Development and application of a microelectrode based scanning voltammetric detector

A large part of the work presented in this thesis describes the development and use of a novel electrochemical detector designed to allow the electrochemical characterisation of compounds in flowing solution by means of cyclic voltammetry. The detector was microprocessor controlled, which provides digital generation of the potential waveform and collection of data for subsequent analysis. Microdisk working electrodes are employed to permit both thermodynamic and kinetically controlled processes to be studied under steady-state conditions in flowing solutions without the distortion or hysteresis normally encountered with larger sized electrodes. The effect of electrode size, potential scan rate, and solution flow rate are studied extensively with the oxidation of ferrocene used as an example of a thermodynamically controlled process and a series of catecholamines as examples of a kinetically controlled process. The performance of the detector was best demonstrated when used as a HPLC post-column detector. The 3-dimensional chromatovoltammograms obtained allow on-line characterisation of each fraction as it elutes from the column. The rest of the work presented in this thesis involves the study of the oxidative degradation pathway of dithranol. The oxidative pathway was shown to involve a complex free radical mechanism, dependent on the presence of both oxygen and, in particular light. The pathway is further complicated by the fact that dithranol may exist in either a keto or enol form, the enol being most susceptible to oxidation. A likely mechanism is proposed from studies performed with cyclic voltammetry and controlled potential electrolysis, then defined by subsequent kinetic studies.

Optimal sensor separation for AoA based localization via linear sensor array

This paper investigates the linear separation requirements for Angle-of-Arrival (AoA) sensors, in order to achieve the optimal performance in estimating the position of a target from multiple and typically noisy sensor measurements. We analyse the sensor-target geometry in terms of the Cramer-Rao inequality and the corresponding Fisher information matrix, in order to characterize localization performance with respect to the linear spacial distribution. Here we consider a situation where one sensor is fixed and the rest are free to be positioned in a linear array.

Tuneable optical waveguide based on dielectrophoresis and microfluidics

In this work, an array of dielectrophoretic curved microelectrodes patterned in a microfluidic channel and integrated with a multimode rib polymeric waveguide is demonstrated. The microfluidic channel is infiltrated with suspended silica (SiO2) and tungsten trioxide (WO3) nanoparticles. The optofluidic system is found to be sensitive and responds not only to the infiltration of nanoparticle suspensions in the microfluidic channel, but also to the magnitude and frequencies of dielectrophoretic forces applied on the nanoparticles. The nanoparticles can be uniformly concentrated or repelled from the region between the curved microelectrode tips forming either a dense stream of flowing nanoparticles or a region void of nanoparticles in the evanescent sensitive region of the polymeric waveguide. The concentration and repulsion of nanoparticles from this region creates a refractive index gradient in the upper cladding of the polymeric waveguide. These conditions made it possible for light to either remain guided or be scattered as a function of dielectrophoretic settings applied on the nanoparticles. The results demonstrate that we successfully developed a novel tuneable polymeric waveguide based on dielectrophoretic assembly of nanoparticles suspended in fluids.

Identification of surface heterogeneity effects in cyclic voltammograms derived from analysis of an individually addressable gold array electrode

Voltammetric behavior at gold electrodes in aqueous media is known to be strongly dependent on electrode polishing and history. In this study, an electrode array consisting of 100 nominally identical and individually addressable gold disks electrodes, each with a radius of 127 µm, has been fabricated. The ability to analyze both individual electrode and total array performance enables microscopic aspects of the overall voltammetric response arising from variable levels of inhomogeneity in each electrode to be identified. The array configuration was initially employed with the reversible and hence relatively surface insensitive [Ru(NH₃)₆]^3+/2+ reaction and then with the more highly surface sensitive quasi-reversible [Fe(CN)₆]^3−/4− process. In both these cases, the reactants and products are solution soluble and, at a scan rate of 50 mV s⁻¹, each electrode in the array is assumed to behave independently, since no evidence of overlapping of the diffusion layers was detected. As would be expected, the variability of the individual electrodesʼ responses was significantly larger than found for the summed electrode behavior. In the case of cytochrome c voltammetry at a 4,4′-dipyridyl disulfide modified electrode, a far greater dependence on electrode history and electrode heterogeneity was detected. In this case, voltammograms derived from individual electrodes in the gold array electrode exhibit shape variations ranging from peak to sigmoidal. However, again the total response was always found to be well-defined. This voltammetry is consistent with a microscopic model of heterogeneity where some parts of each chemically modified electrode surface are electroactive while other parts are less active. The findings are consistent with the common existence of electrode heterogeneity in cyclic voltammetric responses at gold electrodes, that are normally difficult to detect, but fundamentally important, as electrode nonuniformity can give rise to subtle forms of kinetic and other forms of dispersion.

