Preparation and characterization of nanofiltration composite membranes using polyacrylonitrile (PAN). II. Preparation and characterization of polyamide composite membranes

Polyamide (PA) composite membranes in which PA active layers were interconnected with support layers via the formation of ionic bonds were prepared by the interfacial polymerization of piperazine (PIP) with trimesoyl chloride (TMC) on the surfaces of microporous polyacrylonitrile (PAN) supports containing carboxylic acid groups. Formation of the ionic bonds through an acid‐base reaction between ? NH group of PIP and ? COOH of the support was studied using FTIR‐ATR spectroscopy. Variation of the surface morphologies of the composite membranes that was induced by the presence of the ionic bonds was observed with a FESEM and an AFM. Permeation tests with various feed solutions such as PEG 600, Na₂SO₄, MgSO₄, MgCl₂, and NaCl solutions were carried out to see how the characteristics of the PAN supports affected on the flux and rejection of the corresponding PA composite membranes. Chemical stabilities of the composite membranes with the ionic bonds were studied and compared with that of a conventional PA composite membrane, using alcohol solutions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2729–2736, 2001     

聚丙烯腈超滤膜的制备

为了得到高性能的超滤膜,采用相转化法,以聚丙烯腈(PAN)为原料,N-甲基-吡咯烷酮(NMP)为溶剂,制备了聚丙烯腈超滤膜.采用纯水通量以及膜对牛血清蛋白(BSA)的截留率作为评价标准,并使用扫描电镜对膜结构进行表征.研究了聚合物质量分数、添加剂种类、凝胶浴温度、凝胶浴种类对膜性能的影响.研究发现:在一定范围内提高聚合...     

Relationship between structures of polyacrylonitrile (PAN)–copper gradient composite film and electrochemical-reaction conditions

In this article, the relationship between the morphological structure and electrochemical conditions, the crystal structure in the electrochemical deposited phase, and the thermal properties of polyacrylonitrile (PAN)–copper gradient composite films (GCF) were studied. The results showed that the morphology of the GCF depended very much on the electrochemical conditions used in the reactions. The percent area of the deposited phase on the cross section of the GCF decreases with increases of the predrying time of the solution coated on the cathode, the power voltage, and the temperature in the electrochemical reactor. According to the data of a differential scanning calorimeter and a scanning electronic microscope, PAN chains are physically crosslinked by a deposited phase. Under the electrochemical conditions used in this article, the components of PAN are not affected by the electrochemical reactions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1159–1165, 1998     

Enhanced modification technique for polyacrylonitrile UF membranes by direct hydrolysis in the immersion bath

Conventional hydrolysis modification of polyacrylonitrile (PAN) membranes is usually carried out in a post-treatment step during which hydrophilic groups are created on the membrane surface. In this article, however, direct hydrolysis in the immersion bath is proposed as a new and simple approach for simultaneous membrane preparation and modification. The main advantages of this method include lower alkali concentrations, promptness, and the lack of need for elevating temperature compared to other studies. The cast films were immersed in the coagulation bath containing aqueous NaOH solutions of various concentrations (0.003, 0.0125, 0.025, 0.05, and 0.1 M) for 1, 3, 5, and 10 min, which were then transferred to a bath of pure water. Membranes were characterized by pure water flux, porosity, average pore diameter, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle, mechanical properties, rejection, and flux recovery ratio (FRR) measurements. At all treatment times, the pure water flux of modified membranes reached its maximum at low NaOH concentrations with a substantial increase (210%) in the membrane treated with 0.0125 M NaOH for 1 min. Furthermore, the kinetics of the hydrolysis reaction was considered to provide deeper insights into morphological changes occurring during the hydrolysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48583.     

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     

Preparation and characterization of PVA/SA composite nanofiltration membranes

Nanofiltration (NF) composite membranes based on poly(vinyl alcohol) (PVA) and sodium alginate (SA) were prepared by coating PVA/SA (95/5 in wt %) mixture solutions on microporous polysulfone (PSF) supports. For the formation of a defect free thin active layer on a support, the PSF support was multi‐coated with a dilute PVA/SA blend solution. The PVA/SA active layer formed was crosslinked at room temperature by using an acetone solution containing glutaraldehyde as a crosslinking agent. The prepared composite membranes were characterized with a scanning electron microscopy (SEM), a Fourier transform infrared spectroscopy (FTIR), an electrokinetic analyzer (EKA) and permeation tests: The thicknesses of the active layers were about 0.25 μm and 0.01 μm depending on the preparation conditions. The crosslinking reaction of the active layers were completed in less than three minutes via the formation of acetal linkage. The surface of the PVA/SA composite membrane was found to be anionic. The permeation properties of the composite membrane were as follows: 1.3 m³/m² day of flux and > 95% of rejection at 200 psi for 1000 ppm PEG600 solution. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 347–354, 2000     

