Interfacially polymerized thin-film composite membrane on UV-induced surface hydrophilic-modified polypropylene support for nanofiltration

A novel thin-film composite (TFC) nanofiltration membrane was prepared through interfacial polymerization on surface hydrophilic-modified polypropylene (PP) membrane. Firstly, PP membranes were hydrophilized to ensure the formation of separation layer on it by interfacial polymerization. In this work, the UV-induced grafting of acrylic acid (AAc) was applied to modify the surface of PP membranes. Secondly, the TFC membranes were fabricated on PP membranes with different grafting degrees of AAc via interfacial polymerization. Effects of the UV-induced graft polymerization conditions, such as benzophenone concentration, monomer concentration and UV irradiation time, were systematically investigated. The surface-modified PP membranes and the TFC membranes were characterized with water contact angle measurement, attenuated total reflectance infrared and scanning electron microscopy. Furthermore, the permeation experiments were employed to evaluate the membranes’ nanofiltration performance.     

3,5-二氧基苯甲酰哌嗪和均苯三甲酰氯界面聚合法制备复合纳滤膜

A new aromatic diamine,3,5-diaminobenzoylpiperazine (3,5-DABP),was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3,5-DABP as aqueous monomer and trimesoyl chloride (TMC) as organic monomer,thin film composite (TFC) nanofiltration membranes were prepared by interfacial polymerization technology.The salt rejection order of these TFC membranes is Na2SO4>MgSO4>MgCl2>NaCl.This sequence indicates that the membranes are negatively charged.     

Thin-film composite membranes for organophilic nanofiltration based on photo-cross-linkable polyimide

This work demonstrates that it is possible to prepare new, competitive thin-film composite (TFC) membranes with a polyolefin ultrafiltration membrane as support and with a non-porous photo-cross-linked polyimide as separation layer for organic solvent nanofiltration. The commercial polyimide Lenzing P84® was modified by a polymer-analogous reaction to introduce side groups with carbon–carbon double bonds to increase its photo-reactivity with respect to cross-linking. Polymer characterization revealed that this was successfully achieved at acceptable level of main chain scission. The higher reactivity of the photo-cross-linkable polyimide had been confirmed by comparison with the original polymer; i.e., shorter gelation times upon UV irradiation, higher suppression of swelling by solvents and complete stability in strong solvents for not cross-linked polyimide such as dimethylformamide (DMF) had been obtained. For films from unmodified and modified polyimide, the degree of swelling in various solvents could be adjusted by UV irradiation time. Photo-cross-linking of the original polyimide did not lead to stability in DMF. TFC membranes had been prepared by polymer solution casting on a polyethylene ultrafiltration membrane, UV irradiation of the liquid film and subsequent solvent evaporation. Polyimide barrier film thicknesses between 10 and 1 μm were obtained by variation of cast film thickness. Performance in organic solvent nanofiltration was analyzed by using hexane, toluene, isopropanol and DMF as well as two dyes with molar masses of ∼300 and ∼1000 g/mol. Permeances of TFC membranes from unmodified polyimide were low (<0.1 L/hm² bar) while rejections of up to 100% for the dye with ∼1000 g/mol could be achieved. TFC membranes from modified and photo-cross-linked polyimide had adjustable separation performance in DMF with a trade-off between permeance and selectivity, in the same range (e.g.: 0.3 L/hm² bar and 97% rejection for the dye with ∼1000 g/mol) as a commercial conventional polyimide membrane tested in parallel. The established membrane preparation method is promising because by tuning the degree of cross-linking of the polymeric barrier layer, the membrane separation performance could be tailored within the same manufacturing process.     

Interfacially polymerized thin film nanofiltration membranes on TiO2 coated polysulfone substrate

In this study, a new approach was developed to prepare the novel thin film composite nanofiltration membranes. In this new approach, nanoparticles were coated completely under the polymeric thin film layer. Thin film composite (TFC) membranes were fabricated by interfacial polymerization on polysulfone (PSf) sublayer using m-phenylenediamine (MPD) and trimesoyl chloride (TMC) respectively as amine monomer and acid chloride monomer. Scanning electron microscopy and atomic force microscopy were used to study surface morphology and roughness properties of NF membranes. Energy dispersive X-ray microanalysis (EDX) was used to analyze the elemental change before and after filtration experiment. Chemical structure and thickness of polyamide formed on TFC membranes were observed by Fourier transmission infrared attenuated total reflectance (FTIR-ATR) spectroscopy. Permeability, salt rejection and pepsin macromolecule rejection of prepared membranes were tested using dead end filtration cell. Antifouling behavior of the membranes was studied by filtering pure water before and after pepsin solution filtration. A smoother and thicker surface without any defect appeared as the concentration of nanoparticle was increased. NaCl rejection was increased from 70% for neat nanofiltration membrane to 84% for 0.5 wt% TiO₂ modified nanofiltration membrane. Antifouling and permeability behavior of the prepared membranes were improved in the new approach. Antibacterial property of prepared membranes was improved as a result of photocatalytic characteristic of TiO₂ nanoparticles.     

