Simultaneous determination of epinephrine and dopamine by electrochemical reduction on the hybrid material SiO2/graphene oxide decorated with Ag nanoparticles

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

Study of corrosion resistance of laser welded Au-Pd-Ag-In alloy using electrochemical.

The aim of this work was to evaluate the corrosion resistance of AuPdAgIn alloy, submitted to laser beam welding, in 0.9% NaCl solution, using electrochemical techniques. Measures of the open circuit potential (OCP) versus time were applied to electrochemical experiments, as well as potentiodynamic direct scanning (PDS) and electrochemical impedance spectroscopy (EIS) on AuPdAgIn alloy, submitted to laser beam welding in 0.9% NaCl solution. Some differences observed in the microstructure can explain the results obtained for corrosion potential, Ecorr, and corrosion resistance, Rp. EIS spectra have been characterized by distorted capacitive components, presenting linear impedance at low frequencies, including a non-uniform diffusion. The area of the laser weld presented corrosion potential slightly superior when compared to the one of the base metal. The impedance results suggest the best resistant corrosion behavior for laser weld than base metal region. This welding process is a promising alternative to dental prostheses casting.

On-line monitoring of electrochemical degradation of paracetamol through a biomimetic sensor

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

Voltammetric behaviour of a modified electrode with azide copper octa(3-aminopropyl)octasilsesquioxane composite in the oxidation of ascorbic acid

A novel nanostructured composite, azide copper octa (3-aminopropyl)octasilsesquioxane (ASCA) was incorporated into a graphite paste electrode and the electrochemical studies were conducted with cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E  ) = 0.30 V and an irreversible process at 1.1 V (vs Ag/AgCl; NaCl 1.0 mol L-1 ; v = 20 mV s-1 ). The redox couple with (E  ) = 0.30V presents an electrocatalytic response for determination of ascorbic acid. The modified electrode gives a linear range from 1.010-4 – 1.010-3 mol L-1 (r = 0.998) for the determination of ascorbic acid with detection limit of 6.910-5 mol L-1 and standard deviation of 2.3% for n = 3 . The amperometric sensitivity was 122.1 mA/mol L-1 for ascorbic acid. The application this electrode was tested and ascorbic acid in three commercial pharmaceutical product (Cebion, Cewin and Redoxon) have been determined.

Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electrochemical behaviour of (N-R-4-cyanopyridinium)pentaammineruthenium(II) derivatives in acidic medium. Hydrolysis of coordinated nitriles

The electrochemical behaviour of N-R-4-cyanopyridinium (4-rcp) (R = methyl, decyl, dodecyl, or benzyl) coordinated to pentaammineruthenium(II) in CF3COOH-CF3COONa (μ = 0.1 M, pH 3) aqueous medium was studied by means of cyclic voltammetry and constant potential electrolysis. The electrochemical oxidation of the metallic centre (Ep ca 0.51 V/SCE) can be described as a reversible monoelectronic charge-transfer followed by an irreversible chemical reaction, which is the hydrolysis of N-R-4-cyanopyridiniumpentaammineruthenium(III) (A) to N-R-4-carboxamidepyridiniumruthenium (III) (B) with the kf1 values depending on the type of alkyl group. The E 1 2 values are not significantly influenced by the nature of the alkyl group. At more negative potential (ca -0.5 V/SCE), B undergoes an electrochemical reduction followed by an aquation reaction to produce aquopentaammineruthenium(II) and free N-R-4-carboxamidepyridinium. The amide was identified by comparison of its cyclic voltammogram and UV-vis spectrum with that of a sample prepared by chemical reaction. The results were also discussed by comparison with other systems, and show that nitrile-amide conversion catalysed by pentaammineruthenium(II) complexes is possible. © 1994.

Electrochemical investigation of the voltammetric determination of hydrochlorothiazide using a nickel hydroxide modified nickel electrode

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

Electrochemical behaviour of copper electrode in concentrated sulfuric acid solutions

The electrochemical behaviour of copper in 6.0 mol 1-1 sulfuric acid at 30°C, was studied by means of the potentiodynamic method. At low potential sweep rates, v < 200 m V s-1, the data reveal that the anodic process is basically constituted of copper dissolution and a film formation which inhibits further metal oxidation and which may undergo further dissolution. For higher potential sweep rates, a modification in the passivation region of the voltammogram is observed. It can be ascribed to a change in the passivation mechanism which possibly involves different surface species. The kineticrelationships derived from the potentiodynamic I/E curves obtained at low v suggest a film formation via a dissolution/precipitation mechanism. © 1993.

