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     

Effect of diluent on poly(ethylene‐co‐vinyl alcohol) hollow‐fiber membrane formation via thermally induced phase separation

Poly(ethylene‐co‐vinyl alcohol) hollow‐fiber membranes with a 44 mol % ethylene content were prepared by thermally induced phase separation. A mixture of 1,3‐propanediol and glycerol was used as the diluent. The effects of the ratio of 1,3‐propanediol to glycerol in the diluent mixture on the phase diagram, membrane structure, and membrane performance were investigated. As the ratio increased, the cloud point shifted to lower temperatures, and the membrane structure changed from a cellular structure due to liquid–liquid phase separation to a particulate structure due to polymer crystallization. Better pore connectivity was obtained in the hollow‐fiber membrane when the ratio of 1,3‐propanediol to glycerol was 50:50, and the membrane showed about 100 times higher water permeability than the membrane prepared with pure glycerol. For the prepared hollow‐fiber membrane, the solute 20 nm in diameter was almost rejected. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 219–225, 2005     

Formation of porous poly(ethylene‐co‐vinyl alcohol) membrane via thermally induced phase separation

Crystalline poly(ethylene‐co‐vinyl alcohol) (EVOH) membranes were prepared by a thermally induced phase separation (TIPS) process. The diluents used were 1,3‐propanediol and 1,3‐butanediol. The dynamic crystallization temperature was determined by DSC measurement. No structure was detected by an optical microscope in the temperature region higher than the crystallization temperature. This means that porous membrane structures were formed by solid–liquid phase separation (polymer crystallization) rather than by liquid–liquid phase separation. The EVOH/butanediol system showed a higher dynamic crystallization temperature and equilibrium melting temperature than those of the EVOH/propanediol system. SEM observation showed that the sizes of the crystalline particles in the membranes depended on the polymer concentration, cooling rate, and kinds of diluents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2449–2455, 2001     

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     

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     

Effects of bath temperature on the morphology and performance of EVOH membranes prepared by the cold‐solvent induced phase separation (CIPS) method

The development and characteristics of porous EVOH membranes by cold‐solvent induced phase separation (CIPS) process were investigated. Binary dopes of 1,3‐propandiol/EVOH prepared at 80 °C were immersed in 1,3‐propandiol at a lower temperature to engender polymer precipitation. The quench temperature affects phase separation modes, and hence structure and performance of resulting CIPS membranes. When the bath temperature was set below the crystallization line and above the binodal (e.g. 45 °C), the formed membrane was dominated by a packing of semicrystalline EVOH globules. When the bath was set at a temperature just below the spinodal (e.g. 20 °C), spinodal decomposition (SD) dominated the precipitation process to give a lacy‐like bicontinuous structure; yet there is also a clear imprint from polymer crystallization. When the bath temperature was set deeply within the spinodal dome (e.g. 5 °C), polymer crystallization affected only little the SD‐derived bicontinuous morphology. Water permeation flux, wettability, tensile strength, and ultra‐filtration experiments of the membranes were conducted. The results indicated that those properties were closely correlated with the porosity level, pore size, and membrane morphology. Moreover, X‐ray diffraction and DSC analyses indicated that the formed membranes had a crystallinity of 38 to 42%, consistent with the literature data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44553.     

Characteristics of poly(ether ether ketone) microporous membranes prepared via thermally induced phase separation (TIPS)

The morphology and bulk properties of microporous membranes based on poly (ether ether ketone) (PEEK) have been investigated as a function of initial casting composition and thermal and mechanical processing history. Membranes were prepared via solid—liquid phase separation of miscible blends of PEEK and polyetherimide (PEI), with subsequent extraction of the PEI diluent. Scanning electron microscopy studies revealed a microporous morphology with two distinct pore size scales corresponding to diluent extraction from interfibrillar and interspherulitic regions, respectively. The membrane structure was sensitive to both initial blend composition and crystallization temperature, with the resulting pore size distribution reflecting the kinetics of phase separation. For membranes prepared with lower initial diluent content or at lower crystallization temperatures, mercury intrusion porosimetry indicated a relatively narrow distribution of fine interfibrillar pores, with an average pore size of approximately 0.04 microns. Membranes prepared at higher diluent content or at higher crystallization temperatures displayed a broad pore distribution, with a sizeable population of coarse, interspherulitic pores (0.1 to 1 μm in size). Uniaxial drawing led to a fibrillated network structure with markedly higher water flux characteristics compared to the as-cast membranes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2347–2355, 1997     

