石墨烯纤维：制备、性能与应用

石墨烯纤维是一种由石墨烯片层紧密有序排列而成的一维宏观组装材料。通过合理的结构设计和可控制备,石墨烯纤维能够将石墨烯在微观尺度的优异性能有效传递至宏观尺度,展现出优异的力学、电学、热学等性能,从而应用于功能织物、传感、能源等领域。目前,石墨烯纤维主要通过湿法纺丝、限域水热组装等方法制备得到,其性能可以通过对材料体系和制备工艺的优化而进一步提升。本文首先介绍了石墨烯纤维的制备方法,然后详细阐述了石墨烯纤维的性能,讨论了其性能提升策略,并总结了石墨烯纤维的应用,最后对石墨烯纤维的未来发展、挑战和前景进行了展望。     

湿法纺制石墨烯纤维：工艺、结构、性能与智能应用

石墨烯纤维是由石墨烯片层通过组装过程形成的宏观一维材料。其具有较好的耐热性、导热性、导电性以及轻质高强等优点,是实现高品质、功能化纤维的重要突破口。石墨烯纤维在超轻导线、可穿戴储能、传感、生物电极等领域具有广阔应用前景。目前,湿法纺制技术是石墨烯纤维的最主要制备手段,与现有的化学纤维制备过程兼容,是最有望实现规模化制备高品质石墨烯纤维的技术。本文首先介绍了湿法纺制石墨烯纤维工艺中的关键步骤,重点讨论了制备技术与石墨烯纤维结构之间的关系。论述了提升纤维性能的相关策略,总结了石墨烯纤维在功能/智能纤维领域应用。并对提升石墨烯纤维性能的关键问题进行总结阐述,展望了石墨烯纤维的发展前景。     

可控核/壳结构聚合物电纺纤维的制备与应用

核/壳结构纳米纤维是一种兼具核层与壳层优异性能的功能化复合纤维, 通常具有优于核层和壳层自身的性能, 如可控的机械强度和较好的热传导系数等。其特殊的结构极大地提高了纤维的使用价值, 拓宽了纤维的应用领域, 因此, 核/壳结构纳米纤维成为纤维领域的研究热点之一。静电纺丝技术因其简单有效的特点, 近些年来在众多纳米纤维制备技术中一直备受关注, 制备结构和形貌可控的核/壳结构纤维的方法对于指导其在实际中的应用尤为重要。本文系统介绍了以静电纺丝技术制备核/壳结构纳米纤维的方法, 主要包括单喷头相分离法、同轴静电纺丝法、乳液静电纺丝法以及模板法, 重点讨论了影响核/壳结构的主要因素以及核/壳结构对纤维性能的影响。综述了近几年来国内外关于可控核/壳结构电纺纤维制备的研究新进展及其在药物缓释体系、组织工程支架、多功能敷料、污水处理材料、疏水性材料等领域的潜在应用价值。     

静电纺丝法制备聚丙烯腈/聚苯胺复合纳米纤维及其表征

利用静电纺丝技术,以聚丙烯腈(PAN)和苯胺(ANI)为前驱物,用过硫酸胺(APS)溶液在低温下缓慢氧化聚合,制备了PAN/PANI复合纳米纤维,直径约500 nm.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、X射线衍射(XRD)和激光拉曼(RAMAN)光谱仪等测试手段对材料的形貌和结构进行了表征.探讨了材料制备过程中影响纤维形貌、尺寸、均匀度的因素和PANI含量对复合纤维导电性能的影响,结果表明,PAN浓度、ANI的加入量和电压是影响纤维特性的主要因素;PANI在PAN基体中呈纳米尺寸分布,复合纳米纤维具有良好的导电性能,导电率可达10-2S/cm.     

表面活性剂对碳纳米管分散性及其湿法纺丝纤维性能的影响

碳纳米管(CNT)纤维因具有低密度、高强度以及高电导率等特性受到广泛关注。在湿法纺丝技术制备CNT纤维的工艺中，探究纺丝分散液和纺丝条件对CNT纤维性能的影响具有重要意义。本文研究了十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)、胆酸钠(SC)、牛磺脱氧胆酸钠(STDC)等表面活性剂对CNT纤维制备及性能的影响。通过拉曼光谱、紫外可见光谱、偏光显微镜、旋转流变仪、扫描电镜等方法对材料进行表征，以拉伸测试和“四探针”法对材料性能进行测试。结果表明，单壁碳纳米管(SWNTs)在表面活性剂的2(wt)%水溶液中的分散能力顺序依次为STDC> SC> CTAB> SDS;SDS或CTAB修饰的SWNTs分散液无法纺制纤维，SC和STDC修饰的SWNTs分散液具有良好的可纺性。其中以STDC作表面活性剂制备的CNT纤维性能最好，其断裂强度为160MPa,杨氏模量为12.3GPa,电导率为2300S/cm。     

