In this study, two different strategies were carried out to modify the polyvinylidene fluoride (PVDF) distillation membrane for desalination. The first strategy was the addition of TiO2 nanoparticles into the target membranes and a synergistic effect of hydrophilic and hydrophobic nanoparticles was found for the first time in this work. And the other strategy was the introduction of another polymer material, polytetrafluoroethylene (PTFE), to the PVDF membranes to fabricate a flat sheet PVDF-PTFE composite membrane and this is the first attempt that such a membrane to be made. Two types of membranes were characterized by scanning electron microscopy (SEM) detection, porosity measurement, energy dispersive X-ray spectroscopy (EDX), Attenuated total reflectance (ATR)-Fourier transformed infrared spectroscopy (FTIR), contact angle (CA) measurement, atomic force spectroscopy (AFM) detection and liquid entry pressure of water (LEPw) measurement. Their performance was evaluated by vacuum membrane distillation (VMD) experiments. And the best VMD pure water permeate flux of the membranes fabricated under these two modify strategies could achieve 4.26 kg/m2h (M-L5-B2) and 5.61 kg/m2h (M-40), respectively, when that of pure PVDF membrane is only 0.71 kg/m2h. The salt rejection of the prepared composite membranes are all stably higher than 99.5% which demonstrate their capacity for desalination.

This thesis is concerned with the study of different effects in protein ultrafiltration including device configuration, solution chemistry and membrane charge In the recent and more established literature membrane fouling remains a challenging problem that limits the wider application of ultrafiltration. Thus, investigations which can aid understanding and potentially reduce membrane fouling are of particular interest and in this study the problem has been addressed from several different angles Polyethersulfone membranes were studied at varying pH and two ionic strengths using bovine serum albumm and lysozyme as the model proteins. The study was conducted both in a stirred cell and a crossflow configuration in order to evaluate the influence of different system hydrodynamics on filtration This work was further substantiated through the application of filtration models An attempt was also made to modify the membrane surface by low temperature plasma modification with the intention to preferentially alter the characteristics of the membrane surface Both unmodified and plasma-modified polyethersulfone membranes were characterised using a range of analytical methods including flux data, streaming potential, contact angle and MWCO measurements to aid results interpretation. The research showed that MWCO data quoted by manufacturers is mostly greater than that obtained during laboratory studies The MWCO technique was also used to highlight differences between the unmodified and plasma-modified membranes demonstrating that the modification resulted in a membrane with tighter pores in the lower molecular weight region. Concentration polarisation effects were found to be reduced as a result of the plasmamodification The study of protein filtration at different pH and ionic strengths demonstrated that ionic strength effects were more pronounced than pH effects It was also shown that changes m the ionic strength can be used to alter the degree of protein rejection for the given system concentration polarisation was found to be higher during crossflow filtration compared to stirred cell filtration The thesis adds to existing knowledge in the area of ultrafiltration emphasizing the importance of device configuration, solution chemistry as well as the potential of charged membranes

