Preparation and characterization of a poly(vinyl alcohol)/tetraethoxysilane ultrafiltration membrane by a sol–gel method

Using poly(vinyl alcohol) (PVA) with highly hydrophilic properties as membrane material and poly(ethylene glycol) (PEG) as an additive, we prepared PVA/tetraethoxysilane (TEOS) ultrafiltration (UF) membranes with good antifouling properties by a sol–gel method. The PVA/TEOS UF membranes were characterized by X‐ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron microscopy, and static contact angle of measurement of water. The hybridization of TEOS to PVA for preparing the PVA/TEOS UF membranes achieved the required permeation performance and good antifouling behaviors. The morphology and permeation performance of the PVA/TEOS membranes varied with the different TEOS loadings and PEG contents. The pure water fluxes (J_W) increased and the rejections (Rs) decreased with increasing TEOS loading and PEG content. The PVA/TEOS UF membrane with a PVA/TEOS/PEG/H₂O composition mass ratio of 10/3/4/83 in the dope solution had a J_W of 66.5 L m^?2 h^?1 and an R of 60.3% when we filtered it with 300 ppm of bovine serum albumin aqueous solution at an operational pressure difference of 0.1 MPa. In addition, the filtration and backwashing experiment proved that the PVA/TEOS membranes possessed good long‐term antifouling abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4066–4074, 2013     

Synthesis of porous poly(N‐isopropylacrylamide) gel beads by sedimentation polymerization and their morphology

Sedimentation polymerization of aqueous solutions of N‐isopropylacrylamide (NIPA) was carried out to prepare porous poly(N‐isopropylacrylamide) (PNIPA) beads. When small amounts of DMF and a radical accelerator were added to the monomer solution, the polymerization proceeded smoothly to give polymer beads with a very narrow size distribution. The rate of swelling of the resulting bead increased with increasing crosslinker content and was also affected by the type of crosslinker used. When amounts higher than 1 mol % N,N′‐methylenebisacrylamide or 3 mol % diethylene glycol diacrylate (DEGDA) were used as a crosslinker, the resulting beads underwent rapid swelling in water at 20°C, reaching the equilibrium within 5 min. A cross‐sectional photograph of a typical dried bead showed that it had a very complex morphology consisting of a large and irregular void, highly porous region, and nonporous region. The swelling rate was directly dependent on the morphology of the beads. PNIPA beads with well‐developed porous areas show a high swelling rate. Although PNIPA beads produced from DEGDA had well‐developed porous structures, they were able to effectively concentrate blue dextran from the dilute aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 842–850, 2007     

Hydrophilic microporous PES membranes prepared by PES/PEG/DMAc casting solutions

Microporous poly(ether sulfones) (PES) membranes were prepared via phase inversion using poly (ethylene glycol) (PEG) as additive and N,N‐dimethylacetamide (DMAc) as solvent. Thermodynamic of the casting solutions was studied by coagulation value while precipitation rate was observed by light transmittance measurement. It was found that casting solution with PEG200 as additive was thermodynamically less stable than those with PEG400 and PEG600 as additive and easier to cause phase separation in exposure time. With the increase of PEG200 concentration, the casting solution became thermodynamically less stable and easier to cause phase separation in exposure time, but precipitation rate during immersion precipitation decreased because of the increased viscosities. ATR‐FTIR spectra and TGA curves showed that the membranes prepared using PEG200 as additive had less PEG residual than those of PEG400 and PEG600, but it showed better permeation performance than that prepared using PEG400 and PEG600 as additive. With the increase of PEG200 concentration from 30 to 70 wt %, the cross section structure changed from macrovoid to sponge‐like, micropores with a mean pore size around 0.1 μm began to form on the top surface. When the PEG200 concentration is 60 wt %, the pure water flux was 1845 L m^?2 h^?1 bar^?1, which is the highest value. As the PEG200 concentration increased from 30 to 60 wt %, the contact angles decreased from 82.1° to 58.2°. As the addition amount of PEG200 increased, the residual PEG made the prepared membranes more hydrophilic. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of a polyimide nanofiltration membrane for lubricant solvent recovery