静电纺丝技术制备聚苯乙烯/石墨烯复合纳米纤维

通过静电纺丝技术制备了聚苯乙烯/石墨烯复合纳米纤维膜,利用扫描电子显微镜、傅里叶变换红外光谱、粉末X-射线衍射和激光拉曼光谱等技术对所制备的纤维膜结构和组成进行表征,并通过电化学法考察该复合纳米纤维膜的电活性。结果表明,石墨烯已掺杂到聚苯乙烯纤维中。与聚苯乙烯纤维膜相比,聚苯乙烯/石墨烯复合纳米纤维膜导电性能增强,表明本实验成功实现了对聚苯乙烯纤维的改性。     

静电纺丝制备石墨烯基复合纳米纤维研究进展

在静电纺丝纳米纤维中加入纳米填料——石墨烯(G),有助于提高纳米纤维的性能,扩展其应用领域。本文综述了近年来国内外静电纺丝制备石墨烯基复合纳米纤维的研究现状,重点介绍了石墨烯与聚酰胺(PA)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯腈(PAN)、二氧化钛(TiO2)等复合纳米纤维制备的研究进展及其在光催化剂、超级电容器、染料敏化太阳能电池(DSSCs)、传感器、生物医学等方面的应用潜力,展望了石墨烯基复合纳米纤维的发展前景。     

高性能聚酰胺6纤维的制备技术进展

聚酰胺6纤维具有良好的综合性能如力学性能、耐热性、耐磨损性和耐化学药品性等,同时具有很高的理论模量,如果开发制备出高强高模纤维,其在军用纤维和纺织上应用前景非常可观。但是聚酰胺分子间很强的氢键作用制约了分子的取向和纤维的高倍拉伸,从而限制了制备高强高模聚酰胺纤维技术的发展。所以要拉伸得到高取向聚酰胺纤维,需通过减少链间氢键的数量来实现。许多研究者已经通过各种工艺技术提高最大拉伸比,如增塑剂法、干法纺丝、冻胶纺丝、湿法纺丝、区域拉伸和退火等。鉴于已经通过冻胶纺丝法制备出了超高分子量聚乙烯纤维,因此目前冻胶纺丝法制备高强高模聚酰胺纤维具有较大的可行性。本文将介绍各种制备聚酰胺6纤维的工艺技术,主要突出冻胶法制备聚酰胺6纤维的技术。     

聚酰亚胺纤维

聚酰亚胺纤维具有高强度模、耐高温、耐辐射等优越的性能。在多种纺制聚酰亚胺纤维的方法中,湿纺容易制得高强高模的样品。本文主要介绍了聚酰亚胺纤维的一步法湿纺、二步法湿纺和熔融纺丝方法,并对纤维的性能进行了概述。     

稳定射流电纺丝法制备定向排列的壳聚糖超细纤维

采用电驱动纺丝,以壳聚糖(CTS)为研究对象材料,通过引入超高分子量聚氧化乙烯(PEO)调节纺丝液的黏弹性,实现抑制电纺丝固有的射流不稳定弯曲摆动来得到单一的稳定射流,从而可以像传统工业上的干、湿法纺丝一样制备定向的超细CTS纤维(称为稳定射流电纺丝,SJES).系统地研究了SJES的工艺参数(如CTS/PEO质量比、纺丝电压、接收距离、凝固浴成分、辊筒转速等)对制备定向的超细壳聚糖纤维的影响,并通过SEM、FTIR、WAXD、纳米力学拉伸仪等研究了所制备纤维的形貌、结构与性能.结果表明,SJES法制备的CTS纤维直径在10μm以下,优化参数(如电压和辊筒转速)可使纤维直径细化到3μm左右.纤维单丝具有较高的力学性能,断裂强度和纤维模量可以分别达到(762±93)MPa和(11±6)GPa.稳定射流电纺丝方法制备的超细纤维与常规电纺丝法制备的纤维相比,具有较高的微晶取向度.     

Centrifugally spun poly(ethylene oxide) fibers rival the properties of electrospun fibers

Centrifugal force spinning (CFS), also known as centrifugal spinning, forcespinning, or rotary jet spinning, provides considerably higher production rates than electrospinning (ES), but the more widespread use of CFS as an alternative depends on the ability to produce fibers with robust thermal and mechanical properties. Here, we report the CFS of poly(ethylene oxide) (PEO) fibers made using a spinning dope formulated with acetonitrile (AcN) as the volatile solvent, and we describe the thermal and mechanical properties of the centrifugally-spun fibers. Even though the formation, diameter, and morphology of electrospun and centrifugally-spun PEO fibers are relatively well-studied, the article presents three crucial contributions: the pioneering use of PEO solutions in AcN as spinning dope, characterization of crystallinity and mechanical properties of the centrifugally-spun PEO fibers, and a comparison with the corresponding properties of electrospun fibers. We find that fiber formation occurrs for the chosen CFS conditions if polymer concentration exceeds the entanglement concentration, determined from the measured specific viscosity. Most significantly, the centrifugally spun PEO fibers display crystallinity, modulus, elongation-at-break, and fiber diameter that rival the properties of electrospun PEO fibers reported in the literature.     

