Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP) hollow fiber membranes prepared from PVDF‐co‐HFP/PEG‐600Mw/DMAC solution for membrane distillation

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐co‐HFP) hollow fiber membranes were prepared by using the phase inversion method. The effect of polyethylene glycol (PEG‐600Mw) with different concentrations (i.e., 0, 5, 7, 10, 12, 15, 18, and 20 wt %) as a pore former on the preparation and characterization of PVDF‐co‐HFP hollow fibers was investigated. The hollow fiber membranes were characterized using scanning electron microscopy, atomic force microscopy, and porosity measurement. It was found that there is no significant effect of the PEG concentration on the dimensions of the hollow fibers, whereas the porosity of the hollow fibers increases with increase of PEG concentration. The cross‐sectional structure changed from a sponge‐like structure of the hollow fiber prepared from pure PVDF‐co‐HFP to a finger‐like structure with small sponge‐like layer in the middle of the cross section with increase of PEG concentration. A remarkable undescribed shape of the nodules with different sizes in the outer surfaces, which are denoted as “twisted rope nodules,” was observed. The mean surface roughness of the hollow fiber membranes decreased with an increase of PEG concentration in the polymer solution. The mean pore size of the hollow fibers gradually increased from 99.12 to 368.91 nm with increase of PEG concentration in polymer solution. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The effects of air gap length on the internal and external morphology of hollow fiber membranes

A systematic study of the air gap effects on both the internal and the external morphology, permeability and separation performance of polyvinylidene fluoride (PVDF) hollow fiber membranes has been carried out. The hollow fibers were prepared using the dry-jet wet spinning process using a dope solution containing PVDF/ethylene glycol/N, N-dimethylacetamide with a weight ratio of 23/4/73. Ethanol aqueous solution, 50% by volume, was used as internal and external coagulants. The inner and the outer surfaces of the prepared hollow fibers were analyzed by atomic force microscopy (AFM), while their cross-sectional structure was studied by scanning electron microscopy (SEM). Ultrafiltration experiments were conducted using non-ionic solutes of different molecular weights. The results show that both the pore sizes and nodule sizes have a log-normal distribution. The pore size, nodule size and roughness parameters of the inner and outer surfaces of the hollow fibers were affected by the air gap distance. Alignment of nodules to the spinning direction was observed. Experimental results indicate that an increase in air gap distance, from 1 to , results in a hollow fiber with a lower permeation flux and a higher solute separation performance due to the decrease of the pore size. AFM analysis reveals that the air gap introduces an elongational stress because of gravity on the internal or external surfaces of the PVDF hollow fibers. At low air gap distance, the inner surface controls the ultrafiltration performance of the PVDF hollow fiber membranes because of its lower pore size, while at high air gap lengths the inner pore size becomes larger than the outer pore size. The turning point was observed at an air gap distance of .     

Effect of the preparation conditions on the morphology and performance of poly(imide) hollow fiber membranes

Poly(imide) (PI) hollow fiber membranes were prepared by using classical phase inversion process. Effects of different external coagulation bath temperatures (ECBT) and various bore flow rates (BFR) on the morphology and separation performance of the membranes were studied. Cross‐section, inner and outer structures were characterized by using scanning electron microscope and atomic force microscopy (AFM). Mean pore size, pore size distribution, and mean roughness of the PI hollow fibers surfaces were estimated by AFM. It was found that the hollow fibers morphology composed of sponge‐like and finger‐like structures with different ECBT and BFR. A circular shape of the nodules with different sizes was observed in the outer surface of the PI hollow fibers. Mean pore size of the outer surface increases with increasing ECBT and BFR. The important result observed in this study is that the ECBT clearly has the largest effect on hollow fiber PI membrane roughness compared with the BFR. Pure water permeability of the PI hollow fibers was improved with increase of ECBT and BFR. The solute rejection (R%) was reduced when the ECBT and BFR was increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40428.     