碳纳米管/聚丙烯腈复合纤维的制备及结构研究

通过原位聚合的方法制备了碳纳米管/聚丙烯腈(CNTs/PAN)聚合液,用湿法纺丝工艺制备了CNTs/PAN复合纤维,分析了复合纤维流变性能、热性能及截面形貌。结果表明:CNTs的加入使得聚合物溶液出现了假凝胶化,粘度和弹性均有所上升,纺丝时溶液细流的表层遇水迅速凝固成致密的皮层,影响了纤维芯部的二甲基亚砜(DMSO)和水的双扩散作用,凝固丝出现了很明显的皮芯结构,CNTs的加入还使得纤维预氧化放热过程得到了缓和。     

Preparation and characterization of polyamide-urethane thin-film composite membranes

We attempted to produce reverse osmosis membranes with 5-chloroformloxy-isophthaloyl chloride (CFIC) and m-phenylenediamine (MPD) with an interfacial polymerization technique on the polysulphone supporting film. The membranes produced were characterized using permeation experiments with salt water. Attenuated total reflectance infrared (ATR-IR), X-ray photoelectronic spectroscopy (XPS), as well as imaging using scanning electronic microscopy (SEM) were used. The results show that the active layer of a CFIC/MPD TFC membrane is polyamideurethane, including an amide functional group (-CONH-), urethane functional group (-OCONH-) and hydroxyl functional group (-OH). The flux and rejection of a CFIC/MPD TFC membrane are better than a TMC/MPD TFC membrane in the same condition (concentrations of CFIC = 0.15 wt% and contact time with the organic solution is 20 s, which is the best preparation parameter) and the surface of the CFIC/MPD TFC membrane is a dense, finely dispersed grainy structure.     

Preparation and characterization of polysulfone–cyclodextrin composite nanofiltration membrane: Solvent effect

α-Cyclodextrin membranes were prepared by the phase inversion method using four types of casting solvents such as N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethyl acetamide (DMAc), and dimethyl formamide (DMF) herein-after termed as α-CD-NMP, α-CD-DMSO, α-CD-DMAc, and α-CD-DMF, respectively. The membranes were characterized by IR, XRD, TGA-DTA, DSC, and SEM analysis and show that solvents like NMP, DMA, DMF give good uniform morphological membranes and are better than that of DMSO. Thermal decompositions of the pure polymer and composite membranes indicate different range of thermal degradation of the membrane. This study reveals that the casting solvents NMP, DMF, DMAC have nearly same significant effect on morphology and other properties of the membranes. This is explained in terms of demixing behavior of the polymer and the combined effect of solvent volatility and polymer–solvent interactions as estimated from Hansen solubility parameter. Solvent hydrophobicity also affects the performance of the membrane and can be determined in terms of water permeability. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Intensification and optimization of the characteristics of polyacrylonitrile nanofiltration membranes with improved performance through experimental design and statistical analysis

The present study aims to employ experimental design and statistical analysis in order to investigate in detail the effect of various prominent parameters on the characteristics and performance of polyacrylonitrile nanofiltration membranes for the treatment of electroplating wastewaters targeting Ni, Cr, and Zn ions. Incorporation of TiO₂ into the membrane matrix was effective in improving pure water flux (PWF) by ~16%. Also, PWF and Ni rejection of membranes escalated to 118.55 L m⁻² h⁻¹ and 90.79%, respectively upon addition of 1.5 wt% citric acid to the dope. Variation in coagulation bath temperature from 25°C to 45°C led to the formation of membranes having higher porosity with enhanced PWF by about 25% at the expense of only 5% reduction in Ni rejection. Parameters were optimized by analysis of variance (ANOVA). In contrast to the effect of feed concentration, an increase in feed pressure and pH enhanced permeate flux and total ion rejection. Similarly, permeate flux increased at higher operational temperatures without change in total rejection. A mathematical model was developed by applying ANOVA and the best combination of operating parameters was obtained by optimization.     

