Crosslinking is an effective technique for increasing the salt rejection of water purification membranes and the selectivity of gas separation membranes. An abundance of monomers, telechelic oligomers, and novel polymers were synthesized for use as separation membranes. These materials were often imbued with crosslinking functionalities to increase their performance during testing at the University of Texas-Austin. Crosslinking of sulfonated poly(arylene ether sulfone) oligomers was studied systematically with regard to end-group functionality, polymer composition, and polymer hydrophilicity. Sulfonated bisphenol A based poly(arylene ether sulfone) random copolymers were synthesized with reactive amine endgroups and further functionalized with a tetra-epoxy resin, acryloyl chloride, phenylethynyl phthalic anhydride, and maleic anhydride. The reaction between amine terminated oligomers and a tetra-epoxy produced large, ductile membranes with gel fractions approaching 99%, the highest reported for crosslinked sulfonated polysulfone oligomers. This crosslinking reaction was studied by synthesizing two series of oligomers, one based on a bisphenol A monomer and the other based on a 4,4’-biphenol monomer. Both series were synthesized with 40, 50 and 60% degrees of sulfonation, so that hydrophilicity and composition could be studied with regard to water purification properties. All six oligomers were produced with a gel fraction exceeding 90%, and the membranes were evaluated at the University of Texas-Austin. The crosslinked oligomers demonstrated relatively constant salt rejection across a range of hydrophilicity values, which proved that crosslinking restricted the large amount of swelling that non-crosslinked sulfonated polysulfones undergo. The crosslinked oligomers had the best water purification properties reported for sulfonated polysulfone, with similar water permeabilities and an order of magnitude higher selectivity (Pw/Ps = 1.69 ± 0.13 x 103) than analogous linear copolymers (Pw/Ps = 3.67 ± 0.53 x 102). An additional series of linear sulfonated copolymers were also synthesized based upon a hydroquinone bisphenol, which also had superior water purification properties (1.06 ± 0.06 L μm m-2 h-1 bar-1, Pw/Ps = 2.44 ± 0.15 x 103) compared to previously synthesized linear copolymers. Poly(arylene ether)s were also investigated for use as gas separation membranes. A poly(arylene ether ketone) and poly(arylene ether sulfone) were both synthesized with moieties capable of oxidation and/or photocrosslinking through benzylic hydrogen abstraction by an excited ketone. The polymers produced tough, ductile films. Gas transport properties of the linear polymers and crosslinked polymer were compared. The O2 permeability of one exemplary non-crosslinked poly(arylene ether) was 2.8 Barrer, with an O2/N2 selectivity of 5.4. Following UV crosslinking, the O2 permeability decreased to 1.8 Barrer, and the O2/N2 selectivity increased to 6.2. / Ph. D.

