Change of chemical composition and hydrogen bonding behavior due to chlorination of crosslinked polyamide membranes

The effect of membrane exposure to hypochlorite oxidant on property changes (chemical composition and hydrogen bonding behavior) of four FilmTec© thin film composite crosslinked polyamide membranes has been investigated. Crosslinking densities of the membranes were about 25–35%, with about 3–4 chlorines bound to the repeating unit of the polyamide membranes. This was equivalent to ～ 39% of all nitrogens being chlorinated in the polyamide membranes assuming the amide nitrogen is the dominant reaction site with chlorine. FTIR spectra showed the amide I band (C?O stretching peak at 1663 cm^?1) of polyamide membranes shifted to higher wave‐numbers and the peak intensity of the amide II band (N? H bending peak at 1541 cm^?1) decreased after chlorination. The peak shift and decrease of peak intensity resulted from breakage of hydrogen bonds between C?O and N? H groups within the polymers. The XPS and FTIR analytical analysis showed that there is no difference in the chlorine attack of polyamide membranes of higher or lower crosslinking density, and that the chlorination breaks and weakens hydrogen bonding. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The chlorination and chlorine resistance modification of composite polyamide membrane

Membrane‐based separation technology is one of the most active separation technologies being employed in water treatment. Polyamides (PA) are widely used membrane materials because they exhibit excellent performance, such as high flux with high salt rejection, and enhanced stability against wide range of pH and temperature. Unfortunately, PA membranes exhibit extremely poor resistance to chlorine leading to increased operation costs and decreased membrane lifetime. In this study, we find new ways for prolonging membrane lifetime and reducing the operating costs by investigating the chlorination and modification of PA membranes. Varying concentrations of hypochlorite were used to chlorinate a commercial reverse osmosis membrane (BW‐30, DOW). The results showed that short‐time exposure to high concentrations of hypochlorite could cause more serious problems to membranes than long‐time exposure to low concentrations under the similar total exposure. The performance of the chlorinated membranes was recovered to some extent after treatment with NaOH solution (pH 10), indicating that the alkali treatment could initiate the reversible regeneration of chlorinated membranes. Furthermore, an industrial grade epoxy resin was used to modify the membranes to enhance the chlorine resistance via the reaction between the amide nitrogen and epoxy bond. The successful modifications were confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy. Moreover, the chlorination tests showed that the modifications performed in these experiments enhanced the chlorine resistance of the membranes, especially for the membranes exposed to low concentration of chlorine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41584.     

耐氧化芳香聚酰胺纳滤膜的研究进展

芳香聚酰胺纳滤膜不耐氧化,易被活性氯氧化降解,导致膜性能急剧下降,缩短膜的使用寿命,目前已成为制约芳香聚酰胺纳滤膜应用和发展的关键问题之一。本文综述了芳香聚酰胺纳滤膜的材料和结构,重点概述了芳香聚酰胺氯化和膜性能下降的机制,并进一步介绍了近年来耐氧化芳香聚酰胺纳滤膜的研究进展。     

Preparation and characterization of polyamide nanofiltration composite membranes with TiO2 layers chemically connected to the membrane surface

A polyamide (PA) nanofiltration (NF) composite membrane with TiO₂ layers was designed and prepared, in which the TiO₂ layers were chemically linked to the crosslinked polyamide layers of the membrane. In this study, TiO₂, one of the well known photo‐catalysts effectively degrading organics with UV light, was introduced to the PA NF membrane by using 3‐aminopropyltrimethoxysilane (APTMOS), titanium (IV) isopropoxide (TIP) to improve its antifouling property. In particular, for this membrane, SiO₂ layers were formed between the TiO₂ layer and the crosslinked polyamide layer of the membrane to protect the organic parts of the membrane from the TiO₂ catalyzed UV degradation. The prepared membrane with TiO₂ layers was then characterized using several analytical methods: scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), x‐ray diffraction (XRD) and permeation tests. It was found that the prepared membrane was stable; especially the TiO₂ layer of the membrane was found to be stable after several times of use for permeation test. The membrane showed a typical NF property, despite of the presence of the TiO₂ layer. From long time tests with or without UV light, it was found that there was good antifouling effect on the membrane by the TiO₂ layer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

New chlorine‐resistant polyamide reverse osmosis membrane with hollow fiber configuration