Preparation and characterization of poly(vinyl chloride)/polystyrene/poly(ethylene glycol) hollow‐fiber ultrafiltration membranes

Hollow‐fiber ultrafiltration (UF) membranes were prepared from blends of poly(vinyl chloride) (PVC) and polystyrene (PS) with a dry/wet phase inversion method. Poly(ethylene glycol) (PEG) and N,N‐dimethylacetamide were used as the additive and solvent, respectively. The effects of the PEG concentration in the dope solution as an additive on the cross sections and inner and outer surface morphologies, permeability, and separation performance of the hollow fibers were examined. The mean pore size, pore size distribution, and mean roughness of both the inner and outer surfaces of the produced hollow fibers were determined by atomic force microscopy. Also, the mechanical properties of the hollow‐fiber membranes were investigated. UF experiments were conducted with aqueous solutions of poly(vinyl pyrrolidone) (PVP; K‐90, M_w = 360 kDa). From the results, we found that the PVC/PS hollow‐fiber membranes had two layers with a fingerlike structure. These two layers were changed from a wide and long to a thin and short morphology with increasing PEG concentration. A novel and until now undescribed shape of the nodules in the outer surfaces, which was denoted as a sea‐waves shape, was observed. The outer and inner pore sizes both increased with increasing PEG concentration. The water permeation flux of the hollow fibers increased from 104 to 367 L m^?2 h^?1 bar^?1) at higher PEG concentrations. The PVP rejection reached the highest value at a PEG concentration of 4 wt %, whereas at higher values (from 4 to 9 wt %), the rejection decreased. The same trend was found also for the tensile stress at break, Young's modulus, and elongation at break of the hollow fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 989‐1004, 2013     

Influence of oxygen plasma treatment on interfacial properties of poly(p‐phenylene benzobisoxazole) fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite

The influence of oxygen plasma treatment on both surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fibers and interfacial properties of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated. Surface chemical composition, surface roughness, and surface morphologies of PBO fibers were analyzed by X‐ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. Surface free energy of the fibers was characterized by dynamic contact angle analysis (DCAA). The interlaminar shear strength (ILSS) and water absorption of PBO fiber‐reinforced PPESK composite were measured. Fracture mechanisms of the composite were examined by SEM. The results indicated that oxygen plasma treatment significantly improved the interfacial adhesion of PBO fiber‐reinforced PPESK composite by introducing some polar or oxygen‐containing groups to PBO fiber surfaces and by fiber surface roughening. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Nanofibrous ultrafiltration membranes containing cross-linked poly(ethylene glycol) and cellulose nanofiber composite barrier layer

Nanofibrous ultrafiltration membranes based on the thin-film nanofibrous composite (TFNC) format with a nanocomposite barrier layer made of cross-linked poly(ethylene glycol) (PEG) matrix and ultra-fine cellulose nanofibers (CN, ∼5 nm in diameter) were demonstrated. Physical properties, including pore size, chemical composition, morphology, hydrophilicity and surface roughness of these membranes, were characterized by filtration test, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), water contact angle measurements and atomic force microscopy (AFM). It was found the cross-linked PEG/CN barrier layer was highly hydrophilic and had excellent anti-fouling properties, which were confirmed by short-term and long-term fouling tests using bovine serum albumin (BSA) solution (1 g/L). In addition, the membranes exhibited better anti-fouling properties and recovery ability than comparable commercial membranes (e.g., Pall Life Sciences omega membranes and Koch HFK 328 membranes). For example, the flux of the composite layer was about twice as high as that of commercial membranes during the long-term testing, while the rejection was maintained above 90%.     