Polyimide (PI) membrane has been proven to be an efficient approach for solvent recovery. However, the inherent fragility of the PI membrane limits the range of separation conditions and process economics. In this study, copolyimides were synthesized from 3,3′,4,4′‐benzophenone–tetracarboxylic dianhydride (BTDA) and 4,4′‐biamino‐3,3′‐dimethyldiphenyl–methane (DMMDA) by chemical imidization in a two‐step procedure. Then, a PI nanofiltration (NF) membrane was prepared through a phase‐inversion process for solvent recovery from lube oil filtrates. The results indicated that the immersion of the PI (BTDA–DMMDA) NF membrane in a 1,6‐diaminohexane/ethanol crosslinking agent solution carried on the chemical crosslinking modification, which could effectively improve the solvent resistance of the NF membrane. Moreover, the addition of inorganic salt in the polymer solution further enhanced the solvent resistance and pressure resistance of the membrane, which was favorable for the solvent recovery. The lubricant rejection was above 93%, and the solvent flux was about 30 L m^?2 h^?1 with the NF membrane prepared in optimum conditions, and this membrane showed great potential for future development in the application of solvent recovery from lube oil filtrates. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40338.     

Preparation of a heterogeneous hollow‐fiber affinity membrane modified with a mercapto chelating resin

A high‐quality, heterogeneous hollow‐fiber affinity membranes modified with mercapto was prepared through phase separation with blends of a chelating resin and polysulfone as membrane materials, poly(ethylene glycol) as an additive, N,N‐dimethylacetamide as a solvent, and water as an extraction solvent. The effects of the blending ratio and chelating resin grain size on the structure of the hollow‐fiber affinity membrane were studied. The effects of the composition of the spin‐cast solution and process parameters of dry–wet spinning on the structure of the heterogeneous hollow‐fiber affinity membrane were investigated. The pore size, porosity, and water flux of the hollow‐fiber affinity membrane all decreased with an increase in the additive content, bore liquid, and dry‐spinning distance. With an increase in the extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow‐fiber affinity membrane all increased, but the pore size and water flux of the hollow‐fiber affinity membrane decreased. It was also found that the effects of the internal coagulant composition and external coagulant composition on the structure of the heterogeneous hollow‐fiber affinity membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of the heterogeneous hollow‐fiber affinity membrane and decrease the pore size, porosity, and water flux of the heterogeneous hollow‐fiber affinity membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the heterogeneous hollow‐fiber affinity membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Inherent porous structure modified by titanium dioxide nanoparticle incorporation and effect on the fouling behavior of hybrid poly(vinylidene fluoride) membranes

The incorporation of nanoparticles (NPs) into a casting solution is a widely used practice for controlling the membrane fouling tendency, but the specific role of NPs in fouling control from an internal porous structure optimization has seldom been investigated. In this study, we evaluated the specific role of titanium dioxide (TiO₂)–NPs (Degussa P25) in mitigating membrane organic fouling. We prepared the membranes by tailoring the concentrations of the NPs well; this resulted in an optimized membrane microstructure consisting of fingerlike voids (beneath the skin layer of the membrane) and spongy voids (adjacent to the fingerlike voids). The NP incorporation induced the formation of spongy voids beneath the skin layer, and the increase in the NP concentration increased the formation of spongy voids. Moreover, surface images obtained by scanning electron microscopy, X‐ray photoelectron spectroscopy results, and contact angles confirmed that TiO₂–NPs were almost absent on the skin layer. Antifouling experiments were performed with a model organic foulant in two flow orientations [fingerlike voids facing the retentate (FVR) and spongy voids facing the retentate (SVR)]. The results show that the membrane fluxes in FVR decreased more than those in SVR. The membrane with 1.5 wt % TiO₂ operated in SVR exhibited the lowest flux decline; this suggested that spongy voids with TiO₂ exposure could mitigate fouling to a greater extent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43265.     

