Preparation of thin-film-composite polyamide membranes for desalination using novel hydrophilic surface modifying macromolecules

A new concept for the preparation of thin-film-composite (TFC) reverse osmosis (RO) membrane by interfacial polymerization on porous polysulfone (PS) support using novel additives is reported. Hydrophilic surface modifying macromolecules (LSMM) were synthesized both ex situ by conventional method (cLSMM), and in situ within the organic solvent of the TFC system (iLSMM). The effects of these LSMMs on the fouling of the TFC RO membranes used in the desalination processes were studied. FTIR results indicated that both cLSMM and iLSMM were present in the active layer of the TFC membranes. SEM micrographs depicted that heterogeneity of the surface increases for TFC membranes compared to the control PS membrane, and that higher concentrations of LSMM provided smoother surface. AFM characteristic data presented that the surface roughness of the skin surface increases for TFC membranes compared to the control. The RO performance results showed that the addition of the cLSMM significantly decreased the salt rejection of the membrane and slightly reduced the flux, while in the case of the iLSMM, salt rejection was improved but the flux declined at different rates for different iLSMM concentrations. The membrane prepared by the iLSMM exhibited less flux decay over an extended operational period.     

Polyamide thin film composite membrane prepared from m-phenylenediamine and m-phenylenediamine-5-sulfonic acid

Thin film composite (TFC) membranes based polyamide were prepared with m-phenylenediamine (MPD), m-phenylenediamine-5-sulfonic acid (SMPD) and trimesoyl chloride (TMC) through interfacial polymerization technique on the polysulphone supporting film. The membranes were characterized using permeation experiments with salt water, attenuated total reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS) as well as scanning electronic microscopy (SEM). This study has shown that the active layer of TFC membrane is aromatic polyamide, including sulfuric acid function group (-SO₃H) according to the result of ATR-IR and XPS. The NaCl rejection of RO membranes decreased and the flux increased when W_SMPD/W_MPD increased from 0 to 1, and the linear part with pendant -COOH in membrane barrier layer increased with the increase of SMPD content, but the surface of membrane becoming smoother and smoother with the increase of SMPD content. So the membranes performance mainly was determined by chemical structure in their barrier layer.     

Characterization of multilayer nanofiltration membranes using positron annihilation spectroscopy

Positron annihilation spectroscopy (PAS) coupled with a slow positron beam was used to characterize in situ the layer structure and depth profile of the cavity size in thin film composite (TFC) polyamide nanofiltration (NF) membranes prepared by the interfacial polymerization method. Two techniques, using PAS coupled with a slow positron beam of Doppler broadening energy spectra (DBES) and positron annihilation lifetime spectroscopy (PALS) designed to reveal the layer structure and the cavity sizes contained in a multilayer thin film composite NF membrane, were assessed. To the best knowledge of the authors, a characterization of the depth profile of cavities in NF membranes using PAS coupled with a slow positron beam has never been reported. The membranes selected have a composite structure containing three layers: a selective polyamide layer, a transition layer, and a porous support prepared by the phase inversion technique. Furthermore, the cavity size distribution in the selective top layer plays an important role in determining the performance of the NF membranes.     

High flux nanofiltration membranes based on interfacially polymerized polyamide barrier layer on polyacrylonitrile nanofibrous scaffolds

Electrospun polyacrylonitrile (PAN) nanofibrous scaffold was used as a mid-layer support in a new kind of high flux thin film nanofibrous composite (TFNC) membranes for nanofiltration (NF) applications. The top barrier layer was produced by interfacial polymerization of polyamides containing different ratios of piperazine and bipiperidine. The filtration performance (i.e., permeate flux and rejection) of TFNC membranes based on electrospun PAN nanofibrous scaffold was compared with those of conventional thin film composite (TFC) membranes consisting of (1) a commercial PAN ultrafiltration (UF) support with the same barrier layer coating and (2) two kinds of commercial NF membranes (i.e., NF90 and NF270 from Dow Filmtec). The nanofiltration test was carried out by using a divalent salt solution (MgSO₄, 2000 ppm) and a cross-flow filtration cell. The results indicated that TFNC membranes exhibited over 2.4 times more permeate flux than TFC membranes with the same chemical compositions, while maintaining the same rejection rate (ca. 98%). In addition, the permeate flux of hand-cast TFNC membranes was about 38% higher than commercial NF270 membrane with the similar rejection rate.     

