Fabrication of high performance Matrimid/polysulfone dual-layer hollow fiber membranes for O2/N2 separation

Matrimid/polysulfone (PSf) dual-layer hollow fiber membranes were fabricated by using co-extrusion and dry-jet wet-spinning phase-inversion techniques. The effects of the spinning dope composition, spinneret dimension, spinneret temperature and the air gap distance on the hollow fiber membranes separation performance were studied. Aging phenomenon was also studied. After coated by 3 wt% silicon solution, the hollow fiber membranes have an O₂/N₂ selectivity of 7.55 at 25 °C, 506.625 kPa which exceeds the intrinsic value of Matrimid. The membranes have an O₂ permeance of 9.36 GPU with an apparent dense-layer thickness of 1421 Å calculated from the O₂ permeability. SEM images show the high porosity underneath the dense skin. It indicates that non-solvent addition is not necessary in the inner spinning dope to induce the macroviod formation. The binodals of the Matrimid/solvent/H₂O and PSf/solvent/H₂O indicate that the composition of the spinning dope plays an important role in the structure and the gas separation performance of the dual-layer hollow fiber membranes. The delayed demixing of the inner spinning dope may fabricate low resistance support layers in the dual-layer hollow fiber membranes.     

Preparation and characterization of asymmetric polyethersulfone (PES) membranes

Flat‐sheet asymmetric polyethersulfone (PES) membranes were prepared from polyethersulfone (PES)/ polyethylene glycol (PEG)/ N‐methyl‐2‐pyrrolidone (NMP) system via phase inversion induced by immersion precipitation in water coagulation bath. Effects of propionic acid (PA) as a non‐solvent additive (NSA) on morphology and performance of the membranes prepared from PES/PEG 6000/NMP system in water coagulation bath were investigated. The cross section morphology of the membranes was studied by scanning electron microscopy (SEM). In addition, performance of the membranes was studied by water content measurements and separation experiments using pure water and human serum albumin (HSA) protein solution as feeds. According to SEM analysis, it was found out that the NSA has a significant influence on the structure of the skin layer and the sublayer. The obtained results indicated that addition of PA to the casting solution decreases permeation flux of the prepared membranes. Copyright © 2009 John Wiley & Sons, Ltd.     

PREPARATION OF POLYETHERSULFONE ULTRAFILTRATION MEMBRANES FOR MILK CONCENTRATION AND EFFECTS OF ADDITIVES ON THEIR MORPHOLOGY AND PERFORMANCE

Polyethersulfone membranes were prepared from quaternary systems containing N,N-dimethylacetamide （DMAc） as solvent, polyvinylpyrrolidone （PVP） as constant additive and acetic acid, acetone and water as variable additives. Phase inversion via immersion precipitation was employed for manufacturing of membranes. The prepared films were immersed in the mixture of pure water and 2-propanol （30/70 vol%） as the non-solvent. Acetic acid caused an increment in the flux at high polymer concentration （16 wt%） and a decline in the flux at low polymer concentrations （10 wt% and 13 wt%）. Acetone and water as the solvent in the casting solution declined the flux at any polymer concentration tested. The morphology and performance of the prepared membranes were investigated by scanning electron microscopy and separation experiments using milk as the feed.     

Correlation between macrovoid formation and the ternary phase diagram for polyethersulfone membranes prepared from two nearly similar solvents

The morphological structure of membranes prepared from two nearly similar systems consisting of water/N,N-dimethylacetamide (DMAc)/polyethersulfone (PES) and water/N-methyl-2-pyrrolidone (NMP)/polyethersulfone (PES) has been studied. The morphology of the prepared membranes showed that both systems exhibit an instantaneous liquid–liquid demixing that leads to the formation of macrovoids in the resulting structures. Nevertheless, the resulting macrovoid structures were contrary to the generally accepted concepts concerning macrovoid formation. The membranes morphologies showed that in spite of better miscibility between water and DMAc, which must promote the formation of channel- and finger-like structures, more sponge-like structures were observed in membranes prepared from the water/DMAc/PES system compared to those prepared from the water/NMP/PES system. To find the source of this unexpected phenomenon, the complete ternary phase diagrams consisting of theoretical binodal curves, vitrification boundaries, and gelation boundaries were constructed for both systems and it was shown that gelation process occurs earlier in the water/DMAc/PES system compared to the other system, which inhibits the growth of macrovoids in this system.     

