The Online Measurement of Lyocell Fibers and Investigation of Elongational Viscosity of Cellulose N‐methylmorpholine‐N‐oxide Monohydrate Solutions

In this paper, the development of diameter and surface temperature of Lyocell fibers was measured online. The diameter and tensile force on the spin line in the coagulation bath were traced. The velocity, velocity gradient and the tensile stress profiles development of the fibers in the air gap were studied. The apparent elongational viscosity of cellulose N‐methylmorpholine‐N‐oxide monohydrate (NMMO‐MH) solutions was studied by steady‐state melt spinning theory. The decrease of the fiber diameter was mainly taking place near the spinneret, and the decrease of the diameter became more dramatic with increasing taking‐up speed. The surface temperature of the fibers was also dropping faster with increasing taking‐up speed for the heat transfer coefficient increased. The diameter of the Lyocell fibers almost did not change before and after it entered the coagulation bath. The tensile force on the spin line increases with increasing taking‐up speed and coagulation bath length. The velocity and the tensile stress increase slowly near the spinneret, and then accelerate. The apparent elongational viscosity of cellulose NMMO‐MH solutions decreases with increasing temperature at the same elongation rate and decreases with increasing elongation rate at the same temperature. The fiber of the Lyocell process was not really solidified in the air gap and a gel or rubbery state was formed.     

Investigation on the effect of spinning conditions on the properties of hollow fiber membrane for hemodialysis application

Polyethersulfone (PES) hollow fiber membranes were fabricated via the dry‐wet phase inversion spinning technique, aiming to produce an asymmetric, micro porous ultrafiltration hollow‐fiber specifically for hemodialysis membrane. The objective of this study is to investigate the effect of spinning conditions on the morphological and permeation properties of the fabricated membrane. Among the parameters that were studied in this work are air gap distance, dope extrusion rate, bore fluid flow rate, and the take‐up speed. The contact angle was measured to determine the hydrophilicity of the fibers. Membrane with sufficient hydrophilicity properties is desired for hemodialysis application to avoid fouling and increase its biocompatibility. The influences of the hollow fiber's morphology (i.e., diameter and wall thickness) on the performance of the membranes were evaluated by pure water flux and BSA rejection. The experimental results showed that the dope extrusion rate to bore fluid flow rate ratio should be maintained at 1:1 ratio to produce a perfectly rounded asymmetric hollow fiber membrane. Moreover, the flux of the hollow fiber spun at higher air gap distance had better flux than the one spun at lower air gap distance. Furthermore, spinning asymmetric hollow fiber membranes at high air gap distance helps to produce a thin and porous skin layer, leading to a better flux but a relatively low percentage of rejection for BSA separation. Findings from this study would serve as primary data which will be a useful guide for fabricating a high performance hemodialysis hollow fiber membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43633.     

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 .     

Removal of Volatile Organic Compounds from Water by Pervaporation Using Polyetherimide-Polyethersulfone Blend Hollow Fiber Membranes

Abstract

Removal of volatile organic compounds (VOCs) such as 1,2-dichloroethane, trichloroethylene, chlorobenzene and toluene from water solutions through polyetherimide (PEI)-polyethersulfone (PES) blend hollow fiber membranes was investigated by pervaporation (PV) in this work. The separation performances of the membranes were researched by varying the spinning conditions (such as coagulation temperature and air gap distance) for the preparation of the hollow fibers and the operation conditions (such as velocity, concentration, and temperature of feed liquids). For the PEI-PES blend hollow fiber membrane prepared when the air gap was 7 cm and the temperature of coagulation bath was 45°C, it possessed high selectivity to the aqueous solutions containing 0.04 wt.% of VOCs at 20°C. The separation factors to 1,2-dichloroethane, trichloroethylene, chlorobenzene and toluene were 7069, 5759, 3952, and 3205, respectively. It was found that the pervaporation performance of the blend hollow fiber membrane was strongly related to the molecular size of the VOCs. The order of the selectivities was 1,2-dichloroethane > trichloroethylene > chlorobenzene > toluene.     