界面聚合法制备聚哌嗪酰胺复合纳滤膜

以聚醚砜超滤膜为基膜,哌嗪(PIP)为水相单体,均苯三甲酰氯(TMC)为有机相单体,采用界面聚合法制备了复合纳滤膜,扫描电镜、表层的红外分析结果表明在基膜表面聚合了一层聚酰胺膜,膜性能测定结果表明膜表面荷负电,对不同无机盐的截留率为Na2SO4MgSO4MgCl2NaCl。界面聚合条件对膜性能的影响表明,最佳聚合条件为:PIP浓度0.5%～2%,TMC浓度0.15wt%～0.75wt%,聚合时间≥1min,热处理温度60℃～80℃,时间15 min左右。     

聚多巴胺/聚乙烯亚胺共沉积中间层增强薄膜复合正渗透膜性能

以聚多巴胺/聚乙烯亚胺(PDA/PEI)共沉积于三醋酸纤维素(CTA)多孔支撑膜表面形成中间层,再结合界面聚合法获得聚酰胺薄膜,构建了PDA/PEI共沉积中间层改性薄膜复合(TFC)正渗透(FO)膜.通过傅里叶变换衰减全反射红外光谱法、扫描电子显微镜、原子力显微镜、溶质截留法、水接触角仪等研究了PDA/PEI共沉积中间层对CTA膜和TFC膜的表面结构和性质的影响.研究结果表明,PDA/PEI共沉积使得CTA膜表面变得更为平滑,表面孔径减小至(30.0±4.1) nm,且表面孔径分布趋于均一.同时,在PDA/PEI共沉积改性CTA膜表面界面聚合得到的聚酰胺层呈现出更均匀的叶片状结构和优异的亲水性.基于此,具有PDA/PEI共沉积中间层的TFC正渗透膜显著提高了水通量(FO模式:(7.1±2.3) L/(m^2·h)),较空白TFC膜提升了57.6%.同时,中间层改性TFC膜具有更低的反向盐通量(FO模式:1.4±0.1 g/(m^2·h))和"净盐通量"(FO模式:(0.2±0.06) g/L),与空白TFC膜相比分别下降了83.9%和90.6%.说明PDA/PEI共沉积中间层不仅能有效提升TFC正渗透膜的水渗透性,而且大幅提升了膜的截盐性和渗透选择性.     

Effect of silane coupling agents on the performance of RO membranes

This study investigates the effect of silane coupling agents on the performance of reverse osmosis (RO) membranes on the basis of sol–gel coating method. The surfaces of the RO membranes were chemically modified with four different alkoxysilanes in order to reduce their hydrophilicity. The objective of this study is to superpose hydrophobic polysiloxane layer on the surface of a polyamide TFC RO membrane and to increase the extent of salt rejection by the modified membranes. A commercial composite RO membrane (SWC1) was treated with silane coupling agents in ethanol at three different concentrations: 1.0, 1.5, and 2.0% (w/v). The silane coupling agents contain one alkyl or phenyl and three alkoxy groups (e.g., methyltriethoxysilane, octyltriethoxysilane, octadecyltrimethoxysilane and phenyltriethoxysilane). In addition, the effect of alkyl or phenyl group hydrophobicity on the permeability and salt rejection of the modified membrane was examined. The surfaces of the modified membranes were characterized by SEM, AFM, contact angle analyzer, and XPS in order to confirm successful sol–gel methods. The modified membranes showed significantly enhanced salt rejection without a decrease in flux. From the surface analysis results, we can observe the changes in the surface roughness, elemental composition, electron energy, and hydrophilicity.     

