Electrochemical stability of SnO2-based coated Ti electrodes

The electrochemical behavior of SnO2-SbOx, based electrodes, with and without the addition of RuO2, was studied by cyclic voltammetry, service life measurements and electrochemical impedance spectroscopy in 0.5 M H2SO4 the physical characteristics of these materials were investigated using SEM, EDX and XRD. The resulting cyclic voltammograms obtained using SnO2-SbOx, and SnO2-SbOx-RuO2(x), x = 30, 5, 1 and 0.4 % showed that the OER overpotential decreased with the addition of RuO2. In the repetitive triangular potential voltammetry applied to the SnO2 electrode without and with RuO2 (1%), a higher anodic current is observed during the first potential scan; it is explained in terms of the oxidation of the Ti substrate. The addition of 1% RuO2 increased the service life from 8 to 20 hours at 10 mAcm(-2), while at 50 mAcm(-2) this increase was from 1 to 8 hours. AC Impedance diagrams obtained for the Ti/SnO2-SbOx and Ti/SnO2-SbOx-RuO2 electrodes at the rest potential and at a potential in the OER region can be explained by a single equivalent circuit containing two elements in series. The results showed that the charge transfer resistance and the resistance of the oxide film are lower in the oxide film containing RuO2. Surface analysis of Ti/SnO2-SbOx, revealed that it is relatively porous and formed by clusters of small particles. The Ti/SnO2-SbOx-RuO2 (1%) film is more compact, though. XRD analysis showed that a Sn1-xTixO2 oxide is formed on the Ti/SnO2-SbOx with 1% and without RuO2 electrodes.

Electrochemical behavior of metallic chromium in chloride media

The electrochemical behavior of metallic chromium in aqueous solutions containing chloride ions at different pH was studied by means of open-circuit potential vs. time measurements, cyclic voltammetry and electrochemical impedance spectroscopy. The composition of the surface oxides was analyzed by XPS. For solutions with pH<3 the formation of a passive layer occurs via a dissolution/precipitation process while for pH>3 the mechanism changes. XPS analysis revealed that Cr2O3 basically constitutes the passive layer.

Metallic powder injection molding using low pressure

The demand by high performance materials that have to support severe service conditions at a reasonable cost has been forcing the powder metallurgy to improve constantly. The most recent and more important innovation in the area is the process of powder injection.Powder injection molding (PIM) is a technology capable of producing a new range of components from powders. This advanced technology overcomes the existent limitations in the forming of products with complex geometry. The process presents countless variations which are used in the industry today. Invariably, it consists of mixing the powders and a thermo-plastic binder, injecting the mass in the mold in the wanted form, debinding, sintering and making optional secondary operations, as for example, machinery.The purpose of this work is to review the metal injection molding techniques and apply the low pressure injection molding process to family of parts using metallic powder with 10 mum particle size. This work also comments the design and construction of a low pressure injection machine and injection molds. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Electrochemical noise analysis of chalcopyrite carbon paste electrodes by Acidithiobacillus ferrooxidans

The electrochemical response of chalcopyrite was studied using electrochemical noise analysis (ENA). The assay was carried out under constant aeration using 30 mL in two electrochemical cells containing iron-free mineral salts solution. These cells were initially monitored for 56 hours, After 72 hours, 7.25x 10(10) cells mL(-1) of A, ferrooxidans strain LR were added in both cells and monitored until 128 h. Subsequent to this period, 0.927 mmol L-1 of silver ions and 400 mmol L-1 of chloride ions were added each one separately. Both conditions were monitored until 168 hours. According to results obtained, it was observed that Cl- ions addition induced an accelerated corrosion process. However, there is a tendency of the system to reach the stationary state due to repassivation of the electrodic surface. In the other side, the Ag+ addition contributed for the maintenance of the oxidant atmosphere, in spite of controversial effect caused by considerable variations in the R-n values, resulting in a instability in the chalcopyrite reactivity.

