The nanoparticles of zirconium oxide, sulfated and phosphated zirconia were used to modify a Nafion membrane in order to improve its water retention, thermal stability, proton conductivity and methanol permeability so that it can be used at higher temperatures in fuel cell. These modified Nafion nanocomposite membrane with inorganic nanoparticles have been designed to run at operating temperatures between 120 oC and 140 oC because higher temperature operation reduces the impact of carbon monoxide poisoning, allows attainment of high power density and reduces cathode flooding as water is produced as vapor. The inorganic nanoparticles were incorporated within the Nafion matrix by recast, ion exchange and impregnation methods. The membrane properties were determined by ion exchange capacity (IEC), water uptake, methanol permeability and proton conductivity. The characterization of the inorganic nanoparticles within the nanocomposite membranes was determined by X-Ray diffraction (XRD), Brunau-Emmett-Teller (BET) surface area and Fourier transform infrared spectroscopy (FTIR) for structural properties. Thermal gravimetric analysis (TGA) and Differential scanning calorimetry (DSC) were used to determine the thermal properties, and the morphological properties were probed by Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Pristine ZrO2, sulfated and phosphated ZrO2 nanoparticles were synthesized successfully. The particle sizes ranged from 30 nm to 10 nm respectively. The resulted particles were incorporated to a Nafion membrane with good dispersity. The conductivity of the nanocomposite membrane were around 0.1037 S/cm at 25 oC with a higher water uptake of 42 %. These results were confirmed by the highest IEC value of 1.42 meg.g-1 of Nafion/ S-ZrO2 nanocomposites membrane. These high IEC value may due to the incorporation of superacid S-ZrO2 nanoparticles which increased the membrane acid property for providing new strong acid site. / Chemical Engineering / M. Tech. (Chemical Engineering)

Thesis (M. Tech. Engineering: Electrical--Vaal University of Technology) / The air-breathing Direct Methanol Fuel Cell (DMFC) and Zinc Air Fuel Cell (ZAFC)were experimentally studied in a climate chamber in order to investigate the impact of climatic environmental parameters such as varying temperature and relative humidity conditions on their performance. The experimental results presented in the form of polarization curves and discharge characteristic curves indicated that these parameters have a significant effect on the performance of these fuel cells. The results showed that temperature levels below 0ºc are not suitable for the operation of these fuel cells. Instead, it was found that air-breathing DMFC is favored by high temperature conditions while both positive and negative effects were noticed for the air-breathing ZAFC. The results of the varying humidity conditions showed a negative impact on the air-breathing DMFC at a lower temperature level but a performance increase was noticed at a higher temperature level. For air-breathing ZAFC, the effect of humidity on the performance was also found to be influence by the operating temperature. Furthermore, common atmospheric air pollutants such as N20, S02, CO and N02 were experimentally investigated on the air-breathing DMFC and ZAFC. At the concentration of 20 ppm, these air contaminants showed to have a negative effect on the performance of both air-breathing DMFC and ZAFC. For both air-breathing DMFC and ZAFC, performance degradations were found to be irreversible. It is therefore evident from this research that the performance of the air-breathing fuel cell will be affected in an application situated in a highly air-polluted area such as Vaal Triangle or Southern Durban. It is recommended the air-breathing fuel cell design include air filters to counter the day-to-day variations in concentration of air pollutants.

M. Tech. (Engineering: Electrical, Department Electronic Engineering, Faculty of Engineering and Technology), Vaal University of Technology, / “If we think oil is a problem now, just wait 20 years. It’ll be a nightmare.” — Jeremy Rifkin, Foundation of Economic Trends, Washington, D.C., August 2003. This statement harmonises with the reality that human civilisation faces today. As a result, humankind has been forced to look for alternatives to fossil fuels. Among possible solutions, fuel cell (FC) technology has received a lot of attention because of its potential to generate clean energy. Fuel cells have the advantage that they can be used in remote telecommunication sites with no grid connectivity as the majority of telecommunication equipment operates from a DC voltage supply. Power plants based on phosphoric acid fuel cell (PAFC) have been installed worldwide supplying urban areas, shopping centres and medical facilities with electricity, heat and hot water. Although these are facts regarding large scale power plants for on-site use, portable units have been explored as well. Like any other fuel cell, the PAFC output power is highly unregulated leading to a drastic drop in the output voltage with changing load value. Therefore, various DC–DC converter topologies with a wide range of input voltages can be used to regulate the fuel cell voltage to a required DC load. An interleaved synchronous buck converter intended for efficiently stepping down the energy generated by a PAFC was designed and developed. The design is based on the National Semiconductor LM5119 IC. A LM5119 evaluation board was redesigned to meet the requirements for the application. The measurements were performed and it was found that the converter achieved the expectations. The results showed that the converter efficiently stepped down a wide range of input voltages (22 to 46 V) to a regulated 13.8 V while achieving a 93 percent efficiency. The conclusions reached and recommendations for future research are presented. / Telkom Centre of Excellence, TFMC, M-Tech, THRIP.