Porous cellulose acetate membrane prepared by thermally induced phase separation

Microporous cellulose acetate membranes were prepared by a thermally induced phase separation (TIPS) process. Two kinds of cellulose acetate with acetyl content of 51 and 55 mol % and two kinds of diluents, such as 2‐methyl‐2,4‐pentandiol and 2‐ethyl‐1,3‐hexanediol, were used. In all polymer‐diluent systems, cloud points were observed, which indicated that liquid–liquid phase separation occurred during the TIPS process. The growth of droplets formed after the phase separation was followed using three cooling conditions. The obtained pore structure was isotropic, that is, the pore size did not vary across the membrane. In addition, no macrovoids were formed. These pore structures were in contrast with those usually obtained by the immersion precipitation method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3951–3955, 2003     

Preparation and membrane performance of poly(ethylene-co-vinyl alcohol) hollow fiber membrane via thermally induced phase separation

Poly(ethylene-co-vinyl alcohol) (EVOH) hollow fiber membranes with ultrafiltration performance were prepared from EVOH/glycerol systems via thermally induced phase separation (TIPS). The diluent glycerol was used as bore liquid to make a lumen of the hollow fiber for the purpose of prevention of the diluent evaporation and the larger pores formation at the inner surface of the hollow fiber. The obtained hollow fiber membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The formation of the larger pores near the outer surface was due to the enhanced pore growth by the water penetration. Some primary factors affecting the structure and performance of the membranes such as ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed were studied extensively. The water permeability can be improved by increasing the water bath temperature and the take-up speed and by decreasing the EC. Both the pore size at the outer surface and the connectivity between the pores have to be considered together to understand the experimental result of the water permeability and the solute rejection.     

Effect of diluents on the crystallization behavior of poly(4‐methyl‐1‐pentene) and membrane morphology via thermally induced phase separation

The effect of diluents on polymer crystallization and membrane morphology via thermally induced phase separation(TIPS) were studied by changing the composition of the mixed‐diluents systematically, in the system of poly(4‐methyl‐1‐pentene) (TPX)/dibutyl‐phthalate (DBP)/di‐n‐octyl‐phthalate (D‐n‐OP) with TPX concentration of 30 wt %. The TPX crystallization was observed with differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). The membranes were characterized with scanning electron microscopy (SEM), porosity, and pore size measurement. As the content of D‐n‐OP increased in mixed‐diluents, the solubility with TPX increased, inducing the phase separation changing from liquid–liquid phase separation into solid–liquid phase separation, which changed the membrane morphology and structure. When the ratios of DBP to D‐n‐OP were 10 : 0, 7 : 3; 5 : 5, and 3 : 7, membranes were formed with cellular structure and well connected pores, while the ratio was 0 : 10, discernable spherulities were found with not well‐formed pore structure. The effect of composition of the mixed‐diluents on membrane morphology was more remarkable in TPX/dioctyl‐sebacate (DOS)/dimethyl‐phthalate (DMP) system, since good cellular structure was formed when the ratios of DOS to DMP were 10 : 0, 7 : 3, while spherulites were observed when 5 : 5. Dual endotherm peaks behavior on DSC melting curves emerged for all the samples in this study, which was attributed to the special polymer crystallization behavior, primary crystallization, and secondary crystallization occurred when quenching the samples. As the content of D‐n‐OP increased, the secondary crystallization enhanced which induced the first endotherm peak on DSC melting curves moving to a lower temperature and the broadening of the overall melting peak, as well as the increasing of the overall crystallinity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Porous polyphenylene sulfide membrane with high durability against solvents by the thermally induced phase‐separation method

Porous polyphenylene sulfide membranes were prepared as new solvent‐resistant membranes by the thermally induced phase‐separation (TIPS) method. Porous structures were either formed by solid–liquid phase separation (polymer crystallization) or liquid–liquid phase separation. The effects of solvents, cooling rates, and polymer concentrations on the porous structures were investigated. Various characteristics of pore structure can be obtained with suitable diluents and cooling rates using the TIPS method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2959–2966, 2006     

Morphology of membranes formed by the isothermal precipitation of polyamide solutions from water/formic acid systems

Membranes were prepared by the direct and isothermal immersion of polyamide solutions in a formic acid/water bath. A crystalline polycaprolactam homopolymer, nylon 6, and a largely amorphous terpolymer of nylon 6, nylon 66, and nylon 610 were precipitated from solutions to form complex morphologies on the top and bottom surfaces and cross sections of the membranes. Terpolymer membranes exhibited the characteristics of a liquid–liquid phase‐separation process. According to the conditions of the solution and bath, nylon 6 precipitated to form membranes that showed dominance of crystallization or liquid–liquid phase separation. By precipitation from a solution containing a high concentration of a nonsolvent into a bath containing a high concentration of formic acid, skinless nylon 6 microporous membranes were formed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 944–960, 2005     