New asymmetric hollow fiber reverse osmosis (RO) membrane was developed from a new chlorine‐resistant copolyamide [4T‐PIP(30)] with a piperazine moiety by a conventional phase‐separation method. The new 4T‐PIP(30) hollow fiber membrane has the same low‐pressure RO performance as cellulose triacetate hollow fiber membrane (FR = 205 L/m² day, Rj = 99.6%) and superior chlorine resistance as well as pH resistance to conventional aramid RO membranes. Structural analysis and viscoelastic study revealed that the new hollow fiber consisted of a top skin, dense layer, and microporous layer, and that it began to decrease its elasticity at 80°C in water, which is possibly related to its good and stable RO performance around room temperature. Several kinds of RO modules were made from the new hollow fiber membranes, for which RO performances were stable for 2 years in chlorinated feed water desalination (the free residual chlorine ranged from 0.l to 1.1 mg/L). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 517–527, 2001     

Separation of humic acid with nanofiltration polyamide composite membranes

Humic acid, a natural organic matter, was separated with a polyamide (PA) composite membrane with a molecular weight cutoff (MWCO) of 500 g/mol. The PA composite membrane was prepared by the interfacial polymerization of piperazine and trimesoyl chloride on a polysulfone support with an MWCO of about 30,000 g/mol. The separation conditions through the membrane were varied, and factors affecting the permeation performance of the membranes, such as the concentration, pH, and storage time of the humic acid solutions, were studied. The surface chemistry of the membrane changed dynamically as a function of the operating time during the permeation tests, and the size and ζ potential of the colloid of humic acid solutions under different conditions were characterized with a ζ potentiometer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2847–2853, 2002     

Preparation and separation properties of polyamide nanofiltration membrane

Utilizing an interfacial polymerization technique for the preparation of a polymeric composite nanofiltration membrane, both high permeation flux of water and high salt rejection can be achieved. Synthesis conditions, such as concentration of monomer, reaction time, and swelling agent, significantly affected the separation performance of composite membranes. The composite polyamide membrane had a permeation rate of ～2–5 gallon/ft²/day (gfd) and a salt rejection rate of ～94–99% when 2000 ppm aqueous salt solution was fed at 200 psi and 25°C. Also, a higher performance nanofiltration membrane could be prepared by suitably swelling the support matrix in the period of polymerization. The results of various feed concentrations showed that permeate flux decreased with increasing salt concentration in the feed solution. This result may be due to concentration polarization on the surface of polyamide membranes. The separation performance of polyamide membranes showed an almost independent relationship with operation pressure until it was up to 200 psi. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1112–1118, 2002     

New reverse osmosis membrane materials with higher resistance to chlorine

Copolyamides were prepared from mixed diamine components of 3,3′‐ or 4,4′‐diaminodiphenylsulfone, piperazine, and dichlorides such as isophthaloyl or terephthaloyl. The obtained copolyamides are random copolymers, which have good solubilities in organic solvents and good mechanical properties, even in water. The asymmetric membranes prepared from the copolyamides [ex: 4I‐PIP(20)] not only have more excellent reverse osmosis performance, but also higher chlorine resistance than NOMEX‐type aromatic polyamide. New membrane materials with excellent reverse osmosis performance and higher chlorine resistance than the NOMEX‐type aromatic polyamide could be demonstrated successfully. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1357–1364, 2000     

Adsorption of perfluorinated compounds on thin‐film composite polyamide membranes

The adsorption behavior of perfluorinated compounds (PFCs), of various chain lengths and two different functional groups, on widely used thin‐film composite polyamide membranes has been investigated. Three commercially available polyamide membranes and two classes of PFCs were evaluated: Dow‐Filmtech BW30, NF90, and NF270 membranes; perfluorosulfonic and perfluoroalkanoic acid with 5, 7, 9, and 11 carbon atoms. The adsorption of PFCs on the membranes strongly depended on the active skin‐top layer material of the membranes, solution chemistry, and structure of PFCs. The piperazine based NF270 membrane showed higher adsorption of PFCs compared to BW30 and NF90 membranes (FT‐30 type membranes). The BW30 membrane, which has a coating layer of aliphatic carbons and hydroxyl groups on the surface of the polyamide substrate, had less interaction with PFCs than the NF90 polyamide membrane had. The adsorption of PFCs increased with increasing ionic strength, decreasing pH, and in divalent ion solutions. PFCs with longer chain lengths and more hydrophobic functional groups showed more attractive interactions with thin‐film composite membranes and, thus, greater adsorption on the membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