Characterization of electrodes chemically modified with Mn(III) porphyrin/polypyrrole films as catalytic surfaces for an azo dye

In this study we describe the electrochemical behavior of 5,10,15,20-tetrakis(2'-aminophenylporphyrin)manganese(III) chloride supported on a glassy carbon electrode, as well as the electrochemical preparation and characterization of thin films based on pyrrole-3-carboxylic acid. The electrocatalytic action of the electrode modified with the Mn(III) porphyrin toward an azo dye was tested, and the characteristic strong interaction between the incorporated metalloporphyrin and RR120 dye was verified. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.

Analytical procedure for total mercury determination in fishes and shrimps by chronopotentiometric stripping analysis at gold film electrodes after microwave digestion

A method for the total mercury determination in fish and shrimps employing chronopotentiometric stripping analysis on gold film electrodes is described. Fish and shrimp tissues were digested using a microwave oven equipped with closed vessels. We developed a microwave heating program which decomposed all the samples employing diluted nitric acid and hydrogen peroxide. The proposed method was validated by analyzing a certified reference material and then applied for different fish species from fresh water and seawater acquired in local markets of São Paulo city, Brazil. The Brazilian legislation establishes 0.5 and 1 mg per kilogram of fish as upper limit of mercury for omnivorous and predator species, respectively. Except for blue shark tissues, the mercury content was situated below 0.5 mu g g(-1) for all the analyzed samples. The detection limit of the proposed method was calculated as 5 ng g(-1) of sample utilizing 5 minutes of electrodeposition (+300 mV vs. Ag/AgCl) on the gold electrode. (c) 2006 Elsevier Ltd. All rights reserved.

Comparison of metallic and ceramic tubes as atomization cells for tin determination by TS-FF-AAS

This work describes the development of an analytical procedure for on-line tin determination using thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). Two tubes were evaluated as atomization cells: a metallic tube (Ni-Cr, principal components composition: 73.95% Ni and 16.05% Cr) and a ceramic tube (99.8% Al2O3). The use of air as the carrier was made by employing a Rheodyne valve to inject the samples, allowing an analytical frequency of 90 h(-1) and avoiding sample dispersion. The carrier flow rate (air), sample volume injected, and acid concentration (HCl) were evaluated for the optimization of the TS-FF-AAS system. The sensitivity for 50 mL of analytical solution with TS-FF-AAS was 2 and 5 times higher (to metallic and ceramic tube, respectively) than using an acetylene-nitrous oxide flame with pneumatic aspiration (requiring a sample volume of approximately 20 times higher.

Nature of defects for bismuth layered thin films grown on Pt electrodes

The authors investigated the influence of defects on the piezoelectric and dielectric properties of Bi4Ti3O12 (BIT), SrBi4Ti4O15 (SBTi) and CaBi4Ti4O15 (CBTi144) thin films by x-ray photoemission spectroscopy measurements. In the SBTi film, Sr which is a nonpolarizable ion restricting the movement of Ti4+ ions and thus leads to a low piezoresponse. Meanwhile, the oxygen environment is quite different in the BIT and CBTi144 films exhibiting excellent piezoelectric properties. The piezoelectric coefficient and the dielectric behavior were larger for a-b axis oriented than for c axis-oriented films due to the defects created during the films crystallization. (c) 2007 American Institute of Physics.

Electrochemical oxidation of methanol on Pt nanoparticles dispersed on RuO2

Pt-modified RuO2 was prepared by a sol-gel procedure on titanium substrates in the form of thin films of similar to2-mum thickness. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that these films actually consist of Pt nanoparticles dispersed in RuO2 and that neither metallic Ru nor Pt-Ru alloy are present on the surface. Electrodes with different Pt:Ru nominal compositions were prepared and their electrocatalytic activity for the oxidation of methanol was investigated by potential sweeps and chronoamperometry. The results obtained show an enhancement effect for methanol oxidation that can be interpreted as associated to the formation of hydrous oxides on the RuO2 surface.

