• Proceedings of the Membrane Society of Korea Conference
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• 1998.06a
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• pp.135-153
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• 1998

Nanofiltration (NF) is a recently introduced term in membrane separation. In 1988, Eriksson was one of the first authors using the word 'nanofiltration' explicitly. Some years before, FilmTech started to use this term for their NF50 membrane which was supposed to be a very loose reverse osmosis membrane or a very tight ultrafiltration membrane. Since then, this term has been introduced to indicate a specific boundary of membrane technology in between ultrafiltration and reverse osmosis. The application fields of the NF membranes are very broad as follows: Demeneralizing water, Cleaning up contaminated groundwater, Ultrapure water production, Treatment of effleunts containing heavy metals, Offshore oil platforms, Yeast production, Pulp and paper mills, Textile production, Electroless copper plating, Cheese whey production, Cyclodextrin production, Lactose production. The earliest NF membrane was made by Cadotte et al, using piperazine and trimesoyl chloride as monomers for the formation of polyamide active layer of the composite type membrane. They coated very thin interfacially potymerized polyamide on the surface of the microporous polysulfone supports. The NF membrane exhibited low rejections for monovalent anions (chloride) and high rejections for bivalent anions (sulphate). This membrane was called NS300. Some of the earliest NF membranes, like the NF40 membrane of FilmTech, the NTR7250 of Nitto-Denko and the UTC20 and UTC60 of Toray, are formed by a comparable synthesis route as the NS300 membrane. Commercially available NF membranes nowadays are as follows: ASP35 (Advanced Membrane Technology), MPF21; MPF32 (Kiryat Weizmann), UTC20; UTC60; UTC70; UTC90 (Toray), CTA-LP; TFCS (Fluid Systems), NF45; NF70 (FilmTec), BQ01; MX07; HG01; HG19; SX01; SX10 (Osmonics), 8040-LSY-PVDI (Hydranautics), NF CA30; NF PES 10 (Hoechst), WFN0505 (Stork Friesland). The typical ones among the commercially available NF membranes are polyamide composite membrane consisting of interfacially polymerized polyamide active layer and microporous support. While showing high water fluxes and high rejections of multivalent ions and small organic molecules, these membranes have relatively low chemical stability. These membranes have low chlorine tolerance and are unstable in acid or base solution. This chemical instability is appearing to be a big obstacle for their applications. To improve the chemical stability, we have tried, in this study, to prepare chemically stable NF membranes from PVA. The ionomers and interfacially polymerized polyamide were used for the modification of'the PVA membranes. For the detail study of the active layer, homogeneous NF membranes made only from active layer materials were prepared and for the high performance, composite type NF membranes were prepared by coating the active layer materials on microporous polysulfone supports.

• Membrane Journal
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• v.28 no.2
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• pp.96-104
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• 2018

With the rapid increase in seawater desalination, the importance of boron rejection is rising. This study was conducted to investigate the effect of hydrophilic compounds on surface modification to maximize water flux and increase boron rejection. First, polyamide active layer was fabricated by interfacial polymerization of polysulfone ultrafiltration membrane with M-phenylenediamine (MPD) and trimesoyl chloride (TMC) to obtain Control polyamide membrane. Next, D-gluconic acid (DGCA) and D-gluconic acid sodium salt (DGCA-Na) were synthesized with glutaraldehyde (GA) and hydrochloric acid (HCl) by modifying the surface of Control polyamide membrane. XPS analysis was carried out for the surface analysis of the synthesized membrane, and it was confirmed that the reaction of surface with DGCA and DGCA-Na compounds was performed. Also, FE-SEM and AFM analysis were performed for morphology measurement, and polyamide active layer formation and surface roughness were confirmed. In the case of water flux, the membrane fabricated by the surface modification had a value of 10 GFD or less. However, the boron rejection of the membranes synthesized with DGCA and DGCA-Na compounds were 94.38% and 94.64%, respectively, which were 12.03 %p and 12.29 %p larger than the Control polyamide membrane, respectively.

