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.

Reverse osmosis (RO) is widely used for water reclamation and is one of the most feasible technologies for addressing water scarcity around the world. RO membrane fabrication procedures are continually being optimized and modified to enhance the treatment performance and efficacy of the RO process. A review of the existing literature published on membrane fabrication revealed that a detailed and reproducible methodology consistent among prior studies was not available. Therefore, the primary objective of this study was to utilize techniques from prior research to develop a reliable lab-scale membrane fabrication process for studying the potable reuse applications of TFC RO membranes. Phase inversion was used to create a polysulfone (PSF) support layer on a non-woven fabric sheet. Then, the process of interfacial polymerization (IP) between amine and acyl chloride monomers was utilized to form a highly selective and ultrathin polyamide (PA) layer on the PSF support surface. The resulting membrane composition and performance was dependent on a wide range of parameters during the fabrication process. The optimal support materials, reactant types and concentration, and reaction conditions were determined through trial and error. The best performing membranes utilized N-methyl-2-pyrrolidone (NMP) as the solvent, Novatexx-2471 non-woven fabric for mechanical support, and 15 wt% PSF concentration for phase inversion. The optimal immersion duration was five minutes for the aqueous amine monomer solution during the IP process. The flux for membrane triplicates was 20.2  3.6 liters per square meter per hour (LMH) while the salt rejection was 96.8  2.0%. The relatively low standard deviation for flux and salt rejection indicates that the fabrication method developed herein is consistent. A commercial Dow Filmtec BW30 flat sheet PA-TFC RO membrane was tested for comparison and exhibited a flux of 44.9 LMH and a salt rejection of 98.5%. Thus, the membranes developed in this study achieved salt rejection on par with commercial membranes but exhibited a flux that was significantly lower. Furthermore, this study investigated modifications to the traditional TFC membrane using engineered silica nanomaterials with the goal of enhancing the membrane flux while maintaining high salt rejection. Two types of nonporous silicon dioxide nanoparticles (SDNPs), non-functionalized and amine functionalized, were dispersed in the aqueous and organic IP solutions. Ultrasonication of the non-functionalized SDNPs in the aqueous solution was observed to produce the most stable dispersion. Compared to the unmodified TFC membranes, the average flux of the SDNP-modified (TFC-NP) RO membrane triplicates was higher at 25.4  2.0 LMH with 0.1% (w/v) SDNPs incorporated in the PA layer. The salt rejection was lowered to 92.3  0.1% for the TFC-NP membranes. In addition, the membranes fabricated in this study were characterized using scanning electron microscopy (SEM), Fourier Transport Infrared Spectroscopy (FTIR), atomic force microscopy (AFM), and goniometry measurements. SEM images showed that the TFC-NP membranes contained larger spaces between ridges and valleys of the PA pore structure. FTIR confirmed the PA layer formation on the membranes fabricated herein but a spectral peak from the SDNPs was not observed for the TFC-NP membranes. AFM measurements indicated an increase in surface roughness of the modified membranes, likely because of the incorporation of SDNPs. The surface of TFC-NP membranes was found to be more hydrophilic than the unmodified TFC membranes based on contact angle measurements. Further optimization of the fabrication method developed herein is warranted before pursuing additional RO research topics, such as the disinfection byproduct precursor removal of TFC membranes.

Thesis (MScEng (Mechanical and Mechatronic Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: Polysulfone hollow-fibre membranes were fabricated via the dry-wet solution spinning technique. The objective was to demonstrate the influence of the various fabrication parameters on the diameter and mechanical properties of the hollow-fibre membranes and to optimize the spinning process by controlling these parameters with a computer control system. The effects of the operation parameters were investigated using an experimental design based on a fractional factorial method (Taguchi’s design of experiments). The parameters that were considered are the spinneret size, dope solution temperature, bore fluid temperature, coagulation bath temperature, dope extrusion rate, bore flow rate and the take-up speed. A new pilot solution spinning plant was installed and upgraded, and a computer control system, based on LabView, was developed to control, monitor and log the experimental data. The diameter of the hollow-fibres were determined using a scanning electron microscope (SEM) while the mechanical properties were measured using a tensile tester. The effects of diameter size and wall thickness of the hollow-fibres on the performance of the membranes were studied. The results showed the significance of the fabrication parameters that dominate the diameter and strength of the hollow-fibres. / AFRIKAANSE OPSOMMING: Polisulfoon holvesel membrane is met ‘n droë-nat oplossingspin proses vervaardig. Die doel hiermee was om die invloed van verskeie vervaardigingsparameters op die deursnee en meganiese eienskappe van die holvesel membrane te demonstreer asook om die spin proses te optimeer deur gerekenariseerde beheer van die aanleg. ‘n Eksperimentele ontwerp, gebaseer op ‘n gedeeltelike faktoriaal metode (Taguchi se eksperimentele ontwerp) is gebruik om die invloed van die vervaardigingsparameters te ondersoek. Die parameters wat oorweeg is, is spindop grootte, materiaal temperatuur, boorvloeistof temperatuur, stolbad temperatuur, materiaal ekstrusie tempo and opwen spoed. ‘n Nuwe oplossingspin loodsaanleg was geïnstalleer en opgegradeer en ‘n rekenaar beheerstelsel, gebaseer op LabView, is ontwikkel om die aanleg te beheer, moniteer en eksperimentele data te stoor. Die deursnee van die holvesel is gemeet met ‘n skanderingelektron mikroskoop (SEM) terwyl die meganiese eienskappe bepaal is met ‘n trektoets apparaat. Die effek van die deursnee en wanddikte van die holvesels op die werkverrigting van die membrane is ook bestudeer. Die resultate toon watter vervaardigingsparameters is beduidend vir die deursnee en sterkte van die holvesels.