Physical properties of lyocell fibers spun from different solution‐dope phases

The hydration number (n) of NMMO hydrates has a significant effect on the rheological properties and phase of the cellulose solutions in the hydrates. The physical properties of the lyocell fibers spun from the cellulose solutions in NMMO hydrates with different values of n were investigated relative to the phase of the solution dope. NMMO hydrate with n = 1.1 could not fully dissolve cellulose, resulting in a heterogeneous solution. NMMO hydrate with n = 0.72 produced a mesophase solution that exhibited a good spinnability. When NMMO hydrates with n = 0.72 and 1.0 were used, the lyocell fiber spun from 15 wt % solution dope gave higher tensile strength than that spun from 12 wt % solution dope. NMMO hydrate with n = 1.0 produced a lyocell fiber whose tensile strength was slightly affected by spin–draw ratio but the tensile strength of the lyocell fiber prepared from NMMO hydrate with n = 0.72 was monotonically increased with increasing spin–draw ratio. Further, the latter gave higher birefringence. The lyocell fiber spun from 15 wt % solution in NMMO hydrate with n = 0.72 produced finely fibrillated structures. When treated with sonic wave the lyocell fiber prepared from 15 wt % cellulose (DP_w 940) solution in NMMO hydrate with n = 0.72 yielded the most serious fibrillation on the fiber surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 981–989, 2002     

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     

Identifying breach mechanism during air-gap spinning of lignin–cellulose ionic-liquid solutions

To be able to produce highly oriented and strong fibers from polymer solutions, a high elongational rate during the fiber-forming process is necessary. In the air-gap spinning process, a high elongational rate is realized by employing a high draw ratio, the ratio between take-up and extrusion velocity. Air-gap spinning of lignin–cellulose ionic-liquid solutions renders fibers that are promising to use as carbon fiber precursors. To further improve their mechanical properties, the polymer orientation should be maximized. However, achieving high draw ratios is limited by spinning instabilities that occur at high elongational rates. The aim of this experimental study is to understand the link between solution properties and the critical draw ratio during air-gap spinning. A maximum critical draw ratio with respect to temperature is found. Two mechanisms that limit the critical draw ratio are proposed, cohesive breach and draw resonance, the latter identified from high-speed videos. The two mechanisms clearly correlate with different temperature regions. The results from this work are not only of value for future work within the studied system but also for the design of air-gap spinning processes in general. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47800.     

Electrospinning of aqueous lignin/poly(ethylene oxide) complexes

Microfibers of kraft lignin blended with poly(ethylene oxide) (PEO) were produced by electrospinning of the solution of lignin and high molecular weight poly(ethylene oxide) (PEO) in alkaline water. Interactions between lignin and PEO in alkaline aqueous solutions create association complexes, which increases the viscosity of the solution. The effect of polymer concentration, PEO molecular weight, and storage time of solution before spinning on the morphology of the fibers was studied. It showed that after one day the viscosity dropped and fiber diameter decreased. Results from the solutions in alkaline water and N,N‐dimethylformamide (DMF) with different polymer concentrations were compared. The 7 wt % of (Lignin/PEO: 95/5 wt/wt) in alkaline aqueous solution was successfully spun and the ratio of PEO in lignin/PEO mixture could be further reduced. In comparison, higher concentrations were needed to prepare a spinning solution in DMF and fiber diameters were in a much smaller range. The final target of spinning lignin is to produce carbonized fibers. Fibers spun from aqueous solutions had lower PEO content, which is a big advantage for the carbonization process as it reduces the challenges regarding melting of the fibers or void creation during carbonization. Furthermore, the larger diameter of these fibers inhibits disintegration of the carbonized fibers, which happens due to the mass loss during the process. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41260.     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.     

新型碳纤维用原丝——高强高模Lyocell纤维纺丝工艺研究

采用天然高相对分子质量纤维素脱脂棉为原料 ,制备了高强高模纤维素纤维 ( L yocell纤维 ) ,并用此作为碳纤维原丝 ,成功制得了强度优于粘胶基碳纤维的 L yocell基碳纤维。考察了高相对分子质量纤维素的溶解特点 ,纺丝工艺对 L yocell纤维聚集态及性能的影响 ,比较了 L yocell纤维和粘胶原丝的表面及截面形态。实验表明 :高相对分子质量纤维素溶解的静溶胀时间和温度对其溶解有明显的影响 ;纺丝过程中 ,大的气隙长度对提高纤维的性能有利 ;随着凝固浴中 N -甲基吗啉 N -氧化物( NMMO )的浓度增加 ,纤维的强度和模量增加 ,当其在凝固浴中的质量分数达到 10 %时 ,强度模量最大 ,浓度继续增加 ,纤维的力学性能开始下降 ;拉伸比增加 ,L yocell纤维的强度模量增加 ,当拉伸比大于 3.0时 ,纤维的性能略有下降     

