Sulfonated poly(arylene ether sulfone)s can exhibit several ideal features as potential desalination membranes for reverse osmosis applications, including chlorine resistance, low surface fouling, and high water flux. However, this class of polymer membranes has suffered from two major drawbacks that jeopardize effective levels of salt rejection in order to achieve high water flux. In mixed salt feed sources, monovalent salt rejection decreases when divalent cations such as Ca2+ bind with the anionic sulfonate groups to cause charge screening, and this can lead to too much salt passage for the membranes to be competitive with interfacially produced polyamides. Sulfonate fixed charge concentration must be high enough for sufficient membrane water uptake to obtain high membrane water flux, but if the water uptake is too high, this permits increased salt passage. The research described in this dissertation attempts to address both of these challenges through the design of a sulfonated monomer that strategically spaces the ionic groups along the polymer backbone chains to inhibit divalent ion binding. Free radical crosslinking further tunes the hydrated free volume in the RO membranes. A mono-sulfonated comonomer, sodium 3-sulfonate-4,4'-dichlorodiphenylsulfone (ms-DCDPS), was synthesized by stoichiometrically controlled electrophilic aromatic sulfonation of 4,4'-dichlorodiphenylsulfone (DCDPS). HPLC-UV revealed complete isolation of ms-DCDPS free of by-products after the 1st recrystallization and 1H NMR analysis confirmed the structure. A standard calibration curve was developed to accurately determine the leftover quantity of excess NaCl that was used for precipitation during the work-up procedures. A series of linear sulfonated poly(arylene ether sulfone)s with varying ms-DCDPS incorporation was synthesized. 1H NMR confirmed the structure of the polymers and size-exclusion chromatography confirmed that the intended molecular weights were achieved. The copolymers were cast into dense films and the mechanical and transport properties were measured in their fully hydrated states. Tensile tests revealed mechanically robust, tough membranes with glassy elastic moduli and high strains at break. The dense membrane prepared from sulfonated poly(arylene ether sulfone) with 51% of the repeat units sulfonated had NaCl rejection = 99.3% measured at 400 psi and 2000 ppm NaCl with a water permeability coefficient of 0.57 x 10-6 cm2/s. The salt rejection remained greater than 99% when a mixed salt feed source containing Ca2+ in the 0-200 ppm range together with the 2000 ppm NaCl was introduced. Crosslinked mono-sulfonated oligomers were synthesized with targeted molecular weights by utilizing stoichiometric quantities of monomers with the desired degrees of sulfonation, and the endgroups were functionalized with tetrafluorostryene. These end-functionalized sulfonated oligomers were crosslinked by both thermal and UV free radical methods in the presence of initiators without any additional crosslinking agents. Reaction conditions were thoroughly investigated and optimized to produce highly crosslinked membranes that yielded gel fractions greater than 87%, as measured by solvent extraction in dimethylacetamide. The hydrated crosslinked membranes were tested for both mechanical and transport properties, and the results were compared to their linear membrane counterparts. Crosslinking decreased the hydrated free volume and reduced water uptakes when compared to linear sulfonated membranes. Tensile tests of the fully hydrated crosslinked membranes showed good mechanical properties. The transport properties of a dense UV crosslinked membrane prepared with a 10,000 g/mol oligomer having 50% of the repeat units sulfonated was tested under RO cross-flow conditions at 400 psi and 2000 ppm NaCl in the feed. The membrane demonstrated a salt rejection = 98.4% with a water permeability coefficient of 0.49 x 10-6 cm2/s. / Doctor of Philosophy / Billions of individuals across the world lack clean, affordable drinking water, and the unavailability of fresh drinking water can be attributed to both physical and economic reasons. Several techniques have been utilized to produce potable water for human consumption that include both water desalination and recycling procedures. Water desalination is a process that allows for purifying salt contaminated water into drinking water. The two major desalination processes involve either distillation or passage through polymer membranes. Distillation separates water from salt by heating liquid water to form a gas, and collecting the vapor as condensate while impurities remain in the heated bulk material. Polymer membranes separate impurities through filtration where membranes allow water to pass through a physical barrier while rejecting the unwanted contaminants, including salt. Reverse osmosis desalination is the most common membrane separation process. Reverse osmosis membranes are comprised of either short-chain crosslinked oligomers or long-chain linear polymers. Commercial reverse osmosis membranes are largely poly(amide)s where a thin film is formed in an interfacial reaction. The membranes allow for almost quantitative salt rejection with high water fluxes. But, these membranes degrade over time from periodic cleaning with chlorine disinfectants. This dissertation primarily focuses on the implementation of an alternative polymer membrane material known as a mono-sulfonated polysulfone that strategically distributes the fixed sulfonate charged groups along the polymer backbone. Theses reverse osmosis mono-sulfonated polysulfones display comparable salt rejection with better chemical resistance than commercial poly(amide)-based membranes, and could potentially offer a replacement in the market.