纳米结晶纤维素表面修饰聚酰亚胺纤维及其润湿功能性

聚酰亚胺纤维在应用方面存在许多潜在问题，例如聚酰亚胺纤维的低表面活性，使得其界面的润湿性能差，且在水相中易团聚，分散性较差。为此，本文提出在复合路易斯酸及交联剂共同催化作用下，使纳米结晶纤维素（CNC）修饰碱处理后的聚酰亚胺（PI）短切纤维表面，测定了CNC修饰前后PI纤维在水溶液中的分散度及PI纤维成纸的接触角，结果表明PI纤维的浸润功能性得到提高。采用扫描电子显微镜（SEM）观察了纤维的微观形貌，利用傅里叶变换红外光谱（FTIR）和X射线光电子能谱（XPS）表征了纤维表面结构的变化，最后通过多孔材料孔径分析仪测定了纤维成纸的孔径分布变化。结果表明：经CNC处理后的纤维表面发生了酯化反应且存在交联现象，纤维表面氧元素物质分数增加，含氧极性基团和表面粗糙度的增加有助于改善润湿性能，与PI纤维原纸相比，经CNC表面修饰后的纤维所成的纸页与去离子水的接触角降低了14.9°，与乙醇的接触角降低了4.8°，纤维分散度增加了45％，纤维亲水性显著提高，经过表面处理后的纤维在水相体系中的分散性能得到改善。因此，本法可以作为制备高性能纤维和相应复合材料的有效方法。     

Development of ultrafiltration membranes from acrylonitrile co-polymers

Summary Hydrophobic polymer surfaces show higher tendency to protein adsorption and bacteria attachment, thus hydrophobic polymeric membranes foul rapidly in water purification operations. A change in membrane surface properties can reduce fouling; this may be accomplished by increasing the hydrophilicity of the membrane surface, and by using a membrane with smaller pore size. The ultrafiltration membranes were prepared via phase inversion process in our laboratory. Negatively charged hydrophilic ultrafiltration membranes were prepared from acrylonitrile-vinyl acetate (CP16)/Acrylonitrile-vinyl acetate-sodium p-sulfophenyl methallyl ether (CP24). Scanning electron microscopy (SEM) revealed the asymmetric structure of these membranes. The roughness of the surface was measured by atomic force microscopy (AFM). The basic characteristics of these membranes like water permeability, water content and membrane selectivity were also measured. Received: 29 April 2001/Revised version: 14 September 2001/Accepted: 14 September 2001     

Antibacterial polymeric coating based on polypyrrole and polyethylene glycol on a new alloy TiAlZr

In order to enhance properties of the polymer composite films, composite coatings based on polypyrrole (PPy) and polyethylene glycol (PEG), using various percentages of PEG (0.5%, 2%, 4%), were electrodeposited on a new titanium alloy electrode as insulating material. The structure of the coatings was investigated via infrared (FTIR) analysis, and the surface features were studied using contact angle determination, atomic force microscopy (AFM) and scanning electronic microscopy (SEM). When testing the antibacterial properties of the coatings, the best effect was found for the coating with 2% PEG concentration, which has hydrophilic character and small roughness. Such results are in concordance with mechanism of biomaterial–bacteria interaction which involves as factors affecting bacterial adhesion and growth an initial physicochemical interaction stage, where roughness and wettabilitty are factors promoting bacterial adhesion and biofilm deposition.     

Effect of TEP content in cooling bath on porous structure,crystalline and mechanical properties of PVDF hollow fiber membranes

Poly (vinylidene fluoride) (PVDF) hollow fiber membranes were prepared by adding triethyl phosphate (TEP) to the cooling water bath in a modified thermally induced phase separation process. The effect of TEP content in the cooling bath on the porous structure, crystallinity, thermal and mechanical properties of PVDF hollow fiber membranes was investigated. The melting temperature and crystallinity of the membranes were determined using differential scanning calorimetry. The crystalline and cross‐section morphology of the hollow fiber membranes were investigated using wide angle X‐ray diffraction and scanning electron microscopy. The resulting membrane exhibited a nearly symmetric structure. The results showed that the TEP content in the cooling bath had a crucial role on the membrane formation, which was also confirmed from the morphology and mechanical properties of the hollow fibers. The porosity, average pore size, crystallinity, Young's modulus, max stress, and elongation at breakage of the hollow fiber membranes can be related to the amount of TEP in the cooling bath. Better pore connectivity was obtained in hollow fiber membranes when the weight ratio of TEP to water was 40:60. POLYM. ENG. SCI., 54:2207–2214, 2014. © 2013 Society of Plastics Engineers     

