Sulfonated polyaromatic hydrocarbon membranes have emerged as desirable candidates for proton exchange membranes (PEMs) due to their excellent mechanical properties, high thermal and chemical stability, and low cost. Specifically, sulfonated multiblock copolymers are attractive because their phase-separated morphologies aide in facile proton transport. In this work, the functionalization of semicrystalline gels of poly(ether ether ketone) (PEEK) is explored as a novel post-polymerization method to prepared blocky copolymers, and the effect of copolymer architecture on membrane physical properties, structure, and performance is extensively investigated. First, the blocky sulfonation of PEEK was explored to prepare blocky copolymers (SPEEK) with densely sulfonated domains and unfunctionalized, crystallizable domains. Compared to random SPEEK ionomers at similar ion content, blocky SPEEK exhibited enhanced crystallizability, decreased melting point depression, and faster crystallization kinetics. Phase separation between the hydrophilic sulfonated blocks and hydrophobic PEEK blocks, aided by polymer crystallization, resulted in enhanced water uptake, superior proton conductivity, and more closely associated ionic domains than random SPEEK. Furthermore, the random and blocky bromination of PEEK was investigated to prepare PEEK derivatives (BrPEEK) with reactive aryl-bromides. Spectroscopic evidence revealed long domains of unfunctionalized homopolymer for blocky BrPEEK, and this translated to an increased degree of crystallinity, higher melting temperature, and more rapid crystallization kinetics than random BrPEEK at similar degrees of bromination. The subsequent sulfonation of blocky BrPEEK resulted in a hydrophilic-hydrophobic blocky copolymer with clear multi-phase behavior. The phase-separated morphology contributed to decreased water uptake and areal swelling compared to random SPEEK and resulted in considerably higher proton conductivity at much lower hydration levels. Moreover, Ullmann coupling introduced superacidic perfluorosulfonic acid side chains to the BrPEEK backbone, which yielded membranes with less water content and less dimensional swelling than random SPEEK. Superior proton transport than random SPEEK was observed due to the superacid side chain and wider hydrophilic channels within the membranes, resulting in more continuous pathways for proton transport. Overall, this work provided a novel platform for the preparation of functionalized PEEK membranes using a simple post-polymerization functionalization procedure. The established methods produced blocky-type copolymers with properties reminiscent of multiblock copolymers prepared by direct polymerization from monomers/oligomers. / PHD / Block copolymers are an important class of polymers that are composed of two or more blocks of distinct polymeric segments covalently tethered to one another. Dissimilarity in the chemical nature of the blocks leads to self-organization into well-defined structures, and this unique structural order imparts material properties that are different from (and often superior to) the properties of the individual blocks alone. Thus, block copolymers are advantageous for a diverse array of applications including membranes, gas separation, water purification, medical devices, etc. Although considerable synthetic progress has been made towards discovering novel methods to prepare block copolymers, their widespread use is somewhat limited by the complex, energy-intensive procedures necessary to precisely control the block sequencing during polymerization. In this dissertation, a straightforward, inexpensive physical procedure is explored to synthesize blocky copolymers with controlled sequencing from commercially available polymers. This process relies on performing reactions in the gel state, whereby segments of the polymer chain are effectively shielded from the functionalizing chemistry. In particular, the gel state sulfonation and bromination of poly(ether ether ketone), a high performance polymer, is investigated to develop novel, blocky materials for membrane applications. This work not only expands the methodology towards the synthesis of block copolymers, but alaso provides critical insight into the effect of copolymer architecture on membrane physical properties, structure, and performance. Furthermore, this work provides an economically feasible method to prepare blocky copolymers from commercially derived materials, thereby providing a means to progress the widespread use of block copolymers in industry.

