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.     

Diffusion competition between solvent and nonsolvent during the coagulation process of cellulose / ammonia / ammonium thiocynate fiber spinning system

An investigation of the diffusion competition between solvent and nonsolvent in a coagulation bath is presented for the formation of a new cellulosic fiber by wet-spinning. The system consisted of the spinnable cellulose solution with a mixture of liquid ammonia/ammonia thiocynate as the solvent and low-molecular-weight alcohols as the nonsolvents. The diffusion competition between solvent and nonsolvent was quantitatively characterized in terms of their mass transfer rate differences. The measurements of this rate difference were performed on the model filament shaped from gelled cellulose solutions. Results revealed that an increase in molecular size of coagulant, bath temperature, and coagulant concentration in the bath enhanced preferential diffusion of solvent from cellulose solution. Fiber spinning experiments showed that a higher value of the initial modulus of the fiber was attained with a coagulation condition providing a lower value of mass transfer rate difference. The importance of mass transfer rate difference was also shown in the influence of the fiber cross-sectional shapes.     

Membrane formation by isothermal precipitation in polyamide-formic acid-water systems I. Description of membrane morphology

Aliphatic polyamides (Nylon-66 and a Nylon-6, -66, -610 terpolymer) were isothermally precipitated from formic acid solution by immersing in an aqueous nonsolvent bath or a solvent/nonsolvent mixture. Depending on the composition of the polymer solution and nonsolvent bath, phase separation by nucleation and growth can be initiated for a liquid-liquid phase separation process, a crystallization process or a combined process. Under certain conditions, crystallization of Nylon-66 results in a membrane with a uniform skinless microporous structure that was rapidly wetted by water. In contrast, liquid-liquid phase separation produces a polyamide film with largely unconnected cellular voids that is as a result not wetted by water. © 1995 John Wiley & Sons, Inc.     

Investigation of the dynamics of poly(ether sulfone) membrane formation by immersion precipitation

Cast‐leaching experiments were carried out to investigate the dynamics of membrane formation by immersion precipitation, with an emphasis on the outflow of the solvent from casting solutions during the phase‐separation process. The casting solutions, consisting of poly(ether sulfone) as the polymer, N‐methyl‐2‐pyrolidone as the solvent, and water (H₂O), isopropyl alcohol, 1‐butanol, and diethylene glycol as nonsolvent additives (NSAs), were immersed in a coagulation bath. Two thermodynamically vastly different coagulants? H₂O, a strong coagulant, and ethylene glycol, a weak coagulant—were used to study the effect of the coagulant on the dynamics of membrane formation. The results showed that the outflow of the solvent during the initial stage of membrane formation was controlled by Fickian diffusion within the extremely wide range of conditions studied, that is, polymer concentrations of 10–38%, approaching ratios of 0–0.95, and thermodynamically vastly different NSAs and coagulants. The role of the initial state of the membrane‐forming solution, especially the conformational state of macromolecules in the membrane‐forming process, was examined. In contrast to those works on the behavior of small molecules, an attempt was made to qualitatively interpret membrane formation from the viewpoint of macromolecules. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 498–510, 2005     

Formation and gas flux of asymmetric PMMA membranes

In the present work, PMMA membranes were prepared by wet phase immersion methods to improve their gas fluxes. It is found that different membrane structure can be obtained by using different nonsolvent-solvent pairs. To completely describe the membrane formation process, the nonsolvent-solvent miscibility and the interfacial polymer concentration in casting solution should be considered accompanied by the ternary phase diagram. A simplified solution-diffusion model was developed to estimate the interfacial polymer concentration. In addition, the effects of adding solvent into the coagulation bath and adding nonsolvent into the casting solution are discussed.     

Effect of the preparation conditions on the formation of asymmetric poly(vinylidene fluoride) hollow fibre membranes with a dense skin

