不同溶解方法制备的纤维素/[BMIM]Cl纺丝液的性能比较

以离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为溶剂,分别采用直接溶解法和间接溶解法(即在含水[BMIM]Cl中溶胀后再减压蒸馏去除多余的水使之溶解)制备了纤维素/[BMIM]Cl纺丝液,系统地比较了这两种纺丝液的流变行为及可纺性。结果表明:相同条件下,直接溶解法制备的纤维素/[BMIM]Cl纺丝液的表观黏度最大,而间接溶解法制得的纺丝液的表观黏度随着溶胀时[BMIM]Cl的初始含水率的增加而下降。与直接溶解法相比,间接溶解法制得的纺丝液溶解均匀、流动性能好、纺丝过程中断头次数少、可纺性能提高,所得到的再生纤维素纤维具有更好的力学性能。     

两种咪唑型离子液体对纤维素的溶解及纺丝性能的比较

以1-乙基-3-甲基咪唑醋酸盐（[EMIM]Ac）和1-丁基-3-甲基咪唑氯盐（[BMIM]CI）两种咪唑型离子液体为溶剂,研究比较了它们对纤维素的溶解性能及其溶液的纺丝加工性能。结果发现：两种离子液体均能在一定条件下溶解纤维素,但[EMIM]Ac较[BMIM]Cl对纤维素具有更低的溶解温度和更快的溶解速率。从流变分析还发现：纤维素/[EMIM]Ac溶液与纤维素/[BMIMCl溶液均为切力变稀流体,相同条件下纤维素/[EMIM]Ac溶液的黏度远低于纤维素/[BMIM]Cl溶液,使其可在相对低的温度下纺丝。此外,GPC分析结果表明：纤维素在用[EMIM]Ac溶解及纺丝过程中降解程度较小,而用[BMIM]Cl进行溶解纺丝时,降解作用则较明显。对纤维结构与力学性能的分析结果进一步表明：与相同喷头拉伸比下制得的[EMIM]Ac法再生纤维素纤维相比,[BMIM]Cl法再生纤维素纤维的聚集态结构相对较完善,结晶度与取向度更高些,从而使其力学性能也相对较好。     

MWCNTs含量对纤维素/[BMIM]Cl溶液及其纤维性能和形态结构的影响

分析了经表面功能化的MWCNTs(多壁碳纳米管)在纤维素/[BMIM]Cl(1-丁基-3-甲基咪唑氯盐)体系中的分散稳定性,探讨了MWCNTs/纤维素/[BMIM]Cl溶液的流变行为,并通过干湿法制备了不同MWCNTs含量的离子液体法纤维素纤维,对其力学性能和表面形态结构进行了研究。结果表明:MWCNTs/纤维素/[BMIM]Cl溶液为切力变稀流体。随着溶液中MWCNTs添加量的增加,溶液表观黏度先增大后减小;适量的MWCNTs可以均匀分散在纤维素/[BMIM]Cl溶液体系中并具有良好的可纺性,所制得的MWCNTs/纤维素纤维表面较光滑且力学性能明显改善。其中,含1%MWCNTs的纤维素纤维的初始模量和断裂强度较高,分别比未添加MWCNTs的纤维提高66.7%和22.7%。     

凝固浴浓度对离子液体法纤维素纤维结构以及性能的影响

探讨了以离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为溶剂制备的纤维素纤维纺丝工艺条件中凝固浴浓度对纤维结晶结构以及力学性能的影响。实验表明:在相同拉伸比和气隙条件下,凝固浴浓度对再生纤维素纤维的结构以及性能影响较大。随着凝固浴浓度的增加,纤维的结晶度和无定形取向都呈现先增大后减小的趋势,纤维的横向晶粒变小,拉伸强度、初始模量也呈先增大后减小的趋势。     

凝固浴温度对Ionicell纤维结构及性能的影响

以离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为溶剂,水为凝固浴,α-纤维素质量分数95.5%的棉浆为原料,通过干湿法纺丝制备再生纤维素(Ionicell)纤维。探讨了凝固浴温度对纤维结晶结构以及力学性能的影响。结果表明:在其他相同条件下,随着凝固浴温度的升高,纤维的结晶度、双折射和非晶区取向都呈现先增大后减小的趋势,纤维的断裂强度、初始摸量也呈先增大后减小的趋势,当凝固浴温度为20℃时纤维的力学性能最佳,断裂强度为2.98 cN/dtex,断裂伸长率为3.5%,初始模量为59.7 cN/dtex。     