The phase diagrams for the thermoreversible gelation of poly(ether ether ketone) (PEEK) in dichloroacetic acid (DCA) and 4-chlorophenol (4CP) were constructed over broad temperature and concentration ranges, revealing that PEEK is capable of dissolving and forming gels in DCA and 4CP up to a weight fraction of 25 wt.%. Highly porous aerogels of PEEK were prepared through simple solvent exchange and solvent removal of the PEEK/DCA or PEEK/4CP gels. Solvent removal utilized freeze-drying (sublimation) methods or supercritical CO2 drying methods. Varying the weight fraction of PEEK dissolved in solution determined PEEK aerogel density. Mechanical properties (in compression) were shown to improve with increasing density, resulting in equivalent compressive moduli at comparable density regardless of preparation method (concentration variation, gelation solvent, solvent removal method, or annealing parameters). Additionally, density-matched aerogels from various MW PEEK showed a correlation between increasing MW and increasing compressive modulus. Contact angle and contact angle hysteresis revealed that PEEK aerogels have a high contact angle, exceeding the conditions necessary to be classified as superhydrophobic materials. PEEK aerogel contact angle decreases with increasing density and a very low contact angle hysteresis that increases with increasing density, regardless of gelation solvent or drying method. Small angle neutron scattering (SANS) contrast-matching experiments were used to elucidate the morphological origin of scattering features, wherein it was determined that the origin of the scattering feature present in the small angle scattering region was stacked crystalline lamella. Ultra-small angle X-ray scattering (USAXS)/SAXS/Wide angle X-ray scattering (WAXS) was then used to probe the hierarchical nanostructure of PEEK aerogels across a broad range of length scales. The Unified Fit Model was used to extract structural information, which was then used to determine the specific surface areas of PEEK aerogels. Regardless of gelation solvent, gel concentration, or solvent removal method, all PEEK aerogels display high surface areas as determined by SAXS and high surface areas as determined by nitrogen adsorption methods. Surface area values determined from SAXS data were consistently higher than that measured directly using nitrogen adsorption, suggesting that pore densification diminishes the accessible aerogel surface area. / Ph. D. / Poly(ether ether ketone) (PEEK) is a semicrystalline polymer with high temperature thermal transitions and excellent mechanical strength, making it an ideal candidate for many high-performance polymer applications. When PEEK is dissolved in particular solvents, it will form a 3-dimensional network where crystalline polymer is the cross-linking unit of the network. Careful solvent removal does not significantly perturb the gel network structure and produces a low-density aerogel. This work details the first reported instance of the monolithic gelation of PEEK and the first examples of PEEK aerogels. The nanostructure of these gels and aerogels is fully characterized to relate structural features to physical properties such as mechanical stiffness and wettability.

Tertiary butyl alcohol (TBA), methyl tertiary butyl ether (MTBE) and ethyl tertiary butyl ether (ETBE) are compounds with the potential for use as oxygenates in reformulated gasolines. Being relatively soluble in water, these organics, if accidentally discharged into the subsurface, may rapidly spread and pose threats to groundwater. The purpose of this work was to evaluate the biodegradation potential of these oxygenates in soils and to determine the influence of subsurface environments on their degradation. Biodegradation was evaluated in static soil/water microcosms. Aquifer material was collected from various depths at three sites with different soil characteristics. Potential electron acceptors including O₂ in the form of H₂O₂, nitrate or sulfate were added to induce the desired metabolism (aerobic respiration, denitrification, sulfate reduction, or methanogenesis). In each metabolic process, the influence of several subsurface environmental factors on biodegradation was investigated. The data show that biodegradation potential of MTBE, ETBE and TBA varied substantially with site and depth. TBA was the easiest compound to biodegrade, whereas MTBE was the most recalcitrant. Cleavage of the ether bond is the first and rate-limiting step in the degradation of ETBE and possibly MTBE. Addition of H₂O₂, caused chemical oxidation of MTBE and ETBE. The chemical oxidation was faster in the organically rich soils, but slower in the organic-poor soils. Soil microorganisms were able to catalyze the cleavage of the ether bond in ETBE but not MTBE. This biological reaction was not significant when chemical oxidation occurred. TBA, on the other hand, was aerobically biodegraded in all soils. Under denitrifying and anaerobic conditions TBA degradation occurred in all soils but the degradation of ETBE and MTBE was only observed at one of three sites. TBA degradation was enhanced by nutrient addition in the nutrient-poor soil but hindered by the presence of other easily-degraded organic compounds. Degradation of MTBE and ETBE occurred only in soils containing low organic matter with a pH around 5.5. No degradation of MTBE and ETBE was observed in the organic-rich soils and in the organically poor soils, the addition of ethanol inhibited MTBE and ETBE degradation. / Ph. D.

No description available.

