间位芳纶溶解及凝固性能研究

以二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、1-甲基-2-吡咯烷酮(NMP)为溶剂,分别加入LiCl和CaCl_2制备溶解体系,研究了间位芳纶在这几种溶解体系中的溶解性能。再以H_2O-DMAc、H_2O-DMF、H_2O-DMSO、H_2O-NMP为凝固浴,研究了溶剂种类、芳纶溶液质量分数、离子浓度等对间位芳纶溶液的凝固性能的影响。结果显示:Li Cl-DMAc溶解体系具有更强的溶解性能;凝固值随凝固浴中凝固剂H_2O的含量的增加不断减小,而临界浓度几乎没有变化;随着凝固浴温度的增加,凝固值增大,临界浓度减小;凝固值随凝固浴中离子浓度的升高而增大,但临界质量分数则不断降低。另外,间位芳纶溶液的扩散系数随着凝固浴中H_2O的含量的减少不断减小,随着芳纶浓度的增加不断减小。     

Porous hollow fibers with controllable structures templated from high internal phase emulsions

A technique to fabricate hollow fibers with porous walls via templating from high internal phase emulsions (HIPEs) has been demonstrated. This technique provides an environmentally friendly process alternative to conventional methods for hollow-fiber productions that typically use organic solvents. HIPEs containing acrylate monomers were extruded into an aqueous curing bath. Osmotic pressure effects, manipulated through differences in salt concentration between the curing bath and the aqueous phase within the HIPE were used to control the hollow structures of polyHIPE fibers. The technique was used to produce porous fibers (with millimeter-scale diameters and micron-scale pores) having a hollow core (with a diameter of 50%–75% of the fiber diameter). Two potential applications of the hollow fibers were demonstrated. In vitro drug release studies using these hollow fibers show a controlled release profile that is consistent with the microstructure of the porous fiber wall. In addition, the presence of pores in the walls of polyHIPE fibers also enable size-selective loading and separation of functional materials from an external suspension.     

Effects of different coagulation conditions on polyacrylonitrile fibers wet spun in a system of dimethylsulphoxide and water

Polyacrylonitrile (PAN) precursors were prepared by the wet spinning way. The effects of the coagulation conditions, such as coagulation temperature, coagulation ratio, and coagulation concentration, are discussed in detail. While keeping the coagulation bath concentration constant, as the coagulation bath temperature increased, the cross section deviated less from a circular form, and the as‐spun fiber diameter decreased. Measurement to the rate of the boundary movement has been calculated depending on the coagulation rate. While keeping the coagulation bath temperature constant, high coagulation bath concentration can cause more coagulant to diffuse into the solution to the polymer precipitated consequently, which led to a faster coagulation rate. The as‐spun fiber from high coagulation concentration was compacted than those from low concentration. The character of the formed structure reflected the system mobility and capability to crystallize. Improvement in fiber density in the as‐spun fiber resulted in improvements in the tensile strength of the as‐spun fiber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3723–3729, 2007     

Preparation of Hollow Fiber Membranes by Nonsolvent Induced Phase Separation along with Hydrogen Gas Formation Using a Single Orifice Spinneret

Traditional nonsolvent induced phase separation (NIPS) process for fabrication of hollow fiber membranes (HFMs) faces challenges, like design and manufacture of spinneret with two concentric orifices to provide parallel and continuous feed of polymer solution and bore fluid at specific rates. These factors limit the use of traditional technique to produce HFMs. Here, a new direct spinning method for fabricating HFMs by feeding a polymer solution, containing a gas producing agent using single orifice spinneret is reported. Polysulfone‐dimethylacetamide solution containing NaBH₄ is extruded through a stainless‐steel needle (single orifice spinneret) into HCl aqueous solution (coagulation bath) at specific rates. Effects of polysulfone concentration, temperature, and pH of coagulant bath on structure and performance of the HFMs are investigated. Synergy between hydrogen from NaBH₄ hydrolysis and NIPS process benefits fabrication of HFMs with good hollow bore structure and high porous wall. The prepared HFMs show good dye separation.     

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.     

聚醚砜中空纤维膜的成形条件与形态结构研究

采用扫描电镜探讨经双向拉伸聚醚砜(PES)中空纤维膜的纺制工艺条件与结构之间的关系。在膜的中部通入填充液,随着填充液压力的增大,中空纤维膜的壁厚明显减小,同时纤维膜表面的孔明显增多。随着凝固浴质量分数的增加,中空纤维膜表面的孔径先减小后增大,而中空纤维膜接近外表面的皮层逐渐变厚。随着凝固浴拉伸率的提高,中空纤维膜在外径不变的情况下壁厚减小,内表面积增加;纤维变薄而且更为致密。     