Ion-containing block copolymers blend ionic liquid properties with well-defined polymer architectures. This provides conductive materials with robust mechanical stability, efficient processability, and tunable macromolecular design. Conventional free radical polymerization and anion exchange achieved copolymers containing n-butyl acrylate and phosphonium ionic liquids. These compositions incorporated vinylbenzyl triphenyl phosphonium and vinylbenzyl tricyclohexyl phosphonium cations bearing chloride (Cl), or bis(trifluoromethane sulfonyl)imide (Tf2N) counteranions. Differential scanning calorimetry and dynamic mechanical analysis provided corresponding thermomechanical properties. Factors including cyclic substituents, counteranion type, as well as ionic concentration significantly influenced phosphonium cation association. 1, 1\'-(1, 4-Butanediyl)bis(imidazole) neutralized NexarTM sulfonated pentablock copolymers and produced novel electrostatically crosslinked membranes. Variable temperature FTIR and 1H NMR spectroscopy confirmed neutralization. Atomic force microscopy and small angle X-ray scattering studied polymer morphology and revealed electrostatic crosslinking characteristics. Tensile analysis, dynamic mechanical analysis, thermogravimetric analysis, and vapor sorption thermogravimetric analysis investigated polymer properties. The neutralized polymer demonstrated enhanced thermal stability, decreased water adsorption, and well-defined microphase separation. These findings highlight NexarTM sulfonated pentablock copolymers as reactive platforms for novel, bis-imidazolium crosslinked materials. 4-Vinylbenzyl piperidine is a novel styrenic compound that observably autopolymerizes. In situ FTIR spectroscopy monitored styrene and 4-vinylbenzyl piperidine thermal polymerizations. A pseudo-first-order kinetic treatment of the thermal polymerization data provided observed rate constants for both monomers. An Arrhenius analysis derived thermal activation energy values. 4-Vinylbenzyl piperidine exhibited activation energy 80 KJ/mol less than styrene. The monomer differs from styrene in its piperidinyl structure. Consequently, in situ FTIR spectroscopy also monitored styrene thermal polymerization with variable N-benzyl piperidine concentrations. Under these circumstances, styrene revealed activation energy 60 KJ/mol less than its respective bulk value. The similarities in chemical structure between styrene and 4-vinylbenzyl piperidine suggested thermally initiated polymerization occurred by the Mayo mechanism.  The unique substituent is proposed to offer additional cationic effects for enhancing polymerization rates. Living anionic polymerization of 4-vinylbenzyl piperidine achieved novel piperidinyl-containing polymers.  Homopolymer and copolymer architectures of this design offer structural integrity, and emphasize base stability.  Sequential anionic polymerization afforded a 10K g/mol poly(tert-butyl styrene-co-4-vinylbenzyl piperidine) diblock and a 50K poly(tert-butyl styrene-co-isoprene-co-4-vinylbenzyl piperidine) triblock. Alkylation studies involving a phosphonium bromide salt demonstrated the future avenues for piperidinium based polymer designs. These investigations introduce piperidinyl macromolecules as paradigms for a new class of ammonium based ionic materials. / Master of Science

Master of Science

As a consequence of new coal mining practices, coal preparation plants have been inundated with increased loads of coal and clay particles in their wastewaters. Traditionally, the industry has employed primary sedimentation as the fundamental treatment scheme for these sediment-laden blackwaters. This study was undertaken to determine the effects of a combination of coagulant addition and rapid mixing on the settleability of these particles. After initial testing, aluminum sulfate and two low molecular weight cationic polymers, Cyanamid Magnifloc 513C and Cyanamid 515C, were chosen as primary coagulants for use in this work. An artificial wastewater was prepared from finely powdered (62 to <38 microns) raw coal samples and tap water, after initial tests indicated that typical frothing and/or collector agents had no demonstrable effect on coagulant function. Initially determined optimum coagulant dosages, as well as flocculation and sedimentation times, were kept constant while rapid mix intensities were varied at G values of 330 sec⁻¹, 700 sec⁻¹, 2000 sec⁻¹ and 7000 sec⁻¹ for each sample. Using a combination of residual turbidity and particle size analyses to determine the effectiveness of each rapid mix intensity, it was discovered that only the highest mixing intensities and durations (G(t) values) caused floe disintegration due to overmixing. At the lower G(t) matrices floe formation and settleability was consistently good. When aluminum sulfate was used as a coagulant, the wastewater was tested at a high pH of 8.1 to 8.3 and a low pH of 5.5 to observe floe behavior under different conditions of coagulant mechanism. The test results were similar for both pH values except at the lowest mixing intensities where the high pH samples settled well, resulting in low residual turbidities, but the low pH samples had relatively high turbidities. / Master of Science

