Localized corrosion and inhibition studies using the wire beam electrode in conjunction with the electrochemical noise analysis and the scanning reference electrode techniques

Several new technical developments have been made based on the combined use of the wire beam electrode (WBE), electrochemical noise analysis (ENA) and the scanning reference electrode technique (SRET). These have included: (i) The WBE-R n method- the combined use of the WBE and the noise resistance (Rn) to map the rates and patterns of uniform or localized corrosion; (ii) The WBE-Noise Signatures method- the combined use of the WBE and the noise signature to detect the origination and propagation of localized corrosion; and (iii) The WBE-SRET method- the combined use of the WBE and SRET to investigate localized corrosion from both the metallic and electrolyte phases of a corroding metal surface. This paper presents a brief review on these novel methods and their applications for detecting general and localized corrosion, for mapping the rates of corrosion, and for studying corrosion inhibitors.

Studying and evaluating anti-corrosion coatings and inhibitors using the wire beam electrode method in conjunction with electrochemical noise analysis

Purpose – To provide a summary of research work carried out mainly in the authors' group for evaluating various protective coatings including rustproofing oils, and also for studying corrosion inhibitors using the wire beam electrode (WBE) method.

Design/methodology/approach – A range of published papers published during the past 15 years was summarised and reviewed. Recent research work in the authors' group was also included, which involved the combined use of the WBE with electrochemical noise analysis and the scanning reference electrode technique.

Findings – The WBE method has been developed into a very useful tool of evaluating the performance of coatings and inhibitors. In particular, The WBE is uniquely applicable for determining the performance of coatings and inhibitors to control localised corrosion.

Research limitations/implications – Focusing mainly on recent research.

Practical implications – A useful source of information for researchers and graduate students working in the areas of organic coating and inhibitor research.

Originality/value – The first summary or review on this research topic.

Electrical control of nanoscale functionalization in graphene by the scanning probe technique

Functionalized graphene is a versatile material that has well-known physical and chemical properties depending on functional groups and their coverage. However, selective control of functional groups on the nanoscale is hardly achievable by conventional methods utilizing chemical modifications. We demonstrate electrical control of nanoscale functionalization of graphene with the desired chemical coverage of a selective functional group by atomic force microscopy (AFM) lithography and their full recovery through moderate thermal treatments. Surprisingly, our controlled coverage of functional groups can reach 94.9% for oxygen and 49.0% for hydrogen, respectively, well beyond those achieved by conventional methods. This coverage is almost at the theoretical maximum, which is verified through scanning photoelectron microscope measurements as well as first-principles calculations. We believe that the present method is now ready to realize 'chemical pencil drawing' of atomically defined circuit devices on top of a monolayer of graphene. © 2014 Nature Publishing Group All rights reserved.

The fabrication and performance of an Ag/AgCl reference electrode in human serum

A simple set of electric circuits was used to assemble a pulse generator. With pulse potentials and under galvanostatical control, a clean silver wire was anodized electrochemically for 0.2-0.5 min in 1.0 moll(-1) HCl with a pulse current density of 20 mA cm(-2), and the pulse wave parameters of t(a)/t(c) = 1 and a cycle of 4 s forming an Ag/AgCl reference electrode. Even though the AgCl layer was consumed during the working period when the Ag/AgCl electrode was used as a cathode, the AgCl layer could be in situ recovered electrochemically in serum used when a reversed potential was applied to the electrode system immediately after the measuring program was finished. The current response curve of the anode indicated that an AgCl layer in high density was basically accomplished during the first 6 pulse cycles in human serum. In order to keep a stable and uniform AgCl layer on the reference electrode after each measuring cycle, the ratio of the recovery time (t(r)) to the working time (t(w)) was measured and the smallest value was obtained at 0.03. The open-circuit potential of the Ag/AgCl electrode with respect to a SCE in 0.1 moll(-1) KCl was monitored over a period of 14 days and the mean value was 40.09 mV vs SCE with a standard deviation of 2.55 mV. The potential of the Ag/AgCl reference electrode did remain constant when the measurements were repeated more than 600 times in undiluted human serum with a standard deviation of 1.89 mV. This study indicated that the Ag/AgCl reference electrode could been rapidly fabricated with a pulse potential and could be used as a reference electrode with long-term stable properties in human serum samples.

Effect of the mediator in feedback mode-based SECM interrogation of indium tin-oxide and boron-doped diamond electrodes

Indium tin-oxide (ITO) and polycrystalline boron-doped diamond (BDD) have been examined in detail using the scanning electrochemical microscopy technique in feedback mode. For the interrogation of electrodes made from these materials, the choice of mediator has been varied. Using Ru(CN) 4− 6 (aq), ferrocene methanol (FcMeOH), Fe(CN) 3− 6 (aq) and Ru(NH 3) 3+ 6 (aq), approach curve experiments have been performed, and for purposes of comparison, calculations of the apparent heterogeneous electron transfer rates (k app) have been made using these data. In general, it would appear that values of k app are affected mainly by the position of the mediator reversible potential relative to the relevant semiconductor band edge (associated with majority carriers). For both the ITO (n type) and BDD (p type) electrodes, charge transfer is impeded and values are very low when using FcMeOH and Fe(CN) 3− 6 (aq) as mediators, and the use of Ru(NH 3) 3+ 6(aq) results in the largest value of k app. With ITO, the surface is chemically homogeneous and no variation is observed for any given mediator. Data is also presented where the potential of the ITO electrode is fixed using a ratio of the mediators Fe(CN) 3− 6(aq) and Fe(CN) 4− 6(aq). In stark contrast, the BDD electrode is quite the opposite and a range of k app values are observed for all mediators depending on the position on the surface. Both electrode surfaces are very flat and very smooth, and hence, for BDD, variations in feedback current imply a variation in the electrochemical activity. A comparison of the feedback current where the substrate is biased and unbiased shows a surprising degree of proportionality.

