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     

Morphological and grafting modification of natural cellulose fibers

Crystal structure and mechanical properties of cellulose fibers were studied to investigate the effect of chemical treatment on the fiber. Pretreatment by acetone extraction, mercerization with 3–20% wt/v sodium hydroxide (NaOH), and acrylonitrile (AN) grafting initiated by azo‐bis‐isobutylonitrile were performed. From Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction quantitative measurements, the pretreated fibers showed an induced slight decrease of crystallinity index. The structural transformation of the fibers from cellulose I to cellulose II was observed at high NaOH concentration of 10–20% wt/v. The amount of grafting, 1.56, 2.94, 6.04, 8.34, or 10.46%, was dependent upon the initiator concentration and the volume of monomer in the reactor. The AN grafted fibers had no transformation of crystalline structure as observed after mercerization. Only a variation of X‐ray crystallinity index with grafting amount was observed. Moisture regain of pretreated and modified fibers depended on the structure of the fiber and the amount of grafting. The mechanical properties performed by a single fiber test method were strongly influenced by the cellulose structure, lateral index of crystallinity, and fraction of grafting. Scanning electron microscopy was used for analysis of surface morphologies of treated fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2456–2465, 2004     

Fabrication and properties of elastic fibers from electrospinning natural rubber

Electrospinning natural rubber (NR) to get elastic nano-/microfibers has attracted much attention. Suitable solvent such as tetrahydrofuran (THF) was selected by considering solubility, toxicity, and electrospinning results. Dynamic light scattering testing was used to measure the hydrodynamic diameter (D_h) of the solutions with different solvents and the critical concentrations (C*) of NR/THF solution. For NR solutions with the same concentration from different solvents, the larger D_h the solution, the larger the electrospun fiber diameter. Stable electrospinning concentration window ranging from 25 to 50 g/L, which corresponds to 38 > [ŋ]C > 19, was identified. Mechanical properties of both electrospun NR fiber mats and single fibers were estimated from tensile testing. Fibrous mats with excellent elasticity at about 439 to 505% elongation were demonstrated; however, the elongation rate of single fibers was 44%. Electrospun fiber mats with high elasticity of NR materials can be potentially used in soft tissue engineering and strain sensor areas. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48153.     

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     

Preparation and characterization of cellulose nitrate-acetate mixed ester fibers

Cellulose nitrate-acetate mixed esters (CNA) were synthesized by nitration of cellulose diacetate, using HNO₃/H₂SO₄ as nitration agent. The CNA structures were confirmed and analyzed by IR and ¹H NMR. A decrease in molecular weight and an increase in nitrate group content were observed with increasing H₂SO₄ ratio and reaction time. The highest degree of nitrate substitution, 9.2%, for CNA was achieved with the reaction time of 6h in concentrated HNO₃. Increasing HNO₃ ratio in nitration media resulted in more thermally stable CNA. CNA fibers were prepared by altering the polymer concentration from 15 to 30% in an 85:15 (w/w) acetone:water solvent. The electrospun CNA fibers were characterized by SEM to investigate the influence of different NO₂% on fiber formation, diameters and architectures.     

静电纺丝抗菌聚氨酯纳米纤维的结构与性能

在聚氨酯/四氢呋喃-N,-二甲基甲酰胺(PU/THF-DMF)溶液中分别添加质量分数为5%的TiO_2-Ag,HM-98,三氯均二苯胺(TCC),4-氯-3,5-二甲基苯酚(PCMX),2,4,4'-三氯-2'-羟基二苯酚(DP 300),ε-聚赖氨酸(ε-PLYS)抗菌剂通过静电纺丝技术制备了PU抗菌纳米纤维,并对其性能和结构进行了研究。结果表明:含ε-PLYS,HM-98,TiO_2-Ag,DP300抗菌剂的抗菌PU纳米纤维对金黄色葡萄球菌和大肠杆菌的抗菌效果较为优良,抗菌率均达到了99.9%以上,TCC、PCMX抗菌剂的抗菌效果较差;添加HM-98抗菌剂降低了纺丝溶液的可纺性,但纤维直径有所下降;抗菌剂在PU中的分散性好。     

再生纤维素纤维的研究进展

概述了再生纤维素纤维的研究现状;详述了高湿模量粘胶纤维、Lyocell纤维、铜氨纤维、醋酯纤维、秸秆类可再生纤维素纤维、再生竹纤维、再生麻纤维的性能、结构特征及其适用性;探讨了我国再生纤维素纤维的发展趋势,指出超天然的功能再生纤维素纤维材料将成为未来发展的重点,我国应注重开发差别化、功能化粘胶纤维。     

Influence of mechanical treatments on the properties of cellulose nanofibers isolated from microcrystalline cellulose