以离子液体为溶剂的纤维素纤维的结构与性能

以离子液体氯化1-丁基-3-甲基咪唑([BMIM]Cl)为溶剂,制备了纤维素/[BMIM]Cl溶液,探讨了该体系的流变性能,并对所纺得的纤维素纤维的结构与性能进行了分析。结果表明:纤维素/[BMIM]Cl溶液为切力变稀流体,当剪切速率较大时,温度对体系黏度几乎没有影响,因此可以在较高剪切速率下降低纺丝温度;由该体系纺制的纤维具有纤维素II晶型的结构;随着拉伸比的提高,纤维的取向程度及结晶度增大,从而使纤维力学性能提高,所得纤维的表面光滑、结构致密,其染色性能及抗原纤化性能与Lyocell纤维基本相近。从而证明了用离子液体[BMIM]Cl所纺制的纤维素纤维性能良好,可望成为继Lyocell纤维之后的又一新型绿色纤维素纤维。     

纤维素在离子液体水溶液中的溶胀与溶解行为的研究

以含水的离子液体1-丁基-3-甲基咪唑氯盐([BMIM]C)l为溶剂,研究了纤维素在其中的溶胀和溶解行为。通过偏光显微镜观察发现,[BMIM]Cl水溶液中的含水率对纤维素浆粕的溶胀与溶解行为有着重要的影响,主要表现为三种状态:当[BMIM]Cl中含水率小于1%时,浆粕纤维横向被迅速切断并快速溶解,没有发现明显的溶胀现象;当[BMIM]Cl中含水率在2%～5%时,浆粕纤维发生了非常明显的非均相溶胀,但并不溶解;而当[BMIM]Cl中含水率进一步增大到6%～20%时,浆粕纤维不再发生明显的溶胀现象。此外,研究结果还表明,当[BMIM]Cl中含水率在2%～5%时,溶胀温度和[BMIM]Cl中的含水率对于纤维素的溶胀有很大影响,随着温度升高,浆粕纤维的溶胀速度增大,达到最大溶胀比所需要的时间缩短;而随着[BMIM]Cl中含水率的提高,浆粕纤维在[BMIM]Cl水溶液中达到的最大溶胀比减小。     

天然胶乳共混改性的研究进展

概述天然胶乳/天然高分子(包括壳聚糖、淀粉、纤维素和丝素蛋白质)共混、天然胶乳/合成胶乳共混、天然胶乳/合成乳液共混和天然胶乳/纳米材料共混等不同改性方法的研究进展.由于天然胶乳制品的耐油、耐老化等性能不佳,为扩大天然胶乳使用范围,有必要对胶乳进行物理改性或化学改性,使天然胶乳朝高性能化方向发展.     

纺丝工艺对离子液体法新型纤维素纤维性能的影响

以离子液体1-丁基-3-甲基咪唑氯盐（[BMIM]C1）为溶剂,用干湿法纺丝制备了再生纤维素纤维,通过正交试验设计和系统试验,考察了气隙长度、喷头拉伸比、凝固浴浓度和凝固浴温度等工艺参数对制得的再生纤维素纤维的力学性能的影响,找出离子液体法新型纤维素纤维的最佳纺丝工艺。试验结果表明,对于该体系,纺丝工艺参数中凝固浴温度和拉伸比对纤维的拉伸强度、初始模量的影响最大,气隙长度对纤维断裂伸长影响最大。     

纤维素/[BMIM]Cl体系表观黏度影响因素

以1-丁基3-甲基咪唑氯盐([BMIM]Cl)离子液体为溶剂,研究了高聚合度的针叶木浆(DP=1460)在[BMIM]Cl溶剂体系中的活化能,考察了溶解温度、浆粕浓度和介孔硅添加量对纤维素/[BMIM]Cl体系表观黏度的影响.研究表明:纤维素/[BMIM]Cl体系黏流活化能AE=50.8 kJ/mol,针叶浆粕含量对体...     