富勒烯交联季铵化聚苯醚阴离子交换膜的制备

通过富勒烯C₆₀与乙二胺合成立体纳米分子C₆₀(EDA)₈,并以此为交联剂与三阳离子功能化聚苯醚制备了一系列交联型阴离子交换膜。C₆₀(EDA)₈中立体纳米结构有效地支撑了高分子链段,构建了更发达的离子通道,有效地提升了电导率。实验结果表明,随着C₆₀(EDA)₈加入量增加,交联膜的离子交换容量减小,而电导率却逐渐增加。当交联剂C₆₀(EDA)₈加入量为5%时,电导率提高了34%。此外,所制备的离子交换膜均表现出良好的抗溶胀能力、力学性能与耐碱性。     

Factors affecting the interfacial polymerization of polyamide active layers for the formation of polyamide composite membranes

Polyamide (PA) composite membranes were prepared by interfacial polymerization with piperazine, m‐phenylene diamine, and trimesoyl chloride as monomers and polysulfone ultrafiltration membranes as supports. Factors affecting the performances of the composite membranes by changing the characteristics of the PA active layers were studied. First, the monomer compositions were varied, and organic solvents (benzene and 1,2‐dichloroethane) with better solubility for PA than hexane were used for the interfacial polymerization. As chemical additives capable of changing the property of the interface formed between water and organic phases, n‐propanol and i‐propanol were used, and phase‐transfer catalysts such as triethyl benzyl ammonium bromide were used to improve the polymerization efficiency of the PA active layers. The characteristics of the PA composite membranes prepared, including their permeation properties and morphology, were carefully studied with various analytical methods, such as field emission scanning microscopy, atomic force microscopy, differential scanning calorimetry, and permeation testing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2781–2787, 2002     

界面聚合聚酰胺纳滤膜渗透选择性能优化的研究进展

纳滤因其分离效率高、操作压力低、环境友好等优点,在废水处理、海水淡化和工业分离纯化等众多领域有着重要的应用。界面聚合法制备的聚酰胺（PA）纳滤膜是最为常用的纳滤膜种类之一。然而界面聚合反应速度快,如何通过调控界面聚合过程,优化纳滤膜选择分离层的结构从而提高渗透选择性,以满足不同领域对纳滤膜需求仍是亟需解决的问题。本文从影响界面聚合单体扩散因素的角度出发,综述了近年来PA纳滤膜渗透选择性能优化的研究进展,包括新型PA纳滤膜、纳米材料/PA混合基质膜及超薄PA纳滤膜3个方面,探讨了选择分离层结构调控与纳滤膜渗透选择性能优化的关系,最后指出目前界面聚合制备高渗透选择性PA纳滤膜在规模化、稳定性及可控性存在的问题,并对未来界面聚合纳滤膜在微观结构和聚合过程调控方面的研究进行了展望。     

纳滤和反渗透膜形貌结构与膜性能关系探索

纳滤和反渗透膜表面形貌结构、亲疏水性的性质与膜脱盐率、水通量等性能存在一定关系。对几款商用纳滤、反渗透膜进行表面形貌结构、表面粗糙度、亲水性表征。结果表明,纳滤膜表面平整粗糙度低、亲水性强、脱盐率较低,但水通量高。反渗透膜表面存在大量疏松的峰谷结构,比纳滤膜粗糙度更大、亲水性强。对比两款海水反渗透膜,推测调整反渗透膜"叶片"大小和数量可调节反渗透膜的脱盐率和水通量性能。     

Surface-tailoring chlorine resistant materials and strategies for polyamide thin film composite reverse osmosis membranes

Polyamide thin film composite membranes have dominated current reverse osmosis market on account of their excellent separation performances compared to the integrally skinned counterparts. Despite their very promising separation performance, chlorine-induced degradation resulted from the susceptibility of polyamide toward chlorine attack has been regarded as the Achilles’s heel of polyamide thin film composite. The free chlorine species present during chlorine treatment can impair membrane performance through chlorination and depolymerization of the polyamide selective layer. From material point of view, a chemically stable membrane is crucial for the sustainable application of membrane separation process as it warrants a longer membrane lifespan and reduces the cost involved in membrane replacement. Various strategies, particularly those involved membrane material optimization and surface modifications, have been established to address this issue. This review discusses membrane degradation by free chlorine attack and its correlation with the surface chemistry of polyamide. The advancement in the development of chlorine resistant polyamide thin film composite membranes is reviewed based on the state-of-the-art surface modifications and tailoring approaches which include the in situ and post-fabrication membrane modifications using a broad range of functional materials. The challenges and future directions in this field are also highlighted.     