The effect of electrode material on the electrochemical formation of porous copper surfaces using hydrogen bubble templating

The electrodeposition of copper onto copper, gold, palladium and glassy carbon (GC) electrodes via a hydrogen bubble templating method is reported. It is found that the composition of the underlying electrode material significantly influences the morphology of the copper electrodeposit. Highly ordered porous structures are achieved with Cu and Au electrodes, however on Pd this order is disrupted and a rough randomly oriented surface is formed whereas on GC a bubble templating effect is not observed. Chronopotentiograms recorded during the electrodeposition process allows bubble formation and detachment from the surface to be monitored where distinctly different potential versus time profiles are observed at the different electrodes. The porous Cu surfaces are characterised with scanning electron microscopy, X-ray diffraction and cyclic voltammetric measurements recorded under alkaline conditions. The latter demonstrates that there are active sites present on electrodeposited copper whose coverage and reactivity depend on the underlying electrode material. The most active Cu surface is achieved at a Pd substrate for both the hydrogen evolution reaction and the catalytic reduction of ferricyanide ions with thiosulphate ions. This demonstrates that the highly ordered porous structure on the micron scale which typifies the morphology that can be achieved with the hydrogen bubbling template method is not required in producing the most effective material.

Current rectification by a single ZnS nanorod probed using a scanning tunneling microscopic technique

We report on the rectification properties from a single ZnS nanorod measured using the UHV-SPM technique. The rectification behavior is evidenced from the current-voltage characteristics measured on a single ZnS nanorod. We propose a tunneling mechanism where the direct tunneling mechanism is dominant at lower applied bias voltages followed by resonant tunneling through discrete energy levels of the nanorod. A further increase in the bias voltage changes the tunneling mechanism to the Fowler-Nordheim tunneling regime enabling rectification behavior. Realizing rectification from a single ZnS nanorod may provide a means of realizing a single nanorod based miniaturized device.

Formation of hierarchical structures of Fe2O3 by the liquid-liquid interface technique

We report the formation of dendritic hierarchical structures of alpha-Fe2O3 and nanostructures of Fe2O3 by the simple liquid-liquid interface method. The morphology of thin films determined by high-resolution scanning electron microscopy shows nanorods, nanosheets and dendritic Fe2O3. The identification of phases of iron oxide structures is carried out by using XRD and XPS studies. XRD and XPS measurements point out the highly crystalline dendritic alpha-Fe2O3 phase and the mixed phase of alpha- and gamma-Fe2O3 nanostructures. The magnetic measurement also suggests the presence of a mixed phase in the sample grown for 72 hours.

Study of the surface structure of butterfly wings using the scanning electron microscopic moire method

Scanning electron microscopic (SEM) moire method was used to study the surface structure of three kinds of butterfly wings: Papilio maackii Menetries, Euploea midamus (Linnaeus), and Stichophthalma how-qua (Westwood). Gratings composed of curves with different orientations were found on scales. The planar characteristics of gratings and some other planar features of the surface structure of these wings were revealed, respectively, in terms of virtual strain. Experimental results demonstrate that SEM moire method is a simple, nonlocal, economical, effective technique for determining which grating exists on one whole scale, measuring the dimension and the whole planar structural character of the grating on each scale, as well as characterizing the relationship between gratings on different scales of each butterfly wing. Thus, the SEM moire method is a useful tool to assist with characterizing the structure of butterfly wings and explaining their excellent properties. (c) 2007 Optical Society of America.

THEORETICAL-ANALYSIS OF NERNSTIAN PLOTS IN THE THIN-LAYER SPECTROPOTENTIOSTATIC TECHNIQUE

The Nernstian plots in a spectropotentiostatic experiment for complex electrode processes were studied theoretically. The plots are linear for an electron transfer process coupled with a preceding or succeeding chemical reaction, and the electron stoichio

Plasma chloriding of thin-film silver - A novel process in silver-silver chloride reference electrode fabrication

Silver thin films were modified using a novel plasma modification process for the development of thin-film silver-silver chloride reference electrodes. The surface, physical, and electrochemical properties of these electrodes were investigated by atomic force microscopy, thickness and resistivity measurement techniques, as well as impedance spectroscopy and potentiometry. After plasma treatment, thin-film growth was observed and the electrodes, in general, exhibited low interface impedance and a roughened surface. Evidence of a complex surface reorganization was found. Correlating plasma conditions with film properties suggested that increasing pressure and exposure duration increased species availability, therefore governing the reaction rates, while input power appeared to influence the type of surface chemical reactions. Results also indicated that Ar/Cl-2 mixtures should be employed rather than pure chlorine plasmas. (C) 2002 The Electrochemical Society.