Interlaboratory studies of highly permeable thin‐film composite polyamide nanofiltration membrane

The aim of this paper is to survey interlaboratory studies of performance data to produce highly permeable thin‐film composite (TFC) polyamide nanofiltration (NF) membrane in the form of flat sheet at bench scale. TFC polyamide NF membranes were fabricated via interfacial polymerization of 1,3‐phenylenediamine and trimesoyl chloride on porous polyethersulfone (PES) membrane. The NF membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross‐flow filtration. The AFM and SEM analyses indicated that a rough and dense film was formed on the PES support membrane. The permeability and NaCl rejection of the NF membrane prepared at the presence of camphor sulfonic acid as pH regulator and triethylamine as accelerator in the aqueous solution were 21 l m^?2 h^?1 and 70%, respectively. In order to estimate the repeatability and reproducibility standard deviations, the development of an interlaboratory study was conducted by measurements of permeation flux and salt rejection of the synthesized membranes. Repeatability standard deviation of the permeation flux data for the membrane based on optimum formulation was 1.99, and reproducibility standard deviation was 3.55. Also based on this trend, repeatability standard deviation of the salt rejection data was 1.57, and reproducibility standard deviation was 4.11. The American Society for Testing and Materials standard E691‐05 was used for data validation of the repeatability and reproducibility standard deviations and consistency statistics. Copyright © 2011 John Wiley & Sons, Ltd.     

Interfacially polymerized thin film composite membranes on microporous polypropylene supports for solvent-resistant nanofiltration

Interfacial polymerization (IP) is a powerful technique for fabrication of thin film composite (TFC) membranes. The polymers used most often as support are polysulfone (PS) or polyethersulfone (PES). These supports have limited stability in organic solvents. In this work, microporous polypropylene (PP) flat film and hollow fiber membranes were used as a support to fabricate TFC membranes for nanofiltration by the IP technique. Porous polypropylene membranes can provide substantial chemical, pH, and solvent resistance and are therefore suitable as supports for fabricating TFC membranes functioning as solvent-stable nanofiltration membranes. The surface and the pore interior of polypropylene flat sheet and hollow fiber membranes were hydrophilized first by pre-wetting with acetone followed by oxidation with chromic acid solution. A standard procedure to successfully coat the hydrophilized flat film and hollow fiber membranes was developed next. The monomeric system chosen for IP was poly(ethyleneimine) and isophthaloyl dichloride. The TFC hollow fiber membranes were characterized by nanofiltration of safranin O (MW 351) and brilliant blue R (MW 826) dyes in methanol. Rejection values of 88% and 43% were achieved for brilliant blue R and safranin O, respectively at a transmembrane pressure of 413 kPa in the TFC hollow fiber membranes. Pressure dependences of the solvent flux and solute rejection of the TFC membranes were studied using the modified flat sheet membranes up to a pressure of 965–1241 kPa. Solvent flux increased linearly with an increase in the transmembrane pressure. Solute rejection also increased with an increase in the transmembrane pressure. All modified membranes were also characterized using scanning electron microscopy. Extended-term solvent stability of the fabricated membranes was studied in toluene; the membranes demonstrated substantial solvent stability in toluene.     

The influence of the porous support layer of composite membranes on the separation of binary gas mixtures

Thin film composite (TFC) membranes exhibit a high flux for gas and vapor permeation and are viable for a wide range of applications. The high flux may also increase the importance of the resistance of the porous support structure depending on the application and process conditions. A comprehensive modeling approach for TFC membranes is introduced, which considers boundary layer resistances near the membrane surface, solution-diffusion through the coating, and the influence of the porous sublayer. Permeation through the support structure is described by the dusty gas model (DGM) with the support treated as a two-layered structure with a dense but porous skin and a more open substructure.The model accurately describes experimental data on TCE/nitrogen separation using a sweep gas on the permeate side very well. The main resistance towards TCE permeation through two different membranes tested is the porous support. It is shown that changes in the support morphology can greatly enhance the performance of the composite membranes. Model calculations were also performed for vacuum assisted permeation. The pressure drop across the support is considerable depending on the coating thickness. The TCE permeation is again dominated by the resistance of the support layer, which can be reduced by altering the morphological parameters of the structure.The proposed model is able to describe the performance of the composite membrane and to identify optimum process conditions for given performance characteristics. It can be used to aid in the development of membrane structures for enhanced performance.     

