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。     

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。     

成形条件对PAN原丝微孔结构及热性能的影响

将不同浓度的聚丙烯腈(PAN)原液在不同凝固浴温度下进行湿法纺丝,制得PAN原丝,再将PAN原丝在沸水浴中进行5倍拉伸。探讨了成形条件以及拉伸对PAN原丝微孔结构及热性能的影响。结果表明:当PAN纺丝原液质量分数为22%,凝固浴温度为10℃时,可以得到结构均匀致密的PAN原丝。PAN原丝经5倍拉伸后热分解温度降低,残留量减小。     

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     

含氨基螯合纤维的制备 Ⅰ．前驱纤维的制备

将N-乙烯基甲酰胺(NVF)与丙烯腈(AN)的共聚物溶液进行湿法纺丝,制备了含氨基螯合纤维的前驱纤维。研究了凝固条件、纺丝工艺、后处理条件对纤维的结构和性能的影响。结果表明:凝固浴中二甲基甲酰胺溶剂质量分数为20％,湿热拉伸倍数3．0、干热拉伸倍数3．5,纤维断裂强度达3．5 cN／dtex。扫描电镜观察表明纤维为圆形多孔断面,具有较高的孔隙率,适合于制备高效的螯合纤维。     

Investigating the jet stretch in the wet spinning of PAN fiber

The jet stretch of wet‐spun PAN fiber and its effects on the cross‐section shape and properties of fibers were investigated for the PAN‐DMSO‐H₂O system. Evidently, the spinning parameters, such as dope temperature, bath concentration, and bath temperature, influenced the jet stretch. Also, under uniform conditions, the postdrawing ratio changed as well as that of jet stretch. When coagulation temperature was 35°C simultaneously with bath concentration of 70%, jet stretch impacted obviously the cross‐section shapes of PAN fiber, but had little effect when the temperature was below 10°C or above 70°C. As the jet stretch ratio increased, the crystallinity, crystal size, sonic orientation, and mechanical properties of the as‐spun fiber changed rapidly to a major value for jet stretch ratio of 0.9 where the cross section of as‐spun fiber was circular. With further increasing of jet stretch ratio, the properties changed slightly but the fiber shape was not circular. The results indicated that appropriate jet stretch, under milder formation conditions in wet‐spinning, could result in the higher postdrawing ratio and circular profile of PAN fiber, which were helpful to produce round PAN precursor with minor titer and perfect properties for carbon fiber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

干湿法制备异形PAN原丝及其力学性能的研究

对二甲基亚砜(DMSO)干湿法制备三角形截面聚丙烯腈(PAN)基碳纤维原丝的截面形成因素进行了研究,并比较了不同条件下纤维的性能。结果表明:在干湿法纺制三角形截面PAN基碳纤维原丝过程中,凝固浴条件对PAN纤维的截面影响非常明显,同时凝固浴条件和拉伸条件对纤维的力学性能也有非常显著的影响。     

Impact of the wet spinning parameters on the alpaca-based polyacrylonitrile composite fibers: Morphology and enhanced mechanical properties study

The study examined the effect of different wet spinning parameters (e.g., total solid content, coagulation bath concentration, drawing, and stretching) on the morphology and mechanical properties of the wet spun alpaca/polyacrylonitrile (PAN) composite fibers. The alpaca/PAN composite fibers were wet spun using 10, 20, and 30% of alpaca particles along with the PAN polymer. The shear-thinning or non-Newtonian flow behavior was observed among the dope solutions with different solid content. The cross-sectional fiber morphology showed the bean-shaped characteristic for the control PAN fibers, whereas the alpaca/PAN composite fibers exhibited almost circular shape. “Cavity healing” was observed, where noticeable voids and porous areas were demolished in the cross section of the composite fibers, by changing the total solid content and coagulation bath concentration. Although the control PAN fibers exhibited the highest tenacity with lower fiber diameter, the alpaca/PAN composite fibers showed a gradual deterioration in tenacity while adding alpaca particles into the PAN polymeric matrix. Nevertheless, due to the increment in the total solid content, higher draw ratio, and stretching of the fibers, the tenacity, molecular orientation, and the crystallinity of the composite fibers were increased.     

