A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Masters of Science. Johannesburg, 2016 / Gold nanoparticles are ideally suited as catalysts for selected low temperature reactions such as CO oxidation for catalytic convertors in the motor industry due to their high activity. But they are prone to sintering at high temperatures. Platinum-group-metal based catalysts are efficient at elevated temperatures and generally inactive at lower temperatures. This study explored the CO oxidation efficiency of gold nanoparticles and of a combination of gold and rhodium nanoparticles. Variables such as pH, loading concentration and type of support were varied to control the final properties of the Au based catalysts. Possible bimetallic systems of gold and rhodium were explored for wider temperature range activity than gold alone. All catalysts were characterised using Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDS) and X-Ray Diffraction (XRD). Activity was measured using a temperature controlled, custom-built reactor linked to a gas chromatograph. The conditions yielding the smallest gold nanoparticles were established by adding 5, 8 or 10 wt.% loadings of chloroauric acid to aqueous suspensions of either TiO2 or SiO2 at pH 5, 7 or 9 and at 70-75 °C over 60 minutes. Each preparation was sealed in parafilm, aged in the dark at room temperature for 3 days, vacuum-filtered and subsequently calcined at 300 °C. Gold nanoparticles were smallest when deposited onto TiO2 instead of SiO2, at pH 7 and at a loading of 5 wt. %. A combination of gold and rhodium catalysts were subsequently prepared using these conditions, with the simultaneous addition of rhodium at 1, 3, 5 or 10 wt. % loading. Hydrolysis of gold is highly dependent upon pH, resulting in the synthesis of smaller particles under alkaline conditions. Catalytic activity of samples analysed at 70 and 150 °C was highest for gold nanoparticles below 5 nm, in agreement with previous studies. In the proposed bimetallic catalysts, it was difficult to distinguish gold and rhodium nanoparticles in TEM images, although EDS confirmed their combined presence on the TiO2 support. Particle sizes remained below 5 nm, appearing monodispersed on the TiO2 support except at 10 % rhodium loading where some nanoparticle aggregation was observed. CO oxidation activity showed an apparent temperaturedependent shift in the optimal rhodium loading. Au-TiO2 catalysts with a 5% loading showed the highest activity up to 350 °C for a period of 10 hours and the catalyst deactivated due to sintering. At 150 and 200 °C the Au/Rh-TiO2 catalyst remained active for more than 12 hours. It was concluded that the inclusion of rhodium is a potentially-favourable method for stabilising the activity of gold catalysts.

A thesis submitted to the Faculty of Engineering and The Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy in Engineering Johannesburg 12 September 2016 / Comminution and leaching unit processes play a major role in extracting valuable minerals from ore. Most of the research reported in the literature has focused on optimising individual unit operations rather than on integrating the whole process. This thesis develops an integrated approach to mineral processing systems and flow sheets and is intended to create a methodology for process synthesis that can be applied throughout the extractive metallurgical industry. This could lead to improved efficiency in the overall process by obtaining optimum recovery and, most important, a reduction in energy and material costs. In order to illustrate the methodology a particular example was chosen, namely optimizing the joint comminution and leaching of a particular gold ore. In this investigation laboratory scale grinding and leaching profiles for a gold feed sample (1700–850 μm) were measured. In a laboratory mill various combinations of grinding media, filling level and ball size were investigated, and of the three ball sizes used (10, 20 and 30mm) breakage was most pronounced for the 20 mm. Thus for instance it was also established that when using a higher filling ( =30%) and a ball size of 30 mm, more energy was consumed but less liberation occurred, thus a lower amount of gold was extracted during a 24-hour leaching period. Finally, the breakage kinetics of the gold ore was looked at. Using a standard population model the breakage and selection function parameters were successfully calculated. An investigation into the dissolution kinetics of gold ore in a solution of NaCN was also done. These were found to depend on the stirring rate, reaction temperature, particle diameter and the concentration of the leachant. The rate increased with the stirring speed, reaction temperature and leachant concentration, but decreased when the particle size was greater. The activation energy for the dissolution was estimated at about 3 kcal/mol. Furthermore, the linear relationship between the rate constant and the reciprocal of the