Made available in DSpace on 2014-10-09T12:24:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:02Z (GMT). No. of bitstreams: 1 00030.pdf: 1267034 bytes, checksum: 1e237f210ed3dfb273b208a1ff350b2b (MD5) / Dissertacao (Mestrado) / IPEN/D / Escola Politecnica, Universidade de Sao Paulo - POLI/USP

Magister Scientiae - MSc / A new high temperature solid electrolyte composite was developed, with CsHSO4 and CsH2PO4 as the proton conducting material in composition with PTFE and SiO2 to enhance the solid electrolyte composites mechanical strength and conductivity. Conductivity measurements for CsHSO4 and CsH2PO4 and composites thereof, in temperature ranges 0 to 180 oC and 0 to 250 oC respectively, were carried out. The composites with different concentrations PTFE and silica were tested for stability in a enhanced conductivity. hydrogen atmosphere and different degrees of humidity. The CsHSO4 was seen to exhibit a super protonic phase change at temperatures between 132 – 140 C and CsH2PO4 around 230 C. The presence of the PTFE proved to be a stabilizing factor in the reduction of water re-adsorption once the membrane had been dried during thermal conductivity analysis. According to supporting data in the literature it has been found that composites including silica could be influenced by the hydrophilicity and specific surface area of the silica. In the composite system employed it was shown by impedance analysis the presence of two semi-circles in the Nyquist representation for the enhanced conductivity due the presence of silica. / South Africa

Philosophiae Doctor - PhD / A fuel cell is an energy device that converts chemical energy to electrical energy. Low temperature fuel cells, namely the hydrogen fuel cell and the direct methanol fuel cell are preferred amongst other fuel cell types for stationary and vehicular applications, due to their small size and their low operating temperature. The direct methanol fuel cell has several advantages over the hydrogen fuel cell including ease of transport and storage since methanol is a liquid. Since methanol is used directly in the cell there is no need for a reforming process, which results in a less complicated system. However, direct methanol fuel cell are in their infancy and many problems need to be overcome before reaching commercialization. The direct methanol fuel cell has several disadvantages, namely, the sluggish methanol oxidation reaction, the high cost of state-of-the-art proton exchange membranes, the high methanol permeability from anode to cathode and the dependence on the conductivity on membrane water content, which limits their use to temperatures below the boiling point of water, while the need is to work at high temperatures. Attempts to overcome the disadvantages of the state-of-the-art membrane were made in this study, including the development on novel proton exchange membranes and also the modification of existing state-of-the-art membranes. / South Africa

Philosophiae Doctor - PhD / Catalysts play an essential role in nearly every chemical production process. Platinum supported on high surface area carbon substrates (Pt/C) is one of the promising candidates as an electrocatalyst in low temperature polymer electrolyte fuel cells. Developing the activity of the Pt/C catalyst with narrow Pt particle size distribution and good dispersion has been a main concern in current research. In this study, the main objective was the development and characterization of inexpensive and effective nanophase Pt/C electrocatalysts. A set of modified Pt/C electrocatalysts with high electrochemical activity and low loading of noble metal was prepared by the impregnation-reduction method in this research. The four home-made catalysts synthesized by different treatments conditions were characterized by several techniques such as EDS, TEM, XRD, AAS, TGA, BET and CV.Pt electrocatalysts supported on acid treatment Vulcan XC-72 electrocatalysts were produced successfully. The results showed that Pt particle sizes of Pt/C (PrOH)x catalysts between 2.45 and 2.81nm were obtained with homogeneous dispersion, which were more uniform than the commercial Pt/C (JM) catalyst. In the electrochemical activity tests, ORR was confirmed as a structure-sensitive reaction. The Pt/C (PrOH/pH2.5) showed promising results during chemically-active surface area investigation, which compared well with that of the commercial standard Johnson Matthey Pt/C catalyst. The active surface area of Pt/C (PrOH/pH2.5) at 17.98m2/g, was higher than that of the commercial catalyst (17.22 m2/g ) under the conditions applied. In a CV electrochemical activity test of Pt/C catalysts using a Fe2+/Fe3+ mediator system study, Pt/C (PrOH/pH2.5) (67mA/cm2) also showed promise as a catalyst as the current density is comparable to that of the commercial Pt/C (JM) (62mA/cm2).A remarkable achievement was attained in this study: the electrocatalyst Pt supported on CNTs was synthesized effectively. This method resulted in the smallest Pt particle size 2.15nm. In the electrochemically-active surface area study, the Pt/CNT exhibited a significantly greater active surface area (27.03 m2/g) and higher current density (100 mA/cm2) in the Fe2+/Fe3+ electrochemical mediator system than the other home-made Pt/C catalysts, as well as being significantly higher than the commercial Pt/C (JM) catalysts. Pt/CNT catalyst produced the best electrochemical activities in both H2SO4 and K4[Fe(CN)6] electrolytes. As a result of the characteristics of Pt/CNT, it can be deduced that the Pt/CNT is the best electrocatalyst prepared in this study and has great potential for use in fuel cell applications. / South Africa

