EFFECTS OF DOPANT AND SOLVENT ON THE PROPERTIES OF POLYPYRROLE - INVESTIGATIONS WITH CYCLIC VOLTAMMETRY AND ELECTROCHEMICALLY INSITU CONDUCTIVITY

A new method for electrochemically in situ conductivity measurements based on a reusable glassy carbon disc carbon fibre array double electrode is described. Using this technique and cyclic voltammetry, we have investigated the effects of the doping anion and solvent on the electrochemical properties of polypyrrole film. The electroactivity and potential dependent conductivity of polypyrrole film are strongly affected by solvent and the doping anion's solubility in the solvent, and also by the history of electrochemical treatments in different electrolyte solutions. It is very interesting that NO3-doped polypyrrole can completely keep its conducting state (doped state) at a reasonably negative potential (eg -0.8 V vs. sce) in acetonitrile solutions.

CYCLIC VOLTAMMETRIC AND SPECTROELECTROCHEMICAL STUDIES OF COPPER IN ALKALINE-SOLUTION

The behaviour of the electroplated copper film electrode on tin oxide/glass or glassy carbon surface was studied in potassium hydroxide medium by cyclic voltammetry and in situ transmission spectroelectrochemistry. The results indicate that the electroplated copper film electrode is similar to a copper electrode and cyclic voltammetry with this electrode affords more resolution. The anodic peaks were found to correspond successively to the adsorption of oxygen, the formation of a surface layer of Cu2O, the formation of a surface layer of Cu(OH)2 or CuO and formation of a thick multilayer film of CuO. This is the first time it has been proposed that a surface layer of Cu(OH)2 or CuO is formed from the oxidation of the surface layer of Cu2O. Similarly, a clear interpretation is presented that the cathodic peaks correspond successively to the reduction of CuO to Cu2O, the reductions of Cu2O to Cu and the soluble Cu(II) species to Cu. On the other hand, a shoulder peak related to the chemical transformation of Cu(OH)2 to CuO was first observed.

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

Effects of spark discharge on the anodic coatings on magnesium alloy

Spark discharge was the representative phenomenon of Micro-arc oxidation (MAO) method distinguished from other electrochemical oxidation methods. Under the spark discharge treatment, characteristics of the anodic layer were significantly changed. To investigate the influences of the spark discharge, a piece of magnesium alloy AZ91D specimen was partly treated by MAO method in alkaline silicate solution. And the microstructure, element distributions as well as the surface potential distributions of the specimen were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and scanning Kelvin probe (SKP) technique. As a result of intensive spark discharge treatment, porous external layer with dense internal layer were formed on Mg alloy surface. At the same time, the depositions of OH- and SiO32- ions were accelerated, which resulted in the enrichment of element oxygen and silicon at the spark discharge region. Moreover, due to the compact internal layer, the intensive spark discharge region exhibited more positive potentials with respect to other regions, which meant this region could restrain the ejection of electron and provide effective protection to the substrate. In addition, it was found that oxygen played a vital role in determining the intensity and size of sparks, and abundant oxygen resulted in intensive and larger sparks. (c) 2005 Elsevier B.V. All rights reserved.

Characteristics of anodic coatings oxidized to different voltage on AZ91D Mg alloy by micro-arc oxidization technique

With increasing applied voltage, three types of anodic coatings, passive film, micro-spark ceramic coating and spark ceramic coating were made by micro-arc oxidization (MAO) technique on AZ91D magnesium alloy in alkali-silicate solution. The structure, composition characteristics and the electrochemical properties of coatings were also studied with SEM, XRD and EIS (electrochemical impedance spectroscopy) technique, respectively. It is found that the electrochemical properties are closely related to the structure and composition characteristics of the anodic coatings. At the same time, the characteristics of the three types of anodic coatings differ significantly, among them, the micro-spark ceramic coating, prepared in the voltage range of 170similar to220V exhibits compact, homogeneous structure and highest corrosion-resistance.