A new softening agent for melt spinning of softwood kraft lignin

Kraft lignin obtained from the pulping of wood is an interesting new precursor material for carbon fiber production because of its high carbon content and ready availability. However, continuous spinning of softwood kraft lignin (SKL) has been impossible because of its insufficient softening characteristics and neat hardwood kraft lignin (HKL) has required extensive pretreatments to enable fiber formation. Softwood kraft lignin permeate (SKLP) and hardwood kraft lignin permeate (HKLP), fractionated by membrane filtration, were continuously melt spun into fibers. To improve the spinnability of SKL and HKL, HKLP was added as a softening agent. SKL‐ and HKL‐based fibers were obtained by adding 3–98 wt % HKLP. A suitable temperature range for spinning was 20–85°C above the T_g of the lignin samples, and this range gave a flawless appearance according to the SEM analysis. Smooth, homogeneous fibers of SKLP, HKLP, and SKL with HKLP were successfully processed into solid carbon fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure and properties of cellulose fibers from ionic liquids

1‐Butyl‐3‐methylimidazolium chloride ([BMIM]Cl) was used as a solvent for cellulose, the rheological behavior of the cellulose/[BMIM]Cl solution was studied, and the fibers were spun with a dry‐jet–wet‐spinning process. In addition, the structure and properties of the prepared cellulose fibers were investigated and compared with those of lyocell fibers. The results showed that the cellulose/[BMIM]Cl solution was a typical shear‐thinning fluid, and the temperature had little influence on the apparent viscosity of the solution when the shear rate was higher than 100 s^?1. In addition, the prepared fibers had a cellulose II crystal structure just like that of lyocell fibers, and the orientation and crystallinity of the fibers increased with the draw ratio increasing, so the mechanical properties of the fibers improved. Fibers with a tenacity of 4.28cN/dtex and a modulus of 56.8 cN/dtex were prepared. Moreover, the fibers had a smooth surface as well as a round and compact structure, and the dyeing and antifibrillation properties of the fibers were similar to those of lyocell fibers; however, the color of these dyed fibers was brighter than that of lyocell fibers. Therefore, these fibers could be a new kind of environmentally friendly cellulose fiber following lyocell fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

On the characterization and spinning of an organic‐purified lignin toward the manufacture of low‐cost carbon fiber

A Kraft hardwood lignin (HWL) and an organic‐purified hardwood lignin (HWL‐OP) were evaluated as potential precursors for the production of low‐cost carbon fibers. It was found that the unpurified HWL exhibited poor spinnability while the HWL‐OP exhibited excellent spinnability characteristics. Fibers of various diameters were obtained from the HWL‐OP. Thermostabilization studies showed that oxidative stabilization can only be used to convert HWL‐OP‐based fibers into carbon fibers if extremely low heating rates are applied. Carbonized lignin‐based fibers had tensile strength of 0.51 GPa and tensile modulus of 28.6 GPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Orientation of multiwalled carbon nanotubes in composites with polycarbonate by melt spinning

A conductive polycarbonate (PC) composite containing 2 wt% multiwalled carbon nanotubes (MWNT) and pure PC were melt spun using a piston type spinning device. Different take-up velocities up to 800 m/min and throughputs leading to draw down ratios up to 250 were used. The composite material of PC with MWNT was prepared by diluting a PC based masterbatch consisting of 15 wt% MWNT by melt mixing in an extruder. The alignment of the nanotubes within melt spun fibers with draw down ratios up to 126 was investigated by TEM and Raman spectroscopy. The nanotubes align in their length axis along the fiber axis increasingly with the draw down ratio, however, the curved shape of the nanotubes still exist in the melt spun fibers. At higher draw down ratios, the MWNT started to align by reducing their curvature. Polarized Raman spectroscopy indicated that the D/D and G/G ratios parallel/perpendicular to the fiber axis increase for both MWNT bands in a similar manner with the draw down ratio. Interestingly, with increasing alignment electrical conductivity of the fibers is lost. Mechanical investigations revealed that at low spinning speeds elongation at break and tensile strength of the composite are lower than those of the pure PC. However, at the highest take-up velocity of 800 m/min the elongation at break is higher and true stress at break of the composite fiber is comparable to the pure PC fiber.     