This thesis research focused on the synthesis and characterization of disulfonated poly(arylene ether sulfone) hydrophilic-hydrophobic segmented and multiblock copolymers for application as proton exchange membranes (PEMs) in fuel cells or as reverse osmosis (RO) membranes for water desalination. The first objective was to demonstrate that synthesizing blocky copolymers using a one oligomer, two monomer segmented copolymerization afforded copolymers with similar properties to those which used a previous approach of coupling two preformed oligomers. A 4,4′-biphenol based hydrophilic block of disulfonated poly(arylene ether sulfone) oligomer of controlled number average molecular weight (Mn) with phenoxide reactive end groups was first synthesized and isolated. It was then reacted with a calculated amount of hydrophobic monomers, forming that block in-situ. Copolymer and membrane properties, such as intrinsic viscosity, tensile strength, water uptake, and proton conductivity, were consistent with those of multiblock copolymers synthesized via the oligomer-oligomer approach. The segmented polymerization technique was then used to synthesize a variety of other copolymers for PEM applications. The well known bisphenol phenolphthalein was explored as a comonomer for either the hydrophilic and hydrophobic blocks of the copolymer. Membrane properties were explored as a function of block length for both series of copolymers. Both series showed that as block length increases, proton conductivity increases across the entire range of relative humidity (30-100%), as does, water uptake. This was consistent with earlier research which showed that the water self-diffusion coefficient scaled with block length. Copolymers produced with phenolphthalein had higher tensile strength, but lower ultimate elongation than the 4,4′-biphenol based copolymers. Multiblock copolymers were also synthesized and characterized to assess their feasibility as RO membranes. A new series of multiblock copolymers was synthesized by coupling hydrophilic disulfonated poly(arylene ether sulfone) (BisAS100) oligomer with hydrophobic unsulfonated poly(arylene ether sulfone) (BisAS0) oligomer. Both oligomers were derived using 4,´-isopropylidenediphenol (Bis-A) as the bisphenol. Phenoxide-terminated BisAS100 was end-capped with decafluorobiphenyl and reacted at relatively low temperatures (~ 100 oC) with phenoxide-terminated BisAS0. Basic properties were characterized as a function of block length. The initial membrane characterization suggested these copolymers may be suitable candidates for reverse osmosis applications, and water and salt permeability testing should be conducted to determine desalination properties. The latter measurements are being conducted at the University of Texas, Austin and will be reported separately. / Ph. D.

The objective of this dissertation is to demonstrate different applications of ssNMR, with particular emphasis on uses in polymeric and biosciences. First, dynamics investigations on two polymers will be discussed: (1) disulfonated poly(arylene ether sulfone)s /poly(ethylene glycol) blends (BPS-20_PEG), which are under development as chlorine-resistant reverse osmosis (RO) membrane alternatives to aromatic polyamide (PA) technology, and (2) poly(arylene ether sulfone)s modified with 1,4-cyclohexyl ring units to improve processability. Simple cross-polarization magic-angle-spinning (CPMAS) experiments compared the chlorine tolerance of BPS-20_PEG and PA. Techniques capable of detecting motional geometries and rates on timescales from nanoseconds to seconds, including relaxation time measurements, were applied. Correlations were established between relaxation time and water permeability for the RO membranes, and between relaxation time and polydispersity in the 1,4- cyclohexyl ring modified polymer. Next, 31P and 2H static ssNMR experiments evidencing the formation of toroidal pores and thinned bilayers in oriented zwitterionic and anionic phospholipid bilayers, (biomembrane mimetic systems), by the antimicrobial peptides (AMPs) magainin-2 and aurein-3.3, will be mentioned. The toroidal pore geometries induced by magainin-2 were different than those produced by aurien-3.3. The most prominent features were observed in 2H spectra, implying greater interaction of the peptides with hydrophobic lipid acyl chains. Following this, a new two-dimensional homonuclear dipolar recoupling MAS experiment, capable of correlating long range 13C-13C spin pairs in a uniformly/ extensively 13C-labeled biomolecule, will be introduced. This technique was demonstrated on 13C-labeled versions of Glutamine and Glycine-Alanine-Leucine. Experiments involving the recoupling of all 13C-13C spin pairs, and experiments with selective recoupling using Gaussian or cosine-modulated Gaussian pulses, were demonstrated. Finally, work using static 1H- 13C CP ssNMR to selectively detect interfacial water around hydrophobic C60 will be recounted. This project exploited the distance limitation of CP, and 1H spin-lattice relaxation times, to separate the influence of bulk and interfacial water on the spectra. Results indicated that the tumbling of interfacial water is slowed by a factor of 105 compared to bulk water, providing it with a solid-like character, and allowing the hydration shell to be stable at temperatures above the freezing point of water. / Ph. D.