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。     

The formation of polyacrylonitrile nascent fibers in wet‐spinning process

The formation of polyacrylonitrile (PAN) nascent fibers in wet‐spinning process was studied by KMnO₄ back titration method and scanning electron microscopy (SEM). It has been found that the rate of DMSO diffusion was rapid at the beginning of coagulation then decreased and reached balance at 24 s. With coagulation time increase, the nascent fibers became denser and had fewer inner defects gradually, but transverse stripes appeared on the surface at 24 s, and got deeper. The main defects of nascent fibers included transverse stripes, impurity, fish tail, inner microvoids etc. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

DMSO湿法PAN纤维截面形状形成条件的研究

对DMSO(二甲基亚砜)湿法制备PAN(聚丙烯腈)纤维的截面形状的形成因素进行了研究。随着凝固浴浓度的增大和温度的升高,纤维截面形状由椭圆形或肾形逐渐变为圆形。当凝固浴浓度在一定范围(55％-70％)时,不同凝固浴浓度对应一个凝固浴温度下限值,在该下限温度以上都可得到圆形截面纤维,且凝固浴浓度越低,此下限温度越高。纤维离开凝固浴后,截面形状基本形成并固定,水洗、拉伸、喷丝速度和干燥对纤维截面形状的形成影响都很小。     

PAN原丝成形过程中孔隙结构的形成和演变

采用干湿法纺丝在梯级凝固成形条件和后续工艺下得到聚丙烯腈(PAN)原丝,利用扫描电镜、氮气吸附等方法测试研究了PAN原丝中孔隙的形成和演变。结果表明:在凝固成形阶段,PAN原丝内孔隙的形成是溶剂和非溶剂双扩散及PAN相分离双重作用的结果;PAN原丝经过沸水拉伸、干燥致密化、饱和蒸汽拉伸和热定型等处理,其纤维密度、结晶度增大,力学性能提高,其孔隙平均孔径、孔隙体积和孔隙含量均逐渐减小;PAN原丝内闭合孔隙经过拉伸后会形成新的开放孔隙,开放孔隙在干燥致密化后闭合和消失。     

The index of dry‐jet wet spinning for polyacrylonitrile precursor fibers

A new spinning index for a PAN precursor fiber is proposed that includes the viscosity of a spinning dope, the thermodynamic affinity, and the draw ratio during the spinning process. Through dry‐jet wet spinning, six types of PAN precursor fibers with different spinning parameters, including solid content, solvent content in a bath, and draw ratio, were fabricated and analyzed with tensile tests, SEM, and XRD. The results show that the spinning index can reflect the mechanical properties of the fibers but is less indicative of crystallinity. Hence, the current spinning index is recommended for use as an indicator for the mechanical properties of PAN precursor fibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41265.     

高分子量聚丙烯腈纤维的干湿法成形工艺及纤维性能研究

采用正交试验设计法研究了高分子量PAN纤维的干湿法纺丝工艺,开考察了凝固浴温度和浓度及预热和热水拉伸对纤维性能的影响.结果表明,采用干湿法纺制高分子量PAN纤维,在一定的喷出速度下进行喷出正拉伸并给予纤维一定的预热拉伸和高倍热水拉伸,可制得强度较高的纤维.纤维经过热拉伸并热定型后,其强度可达到7.5cN/dtex.     

