Formation of poly‐vinyl‐alcohol structures by supercritical CO2

Poly‐vinyl‐alcohol (PVA) porous structures have been prepared using a supercritical phase inversion process in which supercritical carbon dioxide (SC‐CO₂) acts as the nonsolvent. First, we tested the versatility of the SC‐CO₂ phase inversion process, forming PVA/dimethylsulfoxide (DMSO) solutions with polymer concentrations ranging from 1 to 35% (w/w) and changing the process parameters. We worked at temperatures from 35 to 55°C and pressures from 100 to 200 bar obtaining different membranes morphologies: dense films, membranes with coexisting morphologies, and microparticles. However, we did not produce symmetric or asymmetric porous membranes. To obtain this result, we used casting solutions formed by adding acetone to DMSO with the aim of modifying the affinity between SC‐CO₂ and the liquid solvent. In this series of experiments, we obtained asymmetric membranes with skin layer thicknesses lower than 10 μm. The results obtained in this work have been explained considering that the membranes formation mechanism is related to the kinetics of the process; i.e. the affinity between the solvent (mixture of solvents) and SC‐CO₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Morphology and performance of poly(vinylidene fluoride) flat sheet membranes: Thermodynamic and kinetic aspects

In this study, poly(vinylidene fluoride) (PVDF) membranes were prepared using two different solvents with various polymer concentrations to investigate the predominant kinetic or thermodynamic aspects of membrane preparation in a phase separation process. For this purpose, dimethyl sulfoxide (DMSO) as a weak solvent and N‐2‐methylpyrrolidone (NMP) as a strong solvent were used with polymer concentrations between 8 and 15 wt %. Scanning electron microscopy and water content, contact angle, and pore size measurements were used to assess the factors affecting the physicochemical properties of the prepared membranes. The results showed that in the case of NMP, the membrane structure is mainly controlled by thermodynamic parameters, while when using DMSO, kinetic parameters are predominant. According to the results, the prepared PVDF‐based membranes with DMSO exhibited a relatively denser top layer and less permeation compared to the NMP/PVDF membranes. The difference between the viscosities of the casting solutions with equal polymer concentrations in DMSO and NMP was considered to be the main effective factor in solvent/nonsolvent exchange, resulting in denser top layers in the DMSO/PVDF membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46419.     

Application of supercritical carbon dioxide in the preparation of biodegradable polylactide membranes

The application of supercritical carbon dioxide (SCCO₂) has been attracting more and more attention, especially in the formation of polymer membranes. The membrane formation using SCCO₂ is analogous to conventional immersion precipitation process by using organic nonsolvent. Polylactide (PLA) membranes were prepared by phase separation with SCCO₂ as nonsolvent. Two kinds of solvents were used to study the effect of the solvent on the cross‐section structure of the PLA membrane and the compatibility between the solvent and SCCO₂ was studied. The effect of the solvent and the preconditioning on the morphology of the PLA membrane was also investigated through scanning electron microscope, wide‐angle X‐ray diffraction, and polarizing microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2158–2163, 2004     

Polyimide asymmetric membranes: Elaboration,morphology, and gas permeation performance

Asymmetric 2,2‐bis‐(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA)‐2‐methyl‐1,3‐phenylenediamine (mPDA) polyimide membranes were prepared according to a phase‐inversion mechanism by using different solvent/nonsolvent blends. The membrane formation mechanism and the final performances of the asymmetric membranes have been found both nonsolvent and solvent nature dependent. From the visualization of cross sections of asymmetric membranes by scanning electron microscopy and the study of the permeation of two gases (N₂, CO₂) through asymmetric membranes, a relationship between elaboration conditions and asymmetric membranes characteristics could be drawn. The organization of polymer chains in solution strongly affects the final polymer arrangement and thus the final performances of the membrane. The influence of preliminary solvent evaporation before immersion has been shown to be dependent on the structure of the asymmetric membrane: finger‐like or sponge‐like structures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1838–1848, 2003     

Effect of different experimental conditions on biodegradable polylactide membranes prepared with supercritical CO2 as nonsolvent

