Appearance of a boundary layer during the formation of viscose fibres

Conclusion 1. In the formation of viscose fibres, owing to the formation of a boundary layer, all the bath liquid in the space between the elementary fibres is immobilised as a boundary layer after a very short time.2. All this liquid receives an acceleration from zero velocity to a velocity equal to 90–92% of that of the thread. This acceleration is realised at a distance of 1.5–3 mm from the spinneret, and may cause considerable stresses in the elementary fibre being formed.All-Union Scientific-Research Institute for Man-Made Fibre (VNIIV). Translated from Khimicheskie Volokna, No. 6, pp. 33–35, November–December, 1969.     

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.     

细旦腈纶的生产

研究细旦腈纶的纺丝工艺条件。并在纺丝线上进行试生产。讨论了纺丝原液温度、凝固浴条件、喷丝板负拉伸率、总收缩率、总拉伸倍数、纺丝速度对细旦腈纶质量和生产稳定性的影响。工业化试验表明:纺制0.89 dtex细旦腈纶的主要工艺条件为,纺丝原液温度74~76℃,喷丝板负拉伸率70％,总收缩率23%~25％,总拉伸倍数15,纺丝速度155m/min以及适当的凝固浴条件。     

A study of fiber extrusion in wet spinning. II. Effects of spinning conditions on fiber formation

A study is carried out to investigate the effects of spinning conditions on fiber formation in the wet-spinning process. The spinning conditions studied are free velocity (and hence free diameter), throughput rate, maximum take-up velocity, jet stretch (the ratio of take-up velocity to free velocity), and filament tension. The coagulating bath temperature and concentration are varied, and three spinnerette diameters are used. The spinning dope is an aqueous solution of polyacrylonitrile in sodium thiocyanate. The present study shows that the coagulating bath concentration influences the spinning tension and maximum take-up velocity. Two thread breakage mechanisms are postulated which take into account the rate of coagulation, spinning tension, and thread velocity. An attempt is made to predict the concentration profile of solvent in the moving filament by simultaneously solving the mass and force balance equations, in which the increase in elongational viscosity along the spinning way is assumed to be mainly due to the hardening process.     

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.     

三叶形细旦涤纶纺丝过程的模拟与开发

通过当量直径法对单丝线密度为1 dtex的三叶形细旦涤纶喷丝板的尺寸进行设计、计算,对纺丝成形过程进行了模拟,讨论了喷丝板孔型的尺寸、冷却条件等工艺参数对纤维异形度的影响,并进行优化设计。结果表明:选择喷丝板微孔尺寸0.08 mm×0.25 mm,纺丝温度290℃,卷绕速度1 000 m/m in,吹风速度0.4 m/s,吹风长度1.2 m,在距离喷丝板板面50 mm处增加保温长度450 mm,保温温度80℃,可得到异形度为60.47%的三叶形细旦涤纶。     

Electrospin of polysulfone in N,N’-dimethyl acetamide solutions

Nanofibers of polysulfone (PSU) were prepared by electro-spinning from 10∼20 wt.% PSU solutions in N,N’-dimethyl acetamide (DMAc) mixed with 0.0∼0.1 wt.% LiCl. With increasing PSU concentration, the morphology of fibers electrospun were bead, mixture of bead-fiber and fiber, and smooth fibers when PSU concentration was 10, 12–15, and 18–20 wt.%, respectively. The bead sizes decreased and fiber diameters increased as PSU concentration was increased. The fiber diameter decreased with increases of the LiCl concentration and the distance from spinneret to collection plate. The fiber diameter also decreased with decreasing solution feeding rate. The fiber diameter distribution electrospun from 20 wt.% PSU solutions was much broader than those electrospun from 18 wt.% PSU solution. For 18 wt.% PSU solution, the average fiber diameter (AFD) decreased when the applied voltage V was increased from 7 to 12 kV. However, for 20 wt.% PSU solutions, the AFD increased when V was increased from 7 to 12 kV. The different morphology of fibers electrospun from 18 and 20 wt.% PSU solutions was attributed to the much higher viscosity of 20 wt.% PSU solution than 18 wt.% PSU solution.     

Influence of process parameters on the structure formation of man‐made cellulosic fibers from ionic liquid solution

The influence of dry‐jet wet spinning parameters on the production of man‐made cellulosic fibers from 13 wt % cellulose/1,5‐diazabicyclo[4.3.0]non‐5‐ene acetate solutions was investigated. The spinneret nozzle diameter, extrusion velocity, draw ratio, and coagulation bath temperature were the studied parameters. The production of highly oriented fibers was favored by selecting higher extrusion velocity and lower spinneret diameter. A spinneret size of 100 µm and a draw ratio of 6 were sufficient to highly orient the cellulose macromolecules and achieve tenacities above 40 cN/tex (600 MPa). Total orientation assessed via birefringence measurement, tenacity, and Young's modulus values reached a plateau at a draw of 6 and no further development in properties was observed. A temperature of the aqueous coagulation bath of 15 °C slightly promoted greater orientation of the fibers by hampering structural changes of the cellulose macromolecules in the nascent solid fibers. Furthermore, the determination of the elongational viscosity of the liquid thread via the measurement of radial force tensor was tested and showed promising results. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43718.     

