A cylindrical electrochemical reactor with a 3 in diameter copper or nickel metal foam cathode and a concentric carbon cloth anode was used to destroy aqueous phase carbon tetrachloride (CT). The results show that a high CT conversion can be achieved in regions of the cathode near the anode, but a low CT conversion is obtained in the region around the center of the cathode. This CT conversion distribution in the radial current-conducting direction suggests that a portion of the cathode worked inefficiently even though the overall CT conversion is still adequate. Further research by changing the solution pH and conductivity suggests that the radial conversion distribution is due to radial variations in cathode surface availability. The inherent difficulties that these results imply with regards to reactor scale up suggested a new approach to the design. An annular reactor, consisting of a thin (3.2 mm) nickel foam cathode wrapped around an inert Plexiglas core and separated for an external concentric anode by a semi-permeable membrane was adopted. Under compatible operating conditions, the annular reactor showed a high overall effluent CT conversion. However, experiments at low pH (2.25) yielded higher conversions than under neutral pH conditions. This result suggests that CT conversion is favored by a relatively high proton concentration. This reactor can be simulated by a one dimensional model. The annular reactor was used to destroy PCE and TCE successfully, which suggests that this technique can be employed to treat groundwater contaminated with complex mixtures of chlorinated hydrocarbons.A multi-layer reactor based on the principle of the annular reactor was developed as an option for the scale up of the system. This reactor exhibited high and uniform radial CT conversion.

Lithium-rich transition metal oxides are candidates for the next-generation lithium-ion battery positive electrode materials. They have a much higher first charge and low-rate cycling capacity compared to non-lithium rich transition metal oxides. In this thesis, the preparation of spherical and dense transition metal oxide was studied. The morphology and tap-density of the hydroxide precursor was found to be dependent on the coprecipitation reaction pH. The coprecipitation reaction in the presence of aqueous ammonia was studied by analyzing the relevant chemical equilibria. The electrochemistry of lithium-rich oxides was studied as a function of particle size. The apparent oxygen diffusion coefficients were estimated using the Atlung graph method and were determined to be several orders of magnitude lower than normal lithium deintercalation. Isothermal mass calorimetry measurements showed evidence of a local Jahn-Teller distortion in the MnO6 units during discharge. Other studies of the lithium-rich oxides were also carried out.

<p>Cochlear implant listeners are presented with a time and frequency-quantized version of speech signals. In the frequency domain, resolution is limited by the number of electrodes in each listener's array. Current cochlear implant speech processing strategies implicitly assume that the information presented to each one of these electrodes is perceived as unique and independent. However, previous research suggests that stimuli presented on different electrodes can be indiscriminable (e.g. Zwolan et al., 1997; Throckmorton and Collins, 1999; Henry et al., 2000) . Additional studies suggest that stimuli presented on one electrode can influence the perception of stimuli on neighboring electrodes (e.g. Shannon, 1990; Chatterjee and Shannon, 1998; Boëx et al., 2003). Removing this redundant or occluded information could cause more distinct or perceivable information to be presented to the listener and possibly result in improved speech recognition.</p><p>Previous studies have used psychophysical data to identify the electrodes with the highest potential to confound speech recognition (Zwolan et al., 1997, Boëx et al., 2003, and Garadat et al., 2012). In order to minimize electrode interactions and maximize the amount of perceivable information, each of these studies used a single psychophysical metric to deactivate the electrodes across all time windows of the speech processing strategy. For some listeners, these reduced electrode sets resulted in improved speech recognition over using the of the electrodes in their array. These studies did not compare the results of using different psychophysical metrics to exclude electrodes for a group of listeners nor did they investigate speech recognition performance as a function of the number of electrodes excluded from the array.</p><p>In this work, three different psychophysical metrics were used to obtain a multidimensional estimate of the potential "usefulness'' of each electrode. These results were then used to inform two different methods of psychophysics-motivated electrode selection. The first method incorporated individual data into each listener's energy-driven speech processing strategy. For each time window, the electrodes with the highest energy that were also most likely to be perceived, according to the psychophysical data, were selected for stimulation. The second method sequentially excluded the electrodes with the highest potential to confound from the array across all time windows, resulting in a group of psychophysics-motivated electrode sets for each metric. Evaluating each of these electrode sets exhaustively would require a prohibitive amount of experimental time. To mitigate this problem, an adaptive procedure was developed to estimate performance as a function of cochlear implant parameters in a time-efficient manner. For each metric, the procedure estimated the set with the highest estimated probability of correct phoneme identification. Listeners' speech recognition performance using this electrode set was then compared to their performance using their full electrode array. For both electrode selection methods, listeners' speech recognition scores were generally comparable to those obtained in the clinical condition. This finding supports the hypothesis that listeners were not perceiving all the information presented to them using their clinical speech processing strategy and their complete set of electrodes. Additionally, these results suggest that improvements to the proposed electrode selection strategies should be in investigated in order to increase the amount of perceivable information presented to cochlear implant listeners.</p> / Dissertation