• Membrane Journal
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• v.26 no.4
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• pp.281-290
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• 2016

Thin film composite (TFC) polyamide membranes were prepared on polysulfone (PSF) supports for forward osmosis (FO) applications. To understand the influence of polarity and porosity of support layer on the formation of polyamide structure and the final FO performance, clathochelate metal complex (MC) contained PSF supports were prepared via the phase inversion process from various PSF casting solutions containing 0.1-0.5 wt% of MC in dimethyl formamide (DMF) solvent (18 wt%). A crosslinked aromatic polyamide layer was then fabricated on top of each support to form a TFC membrane. For the porous PSF supports prepared with relatively low concentration casting solutions (12 wt%), the PET film was removed after phase inversion and crosslinked aromatic polyamide layer was then fabricated. The tested sample from PSF (18 wt%)/MC (0.5 wt%) casting solution presented outstanding FO performance, almost similar water flux (9.99 LMH) with lower reverse salt flux (RSF, 0.77 GMH) compared to commercial HTI FO membrane(10.97 LMH of flux and 2.2 GMH of RSF). By addition of MC in casting solution, the thickness of the active layer in FO membranes was reduced, however, the increased RSF value was obtained.

• Membrane and Water Treatment
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• v.3 no.3
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• pp.169-179
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• 2012

One of the major limitations in the use of commercial aromatic polyamide thin film composite (TFC) reverse osmosis (RO) membranes is to maintain high performance over a long period of operation, due to the sensitivity of polyamide (PA) skin layer to oxidizing agents, such as chlorine, even at very low concentrations in feed water. This article reports surface modification of a commercial TFC RO membrane (BW30-Dow Filmtec) by covering it with a thin film of poly(vinyl alcohol) (PVA) crosslinked with glutaraldehyde (GA) to improve its resistance to chlorine. Crosslinking reaction was carried out at 25 and $40^{\circ}C$ by using PVA 1.0 wt.% solutions at different GA/PVA mass ratio, namely 0.0022, 0.0043 and 0.013. Water swelling measurements indicated a maximum crosslinking density for PVA films prepared at $40^{\circ}C$ and GA/PVA 0.0043. ATR-FTIR and TGA analysis confirmed the reaction between GA and PVA. SEM images of the original and modified membranes were used to evaluate the surface coating. Chlorine resistance of original and modified membranes was evaluated by exposing it to an oxidant solution (NaClO 300 mg/L, NaCl 2,000 mg/L, pH 9.5) and measuring water permeability and salt rejection during more than 100 h period. The surface modification effectively was demonstrated by increasing the chlorine resistance of PA commercial membrane from 1,000 ppm.h to more than 15.000 ppm.h.

• Membrane and Water Treatment
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• v.9 no.4
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• pp.211-220
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• 2018

Incorporating nano-materials in thin-film composite (TFC) membranes has been considered to be an approach to achieve higher membrane performance in various water treatment processes. This study investigated the rejection efficiency of three target compounds, i.e., reserpine, norfloxacin and tetracycline hydrochloride, by TFC membranes with different graphene oxide proportions. Graphene oxide (GO) was incorporated into the polyamide active layer of a TFC membrane via an interfacial polymerization (IP) reaction. The TFC membranes were characterized with FTIR, FE-SEM, AFM; in addition, the water contact angle measurements as well as the permeation and separation performance were evaluated. The prepared GO-TFC membranes exhibited a much higher flux ($3.11{\pm}0.04L/m2{\cdot}h{\cdot}bar$) than the pristine TFC membranes ($2.12{\pm}0.05L/m2{\cdot}h{\cdot}bar$) without sacrificing their foulant rejection abilities. At the same time, the GO-modified membrane appeared to be less sensitive to pH changes than the pure TFC membrane. A significant improvement in the anti-fouling property of the membrane was observed, which was ascribed to the favorable change in the membrane's hydrophilicity, surface morphology and surface charge through the addition of an appropriate amount of GO. This study predominantly improved the understanding of the different PA/GO membranes and outlined improved industrial applications of such membranes in the future.

