Gold, amongst other group 11 metals, was almost certainly one of the first three metals known to man. In addition to the economic importance of the metal, gold has a wide variety of applications in the medical, electrocatalytical and micro-electronics fields. However, the determination of gold ions in solution, with accuracy, precision, sensitivity and selectivity is still an interesting and much debated topic in analytical chemistry. A system whereby gold ions have been successfully detected employing an electrochemical technique, known as stripping voltammetry, has been developed. The electrochemical method was chosen over other available techniques for the sensitivity, particularly at low concentrations, and selectivity properties; notably in the presence of other metal ions. Under acidic conditions, the electrochemical technique was applied and the presence of gold(III), at a concentration of 2.53 x 10⁻⁵ mol dm⁻³ in a mine waste water sample, was detected. Biomass, in particular yeast and algal types, have been successfully employed in extracting low concentrations of gold ions from industrial effluents. The manipulation of the biological facility for mineral interaction, biohydrometallurgy, may yield numerous potential new technologies. South Africa in particular would benefit from this area of research, since the country is a major ore and metal refining country and if the output and the efficiency of the mines could be improved, even by a small percentage, the financial rewards would be vast. In this study, the application of adsorptive cathodic stripping voltammetry (AdCSV) of gold(III) in the presence of various Saccharomyces cerevisiae cell wall components, was investigated to determine which, if any, were involved specifically in the chemical binding of the gold ions. The chitin and mannan extracts showed the most promise with detection limits of 1.10 x 10⁻⁶ mol dm⁻³ and 9 x 10⁻⁹ mol dm⁻³, respectively; employing the AdCSV technique. A modification of the stripping voltammetry technique, Osteryoung square wave stripping voltammetry (OSWSV), provided the lowest detection limit, for gold(IIl) in the presence of mannan, of 1.70 x 10⁻¹¹ mol dm⁻³ ; utilising a modified carbon paste electrode. The detection of gold(III) has been shown to be dependent on the type of electrode employed, the electrolyte solution and the presence of interfering agents. The effect of copper(II) and silver(I) on the detection of the gold(III) in solution was investigated; whilst the silver(I) has shown no detrimental effects on gold (III) detection systems, copper(II) has indicated the possibility of forming an inter-metallic compound with the gold(III). However, mannan has shown to selectively and preferentially bind the gold(III) in the presence of a ten-fold excess of copper(II). Nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, as well as computer modelling techniques were employed to further investIgate the mannan-gold(III) interaction and proposed complex formed. The NMR, IR and computer modelling data are in agreement with the electrochemical data on proposing a mannan-gold(III) complex. The co-ordination site was established to be in the vicinity of the H-I and H-2 protons and the gold(III) adopts a square-planar geometry upon co-ordination. The benefits of the research are useful from a biological perspective (i. e. as more is known about the binding sites, microbiologists/biochemists may work on the optimisation of parameters for these sites or work could be furthered into the enhanced expression of the sites) and an industrial one. In addition to the' two major benefits, an improved understanding of gold and its chemistry would be achieved, which is advantageous for other fields of research as well.