没食子酸/乙二胺共沉积聚酯纤维制备及其成纸性能

赋予疏水性聚酯短切纤维亲水性能，可拓展其应用价值。本文提出在碱性Tris缓冲液中，使没食子酸与乙二胺通过迈克尔加成或席夫碱反应共沉积在聚酯短切纤维表面。测定了改性前后聚酯短切纤维的动态接触角，采用扫描电子显微镜（SEM）观察了纤维的微观形貌，利用傅里叶变换红外光谱（FT-IR）和X射线光电子能谱（XPS）表征了纤维表面结构的变化，最后以改性前后聚酯短切纤维和阔叶木浆抄纸，测定了纸张的孔径分布变化和透气性，并测试了纸张物理性能。结果表明：经共沉积改性后的聚酯短切纤维表面存在大量羟基，纤维表面有氮元素生成，同时表面粗糙度提高，与未改性聚酯短切纤维相比，改性后聚酯短切纤维与去离子水的接触角降低了57.2?，显著改善了纤维亲水性；与未改性纤维纸页相比，改性后纤维纸页抗张强度提高35.2%，湿强度提高43.3%，透气度提高11.1%，相同孔径范围内孔径增加了24%-30%，纤维分散性明显提高。本研究成果可制得亲水性优良的聚酯纤维，并可用于高性能纸张的应用。     

Improvement of interfacial properties in bismaleimide composites using functionalized graphene oxide grafted carbon fiber

A hierarchical reinforcement, which was used to improve the interfacial properties of bismaleimide (BMI) composites, was prepared by grafting functionalized graphene oxide (GO) onto a carbon fiber surface. The GO and carbon fibers were first functionalized separately to create interactional functional groups on their surfaces. The grafting process was then realized by an amidation reaction of the amine and acyl chloride function groups formed on GO and carbon fibers, respectively. The surface groups of functionalized GO and carbon fibers were identified by an X‐ray photoelectron spectroscopy (XPS). The resulting reinforcement was further characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and dynamic contact angle analysis. Experimental results showed that the functionalized GO were successfully grafted onto the carbon fibers surfaces and significantly increased the surface energy of carbon fibers. The study also indicated that the prepared hierarchical reinforcement could significantly improve the interfacial adhesion of resulting BMI composite. POLYM. ENG. SCI., 58:886–893, 2018. © 2017 Society of Plastics Engineers     

Preparation of poly(4‐methyl‐1‐pentene) asymmetric or microporous hollow‐fiber membranes by melt‐spun and cold‐stretch method

Poly(4‐methyl‐1‐pentene) (PMP) hollow fibers were prepared and fabricated into gas separation or microporous membranes by the melt‐spun and cold‐stretched method. PMP resin was melt‐extruded into hollow fibers with cold air as the cooling medium. The effects of take‐up speed and thermotreatment on the mechanical behavior and morphology of the fibers were investigated. Scanning electronic microscope (SEM) photos were used to reveal the geometric structure of the section and surface of the hollow fibers. It was found that the original fiber had an asymmetric structure. A “sandwich” mode was used to describe the formation of this special fine structure. And a series of PMP hollow‐fiber membranes were prepared by subsequent drawing, and it was found that there was a “skin–core” structure on the cross section of these hollow‐fiber membranes. Asymmetric or microporous PMP hollow‐fiber membranes could be obtained by controlling posttreatment conditions. The morphology of these membranes were characterized by SEM, and the gas (oxygen, nitrogen, and carbon dioxide) permeation properties of the membranes was measured. The results indicate that the annealing time of the original fiber and the stretching ratio were the key factors influencing the structure of the resulting membrane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2131–2141, 2006     