• Membrane Journal
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• v.23 no.3
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• pp.251-256
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• 2013

In this study, acetylated methyl cellulose (AMC) was successfully used as a support layer of thin film composite (TFC) forward osmosis (FO) membrane. A selective polyamide active layer, interfacially polymerized, was coated on top of various substrate layers. The structure and performance of the TFC FO membrane based on the AMC substrate were compared with those of TFC FO membranes with different polymeric support layers. The experimental results showed that the AMC FO membrane performance was better than other FO membranes due to its characteristic morphology and lower back diffusion rate of salts.

• Membrane Journal
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• v.31 no.1
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• pp.16-34
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• 2021

Water supplies are decreasing in comparison to increasing clean water demands. Using nanofiltration is one of the most effective and economical methods to meet the need for clean water. Common methods for desalination are reverse osmosis and nanofiltration. However, pristine membranes lack the essential features which are, stability, economic efficiency, antibacterial and antifouling performances. To enhance the properties of the pristine membranes, graphene oxide (GO) is a promising and widely researched material for thin film composites (TFC) membrane due to their characteristics that help improve the hydrophilicity and anti-fouling properties. Modification of the membrane can be done on different layers. The thin film composite membranes are composed of three different layers, the top filtering active thin polyamide (PA) layer, supporting porous layer, and supporting fabric. Forward osmosis (FO) process is yet another energy efficient desalination process, but its efficiency is affected due to biofouling. Incorporation of GO enhance antibacterial properties leading to reduction of biofilm formation on the membrane surface. Pressure retarded osmosis (PRO) is an excellent process to generate clean energy from sea water and the biofouling of membrane is reduced by introduction of GO into the active layer of the TFC membrane. Different modifications on the membranes are being researched, each modification with its own advantages and disadvantages. In this review, modifications of nanofiltration membranes and their composites, characterization, and performances are discussed.

• Membrane Journal
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• v.8 no.1
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• pp.29-41
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• 1998

Thin-film composite reverse osmosis membranes of aromatic polyamides were prepared by the interfacial polymerization. Aromatic polyamides as active skin layer were made from the interfacial polymerization of MPD(m-phenylene diamine) in the aqueous and TMC(trimesoyl chloride) in HCFC(1,1-dichloro-1-fluoroethane) organic solvent. The performances of the various reverse osmosis composite membranes prepared by changing processing variables were examined. The performance of membrane manufactured by batch system was varied with organic solvent, monomer concentration, dipping time, heat treatment temperature, acid acceptor, ethanol post treatment, and acid post treatment. Ethanol post treatment was the most dominant factors in increasing permeate amount, while the monomer concentration and dipping time were the main factors in increasing selectivity. The spiral-wound module was produced with the membrane prepared at optimum condition of the continuous process. Comparing the performance of this membrane module made here with that of commercial membrane module, the permeate flux was increased by 33% while the rejection was decreased by 5%.

• Membrane Journal
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• v.28 no.3
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• pp.169-179
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• 2018

The purposes of this paper were to improve both fouling and chlorine resistance by increasing the hydrophilicity of the reverse osmosis membrane. In order to improve chlorine resistance, the surface of RO membrane was activated by ultraviolet irradiation, and then it was modified by the sol-gel method using Octyltriethoxysilane (OcTES) such as the silane coupling agent to low sensitivity to chlorine, thereby the polyamide active layer was protected and chlorine resistance was improved. In addition, polyglycerol polyglycidyl ether (PGPE) and sorbitol polyglycidyl ether (SPE) coating with different number of epoxides, ring opening reaction of epoxide improved the anti-fouling resistance. The surface modification condition was optimized by FT-IR, XPS, and contact angle analysis. As a result, the permeability reduction rate of the silane-epoxy modified membrane after the fouling test was decreased about 1.5 times as compared with that of the commercial membrane. And the salt rejection was maintained over 90% at $20,000ppm{\times}hr$ even after chlorine resistance test.