Study on the melt‐spinnability of poly(L‐lactic acid)

In this work, three kinds of different poly(L ‐lactic acid) (PLLA) materials for melt‐spinning were investigated with respect to the molecular weight (MW) and molecular weight distribution (MWD), racemization, optical purity, thermal properties, and melt‐spinnability. It was found that the high MW was not the only factor to affect the melt spinnability of PLLA, the racemization and the amount of residual monomer would also affect the thermal properties and melt‐spinnability of PLLA. The results showed that it could be melt‐spun and hot‐drawn by using the general melt‐spinning device for PLLA pellet with good stereoregularity and comparatively high MW. For PLLA pellet with high MW and moderate stereoregularity, it must be treated at an appropriate temperature to increase the crystallinity before dry and extrusion, which could make the pellet be spun without agglomeration, whereas the draw ability of such as‐spun fiber was still poor. However, if the stereoregularity of PLLA pellet was poor, it could not be spun even it had very high MW. Only when MW, racemization, and the amount of residual monomer of the PLLA pellets all meet the requirements, PLLA fibers could be prepared by melt‐spinning. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Polypropylene/montmorillonite composites and their application in hybrid fiber preparation by melt‐spinning

Polypropylene (PP)/organomontmorillonite (OMMT) nanocomposites have been successfully prepared by melt intercalation by using the conventional method of twin‐screw extrusion and subsequently submitted for melt‐spinning. The structure and properties of the PP/clay nanocomposites and hybrid fibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and crystallization dynamics, etc. The organoclay layers were found to disperse in the PP resin at the nanometer level. The nanoscaled OMMT layers, dispersed in the PP matrix, actually played the role of heterogeneous nuclei species in the process of PP crystallization and increased the nucleation speed of the composites, hereby leading to the increase of crystallization rate of the as‐spun fiber. Meanwhile, it was found that the crystallinity of PP/OMMT hybrid fibers is much higher than that of pure PP fiber at the same draw ratios, whereas the orientation of PP/OMMT hybrid fibers is much lower than that of pure PP fiber at the same draw ratios. Because of the effective intercalation of OMMT into PP matrix, the nanocomposites have good spinnability, and the moisture absorption of the final PP fiber is improved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 552–558, 2004     

Cellulose fibers from cellulose/1‐ethyl‐3‐methylimidazolium acetate solution by wet spinning with increasing spinning speeds

Cellulose fibers from cellulose/1‐ethyl‐3‐methylimidazolium acetate solution were prepared by wet spinning with increasing extrusion speeds and draw ratios. The effects of spinning speeds on the structures and mechanical properties of these fibers were investigated by using scanning electron microscopy, wide angle X‐ray diffraction, birefringence, thermogravimetric analysis, tensile‐fineness tester, and wet friction. The results showed that the crystallinity, orientation, and mechanical properties of the fibers were improved with increasing draw ratio. The break draw ratios, degrees of crystallinity and orientation, tenacities, and wet friction time of the cellulose fibers decreased with increasing extruding speeds. The wet friction time decreased with increasing draw ratio and decreased faster under higher extrusion speed. Due to the high dope concentration and the increased draw ratio, the maximum tenacity of the regenerated cellulose fibers reached 2.73 cN/dtex. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40225.     

Study on dry spinning and structure of low mole ratio complex of calcium chloride‐polyamide 6

Polyamide 6 (PA 6) filaments with initial modulus around 48 GPa were produced by dry spinning from low mole ratio (MR) complex of calcium chloride and high molecular weight PA 6 (CaCl₂‐PA 6) in formic acid. From the results of XRD, DSC, FTIR, and SEM, the complexation of CaCl₂‐PA 6 in the MR range of 0.15–0.3 was efficient. The spinnability of the complex solution was excellent, which allowed a maximum draw ratio of 14.4 for as‐spun fibers. After decomplexing and annealing, the birefringence of drawn fiber could reach around 0.08. Porous structure was found in fibers spun from formic acid‐chloroform cosolvent but not observed by using pure formic acid. When MR of CaCl₂/PA 6 exceeded 0.3, some irregular particles formed on the fiber surface due to the recrystallization of CaCl₂. However, fibers with smooth surface could be obtained when the MR decreased to 0.15. During the process of decomplexing in ethyl alcohol, an axial shrinkage of drawn fibers in a relaxed state was observed. It turned out that this shrinkage could be avoided by decompexing the fibers under tension. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Carbon fibers derived from wet‐spinning of equi‐component lignin/polyacrylonitrile blends