Integrally skinned asymmetric poly(vinylidene fluoride) hollow fibre membranes were prepared and characterized. The effects of phase inversion methods (dry-wet or wet) and spinning conditions, such as the type of solvent (NMP, DMAc), the concentration of polymer in dope solution, temperature of the external coagulation bath and the composition of the inner coagulant on the morphology and on the formation of a dense skin layer were investigated. The structure of the membranes was analyzed by scanning electron microscopy and the gas permeation properties with six different gases (He, H₂, N₂, O₂, CH₄ and CO₂) were measured at 25 °C to confirm the integrity of the selective skin layer. Under the proper conditions highly selective and permeable PVDF hollow fibre membranes were thus obtained by dry-wet spinning of a 30 wt.% PVDF solution in DMAc, using hot water (50 °C) as the external coagulant and a bore fluid of pure water as the internal coagulant. The best membrane had a selective outer skin with an effective thickness of approximately 0.2 μm. The ideal selectivity of the hollow fibres approached or even exceeded the intrinsic ideal selectivity of a dense PVDF film, for instance the selectivity for He over N₂ was 86.2 for the hollow fibre, whereas it was 83.5 for a dense PVDF reference film. DSC and FT-IR/ATR analysis indicated a higher fraction of the β-crystal phase in the selective skin and a high overall crystallinity than in the melt-processed film. The latter explains the relatively high selectivity and low permeability of the membranes. Intrinsic polymer properties make the membranes also suitable for vapour transport than for gas separation.     

Synthesis and Characterization of Poly(ether-block-amide) Membranes

Poly(ether-block-amide) membranes were made via casting a solution on a nonsolvent (water) surface. In this research, effects of different parameters such as ratio of solvent mixture (n-butanol/isopropanol), temperature, composition of coagulation bath (water) and polymer concentration, on quality of the thin film membranes were studied. The mechanism of membrane formation involves solution spreading, solvent–nonsolvent exchange, and partial evaporation of the solvent steps. Solvent- nonsolvent exchange is the main step in membrane formation and determines membrane morphology. However, at higher temperature of polymeric solution greater portion of solvent evaporates. The results showed that type of demixing process (mutual affinity between solvent and nonsolvent) has important role in film formation. Also, addition of solvent to the nonsolvent bath is effective on membrane morphology. The film quality enhances with increasing isopropanol ratio in the solvent mixture. This behavior can be related to increasing of solution surface tension, reduction of interfacial tension between solution and nonsolvent and delayed solvent-nonsolvent demixing. Uniform films were made at a temperature rang of 60–80 °C and a polymer concentration of 4–7 wt%. Morphology of the membranes was investigated with scanning electron micrograph (SEM). Pervaporation of ethyl butyrate/water mixtures was studied using these membranes and high separation performance was achieved. For ethyl butyrate/water mixtures, It was observed that both permeation flux and separation factor increase with increasing ethyl butyrate content in the feed. Increasing temperature in limited range studied resulted in decreasing separation factor and increasing permeation flux.     

Morphology changes of polyvinylidene fluoride membrane under different phase separation mechanisms

In this study, the strong morphology changes of polyvinylidene fluoride (PVDF) membrane were demonstrated by changing phase separation process from a diffusion induced phase separation (DIPS) to its combination with a thermally induced phase separation (TIPS) which can be attained via changing the diluent – dibutyl phthalate (DBP) content in solvent – N,N-dimethylacetamide (DMAc). The solvent became poor when it mixed with DBP, so TIPS could occur in the quenching process which resulted in a rapid crystallization process. In this process, the porous skin and interlocked small crystallite particle (or bi-continuous) morphologies were formed, while the porous skin and leaf-like network morphology came from the rapidly crystallizing in TIPS, the large spherulite and dense skin could be attributed to the relaxed crystallization in DIPS, the finger-like macro-void and dense skin resulted from the liquid–liquid phase separation in DIPS. Simply speaking, the different membrane morphologies can be obtained by changing the DBP content in DMAc and the coagulation bath temperature.     

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.     

Effect of the polarity of additional solvent on membrane formation in polysulfone/N-methyl-2-pyrrolidone/water ternary system

Asymmetric polysulfone membranes were prepared by wet phase inversion method with different demixing rate of casting solutions. The influent factor of demixing rate was focused on the polarity of additive in the polysulfone/N-methyl-2-pyrrolidone/water ternary system. With increasing the polarity of alcohols in the casting solution, the decrease in skin layer thickness was observed and then a poor separation performance of membranes can be obtained. It was found that the polar additive caused the rapidly demixing of casting solution in coagulation bath and formed porous asymmetric membranes with defective skin layer. In the other case, chloroform was used as the non-polar additive in casting solution. With increasing the mount of chloroform in the casting solution, the increase in skin layer thickness was observed and then lead to a good separation performance of these membranes. It was found that of the non-polar additive delays the demixing rate of casting solution in this ternary system. The separation performance of these asymmetric membranes were characterized by the measurement of dehydration of ethanol/water mixture by pervaporation and observed the morphology by scanning electron microscopy. It was found that the separation performance of asymmetric polysulfone membrane strongly depends on the polarity of adding solvent in polysulfone/N-methyl-2-pyrrolidone/water ternary system.     