square of the particle size is a strong indication that the gold dissolution process is diffusion-controlled. The experimental results were well-fitted to a shrinking core model. In attempting to understand the results, the researcher carried out a number of experiments that involved an investigation into the relationship between comminution and leaching in terms of energy usage and particle size, the former to establish the most efficient application of energy, and the latter to identify the degree of fineness that would ensure optimal recovery. The Attainable Region (AR) method was then used to establish ways of finding the leaching and milling times required to achieve minimum cost (maximise profit). No work on utilizing the AR technique to minimise the cost of milling and leaching on a real industrial ore has previously been published. The investigation aims to show how the AR technique can be used to develop ways of optimising an industrial process that includes milling and leaching. The experimental results were used to show how this method could be successfully applied to identifying opportunities for higher efficiency when performing these operations. The approach however is general and could in principle be used for any two or more unit operations in determining how the product from one unit should be prepared to feed to the next unit so as to optimize the overall process. / MT2017

Catalysts are involved in a very large number of processes leading to the production of industrial chemicals, fuels, pharmaceutical, and to the avoidance, as well as the clean-up of environmental pollutants. In respect to the latter aspect, efforts are being made by different stake-holders (governments, researchers, industrials, etc) in order to prevent or to minimize pollution of our cities. A notably way to reduce pollution for a friendly environment is to make use of clean fuels. After years of research work, it is only recently that dimethyl ether alone or when combined with methanol has been identified as a potential alternative clean fuel. Nonetheless, the technology used for the methanol synthesis from syngas requires high pressure (>120 atm) to reach an acceptable CO conversion. The dimethyl ether production from methanol in a separate unit makes DME more expensive than methanol. However, the transformation of syngas directly into dimethyl ether can be used to relieve the thermodynamic constraints requiring operation at high pressure. If the synthesis of methanol and dimethyl ether takes place in the same reactor, the process should, in principle, be able to operate at a much lower pressure, making it a potentially cheaper process to produce methanol and dimethyl ether. The catalysts that need to be used for this coproduction have to be catalytically stable, selective and able to catalyze the main reactions (methanol and dimethyl ether synthesis) involved in this process at the same temperature. Unfortunately, existing commercial methanol/DME catalysts are not able to function efficiently in the presence of large concentrations of water or at high temperature. Thus, it is relevant to have a catalyst satisfying the above criteria. Recently, it has been reported that a supported gold catalyst could be used for methanol synthesis; accordingly this study has developed bifunctional gold-based catalysts for the methanol and DME synthesis. This study utilized process synthesis approach to determine the optimal operating conditions for methanol/dimethyl ether production that yielded results used to drive an experimental programme to get the most useful information for designing a process route. In a comparative way and by using the feed compressor work load per unit of valuable material generated as objective function, this study showed that the system where methanol is co-produced with DME is more efficient than the one involving the production of methanol alone and this is applicable for the operating reactor temperatures of 500-700K and the loop pressure ranging from 10 to 100 atm. The catalysts systems chosen in this study were consisted in the physical mixture of gold-based catalysts incorporating respectively gamma-alumina and zeolite-Y. The gold-based catalysts were prepared by a co-precipitation method, then characterized by XRD, Raman Spectrometry and Transmission Electron Microscopy and, afterwards tested using a 1/4 inch tubular fixed bed reactor between 573 and 673K at 25 atm. Amongst the catalysts tested at 673K, and 25 atm, 5%Au/ZnO/γ-Al2O3 produced both methanol and dimethyl ether with moderate yield, whereas 5%Au/ZnO/LZ Y-52 gave high dimethyl ether selectivity (75.7%) with a production rate of 252.3 μmol.h-1.g -1 cat . The presence of hydrocarbons detected by the GC-FID in the gas products requires that further investigations be done to determine the eventual source and optimize this new catalyst system based on gold for a large scale coproduction of methanol and dimethyl ether from syngas.