Two‐dimensional simulation of hollow fiber membrane fabricated by phase inversion method

In the steady fabricating process, two‐dimensional hollow fiber membrane near the spinneret was numerically simulated using the finite element method (FEM). The unknown positions of free surface and moving interface were calculated simultaneously by the velocity and pressure fields. The effects of seven relevant parameters, i.e., inertia term, gravity term, dope flow rate, bore flow rate, dope viscosity, tensile force, end velocity and non‐Newtonian on the velocity and diameter profile were studied. On the basis of the simulated results, the inertia term in hollow fiber‐spinning process was safely neglected in low speed, while the effect of gravity was not be neglected. Besides, the outer diameter of the fibers increased with an increase of dope flow rate and bore flow rate; Large tensile force or large end velocity could cause large deformation in the air gap; larger viscous dope solution tended to make less deformation in the air gap. It was found that an increase of the dope flow rate at small dope flow rate resulted in an increase of the inner diameter, while at large dope flow rate, it decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2067–2074, 2006     

干喷湿纺中凝固牵伸对碳纤维前驱体PAN初生纤维的影响

为了研究PAN纤维干喷湿纺中凝固浴牵伸的作用机理。采用DMso水溶液作为凝固浴,利用纤维强伸度仪、分析天平、X射线衍射仪、电子探针等手段,研究了干喷湿纺中凝固牵伸对PAN初生纤维及最终原丝结构及性能的影响。结果表明,干喷瀑纺中,在凝固浴浓度（65％）、温度（20℃）、空气层厚度（2mm）等条件下,随凝固浴牵伸的增加,初生纤维及PAN原丝的孔隙率逐步降低,结晶度逐渐增大,初生纤维表现出较高的断裂强度,纵表面更加光洁,横截面更加致密;适当调整凝固浴牵伸,得到了纤度1．01dtex,强度7．52cN,dtcx的聚丙烯腈原丝。     

Fundamental understanding of the effect of air‐gap distance on the fabrication of hollow fiber membranes

The objectives of this work are, fundamentally, to understand hollow fiber membrane formation from an engineering aspect, to develop the governing equations to describe the velocity profile of nascent hollow fiber during formation in the air gap region, and to predict fiber dimension as a function of air‐gap distance. We have derived the basic equations to relate the velocity profile of a nascent hollow fiber in the air‐gap region as a function of gravity, mass transfer, surface tension, drag forces, spinning stress, and rheological parameters of spinning solutions. Two simplified equations were also derived to predict the inner and outer diameters of hollow fibers. To prove our hypotheses, hollow fiber membranes were spun from 20 : 80 polybezimidazole/polyetherimide dopes with 25.6 wt % solid in N,N‐dimethylacetamide using water as the external and internal coagulants. We found that inner and outer diameters of as‐spun fibers are in agreement with our prediction. The effects of air‐gap distance or spin‐line stress on nascent fiber morphology, gas performance, and mechanical and thermal properties can be qualitatively explained by our mathematical equations. In short, the spin‐line stresses have positive or negative effects on membrane formation and separation performance. A high elongational stress may pull molecular chains or phase‐separated domains apart in the early stage of phase separation and create porosity, whereas a medium stress may induce molecular orientation and reduce membrane porosity or free volume. Scanning electron microscopic photographs, coefficient of thermal expansion, and gas selectivity data confirm these conclusions. T_g of dry‐jet wet‐spun fibers is lower than that of wet‐spun fibers, and T_g decreases with an increase in air‐gap distance possibly because of the reduction in free volume induced by gravity and elongational stress. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 379–395, 1999     

Coimmobilization of malic enzyme and alanine dehydrogenase on organic–inorganic hybrid gel fibers and the production of L‐alanine from malic acid using the fibers with coenzyme regeneration

Malic enzyme (EC 1.1.1.39) and alanine dehydrogenase (EC 1.4.1.1) were entrap‐immobilized on hybrid gel fibers of cellulose acetate (CA) and zirconium (Zr) alkoxide by air‐gap wet spinning. The production of L ‐alanine from malic acid with coenzyme regeneration was examined with the enzymes immobilized on the fibers. The productivity of L ‐alanine of the immobilized enzymes decreased to approximately one‐fifth of that of free enzymes, but the CA–Zr‐fiber‐immobilized enzymes retained a high level of productivity after repeated use. Reduced form of nicotinamide adenine dinucleotide (NADH) recycling also occurred effectively for the enzymes immobilized on the fiber. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of Polypropylene Nanofibers from Polypropylene/Polyvinyl Butyral Blend Films Using Laser-Assisted Melt-Electrospinning

Polypropylene (PP) nanofibers, a few hundred nanometers in diameter, are of immense importance in the fiber industry. This article reports the fabrication of delicate PP nanofibers. Polyvinyl butyral (PVB) was added to PP as a blend component, and a nozzle-free melt-electrospinning system with a line-like CO₂ laser melting device was used to manufacture PP nanofibers. We investigated the effect of PVB ratio on fiber diameter. The addition of PVB was found to be potentially very beneficial in PP/PVB blends, resulting in improved PP crystallinity and a steady decrease of fiber diameter with high productivity. The reduction of fiber diameter was attributed to the decline of viscosity, increase of surface adhesion properties, and polarity of blends due to the inclusion of PVB. To produce PP nanofiber, the PVB was removed from PP/PVB blend fibers with an ethanol treatment. A drastic drop of PP fiber diameter followed by fiber splitting was observed after PVB removal. We obtained PP nanofibers with a diameter as low as 181 ± 105 nm from the blend fiber with 90% PVB. Infrared spectroscopy of fibers demonstrated that PP fibers from pure polymer and blends showed the same characteristic peaks. POLYM. ENG. SCI., 60: 362–370, 2019. © 2019 Society of Plastics Engineers     