abstract: In this thesis, an approach to develop low-frequency accelerometer based on molecular electronic transducers (MET) in an electrochemical cell is presented. Molecular electronic transducers are a class of inertial sensors which are based on an electrochemical mechanism. Motion sensors based on MET technology consist of an electrochemical cell that can be used to detect the movement of liquid electrolyte between electrodes by converting it to an output current. Seismometers based on MET technology are attractive for planetary applications due to their high sensitivity, low noise, small size and independence on the direction of sensitivity axis. In addition, the fact that MET based sensors have a liquid inertial mass with no moving parts makes them rugged and shock tolerant (basic survivability has been demonstrated to >20 kG). A Zn-Cu electrochemical cell (Galvanic cell) was applied in the low-frequency accelerometer. Experimental results show that external vibrations (range from 18 to 70 Hz) were successfully detected by this accelerometer as reactions Zn→〖Zn〗^(2+)+2e^- occurs around the anode and 〖Cu〗^(2+)+2e^-→Cu around the cathode. Accordingly, the sensitivity of this MET device design is to achieve 10.4 V/G at 18 Hz. And the sources of noise have been analyzed. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2015

Made available in DSpace on 2014-06-11T19:29:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2003Bitstream added on 2014-06-13T19:58:48Z : No. of bitstreams: 1 ionashiro_ey_me_araiq.pdf: 2255977 bytes, checksum: 1cb78a04d47dbe28f9a534a5ec698562 (MD5) / Técnicas de análise térmica (TG e DSC), eletroquímica (voltametria cíclica) e de análise de superfície (Microanálise por EDX, mapeamento dos elementos, obtenção das imagens SEM e difratometria de raios X) foram empregadas para o estudo das reações do Hg com o substrato metálico de Pt-Rh 70:30% (m/m). A partir das técnicas de voltametria cíclica e de análise térmica foi possível evidenciar um ataque efetivo do Hg sobre o substrato metálico e ainda a formação de compostos de caráter convalente; caracterizados como PtHg, PtHg2 e RhHg2, caracterizados através da difratometria de Raios X. As análises de superfícies, permitiram revelar, além do aumento da rugosidade do substrato com o avanço da temperatura, a presença de um filme de Hg metálico presente sobre a superfície do substrato (imagem SEM), filme este não observado a partir das imagens para as amostras preparadas por via eletroquímica A liga Pt-Rh 70:30% (m/m) apresentou um comportamento eletroquímico (voltametria cíclica) e térmico (TG) muito semelhante ao observado para o substrato de Rh puro, não revelando um ataque considerável ao substrato, quando comparado ao sistema Pt-Hg, Rh-Hg e Pt-Rh 90:10% (m/m) -Hg. Tal comportamento é muito diferente daquele observado para o substrato de Pt-Rh 90:10% (m/m), situação para a qual o substrato é consideravelmente atacado, assemelhando-se muito ao comportamento eletroquímico e térmico do substrato de Pt pura. Assim o comportamento observado para a liga PtRh 70:30% (m/m) é resultado do aumento do teor do modificador , Rh, na matriz de Pt. / The thermal analysis (TG and DSC), electrochemistry (Cyclic Voltametry) and surface analysis (EDX microanalysis, Mappin and SEM) techniques were used to study of the reaction of Hg with the Pt-Rh 70:30% (m/m) alloy. The cyclic voltametry and thermal analysis showed an effective Hg attack in the metallic alloy and the covalent compounds formation; PtHg, PtHg2 and RhHg2 characterized by X-ray diffraction technique. The surface analysis techniques, could reveal a roughning increase on the alloy surface with the temperature increase and presence of a Hg film on the alloy surface (SEM images). This film wasn’t observed for the electrochemical samples. The Pt-Rh 70:30% (m/m) showed na electrochemical and thermal behavior similar to the Pure Rh alloy, who didn’t reveal an considerable Hg attack in comparison with the Pt-Hg, Rh-Hg and Pt-Rh 90:10% (m/m) systems. This behavior is very different to the Pt-Rh 90:10% (m/m) alloy, which showed an effective Hg attack being very similar to the electrochemical and thermal behavior of pure Pt alloy. The observed comportament of the Pt-Rh 70:10% (m/m) alloy is result of the increase of Rh in the Pt matrix.

No description available.

Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

This work describes, for the first time, the electrochemical and electrocatalytic properties of self-assembled layers of single-walled carbon nanotubes (SWCNTs) intergrated with selected organo-iron complexes and Cysteamine (Cys) forming a base on gold electrodes. The organo-iron complexes selected for this study were octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc), tetraaminophthalocyninatoiron(II) (FeTAPc), tetraaminophthalocyninatocobalt(II) (CoTAPc), ferrocene monocarboxylic acid (FMCA), ferrocene dicarboxylic acid (FDCA) or a mixture of SWCNT and FMCA or FDCA. The successful fabrication of these electrodes were established using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and electrochemical techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), square wave voltammetry (SWV) and chronoamperometry (CA) The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes as the Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (kapp) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (~1.7 x 10-2 cm s-1) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 x 10-3 cm s-1) is attributed to the possible effect of both the central metal on the phthalocyanine core and subsituents on the peripheral positions of the phthalocyanine rings. This work clearly proved that the aligned SWCNTs arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs. The advantageous electron transfer properties of the aligned Au-Cys-SWCNT-FeOHETPc electrode, coupled with its ease of fabrication and electrochemical stability, could be found useful in electrochemical sensing and catalysis. Thiocyanate ion was used as an analytical probe to examine the electrocatalytic properties of these modified gold electrodes. This work shows that SWCNT-FeOHETPc hybrid exhibits excellent sensitivity towards the detection of thiocyanate compared to electrodes containing SWCNT or FeTAPc or FeOHETPc only, indicating the ability of the SWCNTs to function as effective conductive nanowires for the detection of this important analyte. The electrochemical response of the FeOHETPc based electrodes was greater than their FeTAPc-based electrode counterparts, indicative of the impact of peripheral substituents on the phthalocyanine core towards electrocatalytic behaviour of these types of hybrids. Nevertheless, the exchange of the central metal as seen with the case of CoTAPc (see chapter 3), provide useful comparative electrochemical activity of this complexes versus FeTAPc with the same chemical environment with an indication of iron being the best as metal centre. FMCA or FDCA were covalently attached to the base Cysteamine monolayer to form the Au-Cys-FMCA and Au-Cys-FDCA, respectively. The same covalent attachment strategy was used to form the mixed SWCNTs and ferrocene-terminated layers (i.e., Au-Cys-SWCNT/FMCA and Au-Cys-SWCNT/FDCA). The impact of neighbouring SWCNTs on the electron transfer dynamics of the ferrocene molecular assemblies in acidic medium (0.5 M H2SO4) and in a solution (pH 7.2) of an outer-sphere redox probe ([Fe(CN)6]4-/ [Fe(CN) 6]3-) was explored. The electron transfer rate constants in both solution media essentially decrease as Au-Cys-FMCA > Au-Cys-SWCNT/FDCA > Au-Cys-FDCA > Au-Cys-SWCNT/FMCA. This trend has been interpreted in terms of several factors such as the locations of the ferrocene species in a range of environments with a range of potentials, the proximity /interactions of the ferrocenes with one another, and electrostatic interaction or repulsion existing between the negatively-charged redox probe and the modified electrodes. Square wave voltammetry was used to examine the catalytic behaviour of the electrodes. Au-Cys-SWCNT/FDCA proved to be the best electrode, possibly due to the repulsive interactions between the negatively charged SCN- and high number of surface –COOH species at the SWCNT/FDCA. This novel study has provided some useful insights as to how CNTs co-assembled with ferrocene-terminated thiols could impact on the heterogeneous electron transfer kinetics as well as the electrocatalytic detection of the self-assembled ferrocene layers. / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

