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Nitrogen-selective Carbon Molecular Sieve (CMS) membranes were developed for nitrogen/methane separation. Effects of pyrolysis conditions including pyrolysis temperature protocol and pyrolysis atmosphere were studied for Matrimid® and 6FDA:BPDA-DAM precursors. It was revealed that high pyrolysis temperature is essential to achieve attractive nitrogen/methane selectivity due to the subtle size difference between the two gas penetrants. Detailed study on one of the best performing CMS membranes showed that diffusion selection, more specifically, the entropic factor responsible for diffusion selection provides a significant contribution to the high selectivity. The effect of precursor was studied by considering nine carefully selected polymers. The structures and properties of these polymer precursors were compared and correlated with the separation performance of resulting CMS membranes. The translation of intrinsic CMS transport properties into the hollow fiber morphology was also explored. Substructure collapse and asymmetry lost during pyrolysis were observed, which resulted in significant increases of separation layer thickness and decreases in permeance. Vinyltrimethoxy silane (VTMS)-treatment was applied to polymer hollow fiber before pyrolysis to overcome the problem of substructure collapse. The effects of VTMS-treatment on both the substructure and skin layer are discussed.

South Africa is a land blessed with an abundance of mineral deposits. Yet, despite this, very little value adding of minerals exists. Most of the mined minerals are exported, where it is reworked into valued items. The country subsequently imports the valuable items at a much higher cost. In the 2006/7 financial year, the government made the decision to support several projects aimed at adding value to the mined minerals and by so doing, creating job opportunities. One such project was identified for the mineral Fluorite (CaF2). Fluorite is exposed to a controlled burn in a plasma reactor, producing an array of different fluorocarbon gases used in the electronics industry and for commercial polymers like Teflon®. Currently, fluorocarbon gases are separated using a series of cryogenic distillation columns. Although this technique has proven to be successful, it has several negative aspects such as the high cost involved when operating at cryogenic conditions as well as difficulty handling the gases at these sub–zero temperatures. It was proposed to study the possibility of using membranes to separate fluorocarbon gases at ambient conditions. Several membranes were screened to determine which one is best suited for this application. Two Teflon® based membranes were selected from this data. One of the membranes had a PAN support, while the other had a PEI support. Pure gas data for both membranes showed promising results. It yielded the highest flux for C3F6, followed by N2 and CF4. c–C4F8 was not used because it was demonstrated that the gas tends to condensate at low pressures. It is recommended to rather use pressure swing condensation to remove this gas from the mixture before the remainder is purified using membranes. Both membranes behaved similarly, with selectivity between C3F6 and CF4, and N2 and CF4; all above 10. By including the permeate pressure in the Solution–diffusion model, it was possible to model the pure gas data Binary feed gas mixture experiments showed a large amount of coupling existing between the feed gas mixtures. The result is a decrease in the selectivity as well as the total flux of the gas mixture. Partial fluxes were modelled by introducing a thermodynamic factor that was shown to follow a power law equation. The PAN–supported membrane outperformed the PEI–supported one; it was decided to use this membrane from this point onwards. Analysis of the ternary feed mixtures showed a strong selectivity towards the gas abundant in the feed blend. The existence of convective diffusion was proven, and included in the modelling, as well as a breakthrough pressure constant. This is indicative of strong interaction between the different gases and the membrane. Throughout the study it became clear that the difference in surface charge between the gases and the membrane were decisive. Opposite charges between a gas (C3F6) and the membrane aided in gas permeation. Membrane separation of fluorocarbon gases at ambient conditions is possible. Teflon® based membranes are recommended. It will be advantageous to study the effect of elevated temperatures on the separation efficiency of such a system. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

