京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22464号 / 工博第4725号 / 新制||工||1738(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 梅田 眞郷, 教授 水落 憲和, 准教授 菅瀬 謙治 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Membranes are a robust, reliable and economical technology. However, polymeric membranes are manufactured from polymeric and organic solvent sources derived from petrochemical sources. The high volatile organic compounds (VOC) emissions of the organic solvents and the non-recyclability of the polymers often question the membrane manufacture sustainability. The main goal of this dissertation is the preparation of polymeric membranes for liquid separation through more sustainable processes. We report here the green preparations of hollow fibers, thin-film composite and integrally skinned asymmetric membranes. An important part of the work is represented by the development of cellulose hollow fibers from ionic liquid solutions, avoiding strong alkali or harsh solvents. By tuning the manufacturing process, we prove that the membranes can be used for different applications such as oil-water separation, protein separation via ion-exchange chromatography and solvent purification via organic solvent nanofiltration. The main advantages of using cellulose to prepare hollow fiber membranes are the biodegradability of the polymer and the intrinsic chemical stability. Another significant milestone of this work is replacing volatile solvents such as hexane during the thin-film composite membrane manufacture. As green alternative solvents, we decided to use naturally extracted oleic acid and decanoic acid. Due to their low costs and volatility, they represent a valid alternative for industrial membrane preparation through the interfacial polymerization process. The membranes prepared with this process were used for solvent resistant nanofiltration. Finally, by using ionic liquids as solvents, we improved the manufacturing sustainability polytriazole asymmetric membranes synthesized in the lab.

It goes without saying that water scarcity is a widespread and increasingly pressing global challenge. One of the methods which can mitigate water shortage is to increase freshwater production via desalination of saline waters. Seawater and saline aquifer sources represent 97.5% of all water on Earth. Hence, treating even a small portion of saline water could significantly reduce water shortage. Although reverse osmosis is one of the state-of-the-art pressure-driven membrane desalination technologies, it is incapable of desalinating high-salinity streams due to the very high osmotic pressure to overcome. Membrane distillation (MD) is one of the emerging methods, which has attracted much attention for desalinating highly saline brines. MD is a thermally driven process in which only vapor molecules pass through the pores of a microporous hydrophobic membrane. This process, however, has not been fully commercialized due to a number of challenges, including “pore wetting”. Pore wetting refers to the presence of liquid, instead of just water vapor, inside the membrane pores, which may cause a decrease in MD flux and/or deterioration of distillate quality. Herein, a comprehensive review on pore wetting is presented, and then this phenomenon is investigated from four aspects. In the first phase of this project, a theoretical model is presented according to which the pore size distribution of membrane, a parameter affecting pore wetting risk, is estimated by employing only a few experimental data points in accordance with the wet/dry method, reducing the number of data required to be recorded largely. In the next phase, an equation is presented for the estimation of liquid entry pressure (LEP), a membrane parameter closely related to pore wetting, using computational fluid dynamics (CFD) tools and genetic programming (GP) as an intelligent technique. This equation can estimate LEP in closer agreement to experimental values in comparison to the Young-Laplace equation. In the third phase, movement of liquid-gas interface inside the membrane pore is tracked using a well-founded model, and consequently, the pressure and velocity at the interface and the required time for replacement are studied. Finally, in the last phase, a model is developed for pore wetting in vacuum MD, considering heat and mass balances at the vapor-liquid interface. This model assumes that heat only enters the pore inlet and is removed due to liquid vaporization at the vapor-liquid interface, with heat transfer through the pore wall neglected. This model shows that partial pore wetting is possible since the vapor-liquid interface might remain within the pore at the steady-state condition. Further, this model can predict the decrease in temperature from the pore inlet to the vapor-liquid interface, a phenomenon that has been reported in the literature without any proof.