Effect of gelation conditions on gas separation performance for asymmetric polysulfone membranes

Asymmetric gas separation membranes were prepared by the phase inversion technique under different gelation conditions from polysulfone/N,N-dimethylacetamide (DMAc) solutions. The dual bath method was employed to control the skin layer properties: the cast film was immersed in 2-propanol bath and water bath in sequence. The membranes were characterized by the permeance of oxygen and nitrogen gases and the observation with scanning electron microscopy (SEM). A thin layer of silicone rubber (PDMS) was laminated on the surface of each asymmetric polysulfone membrane to eliminate the effect of defects in the skin layer. The oxygen permeance was inversely proportional to the square root of immersion time in the first (2-propanol) bath. The skin layer thickness determined by SEM observation increased with an increase in the immersion time in the first bath. For a given immersion time, the oxygen permeance decreased with an increase in the polymer concentration in the casting solution. Selectivity of oxygen over nitrogen also depended both on the immersion time in the first bath and the polymer concentration.     

Membrane formation mechanism based on precipitation kinetics and membrane morphology: flat and hollow fiber polysulfone membranes

Membrane formation from poly(bisphenol-A sulfone)/poly(vinyl pyrrolidone)/dimethylacetamide/water systems by phase inversion process using immersion–precipitation technique was investigated. The initial precipitation rate was determined from light transmission experiments and the membranes morphologies were observed by scanning electron microscopy (SEM). These results were used to explain an observed oscillatory behavior in macrovoid occurrence, as well as to identify the region where spinodal demixing dominates the early stages of the phase inversion process. It is proposed as a qualitative model dividing the solution in three different layers during the polymer solution mass exchange with the coagulation bath. Each layer is associated with different precipitation kinetics leading to distinct morphologies. The model assumes that the macrovoids development is a function of the resistances created by precipitation kinetics of former layers.     

Preparation, characterization and effect of annealing on performance of cellulose acetate/sulfonated polysulfone and cellulose acetate/epoxy resin blend ultrafiltration membranes

Polymeric membranes based on cellulose acetate (CA)--sulfonated polysulfone blends at three different polymer compositions were prepared by solution blending and phase inversion technique, characterized and subjected to annealing at 70, 80 and 90 °C. The permeate water flux, separation of bovine serum albumin and its flux by the blend membranes before and after thermal treatment, have been compared and discussed. Similarly, CA and epoxy resin (diglycidyl ether of bisphenol-A) were blended in various compositions, in the presence and in the absence of polyethyleneglycol 600 as non-solvent additive, using N,N^′-dimethylformamide as solvent, and used for preparing ultraflltration membranes by phase inversion technique. The polymer blend composition, additive concentration, casting and gelation conditions were optimized. Blend membranes were characterized in terms of compaction, pure water flux, water content and membrane resistance. The effects of polymer blend composition and additive concentration on the above parameters were determined and the results are discussed.     

Polyethersulfone/polyacrylonitrile blend ultrafiltration membranes with different molecular weight of polyethylene glycol: preparation,morphology and antifouling properties

Asymmetric ultrafiltration (UF) membranes were prepared from blends of polyethersulfone (PES)/polyacrylonitrile (PAN) via phase inversion method induced by immersion precipitation. Polyethylene glycol (PEG) with four different molecular weights was used as pore former and hydrophilic polymeric additive. N,N‐dimethylformamide (DMF) and water were used as solvent and coagulant (nonsolvent), respectively. The effects of different proportion of PES/PAN and molecular weight of PEG on morphology and performance of the prepared membranes were investigated. Performance of the membranes was evaluated using UF experiments of pure water and buffered bovine serum albumin (BSA) solution as feed. The contact angle measurements indicated that the hydrophilicities of PES/PAN membrane increase by increasing the PAN concentration in the casting solution. However, performance of the membranes improves by increasing the PAN concentration in the casting solution up to 20% and then decreases with further addition of PAN. It was found out that the rejection of BSA decreases with increasing the PAN concentration in the casting solution. Furthermore, it was found that the performance of the membranes increases by increasing the molecular weight of PEG up to 1500 Da and then decreases with the higher molecular weights. The morphology of the prepared membranes was studied by scanning electron microscopy. Copyright © 2011 John Wiley & Sons, Ltd.     

溶剂对PVDF铸膜液相转化和微孔膜皮-亚两层结构的不同影响

采用皮-亚分步凝固成膜机理分析了3种不同溶剂对聚偏氟乙烯(PVDF)铸膜液相转化和膜结构的影响,采用浊度法测定铸膜液体系的热力学性质,沉淀速度采用光透射仪测定.结果显示,3种膜的皮层分相主要由热力学性质控制,均发生延时液固分相,生成了相互融合的球粒组成的致密皮层.3体系的亚层分相行为由动力学扩散过程控制;对于二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAc)体系亚层发生瞬时液液分相,结晶化对动力学过程影响小,表现为光透射曲线上分相时间t2短,生成了大孔结构为主的亚层,膜厚度、孔隙率和气通量均高、结晶度低;N,N-二甲基甲酰胺(DMF)体系亚层发生延时液液分相,结晶化对动力学过程影响大,t2长,生成蜂窝状孔结构亚层,其膜厚度、孔隙率和气通量较低,但膜的结晶度高.     