There is increasing interest in the application of supercritical CO₂ (SCCO₂) in the preparation of polymer membranes. Membrane formation with SCCO₂ as a nonsolvent is analogous to the conventional immersion precipitation process using an organic nonsolvent. Polylactide membranes were prepared with SCCO₂ as the nonsolvent under different experimental conditions such as different polymer concentrations, different depressurization rates, and different nonsolvent compositions. The effects of these conditions on the cross‐sectional structure were investigated through scanning electron microscopy. In addition, solvent‐induced crystallization and CO₂‐induced crystallization were studied. The crystallinity of PLA membranes prepared with different solvents or at different pressures was characterized by wide‐angle X‐ray diffraction and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 831–837, 2005     

Nanofiltration membranes based on PA6/EVOH with variable composition and morphology

Nanofiltration PA6/EVOH membranes were prepared through a nonsolvent induced phase separation technique. The effects of polymer concentration in the solution and solvent evaporation time on the performance and morphology of the resulting membranes were investigated by cloud point titration, permeation, and scanning electron microscopy (SEM). Experimental cloud point data for various prepared membranes suggested that polymer solutions with higher concentrations of PA6/EVOH need a less content of nonsolvent. SEM observations show that an increase in polymer concentration leads to formation of a thin dense layer on the surface of the membrane thanks to pore size reduction. However, dense top layer of membrane becomes thicker as polymer concentration increases from 15 wt% to 20 wt%. The performance of membranes reveals a decrease with polymer concentration in casting solution. By contrast, Polyamide/Poly(ethylene‐co‐vinyl alcohol) membranes show an optimal performance with various formic acid evaporation times. J. VINYL ADDIT. TECHNOL., 25:E28–E34, 2019. © 2018 Society of Plastics Engineers     

Studies on solvent evaporation and polymer precipitation pertinent to the formation of asymmetric polyetherimide membranes

The characteristics of solvent evaporation and polymer precipitation during the formation of asymmetric aromatic polyetherimide (PEI) membranes via the dry/wet phase inversion method are studied and the results are discussed with reference to membrane preparation. It is shown that the solvent evaporation from the surface of freshly cast films in early evaporation stages can be quantified by an empirical equation with two parameters. Analysis of the evaporation parameters partially explains the interaction effect of membrane preparation variables on membrane performance. The phase separation data for systems PEI/DMAc/H₂O and PEI/NMP/H₂O with and without LiNO₃ additive are determined using the turbidimetric titration method. The kinetic data on solvent–nonsolvent exchange and additive leaching during polymer precipitation in nonsolvent water are measured. The results presented here offer a qualitative basis for the development of asymmetric PEI membranes. © 1995 John Wiley & Sons, Inc.     

Preparation of defect-free asymmetric membranes for gas separations

A technique was developed to prepare defect-free, asymmetric, polymer membranes for gas separation. The preparation method eliminates the need for coatings, which are usually required to render asymmetric, polymer based, membranes gas selective. In this method, a casting solution containing a polymer, solvent, and salt additive is given a desired shape and immersed in a coagulation bath containing a nonsolvent. The nonsolvent is selected to have a low affinity for both the solvent and salt additive. After the complete coagulation of the membrane, the additive salt is leached out in a second bath. This leads to the formation of an asymmetric membrane that has a well-interconnected porous network. The fine membrane structure is preserved by solvent exchange before it is finally dried. Polyetherimide (PEI) (Ultem® 1000) membranes were prepared from casting solutions containing 23, 25, and 26.5% (wt) PEI, various amounts of lithium nitrate and N-methyl-2-pyrrolidinone (NMP). Membrane performance was determined for the separation of oxygen from air. The effects of polymer concentration, additive salt concentration and the drying process on oxygen permeance, and the actual separation factor of the membrane are discussed. The addition of a small amount of solvent to the coagulation bath improved the leaching of the salt additive and produced membranes with a more open structure. A polymer concentration of 23% produced membranes with the highest performance. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1471–1482, 1999     

Development and tuning of Matrimid membrane oxygenators with improved biocompatibility and gas permeance by plasma treatment

In this study, a commercial polyimide is examined in the capacity of membrane oxygenator. The effects of polymer concentration, cosolvent, and nonsolvent additives in dope solution on the performance and morphology of membranes are investigated. In order to improve the performance, surface modification is carried out by using plasma-enhanced chemical vapor deposition. The obtained results reveal that CO₂ permeance decreased from 495 to 78 GPU upon increasing Matrimid concentration at constant tetrahydrofuran (THF) and ethanol (EtOH) concentrations. It was also found that increasing nonsolvent concentration as well as decreasing cosolvent concentration in dope led to increase in membrane gas permeance. According to morphological characterizations, increase in polymer concentration resulted in transformation of membranes from porous into spongy like microstructure with formation of a denser skin layer. In addition, membrane porosity and mean pore size reduced by increasing THF and decreasing EtOH concentrations. On the other hand, plasma treatment successfully introduced fluorine groups onto the membrane surface which promoted biocompatibility of the membranes. Energy-dispersive X-ray spectroscopy results revealed that fluorination of membrane surface was attained up to 23% and contact angle of membrane enhanced up to 120°. Membrane permeance was also increased slightly upon modification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48824.     