The effect of preparation parameters on performance of polyvinyl alcohol thin‐film composite membrane: Experimental study,modeling, and optimization

To systematically investigate the influence of preparation conditions on pure water permeability (PWP) and solute removal performance of polyvinyl alcohol (PVA) thin‐film composite (TFC) membrane, fractional factorial design was applied. The considered conditions were related to 3 steps of the TFC preparation, including support membrane preparation, PVA coating, and cross‐linking. The results showed that among the selected factors, polysulfone concentration (polymer of the support membrane), heat curing time (related to cross‐linking condition), and their interaction have the most significant effects on the both permeability and salt rejection. The effects of significant factors interaction on permeability and solute rejection of PVA TFC membrane were discussed. Finally, optimum preparation conditions were calculated by numerical optimization to achieve maximum permeability and solute removal, simultaneously. The prepared membrane at optimum conditions showed PWP of 1.74 L/m²hbar and 96.19% Na₂SO₄ rejection. It was realized that the prediction of mathematical models at optimum conditions was reliable with absolute average relative error 7.43% and 1.18% for PWP and rejection, respectively.     

Performance enhancement of thin‐film composite membranes in water desalination process by wood sawdust

In this study, polysulfone/wood sawdust (PSf/WSD) mixed matrix membrane (MMM) was prepared as a novel substrate layer of thin‐film composite (TFC) membrane in water desalination. The main aim was to evaluate how different amounts of WSD (0‐5 wt%) and PSf concentrations (12‐16 wt%) in the porous substrate affect the properties of the final TFC membranes in the separation of organic and inorganic compounds. Morphological and wettability studies demonstrated that the addition of small amount of WSD (less than or equal to 1 wt%) in the casting solution resulted in more porous but similar hydrophobic substrates, while high loading (greater than or equal to 2 wt%) of WSD not only changed the substrate wettability and morphology but also increased and decreased the swelling and mechanical properties of substrate layer. Therefore, PA layer formed thereon displayed extensively varying film morphology, interfacial properties, and separation performance. Based on approximately stable permeate flux (ASPF) and apparent salt rejection efficiency (ASRE), the best TFC membrane was prepared over the substrate with 12 to 14 wt% of PSf and around 0.5 to 1 wt% of WSD. Although notable improvements in permeate flux were obtained by adding a small amount of sawdust, the results clearly indicate that the salt rejection mechanism of TFC membrane was different from the glycerin rejection mechanism. Furthermore, durability results of TFC membranes showed that in continuous operation for 30 days, TFC‐14/0.5 and TFC‐14/01 have the maximum plateau levels of stable permeate flux and salt rejection among the all TFC membranes.     

木质素磺酸钠改性聚砜膜的制备及其在正渗透膜中的应用

采用木质素磺酸钠作为亲水添加剂,通过浸没沉淀相转化法制备了木质素磺酸钠共混改性聚砜膜,以改善聚砜膜的亲水性,并用作正渗透膜的支撑层,以降低内浓差极化效应.利用扫描电子显微镜、衰减全反射傅里叶变换红外光谱仪、水接触角仪等研究了不同木质素磺酸钠添加量对聚砜膜的结构和表面性质的影响.结果表明,添加木质素磺酸钠后,聚砜膜的指状孔变得规整且狭长.水接触角实验证实添加木质素磺酸钠能改善聚砜膜的亲水性,当木质素磺酸钠含量为0.4 wt%时,聚砜膜的表面水接触角可降低至65°.正/反渗透测试装置分别用于表征正渗透膜的传质性质和结构参数.结果表明,以0.4 wt%木质素磺酸钠改性聚砜膜为支撑层的正渗透膜的水渗透性能(A=3.12×10~(-5) LMH×Pa~(-1))优于纯聚砜基底正渗透膜(0.76×10~(-5)LMH×Pa~(-1)),而且前者的结构参数(S=2010mm)远小于后者(3450mm),说明木质素磺酸钠改性聚砜膜有效弱化了正渗透膜的内浓差极化效应.     

