Investigating the spinnability in the dry‐jet wet spinning of PAN precursor fiber

The spinnability of a spinning solution using DMSO as the solvent was investigated for dry‐jet wet spinning of PAN precursor fiber. Among many variables responsible for spinnability, the coagulating conditions, the air gap length, the nonsolvent content in spinning solution, and the spinning temperature have been viewed as the key factors, and they were investigated in this study. It was found however, unlike in the wet spinning, the spinnability in dry‐jet wet spinning process was barely influenced by the coagulating conditions, likely attributable to the existence of the air gap. However, the spinnability worsened when the air gap was longer than 30 mm. The quality of the spinning solution deteriorated with the increasing water content in it. The spinnability improved when the spinning temperature was maintained between 60 and 72°C and turned down once the temperature was over 72°C. The experimental results indicated that all the factors should be comprehensively considered to ensure good spinnability in dry‐jet wet spinning process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Numerical investigation of spinneret geometric effect on spinning dynamics of dry‐jet wet‐spinning of cellulose/[BMIM]Cl solution

In this study, the effect of spinneret geometry, including the entrance angle α of the entrance channel, the length L_s, and the diameter D₀ of the exit channel, on the spinning dynamics of dry‐jet wet‐spinning of cellulose/1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) solution was simulated by using finite element method. Based on the mathematical model of dry‐jet wet‐spinning established in our previous work (Xia et al., Cellulose 2015, 22, 1963) the radial and axial profiles of velocity, pressure, and shear rate in the spinneret and the profiles of diameter, temperature, and tensile stress in the air‐gap region were obtained. From the simulated profiles, the effect of spinneret geometric parameters on the flow behavior and the pressure drop of polymer solution in the spinneret and the die‐swell ratio near the spinneret was discussed. The entrance angle α of the entrance channel mainly influences the flow behavior of polymer solution in the spinneret and the die‐swell effect near the spinneret. As the decrease of the entrance angle α of the entrance channel, the vortices in the spinneret could be removed and the die‐swell ratio decreases. The increase of the length L_s of the exit channel results in the increase of pressure drop in the spinneret and the decrease of the die‐swell ratio. It is also found that the increase of the diameter D₀ of the exit channel reduces the flow velocity of polymer solution and decreases the pressure drop in the spinneret at a constant mass flow rate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43962.     

喷丝头长径比对PANCF原丝性能的影响

采用不同长径比(L/D)的陶瓷喷丝头进行湿法、干湿法纺丝制备聚丙烯腈基碳纤维(PANCF);研究了L/D对聚丙烯腈/二甲基亚砜(PAN/DMSO)纺丝原液的可纺性及原丝性能的影响。结果表明:随着喷丝头L/D的增大,PAN/DMSO纺丝原液的可纺性提高,PANCF原丝的膨润度逐渐减少,PANCF原丝的结晶度、取向度及强度随之增大,有利于提高纤维的性能。     

锦纶6长丝生产中喷丝板选型的影响因素

研究了喷丝头拉伸倍数、熔体切变速率、喷丝板压力降等因素对锦纶6喷丝板选型的影响,分析了喷丝板参数之间的关系及对纺丝质量的作用,提出喷丝板选型参数的合理取值范围:喷丝头拉伸倍数在210~250倍,微孔长径比在2.5,熔体的切变速率在8 000~10 000 s~(-1),初始压力降在12~15 MPa时,有利于纺丝的顺利进行和纺丝质量的保证。     

Investigation the jet stretch in PAN fiber dry‐jet wet spinning for PAN‐DMSO‐H2O system

The jet stretch of dry‐jet wet spun PAN fiber and its effects on the cross‐section shape of fibers were investigated for a PAN‐DMSO‐H₂O system. Clearly, the spinning parameters, such as dope temperature, bath concentration, bath temperature, and air gap, all influenced the jet stretch. Also, under uniform conditions, the postdrawing ratio as well as that of jet stretch changed. Under given conditions, as the bath temperature was below 30°C or above 45°C, jet stretch had little effect on the cross‐sectional shapes of PAN fiber. Within the temperature of 30–45°C, fiber's cross‐section shapes change obviously from round over an approximate circular shape into to an elliptical or a flat shape. The scope of jet stretch produced PAN fiber with circular cross‐section was bigger than that in wet spinning. These results indicated that appropriate air gap height, under milder formation conditions in dry‐jet wet spinning, could result in higher jet stretch and higher postdrawing ratio. The appropriate jet stretch and postdrawing ratio could result in circular profile of PAN fiber, which were helpful to produce round PAN precursor with finer size and better properties for carbon fiber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Gel‐spun polyacrylonitrile fiber from pregelled spinning solution