Ph. D., Faculty of Arts, University of the Witwatersrand, 1985

Thesis (M.M. (Finance & Investment))--University of the Witwatersrand, Faculty of Commerce, Law and Management, Graduate School of Business Administration, 2013. / This study examines potential benefits of investing in various gold investment vehicles in terms of risk and return from a typical South African investor’s perspective. Furthermore, the study examines the relationship between gold price and South African macroeconomic variables. Data used in the study comprises of monthly closing share price data of JSE listed gold mining companies, gold price, Krugerrand coin, NewGold ETF, FTSE/JSE all share index, gold mining index, unit trust index (gold & precious metals), real GDP, rand/dollar exchange rate, repo rate and CPI. It was found that gold bullion produced superior abnormal returns and yielded greater capital growth compared to the JSE all share index. However, the JSE all share index exhibit lower volatility compared to gold bullion. Abnormal returns for JSE listed gold mining companies tend to differ substantially from gold bullion abnormal returns. Gold mining companies exhibit added risk which cannot be attributed to the gold bullion. Gold has a potential to reduce systematic risk when added to a portfolio of stocks. A multiple regression model was estimated which relates gold price to South African macroeconomic variables. It was found that gold price depends on real GDP and rand/dollar exchange rate.

MDent, Faculty of Health Sciences, University of the Witwatersrand / PURPOSE The purpose of this in vitro investigation was to determine the effect of using either gold or titanium retaining screws on preload in the dental implant body-abutment complex. This preload is of vital importance for the long term success of the dental implant complex. Inadequate preload results in either loosening or fracture of the retaining screw, and is the most commonly occurring mechanical complication in implant supported/retained prostheses. Similar complications occur when excessive preload is applied to the retaining screws. These complications can result in unscheduled visits with costly and time consuming repairs for the clinician and patient. Routine maintenance protocols for implant supported prostheses range from biannually to five year visits to the dentist. Maintenance visits involve removal of the prosthesis facilitating cleaning of both the implant and prosthesis and inspection of retaining screws . This study sought to gain insight into changes in preload generation after repeated torque application to gold and titanium screws and to observe whether gold or titanium generated better preload. A maintenance protocol would be suggested if any observable pattern was noted. MATERIALS AND METHODS The test setup consisted of an implant body, a cylindrical transmucosal abutment and the retaining screws (gold or titanium). The implant body was anchored using a load cell. Transmucosal abutments were attached to the implant body using either a gold or titanium v retaining screw. A torque gauge was used to apply torque of 20Ncm, 32Ncm and 40Ncm to the retaining screws. This was undertaken to investigate the effect of gold or titanium on preload generated. The effect of applying torque beyond manufacturers recommended 32Ncm was carried out to see if greater preloads could be achieved. All components were from the Southern Implant system. RESULTS Gold retaining screws were found to achieve consistently higher preload values than titanium retaining screws. Preload values were not significantly different from the first to the tenth torque cycle. Titanium screws showed more consistent preload values, albeit lower than those of gold retaining screws. However due to possible galling of the internal thread of the implant body by titanium screws, gold screws remain the retaining screw of choice. Maintenance protocols suggest replacing retaining screws every 20 years. After ten torque cycles were applied to each screw there was an insignificant change in preload generated in both titanium and gold screws. This study was therefore inconclusive with regards to maintenance protocols. CONCLUSION Within the limitations of this study, gold retaining screws generated better preload than titanium. Torque application beyond manufacturers’ recommendations resulted in a more stable implant complex. Further investigation into repeated torque application to retaining screws is required, to determine ideal maintenance protocols.