The possibility of preparing cellulose whiskers-like materials by mechanical treatment of commercially available microcrystalline cellulose (MCC) was explored. High shear homogenization, grinding with a supermass colloider, and hammer-milling were the processes selected to disintegrate the MCC, which yielded F-MCC, G-MCC and H-MCC, respectively. Processing aqueous dispersions with high solid content allowed for the production of cellulose particles with greatly reduced dimensions. Morphological characterization revealed that homogenization and grinding reduced the particle size more effectively than hammer-milling, although the disintegration was incomplete in all cases. The reinforcing potential of the materials was evaluated against commercially available whiskers by using the various particles as fillers to mechanically reinforce hydroxypropylcellulose. Nanocomposite films containing 5, 10, or 20 wt.% of the filler were prepared and the mechanical properties were characterized. The results show that H-MCCs are just slightly better than the original MCC, whereas F-MCC and G-MCC performed similar to whiskers at 10 wt.% loading, despite the presence of a fraction of micrometer-sized particles. It is therefore reasonable to envision the use of the more easily produced F-MCC and G-MCC as replacement of cellulose whiskers in some applications.     

Extraction and characterization of natural cellulose fibers from common milkweed stems

Natural cellulose fibers with cellulose content, strength, and elongation higher than that of milkweed floss and between that of cotton and linen have been obtained from the stems of common milkweed plants. Although milkweed floss is a unique natural cellulose fiber with low density, the short length and low elongation make milkweed floss unsuitable as a textile fiber. The possibility of using the stems of milkweed plant as a source for natural cellulose fibers was explored in this research. Natural cellulose fibers extracted from milkweed stems have been characterized for their composition, structure, and properties. Fibers obtained from milkweed stems have about 75% cellulose, higher than the cellulose in milkweed floss but lower than that in cotton and linen. Milkweed stem fibers have low % crystallinity when compared with cotton and linen but the strength of the fibers is similar to cotton and elongation is higher than that of linen fibers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

吸附腈氯纶的结构与热性能

采用扫描电镜、傅里叶变换红外光谱仪、X射线衍射仪、差示扫描量热仪、差热分析和热重分析仪等对湿法纺丝工艺制备的活性炭质量分数为0-26．6％的吸附腈氯纶的结构及热性能进行分析。结果表明,吸附腈氯纶中的活性炭均匀分布,纤维耐热性提高,傅里叶变换红外吸收光谱图变化不大。随活性炭含量的增加,纤维在差热分析图上则表现为各种热行为的不明显;结晶度呈下降趋势,活性炭质量分数为 26．6％的纤维的结晶度约为42．18％。     

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.     

Miscibility, free volume behavior and properties of blends from cellulose acetate and castor oil-based polyurethane

A series of blend films from cellulose acetate (CA) and castor oil-based polyurethane (PU) were prepared. Morphology, miscibility, free volume behavior and properties of such blend films were investigated by wide-angle X-ray diffraction (WXRD), infrared, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), positron annihilation lifetime spectroscopy (PALS), thermogravimetric analysis and tensile test. The results indicated that lager free volume cavities did not form at the interface of two polymers although a certain degree of phase separation was found by the studies of SEM and DSC. Strong intermolecular hydrogen bonding interactions at the interface, which was proved by Fourier transform infrared spectroscopy, favors even better molecular packing, that is, PU dispersed in CA continuous phase to form fine microphase separation domain in the CA-rich blends. Due to such special interactions in the fine microphase separation domain structure, optimized properties of tensile strength, breaking elongation and cold-resistivity were obtained in the blend film with 75 wt% CA. The toughness of all the blend films was significantly higher than that of the film CA, owing to the plasticizing of PU elastomer in the blends.     

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.     

Surface chemical modification of natural cellulose fibers

Simple esterification and etherification reactions were applied to steam‐exploded Flax (Linum usitatissimum) with the aim of changing the surface properties through modification of fiber surface chemistry. Native and chemically modified cellulose fibers were characterized in terms of thermal stability, surface chemistry, morphology, and crystal structure. Independent of the substituent nature, chemically modified fibers exhibited a thermal stability comparable to that of native cellulose. Introduction of the desired chemical groups at the fiber surface was demonstrated by TOF‐SIMS analysis, whereas FTIR showed that the substitution reaction involved only a small fraction of the cellulose hydroxyls. No change of the native crystalline structure of cellulose fibers was caused by chemical modification, except in the case where ether substitution was carried out in water‐isopropanol medium. Cellulose fibers with unchanged structure and morphology and carrying at the surface the desired chemical groups were obtained for reinforcing applications in polymer composites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 38–45, 2002     

Characterisation of the microstructure and deformation of high modulus cellulose fibres

