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.     

Preparation of enduringly antifouling PVDF membrane with compatible zwitterionic copolymer via thermally induced phase separation

The compatible zwitterionic copolymers of poly(methyl methacrylate [3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium‐hydroxide) p(MMA‐MPDSAH) with different MPDSAH ratio are synthesized by free radical polymerization. A serial of copolymers are obtained successfully with narrow molecular weight dispersion. The MPDSAH branch ratio varies from 5% to 20%. It is initially applied to fabricate enduringly antifouling poly(vinylidene fluoride) (PVDF) membrane through a simple approach of blending by thermally induced phase separation (TIPS). The influence of zwitterionic copolymer on membrane morphology is studied by scanning electron microscopy. It was proven effective to improve the hydrophilic property of PVDF membrane as the water contact angles dramatically decreased from 80° to 40°, leading to a significant enhancement of antifouling ability. The absorbed bull serum albumin (BSA) content on modified membranes has cut almost 50%. The residual content of p(MMA‐MPDSAH) in membrane is over 40% and able to reach 80% even at vigorous rinsing by controlling copolymer structure. It guarantees the modified membrane has vested enduringly antifouling ability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41362.     

热致相分离法iPP/nano-SiO2杂化中空纤维膜的结构与透过性能

通过熔融共混等规聚丙烯(iPP)/邻苯二甲酸二丁酯(DBP)/邻苯二甲酸二辛酯(DOP)/纳米二氧化硅(nano-SiO2)体系,采用热致相分离法(TIPS)制备了iPP中空纤维膜。对膜结构与透过性能进行了表征。用示差扫描量热仪(DSC)测定了体系的iPP动态结晶温度,融化峰值温度数值表明结晶只存在α晶型。X光电子能谱(XPS)表明nano-SiO2向膜表面发生了迁移,使得膜的亲水性有所提高,膜的接触角由120.05°降低到101.05°,降低了19.7%。随着nano-SiO2添加量的增加,膜的孔隙率和纯水通量均呈现先增大后减小的趋势。膜的孔隙率增加了20.2%,纯水通量增大了21.7%。经过拉伸后的杂化膜,孔隙率增大了27.4%,纯水通量增加了211%。研究表明:通过向铸膜液中添加nano-SiO2,可以优化膜结构,并改善膜的亲/疏水性以及透过性能。     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

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.     

热致相分离法制备聚乙烯/纳米二氧化钛共混膜

采用相对分子质量为130 000的聚乙烯(PE)为膜材、DIDP为稀释剂、平均直径为180 nm的TiO2粉末作添加剂,用热致相分离(TIPS)法制备了PE膜和PE/TiO2共混膜。研究了共混组成和冷却速率对膜结构的影响。所有制备的膜均是海绵状孔,冷却速率越大,膜孔越小。对PE质量分数为15%,当PE与TiO2的质量比大于1时,TiO2在膜内的分布不均匀,当PE与TiO2的质量比为0.5时,TiO2能比较均匀的分布于膜内。共混膜浸于水中经过紫外照射后,其亲水性显著增加。     

F127对热致相分离法制备的亲水性PVB/F127共混中空纤维膜性能的影响(英文)

Hydrophilic poly(vinyl butyral) (PVB)/Pluronic F127 (F127) blend hollow fiber membranes were prepared via thermally induced phase separation (TIPS), and the effects of blend composition on the performance of hydrophilic PVB/F127 blend hollow fiber membrane were investigated. The addition of F127 to PVB/polyethylene glycol (PEG) system decreases the cloud point temperature, while the cloud point temperature increases slightly with the addition of F127 to 20% (by mass) PVB/F127/PEG200 system when the concentration of F127 is not higher than 5% (by mass). Light scattering results show that the initial inter-phase periodic distance formed from the phase separation of 20% (by mass) PVB/F127/PEG200 system decreases with the addition of F127, so does the growth rate during cooling process. The blend hollow fiber membrane prepared at air-gap 5mm, of which the water permeability increases and the rejection changes little with the increase of F127 concentration. For the membrane prepared at zero air-gap, both water permeability and rejection of the PVB/F127 blend membrane are greater than those of PVB membrane, while the tensile strength changes little. Elementary analysis shows that most F127 in the polymer solution can firmly exist in the polymer matrix, increasing the hydrophilicity of the blend membrane prepared at air-gap of 5mm.     