O objetivo principal deste trabalho de doutorado foi a confecção de materiais híbridos formados a partir da união de nanopartículas de ouro com o polímero poli(3-hexiltiofeno) (P3HT). Os materiais híbridos foram obtidos através da produção de filmes de Langmuir e Langmuir-Schaefer (LS). Nanopartículas de ouro foram sintetizadas em fase aquosa (NpAu), utilizando o método de Turkevich e também, encapsuladas com 1-Octadecanotiol (NpAuOctatiol), apresentando solubilidade em clorofórmio. As NpAu foram utilizadas na subfase de uma cuba de Langmuir e o P3HT espalhado na interface ar/água. Ao transferir o filme de Langmuir formado para um substrato sólido, na forma de filme de Langmuir-Schaefer (deposição horizontal) foi possível obter um material híbrido contendo NpAu e P3HT. As NpAuOctatiol foram utilizadas para preparação de filmes LS híbridos através do espalhamento de soluções contendo uma mistura de P3HT com NpAuOctatiol com diferentes proporções. A presença das nanopartículas de ouro foi comprovada, principalmente, pelas imagens de MEV-FEG. Os filmes LS do P3HT apresentaram anisotropia ótica, permitindo inferir o tipo de orientação das moléculas tanto nos filmes de Langmuir como LS. A incorporação das nanopartículas de ouro no filme influencia na orientação do P3HT, bem como no processo fotodegradativo. Esses filmes foram utilizados em testes de sensibilidade para vapores de compostos orgânicos e água através de medidas de absorção da luz visível. Os filmes apresentaram sensibilidade apenas para três dos solventes testados: tolueno, THF e clorofórmio. Os filmes de P3HT apresentam comportamento eletrocrômico, e esse efeito pode ser observado através da aplicação de potencial por voltametria cíclica durante o registro do espectro de absorção no visível dos filmes. Comportamento eletrocrômico similar foi observado em todos os filmes LS, os quais apresentaram reversibilidade da cor inicial somente com a passagem do potencial inverso ou após certo tempo, o que não se observou para os filmes spin-coating, que apresentou recuperação da cor imediatamente após o potencial ser interrompido. Esse fato indica que o maior ordenamento dos filmes LS mantém a dopagem do filme por mais tempo, e que a presença das nanopartículas de ouro não altera essa propriedade. / The main aim of this doctorate work was the preparation of hybrid materials formed from the union of gold nanoparticles with the polymer poly (3-hexylthiophene) (P3HT). The hybrid material was obtained through the production of Langmuir and Langmuir-Schaefer (LS) films. Gold nanoparticles were synthesized in aqueous phase (AuNp) using the Turkvich method and encapsulated with 1-Octadecanethiol (AuNpOctathiol) with solubility in chloroform. The AuNp were used in the subphase of a Langmuir trough and the P3HT was spread at the air/water interface. When the Langmuir film was transferred, forming the Langmuir-Schaefer films (horizontal deposition), it was possible to get a hybrid material containing AuNp and P3HT. The AuNpOctathiol were used for the preparation of hybrid LS films through the spreading of a solution containing a mixture of P3HT and AuNpOctathiol with different proportions. The presence of gold nanoparticles has been demonstrated mainly by FEG-SEM images. The LS films of P3HT showed optical anisotropy, allowing to infer the type of orientation of the molecules in both Langmuir and LS films. The incorporation of gold nanoparticle in the film influenced the orientation of P3HT, as well as the process of photodegradation of LS films. These films were used in sensitivity tests for vapor of volatile organic compounds and water through measurements of visible light. The films showed sensitivity only for three of the tested compounds: toluene, THF and chloroform. P3HT films exhibited electrochromic behavior and this effect can be observed by applying potential through cyclic voltammetry during the registration of the absorption in the visible spectrum of the film. A similar Electrochromic behavior was observed in all LS films, showing reversibility of the initial color only with the passage of the reverse potential, or after a certain time. Such behavior was not observed in Spin-coating films, which showed recovery of the color immediately after stopping the potential. This fact indicates not only that greater order of LS films maintains the film doping, but also the presence of gold nanoparticles does not change this property.