Chlorine-resistance of reverse osmosis (RO) polyamide membranes

Polyamide (PA) reverse osmosis (RO) membranes suffer performance decay when exposed to oxidizing species, limiting their lifetime and increasing operation costs. This article aims at reviewing the effect of chlorine species on the performance and characteristics of PA-membranes. Experimental evidence supporting different competing mechanisms for chlorine-polymer interaction will be presented, together with the influence of operational parameters. Additionally, an overview of different modification methods that exist to render PA-membranes more chlorine-resistant is given.     

改性化合物对聚酰胺膜材料亲水性及抗污染性能影响的分子力学计算与实验研究

以反渗透技术应用于海水淡化为背景,采用分子力学方法计算聚酰胺反渗透膜材料PA及3种改性化合物(PEGMA,SPM,AMPS)与水分子、典型有机污染物海藻酸AA形成各种氢键复合物的相互作用能、生成几率与平均相互作用能,以此为基础选择适宜的膜改性化合物,增加膜表面亲水性,降低海藻酸污染。分子力学计算表明,PA及三种改性化合物与水分子结合的强弱顺序为：PEGMA＞PA＞SPM＞AMPS;它们与海藻酸AA分子结合的强弱顺序为：AMPS＞PA＞SPM＞PEGMA。将PEGA“链接”到聚酰胺膜SW30表面,制得改性聚酰胺膜MSW30。实验表明,改性聚酰胺膜MSW30的亲水性能及抗污染性能均较原膜SW30有显著提高,实验结果与分子力学计算结果一致。     

制备聚酰胺复合膜中界面聚合反应添加剂研究进展

聚酰胺复合膜以其优良的稳定性及良好的分离选择性成为水处理和化工分离领域应用范围最广的分离材料之一。聚酰胺复合膜一般采用界面聚合法制备,由于界面聚合反应活性高、反应参数多,致使界面层结构难以控制,膜的渗透性或选择性不理想。因此,如何有效调控膜结构,实现膜的高渗透性或选择性是目前面临的重要挑战。近期诸多研究表明,在水相或有机相中引入添加剂可以改变油水界面张力进而调控单体界面扩散速率及界面分布,或通过改变反应机理影响聚合反应速率,最终实现对界面层结构和膜性能的调控。本文从添加剂种类、性质和调控作用等角度总结了近年来添加剂对复合膜结构及性能调控的研究进展,分析了现有研究存在的问题,并建议从微观层面探究界面过程的物理化学性质以及开发高时间分辨率原位表征方法等。     

优化聚酰胺分离层制备高选择透过性反渗透膜

反渗透(RO)膜分离技术由于具有高效、低耗和产水水质高等优点,已成为现阶段解决水资源短缺的有效手段。进一步提高RO膜的选择透过性能有利于降低产水成本和提高产水质量,因此制备高选择透过性能的RO膜一直是膜领域研究的重点。从优化界面聚合工艺、优化基膜及开发新型制膜工艺三方面对近年来改善RO膜选择透过性能的研究进行了综述。通过优化界面聚合工艺和开发新型制膜工艺可以直接改变分离层的结构和性质,通过调节基膜的孔径、孔隙率及亲疏水性可以影响分离层的结构,从而改善RO膜的性能。最后对制备高选择透过性能的反渗透膜的研究方向与发展前景进行了总结与展望。     

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.     

A study on the characteristics and pervaporation performance of polyamide thin‐film composite membranes with modified polyacrylonitrile as substrate for bioethanol dehydration

To improve the pervaporation performance in separating an aqueous ethanol solution, polyamide thin‐film composite (TFC) membranes (m‐tolidine‐H‐TMC/mPAN) were prepared through the interfacial polymerization reaction between trimesoyl chloride (TMC) and 2,2'‐dimethylbenzidine hydrochloride (m‐tolidine‐H) on the surface of a modified polyacrylonitrile (mPAN) membrane. The effects of the feed ethanol concentration on the pervaporation performance and the durability of m‐tolidine‐H‐TMC/mPAN TFC membranes were investigated. To choose the optimal mPAN membrane as the TFC substrate, the effect of hydrolysis time on the chemical properties and separation performance of an mPAN substrate was also studied. An appropriate hydrolysis time of 15 min was chosen to obtain the mPAN substrate due to the corresponding high permeation flux. The m‐tolidine‐H‐TMC/mPAN TFC membrane exhibited a high pervaporation performance for ethanol dehydration. A positron annihilation lifetime spectroscopy experiment was used to estimate the mean free‐volume radius of the m‐tolidine‐H‐TMC polyamide selective layer, which lay between the radii of the water and ethanol molecules. © 2013 Society of Chemical Industry