Using PDMS coated TFC-RO membranes for CO2/N2 gas separation: Experimental study,modeling and optimization

Thin film composite (TFC) reverse osmosis (RO) membranes are semipermeable membranes that are utilized in water purification or water desalination systems. Discarding these membranes after end-of-life leads to environmental problems. Reusing old TFC-RO membranes is one way to solve this problem. For this reason, in this study, used TFC-RO membranes were coated with polydimethylsiloxane (PDMS) for CO₂/N₂ gas separation application. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized to confirm the crosslinking of coated PDMS. The morphology of PDMS/TFC-RO membranes was characterized using scanning electron microscopy (SEM). The parameters that can affect performance of prepared membranes (N₂ permeance and CO₂/N₂ selectivity) are concentration of PDMS solution, coating time, solvent evaporation time and curing temperature and time. Given that the used membranes don't have uniform surfaces, the first step of this study was to investigate the effect of the above mentioned factors on virgin membranes using fractional factorial design (FFD) of experiments. The results obtained showed that PDMS concentration is the most significant factor that has a negative effect on N₂ permeance and positive effect on CO₂/N₂ selectivity. The reported CO₂/N₂ selectivity of PDMS membranes was 11–12, but this selectivity for prepared PDMS/TFC-RO membranes was in the range of 6.7–22.5. After determining optimum conditions, the gas separation performance of PDMS coated used TFC-RO membrane under these conditions was finally determined. The results showed that the used membranes had a better performance than virgin membranes.     

Analysis of transport through thin film composite membranes using an improved Wheatstone bridge resistance model

The two-dimensional Wheatstone bridge resistance analog model for permeation through thin film composite (TFC) membranes proposed by Karode et al. [5] has been extended to also include the cases where the coating layer thickness is of similar magnitude as the pore radius in the support matrix. The effect of the constriction resistance, i.e. the resistance encountered by the permeating species in traveling in a radial direction to find a pore to diffuse through is highlighted by considering three generic types of TFC membranes: (i) TFC membranes where the support has very low surface porosity; (ii) TFC membranes with moderate support layer surface porosity; and (iii) TFC membranes incorporating an intermediate gutter layer between the top coating and the bottom support. The model predictions are compared with experimental data reported in literature and various effects are highlighted by considering a few hypothetical cases. The calculations indicate that PRISM type membranes do not require pore filling in order to achieve a composite selectivity close to that of the support material as the high constriction resistance due to low surface porosity effectively prevents transport along the less permselective pathway. In case of less permeable but highly selective top layers, the constriction resistance can be significantly decreased by the gutter layer concept resulting in higher permeabilities and selectivities controlled by the coating layer. In general, the constriction resistance becomes dominant when the permeability of the top layer is low or when the support surface porosity is low.     

Preparation of sulfonated poly(phthalazinone ether sulfone ketone) composite nanofiltration membrane

Thin film composite (TFC) membranes were prepared from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) as a top layer coated onto poly(phthalazinone ether sulfone ketone) (PPESK) ultrafiltration (UF) support membranes. The effects of different preparation conditions such as the SPPESK concentration, organic additives, solvent, degree of substitution (DS) of SPPEK and curing treatment temperature and time on the membrane performance were studied. The SPPESK concentration in the coating solution was the dominant factor for the rejection and permeation flux. The TFC membranes prepared from glycerol as an organic additive show better performance then those prepared from other additives. The rejection increased and the flux decreased with increasing curing treatment temperatures. The salt rejections of the TFC nanofiltration (NF) membranes increased in the order MgCl₂ < MgSO₄ < NaCl < Na₂SO₄. TFC membranes showed high water flux at low pressure. SPPESK composite membranes rejections for a 1000 mg L⁻¹ Na₂SO₄ feed solution was 82%, and solution flux was 68 L m⁻² h⁻¹ at 0.25 MPa pressure.     