O ouro tem recebido cada vez mais atenção dentro da catálise, especialmente quando em sua forma nanoparticulada. O trabalho descrito nesta dissertação compreende o desenvolvimento de um catalisador de ouro nanoparticulado que, quando auxiliado por ligantes nitrogenados, realiza a hidrogenação de aldeídos. O catalisador Au/SiO2 foi estudado na ausência e presença de aminas durante a hidrogenação do benzaldeído utilizando H2 como agente redutor. A colidina foi a amina que apresentou a maior contribuição na atividade catalítica do ouro, sendo ela utilizada nos testes de otimização das condições reacionais e no estudo da influência da concentração da amina. Foram determinadas como condições reacionais ideais, a temperatura de 80 °C, 6 bar de H2, i-PrOH como solvente e uma relação colidina/ouro de 5 equivalentes. Nestas condições, foi realizado um teste de filtração a quente em que foi concluído que não há espécies homogêneas ativas na reação. O escopo reacional foi expandido para a hidrogenação de outros aldeídos com altas taxas de conversão e seletividade. Um dos aldeídos estudados foi o cinamaldeído, um aldeído α,β-insaturado cuja hidrogenação seletiva levou ao álcool alílico correspondente, sendo preservada a ligação dupla carbono-carbono. Aldeídos oriundos de fontes renováveis, como o 5-HMF e furfural, foram hidrogenados aos álcoois correspondentes, sendo preservado o anel furano. Os resultados experimentais aqui apresentados e os cálculos teóricos presentes na literatura tornaram possível propor que a hidrogenação do grupo aldeído se dá por meio da quebra heterolítica do H2 levando à formação do par H-/H+. Esse par é transferido para a redução da carbonila, sem afetar outros grupos funcionais presentes na molécula, como alquenos, sem causar a dealogenação ou redução do anel aromático, entre outras vantagens que são inerentes ao uso de ouro como catalisador / Gold has received increasing attention within catalysis, especially as metal nanoparticles. The results described in this dissertation include the development of a nanoparticulate gold catalyst that, when aided by nitrogen-containing ligands, performs the hydrogenation of aldehydes. The Au/SiO2 catalyst was studied in the absence and presence of amines during the hydrogenation of the benzaldehyde using H2 as the reducing agent. Collidine presented the greatest contribution, among other amines, in the catalytic activity of gold, being used in optimization tests for the reaction conditions and to study the influence of the amine concentration. The ideal reaction conditions were determined as 80°C, 6 bar H2, i-PrOH as solvent and a 5 equivalents collidine-togold. Under these conditions, a hot filtration test was performed to concluded that there are no homogeneous species active in the reaction. The reaction scope was expanded to the hydrogenation of other aldehydes with high conversion rates and selectivity. One of the aldehydes studied was cinnamaldehyde, an α,β-unsaturated aldehyde whose selective hydrogenation led to the corresponding allylic alcohol with the carbon-carbon double bond being preserved. Aldehydes from renewable resources, such as 5-HMF and furfural, were hydrogenated to the corresponding alcohols and the furan ring was preserved. The experimental results presented here and the theoretical calculations from the literature allowed us to propose that the hydrogenation of the aldehyde group occurs by means of the heterolytic cleavage of H2 leading to the formation of the H-/H+ pair. This pair is transferred, leading to carbonyl reduction, without affecting other functional groups present in the molecule, such as alkenes, without causing dehalogenation or reduction of the aromatic ring, among other advantages that are inherent to the use of gold as a catalyst.

När en medlemsstats genomförande av ett EU-direktiv innebär tillförsel av ytterligare bestämmelser vilka medför en förhöjd skyddsnivå i förhållande till direktivet, innebär det utförande av gold plating. Eftersom förfarandet leder till särreglering i förhållande till andra medlemsstater uppstår därmed en konflikt med EU:s harmoniseringsambitioner på den inre marknaden. Det saknas emellertid en allmängiltig definition av gold plating; kommissionens definition är exempelvis snävare än hur definitionen görs gällande i andra fall. Uppsatsen har till syfte att besvara hur gold plating bör definieras och för att ge ytterligare förståelse för begreppet undersöks det svenska genomförandet av IDD, vilket innebar strängare nationella krav i förhållande till direktivet på ett antal områden. IDD beskrivs som ett minimiharmoniseringsdirektiv, men är utformat enligt en lagstiftningsmodell som förutsätter ett enhetligt lagstiftningsgenomförande i medlemsstaterna. IDD kan även relateras till ett flertal rättsområden inom vilka fullharmonisering råder, exempelvis finansmarknadsområdet och direktivet MiFID II. I uppsatsens analys framförs ett ställningstagande om att en definition av gold plating bör tydliggöra åtskillnad mellan å ena sidan ett utvidgat tillämpningsområde, å andra sidan tillförsel av materiella krav, eftersom de olika förfarandena innebär olika juridiska problem. Det framhålls dessutom att en bred och deskriptiv definition av gold plating kan vara användbar vid identifiering av direktivs miniminivå. Analysen innebär vidare några kommentarer avseende IDD:s harmoniseringsgrad och en övergripande kategorisering av de avvikelser från miniminivån som har identifierats i genomförandet av direktivet. Därtill framhålls att ett nationellt införande av en norm eller princip som innebär att minimikraven ska vara vägledande vid genomförande av minimiharmoniseringsdirektiv kan strida mot direktivet i det enskilda fallet. Med tanke på EU:s höga regleringsaktivitet och det faktum att medlemsstaternas lagstiftningsmakt har fått ta ett steg tillbaka, kan gold plating mer eller mindre vara en förutsättning för åtgärdade av nationella reformbehov. För att säkerställa att gold plating utförs i enlighet med direktivet och EU-rätten i övrigt, krävs ett tidigare nationellt engagemang och deltagande i den EU-rättsliga beslutsprocessen.