Magister Scientiae - MSc / For a direct methanol fuel cell (DMFC), the proton exchange membrane must conduct protons and be a good methanol barrier. In addition to the high methanol permeability achieved by these membranes, they are very expensive and contribute greatly to theoverall cost of fuel cell set up. The high cost of the DMFC components is one of the main issues preventing its commercialization. The main objective of this study was thus to produce highly proton conductive membranes that are cheap to manufacture and have low methanol permeability. / South Africa

The purpose of this research project is twofold. Firstly to establish whether South African biodiesel producers can profitably manufacture biodiesel on a commercial scale. Secondly to understand the readiness of owners of passenger vehicles to use biodiesel. Buyers pass through six stages before purchasing a new product, namely awareness, knowledge, liking, preference, conviction, and finally purchase. Based on the literature review, five research questions were developed to understand the capability of producers to commercially manufacture biodiesel. In this qualitative research section a series of face-to-face, semi-structured interviews were conducted with the current major players in the biodiesel industry. The data from each of these interviews was analysed to assess the producers’ capability to commercially manufacture biodiesel. Six research hypotheses were developed to understand the readiness of buyers to use biodiesel. In this quantitative research section a Likert scale questionnaire was presented in person to respondents at petroleum fuel stations. The data from each questionnaire was analysed to assess the buyer-readiness of passenger vehicle owners. An investigation revealed that there is currently only one producer commercially manufacturing biodiesel. South African producers have the capability to manufacture biodiesel on a commercial scale however sustainable feedstock supply is concerning. The producers claim that they can manufacture biodiesel to quality standards. No facility in South Africa can however test the full spectrum of the SANS 1935 quality standard. The industry requires additional encouragement and support from the South African government. Vehicle owners are at a Conviction buyer-readiness stage. Only 2.8% of the consumers have used biodiesel before. This is probably due to the commercial unavailability of biodiesel fuels. It is further identified that different age groups are at the same buyer-readiness stage. Marketers and sellers should however know that vehicle owners agree that biodiesel is better for their vehicle engines than petroleum diesel. Sellers should be sensitive to the fact that consumers are not prepared to pay a higher price for biodiesel than for petroleum diesel. / Dissertation (MBA)--University of Pretoria, 2010. / Gordon Institute of Business Science (GIBS) / unrestricted