Preparation,structure characteristics and separation properties of thin-film composite polyamide-urethane seawater reverse osmosis membrane

A novel thin-film composite (TFC) seawater reverse osmosis membrane was developed by the interfacial polymerization of 5-chloroformyloxyisophthaloyl chloride (CFIC) and metaphenylenediamine (MPD) on the polysulphone supporting membrane. The performance of the TFC membrane was optimized by studying the preparation parameters, which included the reaction time, pH of the aqueous-MPD solution, monomer CFIC concentration, additive isopropyl alcohol content in aqueous solution, curing temperature and time. The reverse osmosis performance of the resulting membrane was evaluated through permeation experiment with synthetic seawater, and the structure of the novel membrane was characterized by using SEM, AFM and XPS. Furthermore, the separation properties of the TFC membrane were tested by examining the reverse osmosis performances of various conditions, the boron rejection performance and the long-term stability. The results show that the desired TFC seawater reverse osmosis membrane has a typical salt rejection of 99.4% and a flux of about 35 L/m² h for a feed aqueous solution containing 3.5 wt.% NaCl at 5.5 MPa, and an attractive boron rejection of more than 92% at natural pH of 7–8; that the novel seawater reverse osmosis membrane appears to comprise a thicker, smoother and less cross-linking film structure. Additionally, the TFC membrane exhibits good long-term stability.     

A novel method of surface modification on thin-film-composite reverse osmosis membrane by grafting hydantoin derivative

Membrane degradations by biofouling and free chlorine oxidation are the major obstacles for aromatic polyamide thin-film-composite (TFC) reverse osmosis (RO) membranes to realize high performance over a long period of operation. In this work, a hydantoin derivative, 3-monomethylol-5,5-dimethylhydantoin (MDMH), was grafted onto the nascent aromatic polyamide membrane surfaces by the reactions with active groups (e.g., acyl chloride groups) in the surfaces. The grafted MDMH moieties with high reaction activity and free chlorine could play as sacrificial pendant groups when membranes suffer from chlorine attacks, and the chlorination products N-halamines with strong antimicrobial function could sterilize microorganisms on membrane surfaces and then regenerate to MDMH. This was designed as a novel means to improve both chlorine resistances and anti-biofouling properties of the aromatic polyamide TFC RO membranes.Attenuated total reflectance mode Fourier transform infrared spectroscopy (ATR-FTIR) revealed that the MDMH-modified membranes had two characteristic bands at 1772 and 1709 cm⁻¹ corresponding to two carbonyl groups in hydantoin ring. This suggested the successful grafting of MDMH onto the membrane surfaces, which was further confirmed and quantified by X-ray photoelectron spectroscopy (XPS) analysis. After modification with MDMH, the membrane surface hydrophilicity increased obviously as contact angles decreased from 57.7° to 50.4–31.5°. But, there was no obvious change in membrane surface roughness after modification. The MDMH-modified membranes were shown to possess high chlorine resistances with small changes in water fluxes and salt rejections after chlorination with 100–2000 ppm h chlorine at pH 4. The chlorinated MDMH-modified membranes demonstrated obvious sterilization effects on Escherchia coli and substantial preventions against microbial fouling. Therefore, the MDMH-modified membranes offer a potential use as a new type of chlorine resistance and anti-biofouling TFC RO membranes.     

Boron reduction performance of reverse osmosis seawater desalination process

In recent years, seawater desalination systems using reverse osmosis (RO) membranes have been constructed to settle the lack of drinking water. RO desalination membranes have high rejection for most of solutes in seawater. Japanese drinking water standards for the water quality of the permeate can be achieved except for boron. Therefore, the boron rejection needs to be considered in the design of the RO process and during the operation of the plant. Luckily, there is a simple and easy method to estimate boron concentration.In this paper, we report measured boron permeabilities and their relation to salt permeabilities using cross-linked polyamide membranes. Chemical degradation of the membranes affected these permeabilities to different degrees. Boron concentrations in the permeate were then calculated using a computer program that was based on the boron permeabilities calculated from the measured salt permeabilities. Results obtained were compared with actual data taken at a RO plant of Toray Industries, Inc., Ehime. The model data fitted the experimental result, well. It was also found that a relationship existed in the permeate between salt and boron concentrations and that the boron concentration can be obtained from measurement of the salt concentration.