Control of the porosity of asymmetric TPX membranes

In the present work, the effect of adding nonsolvent in the casting solution on the porosity of asymmetric TPX (poly(4-methyl-1-pentene)) membranes was systematically investigated. A series of alcohols, with carbon number ranging from 2 to 14, was added in the casting solution (TPX/cyclohexane) to alter the porosity of two types of asymmetric TPX membranes, prepared by using ethanol and 1-propanol as the coagulation medium. It was found that the effect of nonsolvent on membrane porosity is different for the two types of membranes and the difference can be reasoned by considering the exchange rate between the polymer solvent and the coagulation medium during membrane formation. The results indicate that, for the membrane formation system with low exchange rate between coagulant and solvent, the membrane porosity is controlled by the coagulation value, defined as the volume of coagulant required to demix the casting solution. On the other hand, for the system with high exchange rate, the membrane porosity is not controlled by the coagulation value but by the penetration speed of the coagulant front moving through the casting solution.     

扩散致相转化法制备结晶性聚合物多孔膜

介绍了扩散致相转化法制备结晶性聚合物多孔膜的研究现状。其三元等温成膜体系的相图包含液-液分相和固-液分相两种相分离方式,是理解成膜过程的重要工具,总结了成膜机理和膜的结构形貌：单纯S-L相分离生成粒子状对称膜结构;单纯L-L相分离生成蜂窝状非对称膜结构;两种相分离方式竞争发生将生成多样的混合膜结构。铸膜液浓度、非溶剂种类、铸膜溶剂组成、凝胶浴组成、制膜温度是影响膜结构形貌的主要因素。     

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.     

INFLUENCE OF ALCOHOL-BASED NONSOLVENTS ON THE FORMATION AND MORPHOLOGY OF PVDF MEMBRANES IN PHASE INVERSION PROCESS

Through the preparation of PVDF membranes using various nonsolvent coagulation baths following the phase inversion process, the influence of alcohol-based nonsolvents on the formation and structure of PVDF membranes were investigated. The light scattering and light transmission measurements were used to characterize the equilibrium phase diagram and the gelation speed, respectively. The locations of the crystallization-induced gelation boundaries for various systems and precipitation processes were explained from the corresponding thermodynamic and kinetic parameters. It was found that the better affinity between alcohol-based nonsolvents and DMAc solvent caused the gelation boundaries further away from the PVDF-DMAc axis with the coagulation bath varying from water, methanol, ethanol to iso-propanol. Due to the lower exchange rate of DMAc and alcohols, the delayed demixing took place for the membrane-forming using alcohols as baths, and the delayed time became longer when the coagulation bath was changed from methanol, ethanol to iso-propanol. The characterization results of membranes indicate that the influence of nonsolvents on the phase diagram and the precipitation process are in agreement with those on the membrane morphology. The better thermodynamic stability and a low exchange diffusion rate of PVDF/DMAc/alcohols favor the liquid-solid phase separation in gelation process, and therefore yield the membranes with a porous upper surface, a particular bottom surface and symmetrical structure.     

溶剂对相分离法制备聚偏氟乙烯微孔膜性质的影响

研究了用相转换法制备聚偏氟乙烯（PVDF）微孔膜时溶剂对成膜性质的影响.用浊点法测定了二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、磷酸三甲酯等五种溶剂配制的质量分数为wPVDF=0.12的铸膜液在30℃时的相分离点,显微镜拍照法测定了这些铸膜液与水接触时相分离前沿推进速率,泡点法测定了膜孔径,并测定了气体通量.结果表明,二甲基亚砜、磷酸三甲酯、N,N-二甲基乙酰胺是适于制作聚偏氟乙烯微孔膜的溶剂.     

