Electrochemical behavior of redox species at carbon fibre microdisk array electrode modified with mixed-valent molybdenum(VI, V) oxide

In this study, electrode responses to a large number of electroactive species with different standard potentials at the molybdenum oxide-modified carbon fibre microdisk array (CFMA) electrode were investigated. The results demonstrated that the electrochemical behavior for those redox species with formal potentials more positive than similar to 0.0 V at the molybdenum oxide-modified CFMA electrode were affected by the range and direction of the potential scan, which were different from that at a bare CFMA electrode. If the lower limit of the potential scan was more positive than the reduction potential of the molybdenum oxide film, neither the oxidation nor the reduction peaks of the redox species tested could be observed. This indicates that electron transfer between the molybdenum oxide film on the electrode and the electroactive species in solution is blocked due to the existence of a high resistance between the film and electrolyte in these potential ranges. If the lower limit of the potential scan was more negative than the reduction potential of the molybdenum oxide film (similar to - 0.6 V), the oxidation peaks of these species occurred at the potentials near their formal potentials. In addition, the electrochemical behavior of these redox species at the molybdenum oxide-modified CFMA electrode showed a diffusionless electron transfer process. On the other hand, the redox species with formal potentials more negative than similar to - 0.2 V showed similar reversible voltammetric behaviors at both the molybdenum oxide-modified CFMA electrode and the bare electrode. This can be explained by the structure changes of the film before and after reduction of the film. In addition we also observed that the peak currents of some redox species at the modified electrode were much larger than those at a bare electrode under the same conditions, which has been explained by the interaction between these redox species and the reduction state of the molybdenum oxide film. (C) 2000 Elsevier Science Ltd. All rights reserved.

INSITU CONDUCTIVITY ELECTROCHEMISTRY OF CONDUCTIVE POLYMERS - POLY(3-METHYLTHIOPHENE) AND POLYTHIOPHENE

In situ monitoring of conductivity and potential response of conductive polymers during electrochemical process had been described. A renewable carbon fibre array ring-glassy carbon disk electrode was used for this purpose. Poly(3-methylthiophene) and polythiophene were investigated with this method, and some 5 orders in magnitude of conductivity changes were observed during the electrochemical redox process.

Micro- and macroscopic characterizations of the viscoelastic fracture of resin-based fibre composites

Micro- and macroscopic characterizations of the viscoelastic fracture of a unidirectional carbon-fibre-reinforced epoxy composite are presented. First, the micro-cracking behavior of the material is studied by the use of scanning electron microscopy; the in situ creep cracking process is observed and the crack propagation is measured. In order to obtain insight into the mechanisms of the observed creep cracking, macroscopic investigations were also carried out. Finite-element method simulations were carried out to calculate the stress distribution and the variation of stresses with time. A theoretical analysis of the orthotropy of viscoelastic fracture behavior of the material is also conducted.

The interlaminar fracture-behavior and toughening mechanisms of new carbon-fiber-reinforced bismaleimide composites

The interlaminar fracture behaviour of carbon fibre-reinforced bismaleimide (BMI) composites prepared by using a new modified BMI matrix has been investigated by various methods. Laminates of three typical stacking sequences were evaluated. Double cantilever beam, end-notch flexure and edge-delamination tension tests were conducted under conventional conditions and in a scanning electron microscope. The strain energy release rates in Mode I and Mode III G(lc) and G(llc), as well as the total strain energy release rate, G(mc), have been determined and found to be higher than those for laminates with an epoxy matrix. Dynamic delamination propagation was also studied. The toughening mechanisms are discussed.

DETERMINATION OF HYDRAZINES BY CAPILLARY ZONE ELECTROPHORESIS WITH AMPEROMETRIC DETECTION AT A PLATINUM PARTICLE-MODIFIED CARBON-FIBER MICROELECTRODE

A novel modified electrode dispersed with ultrafine platinum particles on the surface of a 30-mu m carbon fibre microelectrode was investigated as an amperometric detector in capillary zone electrophoresis (CEEC) for determining hydrazines. The unique cha

DIRECT-INJECTION OF URINE AND DETERMINATION OF ACETAMINOPHEN BY MICELLAR LIQUID-CHROMATOGRAPHY WITH A WALL-JET CELL CARBON-FIBER MICROELECTRODE

A wall-jet cell/carbon fibre microelectrode detector was designed and used for the micellar liquid chromatographic assay of acetaminophen. The separations were carried out in an analytical column packed with C-18 stationary phase and the mobile phase was