Microporous polyethersulfone membranes prepared under the combined precipitation conditions with non‐solvent additives

Using diethylene glycol (DegOH) as non‐solvent additive (NSA) and N, N‐dimethylacetamide (DMAc) as solvent (S), polyethersulfone (PES) flat sheet membranes were prepared via immersion precipitation combined with the vapor induced phase separation (VIPS) process. Light transmittance was used to follow the precipitation rate during the immersion process as well as during the VIPS stage. As the addition of the NSA, the viscosity of casting solutions increased, which led to a slow precipitation rate. Though the precipitation rate decreased, the instantaneous demixing type was maintained. High flux membranes were obtained only at a high mass ratio of NSA/S; producing membranes had cellular pores on the top surface and sponge‐like structure on cross section. The VIPS process prior to immersion precipitation was important for the formation of cellular pore on the surface. With the increase in exposure time, the liquid–liquid phase separation took place on the surface of casting solution; nucleation and growth induced the formation of cellular pore on the top surface. Coagulation bath temperature also had large effect on the precipitation rate; high temperature on coagulation bath mainly accelerated the transfer of solvent and non‐solvent. Higher flux membrane with a porous skin layer could be obtained at a high coagulation bath temperature, but at the same time the mechanism properties were weakened. Copyright © 2007 John Wiley & Sons, Ltd.     

Two‐stage phase separation of cellulose acetate membranes modified with plasma‐treated natural zeolite: Response surface modeling

Cellulose acetate (CA) microfiltration membranes were prepared by two‐stage vapor‐induced phase separation (VIPS) and immersion precipitation. To improve the hydrophilicity and permeability of the membranes at low operating pressures, plasma‐treated natural zeolite was incorporated into the membranes. A response surface methodology based on the three‐level central composite design (CCD) was used to model and optimize the casting solution composition of the membranes with the aim of maximizing membranes permeability. Three independent variables for CCD optimization were concentration of CA, polyvinylpyrrolidone (PVP) pore former, and plasma‐treated zeolite additive. The results showed that a second‐order polynomial model could properly predict the response (pure water flux) at any input variable values with a satisfying determination coefficient (R²) of 0.954. Also, analysis of variance (ANOVA) confirmed the adequacy of the obtained model. The permeability of the prepared membranes increased by increasing zeolite loading from 0.10 to 0.50 wt%, which was related to the membranes morphology and porosity and confirmed by scanning electron microscopy (SEM) images. Pure water flux of the membranes decreased by increasing CA concentration while an optimum PVP amount was required to reach the maximum flux. The result of the bubble point analysis well matched with surface SEM images of the membranes and permeability trend predicted by CCD model. Also, the prepared CA membranes with different compositions showed no toxicity for mouse L929 fibroblast, which indicated their nontoxic and biocompatible nature.     

Mixed matrix membranes of polysulfone/polyimide reinforced with modified zeolite based filler: Preparation,properties and application

In this work,polysulfone/polyimide (PSf/PI) mixed matrix membranes were fabricated by reinforcement of modified zeolite (MZ) particles through solution casting method for investigation of antibacterial activity against two gram negative bacteria (Salmonella typhi,Klebsellapneumonia) and two gram positive bacteria (Staphylococcus aureus,Bacillus subtilis).The modified zeolite particles were incorporated to PSf and PI matrix and the influence of these particles on thermal,mechanical and structural properties was evaluated.The morphological evolution was investigated through scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis,which revealed good compatibility between organic polymer matrix and inorganic filler.Mechanical stability was investigated by tensile testing while thermal analysis was evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).This revealed improvement in thermal properties with increasing filler concentration from 1 wt％ to 10 wt％.Structural analysis was successfully done using X-ray diffraction analysis (XRD) and Fourier transform infrared (FTIR) spectroscopy.Solvent content of fabricated mixed matrix membranes was observed to decrease while moving from more hydrophilic to less hydrophilic solvent.However,addition of filler content enhanced the porosity of fabricated membranes.The synthesized mixed matrix membranes exhibited good antibacterial activity and the highest activity was shown by PSf/PI/MZ mixed matrix membrane.Therefore,the combination effect of PSf,PI and MZ sufficiently enhanced the antibacterial activity of mixed matrix membranes.     