Biocomposite membranes of sodium alginate and silk fibroin fibers for biomedical applications

Biocomposite membranes from biodegradable and biocompatible natural polymers were prepared from sodium alginate solution reinforced with silk fibroin fibers in several fiber content by casting and solvent evaporation. The properties of these biocomposites were investigated by scanning electron microscopy, swelling test, water vapor transmission, mechanical and thermal analyses, and cytotoxicity test. A biocomposite with uniform fiber dispersion and good fiber–matrix interaction was obtained through the incorporation of fibroin fibers in the alginate membrane, even though the fibers were used without any surface treatment to enhance the interfacial adhesion. The incorporation of fibroin fibers improved the tensile strength and also provided a new property to the alginate, that is, the resistance to tear. Moreover, the use of silk fibroin fibers in polymeric composites can result in a material with adequate characteristics for application in the biomaterial field, especially as wound dressings, because of its nontoxic effect to cells, flexibility, and resistance to tear. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3451–3457, 2013     

新型仿生化纤维的制备与纤维性能评价

为提高纤维素纤维和壳聚糖纤维的生物相容性能并保持纤维原有的力学机械强度,在其单纤维纺丝溶液中添加原胶原蛋白、丝素蛋白、甲壳素等,经湿法纺丝,考察了各种混合纤维的密度、直径、纤度、强度、伸长率等性能的变化。研究结果表明:壳聚糖纤维中混合原胶原蛋白后,纤维纤度增加,但对纤维的伸长和强度影响不大;当原胶原蛋白含量达10%时,纤维伸长率最大。纤维素纤维因添加了丝素后,强度、伸长下降,但添加第三组分甲壳素后表现出优异的机械性能。扫描电镜对混合纤维的形貌分析证实了生物材料与甲壳素、壳聚糖及纤维素间存在着良好的共混相容性,对纤维性能起到改善的作用。     

Fibers based on cellulose–silk fibroin blend

Fibers made of cellulose (CE) and silk fibroin (SF) are wet spun from solutions in N,N‐dimethylacetamide containing 7% LiCl (w/w). Different coagulation baths (water and ethanol) and spinning conditions are used. By using water as the coagulant, a partial dissolution of SF occurs and negligible variation of the mechanical properties of the CE–SF fibers with respect to the CE fibers is found. Fibers coagulated in ethanol are dimensionally homogeneous and show better properties. A modulus of about 13 GPa and elongation to break of 16% for the blend containing 30% (w/w) SF are obtained with a 20‐mm air gap. The fibers are characterized by FTIR micro‐Raman, scanning electron microscopy, and wide‐ and small‐angle X‐ray analyses. In particular, the X‐ray results show that CE–SF fibers are amorphous with a homogeneous dispersion of small SF domains (1.3 nm) in the CE matrix. These results confirm the good compatibility between the two natural polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2187–2196, 2007     

纤维素与透明质酸、肝素、丝素、甲壳素湿纺复合生物纤维的制备与性能研究

室温下,将再生纤维素与透明质酸(HA)、肝素(Hep)、丝素(SF)、甲壳素(N-ACS)等的复合纤维的纺丝液溶于NaOH溶液中,通过喷丝头(孔径0.1mm)喷入含有40%~43%硫酸铵的10%硫酸溶液中,得到产率为75%~98%的新型白色、柔韧性较好的复合生物纤维。FT-IR结果显示,复合纤维组分间存在物理吸附和氢键相互作用;少量的HA、Hep、SF和N-ACS等纤维的添加可增加复合纤维的韧能,其中纤维素-SF复合纤维在SF含量为10%时纤度为9.9旦,韧度值为1.08g/旦,伸长率为35.0%,机械性能相对最好。SEM图像中可以看出复合纤维表面呈现条纹、鳞状、填充和均匀包覆的结构,复合纤维间存在一定的相容性;复合纤维直径为19~55μm,密度为0.1~0.36旦/μm。     

Surface modification of textile material through deposition of regenerated silk fibroin

Regeneration of silk fibroin from calcium chloride/ethanol/water solution is of high interest to shape biomaterial based products for medical and technical application. In this study a continuous process for surface modification of cellulose or polyamide fibers by regenerated fibroin deposits has been investigated. The decomposition of the fibroin‐calcium complex was initiated by addition of K₂CO₃ followed by a methanol rinse. Reactive Blue 19 labeled fibroin was used to monitor the deposition of fibroin on the substrates by colour measurement. The fibroin deposits on the fabric were characterized by microscopy, N‐content, calcium, and protein content. Stiffness and surface resistivity of modified fabrics were determined as representative physical parameters. The reduced mobility of fibers increased fabric stiffness. Surface resistivity of treated samples was reduced by a factor of 10 to 100, which gives an example for the potential of the technique as coating for man‐made fiber textiles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45098.     