Preparation of porous poly(oxymethylene) membrane with high durability against solvents by a thermally induced phase‐separation method

Porous poly(oxymethylene) membranes were prepared as new solvent‐resistant membranes by a thermally induced phase‐separation method. Porous structures were formed by solid–liquid phase separation (polymer crystallization) rather than liquid–liquid phase separation. The pores existed in the intraspherulitic and interspherulitic regions. The effects of the polymer weight percentage and cooling rate on toluene permeance and solute rejection were investigated. The solvent resistance of the membranes was tested by the immersion of the membranes in organic solvents for 1 month, and high durability against the solvents was confirmed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1993–1999, 2002     

Investigating the membrane morphology of water/solvent/nylon 6 systems

In this study, nylon 6 membranes were prepared in a water coagulation bath with two types of solvents, CaCl₂–methanol (CaClMe) and formic acid (FA). The morphology of the membranes, which was controlled by the phase behavior of their solutions, were connected to the mechanism of demixing, including liquid–liquid and liquid‐crystallization. Ternary phase diagrams showed that the CaClMe system coagulated significantly faster than the FA system. As observed by scanning electron microscopy, the CaClMe membrane had a porous, interconnected pore structure with macrovoids, whereas the FA membrane had a dense, spherulitic surface with a closed cell morphology. The high reaction surface of the CaClMe membrane with dye molecules provided outstanding dye rejection. Also, thermal analysis by differential scanning calorimetry showed that the slow coagulation of the FA system facilitated the formation of stable α‐form crystals rather than a metastable γ‐form structure. The results show that the phase‐separation mechanism was switched from liquid–liquid to liquid‐crystallization through a change in the solvent type from CaClMe to FA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Solubility parameter estimation and phase inversion modeling of bentonite-doped polymeric membrane systems

Effects of bentonite concentration on morphology and permeation characteristics of bentonite-doped polysulfone membranes were investigated. Solubility sphere for bentonite was constructed to estimate its solubility parameter. Thermodynamic modeling of phase inversion of this system was carried out using Flory–Huggins theory. The trade-off between thermodynamic and kinetic parameters was used to predict the membrane morphology for bentonite concentration varying from 0 to 5 wt %. The porosity of bentonite-doped membranes decreased up to 3 wt % that increased thereafter. Morphological analysis showed dense cross section with finger-like macrovoids at 3 wt % beyond which it changed to honeycomb structure with large circular voids. Permeability of 3 wt % membrane was the lowest (5.6 × 10⁻¹² m/Pa s) with 95% bovine serum albumin rejection. Contact angle of the membranes decreased from 83 to 66° with bentonite addition making the membrane more hydrophilic. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48450.     

Correlation of the polymer hydrophilicity and membrane fabrication process on the properties of asymmetric membranes in a vapor‐induced phase‐inversion process

In this study, we sought a better understanding of how the hydrophilicity of a polymer affects the morphology and performance of membranes. Three types of polymer with different hydrophilicity solution systems were considered: poly(aryl ether ketone) bearing a hydroxyl group (PEK–OH‐100) with N,N ‐dimethylformamide (DMF); poly(aryl ether ketone) bearing a 50% fraction hydroxyl group with DMF, and cardo poly(aryl ether ketone) with DMF. These systems were used to investigate the evolution of the morphology and variation in performance versus a change in the hydrophilicity of the polymer. In addition, the fundamental thermodynamic influence of the solution systems on the phase‐inversion process was investigated by cloud‐point measurement and Hansen solubility parameter theory to determine the role of polymer hydrophilicity on the stability of the polymer solution in humid surroundings. The performance of the membranes was tested via testing of the pure water flux, porosity, and rejection of bovine serum albumin (BSA) with respect to variations in the polymer hydrophilicity, evaporation time, relative humidity, and molecular weight of the polymer. The resulting optimal membrane exhibited a flux of 329.3 L m^?2 h^?1 and a 99.3% rejection of BSA at a relative humidity of 90% and an evaporation time of 3 s. The hydrophilic PEK–OH‐100 membranes have promising applications in protein separation and the porous support of reverse‐osmosis membranes and so on. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44701.     