Gel spinning of poly(vinyl alcohol) from dimethyl sulfoxide/water mixture

Gel spinning of poly(vinyl alcohol) (PVA) was attempted from the PVA dope prepared from the mixture of dimethyl sulfoxide (DMSO) and water. The DMSO/H₂O = 80/20 (w/w) mixture and methanol were found to be the best solvent for the spinning dope and the coagulant, respectively, to give PVA fiber with the highest drawability. PVA fiber with the highest strength and Young's modulus were obtained from the undrawn gel fibers when subjected to hot two-stage drawing under conditions such as to produce maximum drawability. Furthermore, higher draw ratios of PVA fiber were attained at 6 wt % dope by lowering the coagulating temperature of methanol. In the present work, the highest tensile strength (2.8 GPa) and the highest Young's modulus (64 GPa) were realized, when the spinning dope was prepared from PVA with DP of 5,000 and the DMSO/H₂O (80/20) mixed solvent to have the PVA concentration of 6 wt %, the coagulating temperature of methanol was ?20°C, and the two-stage drawing was carried out at 160 (first) and 200°C (second). The PVA fiber prepared under this gel spinning condition could be elongated to 45 times draw ratio. The very high drawability of PVA fibers obtained from the DMSO/H₂O (80/20) mixture dope was ascribed to the ability of the DMSO/H₂O mixture to promote gelation. © 1994 John Wiley & Sons, Inc.     

喷头拉伸对超高分子量聚乙烯后续牵伸的影响

利用干法纺丝制备超高分子量聚乙烯纤维,研究了喷头拉伸对超高分子量聚乙烯后续牵伸的影响。通过张力仪测量不同喷头拉伸倍率下的张力,计算出拉伸应力。利用拉伸应力—粘滞二元组合模型,计算机拟合出NSkT值,根据该值确定喷头拉伸倍率。结果发现,13倍的喷头拉伸能够使最大后续牵伸倍率达到23.3倍,最终的纤维强度和模量分别为30cN·dtex-1和1200cN·dtex-1。     

桑蚕丝腺体和丝纤维中金属离子的含量

用不同的测试方法, 即质子诱导X射线发射(PIXE)、电感耦合等离子体质谱(ICP-MS)和原子吸收光谱(AAS)对桑蚕丝腺体和丝纤维中金属元素的含量进行了详细的表征. 结果表明, 在桑蚕丝腺体和丝纤维中含有钠、镁、钾、钙、铜、锌、铁、锰八种金属元素, 同时还可能含有微量的铷和锶. 这些金属元素在丝腺体和各种丝纤维(蚕茧丝、强拉丝和脱胶丝)中的含量都有所变化, 而这些变化可能与之在成丝过程(丝蛋白的构象转变过程)中所起的作用有关.     

The melt hollow fiber spinning process: steady-state behavior,sensitivity and stability

The rheology of the melt hollow fiber spinning process is examined in the thin filament limit. The resulting thin filament equations are also applicable to single-phase and two-phase extensional flows. Using a novel numerical solution procedure, the sensitivity of the fiber spinning equations to material property and process variations is investigated. Fiber geometry is directly controlled by the mass flowrates of the core and clad fluids while the spinline tension is most strongly influenced by clad viscosity. A maximum can occur in the clad stress profile if a core liquid is used and the ratio of core to clad viscosity increases greatly with temperature. Isothermal spinning of high viscosity clad liquids with either a core gas or liquid is unstable for draw ratios greater than 20.2 as found for solid fibers.     

Multiband Transport in CoSb3 Prepared by Rapid Solidification

Nano‐grained CoSb₃ was prepared by melt‐spinning and subsequent spark plasma sintering. The phonon thermal conductivity of skutterudites is known to be sensitive to the kind and the amount of guest atoms. Thus, unfilled CoSb₃ can serve as model compound to study the impact of a nanostructure on the thermoelectric properties, especially the phonon thermal conductivity. Therefore, a series of materials was prepared differing only by the cooling speed during the quenching procedure. In contrast to clathrates, the microstructure of meltspun CoSb₃ was found to be sensitive to the cooling speed. Although the phonon thermal conductivity, studied by means of Flash and 3ω measurements, was found to be correlated with the grain size, the bulk density of the sintered materials had an even stronger impact. Interestingly, the reduced bulk density did not result in an increased electrical resistivity. The influence of Sb and CoSb₂ as foreign phase on the electronic properties of CoSb₃ was revealed by a multi‐band Hall effect analysis. While CoSb₂ increases the charge carrier density, the influence of the highly mobile charge carriers introduced by elemental Sb on the thermoelectric properties of the composite offer an interesting perspective for the preparation of efficient thermoelectric composite materials.     