The purpose of this work is to develop and evaluate electroding methods for a reverse osmosis (RO) membrane that results in an in situ sensor able to detect RO membrane protein fouling. Four electroding techniques were explored: i) gold exchange-reduction, ii) encapsulated carbon grease, iii) "direct assembly process" (DAP), and iv) platinized polymer graft. The novel platinized polymer graft method involves chemically modifying the RO membrane surface to facilitate platinization based on the hypothesis that deposition of foulant on the platinized surface will affect platinum/foulant/solution interfacial regions, thus sensor impedance. Platinized polymer graft sensors were shown to be sensitive to protein fouling. Electrodes were characterized by their electrical properties, SEM and XPS. Assembled sensors were evaluated for sensitivity to electrolyte concentration and protein fouling. Micrographs showed coating layers and pre-soak solution influence gold exchange-reduction electrode formation. High surface resistance makes gold exchange-reduction an unsuitable method. Concentration sensitivity experiments showed carbon grease and DAP electroding methods produce unusable sensors. Carbon grease sensors have time-dependent impedance response due to electrolyte diffusion within the micro-porous polysulfone support. DAP electroded sensors proved quite fragile upon hydration; their impedance response is transient and lacks predictable trends with changes in concentration. A parametric study of the platinized polymer graft method shows amount of grafted monomer correlates to grafting time, and deposited platinum is a function of exchange-reduction repetitions and amount of grafted monomer. Platinized polymer graft sensors were fouled in both dead-end and cross-flow RO systems, and their impedance trends, while varying between sensors, indicate protein-fouling sensitivity. / Master of Science

Yes / Reverse Osmosis (RO) is one of the most widely used technologies for wastewater treatment for the removal of toxic impurities, such as phenol and phenolic compounds from industrial effluents. In this research, performance of multi-stage RO wastewater treatment system is evaluated for the removal of chlorophenol from wastewater using model-based techniques. A number of alternative configurations with recycling of permeate, retentate, and permeate-retentate streams are considered. The performance is measured in terms of total recovery rate, permeate product concentration, overall chlorophenol rejection and energy consumption and the effect of a number of operating parameters on the overall performance of the alternative configurations are evaluated. The results clearly show that the permeate recycling scheme at fixed plant feed flow rate can remarkably improve the final chlorophenol concentration of the product despite a reduction in the total recovery rate.

Yes / Reverse osmosis (RO) has become a significant method for removing salts and organic compounds from seawater and wastewater in recent decades. Spiral-wound module has been widely used due to a number of special features such as high packing density, premium separation and low operating cost. In this paper, a two-dimensional mathematical model is developed for the transport of dilute aqueous solutions through a spiral-wound RO module and the operational characteristics of the process under steady state conditions are analysed. The model is based on the solution-diffusion model coupled with the concentration polarization mechanism. This model yields a set of Differential and Algebraic Equations (DAEs), which are solved using the gPROMS software. The model is validated using experimental data from the literature for the rejection of dimethylphenol as solute in aqueous solutions. The model is then used to simulate the process under steady state conditions to gain deeper insight of the process.