泡沫分离法制备聚苯乙烯多孔微球

以一种新型、简单、高效的溶剂挥发法制备不同孔形态和粒径分布的聚苯乙烯微球。该方法利用机械搅拌和升温过程中溶剂挥发产生的泡沫,将油相液滴夹带进入泡沫相,使溶剂在气相中迅速挥发,诱导聚合物与非良溶剂发生相分离成孔。结果表明：随着聚合物与致孔剂用量比减小,微球结构形态由多孔演变到中空结构;聚乙烯醇（PVA）质量分数由1%增大至3%时,微球的平均粒径由52μm±23μm减小至23μm±20μm及转速由300r/min增大至700r/min时,微球粒径由107μm±40μm减小到45μm±20μm,但由于产生的泡沫量和泡沫形态不同影响了溶剂的挥发过程,故得到微球的多孔形态不同,增大PVA浓度得到的微球表面孔数目较少、孔径较大,而增大转速得到的微球孔数目较多。此外,该方法在油水相比≥1时,在泡沫中也能得到稳定规则的多孔微球,而传统的在水相中引发相分离的方法因水相无法完全分散油相,故无法成球。     

Preparation of uniform hollow polystyrene particles with large voids by a glass‐membrane emulsification technique and a subsequent suspension polymerization

Hollow polymer particles with large voids were prepared with styrene (St) as the main component and in the presence of a small amount of N,N′‐dimethylaminoethyl methacrylate (DMAEMA) via a glass‐membrane emulsification technique and a subsequent suspension polymerization. A mixture of the monomer, hexadecane (HD), and N,N′‐azobis(2,4‐dimethylvaleronitrile) as an initiator was used as a dispersed phase (oil phase). By the careful pushing of the dispersed phase through the pores of the glass membrane into the aqueous phase, an emulsion of fairly monodisperse monomer droplets was formed. Then, the polymerization was performed by temperature being elevated to 70°C. The aqueous phase (continuous phase) contained poly(N‐vinyl pyrrolidone) as a stabilizer, sodium lauryl sulfate as a surfactant, Na₂SO₄ as an electrolyte, and sodium nitrite (NaNO₂) as a water‐soluble inhibitor. Results related to the effects of the HD content, DMAEMA, and the composition of the comonomer, including the crosslinker and flexible segment, on the features of the hollow particles were investigated. When the content of DMAEMA was higher than 1.0 wt % based on the total monomer, small, secondary particles were generated in the aqueous phase, but the generation was effectively prevented when DMAEMA was limited to 0.5 wt %. Hollow particles, with an average diameter of around 7 μm, were obtained with an St–DMAEMA system. The void size of the hollow particles was controlled by the HD content. When the HD content was lower (<25 wt % based on the oil phase), unbroken hollow particles were easily obtained. However, they tended to break into halves after drying when the HD content was increased to 50 wt %. A soft segment, lauryl acrylate, and a crosslinker, ethylene glycol dimethacrylate, were added to overcome this problem. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 244–251, 2003     

Preparation and characterization of a novel positively charged nanofiltration membrane based on polysulfone

The goal of this study was to prepare positively charged nanofiltration (NF) membranes to remove cations from aqueous solutions. A composite NF membrane was fabricated by the modification of a polysulfone ultrafiltration support. The active top layer was formed by the interfacial crosslinking polymerization of poly(ethylene imine) (PEI) with p‐xylene dichloride (XDC). Then, it was quaternized by methyl iodide (MI) to form a perpetually positively charged layer. The chemical and morphological changes of the membrane surfaces were studied by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy. To optimize the membrane operation, the PEI solution concentration, PEI coating time, XDC concentration, crosslinking time, and MI concentration were optimized. Consequently, high water flux (5.4 L m^?2 h^?1 bar^?1) and CaCl₂ rejection (94%) values were obtained for the composite membranes at 4 bars and 30°C. The rejections of the NF membrane for different salt solutions, obtained from pH testing, followed the order Na₂SO₄ < MgSO₄ < NaCl < CaCl₂. The molecular weight cutoff was calculated by the retention of poly(ethylene glycol) solutions with different molecular weights, and finally, the stoke radius was calculated as 1.47 nm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41988.     