M. Tech. (Electrical, Applied Electronics and Electronic Communication, Faculty of Engineering and Technology) Vaal University of Technology| / The demand for efficient and environmentally friendly power sources has become a major topic around the world. This research explores the capability of the zinc-air fuel cell to replace conventional power sources for various applications, more specifically telecommunication systems. The research consisted of a theoretical study of the zinc-air fuel cell and its components, as well as their performance characteristics. A zinc-air fuel ce.ll and test rig were built, and the system was tested under various conditions. It was found that the zinc-air fuel cell has an advantage over other fuel cells in that it does not require any expensive materials or noble metals, reducing the overall cost of such a system. The fuel cell showed the potential to power various applications, but problems persisted in the fueling process as well as constant leaking of the aqueous electrolyte.

M. Tech. (Engineering, Electrical, Department Applied Electronics and Electronic Communication, Faculty of Engineering and Technology) -- Vaal University of Technology / This dissertation presents the design and development of a remote monitoring system (RMS) for polymer electrolyte membrane fuel cells (PEMFC) to facilitate their efficient operation. The RMS consists of a data acquisition system built around the PIC 16F874 microcontroller that communicates with a personal computer (PC) by use of the RS232 serial communication standard, using a simple wired connection between the two. The design also consists of a human machine interface (HMI) developed in Visual Basic 6.0 to provide a platform for display of the monitored parameters in real time. The first objective was to establish performance variables and past studies on PEM fuel cells revealed that variables that affect the system's performance include: fuel and oxidant input pressure and mass flow rates as well as operation temperature and stack hydration. The next objective was to design and develop a data acquisition system (DAS) that could accurately measure the performance variables and convey the data to a PC. This consisted of sensors whose outputs were input into two microcontrollers that were programmed to process the data received and transfer it to the PC. A HMI was developed that provided graphical display of the data as well as options for storage and reviewing the data. The developed system was then tested on a 150Watt PEM fuel cell stack and the data acquisition system was found to reliably capture the fuel cell variables. The HMI provided a real-time display of the data, with alarms indicating when set minimums were exceeded and all data acquired was saved as a Microsoft Excel file. Some recommendations for improved system performance are suggested. / Vaal University of Technology -- National Research Foundations

A biofuel cell electrochemical system based on the oxidation of glucose by glucose oxidase has been developed. The glucose oxidase was immobilised at the electrode surface by a cast Nafion polymer membrane neutralised and modified by tetrabutylammonium bromide to stabilise the membrane. Electrochemical communication with the electrode was established with ferrocene derivatives in solution or co-cast with the Nafion. The individual and combined properties of the components of the system were investigated to select the best components to create a biofuel cell. After establishing a functioning biofuel cell a scale-up procedure was followed in which the chemical system was transferred to higher area electrodes. A laboratory prototype biofuel cell was designed and used to test larger 3-d electrode materials. Before use as an electrochemical reactor the flow properties of the test cell and electrodes were investigated by pulse injections of concentrated buffer tracked with an inline conductivity probe. The biofuel cell generated a steady state power density of up to 50 μW cm-2 superficial area at a graphite plate electrode or 6 μW cm-2 (actual surface basis) at a reticulated vitreous carbon electrode. The test cell demonstrated high cell potentials for a biofuel cell based on a single enzyme electrode and gave a stable output for several days.