Preparation and characterization of polyzwitterionic hydrogel coated polyamide-based mixed matrix membrane for heavy metal ions removal

A novel polyzwitterionic hydrogel coated mixed matrix membrane (MMM) was successfully prepared, characterized and used for Cu²⁺, Mn²⁺, and Pb²⁺ heavy metal ions removal from water. Hydrophilic and porous covalent organic framework (COF) nanoparticles (NP) as filler were synthesized from melamine and terephthalaldehyde, and then incorporated into polyamide (PA) thin film composite (TFC) membrane. The hydrogel coating was applied by using a tailored cross-linkable polymer system in combination with concentration polarization enabled cross-linking. The effects of COF NP loading into PA layer and polyzwitterionic hydrogel coating on the membrane morphology and separation performance were studied using different analyses. The MMM prepared with a COF NP loading of 0.02 wt/wt% in the hexane dispersion used for NP deposition during PA layer formation (leading to 0.42 g/m²) exhibited an increased pure water permeability of around 200% compared with the neat PA TFC membrane while the Mn²⁺ ion rejection maintained above 98%. Scanning electron microscopy surface images and zeta potential profiles showed that the hydrogel was successfully deposited on the membrane surface. Furthermore, the hydrogel coating could decrease net surface charge of membranes but did not significantly influence the heavy metal ions rejections under nanofiltration conditions. The results of filtration experiment with protein solution indicated that the hydrogel coated membranes exhibited superior antifouling property, as shown by higher flux recovery ratio after washing with water, compared with neat PA TFC membrane and not coated MMM, respectively.     

Separation performance of thin-film composite nanofiltration membrane through interfacial polymerization using different amine monomers

Four kinds of thin-film composite (TFC) membranes were prepared via interfacial polymerization using diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and piperazidine (PIP) as water-soluble monomer, and trimesoyl chloride (TMC) as organic-soluble monomer. The surface chemical features of the resultant membranes were confirmed by contact angle measurement and Fourier transform infrared spectroscopy (FTIR). The membrane morphology and surface charges were investigated through Scanning electronic microscopy (SEM) and Zeta potential, respectively. Salt rejection was used to evaluate the separation performance of the four kinds of TFC membranes. The results showed that all the four kinds of TFC membranes exhibited typical negatively charged nanofiltration membrane characteristics. The salt rejections followed the sequence: Na₂SO₄ > MgSO₄ > MgCl₂ and the rejection of Na₂SO₄ was all over 80%. It was also found that the solubility of water-soluble monomer in organic solvent played an important role in manipulating the membrane structure, charge properties and thus the separation performance.     

Highly improved permeation property of thin-film-composite polyamide membrane for water desalination

Thin-film-composite (TFC) polyamide membranes with flux-enhancement were prepared by the interfacial polymerization of m-phenylenediamine with trimesoyl chloride on porous polysulfone support. The addition of 1,3-propanesultone (PS) in the organic phase is used to influence the interfacial polymerization process and the morphology of polyamide layer to improve water flux. FTIR, ¹H NMR and UV spectra were performed to investigate the effect of PS on interfacial polymerization process. In order to study the forming mechanism of TFC membrane, the resulting TFC membranes were characterized by SEM, AFM, ATR-FTIR, XPS, as well as static contact angle. In comparison with conventional polyamide membrane, the TFC membranes fabricated with PS as the additive exhibit much more improved water flux without NaCl rejection decreasing. Notably, the optimal TFC membrane with 0.04% (wt/v) PS as the additive in organic phase shows the best performance with a NaCl rejection of 99.39% and a water flux of 48.57 L m^?2 h^?1 at 1.55 MPa, which has increased 41% compared to the value of the conventional TFC membrane.     

Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite-based carbon material for desalination

The properties of polyamide (PA) thin film composite (TFC) membranes are affected by many variables, especially the additives in the process of interfacial polymerization that play an important role in the properties of membranes. In this study, a new type graphite carbon was added into organic phase containing trimesoyl chloride for interfacial polymerization with aqueous phase containing m-phenylenediamine to prepare modified polyamide thin film nanocomposite (TFN) membranes for reverse osmosis (RO) adhibition. Polysulfone ultrafiltration membranes were used as the carrier of the interfacial polymerization. The concentration of graphite carbon was selected from 0.002 to 0.01 wt%. The polyamide nanocomposite membrane prepared with the concentration of 0.004 wt% graphite carbon showed the best RO desalination performance, which the water flux of this TFN membrane is over 2.3 times as much as pristine TFC membrane, and the salt rejection is over 99%. This article provides a well-performing polyamide thin film nanocomposite membrane modified by a new-type carbon nanoparticles consequently.     

Nanofiltration thin-film composite membrane on either the internal or the external surface of a polysulfone hollow fiber

The inner and outer surfaces of a porous hollow fiber polysulfone support are compared as substrates for the synthesis of polyamide thin-film composite (TFC) membranes by interfacial polymerization. While both surfaces have pores common of microfiltration membranes, the inner surface has a larger pore diameter than the outer surface (2,700 nm compared to 950 nm). The inner TFC membrane showed higher water nanofiltration permeance than the outer (2.20 ± 0.17 compared to 0.13 ± 0.03 L m⁻² hr⁻¹ bar⁻¹). This was due to the influence of the porosity and roughness, which were different on both support surfaces. These membranes are interesting because they were synthesized in a hollow fiber support with a high membrane area per volume unit (~6,900 m²/m³) and the substrate used was commercial, which means that the TFC membrane obtained is suitable for industrial application. A mathematical simulation of the nanofiltration run with COMSOL Multiphysics 5.3 software confirmed the experimental trends observed.     

Preparation,characterization, and application of thin film composite nanofiltration membranes

The active aromatic polyamide layers of thin film composite nanofiltration (NF‐TFC) membranes were prepared via interfacial polymerization (IP) from three different types of polyamine: p‐phenylenediamine (PPD), m‐phenylenediamine (MPD), or piperazine (PRP), and trimesoyl chloride (TMC) on polysulfone/sulfonated polysulfone (PSf/SPSf) alloy substrates. Chemical components, cross section structures, and thermal properties of the polyamide active layers and the bulk membranes, characterized by Fourier transfer IR spectroscopy and attenuated total reflection IR spectroscopy, scanning electron microscopy, and differential scanning calorimetry and thermogravimetry, respectively, revealed an interpenetrating layer between the polyamide active layer and the substrate. A ridge–valley structural active layer was formed on the PSf/SPSf substrate for the NF‐TFC membrane with a thick polyacrylamide (PA) layer. Compared with the NF‐TFC membranes on PSf substrates, those on PSf/SPSf alloy substrates had a higher permeability without losing the selectivity by introducing the hydrophilic SPSf into the hydrophobic PSf substrates. The binding between the modified substrate and the active PA layer was also improved. Good separation performances using these NF‐TFC membranes were obtained in the polyvalent ion separation, the ground water softening, and the treatment of wastewater from adipic acid plants in a wide pH range. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1251–1261, 2005     

A thin film composite membrane supported by a hydrophilic poly(vinyl alcohol‐co‐ethylene) nanofiber membrane: Preparation,characterization, and application in nanofiltration

In this study, a fabricated hydrophilic poly(vinyl alcohol‐co‐ethylene) (PVA‐co‐PE) nanofiber membrane was used as the middle support layer to prepare thin film composite (TFC) membranes for nanofiltration. The effects of the supporting nonwoven layer, grams per square meter (GSM) of nanofiber, reaction time, heat treatment, monomer concentration, operating pressure, and pH value on the separation performance of the TFC membranes were analyzed. These results show that the TFC membranes prepared with the PVA‐co‐PE nanofiber membrane can be used to filtrate different metal ions. For NaCl, Na₂SO₄, CaCl₂, CuCl₂, CuSO₄, and methyl orange solutions, the rejection rates of the TFC membrane with nonwoven polyester as the supporting layer and a nanofiber GSM of 12.8 g/m² are 87.9%, 93.4%, 92.0%, 93.1%, 95.8%, and 100%, respectively. This indicates the potential application of the PVA‐co‐PE nanofiber membrane in the preparation of nanofiltration and reverse‐osmosis TFC membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46261.     