介孔Al_2O_3/PVDF复合中空纤维膜的制备及其性能

为了提高PVDF中空纤维膜在处理含油废水过程中的亲水性能、抗压实性能和抗污染性能,实验以介孔Al2O3为无机添加粒子,采用溶液纺丝法制备出介孔Al2O3/PVDF复合中空纤维膜。通过扫描电子显微镜和傅里叶红外光谱观察介孔Al2O3/PVDF复合中空纤维膜的形貌和成分,结果证明介孔Al2O3成功地添加到PVDF中空纤维膜中。通过接触角,纯水和含油废水通量的测试,结果表明介孔Al2O3的添加改善了PVDF膜的亲水性能、抗压实性能和抗污染性能。     

Preparation of polyvinylidene fluoride membrane via a thermally induced phase separation using a mixed diluent

Polyvinylidene fluoride (PVDF) membranes were prepared via a thermally induced phase separation method with a mixed diluent (dibutylphthalate/dioctyl phthalate). The effects of PVDF concentration and cooling bath temperature (CBT) on the structure and properties of the membranes were investigated. Scanning electron microscopy photos showed that the cross‐section of all the membranes, regardless of PVDF concentration and CBT, presented a bi‐continuous structure with the spherulitic pattern; moreover, the spherulitic patterns became clear gradually from the top surface to the bottom surface, and the top surface was denser than the bottom surface. As a result, all the membranes exhibited an asymmetric structure. The membrane property measurement indicated that, as PVDF concentration increased from 25 to 35 wt %, the pure water flux (PWF) decreased from 342 to 80 L m^?2 h^?1, and the porosity decreased slightly, whereas the minimum bubble point pressure (BPP) increased, which indicates maximum pore size decreased. In addition, with the increase in CBT, the PWF increased, but, the minimum BPP and porosity decreased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of several types of polyvinyl butyral hollow fiber membranes by thermally induced phase separation

Hollow fiber membranes were prepared by thermally induced phase separation from three types of polyvinyl butyral (PVB) and a blend of two of these polymers. Although the difference in the chemical composition of the PVB polymers used was not remarkable, their respective membrane performances were quite different. With a high phase separation temperature the pore size of the prepared membrane was large, because structure growth occurred for a long time. Water permeability tests of the wet membranes showed the results that corresponded to the pore sizes of the membranes. By contrast, the results for the dried membrane appeared to be related to the hydrophilicity of the PVB polymer and independent of pore size in the wet condition. Although the membrane with high wettability had low mechanical strength, the membrane from the polymer blend of two different PVB polymers showed adequate wettability and mechanical strength. This produced a hollow fiber membrane with favorable characteristics for application in water treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of highly permeable PDMS@ZIF-8/PVDF hollow fiber composite membrane in module for ethanol-water separation

The construction of high-performance MOF-based hollow fiber composite membrane (HFCM) modules is a significant, yet challenging task for the biofuel production industry. In this study, a novel approach was taken to fabricate PDMS@ZIF-8/PVDF HFCMs in modules through a facile ZIF-8 self-crystallization synthesis followed by pressure-assisted PDMS infusion for pervaporation ethanol-water separation. The as-prepared HFCMs exhibited an ultrathin separation layer (thickness, 370 ± 35 nm), which was achieved through precise regulation of the ZIF-8 membrane and defect repair by PDMS infusion. Moreover, the strategy utilized in this study resolved the defect issues arising from MOF agglomeration in conventional composite membranes. Impressively, at the optimal packing density, the prepared membrane demonstrated a remarkable ethanol flux (1.11 kg m⁻² h⁻¹) with an PSI value (26.59 kg m⁻² h⁻¹) and showed promising long-term stability for the pervaporation of 5 wt% ethanol aqueous solution at 40°C.     