The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated reversible-deactivation radical polymerization. Finally, phase inversion membranes were prepared from polytriazole-polysulfone random copolymers, which were obtained by “clicking” 1,2,3-triazole ring substituents bearing OH groups onto the polysulfone backbone via copperI-catalyzed azide-alkyne cycloaddition. The increased hydrophilicity of membranes imparted the higher water permeability and fouling resistance to the ultrafiltration membranes. Polytriazole-b-polysulfone-b-polytriazole triblock copolymer was synthesized by RAFT and post-polymerization click modification. Hydrogen bond-mediated self-assembly induced the formation of a nanostructured polytriazole-b-polysulfone-b-polytriazole / poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) blend membrane with a 1: 1 stoichiometric ratio of triazole and acid. String-like fused micelles with polytriazole/poly(acrylic acid) corona were present on the membrane surface, after immersion in a coagulation bath of copper2+ aqueous solution.

Water scarcity is a serious global issue, due to the increasing population and developing economy, and membrane technology is an essential way to address this problem. Forward osmosis (FO) is an emerging membrane process, due to its low energy consumption (not considering the draw solute regeneration). A bottleneck to advance this technology is the design of the support layer for FO membranes to minimize the internal concentration polarization. In this dissertation, we focus on the structural study and modification of the support layer for FO membranes. Firstly, we digitally reconstruct different membrane morphologies in 3D and propose a method for predicting performance in ultrafiltration operations. Membranes with analogous morphologies are later used as substrate for FO membranes. Secondly, we experimentally apply substrates with different potentially suitable morphologies as an FO support layer. We investigate their FO performance after generating a selective polyamide layer on the top, by interfacial polymerization. Among the different substrates we include standard asymmetric porous membranes prepared from homopolymers, such as polysulfone. Additionally block copolymer membrane and Anodisc alumina membrane are chosen based on their exceptional structures, with cylindrical pores at least in part. 3D digitally reconstructed porous substrates, analogous to those investigated for ultrafiltration, are then used to model the performance in FO operation. Finally, we analyze the effect of intermediate layers between the porous substrate and the interfacial polymerized layer. We investigate two materials including chitosan and hydrogel. The main results are the following. Pore-scale modeling for digital membrane generation effectively predicts the velocity profile in different layers of the membrane and the performance in UF experiments. Flow simulations confirm the advantage of finger-like substrates over sponge-like ones, when high water permeance is sought. Cylindrical pores are advantageous for mass transfer. Block copolymer substrates have cylindrical pores in the top layer and very regular pore pattern at the surface. The Anodisc alumina membrane has cylindrical pores from top to bottom. Both substrates were experimentally tested for FO application successfully. A Darcy permeability higher than 1E-20 m2 for the intermediate layer would be necessary in order to facilitate the water flow.

In this work polymeric materials were developed to be used as a solvent and heat resistance membrane for different applications. In ultrafiltration, poly (ether imide sulfone) membranes were manufactured by combining phase inversion and functionalization reaction between epoxy groups and amine modified polyether oligomers (Jeffamine®). Polysilsesquioxanes or oligo silsesquioxanes containing epoxy functionalities were in-situ grown in the casting solution and made available for further reaction with amines in the coagulation/annealing baths. Water permeances up to 1500 l m-2 h-1 bar-1 were obtained with sharp pore size distribution and a pore diameter peak at 66 nm, confirmed by porosimetry, allowing 99.2 % rejection of γ-globulin. The membranes were stable in 50:50 dimethylformamide/water, 50:50 N-methyl pyrrolidone/water and 100 % tetrahydrofuran. In pervaporation, Novel hydrophobic Hyflon®/Extem® and Hyflon®/PVDF were developed and investigated for ethylene glycol dehydration and n-butanol dehydration respectively. For ethylene glycol different Extem® concentrations were evaluated with regard to both flux and amount of water in the permeate side. Eighteen (18) wt% gave more than 90 wt% water in the permeate. Increasing feed temperature from 25 to 85°C increased the water flux from 31 to 91 g m-2 h-1 when using 5 wt% water in ethylene glycol as feed. The water flux of 40 wt% water:ethylene glycol at 45°C was found to be 350 g m-2 h-1. And for n-butanol dehydration the coating protocols for thin defect-free Hyflon® selective layer on the PVDF support was optimized. Water and n-butanol transport was measured, analyzing the effect of operating conditions. The water flux through the newly developed membranes was higher than 150 g m-2 h-1 with selectivity for water higher than 99 wt%. The membrane application can be extended to other solvents, supporting an effective and simple method for dehydration with hydrophobic membranes. In membrane distillation, PVDF and Extem® membranes before and after coating with Hyflon® were examined for ionic liquid dehydration on 23.6 mS cm-1 feed concentration. Different feed temperatures and flow rates were evaluated for flux as well as rejection. High flux was obtained at 70°C and increased at high flow rate from 2 Kg m2 h to 10 Kg m2 h.

