Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.     

X-ray studies of regenerated cellulose fibers wet spun from cotton linter pulp in NaOH/thiourea aqueous solutions

Regenerated cellulose fibers were fabricated by dissolution of cotton linter pulp in NaOH (9.5 wt%) and thiourea (4.5 wt%) aqueous solution followed by wet-spinning and multi-roller drawing. The multi-roller drawing process involved three stages: coagulation (I), coagulation (II) and post-treatment (III). The crystalline structure and morphology of regenerated cellulose fiber was investigated by synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. Results indicated that only the cellulose II crystal structure was found in regenerated cellulose fibers, proving that the cellulose crystals were completely transformed from cellulose I to II structure during spinning from NaOH/thiourea aqueous solution. The crystallinity, orientation and crystal size at each stage were determined from the WAXD analysis. Drawing of cellulose fibers in the coagulation (II) bath (H₂SO₄/H₂O) was found to generate higher orientation and crystallinity than drawing in the post-treatment (III). Although the post-treatment process also increased crystal orientation, it led to a decrease in crystallinity with notable reduction in the anisotropic fraction. Compared with commercial rayon fibers fabricated by the viscose process, the regenerated cellulose fibers exhibited higher crystallinity but lower crystal orientation. SAXS results revealed a clear scattering maximum along the meridian direction in all regenerated cellulose fibers, indicating the formation of lamellar structure during spinning.     

Cellulose-based fibers from liquid crystalline solutions. III. Processing and morphology of cellulose and cellulose hexanoate esters

Cellulose and a cellulose hexanoate ester (DS 0.69) exhibited liquid crystalline behavior in dimethylacetamide/lithium chloride and dimethylacetamide, respectively. The experimentally observed critical volume fraction (V^c_p) of cellulose was lower than that predicted by Flory's theory, whereas the experimental and theoretical values of V^c_p were within 70% of prediction for cellulose hexanoate. The V^c_p value obtained for cellulose hexanoate was lower than that previously reported for cellulose acetate butyrate with a maximum degree of butyration (CAB-3). This indicates that bulky substituents may lower V^c_p values. Fibers were spun from isotropic and anisotropic solutions of cellulose and cellulose hexanoate by a dry jet/wet spinning method. There was an increase in mechanical properties through the isotropic to anisotropic transition with moduli reaching 152 g/d (20.8 GPa) for cellulose fibers. The formation of cellulose fibers with high modulus at large extrusion rates and large takeup speeds (draw ratio) is explained with molecular organization prior to coagulation. This unexpected enhancement is attributed to the air gap that exists in the dry jet/wet spinning process. Similar improvements were not observed for cellulose hexanoate fibers. This is explained with incomplete development of liquid crystalline structure at the solution concentrations from which the fibers were spun. © 1993 John Wiley & Sons, Inc.     

Novel regenerated cellulose fibers from rice straw

Regenerated cellulose fibers from rice straws with a diameter of 10 to 25 μm and initial modulus of 11 to 13 GPa were prepared by wet spinning in rice straw/N‐methylmorpholine‐N‐oxide (MMNO) solution. X‐ray diffraction analysis indicates that the rice straw regenerated fibers are classified as cellulose (II). This observation indicates a potential utility of rice straw as an alternative to wood pulp as a cellulose‐based fiber material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1705–1708, 2001     

离子液体法再生纤维素纤维制造技术及发展趋势

首先概述了再生纤维素纤维制造技术的发展历史,总结了以天然纤维素为原料的黏胶纤维、Lyocell纤维和离子液体纤维（Ioncell）及其技术发展现状。重点介绍了这三种再生纤维素纤维的性能、应用领域及市场前景,并比较了其生产工艺,包括纺丝原液的制备、纺丝工艺、溶剂回收等。与黏胶纤维相比,Lyocell 纤维和Ioncell纤维在溶解纤维素及干喷湿纺纺丝方面具有独特的优势。进一步对该类技术的重点和难点,如纺丝原液的连续制备和溶剂的高效回收进行了分析。与Lyocell纤维使用的NMMO溶剂相比,Ioncell纤维使用的离子液体具有离子液体可设计等优点,可根据纤维素原料的不同来源,设计合成对纤维素具有更好的溶解能力而无降解特征且环境友好的离子液体溶剂,同时对温度、金属离子具有很好的稳定性,为发展新一代纤维素绿色制造技术提供了新途径。另外,对Ioncell纤维存在的问题也进行了详细的分析,提出了未来拟开展的重点研究方向和拟解决的关键难题。     