The synergy between deformation and anodic dissolution of an austenitic stainless steel in acidic chloride solution

In corrosion medium, metals can deform under tensile stress and form a new active surface with the anodic dissolution of the metals being accelerated. At the same time, the anodic dissolution may accelerate the deformation of the metals. The synergy can lead to crack nucleation and development and shorten the service life of the component. Austenitic stainless steel in acidic chloride solution was in active dissolution condition when stress corrosion cracking (SCC) occurred. It is reasonable to assume that the anodic dissolution play an important role, so it's necessary to study the synergy between anodic dissolution and deformation of austenitic stainless steels. The synergy between deformation and anodic dissolution of AISI 321 austenitic stainless steel in an acidic chloride solution was studied in this paper. The corrosion rate of the steel increased remarkably due to the deformation-accelerated anodic and cathodic processes. The creep rate was increased while the yield strength was reduced by anodic dissolution. The analysis by thermal activation theory of deformation showed a linear relationship between the logarithm of creep rate and the logarithm of anodic cur-rent. Besides, the reciprocal of yield strength was also linearly dependent on the logarithm of anodic current. The theoretical deductions were in good agreement with experimental results.

Selective and specific detection of sulfate-reducing bacteria using potentiometric stripping analysis

A fast, sensitive and reliable potentiometric stripping analysis (PSA) is described for the selective detection of the marine pathogenic sulfate-reducing bacterium (SRB). Desulforibrio caledoiensis. The chemical and electrochemical parameters that exert influence on the deposition and stripping of lead ion, such as deposition potential, deposition time and pH value were carefully studied. The concentration of SRB was determined in acetate buffer solution (pH 5.2) under the optimized condition (deposition potential of -1.3 V. deposition time of 250 s, ionic strength of 0.2 mol L-1 and oxidant mercury (II) concentration of 40 mg L-1). A linear relationship between the stripping response and the logarithm of the bacterial concentration was observed in the range of 2.3 x 10 to 2.3 x 10(7) cfu mL(-1). In addition, the potentiometric stripping technique gave a distinct response to the SRB, but had no obvious response to Escherichia coli. The measurement system has a potential for further applications and provides a facile and sample method for detection of pathogenic bacteria. (C) 2010 Elsevier B.V. All rights reserved.

Preparation of supported PtRu/C electrocatalyst for direct methanol fuel cells

In this work, high-surface supported PtRu/C were prepared with Ru(NO)(NO3)(3) and [Pt(H2NCH2CH2NH2)(2)]Cl-2 as the precursors and hydrogen as a reducing agent. XRD and TEM analyses showed that the PtRu/C catalysts with different loadings possessed small and homogeneous metal particles. Even at high metal loading (40 wt.% Pt, 20 wt.% Ru) the mean metal particle size is less than 4 nm. Meanwhile, the calculated Pt crystalline lattice parameter and Pt (220) peak position indicated that the geometric structure of Pt was modified by Ru atoms. Among the prepared catalysts, the lattice parameter of 40-20 wt.% PtRu/C contract most. Cyclic voltammetry (CV), chronoamperometry (CA), CO stripping and single direct methanol fuel cell tests jointly suggested that the 40-20 wt.% PtRu/C catalyst has the highest electrochemical activity for methanol oxidation. (c) 2004 Elsevier Ltd. All rights reserved.

Determination of ionic resistance and optimal composition in the anodic catalyst layers of DMFC using AC impedance

In the present study, a method based on transmission-line mode for a porous electrode was used to measure the ionic resistance of the anode catalyst layer under in situ fuel cell operation condition. The influence of Nafion content and catalyst loading in the anode catalyst layer on the methanol electro-oxidation and direct methanol fuel cell (DMFC) performance based on unsupported Pt-Ru black was investigated by using the AC impedance method. The optimal Nafion content was found to be 15 wt% at 75 degrees C. The optimal Pt-Ru loading is related to the operating temperature, for example, about 2.0 mg/cm(2) for 75-90 degrees C, 3.0 mg/cm2 for 50 degrees C. Over these values, the cell performance decreased due to the increases in ohmic and mass transfer resistances. It was found that the peak power density obtained was 217 mW/cm(2) with optimal catalyst and Nafion loading at 75 degrees C using oxygen. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Adlayer Structures of DL-Homocysteine and L-Homocysteine Thiolactone on Au(111) Surface: an in situ STM Study