Preparation and performance of novel thermal stable composite nanofiltration membrane

The novel thermal stable composite nanofiltration membranes were prepared through the interfacial polymerization of piperazine and trimesoyl chloride on the poly (phthalazinone ether) ultrafiltration substrate. The effects of polymerization and testing conditions on membrane performance were studied. The surface morphologies of the substrate and the composite membranes were observed by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The separation properties of membranes for dyes and salts were tested. The composite membranes show good thermal stability. The rejection for Na2SO4 was kept over 96%, while the flux reached 400 L·m⁻²·h⁻¹ when it was tested at 1.0 MPa and 80°C. When tested at 1.0 MPa and 60°C, the rejection of the composite membrane for dyes was kept at high level, and the flux reached 180–210 L·m⁻²·h⁻¹, while the rejection for NaCl was lower than 20%. __________ Translated from the Journal of Functional Materials, 2007, 38(12): 2025–2027, 2031 [译自: 功能材料]     

Solvent-resistant porous membranes using poly(ether−ether ketone): preparation and application

Poly(ether−ether ketone) (PEEK) is a linear aromatic macromolecule, which can form semi-crystalline aggregative status, allowing PEEK materials to have strong environment tolerance and excellent physicochemical properties. PEEK materials have become a promising alternative to fabricate particular membranes used in extreme conditions. In the past few decades, many researches and evolutions have emerged in membrane fabrication with PEEK materials and its applications for treating organic solvents and their mixtures; however, there are little systematic and comprehensive literature to summarize fabrication approaches, compile applications, and elaborate PEEK property-structure relationship. In this review, the main approaches to fabricate PEEK-based membranes are illustrated concretely, including conventional thermal-induced and non-solvent-induced phase separation, and novel chemical-induced crystallization; the representative applications in ultrafiltration, nanofiltration and membrane contactor containing organic solvents are demonstrated systematically. Meanwhile, the mechanism to tune PEEK solubility in solvents, which can be achieved by altering monomers in synthesis processes or changing membrane preparation routes, is deeply analyzed. Moreover, the existing problems and the future prospects are also discussed. This review provides positive guidance for designing and fabricating membranes using PEEK and its derivative materials for task-specific applications in harsh conditions.     

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     

界面聚合法PI/PP耐溶剂复合纳滤膜的制备与表征

以丙烯酰胺接枝的聚丙烯(PP)超滤膜为支撑层,间苯二胺(MPD)、均苯四甲酰氯(BTAC)分别为水相及有机相功能单体,通过界面聚合及其后续的酰亚胺化制备了聚酰亚胺(PI)/PP耐溶剂复合纳滤膜。讨论了水相浓度、有机相浓度及酰亚胺化溶液配方等条件对复合膜结构及其分离性能的影响。分别采用傅里叶红外光谱仪(FTIR)、扫描电子显微镜(SEM)表征分离层的化学组成及复合膜的形态结构,得到膜的分离、透过及其耐溶剂性能。结果表明,有机相浓度的影响最为显著,支撑膜表面形成了均匀致密的PI分离层,复合膜呈负电性,并具备优秀的耐溶剂性能。实验范围内,MPD、BTAC的浓度分别为8、2 g·L-1,酰亚胺化溶液乙酸酐∶三乙胺∶苯体积比为1∶1∶10时,所制备膜的分离性能较佳,对Na2SO4、酸性艳蓝6B的截留率分别达93.8%和96.9%。     

Understanding and guiding the phase inversion process for synthesis of solvent resistant nanofiltration membranes

Since its introduction in membrane technology in the 1960's, phase inversion by means of immersion precipitation has been widely studied for the preparation of membranes to be applied in the fields of microfiltration (MF) and ultrafiltration (UF). However, much less knowledge is available about this process in terms of integrally skinned asymmetric nanofiltration membranes, especially for more hydrophobic polymers applied in solvent resistant nanofiltration (SRNF). This review focuses on the preparation aspects of integrally skinned asymmetric membranes to be applied in the field of SRNF via phase inversion. It starts with the explanation of the basic principles of the phase inversion process, covering both thermodynamic and kinetic aspects. Further, it summarizes the parameters that significantly influence final membrane performance and morphology, including polymer type and concentration, casting solvent, additives, evaporation time, and temperature, humidity, membrane thickness, composition, and temperature of coagulation bath and post‐treatment. Literature contained within this review constitutes the core references in the field of SRNF, but also several references on preparation of MF, UF, aqueous NF, and reverse osmosis (RO) membranes have been included to better clarify or illustrate certain aspects of the process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42130.     