Mesoporous Carbon Fibers Prepared from Regenerated Rice Straw Fibers

Regenerated cellulose fibers from rice straws with a diameter of 10 to 25 μm and initial modulus of 11 to 13 GPa were prepared by wet spinning in rice straw/N‐methylmorpholine‐N‐oxide (MMO) solution. X‐ray diffraction analysis indicates that the rice straw regenerated fibers are classified as cellulose (II). From the regenerated cellulose fiber based on rice straw, mesoporous carbon fiber was prepared by carbonization. This observation indicates that a potential utility of rice straw as a new mesoporous materials.     

Melt spinning of thermotropic cellulose derivatives

The melt spinning of two thermotropic cellulose derivatives—trimethyl silyl cellulose and phenyl acetoxy cellulose—is described in this article. Removal of the substituents was facile, rapid, and essentially complete. Both the melt‐spun and regenerated fibers had banded textures typical of fibers spun from a liquid crystalline phase. The regenerated cellulose fibers had high strengths and moduli compared to viscose rayon and Lyocel cellulose fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 418–423, 2000     

Preparation of high-strength/high-modulus regenerated cellulose fibers from lyotropic mesophases

Cellulose triacetate (CTA) fibers were spun from a 35% (w/v) solution of CTA (molecular weight, 95,000) in trifluoroacetic acid (TFA)/CH₂CL₂ (60/40, v/v) using laboratory-scale spinning equipment, an air gap, and cold MeOH as the coagulant. The resulting fibers, of large diameter (ca. 80 μm) were saponified with a variety of reagents. The regenerated cellulose fibers had tenacities and moduli as high as 1.6 and 50 GPa, respectively. The fiber properties did not show a dependence on which cellulose polymorph was present. It is suggestes that for highly oriented fibers, the cellulose molecular weight is the primary parameter that determines the strength and modulus. This emphasizes the advantages of using a lyotropic cellulosic mesophase which permits relatively low solution viscosities at high concentrations and high polymer molecular weights. © 1995 John Wiley & Sons, Inc.     

Comparison of cellulose and chitin nanocrystals for reinforcing regenerated cellulose fibers

In this study, regenerated cellulose fibers reinforced by cellulose nanocrystals (CENC) and chitin nanocrystals (CHNC) were prepared by blending the nanocrystals suspensions with the cellulose solution in NaOH/urea/water solvent at room temperature. The effect of nanocrystals' addition on the properties of spinning dopes and regenerated fibers were investigated and compared. Results showed that the obtained CENC and CHNC had different dimensions, and both of them increased the viscosity and decreased the transparency of the spinning dopes. However, the dissolution state of cellulose was not changed. CHNC had a greater influence on the properties of spinning dopes, while CENC had more obvious effect on the performance of regenerated fibers. The CENC reinforced fibers showed a higher crystallinity index as compared to the CHNC reinforced fibers. The tensile strength of the regenerated fibers was evidently improved when 3 wt % CENC or 2 wt % CHNC were added, while the elongation at break of the fibers was slightly decreased with the increase of nanocrystals content. The morphology and thermal stability of the regenerated fibers was not affected by the addition of nanocrystals. This study suggested that the dimension, group and content of nanocrystals were important factors for the reinforcement of regenerated cellulose fibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44880.     

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.     