INTERLAMINAR FRACTURE OF CARBON THERMOPLASTIC POLYIMIDE COMPOSITES

Mode I interlaminar fracture of a novel amorphous thermoplastic polyimide reinforced with unidirectional carbon fibre has been studied experimentally using double cantilever beam specimens and scanning electron microscopy. Three kinds of composite were ma

PREPARATION AND CHARACTERIZATION OF A MULTICYLINDER MICROELECTRODE COUPLED WITH A CONVENTIONAL GLASSY-CARBON ELECTRODE AND ITS APPLICATION TO THE DETECTION OF DOPAMINE

A multi-cylinder microelectrode coupled with a conventional glassy carbon disc electrode (MCM/GC) was prepared and characterized using cyclic voltammetry and chronoamperometry. It was demonstrated that in the same way as one observed a steady-state current at closely spaced microelectrodes when redox recycling takes place, the same effect can be obtained with the MCM/GC device. The experimental results obtained with K3Fe(CN)6 solutions were compared with a previously developed theory. Further, it was demonstrated that with a carbon fibre MCM/GC device, the voltammetric behaviour of dopamine is greatly improved by virtue of redox recycling, hence giving high sensitivity. The steady-state collection current was linearly related to dopamine concentration in the range 1 X 10(-4) to 5 x 10(-7) Mol l-1, and the detection limit was 2 x 10(-7) mol l-1. The influence of coexisting ascorbic acid was also investigated. This device was applied successfully in the determination of dopamine hydrochloride in pharmaceutical preparations.

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATE AND HETEROPOLY-OXOMETALLATE FILM MODIFIED MICROELECTRODES .2. ELECTROCHEMICAL-BEHAVIOR OF ISOPOLYMOLYBDIC ACID MONOLAYER MODIFIED CARBON-FIBER MICROELECTRODES

In this paper the electrochemical properties of isopolymolybdic anion thin film modified carbon fibre (CF) microelectrode prepared by simple dip coating have been described. The modified electrode shows three couples of surface redox waves between + 0.70 and - 0.1 V vs. sce in 2 M H2SO4 solution with good stability and reversibility. The pH of solution has a marked effect on the electrochemical behaviour and stability of the film, the stronger the acidity of electrolyte solution is, the better the stability and reversibility of isopolymolybdic anion film CF microelectrode will be. The scanning potential range strongly influences on the electrochemical behaviour of the film. The isopolymolybdic anion film prepared by the dip coating resulting a monolayer with estimated surface concentration (F) 2.8 x 10(-11) mol cm-2. From the half-peak widths and peak areas of the surface redox waves of the film electrode, the first three surface waves are corresponding to two-electron processes. The electron energy spectra show the products by six electrons reduction are a mixture of Mo(VI) and Mo(V) species. The electrochemical reaction of the isopolymolybdic anion monolayer can be expressed as Mo8O264- + mH+ + 2ne half arrow right over half arrow left [HmMo8-2n(VI)Mo2n(V)O26](4,2n-m)-n = 1, 2, 3; m = 2, 5, 7.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

A NEW KIND OF FLOW-THROUGH ELECTROCHEMICAL DETECTOR USING CARBON-FIBER ELECTRODE FOR LIQUID-CHROMATOGRAPHY

An electrochemical detector which was constracted by using a carbon fibre electrode in a flow-through cell was connected with a liquid chromatographic column. Thus a sensitive,

DETERMINATION OF AMINOPYRINE AND ITS METABOLITE BY CAPILLARY ELECTROPHORESIS ELECTROCHEMICAL DETECTION

An electrochemical pretreatment regime for a cylindrical carbon fibre microelectrode was optimized for the determination of aminopyrine (AM) and its metabolite 4-aminoantipyrine (AAN) by capillary electrophoresis (CE)-electrochemical detection (ED). Under optimized conditions, a response of high sensitivity and stability was obtained for AM and AAN at a detection voltage as low as 0.9 V following CE-ED, by which AM and AAN were separated satisfactorily. The calibration graph was linear over three orders of magnitude and the limits of detection for AM and AAN were in the femtomole range.

ELECTROCATALYTIC PROPERTIES OF MIXED-VALENCE MOLYBDENUM OXIDE THIN-FILM MODIFIED MICROELECTRODES

A compact blue conducting mixed-valence Mo (VI,V) oxide film was grown on the surface of a carbon fibre (CF) microelectrode by cycling the potential between +0.20 and similar to 0.70 V SCE in freshly prepared Na2MoO4 solution in H2SO4 (pH 2). The thicknes

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.