Estimation of phase diagrams for copolymer‐diluent systems in thermally induced phase separation

The binary interaction model was introduced to estimate phase diagrams of copolymer‐diluent systems in thermally induced phase separation. The crystallization curves and cloud points of poly(ethylene‐co‐vinyl alcohol) (EVOH) with 1,4‐butanediol, EVOH/1,3‐propanediol, and EVOH/glycerol were calculated and compared with experimental value or literature data. Fair agreement was obtained. To confirm the importance of incorporating intramolecular interactions, calculations with and without the consideration of intramolecular interactions were performed and compared. It was found that better results can be obtained if intramolecular interaction was introduced. The reason for the small differences between the calculated value and the experimental data of the liquid–liquid phase separation is discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Formation of a bicontinuous structure membrane of polyvinylidene fluoride in diphenyl ketone diluent via thermally induced phase separation

The polyvinylidene fluoride (PVDF)‐diphenyl ketone (DPK) mixture was studied as a new system to prepare PVDF membranes via thermally induced phase separation (TIPS). The phenomena of liquid–liquid phase separation was found in this mixture when the temperature of mixture was decreasing and the PVDF concentration was less than 30 wt %. Using DPK as diluent, PVDF membrane with bicontinuous structure was obtained without necessity to add a nonsolvent or a stretching process further. The phase diagram of PVDF‐DPK system was also constructed to help investigate the effect of PVDF concentration and coarsening temperature on morphology of resulting membrane. The experiments showed that high coarsening temperatures and low PVDF concentrations resulted in the formation of the large pore size membrane. The strength of the wet membrane was decreasing with decreasing PVDF concentration. On condition that the PVDF concentration was larger than 30 wt %, thermally induced solid–liquid separation occurred and bicontinuous structure disappeared. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

TIPS behavior for IPP/nano-SiO2 blend membrane formation and its contribution to membrane morphology and performance

In the present work, the TIPS behavior of isotactic polypropylene(iP P)/di-n-butyl phthalate(DBP)/dioctyl phthalate(DOP)/nano-SiO_2 system and the competition relation between liquid–liquid phase separation and polymer crystallization are successfully adjusted by adding nano-SiO_2. The liquid–liquid phase separation temperature of the system increases with increasing nano-SiO_2 content. Besides, iP P crystallization temperature is also changed after adding nano-SiO_2. IPP/nano-SiO_2 blend hollow fiber microporous membrane is prepared via TIPS method. SEM photos show that the membrane exhibits mixed morphology combining cellular structure relating to liquid–liquid phase separation and branch structure originating from polymer crystallization. The relative weight of cellular structure first decreases and then increases with the increase of nano-SiO_2 content. Furthermore, porosity, connectivity among pores and pure water flux of the membrane first increase and then decrease with increasing nano-SiO_2 content. However, mechanical performance of the membrane is improved at all times with increasing nano-SiO_2 content.     

Effect of the exposure time on the structure and performance of hydrophobic polydimethylsiloxane–poly(vinylidene fluoride) membranes via a non‐solvent‐induced phase separation process in a clean room

The objective of this study was to investigate the effects of the exposure time on the properties and permeability of polydimethylsiloxane (PDMS)–poly(vinylidene fluoride) (PVDF) blend hydrophobic microporous membranes, which were fabricated via a non‐solvent‐induced phase separation process at 25 °C and 60% relative humidity in a clean‐room circumstance. For the prepared PDMS–PVDF membranes, the membrane morphologies were observed by scanning electron microscopy. Crystalline structures were observed by X‐ray diffraction. Pore structures were analyzed by membrane porosity and mean pore size. Hydrophobicity was measured by contact angle measurement, and the mechanical properties were characterized by tensile strength testing. Our study results show that with increasing exposure time from 10 to 110 s, all of the membranes showed a similar pore structure: a spongelike substrate layer with a thin realm of fingerlike structures under the top surface. Phase separation between PDMS and PVDF occurred. The membrane porosity and mean pore radius decreased, and the membrane thickness increased. The membrane hydrophobicity decreased, and the mechanical properties first increased and then decreased. In addition, vacuum membrane distillation experiments were conducted. With the increase in the exposure time from 10 to 110 s, the membrane permeate flux decreased from 16.54 to 6.65 kg m⁻²·h⁻¹, and the salt rejection was higher than 99.9%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43842.     