Inhibiting localized corrosion of aluminum and aluminum alloy by rare earth metal compounds : behaviors and characteristics observed using an electrochemically integrated multi-electrode array

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) has been used to characterize the behavior of cerium chloride (CeCl3) and lanthanum chloride (LaCl3) in inhibiting localized corrosion of AA2024-T3 and AA1100. CeCl3 has been found to inhibit AA2024-T3 corrosion in 0.005 M sodium chloride (NaCl) solution by suppressing galvanic corrosion activities and by creating a large number of insignificant anodes. It has also been shown to inhibit localized corrosion of AA1100 in 0.5 M NaCl solution by promoting the random distribution of minor anodes. LaCl3 has been found to inhibit localized corrosion of AA2024-T3 at 1000 ppm, although its efficiency dropped significantly when its concentration decreased to 500 ppm. The addition of CeCl3 and LaCl3 to corrosion testing cells at later stages was unable to effectively suppress existing corrosion anodes.

Characterising localised corrosion inhibition by means of parameters measured by an electrochemically integrated multielectrode array

Electrochemical parameters including maximum anodic current density, total anodic current density, the number of anodic sites and the localised corrosion intensity index have been extracted from galvanic current distribution maps that were acquired using an electrochemically integrated multielectrode array, namely, the wire beam electrode. Experiments have been carried out to demonstrate the application of these new electrochemical parameters for characterising localised corrosion inhibition of metals. A typical corrosion inhibitor, potassium dichromate, was found to affect localised corrosion processes in various ways, for instance in sodium chloride solutions, it was found to inhibit localised corrosion of aluminium alloy AA 2024-T3 by suppressing galvanic corrosion activities occurring over the alloy surface, whereas it was found to control localised corrosion of AA 1100 by creating a large number of minor anodes distributing randomly over the metal surface.

Maximum power point tracking of partial shaded photovoltaic array using an evolutionary algorithm: a particle swarm optimization technique

 Partial shading is one of the unavoidable complications in the field of solar power generation. Although the most common approach in increasing a photovoltaic (PV) array’s efficiency has always been to introduce a bypass diode to the said array, this poses another problem in the form of multi-peaks curves whenever the modules are partially shaded. To further complicate matters, most conventional Maximum Power Point Tracking methods develop errors under certain circumstances (for example, they detect the local Maximum Power Point (MPP) instead of the global MPP) and reduce the efficiency of PV systems even further. Presently, much research has been undertaken to improve upon them. This study aims to employ an evolutionary algorithm technique, also known as particle swarm optimization, in MPP detection. VC 2014 Author(s).

Neurophysiology of insects using microelectrode arrays: Current trends and future prospects

Simple to complex behaviors are directed by the brain, which possess nervous cells, called neurons. Mammals have billions of neurons, organized in networks, making their study difficult. Although methods have well evolved since the last century, studying a simpler model is the key to resolving neuronal communication. In this review, we demonstrate that insects are an excellent model and tool to understand neural mechanisms. Moreover, new technology, such as Microelectrodes Arrays (MEAs), is an innovative method which opens the possibility to study neuron clusters, rather than individual cells. A combined method of an insect model and MEAs technology may lead to great discoveries in neurophysiology, advancing progress in pharmacology, infectious and neurodegenerative diseases, agriculture maintenance and robotics.

Step by step analyzing, modeling and simulation of single and double array PV system in different environmental variability

This research analyses the mathematical model of the PV array with all the parameters involved, in the sequential steps. Then it is going to simulate the I-V and P-V characteristics of PV array in different climatology conditions, by using both MATLAB M-file and Simulink. Finally the capability of this method is demonstrated in simulated results, which are performed for both Single and Double Array PV system.

Cobalt carbonate hydroxide nanowire array on ti mesh: an efficient and robust 3D catalyst for on-demand hydrogen generation from alkaline naBH4 solution.

In this work, for the first time, a cobalt carbonate hydroxide (Co(CO3 )0.5 (OH)⋅0.11 H2 O) nanowire array on Ti mesh (CHNA/Ti) was applied to drive the dehydrogenation of alkaline NaBH4 solution for on-demand hydrogen production. Compared with other nanostructured Co-based catalyst systems, CHNA/Ti can be activated more quickly and separated easily from fuel solutions. This self-supported cobalt salt nanowire array catalyst works as an efficient and robust 3D catalyst for the hydrolysis reaction of NaBH4 with a hydrogen generation rate of 4000 mL min(-1)  gCo (-1) and a low apparent activation energy of 39.78 kJ mol(-1) and offers an attractive system for on-demand hydrogen generation.