喷丝温度对PAN中空纤维成形与性能的影响

利用双弧狭缝孔形喷丝板,采用干喷湿法纺丝工艺,研究了PAN纺丝液在40～70℃喷丝温度范围内,对中空初生纤维成形与性能的影响。结果表明:喷丝温度对纤维截面的成形、外皮层厚度、异形度、中空度、声速取向等均会产生影响。随喷丝温度的增加,初生纤维外皮层厚度减小,纤维内外沿异形度逐渐降低且差距逐渐增加,中空度与声速取向在低温段降低幅度较大,而在高温段降幅减缓。     

Tailoring the morphology of self-assembled block copolymer hollow fiber membranes

Isoporous asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) hollow fiber membranes were successfully made by a dry-jet wet spinning process. Well-defined nanometer-scale pores around 20–40 nm in diameter were tailored on the top surface of the fiber above a non-ordered macroporous layer by combining block copolymer self-assembly and non-solvent induced phase separation (SNIPS). Uniformity of the surface-assembled pores and fiber cross-section morphology was improved by adjusting the solution concentration, solvent composition as well as some important spinning parameters such as bore fluid flow rate, polymer solution flow rate and air gap distance between the spinneret and the precipitation bath. The formation of the well-organized self-assembled pores is a result of the interplay of fast relaxation of the shear-induced oriented block copolymer chains, the rapid evaporation of the solvent mixture on the outer surface and solvent extraction into the bore liquid on the lumen side, and gravity force during spinning. Structural features of the block copolymer solutions were investigated by small-angle X-ray scattering (SAXS) and rheological properties of the solutions were examined as well. The scattering patterns of the optimal solutions for membrane formation indicate a disordered phase which is very close to the disorder-order transition. The nanostructured surface and cross-section morphology of the membranes were characterized by scanning electron microscopy (SEM). The water flux of the membranes was measured and gas permeation was examined to test the pressure stability of the hollow fibers.     

静电纺工艺参数对SEBS纤维形貌和直径的影响

通过静电纺丝,将苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)溶解于四氢呋喃(THF)中的纺丝液制备成SEBS纤维,探索了纺丝液质量分数、纺丝电压和接收距离对纤维形貌及直径的影响.通过扫描电镜观察SEBS纤维的形貌以及Photoshop软件测量了SEBS纤维的直径.结果表明,纺丝液质量分数为25％、纺丝电压为10 k...     

Production of Polyethersulfone Hollow Fiber Ultrafiltration Membranes. II. Effects of Fiber Extrusion Pressure (EP) and PVP Concentration in the Spinning Solution

Abstract

The dimensional and UF performance characteristics of hollow fiber membranes produced by the solution spinning technique using three polymer solutions (C3, C4, and C5) were studied experimentally. The polymer (polyethersulfone, PES)/solvent (1-methyl-2-pyrrolidone, NMP)/additive (polyvinyl pyrrolidone, PVP) concentration (wt%) used were 20/65/15, 20/60/20, and 25/63/12, respectively, for C3, C4, and C5 solutions, and their corresponding viscosities were 9222, 22,809, and 29,286 cP. The extrusion pressures (EP) used in fiber production were 5 to 15, 20 to 40, and 20 to 60 psig, respectively, for C3, C4, and C5 solutions; the internal coagulant water flow rate (WFR) used were 7.5 and 10 mL/min for C3 fibers, and 5 mL/min for C4 and C5 fibers; and the length of air gap (LAG) was held constant at 80 cm in the production of all the fibers. An increase in EP always tended to increase OD, while ID decreased, increased, or remained constant depending on the WFR used. An increase in PVP concentration in the fiber spinning solution contributed to greater fiber swelling effects. Nascent fiber velocity (NFV) tended to increase with an increase in EP, but it decreased considerably with an increase in PVP concentration in the fiber spinning solution and the consequent increase in solution viscosity. Both fiber dimensions and skin layer morphology were found to be governed by the combined effects of desolvation, fiber swelling, and fiber stretching during fiber production.     