热水浴拉伸对聚丙烯腈初生纤维结构和性能的影响

研究了聚丙烯腈(PAN)初生纤维在热水浴拉伸过程中超分子结构和力学性能的变化。结果表明:PAN初生纤维中的内应力随拉伸温度的升高而减小,随拉伸速率和拉伸倍数的提高而增大;初生纤维在热水浴中的玻璃化转变温度约为80℃,当水浴温度低于和高于80℃时,纤维分别发生冷拉和高弹形变;PAN初生纤维的结晶度和晶区取向度随拉伸温度的升高先增大后减小,随拉伸速率和拉伸倍数的升高而增大。     

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原丝生产中的断头原因分析

简介了PAN原丝的工艺流程及主要控制参数,并结合研发和生产实际,从原料、工艺和操作3个方面分析了影响PAN原丝产生断头的原因。研究表明：选用特性粘度1.85 Pa.s,残单≤0.1%的聚合液,严格控制凝固浴的温度和浓度,同时控制各牵伸工序温度及牵伸倍数与牵伸梯度,可明显降低PAN原丝的断头率。     

Gel spinning of polyacrylonitrile fibers with medium molecular weight

A new gel‐spinning method was employed to prepare polyacrylonitrile (PAN) fibers from a PAN spinning solution with dimethylsulfoxide and water as a mixed solvent. Aging at 25 °C for 120 min brought the spinning solution to the sol–gel transition and a three‐dimensional gel formed before entering the coagulation bath. The as‐spun fibers from the solution at the sol–gel transition and in the gel state possess a circular cross‐section. Compared with dry‐jet wet‐spun fibers, the gel‐spun fibers have a more compact structure, fewer voids and better mechanical properties after a three‐stage drawing. Moreover, the gel‐spun fibers obtained from the extraction bath have a more homogeneous microstructure and better packed supermolecular structure. The physical properties of the extracted gel‐spun fibers are also better than those of coagulated gel‐spun fibers. Copyright © 2010 Society of Chemical Industry     

Preparation of conductive polyaniline fibers by a continuous forming‐drawn processing routine

Polyaniline fibers were prepared with a continuous forming‐drawn processing routine that better met practical production requirements. The continuous forming drawing of the fibers was conducted successfully with the following methods. A reducing agent was added to a polymer solution during the dissolution of a polyaniline emeraldine base in N‐methyl‐2‐pyrrolidinone (NMP). After the entire wet‐spinning process was finished, the fibers were reoxidized and doped to obtain electric conductivity. The as‐spun fibers were predrawn at a low drawing ratio in a warm water bath before a plasticization drawing process on a hot plate. After the fibers were predrawn, some solvent was still kept in the fibers and used as a plasticizer of the fibers so that the plasticization drawing process would be performed successfully. The spinning conditions that affected the mechanical properties and conductivity of the fibers were the content of NMP in the coagulation bath, the coagulation‐bath temperature, the warm‐water‐bath temperature, the predrawing ratio, the hot‐plate temperature, the plasticization drawing ratio, and the reoxidation and protonation treatment time. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 956–960, 2004     

Correlation between fibril structures and mechanical properties of polyacrylonitrile fibers during the dry-jet wet spinning process

The high quality polyacrylonitrile (PAN) fibers, which were used to manufacture the high performance carbon fibers, were prepared by the dry-jet wet spinning process. The fiber samples were treated by using the ultrathin sectioning and solution etching methods. Subsequently, the changes of the fibril structures and mechanical properties were investigated by utilizing scanning electron microscopy, high-resolution transmission electron microscopy and mechanical tester. The fiber titer and diameters, the amount of the pores decreased during the spinning process. The microfibrils were oriented along the fiber axis to form the fiber backbone in PAN fibers. Furthermore, the microfibrils with small size were incorporated into the large fibrils and some fold chains formed the interfibril transverse joint bridges to reinforce the connection of the fibril elements. The fibrils served as self-reinforcing element to efficiently resist the cracks propagation and dissipate much energy to increase the tensile strength and initial modulus. Consequently, the PAN precursor fibers with the homogeneous, compact, well-oriented, and closely interlinked fibrils, presented high tensile strength and initial modulus. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47336.