Morphology of solidified polysulfone structures obtained by wet phase separation

Evidence is presented that all three theoretically predicted modes of phase separation take place in the ternary system polysulfone(PSf)/N,N-dimethyl acetamide(DMA)/water during the process of wet phase separation (WPS). The elementary process of solidification is reconsidered with regard to the (non-) equilibrium phase separation. Cast solutions with more than 15 wt% of PSf undergo nucleation and growth of the polymer lean phase with formation of separation membranes characterised by a cellular structure. When cast solutions with about 5-7 wt% of PSf undergo WPS, somewhere inside the ternary system conditions are established so that alongside other solidified PSf structures the bicontinuous spinodal structures superimposed by bead-like structures are also formed. Variety of lacy PSf structures with less/more polymer beads is the manifestation of the primary phase separation by the spinodal mode superimposed by the secondary phase separation taking place by heterogeneous nucleation and growth of the polymer rich phase mode. Latex formation during the WPS will also be explained. Skin formation on the cast solution - coagulation bath interface by direct accumulation of polymer is established regardless of the PSf content in the cast solution.     

Polyethersulfone sulfonated by chlorosulfonic acid and its membrane characteristics

Sulfonated polyethersulfone (SPES) was prepared by homogeneous method with chlorosulfonic acid as sulfonating agent and concentrated sulfuric acid as solvent. The presence of sulfonic acid groups in SPES was confirmed by ¹H NMR and FTIR. Thermogravimetric analysis (TGA) studies were carried out to investigate the thermal stability of SPES. Membranes were cast from SPES solutions in N-methyl-2-pyrrolidone. Tensile strength of prepared membranes decreased with degree of sulfonation (DS) but water uptakes of SPES membranes increased with DS. Compared with unsulfonated polyethersulfone membrane, the hydrophilicity of SPES membranes was increased, as shown by a reduced contact angle with water. Amorphous structures for SPES membranes were detected by X-ray diffraction. Atomic force microscopy phase images of the membranes clearly showed the hydrophilic domains at higher DS.     

Preparation and characterization of TiO2/Pebax/(PSf‐PES) thin film nanocomposite membrane for humic acid removal from water

New thin film composite (TFC) membrane was prepared via coating of Pebax on PSf‐PES blend membrane as support, and its application in wastewater treatment was investigated. To modify this membrane, hydrophilic TiO₂ nanoparticles were coated on its surface at different loadings via dip coating technique. The as‐prepared membrane was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), field emission SEM, and contact angle analysis. The Fourier transform infrared spectroscopy analysis and surface SEM images indicated that TiO₂ was successfully coated on the membrane surface. In addition, the results stated that the hydrophilicity and roughness of membrane surface increased by addition of TiO₂ nanoparticles. Performance of TFC and modified TFC membranes was evaluated through humic acid removal from aqueous solution. Maximum permeate flux and humic acid rejection were obtained at 0.03 and 0.01 wt% TiO₂ loadings, respectively. Rejection was enhanced from 96.38% to 98.92% by the increase of feed concentration from 10 to 30 ppm. Additionally, membrane antifouling parameters at different pressures and feed concentration were determined. The results indicated that surface modification of membranes could be an effective method for improvement of membrane antifouling property.     

The influence of phase inversion process modified by chemical reaction on membrane properties and morphology

In this study, the chemical reaction between acetic acid (CH₃COOH) used as non-solvent additive of casting solution and sodium carbonate (Na₂CO₃) dissolved in water as coagulant was employed to modify the classical phase inversion process. By means of this method, the polyethersulphone (PES) ultrafiltration (UF) membranes were prepared. The influence of acetic acid on the properties of the polymer solution was examined by viscometry and related to the morphology of the membrane prepared from the casting solution. The membranes were characterized in terms of the pure water flux, solute transport and field emission scanning electron microscope (FESEM) observation. It was found that chemical reaction between the additive and coagulant increases membrane permeability and mean pore size while maintaining the relatively narrow pore size distribution. FESEM images also confirmed that the chemical reaction contributes to suppress the formation of macrovoid and enhance the interconnectivity of pore. Furthermore, the potential mechanism of membrane formation influenced by chemical reaction was explored tentatively.     