Reverse osmosis (RO) is widely used for water reuse and desalination. Although RO membranes are known for their high salt rejection and practical permeate flux, their performance can be impaired by fouling, and their removal of some disinfection byproducts and their precursors (e.g., bromide, N-Nitrosodimethylamine [NDMA]) does not meet drinking water standards. RO membrane modifications have been widely studied to overcome these limitations. In this research, RO membranes were grafted with cationic polymers to induce a positive charge on the RO membrane surface. This modification aimed at enhancing the rejection of negatively charged bromide ions by removing them from solution by binding them to the membrane surface. The results showed that the modified (positively charged) RO membranes achieved lower rejection (82% rejection) for bromide ions compared to the unmodified ones (94.5% rejection). This behavior was likely a result of increased concentration polarization of the bromide ions at the membrane surface and/or increase in porosity of the modified membranes. Calculations based on the film theory indicate that the concentration of bromide ions at the surface of the modified membrane was 1371 ppm compared to 1307 ppm at the surface of the unmodified membrane. Evidently, the polymer attraction energy was not sufficient to keep the bromide ions attached to the membrane surface and prevent their diffusion across the membrane. Although the goal of the modification in the current study (i.e., enhancing removal of bromide ions) was not met, the permeate flux of the modified membrane was improved compared to the unmodified one. The literature suggests that increasing flux after modification is likely a result of increase in membrane pore size and hydrophilicity. In addition to the experimental work conducted in this study, a multi-criteria decision analysis was performed to prioritize research on surface modifications of reverse osmosis membranes. It was found that surface modifications have been mainly focused on reducing membrane fouling and to a much lower extent on removal of disinfection byproducts and their precursors. The RO membrane modification alternatives for fouling reduction and N-Nitrosodimethylamine (NDMA) removal were ranked based on multiple criteria using the Analytical Hierarchy Process (AHP) and the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). This multi-criteria decision analysis process resulted in the identification of the top five promising modifications to reduce fouling and improve NDMA rejection. Grafting and coating the RO membranes with complex polymeric salts were the highest ranked modification approaches to reduce fouling. Heat-treatment of RO membranes achieved the highest NDMA rejection (98%); however, this technique was the second highest ranked modification approach for NDMA removal because it scored lower for other evaluation criteria.

No description available.

No description available.

Kommerziell erhältliche Ionenaustauscher basieren häufig auf funktionalisierten Cellulosemembranen, die mit CerIV und Glycidylmethacrylat (GMA) gepfropft und anschließend sulfoniert werden.  Die Untersuchung dieser Polymerisation zeigte, dass während der Pfropfung eine Vernetzung des Polymers über die Epoxidfunktion des Monomers auftritt. Daher konnte keine direkte Analyse des entstandenen Hydrogels durchgeführt werden und es wurde stattdessen Methylmethacrylat (MMA) auf der Oberfläche polymerisiert. Nach Entwicklung eines geeigneten Verfahrens zur Zersetzung der Membranen und Isolierung des Pfropfpolymers konnte dieses mit Gel-Permeations-Chromatographie (GPC) analysiert werden. Zusätzlich wurden Polymerisationen auf nicht-porösem Cellophan durchgeführt und die erhaltenen Proben mittels Rasterkraftmikroskopie (Atomic Force Microscopy, AFM) untersucht.  Die Ergebnisse zeigen, dass das gepfropfte PMMA einen Polymerisationsgrad von 2100 und eine Dichte von 0,45 Ketten pro nm2 auf der Oberfläche hat. Wird die gleiche Anzahl an Polymeren auch für Pfropfung mit PGMA angenommen und mit dem Pfropfgrad verglichen, ergibt sich damit unter Vernachlässigung der Vernetzung ein Polymerisationsgrad von etwa 800. Es konnte gezeigt werden, dass die für die Pfropfung verwendete Emulsion unter anderem aus Tröpfchen besteht, deren Größe mit der der Poren der Membran übereinstimmt. Dennoch treten bei der Polymerisation keine Ausschlusseffekte auf und die Größenverteilung der Emulsionspartikel stellt sich auch nach Filtration zügig wieder ein. Zusätzlich wurde eine Methode der Atom-Transfer radikalischen Polymerisation (ATRP) auf mikroporösen Membranen entwickelt und eingesetzt, um gezielt bestimmte Eigenschaften des Hydrogels zu variieren. Bei Versuchen mit MMA wurde der reversibel deaktivierte Charakter unter den verwendeten Bedingungen untersucht und nachgewiesen.  Die verwendete Methode erlaubt, die Kettenanzahl und –länge separat voneinander einzustellen, sodass der Einfluss dieser Größen auf die Eigenschaften des resultierenden Membranadsorbers gezielt untersucht werden konnte. Es zeigte sich, dass die Dichte der Ketten einen komplexen Einfluss sowohl auf die Permeabilität als auch auf die Bindungskapazität des Ionentauschers hat. Der Einfluss der Kettenlänge ist dagegen weniger subtil und entspricht den Erwartungen.  Aus den gewonnenen Daten wurde ein Modell für die Bindung von Proteinen an der gepfropften Oberfläche des Austauschers entwickelt und daraus die Kettenlänge und –dichte des Hydrogels abgeschätzt und mit alternativen Methoden verglichen.