Properties and structure of MWNTs/cellulose composite fibers prepared by Lyocell process

Lyocell fiber is a new kind of regenerated cellulose fiber and expected to replace the Rayon fiber to be not only used in the textile field but also used in the fields of industry and aerospace after being modified. In this work, the multi‐walled carbon nanotubes (MWNTs)/Lyocell composite fibers were prepared under different draw ratios by dry‐wet spinning and their electrical properties, mechanical properties, and structure were investigated. It was found that an appropriate amount of MWNTs could be dispersed homogeneously in the Lyocell matrix and could improve the mechanical and thermal properties of composite fiber. The results of wide angle X‐ray diffraction (WAXD) showed that the MWNTs in the composite fiber almost aligned along the axis of the fibers and the orientation of MWNTs increased with the increasing draw ratio. Furthermore, it was found that more MWNTs content and lower draw ratio could improve the electrical conductance of the composite fiber. The composite fiber containing 5 wt % MWNTs has a volume conductivity of 8.8 × 10^?4 S/cm, which is five orders higher than that of pure Lyocell fiber. These results indicate that the MWNTs/Lyocell composite fiber has potential applications in the areas of precursor of carbon fiber and conductive fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Process and fiber spinning studies for the cellulose/paraformaldehyde/dimethyl sulfoxide system

A cellulose pulp of about 550 D.P. was readily dissolved in a combination of (CH₂O)x/DMSO to afford an initial 6/6/88 cellulose/(CH₂O)x/DMSO composition solution. The concentration of formaldehyde was found to be a function of solution heating time and temperature. The solutions were microscopically free of gels and undissolved cellulose fibers. Cellulosic articles such as fibers and films are easily regenerated from these cellulose solutions in the presence of coagulants such as methanol or water. Fibers with high wet modulus, intermediate tenacity, and low elongations were produced from these regenerations systems. Fibers have been spun with conditioned and wet tenacities as high as 2.9 and 2.1 g/d, respectively, with wet modulus (at 5% elongation) as high as 1.3 g/d and solubility in 6.5% NaOH in the low range of 3.0%–15%. In many respects, these fibers are comparable to those produced in the viscose process. However, the low elongations of these fibers probably would not permit normal textile processing. The cellulose/(CH₂O)x/DMSO solutions were modified with compounds containing reactive N? H functional groups which are known to react with excess formaldehyde to yield the corresponding N-methylol derivatives. However, the resulting fiber physical properties were not significantly improved compared to those obtained from unmodified cellulose solutions. Addition of acrylic acid derivatives such as methyl acrylate, butyl methacrylate, or acrylonitrile to the cellulose solutions did not result in the formation of the expected 1,4-type adducts.     

Effect of coagulation conditions on fine structure of regenerated cellulosic films made from cellulose/N-methylmorpholine-N-oxide/H2O systems

The important properties of cellulosic fibers in the conditioned state are mainly influenced by fine structure. In particular, the development of new methods of spinning regenerated cellulosic fibers made from a cellulose/N-methylmorpholine-N-oxide (NMMO)/H₂O system require a better understanding of their fine structures in order to explain their special physical properties. The regenerated cellulosic films were made from cellulose/NMMO/H₂O according to the degree of polymerization and solution concentration (wt %) of cellulose and the concentration (wt %) of NMMO in the coagulation bath. The quantification of crystal content was carried out by the resolution of the wide angle X-ray diffraction intensity distribution on the assumption that all diffracted intensities take the form of a symmetrical Gaussian distribution centering at its Bragg angle. The X-ray diffraction patterns resolved into individual integral intensities showed that the polymorphic structure mixed with part cellulose III and II was obtained for only coagulated cellulose films. The degree of crystallinity and apparent crystalline size of regenerated cellulosic films depended on the degree of polymerization, the solution concentration of cellulose, and the concentration of NMMO. The diameter of the microfibril decreased with an increase in the concentration of NMMO. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2681–2690, 1999     

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.     