Diffusion coefficient of DMF in acrylic fiber formation

A H₂O/dimethyl formamide (DMF) mixture was used as the coagulation bath of wet‐spun process for acrylic fibers. Diffusion coefficient of DMF in the protofibers prepared by acrylonitrile/acrylamide copolymers was determined. It has been found that diffusion coefficient of DMF outflow of the protofibers prepared by acrylonitrile/acrylamide copolymers synthesized by solution polymerization is highest compared with those of acrylonitrile/acrylamide copolymers synthesized by H₂O/DMF mixture suspension polymerization and aqueous suspension polymerization. With an increase of copolymer concentration in the dope, diffusion coefficient of DMF decreases continuously. Diffusion coefficient of DMF increases along with the bath temperature, but the changes in diffusion coefficient values are less prominent as temperature goes beyond 55°C. When DMF concentration in the coagulation bath was 50%, the value of the diffusion coefficient of DMF was minimal. Diffusion coefficient of DMF increases along with jet stretch minus ratio increase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3616–3619, 2006     

三角形PAN纤维湿法纺丝工艺研究

采用三角形喷丝板,以二甲基亚砜为溶剂,进行聚丙烯腈(PAN)湿法纺丝。探讨凝固成形条件及后拉伸对三角形PAN纤维截面形状、声速和力学性能的影响。结果表明:随着凝固浴浓度的升高,PAN初生纤维的异形度降低,声速和力学性能均先升高后降低;随着凝固浴温度的升高,PAN初生纤维的异形度增大,声速和力学性能均降低;随着喷丝头拉伸比的增加,PAN初生纤维的异形度增加,声速和力学性能也都呈上升趋势,随着后拉伸的进行,三角形PAN纤维的异形度基本保持不变,其力学性能和声速均逐渐升高。     

凝固浴浓度对Lyocell纤维性能及最大纺丝速度的影响

探讨了Lyocell纤维纺丝工艺中凝固浴浓度对最大纺丝速度及纤维相对强度、断裂伸长、初始模量的影响.结果表明:随着凝固浴浓度增大,最大纺丝速度减小;而在凝固浴浓度为10%时,纤维的相对强度和初始模量为最大,延伸度则为最小.     

Integrally skinned polysulfone hollow fiber membranes for pervaporation

From polysulfone as polymer, integrally skinned hollow fiber membranes with a defect-free top layer have been spun. The spinning process described here differs from the traditional dry-wet spinning process where the fiber enters the coagulation bath after passing a certain air gap. In the present process, a specially designed tripple orifice spinneret has been used that allows spinning without contact with the air. This spinneret makes it possible to use two different nonsolvents subsequently. During the contact time with the first nonsolvent, the polymer concentration in the top layer is enhanced, after which the second coagulation bath causes further phase separation and solidification of the ultimate hollow fiber membrane. Top layers of ± 1 μm have been obtained, supported by a porous sublayer. The effect of spinning parameters that might influence the membrane structure and, therefore, the membrane properties, are studied by scanning electron microscopy and pervaporation experiments, using a mixture of 80 wt % acetic acid and 20 wt % water at a temperature of 70°C. Higher fluxes as a result of a lower resistance in the substructure could be obtained by adding glycerol to the spinning dope, by decreasing the polymer concentration, and by adding a certain amount of solvent to the bore liquid. Other parameters studied are the type of the solvent in the spinning dope and the type of the first nonsolvent. © 1994 John Wiley & Sons, Inc.     

Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

PPD对PAA溶液性质及其纤维结构的影响

以均苯四酸二酐(PMDA)和4,4,-二氨基二苯醚(ODA)以及PMDA,ODA和对苯二胺(PPD)共聚合成聚酰胺酸(PAA),经湿法纺丝制备PAA纤维.研究了PPD的引入对PAA原液性质及其纤维形态结构的影响.结果表明:PAA的特性粘数随着PPD含量增加而提高;PPD的引入使PAA的凝固性能及其纤维力学性能提高;凝固浴为水/乙醇,水含量较高时,含有PPD的PAA纤维截面结构变得疏松多孔;凝固浴为水/N甲基吡咯烷酮,水体积分数为70%～80%时,得到致密无孔的改性PAA纤维.     

纳米二氧化硅填充PVDF聚合物微孔膜的研究

以丙酮及N,N-二甲基甲酰胺为混合溶剂、聚偏氟乙烯为成膜物质、纳米二氧化硅为填料,通过溶液共混法制备了聚偏氟乙烯/二氧化硅(PVDF/SiO2)复合微孔薄膜。研究发现,溶剂组分质量比对薄膜力学性能有重要影响,当m(丙酮)∶m(N,N-二甲基甲酰胺)=19∶1时,薄膜力学性能最佳,其拉伸强度为3.26 MPa;经纳米SiO2改性后,复合薄膜力学性能随SiO2质量分数的增大先提高后降低,在w(SiO2)=20%时,薄膜拉伸强度达最大值6.36 MPa;复合薄膜孔隙率随SiO2质量分数的升高而增大,当w(SiO2)=40%时,孔隙率达最大值113.9%。     

加压溶气气浮工艺用于Lyocell纤维纺丝溶剂回收的研究

探讨了加压溶气气浮工艺用于Lyocell纤维纺丝溶剂回收的可行性,考察了助凝剂PAM质量浓度、PAM流量比例、絮凝剂PAC质量浓度、PAC流量比例、溶气压力、回流比、刮渣机运行频次对加压溶气气浮工艺处理凝固浴溶液效果的影响。研究表明,当PAM质量浓度为1.0 g/L,PAM流量比例为0.6%,PAC质量浓度为150 g/L,PAC流量比例为0.15%,溶气压力为0.5 MPa,回流比为30%,刮渣机运行频次为10 min/60 min时,凝固浴溶液污染物去除效果最好。     