Effect of polyethylene glycol molecular weights and concentrations on polyethersulfone hollow fiber ultrafiltration membranes

Polyethersulfone (PES) hollow‐fiber membranes were fabricated using poly(ethyleneglycol) (PEG) with different molecular weights (MW = PEG200, PEG600, PEG2000, PEG6000, and PEG10000) and poly(vinyl pyrrolidone) PVP40000 as additives and N‐methyl‐2‐pyrrolidone (NMP) as a solvent. Asymmetric hollow‐fiber membranes were spun by a wet phase‐inversion method from 25 wt % solids of 20 : 5 : 75 (weight ratio) PES/PEG/NMP or 18 : 7 : 75 of PES/(PEG600 + PVP40000)/NMP solutions, whereas both the bore fluid and the external coagulant were water. Effects of PEG molecular weights and PEG600 concentrations in the dope solution on separation properties, morphology, and mechanical properties of PES hollow‐fiber membranes were investigated. The membrane structures of PES hollow‐fiber membranes including cross section, external surface, and internal surface were characterized by scanning electron microscopy and the mechanical properties of PES hollow‐fiber membranes were discussed. Bovine serum albumin (BSA, MW 67,000), chicken egg albumin (CEA, MW 45,000), and lysozyme (MW 14,400) were used for the measurement of rejection. It was found that with an increase of PEG molecular weights from 200 to 10,000 in the dope solution, membrane structures were changed from double‐layer fingerlike structure to voids in the shape of spheres or ellipsoids; moreover, there were crack phenomena on the internal surfaces and external surfaces of PES hollow‐fiber membranes, pure water permeation fluxes increased from 22.0 to 64.0 L m^?2 h^?1 bar^?1, rejections of three protein for PES/PEG hollow‐fiber membranes were not significant, and changes in mechanical properties were decreased. Besides, with a decrease of PEG600 concentrations in the dope solution, permeation flux and elongation at break decreased, whereas the addition of PVP40000 in the dope solution resulted in more smooth surfaces (internal or external) of PES/(PEG600 + PVP40000) hollow‐fiber membranes than those of PES/PEG hollow‐fiber membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3398–3407, 2004     

Hollow Fiber Ultrafiltration Membranes from Poly(Vinyl Chloride): Preparation,Morphologies, and Properties

Hollow fiber poly(vinyl chloride) membranes were prepared by using the dry/wet spinning method. Cross-section, internal, and external surfaces of the hollow fibers structure were studied by SEM. The pore size and pore size distribution of the hollow fibers were measured by a PMI capillary flow porometer. UF experiments of pure water and aqueous solution of PVP K-90 were carried out. The effect of the PVC concentration on the hollow fibers mechanical properties was also investigated. It was found that the PVC fibers cross-sectional structure was affected by the polymer concentration in the dope solution. In particular, reduction of macrovoids size was observed when increasing PVC concentration from 15 to 19 wt%. The pore size distribution of the PVC hollow fibers was controlled by adjusting the PVC concentration. Indeed, an increase of PVC concentration up to 19 wt% leads to fibers with sharp pore size distribution (the 99% of pores is about 0.15 µm).The pure water permeation flux decreased from 162 to 128 (l/m² · h · bar), while the solute separation performance increased from 82 to 97.5%, when increasing the PVC concentration. The elongation at break, the tensile strength, and the Young's modulus of the PVC hollow fibers were improved with PVC concentration in dope solution.     

