一步法聚酰亚胺纤维的制备及其性能研究

利用实验室自制的聚酰亚胺(P)I溶液,通过干湿法纺丝制得PI初生纤维。在以水和N-甲基吡咯烷酮(NMP)混合溶液(体积比8∶2)作为凝固浴,凝固浴温度为5～15℃的条件下,所得初生纤维结构均匀密实,纤维截面呈圆形或腰圆形。在对初生纤维进行热处理时,随着热处理温度升高和时间增加,PI纤维的力学性能增强。当热处理温度为300～320℃、时间为30 min时,PI纤维的力学性能最优,其断裂强度和初始模量达到2.474 cN/dtex和50.066 cN/dtex;当热处理温度高于320℃,时间超过1 h,纤维力学性能又缓慢下降。纤维的热稳定性较好,在500℃左右仍具有较好的热稳定性。     

PI/NMP/H_2O三元体系相行为与纤维成形研究

介绍了湿法纺丝中凝固剂/溶剂/聚合物三元体系热力学理论及三元相图双节线和旋节线的计算方法;在聚酰亚胺/N-甲基-2-吡咯烷酮/水(PI/NMP/H2O)三元体系中,采用黏度法计算了PI-NMP相互作用参数(χ23),平衡溶胀法测得PI-H2O相互作用参数(χ13),结合NMP-H2O相互作用参数,并根据FloryHuggins溶液理论绘制出不同温度下PI/NMP/H2O三元体系的理论相图,并研究了不同凝固浴温度下PI纤维纺制中的相分离及成形过程。结果表明:在25,40,60℃时,χ23分别为0.489 6,0.480 1,0.473 4,χ13分别为1.52,1.47,1.30;随着凝固浴温度升高至60℃时,纤维表面逐渐变得致密光滑,断面形态由肾形变为规则的圆形;凝固浴温度升高时,相图中亚稳态区域扩大,纤维成形过程更加缓和,有利于制备结构致密的PI纤维。     

聚酰亚胺纤维的制备及其结构研究

将均苯四甲酸二酐(PMDA)和4,4’-二氨基二苯醚(ODA)在N-甲基吡咯烷酮(NMP)中进行溶液聚合得到聚酰胺酸(PAA)溶液,并用该溶液进行干湿法纺丝得到PAA纤维,分别用化学酰亚胺化法和热酰亚胺化法得到聚酰亚胺(PI)纤维。研究了凝固浴组成和工艺条件对PAA形态结构和纤维性能的影响,以及不同酰亚胺化方法对PI纤维形态结构和性能的影响。结果表明:以甲醇为凝固浴制备的PAA初生纤维,无孔致密,最高拉伸强度和初始模量分别为2．21 cN/dtex和40．73 cN/dtex;采用化学酰亚胺化法制得的PI纤维中存在少许孔洞缺陷,其强度较低,热酰亚胺化法制得的PI纤维无孔致密,其强度和模量分别达到2．83 cN/ dtex和43．4 cN/dtex。     

溶剂对聚乙烯醇纺丝原液及纤维结构和性能的影响

采用不同的溶剂溶解高相对分子质量聚乙烯醇(PVA),制备PVA纺丝原液及初生纤维,对其结构和性能进行了研究。结果表明:二甲基亚砜(DMSO)/H2O溶剂中DMSO的质量分数为92%时,对PVA的的溶解性能最好。相同条件下,与DMSO相比,N-甲基-N-氧化吗啉(NMMO)使PVA溶液粘度降低更快;DMSO/NMMO.2.5H2O混合溶剂中,当NMMO.2.5H2O质量分数为15%时,PVA纺丝的凝固性能较好,其初生纤维的结晶度较低。     

聚苯胺/聚酰胺导电初生纤维形态结构的研究

以聚苯胺 ( PANI)为导电组分 ,聚酰胺 -11为基体 ,浓硫酸为溶剂制备纺丝浆液 ,采用湿法纺丝路线纺制导电纤维。当 PAN I在纤维中的质量分数为 5 %和 12 %时 ,纤维的电导率分别提高到10 -5S/ cm和 10 -2 S/ cm。采用扫描电子显微镜 ( SEM)研究了凝固浴中酸的含量以及纺丝浆液中 PANI的含量对初生纤维形态结构的影响 ,并探讨了初生纤维的微观结构对纤维的拉伸性能的影响     

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。     

PAN原丝沸水收缩率影响因素的探讨

采用溶液聚合和湿法纺丝制备碳纤维用聚丙烯腈(PAN)原丝,探讨了共聚组成、凝固浴温度、凝固浴浓度、拉伸介质和热定型温度对PAN纤维沸水收缩率的影响。结果表明,采用二元共聚物丙烯腈/甲叉丁二酸的质量比为99/1,凝固浴温度为30℃、凝固剂中二甲基亚砜质量分数为70%,热定型温度为160℃,拉伸介质为加压饱和蒸汽时,制备的PAN原丝沸水收缩率最低。     