Structural characteristics of 2-hydroxyethylmethacrylate (HEMA)/methacrylamide (MAA)-grafted silk fibers

A series of 2-hydroxyethylmethacrylate (HEMA)/methacrylamide (MAA)-grafted silk fibers obtained in various comonomer compositions was prepared and their structural characteristics were studied by X-ray diffractometry, differential scanning calorimetry, and scanning electron microscopy. HEMA/MAA-grafted silk fibers with a graft yield of about 60% obtained in a HEMA/MAA mixture system containing 20% of HEMA and 80% of MAA on a weight basis showed endothermic peaks at 280 and 420°C (shoulder form), which are attributed to the thermal decomposition of the MAA and HEMA polymers, respectively, in addition to the thermal decomposition peak of the silk fibroin fiber which appeared at 323°C. These DSC results suggest that the HEMA/MAA-grafted silk fiber showed a low compatibility in the relation between the silk fibroin molecules and HEMA and/or MAA polymers. The crystalline structure of the HEMA/MAA-grafted silk fiber remained unchanged regardless of the HEMA/MAA grafting ratio even when the graft yield value reached 120%.     

改性酪蛋白/羧甲基纤维素钠共混纤维制备与性能

采用湿法纺丝,以乙醇、氯化钙和盐酸的混合溶液为凝固浴制备了改性酪蛋白(CLC)/羧甲基纤维素钠(CMC-Na)共混纤维。通过测试纺丝液流动性以及纤维的红外光谱、表面形态和力学性能,研究了CLC和CMC-Na不同配比与纺丝溶液pH改性后酪蛋白纤维的力学性能增加,纺丝溶液的流动性与CMC-Na维的红外光谱分析表明CLC与CMC-Na之间有良好的相互作用。CMC-Na质量分数为30%(相对于改性酪蛋白)的共混纤维性能较好,纤维表面较致密,有沿着纤维轴向取向的明显条纹,其断裂强度为341.19MPa。     

Structure for electro‐spun silk fibroin nanofibers

Electro‐spinning was made using silk fibroin and it was found that silk fibroin nanofibers of partially oriented amorphous structure are producible using HFIP(1,1,1,3,3,3 hexafluoro‐2‐propanol) as a solvent for fibroin via the electro‐spinning setup equipped with parallel electrodes as a collector. Transformation from amorphous to silk I of a highly contracted beta‐turn form or amorphous to silk II of a regular array of antiparallel beta‐sheets occurred preferentially via the treatment with water vapor or ethanol, respectively. In addition the c‐axis of crystallites was oriented parallel to the fiber axis. When the electro‐spinning was made using a dish‐type collector filled with ethanol, a peculiar web texture was obtained. Such a web texture seems to be brought about by the shrinkage of fiber due to the crystallization of fibroin and/or surface tension of ethanol droplets formed between the fibers. In this spinning setup, the c‐axis of crystallites was also oriented parallel to the fiber axis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Separation of alcohol–water mixture by pervaporation through a novel natural polymer blend membrane–chitosan/silk fibroin blend membrane

A novel natural polymer blend membrane, namely chitosan/silk fibroin blend membrane, was prepared. The selective solubility and the pervaporation properties of alcohol–water mixture were studied. The results showed that the membrane was water selective and the separation factor of ethanol–water mixture could be improved compared to pure chitosan membrane, when silk fibroin content in blend membrane was no more than 40 wt %. The blend membrane exhibited a best performance, (i.e., the water in permeate was large than 99 wt % when silk content was 20 wt % and the crosslinking agent–glutaraldehyde content was 0.5 mol %). The mechanism of improvement on pervaporation properties was explained by reducing the free volume and freeing hydrophilic groups of chitosan because of the strong intermolecular hydrogen bond forming between chitosan and silk fibroin in blend membrane. In addition, the influence of operation temperature and feed concentration as well as the pervaporation properties of isopropanol–water mixture were also studied. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 975–980, 1999     

Silk fibroin/cellulose blend films: Preparation,structure, and physical properties

This article deals with the preparation and characterization of silk fibroin (Bombyx mori)/cellulose blend films. Following dissolution with a metal complex solution, the average molecular weight of silk fibroin slightly decreased. While cellulose was almost unaffected. After coagulation and washing, transparent films were obtained by blending fibroin and cellulose in all proportions. The crystalline structures of regenerated fibroin and cellulose were β-form and cellulose II, respectively, as shown by the characteristic x-ray diffraction profiles. Density values increased with cellulose content, though less than expected from a pure additive behavior. Moisture regain increased following the addition of a small amount of cellulose to silk fibroin. The mechanical properties showed that both strength and elongation at break of silk fibroin films were improved by blending with cellulose. IR spectra exhibited changes in the skeletal frequences of silk fibroin, suggesting the occurrence of intermolecular interactions between fibroin and cellulose through hydrogen bond formation. © 1995 John Wiley & Sons, Inc.