Thesis (Master of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2018. / The rate of waste electrical and electronic equipment (WEEE) is growing at an alarming rate, especially in countries where markets are saturated with huge quantities of new electronic goods. Printed circuit boards (PCBs) are a substantial portion of the value contained in waste from WEEE although they are only 6% of the total weight. It is reported that WEEE is currently the fastest growing waste stream in South Africa as the general population’s access to electronic goods in the last decade has increased, especially access to mobile phones. PCBs are found in any piece of electrical or electronic equipment and consist of various metals including precious metals such as gold (Au), silver (Ag) and palladium (Pd). It is reported that gold has the highest economic incentive at 15,200 $ per ton of PCBs. The rapid introduction of new and advanced technology into mobile phones has caused mobile phones to have a relatively short life span, 1 to 2 years to be exact. Mobile phones printed circuit boards (MPPCBs) have more Au content compared to computer circuit boards. They contain 350 g/ton Au whereas computer (PC) PCBs contains 250 g/ton. This research project will recover gold from waste mobile phones PCBs pregnant ammonia thiosulphate leach solution using copper cementation. The cementation process is preferred to all the other technologies of metals extraction from solution due to ultrahigh purity metals that can be obtained and to the less consumption of materials and energy. Electronic parts on the PCBs were manually removed using pliers and screwdrivers. PCBs were then cut to smaller pieces of about 2 x 2 m. The pieces were crushed and milled respectively. Some of the particles were recycled back to the crusher to get finer particles. The particles were separated to particles of sizes between 0 and 1350 μm using a shaker. The comminuted fractions of the PCBs were then used in the leaching step. Batch cementation experiments were performed by bubbling N2 in glass reaction vessel with a working volume of 0.5 L. The reactor was connected to a circulating water bath for temperature control. The recovery percentage of gold at various temperatures, agitation speeds and different amounts of copper powder used, was determined while pH was monitored. The temperature was varied at 30 °C, 40 °C, and 50 °C and the agitation speeds at 300 RPM and 900 RPM. Copper powder was added at 0.5 g/L, 1 g/L, and 1.5 g/L. Gold concentrations were measured by atomic adsorption spectrophotometer (AAS). Scanning electron microscope (SEM) and Energy-dispersive x-ray spectrometry (EDS) analyses of the copper powder after cementation (precipitates) were used to determine the surface morphology and to evaluate the quantitative aspect of the precipitate. It was found that the recovery of gold from ammonia thiosulphate leach solution was greatly affected by agitation speed. At an agitation speed of 900 rpm, 40 °C and 0.5 g of Copper powder, 96% of the gold was recovered from the leach solution. The cementation rate increased as temperature was elevated from 30 to 40 °C, but slightly decreased as the temperature reached 50 °C. The change in experimental conditions affected the gold concentration on the precipitate recovered. This study will provide a possible solution to the WEEE problem and more specifically mobile cell phones, in South Africa.