PVA/PTFE浆液中硼酸质量分数对PVA/PTFE纤维性能的影响

实验研究了添加不同质量分数的硼酸凝胶剂对以聚乙烯醇(PVA)为载体,制备干质量比为1∶6的PVA/聚四氟乙烯(PTFE)纤维的纺丝工艺工艺参数和复合初生纤维质量的影响;实验还探讨了将硼酸作为外部凝固浴纺制PVA/PTFE纤维的可行性。结果表明:凝胶剂质量分数多的浆液在其本身最佳的纺制参数条件下纺制出的PVA/PTFE复合纤维的强度较佳;将硼酸作为外部凝固浴纺制具有一定的可行性。     

氨化对PAN原丝结构性能的影响

在聚丙烯腈(PAN)原丝湿法纺丝生产过程中,以二甲基亚砜/水(DMSO/H_2O)为凝固体系,在DMSO质量分数为72%,温度为52℃的凝固浴中通过流量计定量加入氨,以凝固浴溶液的pH值衡量氨化量的大小,研究了不同pH值对PAN原丝结构、性能及可纺性的影响。结果表明:在凝固浴溶液的pH值为8.6~10.0时,PAN原丝径向形态由腰形变成腰圆形,最后变成圆形;随着凝固浴溶液pH值的升高,PAN原丝的结晶度先升高后下降,膨润度则先降低后升高,直径不均率下降,强力不均率先下降后升高;凝固浴溶液pH值为9.5时,PAN原丝的结晶度最高,膨润度最小,直径不均率和强力不均率最低,可纺性最好,最终PAN基碳纤维的强度最高为3.83 GPa。     

凝固浴组分对纤维素纤维结构和力学性能的影响

采用新型碱复合溶剂NaOH／j琉脲／尿素水溶液对纤维素进行溶解,并采用H2S04／Na2SO4溶液作为凝固浴,对纤维素溶液进行湿法纺丝,获得纤维素纤维。通过改变凝固浴组分,研究纤维素纤维结构和性能的变化,获得更好的纺丝条件。研究表明,当H2S04质量分数为8％～10％,Na2SO4质量分数6％～12％时,纺丝过程稳定,纤维素纤维的力学性能较好且相对稳定。纤维素纤维的断裂强度最大值可达2．06cN／dtex,纤维素纤维横截面均呈近圆形结构,且无明显的皮芯结构,同时纤维素纤维具有纤维素II的结晶特征,凝固浴组分变化对纤维素纤维的结晶度和取向因子影响不大。     

聚酰亚胺初生纤维的形态结构

以聚酰亚胺浓溶液为纺丝浆液 ,以乙醇及其与水的混合物为凝固浴 ,采用干湿法纺丝工艺路线纺制聚酰亚胺纤维。用扫描电子显微镜研究了初生纤维形态结构 ,发现聚酰亚胺初生纤维的内部孔洞较小 ,而且受凝固浴配比的影响也较小。同时发现聚酰亚胺干湿法成形过程中存在轻微的原纤化现象     

凝固条件对羽毛角蛋白／PVA初生纤维结构与性能的影响

采用还原法从羽毛中提取角蛋白,制得羽毛蛋白质粉,再将其与聚乙烯醇（PVA）共混进行湿法纺丝,制备羽毛角蛋白／PVA共混纤维;借助X射线衍射、扫描电子显微镜等,研究了凝固浴温度和浓度对初生纤维力学性能、结晶结构、形态结构的影响。结果表明：较高的凝固浴浓度和凝固浴温度有利形成物理机械性能良好的初生纤维;羽毛角蛋白／PVA初生纤维的结晶度在50％左右,其结晶度和结晶尺寸受凝固浴温度和浓度的影响;可以通过改变凝固浴温度和浓度条件,得到沟槽比较浅表面光滑的初生纤维。     

湿纺凝固条件对PAN初生纤维形态结构的影响

分析了凝固浴温度、浓度、表观负拉伸等凝固条件对聚丙烯睛初生纤维形态结构的影响规律及作用机理,得出最佳的凝固工艺参数。结果表明:在其他凝固参数不变时,凝固浴温度、浓度及表观负拉伸均存在各自的临界值,低于或超过此临界值,初生纤维及原丝的性能均下降;采用凝固浴温度60℃、凝固浴质量分数为65％的最佳凝固工艺参数,可获得截面圆形且结构致密的初生纤维,并制得力学性能优异的原丝。     