Membrane technology has great potential to complement traditional energy-intensive molecular separation processes such as distillation, with the advantage of low footprint generation. However, this would only be achieved with the development of better membranes able to operate in challenging conditions, including combinations of organic solvents, high temperatures, extreme pHs, and oxidative environments. This dissertation aims to use high-performance polymeric materials that can withstand temperatures of 120 °C in polar aprotic solvents like N,N-dimethylformamide as separation membranes, using different crosslinking strategies and alternative routes for commercially available material processing. The thesis will be divided into two main approaches. The first approach will start from soluble polyimides as precursors, with designed functionalities that allow post-membrane modifications, such as chemical crosslinking, thermal crosslinking, and thermal rearrangement to enhance the material's chemical resistance. The focus will be on the polyimide synthesis by an alternative one-step room-temperature polyhydroxyalkylation reaction. The chemical and thermal crosslinking take place without involving the imide bond, by incorporating a highly tunable functional group (isatin) in the synthesis of the materials. Propargyl as a pendant group will be used for the thermal crosslinking, and hydroxyl group for the thermal rearrangement. In all cases, the obtained membranes were stable in common organic solvents at 120 °C. The second approach will start from intrinsically solvent-resistant and commercially available poly(aryl ether ketone)s, turned into membranes by a closed-loop modification-regeneration strategy, to address long-term separations in organic solvents at high temperatures. We present for the first time porous poly(aryl ether ketone) flat-sheet and hollow fiber membranes prepared without the use of strong acids or high temperatures. Two methodologies are proposed. The developed strategies shall contribute toward avoiding the regular consumption of new materials and waste generation since the polymer used does not require crosslinking for its stability under organic solvents.

published_or_final_version / abstract / Ecology and Biodiversity / Doctoral / Doctor of Philosophy

The effect of the physical state and chemical composition on molecular interactions has been studied for a number of chemically modified adsorbents. During the course of the study a reaction scheme was put together for the synthesis of a particular substituted crown ether. The synthesized allyl-benzo-15crown-5, which is not reported in the literature to date, was silylated and immobilized on a silica surface. The bonded phase was characterized by UV spectroscopy and by chromatography under both "normal" and "reverse" phase conditions. UV spectroscopy was also used to elucidate the physical state of several other phenyl alkyl bonded phases. Chromatographically, the bonded crown ether phase was found to be more polar than a C₈ stationary phase. A comparison of the selectivity of the two phases revealed that the former has a better selectivity towards a homologous series of alkyl benzenes under different reverse phase conditions. The selectivity of the crown ether phase was found to be dependent on the nature of the organic modifier in the mobile phase. This dependence was considered to be added evidence for the universality of the dynamic solvated stationary phase model. Both normal and reverse phase chromatographic conditions indicated an acid-base type of interaction between the crown ether and a number of substituted phenols. This was reflected in an increase in the retention of these probes as a function of their increasing acidity. A dramatic temperature effect observed on the crown ether stationary phase under aqueous THF mobile phase, but not under aqueous MeOH, was attributed to a temperature and/or solvent-induced phase change. A hysteresis effect, also seen only with aqueous THF, indicated that the crown ether phase undergoes a solvent-assisted conformational change. Further evidences for such a change was found spectroscopically in the abrupt break in the UV absorbance of these molecules as a function of temperature, as well as the irreversibility of the absorbance of the n- π* band on cooling. UV spectroscopy of bonded phenyl alkyls showed that there are about two monolayers of water molecule strongly adsorbed to the surface and totally impermeable to lypophilic species. Evidence for the existence of a solvated crystal, or liquid crystal, like clusters was rationalized with a cooperative sorption effect which may be dependent on the reaction conditions during immobilization. Despite a significant increase in the liquid character observed as the chain length is increased to 4-7 methylene groups, the bonded clusters still appear to preserve a fairly ordered environment. The physical state of the immobilized species was found to change with the experimental conditions and the change was reflected on the selectivity of the system.

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.

A Thesis submitted to the faculty of Engineering, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Doctor of Philosophy / Thermodynamic analysis techniques for the study of combustion in compression ignition engines were developed and refined. The techniques were validated against test runs of diesel fuelling, and were then applied to the almost unexplored case of combustion of aspirated dimethyl either (DME) acting as ignition promotor and supplementary fuel, and injected methanol as main fuel. Combustion chamber pressure versus crank angle data were captured for single engine cycle on normal fuelling (methanol and DME), fuelling with DME alone and pure motoring (no fuel) all at essentially identical engine conditions. These data were analysed by a number of mutually complementary techniques. / AC2017