La pénurie d'eau est devenue un des problèmes clés à résoudre, et pour y faire face, il est nécessaire de disposer d'unités de traitement de l'eau efficaces. Au cours des dernières décennies la technologie des membranes est devenue l'une des techniques les plus prometteuses pour le traitement de l'eau. Néanmoins, les membranes ont une durée de vie limitée et sont, par ailleurs, sujettes à des phénomènes de colmatage - le dépôt, l'adsorption et l'absorption de particules dans la structure de la membrane -, ce qui réduit leur productivité, et augmente les coûts opérationnels. Une approche pour minimiser ce problème consiste à modifier des membranes hydrophobes, mécaniquement et chimiquement stables, en y greffant des matériaux amphiphiles afin de réduire le colmatage. L'objectif principal de ce travail est de caractériser les propriétés anti-colmatage des membranes de PVDF (Polyvinylidene fluoride) modifiées avec différents types de copolymères PS-PEGMA (Polystyrene - Poly(ethylene glycol) methacrylate), tout d'abord par l'utilisation de techniques classiques, puis, par le développement et / ou l'adaptation de techniques microfluidiques couplés à la microscopie à fluorescence et l'utilisation de la cartographie par microspectroscopie infrarouge à transformée de Fourier (IRTF). La cartographie IRTF a permis de quantifier localement le greffage et de mettre en évidence l'hétérogénéité du greffage sur la membrane. Ces cartes, représentant l'importance du greffage sur la membrane, ont par ailleurs été corrélées au dépôt de protéines sur la surface. Des systèmes microfluidiques ont également été développés pour caractériser sous microscope à fluorescence l'adsorption de protéines fluorescentes sur une membrane en présence d'un débit. Cette étude permet de suivre in situ et en dynamique l'adsorption (lors de cycles de filtration) et la désorption (lors de cycles de rinçage) de protéines sur la membrane. Ces mesures locales ont été mises en regard avec des mesures de permeabilité lors de cycles filtrations/rinçage mettant en évidence un rôle anti-fouling en particulier pour les copolymères tri-blocs ou pour les copolymères à enchaînement aléatoire. / Water scarcity has become one of the key issues to solve, and efficient water treatment is paramount to treat water sources. In recent decades membrane technology has become one of the promising solutions for water treatment. Nevertheless, membranes are prone to fouling phenomena - the deposition, adsorption, and absorption of particles in the membrane structure -, which hinders their life-span and productivity, and raise operative costs. One approach to minimize this issue is to modify the already mechanically and chemically stable hydrophobic membranes with amphiphilic materials. The main aim of this work is to characterise the anti-fouling properties of PVDF (Polyvinylidene fluoride) membranes modified with different types of PS-PEGMA (Polystyrene - Poly(ethylene glycol) methacrylate) copolymers, firstly by using classical techniques, and then, by developing and/or adapting new ones: microfluidic devices coupled with fluorescence microscopy, and the use of Fourier Transform Infrared microspectroscopy (FTIR mapping). FTIR mapping allowed the local detection of the coating layer and showed its heterogeneous distribution on the surface of the membrane. These maps, that represent the importance of the coating on the membrane, were correlated with the deposit of proteins on the surface. Microfluidic systems were also developed to characterise the adsorption of fluorescent proteins on the membrane under a fluorescent microscope in the presence of a flow. This study allowed the in-situ and dynamic follow-up of the adsorption - during filtration cycles - and of the desorption - during rinsing cycles - of the proteins on the membrane. These local measurements were compared against permeability measurements during the filtration/rinsing cycles evidencing the anti-fouling role of the copolymers used for the modification of the membranes, particularly for the triblock and random copolymers.

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.