Nano-enabled microtechnology: polysulfone nanocomposites incorporating cellulose nanocrystals

Microchannel devices hold the potential to transform many separation processes. This preliminary study investigated the feasibility of incorporating cellulose nanocrystals (CNXLs) into polysulfone, a commonly used ultrafiltration membrane polymer. Incorporating CNXLs into non-water soluble polymers without aggregation has been problematic. A solvent exchange process was developed that successfully transferred an aqueous CNXL dispersion into the organic solvent N-methylpyrrolidone (NMP), which is a solvent for polysulfone (PSf). Films were prepared from the solution of PSf in NMP with dispersed CNXLs by a phase inversion process. Films were then examined by scanning electron microscopy and tested for their transport and mechanical properties. The interaction between the polymer matrix and the CNXL filler was studied by means of thermogravimetric analysis (TGA), which suggested a close interaction between the polymer and filler at the 2% filler loading. The tensile modulus showed a large increase beyond 1% filler loading, which could be due to a percolation effect. The water vapor transport rate increased with increase in filler loading. Agglomeration of the CNXLs seemed to be taking place at filler loadings >7%.     

Enhancing the performance of TFC nanofiltration membranes by adding organic acids in polysulfone support layer

Throughout this study, the effect of certain organic acids, methacrylic acid, lactic acid and tartaric acid, doped in polysulfone (PSF) casting solution onto the performance of nanofiltration (NF) membranes was investigated. Different NF membranes have been prepared from m-phenylenediamine and trimesoylchloride onto the top surface of the acid-modified PSF membranes through regulating the concentration and contact time of the conventional interfacial polymerization process. The study of scanning electron microscopy (SEM) was used to investigate the influence of acids on the morphology of membranes and cross-sectional structures. The functional groups, hydroxyl and carboxylic acid, of the acids have resulted in a significant increase in membrane thickness, porosity and hydrophilicity, with a decrease in macrovoid capacity of the PSF layer. The acid-modified PSF/TFC membranes showed higher rejection of salt, with an increment in water flux compared to the neat membrane. Water flux and salt rejection (R_s %) of the control membrane was 7.6 L/m² h and 65.4%, whereas polysulfone/methacrylic acid (PSF/MAAc), polysulfone/tartaric acid (PSF/TAc), and polysulfone/lactic acid (PSF/LAc) were 16.8, 18.5, and 20.2 L/m² h and 88, 88.2 and 94.1%, respectively. Efficiency of prepared NF membranes under various inlet pressures and specific salts was investigated with selectivity and salt rejection. The salt rejection of a mixed salt solution was found to meet the order of R_s % CaSO₄ ≥ R_s % Na₂SO₄ ˃ R_s % MgSO₄ ˃ R_s MgCl₂ ˃ Rs % NaCl.     

Solution properties of poly(amic acid)–NMP containing LiCl and their effects on membrane morphologies

Physical properties of poly(amic acid) (PAA) casting solutions in N-methyl-2-pyrrolidone (NMP) containing lithium chloride (LiCl) were characterized by viscometry and dynamic light scattering (DLS) and were related to the morphological properties of asymmetric membranes prepared from these solutions. At a fixed polymer concentration, the increase in viscosity of the PAA solutions with increasing LiCl content is mainly determined by the viscosity of the salt–solvent medium, implying that the LiCl–NMP interactions are stronger than those between LiCl and PAA. Because of the strong salt–solvent interactions, complexes between LiCl and NMP are formed. The complexes reduce the solvent power of NMP for PAA inducing polymer aggregation (clustering) and/or transient cross-links in the solutions. Dynamic light scattering results for salt-containing solutions at low PAA concentrations support the existence of these aggregations. Solutions without salt showed a single relaxation, but solutions with LiCl exhibit multiple relaxation modes; two diffusional modes of cooperative and aggregates, and one angle independent transient network mode. The polymer aggregates and transient cross-links form a gel-like structure in the casting solution film and hinder macrovoid formation during phase inversion, resulting in asymmetric membranes with a primarily sponge-like structure.     

Effect of PEG additive on membrane formation by phase inversion

This study investigates the effect of PEG additive as a pore-former on the structure formation of membranes and their permeation properties connected with the changes of thermodynamic and kinetic properties in phase inversion process. The membranes were prepared by using polysulfone (PSf)/N-methyl-2-pyrrolidone (NMP)/poly(ethylene glycol) (PEG) casting solution and water coagulant. The resulting membranes prepared by changing the molecular weight of PEG additive and the ratio of PEG to NMP were characterized by scanning electron microscope observations, measurements of water flux and PEG rejection. The thermodynamic and kinetic properties of membrane-forming system were studied through coagulation value, light transmittance and viscosity. The correlations between the final membrane structure/permeation properties and thermodynamic/kinetic properties of membrane forming system are discussed extensively.