Microbial fuel cell (MFC) systems capable of both treating wastewaters and recovering energy have the potential for successful scale-up as a low carbon technology. These systems utilize microorganisms residing in biofilms as biocatalytic agents in the conversion of reduced substrates to electrical energy. As such, it is important to understand how MFC anodic biofilms develop over time and also how environmental parameters such as substrate type, temperature, carbon support material, anode architecture and optimized applied potentials also affect electrogenic performance. The type of substrate was found to have a large impact on the acclimation and performance of electrogenic biofilms. Acetate produced the highest power density of 7.2 W m 3 and butyrate the lowest at 0.29 W m"3, but it was also found that biofilm acclimation to these different trophic conditions also determined the MFC response to different substrate types i.e. both acetate and butyrate substrates produced power densities of 1.07 and 1.0 W m"3 respectively in a sucrose enriched reactor. The use of MFCs for wastewater treatment in temperate regions requires the development of reactor systems that are robust to seasonal fluctuations and are energy efficient. As such, system performance was examined at three different operating temperatures (10°C, 20°C and 35°C). At each temperature a maximum steady-state voltage of 0.49 V ± 0.02V was achieved after an operational period of 47 weeks, with the time to reach steady-state voltage being dependent on acclimation temperature. The highest COD removal rates of 2.98g COD L^d * were produced in the 35°C reactor but coulombic efficiencies (CE) were found to be significantly higher at pyschrophilic temperatures. Acclimation at different operating temperatures was found to a have a significant effect on the dynamic selection of psychrophilic, psychrotolerant and mesophilic anode respiring bacteria (ARB) and also influence the development of biofilm biomass, methanogenesis and electrogenic activity. Although start-up times were inversely influenced by temperature the amount of biomass accumulation increased with higher operational temperatures and this had a direct impact on biocatalytic performance. The three dimensional structure and porosity of different carbon anode materials affected anodic performance by determining the levels of surface area available for biofilm growth and the capacity for mass transfer to occur. Novel helical electrode configurations were used to look at the effect of altering turbulent flows to increase mass transfer rates and carbon surface areas available for electrogenic growth. The spiral with the highest amount of carbon veil and the smallest gap produced the highest power production of 11.63 W m"3 . Comparative studies of a logic controlled and un-controlled external load impedance showed that control affected the biocatalyst development and hence MFC performance. The controlled MFC better optimized the electrogenic anodic biofilm for power production, indicating that improved power and substrate conversion can be achieved by ensuring sustainable current demand, applied microbial selection pressures and near-optimal impedance for power transference.

A key engineering challenge is a transition to cleaner sustainable energy supply that is derived from renewable resources. Furthermore, affordable access to this modern sustainable energy services for communities in particular poor rural and urban communities is crucial. Microbial fuel cell (MFCs) is an emerging renewable alternative technology with potential to be self-sustaining that could alleviate the energy crisis and reduce environmental pollution. The use of the MFC as a dual system for electricity generation and wastewater treatment is been well reported in literature. Manganese dioxide (MnO2) is an effective electro-catalyst that have been used for alkaline fuel cells and battery application. MnO2 have a high conductivity and high structural porosity for ion and gas transport. In addition, MnO2 have a favourable crystal morphology, which makes it particularly useful for improving oxygen reduction reaction in the fuel cell. Graphene (GO) will be loaded on MnO2 surface as an effective support material. GO is a material good for electrical conductivity and their mechanical strength is applicable in electro-catalytic activities and is cost effective. In this work, a constructed dual chamber MFC configuration with graphite rod electrodes, MnO2-GO electrocatalyst and proton exchange membrane (PEM) using municipal sewage wastewater to generate electricity. The MnO2 as an alternative electro catalyst used for oxygen reduction reaction (ORR) in the MFC while using reduced graphene (rGO) as a support to enhance electrode surface area. Also addressing the effect of graphene material loading on MnOx catalyst for electrochemistry. The characterization of the MnO2-GO electrocatalyst have been analysed using X-Ray diffraction (XRD), Brunau-Emmett-Teller (BET) surface area and Fourier transform infrared spectroscopy (FTIR) for structural properties. Electrochemical techniques such as cyclic voltammetry (CV) for MnO2-GO electrocatalyst. Thermal gravimetric analysis (TGA) for the thermal properties, and the morphological properties probed by Scanning Electron Microscopy (SEM). The dual chamber MFC design functioned successfully and tested for energy generation from municipality sewage wastewater. The maximum voltage of 586 mV reached during MFC operation with various sewage municipal wastewater COD of 100-300mg/L. The maximum power density of 248 mW/m2 with resistance of 16.98 Ω and highest current density of 1.72mA/m2 was observed at the first cycle as compare to other cycle. The lowest value of 0.002159 mA/m2 obtained at the end of 10 days. The content of municipality sewage wastewater is capable of generating electricity. The physico-chemical properties of α-MnO2 exhibits excellent cycling stability on the electrochemical. This excellent cycling stability of α-MnO2 as a super capacitor electrode material. In addition, the graphene material loading on α-MnO2 has improved the electro catalytic activity, which influences the kinetics of the reduction reaction. The α-MnO2 synthesized BET analysis specific surface area of 134.61m2 g-1 reported. MFC technology has the potential to finds its own niche in the energy industry as it is becoming more and more sustainable due to the lower cost of electro catalyst materials. Power densities of 248 mW/m2 using wastewater with COD of 291mg/l were much higher than those previously obtained using low strength wastewater. These results have opened doors for further investigation of improving electro catalysis, utilized high concentration wastewater with high COD and improved MFC design including electrode materials. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

