Influence of sodium bromide additive on polyethersulfone ultrafiltration membranes

The effect of sodium bromide (NaBr) on performance and characteristics of ultrafiltration (UF) membranes was studied. Asymmetric UF membranes were prepared by phase inversion technique from a multicomponent dope polymer solution consisting of the polymer; polyethersulfone (PES), solvent; N, N‐dimethylformamide (DMF) and NaBr as micromolecular additive. The dissolution of PES‐DMF‐NaBr was carried out using microwave irradiation technique to induce rapid dissolution through minimal heating time. Various concentrations of NaBr were mixed with PES in the range of 1–5 wt % and its influence on membrane characteristics such as surface hydrophilicity was measured by contact angle and the performance in terms of water flux and rejection rates were evaluated using micromolecular test substances. The morphology and streaming potential of PES UF membranes were analyzed using scanning electron microscopy (SEM) and ζ‐potential measurement, respectively. Overall, the results suggest that the membrane consisting of 1 wt % NaBr exhibits the best performance in terms of rejection and flux rates with molecular weight cutoff (MWCO) of 45 kDa and mean pore size of 6 nm. The membrane with the 1 wt % addition of NaBr demonstrates most negative charge which indicates less fouling characteristics and displays approximately three times higher permeation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The effects of spinning temperature on morphologies and properties of polyethersulfone hollow fiber membranes

Polyethersulfone (PES) hollow fiber membranes were prepared by traditional dry‐wet spinning technique. Scanning electronic microscopy (SEM) was used to characterize membrane morphologies, and the membrane properties were evaluated via bubble point measurements and ultrafiltration experiments. The effects of spinning temperature on the morphologies and properties of PES fibers were investigated in detail. At a high spinning temperature, the obtained membrane structure consisting of a thin skin‐layer and loose sponge‐like sublayer endows PES membrane with not only good permeability, but also high solute rejection. Based on the determination of ternary phase diagrams and light transmittance curves, the relationship of membrane morphologies with thermodynamics and precipitation kinetics of membrane‐forming system was discussed. It was concluded that the morphologies and properties of PES hollow fiber membrane could be conveniently tuned by the adjustment of the spinning temperature and air gap. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of membrane pore size on the pH‐sensitivity of polyethersulfone hollow fiber ultrafiltration membrane

In our recent study, pH‐sensitive polyethersulfone (PES) hollow fiber membranes were prepared by blending poly (acrylonitrile‐co‐acrylic acid) (PANAA), and the electroviscous effect had great effect on the water flux change. While the question remains: is the water flux change caused by the electroviscous effect for all the membranes with different pore sizes? Herein, pH‐sensitive hollow fiber membranes with different pore sizes were prepared. The pore size and the theoretic water flux were calculated through the ultrafiltration of polyethylene glycol (PEG) solution. Comparing the calculated fluxes and the experimental ones, we found that the water flux change was mainly caused by the pore size change at the pH value larger than pKa, while that was caused by both the pore size change and the electroviscous effect when pH value was smaller than the pKa, and the pore size change was caused by the ionization of the ? COOH in the copolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of polyvinylpyrrolidone molecular weights on morphology,oil/water separation,mechanical and thermal properties of polyetherimide/polyvinylpyrrolidone hollow fiber membranes

We prepared polyetherimide (PEI) hollow fiber membranes using polyvinylpyrrolidones (PVP) with different molecular weights (PVP 10,000, PVP 40,000, and PVP 1,300,000) as additives for oil/water separation. Asymmetric hollow fiber membranes were fabricated by wet phase inversion technique from 25 wt % or 30 wt % solids of 20 : 5 : 75 or 20 : 10 : 70 (weight ratio) PEI/PVP/N‐metyl‐2‐pyrrolidone (NMP) solutions and a 95 : 5 NMP/water solution was used as bore fluid to eliminate resistance on the internal surface. Effects of PVP molecular weights on morphology, oil‐surfactant‐water separation characteristics, mechanical, and thermal properties of PEI/PVP hollow fiber membranes were investigated. It was found that an increase in PVP molecular weight and percentage in PEI/PVP dope solution resulted in the membrane morphology change from the finger‐like structure to the spongy structure. Without sodium hypochlorite posttreatment, hollow fiber membranes with higher PVP molecular weights had a higher rejection but with a lower water flux. For oil‐surfactant‐water emulsion systems (1600 ppm surfactant of sodium dodecylbenzenesulfonate and 2500 ppm oil of n‐decane), experimental results illustrated that the rejection rates for surfactant, total organic carbon, and oil were 76.1 ≈ 79.8%, 91.0 ≈ 93.0%, and more than 99%, respectively. Based on the glass transition temperature values, PVP existed in hollow fiber membranes and resulted in the hydrophilicity of membranes. In addition, using NaOCl as a posttreatment agent for membranes showed a significant improvement in membrane permeability for PVP with a molecular weight of 1300 K, whereas the elongation at break of the treated hollow fiber membranes decreased significantly. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2220–2233, 1999     