Fabrication study of polysulfone hollow-fiber microfiltration membranes: Optimal dope viscosity for nucleation and growth

Fabrication of polysulfone hollow-fiber microfiltration membranes through non-solvent induced phase separation (NIPS) by dry–wet spinning was studied. For all sample preparations, we used N-methylpyrrolidone (NMP) as solvent, polyethylene glycol (PEG) as additive, aqueous NMP solution as bore liquid, and water as coagulation bath. Particular focus was placed on the influence of PEG molecular weight (Mw) on membrane structure. Characterization of the obtained membranes was performed by measuring pure water permeate flux, tensile strength, and tensile elongation at break, and by analyzing scanning electron microscope (SEM) images of hollow-fiber cross-sections, outer surfaces, and inner surfaces.     

A new modeling of asymmetric membrane formation in rapid mass transfer system

Mass transfer process involved in the immersion precipitation of polyurethane/dimethylformamide (DMF)/water system was investigated. The set of diffusion equations describing the local composition of the membrane solution as a function of space coordinate and time were solved by numerical method, and the composition path in the phase diagram was obtained. Instead of boundary conditions based on the instantaneous equilibrium assumption between membrane solution and coagulation bath, new boundary conditions were set up by using mass transfer formalism at the interface which is especially valid in the condition that the mass transfer rate is extremely rapid. Phase separation phenomena during immersion precipitation were taken into account to continue the calculation after phase separation. The calculated results showed that the chance of phase separation via spinodal decomposition increases with the strength of nonsolvent, addition of nonsolvent to the dope solution, and the use of more hydrophobic polymer. The proposed model is the improvement of the previous works eliminating the equilibrium assumption at the interface and extending the calculation after phase separation.     

Solid scintillation proximity membranes: I: Characterization of polysulfone-inorganic fluor morphologies precipitated from NMP solutions

Solid scintillation proximity membranes were prepared by coagulation of polysulfone polymer solutions containing cerium-activated yttrium silicate particles (CAYS) as a fluor. Membranes were formed by three different solidification processes: precipitation of the polymer-rich phase after liquid–liquid phase separation, vitrification via solvent evaporation, or rapid polymer collapse due to fast exchange between solvent in the solution and nonsolvent in the coagulation bath. The results indicate that when the coagulation process includes the liquid–liquid phase separation due to nucleation of the polymer-lean phase, the inorganic fluor particles are expressed out of the polymer-rich phase and separated from the polymer matrix. On the contrary, solidification by the vitrification of the polymer solution through solvent evaporation results in the inorganic fluors being surrounded by the polymer matrix, much like the dispersed state in the solution. In contrast, rapid collapse of the polymer also induces entrapment of the fluor in the polymer structure. However, fluor impregnation in the polymer matrix is distinguished from that in the vitrified membrane in that the impregnation is due to localized impingement of the fluor on the polymer structure rather than envelopment by polymer molecules.     

凝固浴温度对纤维素中空纤维膜结构及气体渗透分离性能影响研究

利用新型溶解工艺,在不同的凝固浴温度(0～60℃)下制备了纤维素中空纤维膜,考察了凝固浴温度对纤维素中空纤维膜结晶结构、机械性能和气体渗透分离性能的影响.扫描电镜表征表明凝固浴温度的升高使得纤维素中空纤维膜更加疏松,并且内侧的指状孔变大变多;膜的机械性能随凝固浴温度的升高而变差;XRD谱图显示凝固浴温度对纤维素中空纤维...     

Influence of Polymer Solvents on the Properties of Halloysite-Modified Polyethersulfone Membranes Prepared by Wet Phase Inversion

Ultrafiltration polyethersulfone (PES) membranes were prepared by wet phase inversion. Commercial halloysite nanotubes (HNTs) in the quantities of 0.5 wt% vs. PES (15 wt%) were introduced into the casting solution containing the polymer and different solvents: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), or 1-methyl-2-pyrrolidinone (NMP). The type of solvent influenced the membranes’ morphology and topography, as well as permeability, separation characteristics, and antifouling and antibacterial properties. The membranes prepared using DMA exhibited the loosest cross-section structure with the thinnest skin and the roughest surface, while the densest and smoothest were the DMF-based membranes. The advanced contact angles were visibly lower in the case of the membranes prepared using DMF compared to the other solvents. The highest water permeability was observed for the DMA-based membranes, however, the most significant effect of the modification with HNTs was found for the NMP-based series. Regardless of the solvent, the introduction of HNTs resulted in an improvement of the separation properties of membranes. A noticeable enhancement of antifouling performance upon application of HNTs was found only in the case of DMF-based membranes. The study of the antibacterial properties showed that the increase in surface roughness had a positive effect on the inhibition of E. coli growth.