静电纺丝工艺参数对丝素/壳聚糖纳米纤维的形貌及直径的影响

以98%的甲酸为溶剂,不同质量分数的再生丝素溶液和3.5%的壳聚糖溶液以质量比70:30共混静电纺丝。用扫描电子显微镜(SEM)观察了丝素质量分数、电压和极距(喷丝口到收集装置的距离)对丝素/壳聚糖纳米纤维的形貌及直径的影响。正交试验结果表明:在丝素/壳聚糖溶液静电纺丝的工艺参数中,对纤维平均直径的影响因素由大到小依次为丝素质量分数、电压、极距。单因素试验表明:丝素/壳聚糖纳米纤维的平均直径及其分布范围随丝素质量分数的增加而增大;在15￣30kV范围内纤维的平均直径随电压增大而减小;当极距大于12cm时,对纤维直径影响不大。最佳工艺条件为:丝素质量分数13%,电压30kV,极距为12cm,制得的纳米纤维平均直径104nm。     

再生丝素/壳聚糖共混纳米纤维的结构与性能

以98%的甲酸为溶剂,不同质量分数的再生丝素溶液和3.5%的壳聚糖溶液以质量比70∶30共混静电纺丝。测定了壳聚糖的含量对共混膜的结构及力学、溶解等性能的影响。结果表明:随着壳聚糖相对含量的增加,丝素β化程度提高,纤维结晶度增大,丝素与壳聚糖以70∶30共混时的溶失率最小;甲醇处理后,溶失率明显降低;共混纳米纤维的断裂强度随着壳聚糖相对含量的增大而增加,柔软性也逐渐提高;共混纤维膜具有优异的抗菌性。     

Wet-spun conductive silk fibroin–polyaniline filaments prepared from a formic acid–shell solution

Shell wastes represent a considerable quantity of byproducts in the coastal area. From the viewpoint of ecofriendly and economical disposal, shell wastes are dissolved in formic acid to prepare an ionic liquid at room temperature and dissolve silk fibers to prepare a spinning solution. In this study, we developed conductive filaments made of silk fibroin (SF) and polyaniline (PANI) with wet-spinning techniques and a water coagulation bath. We then evaluated its surface morphologies and structural, mechanical, and electrical properties. The average diameters of the SF–PANI filaments increased with SF concentration from 8.0 to 14.0 wt % when PANI content was 0.1 wt %. The structure of SF–PANI filaments included the coexistence of silk I and silk II and was not affected by the addition of PANI. Moreover, the stress and strain of the SF–PANI filament were 4.46 ± 0.57 MPa and 16.18 ± 2.35%, respectively. After three drafts, the stress and strain of the SF–PANI filaments reached their maxima: 22.08 ± 0.2 MPa and 63.2 ± 2.56%, respectively. In addition, the electrical properties of the SF–PANI filaments increased with the addition of PANI. Thus, all data in this study suggest that recycled shell wastes can be reused as dissolution systems to prepare SF-based functional conductive filaments. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47127.     

高浓度纤维素纺丝液湿法纺丝工艺研究

以棉纤维为原料,采用离子液体-二甲基亚砜复合溶剂配制固含量17%的纺丝液,通过湿法纺丝制备纤维素纤维,探讨了凝固牵伸比、水洗牵伸比及水洗温度对纤维结构和性能的影响。研究结果表明:采用凝固正牵伸,可以有效提高纤维力学性能与结晶性能。当凝固牵伸比为1.05、水洗牵伸比为1.3、水洗牵伸温度为60℃时,得到的再生纤维素纤维性能较好,断裂强度为2.11cN/dtex,断裂伸长率为10.29%;纤维素纤维取向度较高,结晶比较完善。     

聚苯胺/聚酰胺导电初生纤维形态结构的研究

以聚苯胺 ( PANI)为导电组分 ,聚酰胺 -11为基体 ,浓硫酸为溶剂制备纺丝浆液 ,采用湿法纺丝路线纺制导电纤维。当 PAN I在纤维中的质量分数为 5 %和 12 %时 ,纤维的电导率分别提高到10 -5S/ cm和 10 -2 S/ cm。采用扫描电子显微镜 ( SEM)研究了凝固浴中酸的含量以及纺丝浆液中 PANI的含量对初生纤维形态结构的影响 ,并探讨了初生纤维的微观结构对纤维的拉伸性能的影响     

Effect of chitosan on morphology and conformation of electrospun silk fibroin nanofibers

The electrospinning of silk fibroin(SF)/chitosan(CS) blends with different composition ratios was performed with formic acid as a spinning solvent. The SF/CS blends containing up to the CS content of 30% could be electrospun into the continuous fibrous structure, although pure CS was not able to be electrospun into the fibrous structure. As-spun SF/CS blend nanofibers showed smaller diameter and narrower diameter distribution than pure SF nanofibers, and the diameter gradually decreased from 450 to 130 nm with the addition of CS in blends. However, at the blend compositions with above 40 wt% chitosan, the continuous SF nanofibers containing CS beads were produced. We also investigated the influence of the methanol treatment on the secondary structure of as-spun SF or SF/CS blend nanofibers by means of ATR-IR and solid-state CP-MAS ¹³C-NMR. Comparing with the pure SF nanofibers, the conformational change of the as-spun SF/CS blend nanofibers into β-sheet was faster because the CS with rigid backbone synergistically might promote the conformational transition of SF by an intermolecular interaction.     