Ultra-thin skin carbon hollow fiber membranes for sustainable molecular separations

A transformative platform is reported to derive ultra-thin carbon molecular sieve (CMS) hollow fiber membranes from dual-layer precursor hollow fibers with independently tuned skin layer and substrate properties. These ultra-thin CMS hollow fiber membranes show attractive CO₂/CH₄ separation factors and excellent CO₂ permeances up to ~1,400% higher than state-of-the-art asymmetric CMS hollow fiber membranes. They provide a unique combination of permeance and selectivity competitive with zeolite membranes, but with much higher membrane packing density and potentially much lower costs.     

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     

Effect of surface‐modifying macromolecules and membrane morphology on fouling of polyethersulfone ultrafiltration membranes

Polyethersulfone (PES) ultrafiltration (UF) membranes with and without surface‐modifying macromolecules (SMMs) were prepared and characterized in terms of the mean pore size and pore‐size distribution, surface porosity, and pore density. The results demonstrated that both the mean pore size and the molecular weight cutoff (MWCO) of the SMM‐modified membranes are lower than those of the corresponding unmodified ones. Membrane fouling tests with humic acid as the foulant indicated that the permeate flux reduction of the SMM‐modified membranes was much less than that of the unmodified ones. Therefore, fouling was more severe for the unmodified membranes. Moreover, the dry weight of the humic acid deposited on the membrane surface was considerably higher for the unmodified membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3132–3138, 2003     

聚乙二醇对聚甲醛结晶行为及其纤维性能的影响

在聚甲醛(POM)中添加少量的聚乙二醇(PEG),熔融纺丝制得POM/PEG共混纤维。通过光学解偏振法、偏光显微镜观察(PLM)研究了POM与不同相对分子质量的聚乙二醇(PEG)的不同比例共混物的等温结晶行为,通过单纤强力测试仪、差示扫描量热(DSC)测试分析了共混纤维的力学性能。结果表明:PEG的加入能够加快POM的结晶,结晶温度升高,晶粒生长尺寸减小;随着PEG加入比例的增加,纤维断裂强度先降低后升高;相对分子质量为2 000的PEG与POM质量比为99/1时,纤维断裂强度比纯POM纤维提高约7%。     

Effects of preparation conditions on the surface modification and performance of polyethersulfone ultrafiltration membranes

The impact that some membrane preparation steps had on ultrafiltration (UF) membrane characteristics and performance was studied. Polyethersulfone (PES) was employed as base polymer, while N‐methyl pyrrolidone (NMP) was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a nonsolvent pore‐forming additive. The manufacturing variables studied were solvent evaporation time and membrane surface modification, using a fluorine‐based copolymer referred to as surface‐modifying macromolecule (SMM). The flat sheet membranes, prepared via phase inversion, were characterized using solute transport data, X‐ray photoelectron spectroscopy (XPS), and contact angle measurements. Membrane performance was evaluated via filtration test protocol that included a 6‐day filtration of concentrated river water. The flux reduction with time was modeled using single and dual mechanisms of fouling. The pore blockage/cake filtration model described better the behavior of the permeation rate along the experiments. Increasing the solvent evaporation time decreased the size of the pores and the permeation rate. However, it did not significantly affect the removal of the organic compounds naturally present in the river water used as feed. XPS and contact angle measurements proved that the short evaporation periods did not allow enough SMM migration to the surface to provoke a significant effect on the membrane performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Characterization of surface‐modified hollow fiber polyethersulfone membranes prepared at different air gaps

Hollow fibers were spun from a solution of surface‐modifying macromolecule blended polyethersulfone in dimethyl acetamide by using dry‐wet spinning method at different air gaps and at room temperature. The air gap was varied from 10 to 90 cm. The ultrafiltration performance of hollow fibers was studied by using aqueous solutions of polyethylene glycols and polyethylene oxides of different molecular weights. Significant difference in surface morphology between the inner and outer surface of the hollow fibers was observed by atomic force microscopy (AFM). Similar results were obtained by contact angle measurement and XPS. Mean pore sizes of the inner surface and outer surface were calculated from AFM images and compared with the pore sizes obtained from mass transport data. Pore size distribution curves were drawn from both data, i.e., from AFM images and mass‐transport data, both methods gave similar results. Roughness parameters of the inner and outer surfaces and the sizes of nodular aggregates on both surfaces were measured. An attempt was made to correlate the above parameters with the performance of the membranes. Unexpected values of contact angles of both inner surface and outer surface were obtained. It was observed that the studied membranes could be put into two groups: (i) the membranes fabricated between 10 and 50 cm air gap and (ii) fabricated at higher than 50 cm air gap. A plausible mechanism for the unexpected results was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 710–721, 2007     