Modification of planar graphitic carbon surfaces by the attachment of molecular films has been investigated in this work. Molecular layers have been grafted to glassy carbon (GC) and pyrolyzed photoresist film (PPF) by employing a range of techniques, which involved electrochemically and photochemically assisted procedures. Modification methods involve the electrochemical reduction of aryldiazonium salt, electrochemical oxidation of arylcarboxylate and photolysis of alkene, alkyne and azide on carbon surfaces. For these methods, it is proposed that reactive species are generated by the procedures, which leads to the grafting of modifiers to the carbon surfaces. A selection of molecular species was grafted to GC and PPF by these method containing different terminal R-functional groups that include —COOH, -NO₂, -NH₂, and —NCS. The grafted R-functional groups permit for further chemical reactions on the surface. Electrochemically and photochemically grafted films were examined with a combination of water contact angle measurements, cyclic voltammetry, X-ray electron spectroscopy XPS, optical microscopy, scanning electron microscopy SEM and atomic force microscopy AFM. Film properties such as surface concentration, film thickness, wettability, chemical composition and reactivity were characterized by the above mentioned techniques. Films electrochemically prepared from aryldiazonium salts and arylcarboxylates, under the conditions applied in this work, formed loosely packed multilayers with typical film thicknesses of les than 5 nm. Photochemically grafted films prepared from alkenes and azides, in general, formed loosely packed monolayers with film thicknesses of less than 2 nm. Loosely packed multilayers were also prepared from alkene and alkyne by photochemical procedures. ii Chemical reactions on grafted films were demonstrated and analyzed by a combination of the above mentioned characterization techniques. In particular, the reduction of nitrophenyl (NP)films, amine-coupling reactions, photoactivation of grafted films with oxalyl chloride and electrostatic assembly of anionic gold nanoparticles were investigated. Selected chemical reactions permitted identification and evaluation of the grafted layers, and demonstrated the ability to control the immobilization of chemical species. Microscale chemical patterning of two different types of modifiers on carbon surfaces was demonstrated using photolithographical techniques that utilized photochemical reactions with azides. Patterns of line-arrays with line widths of hundreds of micrometers to 10 µm were formed.

Silicon is a promising negative electrode material for lithium-ion (Li-ion) batteries, with volumetric and gravimetric capacities much higher than those in current commercial batteries. Implementation of Si as a negative electrode is halted, however, by a large irreversible capacity and declining reversible capacity over cycle life. These problems are linked to the large volume expansion that Si undergoes when reacted with lithium, and overcoming them is the focus of this thesis. To overcome this expansion, in the first part titanium silicides were proposed to buffer the volume expansion problem as Ti does not react with Li and is robust. A pure phase of the targeted TiSi and TiSi2 was not achieved, however one product mixture containing TiSi2 and Ti5Si3 was cycled against Li at C/20. A capacity of 715 mAh g-1 was achieved, however rapid capacity fade occurred over the first 10 cycles. The second part of the thesis focused on heterostructured Si-Ge and Ge-Si core- shell nanowires. The morphology of the nanowires allows for better accommodation of strain due to lithiation, and Ge functions as an active matrix, as it can store Li in a similar manner as Si. The specific capacities of the nanowires were good at 1346 mAh g-1 and 1276 mAh g-1, however after 50 cycles the Si-Ge nanowires had a capacity retention of 72.4 % and the Ge-Si retained 62.4 %. The diffusion coefficient of Li was determined from GITT and EIS to be within the range of 10-16 to 10-13 cm2s-1 and was slightly lower than other reported values, attributed to the dense structure of the nanowires slowing diffusion.