含中草药成分的纤维制备与性能研究Ⅰ.柿叶/纤维素共混纤维的制备及力学性能

以二甲基亚砜(DMSO)／多聚甲醛(PF)为溶剂,添加柿叶活性成分,应用湿法纺丝技术,制得含柿叶提取物的再生纤维素纤维。研究了纺丝原液浓度、凝固浴温度、柿叶添加量对共混纤维的力学性能的影响。结果表明,当纺丝原液质量分数在10％-12％,凝固浴温度在40-50℃,柿叶提取物质量分数在5％左右,纤维具有较好的可纺性,柿叶的添加使共混纤维的结晶度、取向度、强度均有一定程度的下降。DSC测试表明柿叶与纤维素之间有较好的相容性。     

塑化拉伸对芳纶Ⅲ结构性能的影响

芳纶Ⅲ主要采用湿法纺丝,在纺丝成形过程中须经过凝固浴,常采用一凝和二凝凝固成形,其中二凝塑化拉伸比对芳纶Ⅲ的结构及性能有显著影响。对二凝拉伸比进行了系列试验,通过X射线衍射、声速取向度、干纱及浸胶丝力学性能对比分析了凝固浴拉伸对芳纶Ⅲ结构与性能的影响。     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

局部络合PA6纤维和膜的拉伸性能及形态

以氯化钙(CaCl2)为络合剂,分别在纯甲酸溶剂和氯仿/甲酸混合溶剂中对超高相对分子质量聚己内酰胺(UHMWPA6)进行了低摩尔比的局部络合,对UHMWPA6络合液进行了制膜和干法纺丝,研究了纤维及膜的拉伸性能和形态。结果表明:在氯仿/甲酸混合溶剂中,氯仿的加入可明显提高局部络合UHMWPA6纤维及膜的拉伸性能,络合比为0.5时,UHMWPA6膜的最大拉伸倍数达10。SEM观察表明,纤维和膜中所含的络合剂在干燥过程中会重结晶析出,且随络合比的增加,纤维拉伸性能提高,结晶析出量增大。     

溶剂对静电纺PA6纤维可纺性的影响

分别用甲酸、六氟异丙醇(HFIP)或甲酸与醋酸(HAc)、N,N-二甲基甲酰胺(DMF)、HFIP的混合溶剂溶解聚己内酰胺(PA6),通过静电纺丝法制备了纳米级的PA6纤维。结果表明:甲酸作为溶剂时,PA6可纺丝溶液质量分数为8%～22%,所纺出的PA6纤维直径为50～300 nm;HFIP作为溶剂时PA6可纺丝溶液质量分数为8%～18%,纤维直径为50～500 nm;甲酸与HFIP,HAc,DMF的混合溶剂对纺丝状态及纤维直径分布的影响均表现为随第2种溶剂的加入,纤维直径的分布变广,平均直径增加;HAc的加入能提高PA6溶液的可纺性。     

Polyether-segmented nylon hemodialysis membranes. I. Preparation and permeability characteristics of polyether-segmented nylon 610 hemodialysis membrane

The effect of the coagulation condition in the phase inversion method on the permeability characteristics of poly(propylene oxide) or poly(tetramethylene oxide)-segmented nylon 610 (PPO-Ny610 or PTMO-Ny610) hemodialysis membranes, the stability of the membrane performance, and the mechanical strength were investigated. The polymers were dissolved in a solvent such as formic acid and methanol saturated with calcium chloride, and thus PPO-Ny610 and PTMO-Ny610 membranes were prepared using formic acid and a calcium chloride/methanol/water mixture as a polymer solvent and a coagulant, respectively. It is concluded that PPO-Ny610 membrane has better permeability characteristics than PTMO-Ny610 membrane, and possesses additional properties for hemodialysis membranes such as mechanical properties and permeability stability in the drying and sterilizing processes. Furthermore, the blood compatibilities of PPO-Ny610 and PTMO-Ny610 membranes were superior to regenerated cellulose membranes on the basis of the result of platelet adhesion test. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1703–1711, 1997     

Effect of DMSO/H2O coagulation bath on the structure and property of polyacrylonitrile fibers during wet‐spinning