Physicochemical processes occurring during the formation of cellulose diacetate membranes. Research of criteria for optimizing membrane performance. V. Cellulose diacetate–acetone–water–inorganic salt casting solutions

Consideration was given to the effects of casting conditions upon the performance and structure of membranes prepared from CA–acetone–water–inorganic salt solutions. Treating casting solutions as polymer–solvent–nonsolvent ternary systems, the data on equilibrium phase separation conditions were plotted in a triangular diagram for solutions containing Al(NO₃)₃, KSCN, Mg(ClO₄)₂ or no additive. Measurements of casting solution viscosity, membrane thickness, freezing and nonfreezing water contents were used to supplement flux and retention data of membranes made by varying the inorganic salt and holding time in a systematic way. With the aid of scanning and transmission electron microscopy, it was concluded that membranes may consist of one, two, three, or four layers. The data and correlations obtained allow us to propose a mechanism of formation for each of these layers.     

The formation of nodular structures in the top layer of ultrafiltration membranes

The formation of nodular structures in the top layer of ultrafiltration membranes is considered. A critical review of mechanisms described in the literature is given. Flat-sheet poly(ether sulfone) membranes and hollow-fiber poly(ether sulfone)/polyvinylpyrrolidone membranes were made by coagulation of a polymer solution in a nonsolvent medium under different circumstances. From these experiments, a number of empirical rules are found to describe the resulting morphology of the top layer. A new mechanism for the formation of a nodular structure is proposed. It is based on the small diffusion coefficient of the polymer molecules compared to the diffusion coefficient of solvent and nonsolvent combined with a high degree of entanglement of the polymer network. For unstable compositions, phase separation will proceed by growth in amplitude of concentration fluctuations. The rapid diffusional exchange of solvent for nonsolvent in the top layer leads to vitrification of the maxima of the concentration fluctuations that form the nodules. Complete disentanglement of the polymer chains between the nodules is not reached, which explains the small pores and the low porosity of ultrafiltration membranes. © 1994 John Wiley & Sons, Inc.     

An approach to the development of cellulose acetate ultrafiltration membranes

The film-casting solution consisted of a mixture of cellulose acetate, acetone, and aqueous magnesium perchlorate [Mg(ClO₄)₂:H₂O = 1:8.5], designated as polymer P, solvent S, and nonsolvent N, respectively. Using the composition P:S:N = 17: 69.2: 13.8 as reference, films were obtained from 19 different casting solutions in which the weight ratios S/P, N/S, and N/P were varied in different directions. The casting solution temperature was 0°C, and solvent evaporation period during film formation was minimum in most cases. The effects of variations of casting solution temperature and solvent evaporation period were also briefly studied. Reverse osmosis experiments with resulting membranes were carried out at 100 psig using 200 ppm NaCl–H₂O as the feed solution. Decrease in S/P, increase in N/S, and increase in N/P in the casting solution, decrease in temperature of the casting solution, and increase in solvent evaporation period tend to increase the size of pores on the surface of resulting membranes in the ascast condition. Increase in S/P in the casting solution, and increase in the temperature of the casting solution tend to increase the effective number of pores on the membrane surface. These results offer definitive physicochemical criteria in terms on solution structure–evaporation rate concept for developing useful cellulose acetate ultrafiltration membranes.     