Equi‐component blends of polyacrylonitrile (PAN) and lignin, i.e., with a lignin content as large as 50 wt %, were successfully used as precursors to produce carbon fibers. Rheological measurements demonstrated that increasing lignin content in spinning solution reduced shear viscosity and normal stress, indicating a decrease of viscoelastic behavior. This was confirmed by Fourier transform infrared results that show no discernable chemical reaction or crosslinking between PAN and lignin in the solution. However, the resulting carbon fibers display a large I_D/I_G ratio (by Raman spectroscopy) indicating a larger disordered as compared to that from pure PAN. The macro‐voids in the lignin/PAN blend fibers typically generated during wet‐spinning were eliminated by adding lignin in the coagulant bath to counter‐balance the out‐diffusion of lignin. Carbon fibers resulting from lignin/PAN blends with 50 wt % lignin content displayed a tensile strength and modulus of 1.2 ± 0.1 and 130 ± 3 GPa, respectively, establishing that the equi‐component wet‐spun L/P‐based carbon fibers possessed tensile strength and modulus higher than 1 and 100 GPa. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45903.     

Wet spun fibers from solutions of cellulose in an ionic liquid with suspended carbon nanoparticles

Wet spun fibers from solutions of dissolving pulp in 1‐ethyl‐3‐methylimidazolium acetate (EmimAc) with up to 50 wt % (based on cellulose) suspended carbon black and graphene nanoplatelets particles were studied. Carbon fillers were dispersed by simple shearing in a Couette type mixer and the resulting spin dope was extruded into a hot water coagulation bath from a single hole spinneret. Microstructure, mechanical properties, and electrical conductivity were assessed as a function of filler loading and discussed in comparison to melt spun fibers with similar fillers. The coagulation process and subsequent drying of wet spun fibers was found to produce a significant microporosity, more so the higher the filler loading. The electrical percolation threshold was quite high in the wet spun fibers and relatively modest values of conductivity were obtained with regard to the high filler loadings. Carbon black was found to be superior to graphene nanoplatelets. This was related to flow‐induced orientation effects. The mechanical properties of the carbon‐filled fibers were found to be similar or lower compared to the pure cellulose fibers because of low interfacial interactions and formation of microporosity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41417.     

溶剂对醋酸纤维素静电纺丝可纺性的影响

将醋酸纤维素(CA)分别溶于二氯甲烷、甲酸、乙酸和三氟乙酸(TFA)四种溶剂中,用静电纺丝法制备CA纤维。测定了纺丝液的黏度、电导率,并对各种CA溶液电纺纤维的形貌进行表征,分析各种影响可纺性及纤维形貌的因素。结果表明:溶剂的沸点及所配溶液的电导率、黏度是影响电纺丝可纺性的重要因素。以TFA作为溶剂时,8%CA纺丝液具有良好的可纺性。     

PHB/PET/HQ-TPA液晶共聚酯纤维的制备及结构性能研究

对所合成的ＰＨＢ／ＰＥＴ／ＨＱ－ＴＰＡ三元液晶共聚酯进行纺丝实验，制备了初生纤维并对其进行了热处理。利用ＤＳＣ，ＷＡＸＤ，密度，Ｓ－Ｓ曲线等方法对初生纤维及热处理后纤维的结构与性能进行了研究。结果表明：该体系的液晶共聚酯具有较好的可纺性，初生纤维在ＤＳＣ升温过程中有冷结晶峰和熔融双峰现象产生，初生纤维经热处理后，可使其微晶尺寸有较大提高，力学性能得到一定程度改善，但未使其取向性能得到进一步改善。     

Functional hybrid fibers of cellulose/microcrystalline chitosan. I. Manufacture of viscose/microcrystalline chitosan fibers

Blends of microcrystalline chitosan (MCCh) with cellulose xhanthate alkaline solutions were prepared to investigate the effects of aqueous MCCh gel concentration and additives on the spinnability of hybrid cellulose/chitosan fibers and their properties. The properties of the spinning solution were mainly dependent on the concentration of MCCh in the aqueous gel‐like dispersion and the amount mixed into the cellulose xhanthate solution. Sodium alginate chemically close to cellulose and chitosan was used as an additive to improve the miscibility of chitosan due to the ionic bonds formed with chitosan 2‐amino groups. Using an optimized ratio of 2 : 1 of MCCh to the sodium alginate, a maximum of 6% of MCCh calculated from alpha‐cellulose content could be introduced into the sodium xhanthate solution containing originally 9% of alpha‐cellulose. The yield of MCCh in the resulting fibers was dependent on the molecular mass, and varied between 73–82%. The strength, elongation, and color of the resulting hybrid fibers were only slightly changed and the WRV remarkably increased compared to standard fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1725–1730, 2000