The nanoparticles of zirconium oxide, sulfated and phosphated zirconia were used to modify a Nafion membrane in order to improve its water retention, thermal stability, proton conductivity and methanol permeability so that it can be used at higher temperatures in fuel cell. These modified Nafion nanocomposite membrane with inorganic nanoparticles have been designed to run at operating temperatures between 120 oC and 140 oC because higher temperature operation reduces the impact of carbon monoxide poisoning, allows attainment of high power density and reduces cathode flooding as water is produced as vapor. The inorganic nanoparticles were incorporated within the Nafion matrix by recast, ion exchange and impregnation methods. The membrane properties were determined by ion exchange capacity (IEC), water uptake, methanol permeability and proton conductivity. The characterization of the inorganic nanoparticles within the nanocomposite membranes was determined by X-Ray diffraction (XRD), Brunau-Emmett-Teller (BET) surface area and Fourier transform infrared spectroscopy (FTIR) for structural properties. Thermal gravimetric analysis (TGA) and Differential scanning calorimetry (DSC) were used to determine the thermal properties, and the morphological properties were probed by Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). Pristine ZrO2, sulfated and phosphated ZrO2 nanoparticles were synthesized successfully. The particle sizes ranged from 30 nm to 10 nm respectively. The resulted particles were incorporated to a Nafion membrane with good dispersity. The conductivity of the nanocomposite membrane were around 0.1037 S/cm at 25 oC with a higher water uptake of 42 %. These results were confirmed by the highest IEC value of 1.42 meg.g-1 of Nafion/ S-ZrO2 nanocomposites membrane. These high IEC value may due to the incorporation of superacid S-ZrO2 nanoparticles which increased the membrane acid property for providing new strong acid site. / Chemical Engineering / M. Tech. (Chemical Engineering)

The applications of polyaniline (PAni) for use as electrolyte in Polymer-Electrolyte-Membrane Fuel Cells (PEMFC) were investigated. P Ani was dissolved in N-methyl pyrrolidone (NMP), cast as Emeraldine Base membranes (EB) and then doped with halide acids. The proton conductivity was measured according to Hittorf. The chloride ion distribution within the membrane was evaluated using energy-dispersive-X-ray analysis (EDX) and photometric analysers and the diffusion coefficient was calculated. The specific resistance was determined using conventional 4-point measurement. Halide doped membranes were found to be proton conducting, however, during cell operation halide removal occurred causing a rapid decline in the cell performance. The maximum power density achieved was O.3m W·cm-2 for a 70J.1m thick membrane saturate with chloride between 3,5 and 4,5mgchloride per gPAni. Composite membranes with phosphotungstic acid (PWA), antimonic acid (AA) and zirconium phosphate (ZP) were developed and also tested in a standard measuring fuel cell. While membranes produced via ion exchange (ZP) showed the same result like halide doped ones, AA composite membranes showed a stable voltage and current results. The highest measured outcome of 373.3mW·cm-2 was found with a PWA membrane, produced through dispersing 3g of phosphotungstic acid in 300ml of a 1% polyanilinelNMP solution. It was also observed, that the higher power density was obtained from the fuel cell which uses the lower-loaded membrane. It is clear that a positive effect on the cell performance is given by the addition of phosphotungstic acid to the polyaniline membrane. Therefore, the saturation of PW A have to be taken into account to not lower the power density.