Morphological controlling of CTA forward osmosis membrane using different solvent-nonsolvent compositions in first coagulation bath

Cellulose triacetate (CTA) membranes were fabricated via a modified nonsolvent induced phase separation (NIPS) method. Different solvent-nonsolvent compositions in first coagulation bath (FCB) were introduced to optimize CTA membrane structures. The effects of FCB compositions, immersion time and mass ratio of solvent (N-methyl-2-pyrrolidone, NMP) and nonsolvent (water, ethanol, ethylene glycol and glycerol) on membrane morphology and performance were systematically investigated. Prospective membranes with a dense bottom layer and a scaffold-like top layer were obtained under room temperature, owing to the low relative energy difference (RED) between nonsolvent and polymer as well as the high viscosity of FCBs. A high water flux J_v (12.6 L m^?2 h^?1) and a low reserve salt flux J_s (1.32 g m^?2 h^?1) were obtained in the optimized membrane, with a structural parameter S of 119 μm. Compared with membranes prepared via conventional NIPS method and commercial CTA forward osmosis (FO) membranes, a remarkable improvement of J_s/J_v value and S value was achieved, indicating membranes with single dense-layer structure might suffer less from internal concentration polymerization (ICP) which is the main obstacle for the development of FO process. This study might help us pave the way to design superior CTA membrane structures for forward osmosis application.     

Pore morphology control and hydrophilicity of polyacrylonitrile ultrafiltration membranes

The effects of different solvents (dimethyl formamide: DMF and dimethylsulfoxide: DMSO) on the solubility of polyacrylonitrile (PAN) were investigated by the phase diagrams of H₂O/DMF/PAN and H₂O/DMSO/PAN ternary systems through cloud‐point titration method at low polymer concentration. The influences of polymer concentrations and temperatures on the morphologies of PAN ultrafiltration membranes were elucidated. The morphologies of fabricated UF membranes were characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM), and the basic performance of ultrafiltration including pure water flux and rejection of BSA were explored. At 25°C, the pure water flux of ultrafiltration membranes at the lower PAN content (16 wt % PAN in 84 wt % DMSO) reached 213.8 L/m/bar and the rejection of BSA was 100%. Interestingly, the water flux of UF membranes dramatically decreased to 20.6 L/m/bar (20 wt %) and 2.9 L/m/bar (24 wt %) when increasing PAN concentrations in DMSO. On the other hand, the hydrophilicity of membranes can be enhanced by increasing coagulation temperatures and polymer concentrations which were characterized by static contact angle, fitting well with the variation tendency of roughness. Although there are many works concerning on the effects of phase inversion conditions on the performance of PAN UF membranes, to our best knowledge, there is seldom works focusing on investigating the membrane hydrophilicity trend by adjusting phase inversion conditions. To disclose the reason of the enhanced hydrophilicity, the water and glycol contact angles of various membranes were measured and the surface tensions were presented. The results illustrated that the enhanced hydrophilicity of PAN UF membranes fabricated at higher temperatures or higher polymer concentrations was due to the higher polarity on membrane surface. Since the vast majority of ultrafiltration membranes in labs and in industrial scale have been fabricated by immersion phase inversion method, this work can provide a guidance to obtain hydrophilic PAN UF membranes by adjusting the process of phase inversion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41991.     

Cellulose acetate reverse osmosis membranes: Optimization of the composition

Membranes based on cellulose acetate for reverse osmosis can possibly be applied to the so‐called salinity process of energy generation and water desalinization. The requirements for membranes for these two different applications are a relatively high water flux and low salt permeability. In this article, we present the optimization of the composition of such membranes. We started by producing membranes with a patented casting solution with the following composition: 45.77 wt % dioxane, 17.61 wt % acetone, and 8.45 wt % acetic acid (solvents); 14.09 wt % methanol (nonsolvent); and 7.04 wt % cellulose diacetate and 7.04 wt % cellulose triacetate. The membranes produced with this solution were analyzed comparatively, with the membranes obtained by the introduction of modifications to the following parameters: the solvent mix, the nonsolvent mix, the proportion of cellulose diacetate and cellulose triacetate in the casting solution, and the addition of reinforcing cellulose fibers. The results led us to conclude that the best membrane formulation had the following composition: 45.77 wt % dioxane, 17.61 wt % acetone, and 8.45 wt % acetic acid (solvents); 4.22 wt % cellulose triacetate and 9.86 wt % cellulose diacetate (polymers); 14.09 wt % methanol (nonsolvent); and 0.5 wt % cellulose fibers (with respect to the total polymer content). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4052–4058, 2006     

Structure and gas permeation properties of asymmetric polyimide membranes made by dry–wet phase inversion: Influence of the polyimide molecular weight