Charged membranes prepared by SPEEK of very low degree of sulfonation

Novel charged membranes were prepared with sulfonated poly(ether ether ketone) (SPEEK). Methylsulfonic acid was used as solvent to accommodate the very low degree of sulfonation of the SPEEK. Membranes were prepared by immersion phase inversion method, using coagulation baths of different composition and temperature. Low molecular weight and negatively charged dye molecules were used as model solutes to test the nanofiltration (NF) performance of the membranes. Higher than 93% rejection of the two dye molecules, Rose Bengal and Reactive Brilliant Red, was observed at normal operating temperature. A permeate flux as high as 497 L m^?2 h^?1 and higher than 90% of solute rejection at 80°C was achieved in the NF of Reactive Brilliant Red aqueous solution, in contrast to a flux of 226 L m^?2 h^?1 and about 78% of solute rejection at the same temperature in the case of Rose Bengal solute. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Wet‐phase‐separation membranes from the polysulfone/N,N‐dimethylacetamide/water ternary system: The formation and elements of their structure and properties

Asymmetric and porous polysulfone (PSf) membranes were prepared by wet phase separation. Binary (PSf)/N,N‐dimethylacetamide (DMA) solutions with polymer concentrations of 12.5–30 wt % were cast in thicknesses of 80–700 μm and immersed in a coagulation bath of pure water. The morphology of the formed membranes' cross sections consisted of a cellular structure and macrovoids; the cellular structure density was highest when the cast solution contained about 21 wt % PSf, regardless of the cast thickness. The membranes' pure water permeability decreased as the cast thickness increased. The instantaneous onset of the turbidity, regardless of the PSf content and cast thickness, its steep growth, and relatively high end value were the main characteristics of the turbidity phenomena taking place during the formation of the protomembranes. Again, the membrane‐forming system with a PSf/DMA solution with about 21 wt % polymer, regardless of the cast thickness, had the highest turbidity end value. The shrinkage of the cast solutions into the corresponding protomembrane was also examined quantitatively. Inverse experiments showed that the direction of the gravitation field had no influence on the shrinkage of the membrane‐forming ternary system or the membranes' morphology and its water permeability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1667–1674, 2005     

Fabrication of efficient pervaporation desalination membrane by reinforcement of poly(vinyl alcohol)–silica film on porous polysulfone hollow fiber

Pervaporation membrane technology is commercially successful in the dehydration of organic solvents, and the technology has potential for seawater desalination with high recovery because of its capability to treat highly saline water. But to make the technology advantageous over the other available membrane desalination technologies in terms of productivity flux without additional energy cost, the selective barrier layer is required to be extremely thin, defect‐free, hydrophilic, and selective to water. In this work, we prepared an efficient membrane by reinforcing a highly water‐permeable but continuous barrier layer of poly(vinyl alcohol)–silica (PVA‐SiO₂) hybrid material on porous polysulfone hollow fibers. The PVA‐SiO₂ in acidified and hydrated ethanol was aged at room temperature for a period to allow solvent evaporation to obtain the solution concentration desired for the reinforcement. The reinforced hollow fiber membrane with optimal PVA‐SiO₂ barrier layer thickness exhibited a performance with a flux of 20.6 L m^?2 h^?1 and 99.9% salt rejection from a saline feed of 2000 ppm NaCl at 333 K. The effects of PVA‐SiO₂, temperature, and feed salinity on the pervaporation performance of the membrane were also studied. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45718.     