Polyacrylonitrile (PAN) fibers have been gel spun from pregelled PAN spinning solution. The pregelled solution had network structure with elevated spinnability, the as‐spun fiber from which had more circular cross‐section and reduced skin‐core difference. Drawing was more effective in inducing the segmental orientation and crystallization in gel‐spun fiber than in dry–wet spun fiber. The mechanical properties of the gel‐spun fiber were better than those of the dry–wet spun fiber after multi‐stage drawing. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

腈纶NaSCN一步法生产中调整喷丝头负拉伸率的研究

采用硫氰酸钠为溶剂,湿纺一步法工艺生产腈纶,探讨了喷丝头负拉伸率对纤维成形的影响。工业化试验表明:当喷丝头负拉伸率为-73％时,纤维可纺性达到最佳状态。     

聚丙烯腈原丝及其干喷湿纺

介绍了用于 PAN基碳纤维的聚丙烯腈原丝的发展历史 ,阐述了聚丙烯腈纺丝工艺中的主要工序和技术关键 ,指出了可以在聚合、纺丝过程中通过控制杂质及使用高相对分子质量的 PAN树脂纺制 PAN纤维等方法来提高原丝的性能。着重介绍了目前纺丝工艺中 PAN共聚体的制备、纺丝流体的流变行为及其凝固过程等重要工序的研究成果     

A study of rheological limitations in rotary jet spinning of polymer nanofibers through modeling and experimentation

The recently popularized method of rotary jet spinning (RJS) or centrifugal spinning is investigated to evaluate the rheological limitations of polymer solutions and melts to optimal spinnability. The influence of Newtonian or non-Newtonian behavior of the polymer on spinnability is discussed. We observe that highly viscous polymers tend to block the die channels within a rotary jet spinneret and therefore suggest the use of relatively low Newtonian viscosities of between 1 and 10 Pa s for optimal fiber production. Computational fluid dynamics simulations are used in conjunction with experimental data to establish important processing parameters, such as typical shear rates in the device and optimal polymer melt or solution viscosities. A theoretical model for RJS is compared to measured fiber diameters. The comparison shows that although fiber diameters can be estimated very roughly in the case of polymer solutions, the prediction of fiber diameter in the case of polymer melts require further modeling work. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48963.     

利用双螺杆挤出机溶解聚丙烯腈

为了提高生产效率,简化操作步骤,并制得质量稳定的高黏均分子量(M_η)聚丙烯腈(PAN)纺丝原液,研究了利用双螺杆挤出机溶解PAN的新方法。二阶螺杆采用T形搭配方式,并在出料口加装过滤装置。溶剂的选择在PAN溶解理论的基础上综合考虑了不同溶剂的溶解能力,找到了适合螺杆溶解要求的混合溶剂。同时将制得的溶液利用干喷湿纺工艺进行纺丝,得到线密度小、高强度的原丝,以验证此体系的可靠性。结果表明此溶解方式可以满足高性能PAN原丝的纺丝要求,同时产出溶液质量稳定且效率更高。     

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     

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.     

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     

Numerical simulation of gas-assisted polymer-melt electrospinning: Parametric study of a multinozzle system for mass production

In this study, we developed a multiphysics model for simulation of a gas-assisted melt-electrospinning (GAME) process, focusing on jet formation and propagation behavior. By numerically calculating the stresses acting on the jet during a single-nozzle GAME process, the shear viscous stress was identified as the main factor with respect to jet stretch; thus, the relationship between shear viscous stress and jet thickness was investigated. The jet stretch ratio increased sharply when shear viscous stress reached the level at which jet sharpening occurred, leading to stable jet formation. We defined this stress as the critical shear viscous stress to determine stable spinnability. By imposing an electric field distribution calculated for a multi-nozzle array (number of nozzles, tip-to-tip distance, and applied voltage) on the boundary condition of the single-nozzle GAME simulation model, multinozzle GAME was simulated; this enabled proposal of a spinnability diagram for stable spinning.     

A study of shaped fiber formation

An experimental study has been carried out to investigate the effects of spinning conditions on the shape of fibers spun through noncircular spinnerette holes, namely, rectangular holes, trilobal holes, and round holes with lugs. For the study, bench-scale apparatuses of wet spinning and melt spinning were used which had been constructed in connection with an earlier study by Han. In the wet-spinning experiment, the spin dope used was an aqueous solution of polyacrylonitrile (PAN) consisting of approximately 10% polymer and 40% sodium thiocyanate (NaSCN), and the spin dope was spun into aqueous solutions of NaSCN. In the melt-spinning experiment, polystyrene was used. The variables investigated were: size and shape of the spinnerette hole, coagulating bath concentration, throughput rate, and jet stretch. It has been found in wet spinning that, for a given shape of spinnerette hole, the fiber shape is most strongly affected by jet stretch and relatively little by the bath concentration and throughput rate. Also determined in the wet-spinning experiment was the maximum jet stretch at which thread breakage occurs. It has been found that the maximum jet stretch decreases as bath concentration is increased.     