In this article, we report the influence of the polyimide molecular weight (1.2 × 10⁵, 2.6 × 10⁵, and 4.1 × 10⁵) on the structure and the gas permeation properties of asymmetric polyimide membranes made by the dry–wet phase‐inversion process. The apparent skin layer thickness of the asymmetric membrane increased with increasing molecular weight, and the thicknesses of the membranes prepared from the three polyimides with a casting polymer solution containing 8.0 wt % butanol were 132, 350, and 739 nm, respectively. That is, the gas permeance in the asymmetric membranes increased with decreasing molecular weight. In contrast, the gas selectivity of the asymmetric membranes did not depend on the skin layer thickness. The solvent evaporation in the dry phase‐inversion process and the nonsolvent diffusion in the dry process were important factors that determined the formation of the asymmetric membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of solvents on performance of polyethersulfone ultrafiltration membranes: Investigation of metal ion separations

The new polyethersulfone (PES) based ultrafiltration membranes were formed using a two stage process of dry and wet phase inversion in non solvent coagulation bath. The effects of three different solvents such as, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and Dimethyl sulphoxide (DMSO) of 82.5% and 85% concentrations on the performance of final membranes were extensively investigated. Scanning electron microscopy (SEM) image results proved that PES membranes with an asymmetric structure were successfully formed. The number of pores formed on the top layer of PES membranes using above-mentioned three solvents was the result of the combined effect of the thermodynamic properties of the system (composition, concentrations, and phase behaviour) and membrane formation kinetics, whereas, the formation of the macroporous sub layer of those membranes was controlled by the diffusion rate of solvent–nonsolvent. The flux of pure water, membrane resistance, mechanical stability, molecular weight cut-off (MWCO) and separation performance of the PES membranes were studied. Separation of metal ions from aqueous solutions was studied for Ni(II), Cu(II) and Cr(III) using two complexing polymer ligands: polyvinyl alcohol (PVA) and poly(diallyldimethylammonium chloride) (PDDA).The separation and permeate rate (flux) efficiencies of the new membranes are compared using different solvents and different PES/solvent compositions.     

Preparation of crosslinked membranes with controlled pore size distribution

A technique has been developed to prepare crosslinked, porous/asymmetric membranes from poly(styrene-co-divinylbenzene). Mixtures of styrene monomer, divinylbenzene, benzoin (a photo-initiator), and some dead polystyrene are dissolved in a cosolvent and cast on a flat, transparent substrate. The coating is then irradiated with a UV lamp and subsequently phase separated by exposure to a nonsolvent bath. Pores are generated by phase separation induced by nonsolvent ingression. Crosslinking is achieved via the photo-initiated incorporation of divinylbenzene with styrene, while the membrane morphology evolves. A mechanism for the formation of crosslinked membranes prepared by this technique has been proposed. Experimental results systematically examine the effects of crosslinking and nonsolvent/solvent combinations on pore size and overall membrane structure. Temperature and solvent treatments on the finished membrane structure are also studied.     

Physical and electrochemical characterizations of poly(vinylidene fluoride‐co‐hexafluoropropylene)/SiO2‐based polymer electrolytes prepared by the phase‐inversion technique

Highly porous poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF–HFP)‐based polymer membranes filled with fumed silica (SiO₂) were prepared by a phase‐inversion technique, and films were also cast by a conventional casting method for comparison. N‐Methyl‐2‐pyrrolidone as a solvent was used to dissolve the polymer and to make the slurry with SiO₂. Phase inversion occurred just after the impregnation of the applied slurry on a glass plate into flowing water as a nonsolvent, and then a highly porous structure developed by mutual diffusion between the solvent and nonsolvent components. The PVdF–HFP/SiO₂ cast films and phase‐inversion membranes were then characterized by an examination of the morphology, thermal and crystalline properties, absorption ability of an electrolyte solution, ionic conductivity, electrochemical stability, and interfacial resistance with a lithium electrode. LiPF₆ (1M) dissolved in a liquid mixture of ethylene carbonate and dimethyl carbonate (1:1 w/w) was used as the electrolyte solution. Through these characterizations, the phase‐inversion polymer electrolytes were proved to be superior to the cast‐film electrolytes for application to rechargeable lithium batteries. In particular, phase‐inversion PVdF–HFP/SiO₂ (30–40 wt %) electrolytes could be recommended to have optimum properties for the application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 140–148, 2006