Concurrent engineering and virtual prototyping are two emerging techniques that are bringing considerable economical benefits to the manufacturing industry. This work proposes the use of virtual prototyping to produce quantitative measures of product lifecycle performances to facilitate the implementation of concurrent engineering. A multiobjective, virtual prototyping-based global optimization problem is formulated to close the open loop of present virtual prototyping methods and to allow concurrent engineering design to be carried out systematically and automatically. Virtual prototyping-based design optimization faces several technical challenges. First, virtual prototyping is usually computationally intensive; relations between design variables and product life-cycle performances are often implicit. Secondly, the optimization problem usually consists of multi-modal design (objective and constraint) functions. The complexity and multi-modal nature of the optimization problem preclude the direct use of conventional local and global optimization methods. In this work, a new and efficient search method for virtual prototyping-based global design optimization is introduced. The method, called Adaptive Response Surface Method (ARSM), carries out systematic “design experiments” through virtual prototyping to build second-order regression models to approximate the design functions. Through an iterative process, the regression models are improved and the global design optimum is obtained. The ARSM search scheme requires only a modest number of design function evaluations, making virtual prototyping-based global design optimization feasible. The proposed quantitative concurrent design method is then applied to the components, stack and system design of a transportation fuel cell. The approach led to an optimized multi-functional component, a reduction of the system cost, and an improvement of the system performance. The approach can be applied to the concurrent design and design optimization of other complex mechanical components, assemblies and systems. / Graduate

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Understanding the behaviour of heavy metals involved in the nuclear fuel cycle is of paramount importance to the reprocessing and storage of spent nuclear fuel. These studies have attempted to obtain a greater understanding of the fundamental chemistry of these systems, by investigating extraction performance and speciation in current (PUREX) and proposed (GANEX) extraction processes. Various complexes have been shown to exist in the post-extracted organic fraction of the systems analysed. For Zr(IV), U(VI) and Np(VI) separated from aqueous nitric and hydrochloric using TBP, the complexes [Zr(NO3/Cl)4(TBP)4], [UO2(NO3/Cl)2(TBP)2] and [NpO2(NO3/Cl)2(TBP)2] formed, respectively. For Zr(IV) separated from aqueous mixtures of HNO3 and HCl at equal concentration, a preference was shown to [Zr(Cl)4(TBP)4] over the analogous nitrate complex. For U(VI) separated from aqueous mixtures of HNO3 and HCl, a preference was shown to [UO2(Cl)2(TBP)2], even at high aqueous nitrate concentrations. NMR data for Pu(IV) separated from aqueous HNO3, HCl and mixtures of both, using TBP were presented, where possible complexation was observed. It is thought that [Pu(NO3)4(TBP)4] or [PuCl4(TBP)4] species existed within the organic fraction for Pu(IV) separated from aqueous HNO3 and HCl, respectively. These systems showed high distribution ratios where an increase was observed with increasing aqueous acid concentration overall. Distribution ratio data were presented for the lanthanide series separated from aqueous nitric acid, using the proposed GANEX solvent system(s). The lanthanides analysed showed an increase in distribution ratio with increasing aqueous nitric acid concentration and with increasing TODGA concentration in the organic fraction. Heavier lanthanides were observed to give higher distribution ratios overall. The best distribution ratios were observed for lanthanides separated using 0.2 M TODGA with 1-octanol (5 % by volume) over the nitric acid concentration range analysed. For lanthanides separated using 0.5 M DMDOHEMA, an optimum distribution ratio was observed at around 6 M aqueous nitric acid concentration. The distribution ratio data for lanthanides separated from a range of DMDOHEMA concentrations, were observed to increase with increasing organic DMDOHEMA concentration. The distribution ratios observed for isotopes of Np, Am, Eu and Pu separated using 0.2 M TODGA, increased with increasing aqueous nitric acid concentration. The same trend was observed for the aforementioned isotopes separated using 0.5 M DMDOHEMA. However, pertechnetate separated using 0.2 M TODGA from aqueous nitric acid, showed a decrease in the distribution ratios observed over the acid concentration range analysed. This was contrary to pertechnetate separated from aqueous nitric acid using 0.5 M DMDOHEMA, where a small increase in distribution ratio was observed over the concentration range analysed. For Np(VI) separated from some proposed GANEX solvents, the 0.2 M TODGA/0.5 DMDOHEMA combination gave the best distribution of neptunium into the organic fraction. For Np(VI) separated using 0.5 M DMDOHEMA, the complex [Np(DMDOHEMA)2(NO3)4] was observed. Additional attempts to analyse Np(VI) behaviour under GANEX style conditions via EXAFS, were not successful due to immediate reduction of the Np(VI) on the beam line.