Preparation and characterization of microporous polyethylene hollow fiber membranes

Microporous polyethylene (PE) hollow fiber membrane with a porosity of 43% and N₂ permeation of 4.96 cm³ (STP)/cm² s cmHg was prepared by melt‐spinning and cold‐stretching method. It was found that PE with a density higher than 0.96 g/cm³ should be used for the preparation of microporous PE hollow fiber membranes. By increasing the spin–draw ratio, both the porosity and the N₂ permeation of the hollow fiber membranes increased. Annealing the nascent hollow fiber at 115°C for 2 h was suitable for attaining membranes with good performance. By straining the hollow fiber to higher extensions, the amount and size of the micropores in the hollow fiber wall increased, and the N₂ permeation of the membranes increased accordingly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 203–210, 2002; DOI 10.1002/app.10305     

表面偏析法制备用于乙醇渗透蒸发脱水的整体PVA-PES复合膜(英文)

A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometer (EDS) confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surface by PVA reached up to 86.8% when the PVA content in the membrane recipe was 16.7% (by mass). The water contact angle decreased with the increase of PVA content. The effect of co-agulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The mem-brane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.     

Characteristics of the nanofiltration composite membranes based on PVA and sodium alginate

Chemically stable nanofiltration (NF) composite membranes based on poly(vinyl alcohol) (PVA) and sodium alginate (SA) (hereafter, these membranes are called PVA/SA composite membranes) were prepared by coating microporous polysulfone (PSF) supports with dilute PVA/SA blend solutions. The PSF supports were pretreated with small monomeric compounds to reduce their pore size and to improve their hydrophilicity before coating with the PVA/SA blend solutions. The concentration of the PVA/SA blend solutions ranged from 0.1 to 0.3 wt %. The membranes prepared in this study were characterized with various methods such as SEM, FTIR, permeation tests, and z‐potential measurements. Especially, chemical stabilities of the membranes were tested, using three aqueous solutions with different pHs such as a HCl solution (pH 1), a K₂CO₃ solution (pH 12.5), and a NaOH solution (pH 13). Their chemical stabilities were compared with that of a polyamide (PA) composite membrane prepared from piperazine (PIP) and trimesoyl chloride (TMC). In this study, it was found that the PVA/SA composite membranes prepared showed not only good chemical stabilities but also good permeation performances in the range from pH 1 to 13. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2471–2479, 2001     

毛细管Al_2O_3膜的制备及表征:薄膜形成机理对无缺陷膜制备的影响(英文)

Ceramic capillary membrane has received much attention due to its relatively high pack density and favorable mechanical strength.However,it is difficult to prepare capillary membrane on its thin support by a dip-coating method.In this study,alumina microfiltration membranes were prepared on the inner surface of alumina capillary support(outer diameter 4 mm,inner diameter 2.5 mm)by a dip-coating method.Scanning electron microscopy(SEM)observation,gas bubble pressure(GBP)method and membrane permeation test were carried out to evaluate membrane performance.Two major effects in preparation of crack-free membrane,capillary filtration and film-coating,upon the thin support were studied.The as-prepared crack-free membrane presents a narrow pore size distribution,a mean pore size of about 0.6μm and a high pure water flux of 86000 L·m -2 ·h -1 ·MPa.It is proved that the membrane thickness should be sufficiently large to overcome the defects of support surface,but it is only one of the prerequisites for the formation of crack-free membrane.Furthermore,it is demonstrated that the capillary filtration effect is greatly restricted for thin capillary support with the dip-coating method and the film-coating effect plays a crucial role in the formation of crack-free membrane.     

Preparation and characterization of novel sodium alginate/chitosan two ply composite membranes

Sodium alginate/chitosan (SA/CS) two ply composite membranes were prepared by casting and solvent evaporation technique. NaHCO₃ was used as a porogen additive to form pores in the interior of the composite membranes and glycerol was introduced as a plasticizer. The water uptake capacity, mechanical strength, oxygen permeation property, and in vitro cytotoxicity were evaluated to test the feasibility to utilize the composite membranes for wound dressing. The average pore size, water uptake capacity, and oxygen permeation property of the composite membranes could be adjusted by the ratio of NaHCO₃ in the SA solution. The SA/CS two ply composite membranes showed high water uptake capacity, suitable mechanical strength, excellent oxygen permeability, and good biocompatible. It indicates that the SA/CS two ply composite membranes are suitable for wound dressing application. It provides a simple but promising platform to fabricate wound dressing using natural polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007