Preparation and characterization of polyvinylidene fluoride hollow fiber membranes for ultrafiltration

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared using the solvent spinning method. N,N-dimethylacetamide was the solvent and ethylene glycol was employed as non-solvent additive. The effect of the concentration of ethylene glycol in the PVDF spinning solution as well as the effect of ethanol either in the internal or the external coagulant on the morphology of the hollow fibers was investigated. The prepared membranes were characterized in terms of the liquid entry pressure of water measurements, the gas permeation tests, the scanning electron microscopy, the atomic force microscopy, and the solute transport experiments. Ultrafiltration experiments were conducted using polyethylene glycol and polyethylene oxides of different molecular weights cut-off as solutes. A comparative analysis was made between the membrane characteristic parameters obtained from the different characterization techniques.     

Improved microstructure of asymmetric niobium pentoxide hollow fiber membranes

Asymmetric niobium pentoxide (Nb₂O₅) hollow fiber membranes were prepared by the phase inversion and sintering process at temperatures ranging from 1000 to 1350°C. The effects of extrusion parameters on the morphology and properties of the produced membranes were systematically explored. Asymmetric hollow fibers with regular inner contour were obtained at extrusion flow rates of 15 and 25 ml min⁻¹ of ceramic suspension and internal coagulant, respectively. Hollow fibers sintered at temperatures greater than 1200°C presented modifications in the morphology of Nb₂O₅ grains, which were also evidenced by X-ray diffraction and Raman analyses. Hollow fibers produced with an air gap of 50 mm presented a dense outer sponge-like layer and micro-voids formed from the inner surface. These hollow fibers sintered at 1200°C presented suitable bending resistance and water permeability (24.2 ± 0.60 MPa and 3.00 ± 0.01 L h^-1 m^-2 kPa^-1, respectively). The outer sponge like layer was mitigated when the fibers were produced without air-gap.     

Preparation and characterization of asymmetric polyethersulfone nanofiltration membranes: The effects of polyvinylpyrrolidone molecular weights and concentrations

In this study, asymmetric flat‐sheet polyethersulfone (PES) nanofiltration (NF) membranes were prepared via immersion precipitation phase inversion with the addition of polyvinylpyrrolidone (PVP). The effects of PVP with the molecular weights (MW) from 17 to 1400 kDa and the concentration from 0 to 3.0 wt % on the morphologies and performances of PES membranes were systematically studied. The prepared membranes were characterized by SEM, AFM, ATR‐FTIR, contact angle, membrane porosity, the water flux, and the rejection measurement. The results indicated that the porosity and the hydrophilicity of PES NF membrane increased with increasing PVP concentration, and the hydrophilicity of PES NF membrane also improved with increasing PVP MW. The enhancements of the porosity and hydrophilicity resulted in the higher water flux of PES NF membrane. The rejection of Bordeaux S (MW 604.48 Da) for the prepared PES membrane was increased to above 90% with the low PVP concentration, but it turned to decrease remarkably when the PVP concentration reached to a critical value which related to PVP MW. It was concluded that the addition of a small amount of PVP could significantly increase the permeability of PES NF membrane and maintain its rejection of Bordeaux S above 90%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43769.     

Improved spinnerette design for extrusion of polymeric large internal diameter hollow fiber membranes

Spinnerettes for extrusion of large (～ 1 mm) internal diameter (i.d.) hollow fiber membranes must possess certain features to extrude fibers with the proper tensile and geometrical properties. Spinnerette designs that properly extrude small i.d. (< 200 μm) hollow fibers will produce large i.d. hollow fibers with low burst strengths because of poor flow patterns and insufficient time in the spinnerette to knit a strong seam interface. In this report, an alternative design is offered that provides much better fiber properties without creating high pressure drops or shear stresses at the spinnerette wall that would normally result in melt fracture. The equations that guide the presented spinnerette design are provided and the suggested design is successfully guided by the results. The new spinnerette design also has the feature of allowing rapid change of hollow fiber wall thickness by making the core fluid pin replaceable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2157–2163, 2002     

Preparation and characterization of microporous polyethylene hollow fiber membranes