INVESTIGATION INTO CURRENT EFFICIENCY FOR PULSE ELECTROCHEMICAL MACHINING OF NICKEL ALLOY

INVESTIGATION INTO CURRENT EFFICIENCY FOR PULSE ELECTROCHEMICAL MACHINING OF NICKEL ALLOY Yu Zhang, M.S. University of Nebraska, 2010 Adviser: Kamlakar P. Rajurkar Electrochemical machining (ECM) is a nontraditional manufacturing process that can machine difficult-to-cut materials. In ECM, material is removed by controlled electrochemical dissolution of an anodic workpiece in an electrochemical cell. ECM has extensive applications in automotive, petroleum, aerospace, textile, medical, and electronics industries. Improving current efficiency is a challenging task for any electro-physical or electrochemical machining processes. The current efficiency is defined as the ratio of the observed amount of metal dissolved to the theoretical amount predicted from Faraday’s law, for the same specified conditions of electrochemical equivalent, current, etc [1]. In macro ECM, electrolyte conductivity greatly influences the current efficiency of the process. Since there is a certain limit to enhance the conductivity of the electrolyte, a process innovation is needed for further improvement in current efficiency in ECM. Pulse electrochemical machining (PECM) is one such approach in which the electrolyte conductivity is improved by electrolyte flushing in pulse off-time. The aim of this research is to study the influence of major factors on current efficiency in a pulse electrochemical machining process in macro scale and to develop a linear regression model for predicting current efficiency of the process. An in-house designed electrochemical cell was used for machining nickel alloy (ASTM B435) by PECM. The effects of current density, type of electrolyte, and electrolyte flow rate, on current efficiency under different experimental conditions were studied. Results indicated that current efficiency is dependent on electrolyte, electrolyte flow rate, and current density. Linear regression models of current efficiency were compared with twenty new data points graphically and quantitatively. Models developed were close enough to the actual results to be reliable. In addition, an attempt has been made in this work to consider those factors in PECM that have not been investigated in earlier works. This was done by simulating the process by using COMSOL software. However, it was found that the results from this attempt were not substantially different from the earlier reported studies.

Preparation of Coated Microtools for Electrochemical Machining Applications

PREPARATION OF COATED MICROTOOLS FOR ELECTROCHEMICAL MACHINING APPLICATIONS Ajaya K. Swain, M.S. University of Nebraska, 2010 Advisor: K.P. Rajurkar Coated tools have improved the performance of both traditional and nontraditional machining processes and have resulted in higher material removal, better surface finish, and increased wear resistance. However, a study on the performance of coated tools in micromachining has not yet been adequately conducted. One possible reason is the difficulties associated with the preparation of coated microtools. Besides the technical requirement, economic and environmental aspects of the material and the coating technique used also play a significant role in coating microtools. This, in fact, restricts the range of coating materials and the type of coating process. Handling is another major issue in case of microtools purely because of their miniature size. This research focuses on the preparation of coated microtools for pulse electrochemical machining by electrodeposition. The motivation of this research is derived from the fact that although there were reports of improved machining by using insulating coatings on ECM tools, particularly in ECM drilling operations, not much literature was found relating to use of metallic coating materials in other ECM process types. An ideal ECM tool should be good thermal and electrical conductor, corrosion resistant, electrochemically stable, and stiff enough to withstand electrolyte pressure. Tungsten has almost all the properties desired in an ECM tool material except being electrochemically unstable. Tungsten can be oxidized during machining resulting in poor machining quality. Electrochemical stability of a tungsten ECM tool can be improved by electroplating it with nickel which has superior electrochemical resistance. Moreover, a tungsten tool can be coated in situ reducing the tool handling and breakage frequency. The tungsten microtool was electroplated with nickel with direct and pulse current. The effect of the various input parameters on the coating characteristics was studied and performance of the coated microtool was evaluated in pulse ECM. The coated tool removed more material (about 28%) than the uncoated tool under similar conditions and was more electrochemical stable. It was concluded that nickel coated tungsten microtool can improve the pulse ECM performance.