Effect of diluents on membrane formation via thermally induced phase separation

The effect of diluents on isotactic polypropylene (iPP) membrane formation via thermally induced phase separation was investigated. The diluents were methyl salicylate (MS), diphenyl ether (DPE), and diphenylmethane (DPM). The cloud-point curve was shifted to a lower temperature in the order iPP–MS, iPP–DPE, and iPP–DPM, whereas the crystallization temperature was not influenced so much by diluent type. Droplet-growth processes were investigated under two conditions: quenching the polymer solution at the desired temperature and cooling at a constant rate. Although droplet sizes were in the order iPP–MS, iPP–DPE, and iPP–DPM in both cases, the difference was more pronounced with the constant cooling rate condition. Scanning electron microscopy indicated that interconnected structures were obtained when the polymer solution was quenched in ice water. The effect of the diluents on these structures was observed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 169–177, 2001     

Preparation of PET threads reinforced PVDF hollow fiber membrane

PET threads were incorporated in the support layer of hollow fiber membrane in axial direction as a special reinforcement material for the purpose of improving the mechanical properties of PVDF hollow fiber membranes. It was found that the reinforcement threads had a limited effect on the separation-related properties of the membrane, such as porosity and pore size, but the tensile strength of the reinforced membrane was improved several folds. Also, the criterion of choosing reinforced fiber materials was suggested.     

Preparation of thermoplastic polyurethane/graphene oxide composite scaffolds by thermally induced phase separation

In this study, biomedical thermoplastic polyurethane/graphene oxide (TPU/GO) composite scaffolds were successfully prepared using the thermally induced phase separation (TIPS) technique. The microstructure, morphology, and thermal and mechanical properties of the scaffolds were characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and compression tests. Furthermore, NIH 3T3 fibroblast cell viability on the porous scaffolds was investigated via live/dead fluorescent staining and SEM observation. FTIR and Raman results verified the presence of GO in the composites. SEM images showed that the average pore diameter of the composite scaffolds decreased as the amount of GO increased. Additionally, the surface of the specimens became rougher due to the embedded GO. The compressive modulus of composite specimens was increased by nearly 200% and 300% with the addition of 5% and 10% GO, respectively, as compared with pristine TPU. 3T3 fibroblast culture results showed that GO had no apparent cytotoxicity. However, high loading levels of GO may delay cell proliferation on the specimens. POLYM. COMPOS., 35:1408–1417, 2014. © 2013 Society of Plastics Engineers     

Preparation and structural control of polyphenylene sulfide porous fibers via thermally induced phase separation method

The porous fibers are expected to be widely used in liquid filtration, environmental protection, and catalyst carrier field. Polyphenylene sulfide (PPS) porous fiber was prepared using polyethersulfone (PES) as pore-forming agent by a thermally induced phase separation method. The rheological behaviors, crystallization, compatibility of the PPS/PES blending resins and fibers were characterized by the tests of high pressure capillary rheology, differential scanning calorimetry, and dynamic thermodynamic analysis, and so on; meanwhile, the structure and properties of PPS porous fibers were studied through the tests of continuity, scanning electron microscope, mercury injection, and mechanical properties. The results shown that the pore structure of porous PPS fibers can be regulated by controlling the PES content. In the spinning process, the higher winding speed (R = 300 ~ 400) and the larger PES content (60%) are more conducive to the formation of an interpenetrating structure of PES in the blend system. After the extraction of PES, PPS fibers with PES contents of 30% and 40% formed pore structure with uniform shape and size. Nevertheless, a high PES fraction of 60% leads to the collapse of the pore structure, resulting in serious structural damage. The porous fiber with controllable pore dimension is obtained by selecting proper ratio of polymers and appropriate spinning conditions.     

稀释剂对TIPS法等规聚丙烯中空纤维微孔膜孔径及其连通性的影响

热致相分离（TIPS）法制备等规聚丙烯（iPP）中空纤维微孔膜,邻苯二甲酸二丁酯（DBP）与邻苯二甲酸二辛酯（DOP）的混合溶剂作为制膜稀释剂。干/湿氮气流量法测定了α（稀释剂中DBP的质量分数）和β（铸膜液中聚合物的质量分数）对膜样品的平均孔径及其分布的影响,并采用膜孔曲折因子定量表达膜孔连通性。发现全部膜样品均体现窄孔径分布特征。对于相同的β, α增加导致平均孔径及膜孔连通性下降。α=0.20时,β增加,膜的平均孔径先增加后降低,膜孔曲折因子稍下降; α=0.35或0.50时,β增加,膜的平均孔径降低,膜孔曲折因子下降。膜孔连通性体现了膜内部的拓扑结构,共溶剂组成和铸膜液固含量能够调节iPP中空纤维微孔膜的孔径及其连通性。     

