Stripping voltammetry of mercury(II) with a chemically modified carbon paste electrode containing silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole

The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole (DTTPSG-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to +0.8 V (vs. Ag/AgCl), (0.02 mol L-1 KNO3; nu=20 mV s(-1)) show two peaks one at about 0.0 V and other at 0.31 V. However, the cathodic wave peak, around 0.0 V, is irregular and changes its form in each cycle. This peak at about 0.0 V is the reduction current for mercury(II) accumulated in the DTTPSG-CPE. The anodic wave peak at 0.31 V is well-defined and does not change during the cycles. The resultant material was characterized by cyclic and differential pulse anodic stripping voltammetry performed with the electrode in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n=6) of 0.05 and 0.20 mg (L)-(1) Hg(II) was 2.8 and 2.2% (relative standard deviation), respectively. The method was satisfactory and used to determine the concentration of mercury(II) in natural waters contaminated by this metal.

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni2+ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni2+ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni2+ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)2 complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L-1 with detection limit of 2.0 x 10(-9) mol L-1. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 mu mol L-1 Ni2+ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni2+ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni2+ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step. (c) 2006 Elsevier B.V. All rights reserved.

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.

Fatigue life studies in carbon dual-phase steels

An investigation has been conducted to examine the morphological influence on fatigue life of low carbon steel with dual phase microstructure. The results showed that dual-phase microstructure, composed by ferrite and martensite had superior symmetrical bending fatigue strength when compared with ferrite-pearlite steel. Through those tests, evidences of different mechanisms were verified (such as ferrite cyclic hardening, slip band formation and beginning of crack nucleation and propagation). Based on the fatigue tests results, various mechanisms stages were discussed associated with different microstructure morphology. Copyright (C) 1996 Published by Elsevier B.V. Limited.

DEVELOPMENT OF A CHEMICALLY MODIFIED ELECTRODE BASED ON CARBON PASTE AND FUNCTIONALIZED SILICA-GEL FOR PRECONCENTRATION AND VOLTAMMETRIC DETERMINATION OF MERCURY(II)

A mercury-sensitive chemically modified electrode (CME) based on modified silica gel-containing carbon paste was developed. The functional group attached to the silica gel surface was 3-(2-thiobenzimidazolyl)propyl, which is able to complex mercury ions. This electrode was applied to the determination of mercury(II) ions in aqueous solution. The mercury was chemically preconcentrated on the CME prior to voltammetric determination by anodic stripping in the differential-pulse mode. A calibration graph covering the concentration range from 0.08 to 2 mg l-1 was constructed. The precision for six determinations of 0.122 and 0.312 mg l-1 Hg(II) was 3.2 and 2.9% (relative standard deviation), respectively. The detection limit for a 5-min preconcentration period was 0.013 mg l-1. A study for foreign ions was also made.

SAE 1045 steel/WC-Co/Ni-Cu-Ni/SAE 1045 steel joints prepared by dynamic diffusion bonding: Microelectrochemical studies in 0.6 M NaCl solution

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

Optimization of the mechanical properties of low-carbon steels by formation of a multiphase microstructure

In this work five methods of heat treatments are investigated in order to obtained convenient volume fractions of ferrite, bainite, martensite and retained austenite, starting with a low carbon steel and seeking the distinction of the phases, through optical microscopy. Specific chemical etching is improved. The results in tensile and fatigue tests were accomplished and the results were related with the microstructural parameters. The results show that the mechanical properties are closely related with the phases, grains size and the phases morphology. Copyright © 2001 Society of Automotive Engineers, Inc.

Study of electrochemical oxidation and determination of albendazole using a glassy carbon-rotating disk electrode

In this work, electrochemical oxidation of albendazole (ABZ) was carried out using a glassy carbon-rotating disk electrode. Development of electroanalytical methodology for ABZ quantification in pharmaceutical formulations was also proposed by using linear sweep voltammetric technique. Electrochemical oxidation is observed for ABZ at E 1/2 = 0.99:V vs. Ag/AgCl sat, when an anodic wave is observed. Kinetic parameters obtained for ABZ oxidation exhibited a standard heterogeneous rate constant for the electrodic process equal to (1.51 ± 0.07) ± 10 -5:cm:s -1, with a αn a value equal to 0.76. Limiting current dependence against ABZ concentration exhibited linearity on 5.0 ± 10 -5 to 1.0 ± 10 -2:mol:l -1 range, being obtained a detection limit of 2.4 ± 10 -5:mol:l -1. Proposed methodology was applied to ABZ quantification in pharmaceutical formulations. © 2005 Elsevier SAS. All rights reserved.

Screen-printed carbon electrode modified with poly-L-histidine applied to voltammetric determination of chromium (VI)

The present work reports the use of a screen-printed carbon electrode (SPCE) modified by poly-L-histidine film to determine chromium (VI). Stable films can be formed by direct addition of PH solution 1 % (w/v) on the electrode surface, followed by heating at 80°C during 5 min. Calibration curves can be constructed for Cr(VI) from 1.0 × 10-5 mol L-1 to 7.0 × 10-5 mol L-1 Cr (VI) in acetate buffer pH 4 using a preconcentration step of 60s at open circuit potential. A relative standard deviation of 3.2% was for five determination of 4.0 × 10 -5 mol L-1 Cr (VI). The method was successful applied to determination of Cr(VI) in wastewater samples from a leather dyeing industry. copyright The Electrochemical Society.