Nanostructured films employed as sensing units in an electronic tongue system

Nanostructured films of lignin (macromolecule extracted from sugar cane bagasse), polypyrrole (conducting polymer) and bis butylimido perylene (organic dye) were used in the detection of trace levels of fluorine (from H2SiF6), chlorine (from NaCIO), Pb+2, Cu+2, and Cd+2 in aqueous solutions. Langmuir monolayers on ultrapure water were characterised by surface pressure-mean molecular area (II-A) isotherms. Langmuir-Blodgett (LB) films were transferred onto gold interdigitated electrodes and used as individual sensing units of an electronic tongue system. Impedance spectroscopy measurements were taken with the sensor immersed into aqueous solutions containing the ions described above in different molar concentrations. Fourier transform infrared absorption (FTIR) was employed to identify possible interactions between the LB films and the analytes in solution, and no significant changes could be observed in the FTIR spectra of BuPTCD and Ppy. Therefore, the results for lignin point to an interaction involving the electronic cloud of the phenyl groups with the metallic ions.

BaTiO3 obtained through metallic stearate precursors

Metallic stearates were used as precursors to obtain BaTiO3. Barium and titanium stearate mixtures were homogenized in ball mill containing some amount of ammonium stearate. The mixture of the precursors was evaluated by simultaneous TG/ DTA and TMA, and residues from thermal decomposition were characterized by XRD and SEM. It could be verified that the residues from the thermal decomposition in both oxidant and inert atmospheres were the BaTiO3 but with characteristic morphological and crystalline aspects depending on the experimental conditions in which the mixtures of precursors were obtained. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Evaluation of color removal and degradation of a reactive textile azo dye on nanoporous TiO2 thin-film electrodes

The feasibility of the photobleaching of a textile azo dye, reactive orange 16 (C.I. 17757), in aqueous solution using titanium dioxide thin-film electrodes prepared by the sol-gel method was investigated. The best conditions for maximum photoelectrocatalytic degradation were found to be pH > 10 for Na2SO4 medium and pH < 6 for NaCl. In both situations, an applied potential of +1.0 V and low dye concentration are recommended, when 100% of color removal is obtained after 20 min of photoelectrocatalysis. The effects of side reaction pathway on the degradation rate of dye in sulfate and chloride medium were presented and the best performance are optimized to situations closed to that verified in the textile effluent. The influence of variables as applied potential, pH, supporting electrolyte and dye concentration on the kinetics of photoelectrochemical degradation also were investigated. Oxalic acid is identified by HPLC and UV-Vis spectrophotometric methods as the main degradation product generated after 180 min of photoelectrocatalysis of 4 x 10(-5) mol l(-1) dye in sodium sulphate pH 12 and NaCl pH 4.0 and a maximum reduction of 56 and 62% TOC was obtained, respectively. (C) 2004 Elsevier Ltd. All rights reserved.

Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

Fast ultrasound-assisted treatment of urine samples for chronopotentiometric stripping determination of mercury at gold film electrodes

This work describes an efficient, fast, and reliable analytical methodology for mercury determination in urine samples using stripping chronopotentiometry at gold film electrodes. The samples were sonicated in the presence of concentrated HCl and H2O2 for 15 min in order to disrupt the organic ligands and release the mercury. Thirty samples can be treated over the optimized region of the ultrasonic bath. This sample preparation was enough to allow the accurate stripping chronopotentiometric determination of mercury in the treated samples. No background currents and no passivation of the gold film electrode due to the sample matrix were verified. The samples were also analyzed by cold vapour atomic absorption spectrometry (CV-AAS) and good agreement between the results was verified. The analysis of NIST SRM 2670 (Toxic Metals in Freeze-Dried Urine) also validated the proposed electroanalytical method. Finally, this method was applied for mercury evaluation in urine of workers exposed to hospital waste incinerators. (c) 2006 Elsevier B.V. All rights reserved.