Factors controlling surface morphology of porous polystyrene membranes prepared by thermally induced phase separation

A special device for preparing porous polymer membranes through a thermally induced phase separation (TIPS) process was designed and machined; it included a solution container, a membrane‐forming platform, a coldplate, a temperature‐decreasing system and a temperature‐supervising system. Polystyrene was selected as the model polymer from which to prepare porous membranes using the device due to its better understood TIPS and good biocompatibility with cells. The major factors controlling surface morphology and cell size, ie volume fraction of polystyrene (ϕ₂), quench rate and solvent‐removing methods, were studied. Fixing the coldplate temperature, when ϕ₂ is as low as 0.045, provokes the formation of round pores on both the bottom and top surfaces of the membrane; when ϕ₂ = 0.16 no pores are formed on either surface; when ϕ₂ = 0.087 pores form on the top surface, but not on the bottom surface. When ϕ₂ = 0.087 the cell size is very small or no pores are formed on the bottom surface, whereas the top surface shows a regular decrease of the pore sizes and an increase of the pore number and pore area, along with a decrease of the coldplate temperature. The side near the coldplate is dense, and the dense layer aligns along the coldplate, while the side away from the coldplate is like a porous foam, the shape of which is isotropic and the surfaces are interconnected with each other three dimensionally. On the top surface of a membrane obtained by ethanol extraction, the cell size is enlarged and the cell number reduced, but the surface morphology and the whole area remained almost the same when compared to samples obtained by freeze drying in the same membrane‐forming conditions. The isotropic, uniformly distributed and round pores suggest that the mechanism of phase separation is a spinodal liquid–liquid decomposition under our research conditions. © 2000 Society of Chemical Industry     

Preparation and properties of porous polytetrafluoroethylene hollow fiber membrane through mechanical operations

Porous polytetrafluoroethylene (PTFE) hollow fiber membranes were prepared from fine powder through a series of mechanical operations including paste extrusion, heat treatment, stretching and sintering. In contrast to conventional process, the heat treatment used in this study was performed at 200°C to 330°C (near the melting point) on the PTFE nascent hollow fiber (precursor of membrane). The results showed that the introduction of heat treatment step effectively improved the mechanical properties of precursors, the ultimate stress and strain increased observably with heat treatment temperature, which was beneficial to subsequently stretching precursors to make them porous. Furthermore, the morphological changes and improvement of membrane properties caused by stretching operation were investigated for porous PTFE hollow fiber membrane having finer pore size and higher porosity. The porous microstructure of nodes interconnected by fibrils varied depending on the stretching conditions, such as the stretching temperature, rate, and ratio. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42696.     

Filler-polymer combination: a route to modify gas transport properties of a polymeric membrane

Polydimethylsiloxane (PDMS) has been used as host matrix to prepare hybrid membranes, by a dry phase inversion process, where fillers with different surface and molecular sieving properties have been dispersed. The hybrid membranes have been characterised morphologically by scanning electron microscopy (SEM) and their gas transport properties have been measured at different temperatures.The influence of the temperature and different fillers on the gas separation performance of hybrid membranes has been analysed. These membranes showed higher selectivity values for some gas pairs combined to lower permeabilities with respect to pure PDMS films, as consequence of the contribution of the filler to the transport. A proper filler choice could be used to meet some specific requirements in industrial gas separations.     

Preparation and characterization of poly(ethylene‐co‐vinyl alcohol) membranes via thermally induced liquid–liquid phase separation

Porous membranes were prepared through the thermally induced phase separation of poly(ethylene‐co‐vinyl alcohol) (EVOH)/glycerol mixtures. The binodal temperature and dynamic crystallization temperature were determined by optical microscopy and differential scanning calorimetry measurements, respectively. It was determined experimentally that the liquid–liquid phase boundaries were shifted to higher temperatures when the ethylene content in EVOH increased. For EVOHs with ethylene contents of 32–44 mol %, liquid–liquid phase separation occurred before crystallization. Cellular pores were formed in these membranes. However, only polymer crystallization (solid–liquid phase separation) occurred for EVOH with a 27 mol % ethylene content, and the membrane morphology was the particulate structure. Scanning electron microscopy showed that the sizes of the cellular pores and crystalline particles in the membranes depended on the ethylene content in EVOH, the polymer concentration, and the cooling rate. Furthermore, the tendency of the pore and particle sizes was examined in terms of the solution thermodynamics of the binary mixture and the crystallization kinetics. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 853–860, 2003