abstract: Programmable Metallization Cell (PMC) is a technology platform which utilizes mass transport in solid or liquid electrolyte coupled with electrochemical (redox) reactions to form or remove nanoscale metallic electrodeposits on or in the electrolyte. The ability to redistribute metal mass and form metallic nanostructure in or on a structure in situ, via the application of a bias on laterally placed electrodes, creates a large number of promising applications. A novel PMC-based lateral microwave switch was fabricated and characterized for use in microwave systems. It has demonstrated low insertion loss, high isolation, low voltage operation, low power and low energy consumption, and excellent linearity. Due to its non-volatile nature the switch operates with fewer biases and its simple planar geometry makes possible innovative device structures which can be potentially integrated into microwave power distribution circuits. PMC technology is also used to develop lateral dendritic metal electrodes. A lateral metallic dendritic network can be grown in a solid electrolyte (GeSe) or electrodeposited on SiO2 or Si using a water-mediated method. These dendritic electrodes grown in a solid electrolyte (GeSe) can be used to lower resistances for applications like self-healing interconnects despite its relatively low light transparency; while the dendritic electrodes grown using water-mediated method can be potentially integrated into solar cell applications, like replacing conventional Ag screen-printed top electrodes as they not only reduce resistances but also are highly transparent. This research effort also laid a solid foundation for developing dendritic plasmonic structures. A PMC-based lateral dendritic plasmonic structure is a device that has metallic dendritic networks grown electrochemically on SiO2 with a thin layer of surface metal nanoparticles in liquid electrolyte. These structures increase the distribution of particle sizes by connecting pre-deposited Ag nanoparticles into fractal structures and result in three significant effects, resonance red-shift, resonance broadening and resonance enhancement, on surface plasmon resonance for light trapping simultaneously, which can potentially enhance thin film solar cells' performance at longer wavelengths. / Dissertation/Thesis / Ph.D. Electrical Engineering 2011

The purpose of this project is to verify if the so called capacitance method is a sensitive enough method to measure micrometer distance changes in an electrode system. This is done by heating up an electrode system to 60°C and make capacitance measurements during the procedure. With the inverse relationship between the capacitance and the distance between the surfaces the distance is attained. The incitement to find a sensitive measurement method is that in a particle accelerator the temperature is down to 4K and the components of an electrode system will contract which can lead to a breakdown of the system. The change in temperature gives a theoretical change in "gap distance" that is close to the measured change in gap distance, therefore the method is a reliable enough method to measure micrometer distance changes. A possible reason for the small deviation is that the measured temperature is the temperature of the surface of the electrode system. It would be preferable to measure the total temperature of the electrodes, not just the surfaces because it is the whole electrode that expands and contracts with the temperature. This could be done with an IR-camera.