Microporous polyethylene (PE) hollow fiber membrane with a porosity of 43% and N₂ permeation of 4.96 cm³ (STP)/cm² s cmHg was prepared by melt‐spinning and cold‐stretching method. It was found that PE with a density higher than 0.96 g/cm³ should be used for the preparation of microporous PE hollow fiber membranes. By increasing the spin–draw ratio, both the porosity and the N₂ permeation of the hollow fiber membranes increased. Annealing the nascent hollow fiber at 115°C for 2 h was suitable for attaining membranes with good performance. By straining the hollow fiber to higher extensions, the amount and size of the micropores in the hollow fiber wall increased, and the N₂ permeation of the membranes increased accordingly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 203–210, 2002; DOI 10.1002/app.10305     

PEEKWC ultrafiltration hollow‐fiber membranes: Preparation,morphology, and transport properties

A series of hollow‐fiber membranes was produced by the dry–wet spinning method from PEEKWC, a modified poly(ether ether ketone) with good mechanical, thermal, and chemical resistance. The fibers were prepared under different spinning conditions, varying the following spinning parameters: polymer concentration in the spinning solution, height of the air gap, and bore fluid composition. The effect of these parameters on the water permeability, the rejection of macromolecules (using dextrane with an average molecular weight of 68,800 g/mol), and the morphology of the membranes was studied. The results were also correlated to the viscosity of the spinning solution and to the ternary polymer/solvent/nonsolvent phase diagram. The morphology of the cross section and internal and external surfaces of the hollow fibers were analyzed using scanning electron microscopy (SEM). All membranes were shown to have a fingerlike void structure and a skin layer, depending on the spinning conditions, varying from (apparently) dense to porous. Pore size measurements by the bubble‐point method showed maximum pore sizes ranging from 0.3 to 2 μm. Permeability varied from 300 to 1000 L/(h^?1 m^?2 bar) and rejection to the dextrane from 10 to 78%. The viscosity of polymer solutions was in the range of 0.2 to 3.5 Pa s. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 841–853, 2004     

双向拉伸法制备聚醚砜中空纤维

采用双向拉伸的方法制备了聚醚砜中空纤维,探讨了工艺条件对聚醚砜中空纤维取向度和水通量的影响。结果表明:随着纺丝速度的提高,纤维的取向度上升,水通量下降;在总拉伸倍数不变的前提下,随着凝固浴拉伸倍数的提高,纤维的取向度和水通量都减小;随着填充液压力的提高,纤维的取向度下降,水通量增加;随着凝固浴中二甲基亚砜含量的提高,纤维的取向度先增大后减小,出现了一个最大值,水通量先减少后增加,出现了一个最小值。     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m⁻¹. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m⁻²·h⁻¹ which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

Surface characterization of hollow fiber membranes used in artificial kidney

The internal and external curved surfaces of polysulfone hollow fiber membranes were characterized by atomic force microscopy (AFM), contact angle measurement (CAM), and scanning electron microscopy (SEM) with the aim of improving the membrane surface properties for blood compatibility. Novel approaches were applied to evaluate a number of properties, including the roughness, pore size, nodule size, and wettability of the surfaces of the hollow fibers. CAM studies were carried out by directly observing the liquid meniscus at the surfaces of hollow fibers. Observation of the meniscus and measurement of the contact angle became possible by using an imaging system developed in our laboratory. AFM and SEM studies were also conducted on the surfaces of the hollow fiber membranes by cutting them at an inclined angle. The effect of the molecular weight of poly(ethylene glycol) (PEG) in the polymer blend on the surface properties of the hollow fibers was studied. Increasing the PEG molecular weight increased the average pore size whereas it decreased the contact angle. The contact angle depended on the microscopic surface morphology, including nodule size and roughness parameters. The theoretical prediction along with the experimental data showed that the measured contact angle would be greater than the value intrinsic to the membrane material because of the formation of composite surface structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4386–4400, 2006     

New insights into sodium alginate fouling of ceramic hollow fiber membranes by NMR imaging

Ceramic hollow fiber membranes are investigated with respect to the fouling behavior. Constant pressure dead‐end filtration experiments have been performed using alginate as model substance for extracellular polymeric substances. In addition to the evaluation of the filtration data using conventional cake filtration model, nuclear magnetic resonance imaging (MRI) was used to elucidate the influence of Ca²⁺ on the fouling layer structure for alginate filtration within ceramic hollow fiber membranes. To visualize the alginate layers inside the opaque ceramic hollow fiber membranes by means of MRI, specific contrast agents were applied. Supplementary to multi slice multi echo imaging, flow velocity measurements were performed to gain more insight into the hydrodynamics in the fouled membranes. MRI reveals the structure of the alginate layers with the finding that the addition of Ca²⁺ to the alginate feed solution promotes the formation of a dense alginate gel layer on the membrane's surface. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2459–2467, 2016