The adsorption Of DL-homocysteine (Hcy) and L-homocysteine thiolactone (HTL) on Au(1 1 1) electrode was investigated in 0.1 M HClO4 by cyclic voltammetry and in situ scanning tunneling microscopy (STM). Hcy and HTL molecules formed highly ordered adlayers on Au(1 1 1) surface. High-resolution STM images revealed the orientation and packing arrangement in the ordered adlayers. Hcy molecules formed (2root3 x 3root3)R30degrees adlayer structure and H-bonds between carboxyl groups were assumed to be responsible for the origin of tail-to-tail or head-to-head molecular arrangement, while HTL molecules formed (4 x 6) adlayer structure, and two different orientations and appearances in the ordered adlayer were found. Structural models were proposed for the two adlayers.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

Immunosensor Interface Based on Physical and Chemical Immunogylobulin G Adsorption onto Mixed Self-Assembled Monolayers

An immunosensor interface based on mixed hydrophobic self-assembled monolayers (SAMs) of methyl and carboxylic acid terminated thiols with covalently attached human Immunoglobulin G (hIgG), is investigated. The densely packed and organised SAMs were characterised by contact angle measurements and cyclic voltammetry. The effect of the non-ionic surfactant, Tween 20, in preventing nonspecific adsorption is addressed by ellipsometry during physical and covalent hIgG immobilization on pure and mixed SAMs, respectively. It is clearly demonstrated that nonspecific adsorption due to hydrophobic interactions of hIgG on methyl ended groups is totally inhibited, whereas electrostatic/hydrogen bonding interactions with the exposed carboxylic groups prevail in the presence of surfactant. Results of ellipsometry and Atomic Force Microscopy, reveal that the surface concentration of covalently immobilized hIgG is determined by the ratio of COOH/CH3-terminated thiols in SAM forming solution. Moreover, the ellipsometric data demonstrates that the ratio of bound anti-hIgG/hIgG depends on the density of hIgG on the surface and that the highest ratio is close to three. We also report the selectivity and high sensitivity achieved by chronoamperometry in the detection of adsorbed hIgG and the reaction with its antibody.

Formation Of Dendritic Nanostructures In Pyrex Glass Anodically Bonded To Silicon Coated With An Aluminum Thin Film

Anodic bonding with thin films of metal or alloy as an intermediate layer, finds increasing applications in micro/nanoelectromechanical systems. At the bonding temperature of 350 degrees C, voltage of 400 V, and 30 min duration, the anodic bonding is completed between Pyrex glass and crystalline silicon coated with an aluminum thin film with a thickness comprised between 50 and 230 nm. Sodium-depleted layers and dendritic nanostructures were observed in Pyrex 7740 glass adjacent to the bonding interface. The sodium depletion width does not increase remarkably with the thickness of aluminum film. The dendritic nanostructures result from aluminum diffusion into the Pyrex glass. This experimental research is expected to enhance the understanding of how the depletion layer and dendritic nanostructures affect the quality of anodic bonding. (C) 2007 Elsevier B.V. All rights reserved.

Tensile Tests Of Micro Anchors Anodically Bonded Between Pyrex Glass And Aluminum Thin Film Coated On Silicon Wafer

Micro anchor is a kind of typical structures in micro/nano electromechanical systems (MEMS/NEMS), and it can be made by anodic bonding process, with thin films of metal or alloy as an intermediate layer. At the relative low temperature and voltage, specimens with actually sized micro anchor structures were anodically bonded using Pyrex 7740 glass and patterned crystalline silicon chips coated with aluminum thin film with a thickness comprised between 50 nm and 230 nm. To evaluate the bonding quality, tensile pulling tests have been finished with newly designed flexible fixtures for these specimens. The experimental results exhibit that the bonding tensile strength increases with the bonding temperature and voltage, but it decreases with the increase of the thickness of Al intermediate layer. This kind of thickness effect of the intermediate layer was not mentioned in the literature on anodic bonding. (C) 2008 Elsevier Ltd. All rights reserved.