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。     

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.     

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.     

Flow of spinning solution through spinneret openings and deformation resonance

In flow of an anisotropic solution of poly-(p-phenylene terephthalamide) through the channels of spinneret openings in a stream at a distance of 0.7R from the axis of the channel, two layers are formed, and the outer layer is deformed 2.7 times more than the inner layer. Subsequent longitudinal deformation of the jet flowing out primarily causes a break in the outer layer, accompanied by a periodic change in the diameter of the jet, known as “deformation resonance”. Increasing the air gap causes expansion of the jet diameter, accompanied by a further decrease in the flow rate in the outer layer and a decrease in the fibre speed at which deformation resonance appears. The actual critical deformation, calculated as the ratio of the fibre take-off speed to the actual speed in the outer layer, remains constant, equal to 66±6, which is approximately equal to the limiting deformation of the jet of a solution of PPTA in the absence of resonance. All-Russian Scientific-Research Institute of Polymer Fibres, Mytishchi. Translated fromKhimicheskie Volokna. No. 3, pp. 19–22, May–June, 1999.     

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     

Morphology and performance of polysulfone hollow fiber membrane

Polysulfone hollow fiber membranes were prepared via the dry-wet spinning process from dope solutions comprised of polysulfone, n-methyl-2-pyrrolidone, polyvinyl-2-pyrrolidone, and dodecylbenzene sulfonic acid, sodium salt. Morphology and performance of the membranes were affected by the compositions of coagulant and dope solution. Pore size and the water flux of the membrane increased by the addition of dodecylbenzene sulfonic acid, sodium salt to water in the coagulation bath, due to the changes of physicochemical properties of the outer coagulant. Addition of dodecylbenzene sulfonic acid, sodium salt to the dope solution also increased the pore size. The absence of polyvinyl-2-pyrrolidone, the pore forming agent, in the dope solution resulted in a remarkable decrease of pore size of the membrane. The distance between the spinneret and coagulation bath affected the membrane structure and performance. The membranes prepared in this study were suitable for hemofiltration in terms of molecular weight cut-off characteristics. © 1993 John Wiley & Sons, Inc.     

Fiber Bridging during Melt Electrowriting of Poly(ε-Caprolactone) and the Influence of Fiber Diameter and Wall Height

Melt electrowriting (MEW) is a direct-writing technology for small diameter fibers; however, due to electrostatic attraction, the technique is restricted in how close these microfibers can be positioned on the collector. Here, the minimum interfiber distance between parallel poly(ε-caprolactone) MEW microfibers is determined for different fiber diameters and number of layers on noncoated and star-shaped poly(ethylene oxide-stat-propylene oxide) (sP(EO-stat-PO))-coated glass coverslips. The effect of the fiber diameter, the number of fiber layers, and shape of turning loops affect precision and the minimum interfiber distance. Single fibers with diameter of 5, 10, and 15 µm have a minimum interfiber distance without fiber bridging of 33 ± 2.7, 54 ± 2.2, and 62 ± 2.7 µm, respectively. Increasing the number of layers to ten increases this minimum interfiber distance approximately twofold to 60 ± 3.5, 97 ± 4.5, and 102 ± 2.7 µm for the increasing fiber diameters. The sP(EO-stat-PO) slightly increases the minimum interfiber distance for the 15 µm diameter group only, with spacing for the 5 and 10 µm fibers unaffected by the coating. Identifying and determining the fabrication limits for MEW is highly instructional for users working and designing scaffolds with this technology.     

Additive manufacturing of SiO2–Al2O3 refractory products via Direct Ink Writing

The Direct Ink Writing (DIW) method is an approach for fabricating refractory products with complex shapes in an efficient and cost-effective manner. This study investigated the influence of printing parameters on the performance of Al₂O₃ refractory products prepared via DIW. It was found that the layer height is an effective parameter for tuning the inter-space size and the adhesion between layers, under constant extrusion rate and distance between the deposited filaments. The inter-space size could be eliminated by decreasing the layer height to 1.0 mm (i.e., 50% of the nozzle diameter); the flexural strength was enhanced from 45 MPa to 61 MPa when the layer height decreased from 1.8 mm (i.e., 90% of the nozzle diameter) to 0.8 mm (i.e., 40% of the nozzle diameter). Changing the layer height led to a deviation in printing, this deviation could be eliminated by optimizing the travel speed of the nozzle. At a layer height of 0.8 mm, the size deviation could be reduced from 10.5% to 0.59% when the nozzle travel speed changed from 35 mm/s to 70 mm/s. Consequently, there was a considerable improvement in the printing efficiency. These results indicate that, owing to their dense microstructures, samples prepared at a layer height of 0.8 mm exhibit superior slag resistance and a high flexural strength of 61 MPa after sintering at 1600 °C for 3 h.     