Melt‐spun Eu8Ga16–xGe30+x Clathrates

Intermetallic clathrates are promising materials for thermoelectric applications. This is not only due to their low thermal and high electrical conductivities (“phonon glass – electron crystal”) but also due to the expectation that they are semiconductors and thus have large thermopower values. Band structure calculations of the stoichiometric compound Eu₈Ga₁₆Ge₃₀ indeed yield a semiconducting ground state. However, with conventional synthesis methods the exact 8:16:30 stoichiometry could not be reached. Herein we use the melt‐spinning technique to obtain Eu₈Ga_16–xGe_30+x samples with smaller x than previously realized. The quenching procedure and the results of the characterization of the quenched phases by X‐ray powder diffraction and electron microscopy are presented. The electrical resistivity shows that, in contrast to conventional synthesis procedures, semiconducting compounds can be produced.     

Simple Fabrication of Multicomponent Heterogeneous Fibers for Cell Co‐Culture via Microfluidic Spinning

Microfluidic spinning, as a combination of wet spinning and microfluidic technology, has been used to develop microfibers with special structures to facilitate cell 3D culture/co‐culture and microtissue formation in vitro. In this study, a simple microchip‐based microfluidic spinning strategy is presented for the fabrication of multicomponent heterogeneous calcium alginate microfibers. The use of two kinds of microchip enables the one‐step preparation of multicomponent heterogeneous microfibers with various arrangement patterns, including the preparation of one‐, two‐, and three‐component microfibers by a two‐layer microchip and preparation of four component microfibers with different arrangement by a membrane‐sandwiched three‐layer microchip. The obtained microfibers could be used to encapsulate various kinds of cells, such as the human non‐small cell lung cancer cell NCI‐H1650, the human fetal lung fibroblast HFL1, the normal pulmonary bronchial epithelial cell 16HBE, and human umbilical vein endothelial cells. By adding chitosan to the medium to keep the fibers stable, 3D long‐term in vitro cell co‐culture has been carried out up to 21 days. This method is very simple and easy to operate, continuously produces spatially well‐defined heterogeneous microfibers, has important applications for composite functional biomaterials, and shows great potential in organs‐on‐a‐chip and biomimetic systems.     

静电纺丝法制备复合纳米材料

经由溶胶-凝胶法过程,应用静电纺丝机原理,以聚乙烯醇(PVA)和无机盐(LiMn2O4)为前驱物,制备出了含有LiMn2O4无机组分的复合纳米纤维,为复合无机纳米纤维的制备方式供给了一条新的思路。实验中系统地研究了PVA的浓度对其所形成的纤维描摹特征的影响。PVA水溶液用于纺丝的最好质量分数约为8.0%。在实验过程中,随着PVA质量分数的渐渐增加,其所形成纤维的直径也随之渐渐增大,而溶液的黏度也在逐步增大,这就使得溶剂挥发变得越来越难,小液珠的表面难以构成理想的"泰勒锥",电压过小,样品溶液无法纺丝,在针头处成水滴状落在针头下方。电压过大则会在纤维丝上呈现念珠形态,阻碍样品电纺时的形貌。实验表明,在施加18kV的高电压,默认机器的其它设定条件下,依托不同质量分数的PVA溶液可制备出三种不同的纤维。     

Improvement of the spinning electrophorometer for zeta potential measurements

In this study, bubbles are held by centripetal force at the center of a rotating cylinder filled with an aqueous solution. Their velocities along the axe of rotation, after application of an electrophoretic force, are used for the calculation of the so-called electrokinetic potential. But this process necessitates the elimination of the electro-osmosis which occurs on the interior sides of the glass cylinder by superposing a concurrent force on the bubble. Efficiency of DEAE-Dextran reticulated with 1,4 Butanediol Diglycidyl Ether can be tested by the observation of a cloud of latex microspheres injected in the interior of the tube and allowed to move in respect with the application of an electric field. The experimental control of these velocity profiles proves the adequacy of the polymer for many cases such as surfactant solutions, presence of electrolytes, utilization with moderate pH.The dynamic interpretation of the electrophoretic motion of bubbles is possible by considering that small ones behave like rigid spheres moving in a rotating fluid. In the second part of this paper and in a previous publication, we have experimentally proved that the use of the theoretical expressions of the forces involved for rigid spheres is justified for small bubbles. So, the electrokinetic potential can be expressed versus the velocity, leading to possible interpretations of the adsorption on gas-water interfaces.