Fresh water scarcity is an alarming issue for communities across the globe. The development of water recycling and reuse technologies has become crucial in expanding the limited water resources. Reverse osmosis (RO) is among the key processes that can treat wastewater to meet potable water reuse standards. Despite the advancements in RO membrane technologies, many challenges persist regarding the operation and maintenance of RO membranes, such as membrane fouling. Extensive research investigations have focused on developing RO membrane modifications to combat the decreased performance due to fouling. Polyethylenimine (PEI) is a promising polymer used for enhancing the anti-fouling properties of thin film composite (TFC) RO membranes. PEI, a positively charged polymer with high charge density, is commonly grafted on TFC RO membrane surfaces to produce smoother, more hydrophilic membranes to minimize fouling. However, little research is available on the optimal PEI placement within the composite RO membrane layers for enhancing antifouling properties. The current study aimed to investigate whether alternative positions within the membrane layers could yield better anti-fouling performance compared to incorporation PEI on the membrane surface. Unmodified (i.e., control) and PEI-modified TFC RO membranes were fabricated in the laboratory. The PEI-modified membranes were produced in two variations with regards to the position of PEI in the composite membrane layer. The first variation, named PEI-1, involved immersing the polysulfone (Psf) support layer of the membrane in an aqueous PEI solution, before the active polyamide (PA) layer was formed. The second variation, named PEI-2, consisted of immersing the fully formed TFC RO membrane in an aqueous PEI solution to incorporate PEI on the surface of the active PA layer. The PEI used in the study for membrane modification had branched configuration with molecular weight of 1200 g/mole. The laboratory-scale TFC RO membranes produced herein were characterized and tested for water flux, salt rejection, and fouling behavior. The water flux and salt rejection, commonly referred to as permselectivity, of all the membranes produced were evaluated in a crossflow filtration unit. On the other hand, the fouling tests were conducted in a dead-end membrane filtration unit because of operational limitations of the crossflow unit. The PEI-1 membrane produced a water flux of 18.7 LMH (L/m2hr) and a stable salt rejection of 82.1%. The PEI-2 membrane resulted in a water flux of 22.4 LMH and a salt rejection of 85.2%. These results indicate that incorporating PEI on the membrane PA active surface layer achieved better permselectivity compared to PEI-1, which is the membrane with PEI incorporated inside the structure (i.e., incorporated on the Psf support layer). However, both PEI-modified membranes exhibited lower permselectivity performance compared to the unmodified control membrane, which produced a water flux of 23.9 LMH and salt rejection of 88.2%. To test fouling of the unmodified and PEI modified RO membranes, bovine serum albumin (BSA) was chosen as a model foulant based on preliminary investigations conducted herein to compare BSA to sodium alginate. After the foulant was introduced in the feed, the unmodified membrane exhibited a 31.8% total fouling ratio, the decrease in flux from the foulant solution compared to running clean DI water. However, a 90.7% flux recovery ratio was achieved when a final DI water rinse was performed. The PEI-1 membrane had a 39.7% total fouling ratio and a 81.6% flux recovery ratio after rinsing with DI water. The PEI-2 membrane showed a 43.1% total fouling ratio as a result of BSA fouling and a 94% flux recovery ratio when rinsed with DI water at the end of the fouling test. Water contact angle (WCA) analysis confirmed that the PEI-2 membrane had the most hydrophilic surface (WCA 25.1°) compared to the control membrane (WCA 52.9°). The higher hydrophilicity of PEI-2 aligns with its higher flux recovery results, which indicated reduced membrane fouling. Furthermore, the PEI-2 membrane had a drastically lower WCA than those reported in the literature for PEI-modified membranes, which ranged from (63° – 80°). In conclusion, the increased flux recovery and surface hydrophilicity of the PEI-2 membrane indicated that the best anti-fouling performance would likely be obtained when PEI is grafted onto the surface of the active PA membrane surface. Future research is warranted to optimize the PEI-2 membrane by exploring the effect of PEI concentration, molecular weight, and structural configuration (i.e., branched versus linear), on anti-fouling performance of the membranes.

No description available.