耐溶剂复合纳滤膜的研究进展

耐溶剂纳滤是一种新型的膜分离技术,用于有机混合物的分离。商品耐溶剂纳滤膜大多是采用相转化法制备的整体皮层非对称膜,膜皮层较厚,通量较低。耐溶剂复合纳滤膜由基膜和分离层组成,具有薄皮层、高溶剂通量和高溶质截留率的优点。耐溶剂复合纳滤膜的制备与改性也因此成为近年来的研究热点。本文从界面聚合、表面涂覆、层层自组装、原位生长、有机-无机杂化和表面改性六个方面介绍耐溶剂复合纳滤膜的研究进展,最后对其发展前景进行展望。     

Polyamide composite membranes for enhanced organic solvent nanofiltration performance by metal ions assisted interfacial polymerization method

Herein, thin-film composite membranes consisting of poly(m-phenyleneisophthalamide) substrate and polyamide active layer were constructed by transition metal ion-assisted interfacial polymerization method. As compared to the traditional polyamide membranes, a much thinner polyamide layer (33 vs. 200 nm) can be synthesized with higher permeance (3.2 vs. 0.62 L m⁻² h⁻¹ bar⁻¹) in the organic solvent nanofiltration. Similarly, the prepared membranes maintained a high rejection (>99%) for various dyes. Optimal membranes prepared by using Co²⁺ exhibited strong tolerance to various organic solvents with good long-term stability. Positron annihilation spectroscopy and other characterization methods were used to investigate the relationships between the membrane microstructures and the enhanced separation performance. Based on molecular dynamics simulation, it was found that the diffusion coefficient of polyethyleneimine monomer decreased by about 18 times after adding Co²⁺ to the aqueous solution (forming coordination interaction). This procedure has great potential and sustainability for practical organic solvent nanofiltration applications.     

Codeposition of catechol–polyethyleneimine followed by interfacial polymerization for nanofiltration membranes with enhanced stability

Thin‐film composite (TFC) nanofiltration (NF) membranes were fabricated via the codeposition of catechol (CCh) and polyethyleneimine (PEI) followed by subsequent interfacial polymerization with trimesoyl chloride (TMC) on the surface of polysulfone ultrafiltration substrates. The detailed structures and surface properties were characterized by X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, ζ potential analysis, and water contact angle measurement. The surface properties, including the roughness, hydrophilicity, surface potential, and NF performances, were facilely tuned through variation of the codeposition time of CCh–PEI for the prepared TFC membranes. The optimized membrane achieved a high rejection (ca. 93%) of MgCl₂ with a flux of around 31 L m^?2 h^?1 under 0.7 MPa. The results also reveal that the codeposition process endowed the final membranes with much better structural stability in alcohol and improved chlorine resistance compared to commonly interfacial polymerized ones with PEI and TMC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45422.     

氨基化氧化石墨烯界面聚合制备超薄复合纳滤膜

采用氨基化氧化石墨烯（NGO）为界面聚合水相单体,制备了超薄复合纳滤膜。研究采用傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、原子力显微镜（AFM）表征了NGO以及复合纳滤膜的化学组成和形貌。系统考察了水相单体浓度、有机相单体浓度对于制备的超薄复合纳滤膜性能的影响。该超薄复合膜在低压（0.2 MPa）下纯水通量可达27.8 L·m^-2·h^-1,对小分子染料有较高的截留率（甲基橙截留率74.8%,橙黄钠截留率96.0%,刚果红截留率98.5%,甲基蓝截留率99%）,对于无机盐的截留率较低（Na₂SO₄截留率21.4%,MgSO₄截留率10.7%,NaCl截留率5.3%,MgCl₂截留率1.5%）,展现出优异的染料/盐分离性能。同时制备的复合纳滤膜展现了较好的长周期稳定性以及抗污染特性。     

Thin film composite membranes with desirable support layer for MeOH/MTBE pervaporation

A comprehensive study was performed on a new application of thin film composite membranes and selecting a stable sublayer for them as pervaporation membranes in organic solvent separation. For this purpose, four different polymeric sublayers of polyethersulfone (PES), cellulose acetate, polyacrylonitrile, and polyetherimide were prepared, and the interaction of methanol (MeOH) and methyl tert butyl ether (MTBE) with them was investigated. The contact angle results, scanning electron microscopy images, and swelling and mechanical strength measurements obviously displayed the effect of immersion in organic solvents on the sublayers. Finally, a polyamide active layer was subsequently deposited on the PES membrane surface as the stable sublayer via interfacial polymerization based on a multistep statistical optimization strategy involving fractional factorial design and a response surface method. The prepared TFC membranes were tested in the pervaporation of a MeOH/MTBE mixture and exhibited excellent performance compared with the current membranes in this context. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47519.     