The effect of coagulation bath condition on the structure and property of the nascent fibers and polyacrylonitrile fibers during wet‐spinning is studied. The best coagulation condition to produce polyacrylonitrile fibers has been found by examination of EA, XRD, SEM, and so on. The results indicated that when the coagulation bath was DMSO/H₂O system, the temperature was 60°C, the concentration was 65%, the minus stretch ratio was ?10%, fine crystallites and high degree of crystallization in the nascent fibers and polyacrylonitrile fibers could be achieved, and less solvents remained in the nascent fibers with circular cross section morphology. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

离子液体法制备再生细菌纤维素纤维

以离子液体(氯化1-甲基-3-正丁基咪唑)溶解高聚合度细菌纤维素(BC),采用湿法纺丝制备再生细菌纤维素(RBC)初生纤维;通过红外光谱分析(FTIR)、广角X射线衍射(WAXD)分析、热失重(TG)分析、扫描电镜( SEM)、单丝强度拉伸等表征了RBC初生纤维的结构和性能.结果表明:该溶剂体系通过10 h的快速搅拌溶...     

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     

凝固浴温度对再生细菌纤维素纤维结构与性能的影响

以细菌纤维素为原料,N-甲基吗啉-N-氧化物为溶剂制得纺丝原液,在不同的凝固浴温度条件下,制备再生细菌纤维素纤维,对其形貌、结晶度、取向度、力学性能、吸湿保湿性等进行了研究.结果表明:随着凝固浴温度的提高,再生细菌纤维素纤维表面逐渐趋于光滑,且结晶度提高、取向度和断裂强度降低;凝固浴温度为0～45℃,再生细菌纤维素纤维...     

A new synthetic fiber made of nylon 3

Nylon 3 fibers were produced by wet spinning, and properties and structures of the fibers were investigated. Fiber- and film-forming abilities of nylon 3 dopes in various coagulants, using various solvents, were investigated and it was found that only the nylon 3 spinning dope dissolved in formic acid showed excellent fiber- and film-forming abilities in coagulation baths of ethers, esters, or alcohols. As for mass transportation in these coagulants, solvent (formic acid) was diffused into coagulants, with scarce penetration of the coagulants into protofibers. This was due to the fact that these coagulants had moderate solubility parameter values and moderate proton-accepting power, which means the existence of some interaction between solvent and coagulants and no interaction between coagulants and polymer. Protofibers thus obtained were already crystallized and stretching them at room temperature was impossible. However, in such media as silicone oil, hot air, and Wood's metal, which were thought to have no interaction with polyamides, nylon 3 fibers were stretchable above their glass transition temperature (170°–180°C), while in such media as hot water, hot glycerin, and hot steam, which were thought to have some interaction with polyamides, nylon 3 fibers could not be stretched. Mechanical properties of nylon 3 fibers were as follow: strength, 2–3 g/d; elongation, 10%–20%; Young's modulus, 11 × 10⁵–17 × 10⁵ psi. High Young's modulus, high transition temperature, and high moisture regain are pointed out as characteristic features of nylon 3 fibers, compared with other synthetic fibers.     

羧甲基壳聚糖及其纤维的制备及表征

用氯乙酸改性处理壳聚糖(CS)制备羧甲基壳聚糖(CMCS),采用湿法纺丝法制备CMCS纤维,考察了纺丝原液浓度、醋酸水溶液体积分数、凝固时间对CMCS纤维力学性能的影响;通过傅里叶变换红外光谱、X射线衍射以及热失重分析对CS,CMCS及其纤维进行表征。结果表明:CMCS发生了羧甲基取代,同时CMCS结晶度降低;CMCS纤维结构中含有结合水,热分解温度为270℃;纺丝原液CMCS的质量分数为50%,醋酸水溶液的体积分数为2%、凝固时间为12 min时,CMCS纤维的断裂强度达0.644 cN/dtex。     

Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

硼酸凝固浴对MF-PVA纤维结构与性能的影响

以三聚氰胺(M)、甲醛(F)、聚乙烯醇(PVA)水溶液为原料反应制得纺丝原液,经湿法纺丝得到三聚氰胺甲醛-聚乙烯醇(MF-PVA)纤维。研究了在凝固浴中加入硼酸对MF-PVA纤维结构及性能的影响。采用凯氏定氮法、扫描电子显微镜、单纤电子强力仪和极限氧指数(LOI)仪表征了纺丝过程氮流失率、纤维形貌结构、力学性能以及阻燃性能。结果表明:在凝固浴中加入硼酸可以有效地控制MF树脂的溶出,随着硼酸添加量的增加,纤维的氮流失率明显降低,断裂强度增加,断裂伸长率减小,LOI提高。当添加硼酸的质量分数为7%时,纤维的氮流失率只有14.64%,其LOI达到40%,但纤维表面变得粗糙。