The fiber-matrix interface in Ioncell cellulose fiber composites and its implications for the mechanical performance

Fiber-reinforced composites based on natural fibers are promising alternatives for materials made of metal or synthetic polymers. However, the inherent inhomogeneity of natural fibers limits the quality of the respective composites. Man-made cellulose fibers (MMCFs) prepared from cellulose solutions via wet or dry-jet wet spinning processes can overcome these limitations. Herein, MMCFs are used to prepare single fiber epoxy composites and UD composites with 20, 30, 40, and 60 wt% fiber loads. The mechanical properties increase gradually with fiber loading. Young's modulus is improved three times while tensile strength doubles at a loading of 60 wt%. Raman spectroscopy is employed to follow conformational changes of the cellulose chains within the fibers upon mechanical deformation of the composites. The shift of the characteristic Raman band under strain indicates the deformation mechanisms in the fiber. Provided stress transfer occurs through the interface, it is a direct measure of the fiber-matrix interaction, which is investigated herein. The shift rate of the 1095 cm⁻¹ band decreases in single fiber composites compared to the neat fibers and continues to decrease as the fiber loading increased.     

Wet spinning of cellulose from ionic liquid solutions–viscometry and mechanical performance

A series of regenerated cellulose fibers was produced from dopes prepared by mixing and dissolving cellulose of two different degrees of polymerization in different ratios in the ionic liquid 1‐ethyl‐3‐methyl‐imidazolium acetate. Viscoelastic properties of the spin dopes were characterized by controlled stress rheometry. The cellulose solutions were solidified in pure water by the traditional wet spinning technique. The resulting fibers were characterized by means of wet and dry tensile testing and scanning electron microscopy. The characterization revealed a compact and homogeneous fiber. A nonlinear relationship between degree of polymerization and fiber properties was observed with a moderate difference in mechanical properties in a broad interval of fibers while fibers composed of polymers with the highest degree of polymerization stood out as stronger and stiffer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influences of diffusion coefficient of 1-allyl-3-methylimidazolium chloride on structure and properties of regenerated cellulose fiber obtained via dry-jet-wet spinning

The diffusion dynamics of the cellulose/1-allyl-3-methylimidazolium chloride ([Amim]Cl) solution during coagulation of regenerated cellulose fiber in a nonsolvent bath was investigated in detail. According to Fick's second law of diffusion, the experimental data were fitted to obtain the diffusion coefficients of [Amim]Cl (D). The cellulose concentration, bath type, and temperature were varied to analyze their influence on the diffusion coefficient of [Amim]Cl. Furthermore, the dependence of the structure and properties of the regenerated fiber obtained via dry-jet-wet spinning on the diffusion coefficients were analyzed. Many defects were formed in the surface and cross sections of the regenerated fibers prepared with high diffusion coefficients. The crystallization and mechanical properties deteriorated with the increase in the diffusion rate of [Amim]Cl. Therefore, the diffusion coefficients of [Amim]Cl should be kept relatively low to enable the preparation of uniform-structured regenerated cellulose fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47609.     

Luminescent cellulose fibers modified with cerium fluoride doped with terbium particles

This article describes UV‐active cellulose fibers obtained by dry‐wet spinning method. The fibers have been formed from an 8% by weight cellulose solution in N‐methylomorpholine‐N‐oxide (NMMO) modified by Ce_0.85Tb_0.15F₃ nanocrystals. The modifier was synthesized by wet chemical method, coprecipitation approach. The host was chosen as the most promising one for the green emitting Tb³⁺ ions. Photoluminescent nanoparticles were introduced into the polymer matrix during the process of dissolving cellulose in NMMO. The modifier occurred in the form of white paste, consisting of luminescent nanoparticles dispersed in glycerine. The dependencies between the concentration of nanocrystals, emission intensity, and excitation energy of the final cellulosic luminescent products were examined by photoluminescence spectroscopy. The size and structure of Ce_0.85Tb_0.15F₃ nanocrystals were studied by X‐ray powder diffraction analysis. The dispersion of the nanoparticles in the polymer matrix was evaluated using scanning electron microscopy and transmission electron microscopy. The real content of luminescent nanocrystals in the fibers was estimated as well. The influence of different concentrations of modifier particles (in the range from 0.5 to 5% by weight) on the mechanical properties of the fibers was determined. POLYM. COMPOS., 153–160, 2016. © 2014 Society of Plastics Engineers     

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