Probing the Enamel Topography After Acid Erosion by Scanning Electrochemical Microscopy

In this work, we present an investigation on the thickness of the eroded enamel layer in tooth samples after exposure to citric and hydrochloric acid by using Scanning Electrochemical Microscopy (SECM). Approaching curves with typical negative feedback behavior were obtained in enamel samples for evaluation of topographic changes. In a control experiment, SECM images showed no significant difference in the current monitored during the scan, implying that enamel demineralization did not occur in mineral water medium. Topographic SECM images obtained after contact with citric and hydrochloric acid for different periods of time showed a significant increase in the current relative to a previously protected surface, indicating the structural loss of enamel. The thickness of the enamel layer eroded after contact with hydrochloric acid was significantly higher when compared to the one obtained with citric acid. Hence, our results showed that the enamel acid erosion is a relatively fast process, which is strongly dependent on parameters such as pH, time, acid strength and acid concentration.

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Direct ethanol fuel cell: Electrochemical performance at 90 degrees C on Pt and PtSn/C electrocatalysts

Carbon-supported Pt-based electrocatalysts were synthesized by Pechini method for the ethanol oxidation (EOR). Physicochemical characterizations were helpful to estimate the diameters of the obtained materials ranging from 2 nm to 5 nm. Main electrochemical experiments were carried out at 90 degrees C i.e. under the working conditions of performing the single 5 cm(2) direct ethanol fuel cell (DEFC). Pt(80)Sn(20)/C was the anode catalyst which has given the highest power density of 37 mW cm(-2). Importantly, the IR spectroscopy measurements associated with the qualitative analysis done at the output of the anodic compartment of the fuel cell have shown that ethanol oxidation on Pt(80)Sn(20)/C was mainly a two-electron sustainable process. (C) 2011 Elsevier B.V. All rights reserved.

Application of Electrochemical Degradation of Wastewater Composed of Mixtures of Phenol-Formaldehyde

The industrial wastewater from resin production plants contains as major components phenol and formaldehyde, which are traditionally treated by biological methods. As a possible alternative method, electrochemical treatment was tested using solutions containing a mixture of phenol and formaldehyde simulating an industrial effluent. The anode used was a dimensionally stable anode (DSAA (R)) of nominal composition Ti/Ru0.3Ti0.7O2, and the solution composition during the degradation process was analyzed by liquid chromatography and the removal of total organic carbon. From cyclic voltammetry, it is observed that for formaldehyde, a small offset of the beginning of the oxygen evolution reaction occurs, but for phenol, the reaction is inhibited and the current density decreases. From the electrochemical degradations, it was determined that 40 mA cm(-2) is the most efficient current density and the comparison of different supporting electrolytes (Na2SO4, NaNO3, and NaCl) indicated a higher removal of total organic carbon in NaCl medium.

Observation of vinylidene emission in mixed phosphine/diimine complexes of Ru(II) at room temperature in solution

The mixed ruthenium(II) complexes trans-[RuCl(2)(PPh(3))(2)(bipy)] (1), trans-[RuCl(2)(PPh(3))(2)(Me(2)bipy)](2), cis-[RuCl(2)(dcype)(bipy)](3), cis-[RuCl(2)(dcype)(Me(2)bipy)](4) (PPh(3) = triphenylphosphine, dcype = 1,2-bis(dicyclohexylphosphino)ethane, bipy = 2,2'-bipyridine, Me(2)bipy = 4,4'-dimethyl-2,2'-bipyridine) were used as precursors to synthesize the associated vinylidene complexes. The complexes [RuCl(=C=CHPh)(PPh(3))(2)(bipy)]PF(6) (5), [RuCl(=C=CHPh)(PPh(3))(2)(Me(2)bipy)]PF(6) (6), [RuCl(=C=CHPh)(dcype)(bipy)]PF(6) (7), [RuCl(=C=CHPh)(dcype)(bipy)]PF(6) (8) were characterized and their spectral, electrochemical, photochemical and photophysical properties were examined. The emission assigned to the pi-pi* excited state from the vinylidene ligand is irradiation wavelength (340, 400, 430 nm) and solvent (CH(2)Cl(2), CH(3)CN, EtOH/MeOH) dependent. The cyclic voltammograms of (6) and (7) show a reversible metal oxidation peak and two successive ligand reductions in the +1.5-(-0.64) V range. The reduction of the vinylidene leads to the formation of the acetylide complex, but due the hydrogen abstraction the process is irreversible. The studies described here suggest that for practical applications such as functional materials, nonlinear optics, building blocks and supramolecular photochemistry. (C) 2011 Elsevier B.V. All rights reserved.