Hybrid membranes represent a promising alternative to the limitations of organic and inorganic materials for high productivity and selectivity gas separation membranes. In this study, the previously developed concept of emulsion-polymerized mixed matrix (EPMM) membranes was further advanced by investigating the effects of surfactant and compatibilizer on inorganic loading in poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based EPMM membranes, in which inorganic part of the membranes originated from tetraethylorthosilicate (TEOS). The polymerization of TEOS, which consists of hydrolysis of TEOS and condensation of the hydrolyzed TEOS, was carried out as (i) one- and (ii) two-step processes. In the one-step process, the hydrolysis and condensation take place in the same environment of a weak acid provided by the aqueous solution of aluminum hydroxonitrate and sodium carbonate. In the two-step process, the hydrolysis takes place in the environment of a strong acid (solution of hydrochloric acid), whereas the condensation takes place in weak base environment obtained by adding excess of the ammonium hydroxide solution to the acidic solution of the hydrolyzed TEOS. For both one- and two-step processes, the emulsion polymerization of TEOS was carried out in two types of emulsions made of (i) pure trichloroethylene (TCE) solvent, and (ii) 10 w/v% solution of PPO in TCE, using different combinations of the compatibilizer (ethanol) and the surfactant (n-octanol). The experiments with pure TCE, which are referred to as a gravimetric powder method (GPM) allowed assessing the effect of different experimental parameters on the conversion of TEOS. The GPM tests also provided a guide for the synthesis of casting emulsions containing PPO, from which the EPMM membranes were prepared using a spin coating technique. The synthesized EPMM membranes were characterized using 29Si nuclear magnetic resonance (29Si NMR), differential scanning calorimetry (DSC), inductively coupled plasma mass spectrometry (ICP-MS), and gas permeation measurements carried out in a constant pressure (CP) system. The 29Si NMR analysis verified polymerization of TEOS in the emulsions made of pure TCE, and the PPO solution in TCE. The conversions of TEOS in the two-step process in the two types of emulsions were very close to each other. In the case of the one-step process, the conversions in the TCE emulsion were significantly greater than those in the emulsion of the PPO solution in TCE. Consequently, the conversions of TEOS in the EPMM membranes made in the two-step process were greater than those in the EPMM membranes made in the one-step process. The latter ranged between 10 - 20%, while the highest conversion in the two-step process was 74% in the presence of pure compatibilizer with no surfactant. Despite greater conversions and hence the greater inorganic loadings, the EPMM membranes prepared in the two-step process had glass transition temperatures (Tg) only slightly greater than the reference PPO membranes. In contrast, despite relatively low inorganic loadings, the EPMM membranes prepared in the one-step process had Tgs markedly greater than PPO, and showed the expected trend of an increase in Tg with the inorganic loading. These results indicate that in the case of the one-step process the polymerized TEOS was well integrated with the PPO chains and the interactions between the two phases lead to high Tgs. On the other hand, this was not the case for the EPMM membranes prepared in the two-step process, suggesting possible phase separation between the polymerized TEOS and the organic phase. The latter was confirmed by detecting no selectivity in the EPMM membranes prepared by the two-step process. In contrast, the EPMM membranes prepared in the one-step process in the presence of the compatibilizer and no surfactant showed 50% greater O2 permeability coefficient and a slightly greater O2/N2 permeability ratio compared to the reference PPO membranes.

South Africa is a land blessed with an abundance of mineral deposits. Yet, despite this, very little value adding of minerals exists. Most of the mined minerals are exported, where it is reworked into valued items. The country subsequently imports the valuable items at a much higher cost. In the 2006/7 financial year, the government made the decision to support several projects aimed at adding value to the mined minerals and by so doing, creating job opportunities. One such project was identified for the mineral Fluorite (CaF2). Fluorite is exposed to a controlled burn in a plasma reactor, producing an array of different fluorocarbon gases used in the electronics industry and for commercial polymers like Teflon®. Currently, fluorocarbon gases are separated using a series of cryogenic distillation columns. Although this technique has proven to be successful, it has several negative aspects such as the high cost involved when operating at cryogenic conditions as well as difficulty handling the gases at these sub–zero temperatures. It was proposed to study the possibility of using membranes to separate fluorocarbon gases at ambient conditions. Several membranes were screened to determine which one is best suited for this application. Two Teflon® based membranes were selected from this data. One of the membranes had a PAN support, while the other had a PEI support. Pure gas data for both membranes showed promising results. It yielded the highest flux for C3F6, followed by N2 and CF4. c–C4F8 was not used because it was demonstrated that the gas tends to condensate at low pressures. It is recommended to rather use pressure swing condensation to remove this gas from the mixture before the remainder is purified using membranes. Both membranes behaved similarly, with selectivity between C3F6 and CF4, and N2 and CF4; all above 10. By including the permeate pressure in the Solution–diffusion model, it was possible to model the pure gas data Binary feed gas mixture experiments showed a large amount of coupling existing between the feed gas mixtures. The result is a decrease in the selectivity as well as the total flux of the gas mixture. Partial fluxes were modelled by introducing a thermodynamic factor that was shown to follow a power law equation. The PAN–supported membrane outperformed the PEI–supported one; it was decided to use this membrane from this point onwards. Analysis of the ternary feed mixtures showed a strong selectivity towards the gas abundant in the feed blend. The existence of convective diffusion was proven, and included in the modelling, as well as a breakthrough pressure constant. This is indicative of strong interaction between the different gases and the membrane. Throughout the study it became clear that the difference in surface charge between the gases and the membrane were decisive. Opposite charges between a gas (C3F6) and the membrane aided in gas permeation. Membrane separation of fluorocarbon gases at ambient conditions is possible. Teflon® based membranes are recommended. It will be advantageous to study the effect of elevated temperatures on the separation efficiency of such a system. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 227-234). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Koros William; Committee Member: Hess Dennis; Committee Member: Jones Christopher; Committee Member: Meredith Carson; Committee Member: Wong CP. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Dr. William J. Koros; Committee Member: Dr. Amyn Teja; Committee Member: Dr. Christopher W. Jones; Committee Member: Dr. Haskell W. Beckham; Committee Member: Dr. Stephen J. Miller. Part of the SMARTech Electronic Thesis and Dissertation Collection.