This thesis presents numerical and experimental investigations into Electrochemical Machining (ECM). The aim is to develop a computer program to predict the shape of a workpiece machined by the ECM process. The program is able to simulate various applications of EC machining which are drilling, milling, turning and shaped tube electrochemical drilling (STED). The program has been developed in a MATLAB environment. In this present work, EC-drilling, EC-milling and EC-turning are analysed as three-dimensional problems whereas STED is simulated in two-dimensions. Experiments have been carried out to verify the accuracy of the predicted results in the cases of EC-milling and EC-turning. The ECM modeller is based on the boundary element method (BEM) and uses Laplace's equation to determine the current distribution at nodes on the workpiece surface. In 3D, the surfaces of the tool and the workpiece are discretised into continuous linear triangular element types whereas in 2D, the boundaries of the tool and workpiece are discretised into linear elements. The ECM modeller is completely self-contained, i.e. it does not rely on any other commercial package. The program contains modules to automatically discretize the surfaces/boundaries of the tool and workpiece. Since the simulation of the ECM process is a temporal problem, several time steps are required to obtain the final workpiece shape. At the end of each time step, the shape of the workpiece is calculated using Faraday's laws. However, the workpiece's shape changes with progressing time steps causing the elements to become stretched and distorted. Mesh refinement techniques are built in the ECM modeller, and these subdivide the mesh automatically when necessary.The effect of time step on the predicted 3D shape of a hole in EC-drilling is investigated. The effect of discontinuity in the slope between neighbouring elements is also studied. Results obtained from the ECM modeller are compared with 2D analytical results to verify the accuracy that can be obtained from the ECM modeller. Milling features ranging from a simple slot to a pocket with a complex protrusion were machined in order to determine the feasibility of the EC milling process. These features were machined on a 3-axes CNC machine converted to permit EC milling. The effect of tool geometry, tool feed rate, applied voltage and step-over distances on the dimensions, shape and surface finish of the machined features were investigated. A pocket with a human shape protrusion was machined using two different types of tool paths, namely contour-parallel and zig-zag. Both types resulted in the base surface of the pocket being concave and the final dimensions of the pockets are compared with the design drawing to determine the effect of tool path type on the accuracy of machining. The ECM modeller was used to simulate the machining of a thin-walled turned component. The machining parameters, i.e. initial gap, rotational speed, and applied voltage, were specified by the collaborating company. Since only a small amount of material had to be removed from the thin-walled component, the tool was held stationary i.e. a feed in the radial or longitudinal direction was not required. By taking advantage of the axi-symmetric nature of a turned component, only a sector of the component was analysed thereby reducing the computing time considerably. The accuracy of the modeller was verified by comparing the predicted time to machine the thin-walled component with the actual machining time. The initial investigations in STED were both experimental and numerical in nature and they studied the effect of applied voltage, tool feed rate and electrolyte pressure on the dimensions of the holes. Later investigations were numerical and an iterative methodology has been developed to calculate a set of feed rates which could machine a specified turbulator shape.

The Lawrence Livermore National Laboratory (LLNL), in Berkley, California, developed a laboratory scale non-membrane electrosorption process known as Capacitive Deionization Technology™ (CDT™) for the continuous removal of ionic impurities in water. A saline solution flows through an unrestricted capacitor type module consisting of numerous pairs of high-surface area (carbon-aerogel) electrodes. The electrode material (carbon aerogel) contains a high specific surface area (400 – 1 100 m2/g), and a very low electrical resistivety (< 40 m<font face="symbol">W</font>.cm). Anions and cations in solution are electrosorbed by the electric field upon polarization of each electrode pair by a direct current (1,4 Volt DC) power source. Testing conducted on a laboratory scale unit at LLNL has proved that CDT™ has the potential to be an alternative desalination technology (Farmer5 et al., 1995). The primary objective of this research was to continue, where the laboratory scale research ended. Thus taking CDT™ from a laboratory scale technology to an industrial scale process, by developing and evaluating an industrial CDT™ prototype system. First, a process was developed to manufacture a cost effective industrial sized CDT™ module. During this process various manufacturing