On-line studies of structure development during melt spinning of poly(butylene terephthalate)

An on-line study of structure development during poly(butylene terephthalate) melt spinning was carried out. Two polymers with different molecular weights (intrinsic viscosities of 0.75 and 1.0 dL/g) were used. The range of take-up velocities studied was 1500 to 4500 m/min. On-line measurements included diameter, temperature, birefringence, and tension. The phenomenon of diameter thinning (necking) was observed for both polymers at take-up velocities of 3500 and 4500 m/min with a mass throughput of 4 g/min. At a constant mass throughput, the distance from the spinneret at which the necking occurred varied with take-up velocity and molecular weight of the polymer. Increasing the take-up velocity at constant mass throughput caused an increase in cooling rate and a slight increase in the rate at which the temperature decreased with distance from teh spinneret. A small but detectable change in the rate of temperature decrease was observed at a position near or just beyond the formation of the neck. It is suggested that this effect is due to the increased heat transfer caused by the rapid increase in filament velocity and increased surface to volume ration in the neck. Increased take-up velocity also caused necking to occur at higher temperature, as did an increase of polymer molecular weight. Birefringence increased with distance from the spinneret and indicated substantial molecular orientation was developed in the filament prior to the necking zone. A sharp increase of birefringence in the necking zone was observed for take-up velocities of 3500 and 4500 m/min. A discussion of the mechanism of neck formation is presented, and it was concluded that necking is intimately associated with stress-induced crystallization in PBT. An increase of spinline stress resulting from either an increase of take-up velocity or an increase of molecular weight can cause stress-induced crystallization and, hence, necking to occur nearer the spinneret and at higher temperature. For a given polymer this leads to filaments with higher levels of crystallinity, crystalline orientation, and crystalline perfection (greater crystal size). These changes in morphology result in changes in the filament mechanical properties. The effect of molecular weight change on the structure and properties is complicated by the fact that the development of crystallinity seems to be affected by the molecular weight independent of the spinline stress.     

喷丝孔孔径对涤纶单丝直径与双折射的影响

利用具有不同孔径的同一喷丝板生产不同线密度和取向度的涤纶POY。研究了同一喷丝板上不同喷丝孔直径对涤纶POY单丝直径与双折射率的影响。随着喷丝孔孔径的增大,涤纶POY单丝直径增大,单丝的取向度降低,双折射率减小。     

Robocasting of alumina hollow filament lattice structures

Robotic controlled deposition (robocasting) of an aqueous colloidal α-Al₂O₃ gel for manufacturing of cellular ceramics with periodical lattice structure was investigated. The colloidal gel was loaded with 50 vol% α-Al₂O₃ and exhibits shear-thinning behavior, a shear modulus of 288 kPa and a yield-stress of ～700 Pa. Tubular filaments of circular and rectangular cross section having an outer diameter of 1.5 mm and a capillary diameter of 0.75 mm were deposited in an oil bath to fabricate lattice truss structures with free spanning filaments. After freeze drying the robocast grids were sintered in air at 1550 °C. X-ray μ-CT revealed continuity of the tubular filaments for long distances (～650 mm). Critical conditions to avoid capillary collapse were discussed by considering bulging stress and pressure distribution within the hollow filament. At short filament length oil infiltration into the capillary driven by capillary suction supports the tubular filament whereas oil flow driven by movement of the tool nozzle causes pressure difference to increase linearly with increasing filament length.     

High-flux microfiltration filters based on electrospun polyvinylalcohol nanofibrous membranes

A novel class of high-flux microfiltration filters consisting of an electrospun nanofibrous membrane and a conventional non-woven microfibrous support is being presented. The nanofibrous non-woven layer was fabricated by electrospinning of polyvinylalcohol (PVA) directly onto the microfibrous support and then followed by chemical cross-linking with glutaraldehyde (GA) in acetone. By altering the processing parameters, such as the applied voltage and the distance between the spinneret and the collector, as well as the concentration of PVA solution, electrospun PVA membranes with an average fiber diameter of 100 ± 19 nm were obtained. Characterizations revealed that the mean pore size of the electrospun PVA membranes ranged from 0.30 μm to 0.21 μm with the electrospun PVA membrane thickness varying from 10 m to 100 μm. Due to the high porosity, microfiltration filters based on these electrospun membranes showed 3–7 times higher pure water flux than the Millipore GSWP 0.22 μm membrane. The nanofibrous PVA membranes with an average thickness of 20 μm could successfully reject more than 98% of the polycarboxylate microsphere particles with a diameter of 0.209 ± 0.011 μm, and still maintain 1.5–6 times higher permeate flux than that of the Millipore GSWP 0.22 μm membrane.