Preparation of PVDF/CaCO3 hybrid hollow fiber membranes for direct contact membrane distillation through TIPS method

Poly(vinylidene fluoride) (PVDF)–CaCO₃ hybrid hollow fiber membranes with a cellular structure and prominent permeability were fabricated via the thermally induced phase separation method for membrane distillation. CaCO₃ nanoparticles were introduced to the casting solution to improve the properties of the membranes. The effect of CaCO₃ dosage on the morphology was investigated. The prepared membranes were characterized by differential scanning calorimetry, SEM, and atomic force microscopy. The results showed that liquid–liquid phase separation preceded solid–liquid phase separation during the spinning process. Low dosages of CaCO₃ had a strong influence on the crystallization of PVDF molecules. The contact angle of the membrane increased with the addition of CaCO₃ nanoparticles. The maximum dead end pure water flux was as high as 1295.5 L/(m² h). The direct‐contact membrane distillation flux of the optimized PVDF/CaCO₃ hybrid membrane achieved 63.98 kg/(m² h) at the feed temperature of 90 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43372.     

Effect of poly(vinyl pyrrolidone) concentration and coagulation bath temperature on the morphology,permeability, and thermal stability of asymmetric cellulose acetate membranes

Cellulose acetate (CA) is widely used in membrane processes. In this study, CA (weight‐average molecular weight = 52,000) was mixed with poly(vinyl pyrrolidone) (PVP; weight‐average molecular weight = 15,000) as an additive in 1‐methyl‐2‐pyrrolidone as a solvent. The phase‐inversion method was used for the preparation of flat‐sheet membranes. The effects of PVP concentration and coagulation bath temperature (CBT) on the morphology, pure water permeation flux, and thermal stability of the prepared membranes were studied and are discussed in this article. The solute rejection of the developed CA membranes was quantified with an insulin protein solution. The results showed that an increase in the CBT levels from 0 to 23°C along with an increase in the PVP concentration in the cast film from 0 to 1.5 wt % resulted in an increase in the macrovoid formation in the membrane sublayer, an increase in the pure water flux (PWF), and a decrease in insulin rejection. Further increases in the PVP concentration from 1.5 to 3, 6, and 9 wt % resulted in gradual suppression of the macrovoid formation, a decrease in PWF, and an increase in insulin rejection. Higher PVP concentrations and lower CBT levels also appeared to result in higher glass‐transition temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of nucleating agents on the morphologies and performances of poly(vinylidene fluoride) microporous membranes via thermally induced phase separation

The effects of nucleating agents on the morphology and performance of poly(vinylidene fluoride) (PVDF) microporous membranes via thermally induced phase separation were investigated. The nucleating agents studied were dicyclohexyl benzene amide (TMB‐5), 2,2‐methylene bis(4,6‐tertiary butyl phenol) sodium phosphate (TMP‐1), and 1,3 : 2,4‐di‐p‐methylbenzylidene sorbitol (DM–LO). Light transmittance experiments and differential scanning calorimetry (DSC) were performed to obtain phase diagrams of PVDF/tributyl citrate/di(2‐ethylhexyl) phthalate/nucleating agent doped solutions. The morphology and performance of the prepared PVDF microporous membranes were characterized with scanning electron microscopy and microfiltration experiments. The results show that the thermodynamics of liquid–liquid phase separation were not affected by the addition of the nucleating agents, but solid–liquid phase separation was influenced. The system with 0.3 wt % TMB‐5 had the fastest crystallization rate and a better nucleation ability. The PVDF microporous membranes had a partly closed, lacy bicontinuous structure with TMP‐1 and DM–LO, whereas the membrane with 0.3 wt % TMB‐5 had an interconnected bicontinuous structure. The pore size distribution became narrower with the addition of nucleating agent. With 0.3 wt % TMB‐5, the membrane had the minimum mean pore size (0.095 μm), a porosity of 80.3%, and a pure water flux of 270 L·m^?2·h^?1; these values were higher than those of the pure PVDF membrane. The performances of the membranes decreased with additions of TMB‐5 of greater than 0.3 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Phase separation and crystallization behavior in extruded polypropylene/ethylene–propylene rubber blends

Liquid–liquid (L–L) phase separation and its effects on crystallization in polypropylene (PP)/ethylene–propylene rubber (EPR) blends obtained by melt extrusion were investigated by time‐resolved light scattering (TRLS) and optical microscopy. L–L phase separation via spinodal decomposition (SD) was confirmed by TRLS data. After L–L phase separation at 250°C for various durations, blend samples were subjected to a temperature drop to 130°C for isothermal crystallization, and the effects of L–L phase separation on crystallization were investigated. Memory of the L–L phase separation via SD remained for crystallization. The crystallization rate decreased with increasing L–L phase‐separated time at 250°C. Slow crystallization for the long L–L phase‐separated time could be ascribed to decreasing chain mobility of PP with a decrease in the EPR component in the PP‐rich region. The propylene‐rich EPR exhibited good affinity with PP, leading to a slow growth of a concentration fluctuation during annealing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 695–700, 2001