In situ gradient nano-scale fibril formation during polypropylene (PP)/polystyrene (PS) composite fine fiber processing

The nano-scale dispersed fibrils with gradient distribution in PP/PS composite fine fibers were observed by in situ formation during its melt spinning process. The morphology development of polyblends, from granule to as-spun fiber as well as drawn fiber with various PS content from 2 to 8 wt% were investigated. The morphology conversion of PS dispersed phase from ellipse to gradient nano-scale fibril along the radial direction of as-spun composite fibers took palace at 4 wt% by weight of PS component, suggesting the presence of break-up in fiber center and the limited coalescence, especially in 8 wt% PS as-spun composite fibers. This morphology diversity was attributed to the radial variation of parameters including temperature, viscosity, axial velocity and stress in spinning path and was in good agreement with the droplet deformation criteria based on the reduced capillary number. In addition, the post hot-drawing process slightly influence the size and distribution of PS phase in cross-section of composite drawn fibers, while the rheological properties of PP, PS and polyblends were found to be correlated to the morphology of PP/PS composites.     

Air gap spinning of a cellulose solution in [DBNH][OAc] ionic liquid with a novel vertically arranged spinning bath to simulate a closed loop operation in the Ioncell® process

A novel, small-volume vertically arranged spin bath was successfully developed for an air gap lyocell-type spinning process. A maximum regeneration bath length with a minimum free volume characterizes the concept of the new spin bath. Using the ionic liquid (IL) 1,5-diazabicyclo[4.3.0]non-5-enium acetate [DBNH][OAc], the spin bath showed very good spinning performances of IL-cellulose dopes at high draw ratios and spinning duration for single filament spinning experiments. Using this new device, it was possible to get a step further in the optimization of the Ioncell® process and simulate a process closed loop operation by performing single filament spinning in IL/H₂O mixtures. Good dope spinnability and preserved fibers mechanical properties were achieved in a coagulation bath containing up to 30 wt% IL. It is only at 45 wt% of IL in the bath that the spinnability and fibers mechanical properties started to deteriorate. The fibers fibrillar structure was less pronounced in IL-containing spinning bath in comparison to a pure water bath. However, their crystallinity after washing was preserved regardless of the spinning bath composition. The results presented in this work have a high relevance to the upscaling of emerging IL-based cellulose dissolution and spinning processes.     

The development of high performance P84 co-polyimide hollow fibers for pervaporation dehydration of isopropanol

Probably because of material and fabrication limitations, most previously developed hollow fibers were lack of high performance for pervaporation dehydration applications. In this paper, we have successfully developed integrally skinned BTDA-TDI/MDI (P84) co-polyimide hollow fibers for pervaporation dehydration of isopropanol (IPA), which have impressive flux and selectivity towards water. The effects of spinning conditions such as air gap distance, coagulation temperature, and dope/bore fluid flow rates on membrane formation, morphology and pervaporation performance have been determined. Even though spinning conditions affect membrane separation performance, it is found that silicone rubber coating and heat treatment play much more important roles on performance enhancement. Not only can the silicone rubber coating effectively seal the membrane defects, but also triple the selectivity because of its nature of high water permeability while its hydrophobic property does not dominate. A tremendous increase in separation factor/selectivity (20-100 times) is observed after a heat treatment at . The newly developed P84 hollow fibers after heat treatment have a flux of and a separation factor of 10 585 for dehydration of 85/15 (w/w) IPA/water mixture at .     

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。     

Spinnability of low‐substituted hydroxyethylcellulose sodium hydroxide aqueous solutions

Ethylene oxide was used to etherify alkali cellulose with a low substitution degree to replace carbon disulfide to generate cellulose xanthogenate by viscose technology. The resultant low‐substituted hydroxyethylcellulose (LSHEC), with molar substitution of 0.49, was used to attempt to spin LSHEC fibers under spinning and coagulation conditions identical to those used for industrial rayon fibers. The spinnability of LSHEC was investigated by the variation of the storage modulus, loss modulus, and complex viscosity with the concentration of the LSHEC spinning solutions and temperature. It was found that the dissolution of LSHEC in sodium hydroxide aqueous solutions was an exothermic process, whereas the gelation of LSHEC was an endothermic process. Spinning conditions, comprising the concentration of the spinning solutions and corresponding spinning temperatures, were derived from the gelation onset curve theoretically. Moreover, combinations of the concentration of the spinning solution and the temperature of the coagulation bath could be predicted by the gelation onset curve. Finally, LSHEC fibers were prepared under the spinning conditions based on the gelation onset curve. The as‐spun LSHEC fibers had dry and wet tensile strengths of 1.59 and 0.47 cN/dtex, respectively, with a 0.30 ratio of the wet tensile strength to the dry tensile strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010