Determination of the volume fraction of retained austenite in a 300m steel by heat tinting technique

Applying the Heat Tinting Technique the microestrutural characterization of a 300M steel (medium carbon steel) was accomplished. The steel was austenitized for 20 min to 900°C, followed by holding at 400°C (in the bainitic temperature), with maintenance time of the material in the temperature of 1min, 5min and 30min, aiming at the formation of a multiphase structure. Through the metallographic analysis it is verified that, with the use of this technique, it is possible the determination of the volume fraction of the present phases in the 300M steel, especially in the identification and quantification of the retained austenite. Copyright © 2007 SAE International.

Microstructural effects on fatigue crack growth behavior of a microalloyed steel

Thermal transformations on microalloyed steels can produce multiphase microstructures with different amounts of ferrite, martensite, bainite and retained austenite. These different phases, with distinct morphologies, are determinant of the mechanical behavior of the steel and can, for instance, affect the crack path or promote crack shielding, thus resulting in changes on its propagation rate under cyclic loading. The aim of the present work is to evaluate the effects of microstructure on the tensile strength and fatigue crack growth (FCG) behaviour of a 0.08%C-1,5%Mn (wt. pct.) microalloyed steel, recently developed by a Brazilian steel maker under the designation of RD480. This steel is being considered as a promising alternative to replace low carbon steel in wheel components for the automotive industry. Various microstructural conditions were obtained by means of heat treatments followed by water quench, in which the material samples were kept at the temperatures of 800, 950 and 1200 °C. In order to describe the FCG behavior, two models were tested: the conventional Paris equation and a new exponential equation developed for materials showing non-linear FCG behavior. The results allowed correlating the tensile properties and crack growth resistance to the microstructural features. It is also shown that the Region II FCG curves of the dual and multiphase microstructural conditions present crack growth transitions that are better modeled by dividing them in two parts. The fracture surfaces of the fatigued samples were observed via scanning electron microscopy in order to reveal the fracture mechanisms presented by the various material conditions. © 2010 Published by Elsevier Ltd.

Carbon nanotube-reinforced siloxane-PMMA hybrid coatings with high corrosion resistance

Siloxane-polymethyl methacrylate hybrid films containing functionalized multiwall carbon nanotubes (CNTs) were deposited by dip-coating on carbon steel substrates from a sol prepared by radical polymerization of methyl methacrylate and 3-methacryloxy propyl-trimethoxysilane, followed by hydrolytic co-polycondensation of tetraethoxysilane. The correlation between the structural properties and corrosion protection efficiency was studied as a function of the molar ratio of nanotubes carbon to silicon, varied in the range between 0.1% and 5%. 29Si nuclear magnetic resonance and thermogravimetric measurements have shown that hybrids containing carbon nanotubes have a similar degree of polycondensation and thermal stability as the undoped matrix and exhibit and excellent adhesion to the substrate. Microscopy and X-ray photoelectron spectroscopy results revealed a very good dispersion of carbon nanotubes in the hybrid matrix and the presence of carboxylic groups allowing covalent bonding with the end-siloxane nodes. Potentiodynamic polarization curves and electrochemical impedance spectroscopy results demonstrate that CNTs containing coatings maintain the excellent corrosion protection efficiency of the hybrids, showing even a superior performance in acidic solution. The nanocomposite structure acts as efficient corrosion barrier, increasing the total impedance by 4 orders of magnitude and reducing the current densities by more than 3 orders of magnitude, compared to the bare steel electrode. © 2013 Elsevier B.V. All rights reserved.

Glutathione-s-transferase modified electrodes for detecting anticancer drugs

With the fast growth of cancer research, new analytical methods are needed to measure anticancer drugs. This is usually accomplished by using sophisticated analytical instruments. Biosensors are attractive candidates for measuring anticancer drugs, but currently few biosensors can achieve this goal. In particular, it is challenging to have a general method to monitor various types of anticancer drugs with different structures. In this work, a biosensor was developed to detect anticancer drugs by modifying carbon paste electrodes with glutathione-s-transferase (GST) enzymes. GST is widely studied in the metabolism of xenobiotics and is a major contributing factor in resistance to anticancer drugs. The measurement of anticancer drugs is based on competition between 1-chloro-2,4-dinitrobenzene (CDNB) and the drugs for the GST enzyme in the electrochemical potential at 0.1 V vs. Ag/AgCl by square wave voltammetry (SWV) or using a colorimetric method. The sensor shows a detection limit of 8.8 mu M cisplatin and exhibits relatively long life time in daily measurements. (C) 2014 Elsevier B.V. All rights reserved.

Second Phase Precipitation in Ultrafine-grained Ferrite Steel

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

A new and practical carbon paste electrode for insoluble and ground samples

This work presents a new and simple electrode, which may be used to achieve the electrochemical response of ground solids or insoluble samples. Ore samples from Morro Velho Mine (Brazil) were employed to exemplify the use of such electrodes. The new electrode avoids the use of binders or other agents overcoming major deterioration problems. (C) 2002 Published by Elsevier Science B.V.