techniques were evaluated to produce an optimum prototype. As part of the developmental process the prototype was tested and water treatment efficiency results were first compared to results obtained on the laboratory scale module and secondly to established desalination technologies like reverse osmosis, electrodialysis, and distillation. Due to the wide variety of potential saline feed water sources, research for this dissertation focused on brackish water applications (which includes wastewater reuse applications). After establishing a cost effective small-scale model of a potential industrial manufacturing process, the prototype was tested with regard to water treatment efficiency. Test results on brackish type waters (1 000 mg/l), indicated that the industrial CDT™ prototype had an energy requirement of 0,594 kWh/1000 liters. Research results compared well to the laboratory scale energy consumptions of 0,1 kWh/1000 liters (Farmer5 et al, 1995) and to the best available existing brackish water membrane based desalination systems with energy requirements of 1,3 to 2,03 kWh/1 000 liters (AWWA, 1999). The thermodynamic minimum energy required (due to osmotic pressure) to desalinate a 0,1% or 1 000 mg/l sodium chloride solution, is 0,0234 kWh/1 000 liters. Development and evaluation results indicated that CDT™ industrial modules could be manufactured cost effectively on a large scale and that such units have the potential to be very competitive with existing technologies with regards to overall operational and maintenance costs. Therefore Capacitive Deionization Technology™ can be viewed as a potential alternative to membrane technologies in the future. Regardless of the benefits to the potable water industry, CDT™ have the potential to incur a dramatic step reduction in the operational costs of desalination plants, which will make desalination a more viable alternative technology for large-scale agricultural and industrial uses. / Dissertation (MEng (Waterutilization))--University of Pretoria, 2006. / Chemical Engineering / unrestricted

Ionic liquids (ILs) were studied as solvents for electrochemical reactions with the intent to devise metallurgical processes for Al, Mg and Ti that are less energy intensive and operate at lower temperatures than current industrial practice. Tetra-alkyl phosphonium ILs are on the low end of the IL cost spectrum and are regarded as understudied compared with imidazolium and pyridinium ILs. They are also known to be more thermally stable. The density, viscosity and conductivity of the phosphonium ILs and metal salt-IL mixtures were measured. The conductivity of the phosphonium ILs tested were found to be roughly an order of magnitude lower than imidazolium ILs; this is attributed to the relatively large cation size and localized charge. Linear density-temperature functions are presented. The viscosity and conductivity temperature relationship was modeled using the Vogel-Tamman-Fulcher (VTF) equation. The electrochemical window of A10341'14,6,6,610 was studied on a Pt substrate over a wide range of A1C13 concentrations using cyclic voltammetry (CV). It was found that the tetra-alkyl phosphonium cation is on the order of 800 mV more electrochemically stable than the 1-ethyl-3-methyl imidazolium (EMI+). Cathodic and anodic polarization of Al in A1C13-[P14,6,6,6]C1 (Xmc13 = 0.67) was studied at temperatures ranging from 347 to 423 K. The Butler-Volmer equation was fitted to the plots by varying the kinetic parameters. The cathodic reaction was found to be diffusion limited and the anodic reaction is limited by passivation at lower temperatures. The overpotential required for electrodissolution of Al was found to be higher than for electrodeposition. Aluminium was electrodeposited using both an electrowinning setup (chlorine evolution anode reaction) and electrorefining setup (Al dissolution anode reaction). The deposits were characterized in terms of morphology, current efficiency and power consumption. A variety of deposit morphologies were observed ranging from smooth, to spherical to dendritic, and in some cases, the IL was occluded in the deposit. The current efficiency and power consumption were negatively impacted by the presence of H2O and HCl present in the as-received ILs and by C12(g) generated by the anode reaction in the case of the electrowinning setup. HC1 was removed by cyclic polarization or corrosion of pure Al, resulting in current efficiencies above 90%. Aluminium was electrodeposited using the electrorefining setup with anode-cathode spacing of 2 mm at power consumption as low as 0.6 kWhr/kg-Al. This is very low compared with industrial Al electrorefining and Al electroplating using the National Bureau of Standards bath, which require 15-18 kWhr/kg-Al and 18 kWhr/kg-Al, respectively. However, due to low solution conductivity the power consumption increases significantly with increased anode-cathode spacing. Titanium tetrachloride was found to be soluble in [P14,6,6,6]Cl and increases the conductivity of the solution. Attempts to reduce the Ti(IV) included corrosion of titanium metal, corrosion of magnesium metal powder and cathodic polarization. Despite a few attempts, the electro-deposition of Ti was not observed. At this point, titanium electrodeposition from phosphonium based ILs does not appear feasible. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