The use of low-pressure membranes, mainly ultrafiltration (UF), has emerged in the last decade and began to show acceptance as a novel pretreatment process for seawater reverse osmosis (SWRO) desalination. This is mainly due to the superior water quality provided by these membranes, in addition to reduction in chemicals consumption compared to conventional methods. However, membrane fouling remains the main drawback of this technology. Therefore, frequent cleaning of these membranes is required to maintain water flux and its quality. Usually, after a series of backwash using UF permeate chemical cleaning is required under some conditions to fully recover the operating flux. Frequent chemical cleaning will probably decrease the life time of the membrane, increase costs, and will have some effects on the environment. The new cleaning method proposed in this study consists of using a solution saturated with carbon dioxide (CO2) to clean UF membranes. Under the drop in pressure, this solution will become in a supersaturated state and bubbles will start to nucleate on the surface of the membrane and its pores from this solution resulting in the removal of the fouling material deposited on the membrane. Different compositions of fouling solutions including the use of organic compounds such as sodium alginate and colloidal 5 silica with different concentrations were studied using synthetic seawater with different concentrations. This cleaning method was then compared to the backwash using Milli-Q water and showed an improved performance compared to it. An operational modification to this cleaning technique was then investigated which includs a series of sudden pressure drop during the backwash process. This enhanced technique showed an even better performance in cleaning the membrane, especially at severe fouling conditions. In most cases, the membrane permeability was fully recovered even at harsh conditions where conventional backwash failed to maintain a stable operation. Therefore, the new cleaning method might provide an efficient and environmentally friendly alternative cleaning technique to low-pressure membranes technology in the future.

No description available.

The basic of this work is the construction realization of membrane vacuum press, mark out for shaping thermoplastics by force of membrane. Specially designate for material Twintex. The work deals with the general conception and form this machines. Movement material in machine to the warm up parts and after it to moulding.

archives@tulane.edu / Gram-negative bacteria secrete outer membrane vesicles (OMVs) that play critical roles in intraspecies, interspecies, and bacteria-environment interactions. Some OMVs, such as those produced by Pseudomonas aeruginosa, have previously been shown to possess antimicrobial activity against competitor species. In the current work, we demonstrate that OMVs from Burkholderia thailandensis inhibit the growth of drug-sensitive and drug-resistant bacteria and fungi and exhibit antibiofilm activity against methicillin-resistant S. aureus (MRSA) and Streptococcus mutans. We show that a number of compounds, including peptidoglycan hydrolases, 4-hydroxy-3-methyl-2-(2-non-enyl)-quinoline (HMNQ) and long-chain rhamnolipid present in B. thailandensis OMVs exert antimicrobial activity. Furthermore, we demonstrate that HMNQ and rhamnolipid possess antimicrobial and antibiofilm properties against various microbes. Rhamnolipid is superior at reducing the integrity of biofilms while HMNQ displays greater bactericidal activity. We attempted to use HMNQ and rhamnolipid to combat MRSA and promote wound healing in a murine full-thickness wound model. However, further optimization of the model and characterization of the molecules in antimicrobial efficacy, wound healing, and host immune responses are required. Overall, this work indicates that B. thailandensis secretes antimicrobial OMVs that may impart a survival advantage by eliminating competition. In addition, bacterial OMVs may represent an untapped resource of novel therapeutics effective against biofilm-forming and multidrug-resistant organisms. / 1 / Yihui Wang