O gás de síntese (Syngas), proveniente do biogás gerado no tratamento anaeróbio de águas residuárias e o CO2 (presente no biogás) surgem como fontes promissoras para a obtenção de produtos de valor agregado nomeados C2-C4, tais como eteno, propileno, butano, metanol e dimetil éter (DME). Neste trabalho, catalisadores de Cu suportados em argila pilarizada foram estudados visando à produção de compostos C2-C4 a partir da hidrogenação do CO e CO2. Da mesma forma, buscou-se otimizar estes catalisadores, tanto para o processo de Fischer-Tropsch quanto para a síntese direta do DME. Primeiramente, foi avaliado o efeito dos agentes pilarizantes Al e Nb para a conversão do metanol em produtos C2-C4. Após a seleção do agente pilarizante, avaliou-se o efeito do teor de cobre (5% e 10% em massa) no catalisador bifuncional de CuZn/V-Al PILC. Finalmente, foi realizada a adição de Ce, Nb, Fe e/ou Co (5% em massa) sobre o catalisador contendo 10% de Cu suportado na argila pilarizada V-Al PILC. As reações de conversão do metanol foram realizadas em temperaturas de 250 ºC - 400 ºC/2h, sob o fluxo de 1,1 mL.h-1. As reações de hidrogenação (CO e CO2) foram realizadas nas temperaturas de 250 ºC e 300 ºC/3h, P= 40 bar e razão de H2/CO=2 e H2/CO2=3. Os catalisadores foram caracterizadas por difração de raios X (DRX) in situ e ex situ, refinamento de Rietveld, fisissorção de N2, análise da composição química (EDX), microscopia eletrônica de varredura (MEV), redução a temperatura programada (RTP-H2), oxidação do cobre com N2O (TPD-N2O), adsorção de piridina gasosa como molécula modelo para a identificação dos sítios ácidos através do FTIR (FTIR-Py), dessorção de amônia a temperatura programada (DTP- NH3), espectroscopia de absorção de raios X e espectroscopia de fotoelétrons excitados por raios X (XPS). O processo de pilarização somado à impregnação de Cu juntamente com Zn, Ce, Nb, Fe e/ou Co produziu catalisadores com diferentes propriedades estruturais e ácidas, as quais favoreceram as conversões do CO e CO2 para produtos C2-C4. O catalisador bimetálico CuFe/V-Al PILC foi o mais ativo em ambas reações de hidrogenação (CO e CO2) e o mais seletivo para a síntese de DME. Os estudos de caracterização mostraram que a baixa seletividade apresentada para a formação de DME está relacionada com a baixa densidade total de sítios ácidos e com a elevada velocidade espacial experimental. / Syngas, a gas mixture produced from biogas generated in the anaerobic treatment of wastewaters, and carbon dioxide (CO2), a biogas constituent, are promising feedstocks for obtaining value-added chemicals known as C2-C4 products, which include ethylene, propylene, butane, methanol, and dimethyl ether (DME). In this work, Cu catalysts supported on pillared clay were studied aiming at producing C2-C4 compounds from hydrogenation of CO and CO2. The studies were conducted toward optimizing the catalysts performance both for Fischer-Tropsch process and direct synthesis of DME. First, the effect of Al and Nb pillared agents on the conversion of methanol to C2-C4 products was evaluated. The pillared agent was selected and further used to evaluate the Cu content (5 to 10 wt.%) effect on the bifunctional CuZn/V Al-PILC catalyst. Finally, the addition of Ce, Nb, Fe and/or Co (5 wt.%) to the 10 wt.% Cu-containing catalyst supported on V-Al PILC pillared clay was studied. The methanol conversion was performed in the temperature range 250 - 400 °C for 2 h under flow of 1.1 mL h-1. The CO and CO2 hydrogenation reactions were carried out at 250 °C and 300 °C, respectively, for 3 h and P = 40 bar using ratios H2/CO = 2 and H2/CO2 = 3. The catalysts were characterized by means of in situ and ex situ X-ray diffraction (XRD), Rietveld refinement, N2 physisorption, chemical composition analysis (EDX), scanning electron microscopy (SEM), temperature-programmed reduction (TPR-H2), Cu oxidation with N2O (TPD-N2O) pyridine adsorption-FTIR spectroscopy (FTIR-Py), temperature-programmed NH3 desorption (TPD-NH3), and X-ray photoelectron spectroscopy (XPS). The pillaring process along with impregnation of Cu with Zn, Ce, Nb, Fe and/or Co produced catalysts with different structural and acidity properties, which favored the conversion of CO and CO2 into C2 -C4 products. The bimetallic CuFe/V-Al-PILC catalyst presented the highest catalytic activity on the CO and CO2 hydrogenation reactions, and best selectivity for DME synthesis. The low selectivity for obtaining DME was revealed to be most likely due to low total acid sites density of catalysts and high experimental spatial velocity.