This dissertation the syntheses of Pt-based binary and ternary alloy electrocatalysts using the transition metals of Co and Ni are presented. These electrocatalysts were synthesised by an impregnation-reduction procedure at high temperature whereby Pt supported on carbon, (Pt/C (40 percent), was impregnated with the various metal and mixtures thereof and reduced at high temperatures in a H2 atmosphere. The procedure was also designed in such a way so as to prevent the oxidation of the support material (carbon black) during the alloy formation. The resultant nanoparticles (9-12 nm) of Pt3Co/C, Pt3Ni/C and Pt3Co0.5Ni0.5/C were also subjected to a post treatment procedure by acid washing (denoted AW) to produce electrocatalysts of Pt3Co/C-AW, Pt3Ni/C-AW and Pt3Co0.5Ni0.5/C-AW to study the effect of acid treatment on these electrocatalysts. The synthesised electrocatalysts were then characterised by a number of physical and electrochemical techniques and compared to that of commercial Pt/C (Pt/C-JM, HiSpec 4000) as well as Pt/C catalysts (Pt/C-900 and Pt/C-900-AW) treated under the same conditions used for the alloy synthesis. The electrocatalysts were then used to fabricate MEAs that were loaded into commercial single test cells and characterised by means of polarisation curves and Electrochemical Impedance Spectroscopy (EIS). The extensive physical characterisation included Powder X-Ray Diffraction (PXRD) analysis, Transmission Electron Microscopy (TEM), elemental analysis by Energy Dispersive Spectroscopy (EDS) and metal loading by Thermo-Gravimetric Analysis (TGA). These studies showed that Pt-based alloy electrocatalysts were successfully synthesised with particle sizes ranging from 9 - 12 nm, within their respective atomic ratios and whereby no significant loss of carbon support occurred. This indicated that significant sintering or electrocatalyst particles occurred when compared to that of the starting Pt/C catalyst (3 – 4 nm). From the combined results of the physical characterisation procedures, it was also shown that leaching as a result of acid washing was catalyst dependent with Ni containing catalysts showing a significant degree of leaching compared to that of Co containing catalysts. Electrochemical characterisation in terms of Electrochemical Active Surface Area (ECSA) by Cyclic Voltammetry (CV) and ORR activity by Rotating Disc Electrode (RDE) analysis revealed that a significant decrease in the ECSA resulted from the increase in particle size and this had a major influence on the ORR activity. Furthermore it was found that a significant improvement in the ORR activity was achieved by the synthesis of Pt-based alloys. It was also found that catalytic properties of the acid washed electrocatalysts were substantially different from that of non-acid washed electrocatalysts. The experimental data confirmed that it was possibly to achieve better catalytic performance as compared to that of Pt/C at a lower material cost when Pt is alloyed with base transition metals. The trend observed from the ORR activity studies by RDE was successfully repeated in the in-situ fuel cell testing in terms of mass activity of the electrocatalysts. Of the electrocatalysts studied under „real‟ fuel cell conditions Pt/C-JM had the best performance compared to the others, with the ternary Pt3Co0.5Ni0.5/C showing better catalytic performance compared to the Pt3Co/C electrocatalyst. This was found to be due to a higher charge transfer resistance observed in Pt3Co/C as compared to that of Pt3Co0.5Ni0.5/C which was similar than that of the commercial Pt/C-JM catalyst with both Pt3Co/C and Pt3Co0.5Ni0.5/C-AW having similar but higher ohmic resistances than that of Pt/C-JM as determined by electrochemical impedance spectroscopy. The results showed that a great potential exist to improve the catalytic performance of low temperature PEM fuel electrocatalysts at a reduced cost as compared to that of pure Pt provided a method of controlling the particle size was established.