超细CaCO3／PP复合纤维的制备和亲水行为研究

通过共混包粘一熔融纺丝法制备超细CaCO3／PP复合纤维,对复合纤维的亲水性能和力学性能进行了研究,通过接触角测量法研究超细CaCO3／PP复合纤维表面能参数的变化,并用FTIR和SEM对纤维结构和表面形态进行分析,结果表明,超细碳酸钙填充改性可使PP纤维接触角降低76．6％,表面能、粘附功、极化度和积极性分量显著提高。FTIR和SEM测试表明,复合纤维表面极性基团的形成和表面形态粗糙化对PP复合纤维亲水性能的改善有重要作用,且在超细CaCO3含量为6％（w）时,纤维性能最佳,断裂强度提高24．07％,模量提高38．40％,接触角下降57％。     

Preparation of superhydrophobic silica‐based films by using polyethylene glycol and tetraethoxysilane

Preparation of superhydrophobic silica‐based films via sol‐gel process by adding polyethylene glycol (PEG4000) in the silica sol precursor solution has been developed. The casting films were prepared by casting the above solution on the glass and adding poor solvent on it or not. Surface roughness of the films was obtained by removing polymer from the films at high temperature. Then, the hydrophobic group on the surfaces was obtained by reaction with hexamethyldisilazane (HMDS). Characteristic properties of the as‐prepared surface of the films were analyzed by contact angle measurement, scanning electron microscopy (SEM), atomic force microscope (AFM), Fourier transform infrared (FT‐IR) spectrophotometer, and X‐ray photoelectron spectrometer (XPS). The results showed that the contact angles of the films were varied with the PEG weight fraction of the films, the solvent for the PEG solution, the reaction temperature and time, and adding poor solvent (n‐hexane) or not. However, the surface roughness has been controlled by adjusting the experimental parameters during the early period. The contact angle of the film that prepared by spraying the poor solvent (n‐hexane) onto each coating layer for four times after casting process was greater than 150°. It was difficult to obtain superhydrophobic surface without adding n‐hexane onto any coating layer in this system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

高性能碳纤维表面特性及其对浸润性能的影响

以4种不同型号的高性能碳纤维T700、UTS50、T800和IM7为研究对象,采用扫描电子显微镜和原子力显微镜对碳纤维直径、表面形貌和粗糙度进行表征,通过表面/界面张力仪对纤维表面能和树脂体系的表面张力进行分析,利用旋转流变仪对树脂体系的粘度进行测试。最后对碳纤维与不同温度和不同丙酮质量分数的618环氧树脂浸润性能进行测试,以分析纤维表面性能、温度和溶剂质量分数对碳纤维浸润性能的影响。结果表明,升高温度或提高溶剂质量分数有利于降低树脂体系的表面张力和粘度,从而有效改善碳纤维的浸润性能。纤维直径、表面粗糙度和表面能对碳纤维的浸润性能均有一定影响,其中纤维直径是影响浸润速率的主导因素,表面能和表面粗糙度对浸润质量的影响更加显著。     

Structure formation and characterization of PVDF hollow fiber membranes by melt‐spinning and stretching method

Melt‐spinning and stretching (MS‐S) method was proposed for preparing poly(vinylidene fluoride) (PVDF) hollow fiber membranes with excellent mechanical properties. The morphology and properties of PVDF fibers and membranes were investigated by small angle X‐ray scattering (SAXS), differential scanning calorimeter (DSC), field emission scanning electron microscope, mercury porosimeter, and tensile experiment. SAXS results indicated that the stacked lamellar structure aligned normal to the fiber axis was separated and deformed when the fibers were strained, and the long period of the strained fibers increased accordingly. Factors affecting the membrane properties were mainly spin‐draw ratio, annealing temperature, time, and stretching rate. Experimental results showed that the average pore size, porosity, and N₂ permeation of the membranes all increased with the increasing spin‐draw ratios and annealing temperatures. Annealing the nascent PVDF hollow fibers at 145°C for 12 h was suitable for attaining membranes with good performance. In addition, the amount and size of the micropores of the membrane increased obviously with stretching rate. Tensile experiment indicated PVDF hollow fiber membranes made by MS‐S process had excellent mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007