卡拉胶湿法纺丝凝固浴的选择

在探索以新的凝固浴代替BaCl_2凝固浴的过程中,分别设置CaCl_2-CaCl_2、KCl-KCl、KCl-CaCl_2三种不同凝固浴—拉伸浴组合,通过对纺丝过程中凝固浴—拉伸浴溶液分析以及对所得三种卡拉胶纤维的外貌、拉伸强度、结构和元素分析等研究,认为KCl-CaCl_2组合更加适合卡拉胶湿法纺丝,有望取代传统的BaCl_2-BaCl_2组合,成为更加绿色环保的卡拉胶湿法纺丝凝固浴—拉伸浴新组合。     

凝固条件对PAN初生纤维微结构的影响

通过湿法纺丝工艺制备聚丙烯腈(PAN)初生纤维,借助于X射线衍射仪、声速仪、扫描电子显微镜、小角X光散射仪等,研究了凝固浴温度、凝固浴浓度、喷丝头拉伸等凝固条件对初生纤维晶态结构、取向结构、形态结构的影响。结果表明:PAN纤维的凝聚态结构和形态结构在初生纤维形成时已基本形成;PAN初生纤维的结晶度达40%以上,其结晶度和结晶尺寸受凝固浴温度和浓度的影响;PAN初生纤维和原丝的晶区取向和全取向随着喷丝头拉伸的增大而增大;PAN初生纤维具有沿纤维轴向高度取向的沟槽,通过改变成形条件,可以获得沟槽浅且规整性完美的纤维表面;提高凝固浴浓度,可以形成结构均质、致密的PAN初生纤维,避免皮芯结构及芯部出现较多孔洞。     

离子液体法制备再生细菌纤维素纤维

以离子液体(氯化1-甲基-3-正丁基咪唑)溶解高聚合度细菌纤维素(BC),采用湿法纺丝制备再生细菌纤维素(RBC)初生纤维;通过红外光谱分析(FTIR)、广角X射线衍射(WAXD)分析、热失重(TG)分析、扫描电镜( SEM)、单丝强度拉伸等表征了RBC初生纤维的结构和性能.结果表明:该溶剂体系通过10 h的快速搅拌溶...     

Polyvinyl butyral-zirconia hybrid hollow fibers prepared by air gap spinning

In this study, an air gap spinning method was adopted to develop polyvinyl butyral (PVB)-zirconium (Zr) hybrid hollow fibers. With zirconium alkoxide, three kinds of PVB with different degree of acetalization were used as organic polymers. The morphologies, surface Zr content and relative bonding inside the hollow fibers were characterized by changing coagulation solution concentration, spinning dope viscosity and air gap distance. The effect of Zr on PVB structure were examined in terms of x-ray photoelectron spectroscopy, scanning electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy. Results indicate that PVB spinning solution experienced good mixing mechanism at room temperature and immediately develop structural hollow fiber when extruded into coagulation fluid of Zr alkoxide by 2.0 cm air gap distance. Among other prepared fibers, fiber contained 20 wt% PVB with 2 cm air gap confirms effective average diameter of about 1016 μm which strongly influenced by spinning solution viscosity. The variation of maximum Zr content (8.18%–14.36%) confirms the asymmetry of coordinate bonding occurred on internal and external surface. Moreover, changing of spinning solution viscosity, coagulation liquid concentration and air gap can only affect the surface roughness and fiber diameter whereas no micro pores were developed in the fiber sublayers.     

纺丝工艺对离子液体法新型纤维素纤维性能的影响

以离子液体1-丁基-3-甲基咪唑氯盐（[BMIM]C1）为溶剂,用干湿法纺丝制备了再生纤维素纤维,通过正交试验设计和系统试验,考察了气隙长度、喷头拉伸比、凝固浴浓度和凝固浴温度等工艺参数对制得的再生纤维素纤维的力学性能的影响,找出离子液体法新型纤维素纤维的最佳纺丝工艺。试验结果表明,对于该体系,纺丝工艺参数中凝固浴温度和拉伸比对纤维的拉伸强度、初始模量的影响最大,气隙长度对纤维断裂伸长影响最大。     

高强度海藻酸盐纤维的制备

采用湿法纺丝方法制备高强度海藻酸盐纤维,研究了影响纤维断裂强度的因素。结果表明:海藻酸钠的β-D-甘露糖醛酸单元(M)/α-L-古罗糖醛酸单元(G)质量比越高,纤维断裂强度越低。采用M/G值为0.32的海藻酸钠为原料,氯化钙水溶液为凝固液,纺丝液质量分数为5.0%,凝固浴质量分数为4.5%,凝固浴温度为40℃,纤维烘干温度为30℃,可制得断裂强度达4.675 cN/dtex的高强度海藻酸盐纤维。