The application of packed column air stripping systems to the removal of volatile organic contaminants (VOCs) from drinking water sources was investigated. The crucial element for the design of such systems exists in obtaining accurate predictions of mass transfer rates. The first phase of this study evaluated three semi-empirical correlations available for predicting packed column mass transfer rates. From this initial screening, the Onda model was selected for further investigation. A test data base was established from water treatment pilot study results reported in the literature. Ten separate studies were selected for evaluation, encompassing approximately 450 data points. Eleven different VOCs were encountered in these investigations, and the basic packing types tested included rings, saddles, Tri-Packs, and Tellerettes. Comparison of measured mass transfer rates with the corresponding rates predicted by the Onda correlation yielded a relative standard deviation of 17%. A ± 30% accuracy value was therefore assigned to the model based on 90% confidence limits. This assessment agrees with the observed accuracy of the correlation for the chemical engineering-based system results utilized in the model's original derivation. From the overall evaluation, no severe deficiencies and/or limitations with the Onda correlation were noted. In particular, gas-phase resistance predictions appeared reasonably accurate. However, further investigative studies involving observed column performance with larger packing materials (≥2 inches in nominal size) is encouraged to verify the accuracy of the correlation for such situations. Within the context of the evaluation procedure, several related areas were investigated. First, Henry's constant temperature relations reported in the literature were established within approximately 20% for common VOCs at low concentration levels. Secondly, the transfer unit performance model for calculating observed mass transfer rates was found sensitive to experimental measurement errors below a stripping factor of 1.5. Therefore, measured results obtained under such operating conditions must be viewed with appropriate caution. Finally, economic design boundaries for column operational parameters were established based upon optimization study results reported in the literature. / M.S.

Yes / In this paper, a one-dimensional mathematical model based on coupled differential and algebraic equations has been developed for analysing the separation mechanism of a N-nitrosamine in a spiral-wound reverse osmosis process. The model is based on Spiegler and Kedem’s work on mass transport and Darcy’s law and concentration polarization to analyse the pressure drop and mass transfer coefficient in the module feed channel respectively. The model is built using the gPROMS software suite and validated using N-nitrosamine rejection experimental data from the literature, obtained by using a pilot-scale cross-flow reverse osmosis filtration system. Analysis results derived from the model corroborate experimental data.

Physical-chemical treatment has been shown to be highly successful in treating certain wastewaters and, to some degree, this treatment approach has been promoted as a panacea for all wastewater treatment problems. This project was designed to investigate the best method of treating a wastewater composed primarily of soluble organic material resulting from a cellulose acetate manufacturing process. Both physical-chemical and biological treatment processes were applied to the wastewater to determine whether the performance of the physical-chemical approaches would be less than, equal to, or greater than the performance of the biological treatment system. A further intention of the study was to help in generating guidelines concerning the limitations, if any, of physical-chemical systems. Experimental results showed that chemical treatment using lime or ferric chloride produced only marginal reductions in the COD of the wastewater. From these chemical experiments it was discovered that the wastewater had an extremely high buffering capacity. Adsorption with granular carbon produced a significant reduction in COD provided that a sufficient detention time was allowed. However, final COD values were still too high for discharge under most conditions. In a fairly short aeration period, activated sludge treatment produced an effluent COD value almost one-third the minimum effluent COD value from carbon adsorption. It was therefore concluded that for the wastewater studied t biological treatment was much more efficient than a chemical or physical treatment approach. / Master of Science

Up-coming regulations on chlorine dioxide in drinking water treatment require low level measurement of chlorite ion (CI0₂-) and chlorate ion (CI0₃-). This research investigated analysis of CI0₂- and CI0₃-; in drinking water by flow injection analysis with iodometric detection (FIA) and ion chromatography with conductivity detection (IC). Both the FIA and IC methods were accurate for the determination of CIO₂-; and CIO₃-; in reagent water. The IC method was accurate in drinking water, however, FIA responded to chloramines and other oxidants present in drinking water causing inaccurate analysis of CIO₂-; and CIO₃-; by FIA. The two IC eluants investigated, a carbonate/bicarbonate mixture and a borate/boric acid mixture, performed well. By taking advantage of the slightly different separation abilities of each eluant, the IC method can be modified to maximize resolution of CIO₂-; and CIO₃-; in different drinking water matrices. Chlorite was unstable in chlorinated drinking water but was stable for up to three days when sodium oxalate was added and stable up to eighteen days when ethylene diamine was added as a preservative. Chlorate was stable in drinking water for up to eighteen days with or without a preservative. The propagation of errors method for determining detection limits yielded limits of detection for CIO₂- (mg/L) of 0.05 for FIA, 0.03 for the IC carbonate eluant and 0.01 for the IC borate eluant. For CIO₃- the limits of detection (mg/L) were 0.24 for FIA; 0.11 for the IC carbonate eluant and 0.02 for the borate eluant. / Master of Science

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