Engineering design of outer‐selective tribore hollow fiber membranes for forward osmosis and oil‐water separation

Outer‐selective thin‐film composite (TFC) hollow fiber membranes offer advantages like less fiber blockage in the feed stream and high packing density for industrial applications. However, outer‐selective TFC hollow fiber membranes are rarely commercially available due to the lack of effective ways to remove residual reactants from fiber's outer surface during interfacial polymerization and form a defect‐free polyamide film. A new simplified method to fabricate outer‐selective TFC membranes on tribore hollow fiber substrates is reported. Mechanically robust tribore hollow fiber substrates containing three circular‐sector channels were first prepared by spinning a P84/ethylene glycol mixed dope solution with delayed demixing at the fiber lumen. The thin wall tribore hollow fibers have a large pure water permeability up to 300 L m^?2 h^?1 bar^?1. Outer‐selective TFC tribore hollow fiber membranes were then fabricated by interfacial polymerization with the aid of vacuum sucking to ensure the TFC layer well‐attached to the substrate. Under forward osmosis studies, the TFC tribore hollow fiber membrane exhibits a good water flux and a small flux difference between active‐to‐draw (i.e., the active layer facing the draw solution) and active‐to‐feed (i.e., the active layer facing the feed solution) modes due to the small internal concentration polarization. A hyperbranched polyglycerol was further grafted on top of the newly developed TFC tribore hollow fiber membranes for oily wastewater treatment. The membrane displays low fouling propensity and can fully recover its water flux after a simple 20‐min water wash at 0.5 bar from its lumen side, which makes the membrane preferentially suitable for oil‐water separation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4491–4501, 2015     

用于混合一价盐分离的纳滤膜的制备及性能研究

针对有机颜料废水中单价相似离子（例如CH₃COO^-和Cl^-）分离难的问题,以表面活化能与脱水现象协同作用的分离机制为指导,在界面聚合中加入3,5-二氨基苯甲酸（DMA）来调控孔径、电性等性质,制备对醋酸根和氯离子具有高选择性的复合纳滤膜。XPS结果表明DMA参与界面聚合反应,形成疏松选择层;Zeta电位表明膜表面负电性增强。通过pH、操作压力等条件优化,得出0.6%（质量） DMA-TFC膜性能最佳,水通量较未改性复合膜提高44%,对于醋酸钠与硫酸钠的分离比达到15.0。本工作为相似离子分离纳滤膜的设计与制备提供了理论和实践基础,在颜料废水等水处理、物料分离等领域展现了良好的应用前景。     

Synthesis of 4-Aminobenzoylpiperazine for Preparing the Thin Film Composite Nanofiltration Membrane by Interfacial Polymerization with TMC

A new synthesis method of aromatic diamine, 4-aminobenzoylpiperazine (4-ABP), was studied from 4-aminobenzoic acid and 1-formyl piperazine for the preparation of nanofiltration membrane. The structure of 4-ABP was identified by FT-IR spectra and ¹H NMR spectra. The resulting 4-ABP was used as aqueous monomer to fabricate a thin film on porous polyethersulfone (PES) ultra filtration membranes by interfacial polymerization (IP) with trimesoyl chloride (TMC) as organic monomer. The salt rejection order of these thin film composite (TFC) nanofiltration(NF) membranes is Na₂SO₄>MgSO₄>MgCl₂>NaCl. This sequence indicated that the membranes were negatively charged.     

Effective incorporation of TiO2 nanoparticles into polyamide thin‐film composite membranes

The effectiveness of TiO₂ nanoparticles in improving the performance of polyamide (PA) thin‐film composite (TFC) membranes has been investigated. PA TFC membranes were prepared by interfacial polymerization with m‐phenylenediamine (MPD) and 1,3,5‐benzene tricarbonyl trichloride (TMC) where TiO₂ particles were added during and after interfacial polymerization. To distribute the TiO₂ nanoparticles uniformly in the PA films, colloidally stable TiO₂ sols were synthesized and added to the aqueous MPD solution rather than to an organic TMC solution. Through the use of different incorporation methods, TiO₂ particles were located on the top surface, in PA film layer, and in both positions. In the case of dense PA layers, the hydrophilicity of the membranes was significantly improved due to the presence of TiO₂ particles, resulting in an increased water flux. On the other hand, the enhancement of water flux was less significant when TiO₂ particles were incorporated into a loose PA film that was prepared with additives. In addition, a BSA fouling test confirmed that TiO₂ nanoparticles effectively improve the antifouling properties of the membranes for both dense and loose PA films. This effect is possibly due to increased hydrophilicity, covering of the fouling space, and a reduction in surface roughness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43383.