Preparation of dual‐layer acetylated methyl cellulose hollow fiber membranes via co‐extrusion using thermally induced phase separation and non‐solvent induced phase separation methods

Dual‐layer acetylated methyl cellulose (AMC) hollow fiber membranes were prepared by coupling the thermally induced phase separation (TIPS) and non‐solvent induced phase separation (NIPS) methods through a co‐extrusion process. The TIPS layer was optimized by investigating the effects of coagulant composition on morphology and tensile strength. The solvent in the aqueous coagulation bath caused both delayed liquid–liquid demixing and decreased polymer concentration at the membrane surface, leading to porous structure. The addition of an additive (triethylene glycol, (TEG)) to the NIPS solution resolved the adhesion instability problem of the TIPS and NIPS layers, which occurred due to the different phase separation rates. The dual‐layer AMC membrane showed good mechanical strength and performance. Comparison of the fouling resistance of the AMC membranes with dual‐layer polyvinylidene fluoride (PVDF) hollow fiber membranes fabricated with the same method revealed less fouling of the AMC than the PVDF hollow fiber membrane. This study demonstrated that a dual‐layer AMC membrane with good mechanical strength, performance, and fouling resistance can be successfully fabricated by a one‐step process of TIPS and NIPS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42715.     

Crystallization behavior of PVDF in PVDF‐DMP system via thermally induced phase separation

The crystallization behavior of PVDF (poly (vinylidene) fluoride) in PVDF‐dimethylphthalate(DMP) system was investigated in the liquid–liquid (L–L) phase separation region, solid–liquid (S–L) phase separation region and different quenching conditions via thermally induced phase separation (TIPS). Differential scanning calorimetry (DSC) indicated the crystallinity of PVDF in PVDF‐DMP system increased in the early stage of phase separation and polymer‐rich phase crystallized completely in the late stage of phase separation. The scanning electron microscopy (SEM) showed the different quenching temperatures had effects on the spherulite size of polymer rich phase and the ultimate membrane structure in the different phase separation regions. The wide angle X‐ray diffraction (WAXD) was used to quantify the crystal structure of PVDF in PVDF‐DMP system. The α‐phase PVDF was obtained when the system quenched to different temperatures above 40°C, and the area of diffraction peaks changed when quenching temperatures changed. While the β‐phase PVDF was formed when PVDF‐DMP system was quenched form liquid nitrogen and crystallized for 24 h in 25°C water bath. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3714–3719, 2006     

Pervaporative separation of butanol using a composite PDMS/PEI hollow fiber membrane

In the study, the separation and purification of butanol was carried out using the composite hollow fiber membrane having the active layer of polydimethylsiloxane (PDMS) on the macroporous support of polyetherimide (PEI). The pervaporation results with the initial butanol concentration showed a trade-off between flux and separation factor. However, both the flux and the separation factor increased as the operating temperature increased. The pervaporation results showed the butanol flux and the separation factor were higher than those of the reported results. In this study, butanol was concentrated by the pervaporation as a feasibility study for the biofuel applications.     

Preparation and characterization of cellulose triacetate membranes via thermally induced phase separation

A series of cellulose triacetate (CTA) membranes were prepared via thermally induced phase separation (TIPS) process with dimethyl sulfone (DMSO2) and polyethylene glycol (PEG400) as a crystallizable diluent and an additive, respectively. The phase separation behavior of CTA/DMSO2/PEG400 ternary system was investigated in detail by optical microscopy, differential scanning calorimetry and wide angle X‐ray diffraction. This ternary system dynamically undergoes solid‐solid phase separation and thus the CTA membranes possess cellular, lacy, plate‐, or even ellipse‐shaped pores. However, we can modulate the pore structure, porosity, water flux, and mechanical properties of the membranes by varying polymer concentration, composition of the mixed diluent, and cooling condition. Due to the intrinsic hydrophilicity, the prepared CTA membranes have better antifouling property than polysulfone membranes. These porous membranes were used as supports to fabricate thin‐film composite forward osmosis (FO) membranes, which show good water permeability and selectivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44454.