and dissipation factor at a frequency of 100 kHz were 250 and 0.01, respectively, for a 360 nm thick film annealed at 600 degreesC. The capacitance versus applied voltage characteristics showed that the capacitance was almost independent of the applied voltage. The I-V characteristics were ohmic in low fields and a Schottky emission and/or Poole-Frenkel emission were postulated in high fields. Room temperature leakage current density was found to be in the order of 10(-7) A/cm(2) for a 360 nm thick film in an applied electric field of about 100 kV/cm. The charge storage density of 36 fC/mum(2) was obtained in an applied electric field of about 100 kV/cm. (C) 2001 Published by Elsevier B.V. Ltd. All rights reserved.

Thermogravimetry (TG) applied to the study of the reaction of mercury with platinum-rhodium alloy

Thermogravimetry (TG) energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface, X-ray diffraction (XRD), inductively coupled plasma emission spectroscopy and atomic spectroscopy with cold vapor generation have been used to study the reaction of mercury with platinum-rhodium (Pt-Rh) alloy. The results suggest that, the electrodeposited Hg film reacts with Pt-Rh to form intermetallic compounds of different stability, when heated indicated by at least four weight loss steps. Intermetallic compounds as PtHg4 and PtHg2 was characterized by XRD. These intermetallic compound are the main product presents on the surface of the samples after remotion of the bulk mercury via thermal desorption techniques. (C) 2002 Elsevier B.V. B.V. All rights reserved.

SURFACE EFFECTS IN THE HYDROGEN EVOLUTION REACTION ON NI-ZN ALLOY ELECTRODES IN ALKALINE-SOLUTIONS

Hydrogen evolution reaction was studied on Ni-Zn (25% of Ni before leaching) in 1 M NaOH at 25 degrees C. These electrodes were characterized by very low Tafel slopes of 67 mV dec(-1). Other techniques used included potential and current pulse, potential relaxation in an open circuit, and ac impedance spectroscopy. Analysis of the experimental results led to the conclusion that hydrogen adsorption in the surface layers was responsible for the observed behavior. Influence of the oxidation of the electrode surface and the addition of poisons, thiourea and cyanides, were also studied. These processes inhibit the hydrogen absorption and restore ''normal'' Tafel slopes. Kinetic parameters of the hydrogen evolution reaction were determined.

Electrochemical decomposition of cyanides on tin dioxide electrodes in alkaline media

The electrochemical oxidation of cyanide in alkaline media was studied at different pH levels on SnO2 doped with Sb supported on titanium, at 25 degrees C, the electrooxidation of CN- at constant current follows a first-order rate law with a half life of t(1/2) = 35 min on SnO2-SbOx electrodes and t(1/2) = 69 min on SnO2-SbOx-RuO2 electrodes, in K2SO4(aq), pH 12, the reaction rate increases with the applied current and tends to reach a plateau when j > 20 mA cm(-2), In the pH range 10-13.5 the reaction rate diminishes as pH is increased owing to an increasing competition between CN- and OH- ions for the electrode surface. Addition of chloride to the solution does not alter the rate law but increases the reaction rate, A mechanism is proposed to explain the observed behaviour.

Electrochemical measurements of oligonucleotides in the presence of chromosomal DNA using membrane-covered carbon electrodes

Substantial improvements in the selectivity of electrochemical measurements of trace nucleic adds are obtained by using membrane-covered carbon disk electrodes. Access to the electrode surface can be manipulated via a judicious choice of the membrane molecular weight cutoff (MWCO). The resulting separation step, performed in situ at the electrode surface, adds a new dimension of selectivity based on molecular size to electroanalysis of nucleic acids, Transport properties are evaluated with respect to the oligonucleotide length and membrane MWCO. A highly selective response is observed for synthetic oligonucleotides in the presence of otherwise interfering chromosomal DNAs. Discrimination among oligonucleotides of different lengths is also possible, Short accumulation periods (1-5 min) are sufficient for convenient measurements of low milligram per liter concentrations.

Preparation of SrBi2Ta2O9 ferroelectric thick films by electrophoretic deposition using aqueous suspensions

SrBi2Ta2O9 ferroelectric thick films were prepared by electrophoretic deposition (EPD). For that, ceramic powders were prepared by chemical method in order to obtain compounds with chemical homogeneity. The polymeric precursor method was used for the synthesis of the SrBi2Ta2O9 powder. The crystallographic structure of the powder was examined by X-ray diffraction, and the surface area was determined by single point BET adsorption. The 0.03 vol% suspension was formed by dispersing the powder in water using two different polymers as dispersants: an ester polyphosphate (C213) and an ammonium polyacrilate (Darvan 821-A). The influence of the different dispersants on the powder surface properties were investigated by zeta potential measurements. The films were deposited on platinum-coated alumina and Pt/Ti/SiO2/Si substrates by electrophoretic deposition using a 4 mA constant current, for 10 min, with two parallel electrodes placed at a separation distance of 3 min in the suspension. Several cycles of deposition-drying of the deposit was carried out until the desired thickness was obtained. After thermal treatment at temperatures ranging from 700 to 1000degreesC, the films were characterized by X-ray diffraction and scanning electron microscopy.

Electrostatic force microscopy as a tool to estimate the number of active potential barriers in dense non-Ohmic polycrystalline SnO2 devices

In the present work, electroactive grain boundaries of highly dense metal oxide SnO2-based polycrystalline varistors were determined by electrostatic force microscopy (EFM). The EFM technique was applied to identify electroactive grain boundaries and thus estimate the amount of active grain boundary, which, in the metal oxide SnO2-based varistor, was calculated at around 85%, i.e., much higher than that found in traditional metal oxide ZnO-based varistors. The mean potential barrier height value obtained from the EFM analysis was in complete agreement with the values calculated from the C-V measurements, together with a complex capacitance plane analysis that validates the methodology proposed here. (c) 2006 American Institute of Physics.