Yes / Reverse osmosis (RO) has found extensive applications in industry as an efficient separation process in comparison with thermal process. In this study, a one-dimensional distributed model based on a wastewater treatment spiral-wound RO system is developed to simulate the transport phenomena of solute and water through the membrane and describe the variation of operating parameters along the x-axis of membrane. The distributed model is tested against experimental data available in the literature derived from a chlorophenol rejection system implemented on a pilot-scale cross-flow RO filtration system with an individual spiral-wound membrane at different operating conditions. The proposed model is then used to carry out an optimisation study using a genetic algorithm (GA). The GA is developed to solve a formulated optimisation problem involving two objective functions of RO wastewater system performance. The model code is written in MATLAB, and the optimisation problem is solved using an optimisation platform written in C++. The objective function is to maximize the solute rejection at different cases of feed concentration and minimize the operating pressure to improve economic aspects. The operating feed flow rate, pressure and temperature are considered as decision variables. The optimisation problem is subjected to a number of upper and lower limits of decision variables, as recommended by the module’s manufacturer, and the constraint of the pressure loss along the membrane length to be within the allowable value. The algorithm developed has yielded a low optimisation execution time and resulted in improved unit performance based on a set of optimal operating conditions.

Yes / The removal of the ubiquitous phenol and phenolic compounds in industrial wastes is a critical environmental issue due to their harmful threats to wildlife and potential adverse human health effects. The removal of such compounds is therefore of significant importance in water treatment and reuse. In recent years, reverse osmosis (RO) has been successfully utilised in several industrial processes and wastewater treatment including phenol removal. In this paper, a new model based on a spiral-wound RO process is developed for the removal of phenol from wastewater. A simplified mathematical algorithm using an irreversible thermodynamic approach is developed. This results in a set of non-linear Differential and Algebraic Equations (DAEs), which are solved based on a number of optimised model parameters using a combined methodology of parameter estimation and experimental phenol-water data derived from the literature. The effects of several operational parameters on the performance (in terms of removal of phenol) of the process are explored using the model.

Yes / Reverse Osmosis (RO) membrane process has been commonly used for clarification and concentration of apple juice processes, due to significant advance in membrane technology, requirements for low energy and cost, and effective retention of aroma components. In this paper, a multi-stage RO industrial full-scale plant based on the MSCB 2521 RE99 spiral-wound membrane module has been used to simulate the process of concentrating apple juice and to identify an optimal multi-stage RO process for a specified apple juice product of high concentration measured in Brix. The optimisation problem is formulated as a Nonlinear Programming (NLP) problem with five different RO superstructures to maximise the apple juice concentration as well as the operating parameters such as feed pressure, flow rate and temperature are optimised. A simple lumped parameter model based on the solution-diffusion model and the contribution of all sugar species (sucrose, glucose, malic acid, fructose and sorbitol) to the osmotic pressure is assumed to represent the process. The study revealed that the multi-stage series RO process can optimise the product concentration of apple juice better than other configurations. It has been concluded that the series configuration of twelve elements of 1.03 m2 area improves the product apple juice concentration by about 142% compared to one element. Furthermore, the feed pressure and flow rate were found to have a significant impact on the concentration of the apple juice.

Yes / The removal of pollutants such as N-nitrosamine present in drinking and reuse water resources is of significant interest for health and safety professionals. Reverse osmosis (RO) is one of the most promising and efficient methodologies for removing such harmful organic compounds from wastewater. Having said this, the literature confirms that the multi-stage RO process with retentate reprocessing design has not yet achieved an effective removal of N-nitrosodimethylamine-D6 (NDMA) from wastewater. This research emphasizes on this particular challenge and aims to explore several conceptual designs of multi-stage RO processes for NDMA rejection considering model-based techniques and compute the total recovery rate and energy consumption for different configurations of retentate reprocessing techniques. In this research, the permeate reprocessing design methodology is proposed to increase the process efficiency. An extensive simulation analysis is carried out using high NDMA concentration to evaluate the performance of each configuration under similar operational conditions, thus providing a deep insight on the performance of the multi-stage RO permeate reprocessing predictive design. Furthermore, an optimisation analysis is carried out on the final design to optimise the process with a high NDMA rejection performance and the practical recovery rate by manipulating the operating conditions of the plant within specified constraints bounds. The results show a superior removal of NDMA from wastewater.