聚醚砜的静电纺丝研究

采用聚醚砜(PES)的良溶剂二甲基甲酰胺(DMF)和非良溶剂丙酮(AC)为共溶剂体系,研究了溶剂组成、纺丝成形条件对静电纺丝PES纤维的形貌及纤维直径的影响。结果表明:DMF/AC的配比对于静电纺丝PES纤维形貌具有直接的调控作用,随着DMF/AC混合溶剂中AC用量的增加,纤维平均直径变大,纤维毡中串珠数目明显减少,纤维均一性变好;随着纺丝液浓度的升高,纺丝电压的增大,纤维的平均直径变大;接收距离的变化对纤维平均直径影响不大;PES最佳纺丝工艺条件为纺丝溶液质量分数13%,纺丝电压15 kV,接收距离10 cm,mDMF/mAC为8.5/1.5,在此条件下,可以获得纤维平均直径为96 nm的PES纤维毡。     

Pervaporation of water/alcohol mixtures through chitosan/cellulose acetate composite hollow‐fiber membranes

For the purpose of separating aqueous alcohol by the use of pervaporation technique, a composite membrane of chitosan (CT) dip‐coated cellulose acetate (CA) hollow‐fiber membranes, CT‐d‐CA, was investigated. The effects of air‐gap distance in the spinning of CA hollow‐fiber membranes, chitosan concentration, and sorts of aqueous alcohol solutions on the pervaporation performances were studied. Compared with unmodified CA hollow‐fiber membrane, the CT‐d‐CA composite hollow‐fiber membrane effectively increases the permselectivity of water. The thickness of coating layer increases with an increase in chitosan concentration. As the concentration of chitosan solution increased, the permeation rate decreased and the concentration of water in the permeate increased. In addition, the effects of feed composition and feed solution temperature on the pervaporation performances were also investigated. The permeation rate and water content in permeate at 25°C for a 90 wt % aqueous isopropanol solution through the CT‐d‐CA composite hollow‐fiber membrane with a 5‐cm air‐gap distance spun, 2 wt % chitosan dip‐coated system were 169.5 g/m² h and 98.9 wt %, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1562–1568, 2004     

改性酪蛋白/羧甲基纤维素钠共混纤维制备与性能

采用湿法纺丝,以乙醇、氯化钙和盐酸的混合溶液为凝固浴制备了改性酪蛋白(CLC)/羧甲基纤维素钠(CMC-Na)共混纤维。通过测试纺丝液流动性以及纤维的红外光谱、表面形态和力学性能,研究了CLC和CMC-Na不同配比与纺丝溶液pH改性后酪蛋白纤维的力学性能增加,纺丝溶液的流动性与CMC-Na维的红外光谱分析表明CLC与CMC-Na之间有良好的相互作用。CMC-Na质量分数为30%(相对于改性酪蛋白)的共混纤维性能较好,纤维表面较致密,有沿着纤维轴向取向的明显条纹,其断裂强度为341.19MPa。     

Crystallinity development in polyacrylonitrile nascent fibers during coagulation

This paper has studied the crystal and thermal property of nascent fibers during the polyacrylonitrile coagulation process. A water (H₂O)/dimethyl sulphoxide (DMSO) mixture was used as the coagulation bath for the coagulation process of acrylonitrile(AN)/itaconic acid(IA) copolymer fibers in the study. By transforming the spinning conditions, especially air gap distance between the spinneret and coagulation bath, draw ratios, coagulation time, we received the crystal and thermal properties of nascent fibers under different conditions. The relationship between the property of nascent fibers and the spinning conditions has been studied by use of X-rays, SEM, differential scanning calorimetry (DSC) and so on. The results indicated that the degree of crystallization gradually increased with the rise of coagulation time and tended to a fixed value when reached some time. With the augment of draw ratios, the crystal degree appeared differently, in which it decreased when the air gap distance was 0 mm and it increased when the air gap distance was 1 mm and 2 mm. At the same time, the thermal properties showed little difference in peak position and biggish difference in heat energy, which indicated the ability to endure heat for latter spinning process and thermal stabilization process.     

Microfluidic behavior in melt-spun hollow and liquid core fibers

The development of thermoplastic fibers containing a liquid core is described. Internal morphology analysis confirms that the liquid-containing core is composed of a continuous cylindrical microchannel of constant diameter. Microfluidic experiments on both liquid core and reference hollow fibers were conducted by pumping distilled water through several filaments simultaneously. The observed fluid motions are satisfactorily described by the Hagen-Poiseuille law, indicating that the hollow and liquid core fibers have internal diameters of 31.6 and 14.8 µm, respectively. Flushing the liquid core fibers with a surfactant solution efficiently removes the saturated ester initially used during the melt spinning of the fiber.     

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     

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