Aromatic poly(1,4-phenylene-1,3,4-oxadiazole) fibers by dry jet-wet spinning

Fibers of poly(1,4-phenylene-1,3,4-oxadiazole) have been prepared by dry jet-wet spinning sulfuric acid solutions of the polymer. Polymer was prepared by polymerizing terephthalic acid and hydrazine dihydrochloride in 30% fuming sulfuric acid and directly spinning the resulting solution. Dry jet-wet spinning allows greater flexibility in conditions than does wet spinning in that spinneret temperature and coagulation bath temperature are independent of one another. Therefore, coagulation may be at temperatures well below those needed at the spinneret to maintain a flowing, extrudable solution. Another common advantage of dry jet-wet spinning is application of draw to the extruded fiber before coagulation, but in this system, drawing the fiber before coagulation was shown to be a disadvantage. Fiber properties were maximized by spinning with a spinneret temperature of 58–73°C into a coagulation bath at 3–4°C and with an air gap of 1/4 in. Water as a coagulation medium allowed operation at speeds up to 40 m/min, while with 50% sulfuric acid less than half that speed was reached. Application of draw ratios of 3/1 on the coagulated but still swollen fiber combined with high-temperature treatments at low draw ratios (1.05/l) gave maximum fiber properties–tenacity 6 g/denier, elongation 20–25%, and modulus 200–240 g/denier.     

Simulation of polyimide fibers with trilobal cross section produced by dry‐spinning technology

As one type of high performance fibers, polyimide fibers can be prepared from polyamic acid (PAA) solution by dry‐spinning technology. The transformation from the precursor of polyamic acid to polyimides via thermal cyclization reaction in the dry‐spinning process is a main distinguishing feature, which is very different from other fibers produced by dry‐spinning such as cellulose acetate fiber and polyurethane fiber. In this report, the dry‐spinning formation of polyimide fibers with trilobal cross section from PAA solution in N,N‐dimethylacetamide is simulated via a one‐dimensional model based on a viscoelastic constitutive equation, combined with profile degree equation of cross section and imidization kinetics equation. The glass transition temperature, imidization degree and profile degree of the filament along the spinline are predicted by the model, as well as relative parameters such as solvent mass fraction and temperature. As a simulated result, solidification of polyimide fibers take place about 150 cm from the spinneret which is farther than for cellulose acetate fiber (70 cm). Moreover, the final profile degree of fiber is affected by many spinning parameters, such as spinning temperature, surface tension, spinning solution concentration, major, and minor axis length of the spinneret hole. POLYM. ENG. SCI., 55:2148–2155, 2015. © 2015 Society of Plastics Engineers     

Characteristics of polyacrylonitrile solutions and fibers varied with the dissolution process in ionic liquid

The concentrated polyacrylonitrile (PAN) solutions were prepared with 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) as solvent by static state, stirring, and kneading. The steady and oscillatory shear tests were carried out to investigate the viscoelastic behaviors of the PAN/[BMIM]Cl solutions by rotational rheometer. It was found that the zero shear‐rate viscosity and relaxation time of the solution prepared by kneading were lowest and the non‐Newtonian index was largest among the solution. During kneading, the gelation temperature of the viscous and homogenous solution was at the lowest temperature 22.7°C among the all three solutions. Only the solutions prepared by stirring and kneading could be spun by dry‐jet wet spinning technology. The fiber processed with the solution prepared by kneading could be drawn with a higher draw ratio, showing the larger draw ability. The supramolecular structure and properties of the fibers were studied by synchrotron wide‐angle X‐ray diffraction (WAXD) technologies, dynamic mechanical analysis (DMA), and mechanical tests. All the results showed that the kneading is an efficient method for PAN fiber spinning with [BMIM]Cl as solvent. It lead to the investigation of the methods of preparation of PAN solution in [BMIM]Cl, which affect the homogeneity of the solutions and hence the resulting characteristics of PAN fibers. POLYM. ENG. SCI., 55:558–564, 2015. © 2014 Society of Plastics Engineers     

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。     

Effect of the solvent type on the formation and physical properties of polyacrylonitrile fibers via a solvent‐free coagulation bath

Polyacrylonitrile (PAN) fibers were fabricated via a dry‐jet wet‐spinning technique, and a solvent‐free coagulation bath system was adopted. The effects of different types of dope solvent on the formation and physical properties of the PAN fibers were investigated. Dimethylformamide and dimethyl sulfoxide (DMSO) were selected as the solvents and were added to a spinning solution consisting of 18 wt % PAN. The PAN fibers were examined with field emission scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The field emission scanning electron micrographs revealed that the PAN fibers with the DMSO solvent exhibited a more circular shape and a smoother skin. The PAN fibers with the DMSO solvent had their glass‐transition temperature (T_g) at 121°C. This study indicated that the different types of dope solvent used in the dope preparation did not affect T_g of the PAN fibers because of the solvent‐free coagulation bath system; however, they significantly affected the physical formation of the PAN fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011