Non-Ohmic and dielectric properties of a Ca2Cu2Ti4O12 polycrystalline system

An investigation was made into the non-Ohmic and dielectric properties of a Ca2Cu2Ti4O12 perovskite-type system. Compared to the traditional CaCu3Ti4O12-based composition, the imbalance between the Ca and Cu atoms caused the formation of a polycrystalline system presenting similar to 33.3 mol % of CaCu3Ti4O12 (traditional composition) and similar to 66.7 mol % of CaTiO3. As for non-Ohmic properties, the effect of this Ca and Cu atom imbalance was that a nonlinear electric behavior of similar to 1500 was obtained. This high nonlinear electrical behavior emerged in detriment to the ultrahigh dielectric property frequently reported. The high non-Ohmic property was explained by the existence of Schottky-type barriers, whose formation mechanism may be similar to that proposed for traditional metal oxide non-Ohmic devices, according to similarities discussed herein. (c) 2006 American Institute of Physics.

Gold electrodes from recordable CDs

Gold electrodes are widely used in electrochemistry and electroanalytical chemistry. The notable performance when used in stripping analysis of many ionic species and the extraordinary affinity of thio compounds for its surface make these electrodes very suitable for many applications. This paper reports a simple and novel way to construct gold electrodes (CDtrodes) using recordable CDs as the gold source. The nanometer thickness of the gold layer of recordable disks (50-100 mm) favors the construction of band nanoelectrodes with areas as small as 10(-6) cm(2). The plane surface can be easily used for the construction of conventional-sized gold electrodes for batch or now injection analysis or even to obtain electrodes as large as 100 cm(2). The low price of commercial recordable CDs allows a one way use. The evaluation and applicability of these electrodes in the form of nanoelectrodes, in batch and associated with flow cells, are illustrated in this paper.

Compounds of triphenylstibine and platinum: synthesis, properties and reactivity

The reactivity of [Pt(SbPh3)(3)], a compound of zerovalent platinum, exceptionally stable in air, is described. The compounds [{Pt(SbPh3)(3)}(2)N-2], containing bridging dinitrogen, [{Pt(SbPh3)(3)}(2)C-2], with an ethynediyl group also bridging, and [Pt(CO)(2)(SbPh3)(2)], were all obtained under ordinary pressure of nitrogen, acetylene or carbon monoxide, respectively, and are also described. Among the products of the reactions, the dimer [PtBr3(SbPh3)(2)](2) and the mixed complexes [PtL2(SbPh3)(2)] (L = PPh3, AsPh3) were also obtained. Some of these complexes are luminescent when excited by u.v. radiation.

Degradation of metallophtalocyanine dye by combined processes of electrochemistry and photoelectrochemistry

Photoelectrocatalytic degradation of metallophtalocyanine reactive dye (turquoise blue 15) was performed using a Ti/TiO2 thin film photoanode prepared by sol-get method. Hundred percent of color removal and almost complete mineralization (95% at pH 2 and 85% at pH 8) where achieved after 6 h of photolectrocatalytic oxidation of 2.5 x 10(-5) mol L-1 AT15 dye in Na2SO4 mol L-1 under E = +1.2 V versus SCE. The method limitation occurs at dye concentration higher than 4 x 10-5 mol L-1, where the degradation rate becomes markedly slower. An important improvement in color removal and TOC reduction for 1 x 10(-3) mol L-1 metallophtalocyanine dye was achieved using a combined process. After 4 h of potential controlled electrolysis at -1.2 V on a cathode of platinum followed by 6 h of photoelectrocatalytic oxidation leads to 100% of color removal and 83% of TOC decay and eletrodeposition of 69% of the released copper originally presented as copperphtalocyanine complex, by electrodeposition on the cathode without any other treatment. (C) 2005 Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic characterization and molecular modeling of a tetranuclear platinum(II) complex with thiazolidine-4-carboxylic acid

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Platinum surface modification with cerium species and the effect against the methanol anodic reaction

Spontaneous deposition and electrochemical deposition by potential perturbation programs were used to place cerium-containing species on platinum surfaces in acid solution. Cyclic voltammetric profiles of cerium-modified platinum surfaces obtained after potentiostatic or potentiodynamic procedures (applied in the true hydrogen evolution region) differ from those recorded after spontaneous methods. However, the catalytic effects are nearly the same on these cerium-modified platinum surfaces for methanol electrooxidation, i.e. lower onset potential values for the anodic reaction. Besides, a different electrocatalytic effect was observed at large positive potentials on methanol oxidation due to the cerium oxide capability of oxygen storage. This effect is observed on platinum modified by a drastic potentiostatic procedure (by applying -2.0 V) in cerium(IV) acid solution. (C) 2008 Elsevier B.V. All rights reserved.

Modifying glassy carbon (GC) electrodes to confer selectivity for the voltammetric detection of L-cysteine in the presence of DL-homocysteine and glutathione

In this communication we report a proof of concept study of the use of cyclic voltammetry with a polyeugenol-modified glassy carbon (GC) electrode to selectively detect L-cysteine in the presence of both DL-homocysteine and glutathione in perchloric acid. The formation of a polyeugenol-modified gold electrode is also reported for the first time.