This paper reports on the microstructure and deformation of one type of high modulus cellulose fibre characterised using the techniques of Raman spectroscopy and synchrotron X-ray diffraction and it compares this fibre to a lower modulus conventional viscose fibre. The crystallinity of the fibres has been determined using X-ray diffraction. The orientation parameter has been determined by measuring the width of the (200) equatorial reflections for each fibre using microfocus synchrotron radiation and it has also been shown that the crystal orientation parameter varies from the skin to core of the fibres and is different for each type. Mechanical properties of the fibres are reported and it is shown that the high modulus cellulose fibres have very different stress-strain behaviour to the viscose fibres. Finally, it is shown for the high modulus fibre that the 1414, 1260, 1095 and 895 cm⁻¹ Raman bands shift under the application of tensile deformation towards a lower wavenumber with the 1095 cm⁻¹ band giving information about the backbone chain stretching of the cellulose. The viscose fibres show less significant shifts in this peak. The crystal modulus of the high modulus cellulose fibre has also been determined by calculating the change in the c-spacing upon the application of tensile deformation to individual cellulose monofilaments. This change in the c-spacing is determined from the change in position of the (002) meridional reflection giving a crystal modulus of 77 GPa. This value is a little low compared to other published data, and reasons for this are discussed. The shear modulus between crystallites is also calculated and compared to previously published data.     

胶原蛋白/PVA/碳纳米管复合纤维的结构与性能

在胶原蛋白与聚乙烯醇(PVA)复合后的溶液中加入少量质量分数为0.05%~0.25%的碳纳米管,通过湿法纺丝制得PVA/胶原蛋白/碳纳米管复合纤维,研究了复合纤维的结构和性能。结果表明:碳纳米管与PVA和胶原蛋白有较好的相容性,在复合纤维中分散比较均匀。添加质量分数为0.25%碳纳米管时,复合纤维结晶度提高了37.62%,水中软化点提高了5℃,回潮率从11.50%下降到10.83%;加入质量分数为0.05%的碳纳米管时,复合纤维的断裂强度提高57.07%。     

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.     

Preparation and properties of boron nitride nanosheets/cellulose nanofiber shear-oriented films with high thermal conductivity

A highly thermally conductive boron nitride nanosheets/cellulose nanofiber (BNNS/CNF) oriented film was prepared by doctor blading method via mechanical shear-induced orientation. The SEM images for cross-sectional parts showed that BNNS were well aligned within the film, forming a good layered structure. The XRD results further confirmed the high orientation effect of BNNS. Due to the excellent thermal stability of BNNS and its good physical barrier effect on the matrix after the orientation treatment, the thermal stability of shear-oriented films was largely improved. Resulting from the shear-induced orientation, BNNS were closely contacted with each other, forming a good thermally conductive pathway within the CNF matrix. Thus the influence of the interfacial thermal resistance was dramatically reduced, and the thermal conductivity of shear-oriented films increased in proportion to filler loading. With 50 wt% BNNS, the thermal conductivity of the shear-oriented film reached 24.66 W/(m·K), which exhibited 1106% enhancement compared to the pure CNF.     

Polyester biocomposites from recycled natural fibers: Characterization and biodegradability

The structure, biodegradability, and morphological properties of composite materials composed of poly(butylene succinate adipate) (PBSA) and bamboo fiber (BF) were evaluated. Composites containing acrylic acid‐grafted PBSA (PBSA‐g‐AA/BF) exhibited noticeably enhanced compatibility between the two components. The dispersion of BF in the PBSA‐g‐AA matrix was highly homogeneous as a result of ester formation and the consequent creation of branched and crosslinked macromolecules between the carboxyl groups of PBSA‐g‐AA and hydroxyl groups in BF. In addition, the PBSA‐g‐AA/BF composite was more easily processed due to a lower melt viscosity. Each composite was subjected to biodegradation tests in an Acinetobacter baumannii compost. Morphological observations indicated severe disruption of film structure after 10–20 days of incubation, and both the PBSA and the PBSA‐g‐AA/BF composite films were eventually completely degraded. The PBSA‐g‐AA/BF films were more biodegradable than those made of PBSA and exhibited a lower molecular weight and intrinsic viscosity, implying a strong connection between these characteristics and biodegradability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Regioselective combinatorial-type synthesis, characterization, and physical properties of dendronized cellulose

Novel regioselective, homo-(4-6) and heterogeneous (7-10) dendronized cellulose derivatives have been prepared by the reaction of cellulose in a N,N-dimethylacetamide (DMAc)/LiCl solvent system with diverse dendrons (1-3) possessing an isocyanate focal group. The dendronized cellulose derivatives were characterized using Fourier transform infrared (FTIR), ¹³C NMR, thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). These polyfunctionally coated cellulose-based materials showed diverse solubility characteristics in organic solvents ranging from DMAc to methyl alcohol.