>Magister Scientiae - MSc / This thesis focuses on the electroanalysis of some dienes (2-methyl-1.3-butadiene (MBD), tran-1.3-pentadiene (PD), 1.3-cyclohexadiene (CHD) and 3-cyclooctadiene (COD)) found in gasoline and the development of simple electrochemical diene sensors. The detection of dienes in fuels is important as they readily polymerise and form gum in fuel tanks. The electroctivity of the dienes was studied with glassy carbon electrode (GCE) and Pt electrode in tetrabutylammonium perchlorate (TBAP)/acetonitrile solution. Polyaniline-polystyrene sulfonic acid (PANi-PSSA) composite films were electro-deposited or drop-coated on GCE, with and without gold nanoparticles (AuNPs) and characterized by cyclic voltammetry (CV), high resolution transmission electron microscopy (HRTEM) and ultraviolet-visible (UV-vis) spectroscopy. Both composite polymers were found to be of nanofibral structure, and the spherical gold nanoparticles were dispersed uniformly within the polymer. The dienes exhibited no redox peaks on GCE/PANi-PSSA and GCE/PANi-PSSA/AuNPs electrode systems from -1.0 V to +1.5 V, beyond which PANi would overoxidize and lose its electroactivity. Therefore, cyclic voltammetry and steady state amperometry of the four dienes (MBD, PD, CHD and COD) were studied with unmodified Pt and GCE electrodes. Subtractively normalised interfacial-fourier transform infra-red (SNIFTIR) spectroscopic studies of the dienes were performed with Pt electrode. SNIFTIR data showed that there was a definite electro-oxidation of 1.3-cyclohexadiene as electrode potential was changed from E = 770 mV to E = 1638 mV. Severe electrode fouling was observed when steady state amperometric detection of CHD, as a representative diene, was performed on Pt electrode. Randel-Sevčik analysis of the CVs of the dienes on Pt electrode gave diffusion coefficient (Dox) values of 10.65 cm²/s, 9.55 cm²/s, 3.20 cm²/s and 3.96 cm²/s for CHD, COD, PD, and MBD, respectively. The corresponding detection limits (3σn-1) were 0.0106 M, 0.0111 M, 0.0109 M, and 0.0107 M.

Philosophiae Doctor - PhD / Tuberculosis (TB) is an infectious disease with adverse effect on a global scale. The disease is one of the major causes of death in sub-Saharan Africa. Nearly 70% of TB-infected persons are co-infected by the human immunodeficiency virus (HIV). About 50% of TB/HIV patients are smear negative and up to 28% are sputum scarce, which is a significant problem in South Africa since sputum smear microscopy is the most widely used diagnostic test for TB. The detection of Mycobacterium tuberculosis (MTB) and resistance to the TB drug rifampicin (RIF) are the basis of the GeneXpert MTB/RIF protocol. The GeneXpert MTB/RIF is an automated nucleic acid amplification technique for detecting the DNA that originates from MTB. However, low sensitivity and low concentrations of MTB for DNA amplification are a serious issue associated with the protocol. Therefore, other TB diagnostic methods, such as the ones involving biochemical markers of TB, are becoming very important. / 2020-08-31

Magister Scientiae - MSc (Chemistry) / Electrochemical platforms were developed based on pencil graphite electrodes (PGEs) modified electrochemically with reduced graphene oxide metal nanoparticles (ERGO-metalNPs) composite and used for the high-sensitivity determination of Bisphenol A (BPA) in water samples. Synergistic effects of both reduced Graphene Oxide sheets and metal nanoparticles on the performance of the pencil graphite electrode (PGE) were demonstrated in the oxidation of BPA by differential pulse voltammetry (DPV). A solution of graphene oxide (GO) 1 mg mL-1 and 15 ppm of metal stock solutions (1,000 mg L-1, atomic absorption standard solution) (Antimony or Gold) was prepared and after sonication deposited onto pencil graphite electrodes by cyclic voltammetry reduction. Different characterization techniques such as FT-IR, HR-SEM, XRD and Raman spectroscopy were used to characterize the GO and ERGO-metalNPs. Parameters that influence the electroanalytical response of the ERGO-SbNPs and ERGO-AuNPs such as, pH, deposition time, deposition potential, purging time were investigated and optimized. Well-defined, reproducible peaks with detection limits of 0.0125 ?M and 0.062 ?M were obtained for BPA using ERGO-SbNPs and ERGO-AuNPs respectively. The rGO-metalNPs-PGE was used for the quantification of BPA in tap water sample and proved to be suitable for the detection of BPA below USEPA prescribed drinking water standards of 0.087 ?M. / 2021-12-31