Electrospinning of polyvinylidene difluoride with carbon nanotubes: synergistic effects of extensional force and interfacial interaction on crystalline structures

Polyvinylidene difluoride (PVDF) solutions containing a very low concentration of single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs) of similar surface chemistry, respectively, were electrospun, and the nanofibers formed were collected using a modified rotating disk collector. The polymorphic behavior and crystal orientation of the nanofibers were studied using wide-angle X-ray diffraction and infrared spectroscopy, while the nanotube alignment and interfacial interactions in the nanofibers were probed by transmission electron microscopy and Raman spectroscopy. It is shown that the interfacial interaction between the SWCNTs and PVDF and the extensional force experienced by the nanofibers in the electrospinning and collection processes can work synergistically to induce highly oriented beta-form crystallites extensively. In contrast, the MWCNTs could not be well aligned along the nanofiber axis, which leads to a lower degree of crystal orientation.     

静电纺聚丙烯腈纳米纤维晶态结构及取向的形成

采用新型流动水浴收集方式制备出连续单向排列的静电纺聚丙烯腈(PAN)纳米初生纤维,收集静电纺丝不同阶段的静电纺PAN纳米纤维,并在热水中进行后牵伸,使其伸长至原长的2倍、3倍.通过扫描电子显微镜(SEM)、广角X射线衍射(WAXD)等方法对静电纺丝过程不同阶段的PAN纳米纤维的形貌、直径、致密性、晶态结构及取向进行了表征.研究表明,(1)在静电纺丝过程中PAN纺丝液射流受到牵伸作用,静电纺PAN纳米纤维的晶态结构形成并逐渐完善.纳米纤维的直径随着静电纺丝过程逐渐减小(从664 nm减小至353 nm),结晶度从42.55％增加至47.76％,晶区取向由37.48％提高至43.93％.纳米纤维致密性也逐渐提高(密度由1.1917 g/cm3增加至1.1943 g/cm3).(2)静电纺丝过程进入PAN射流溶剂含量较低的阶段后,继续通过静电纺丝过程提高纳米初生纤维晶态结构及取向的效果很有限,而通过热水后牵伸过程可进一步使晶态结构及取向得到有效果的完善.研究同时发现,静电纺初生纤维的晶态结构及取向与其在热水牵伸过程中的进一步完善具有相关性.     

Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets

Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CN[triple bond]N:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to approximately 1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 x 10(-6)/ degrees C along the axis of aligned nanofibers containing 20 wt % MWNTs.     

Processing and characterization of oriented electrospun poly(vinylidene fluoride) mats

Mats of highly oriented poly(vinylidene fluoride) nanofibers were electrospun by means of a conventional electrospinning equipment; the orientation, however, was obtained using a disk collector rotating at a speed of 4000 rpm and a device that reduced the influence of air displacement during nanofiber orientation. Thermal transitions of the mats were determined by differential scanning calorimetry, the predominant crystalline phase by Fourier transform infrared spectroscopy and wide‐angle X‐ray scattering and the nanofiber orientation and morphology by scanning electron microscopy. Relative permittivity, loss index, stable remnant polarization, and coercive field of the mats were also determined and compared with those obtained for a mat electrospun at 2000 rpm and an oriented commercial film. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 000: 000–000, 2012     

Enhancement of conductivity by diameter control of polyimide-based electrospun carbon nanofibers

Oxydianiline-pyromellitic dianhydride poly(amic acid) (ODA-PMDA PAA) was polymerized with a catalyst support of triethyl amine for controlling molecular weight. This polymer was used for electrospinning in the preparation of PAA nanofibers, a precursor of carbon nanofibers. Here the amount of catalyst and concentration of PAA solution were optimized to produce polyimide-based carbon nanofibers approximately 80 nm in diameter. The effects of molecular weight of PAA, bias voltage, and spinning rate on the morphology of electrospun PAA and polyimide nanofibers have been evaluated. We showed that the conductivity of the carbon nanofiber mat decreased with increasing nanofiber diameter, where the conductivity of polyimide-based carbon nanofiber mat was much higher than those of other types of carbon nanofiber mat. The key ingredient to increase conductivity in a carbon nanofiber mat was found to be the number of cross junctions between nanofibers.     

静电纺丝制备有机盐类非线性光学材料纳米纤维

采用静电纺丝技术制备的有机非线性光学材料纳米纤维可有效控制非线性光学材料的分子取向,其生色团可实现与有机单晶类似的优化排列结构,表现出了与纯生色团分子相近的宏观二阶非线性光学性质。 本文将有机盐类非线性光学材料掺杂在聚乙烯吡咯烷酮中制备出了具有各向异性结构且表面光滑、排列有序的纳米纤维薄膜,Kurtz非线性测试结果表明,随着薄膜厚度增加,其二次谐波信号强度成正比增大。     

Parameter study and characterization for polyacrylonitrile nanofibers fabricated via centrifugal spinning process

Electrospinning is currently the most popular method for producing polymer nanofibers. However, the low production rate and safety concern limit the practical use of electrospinning as a cost-effective nanofiber fabrication approach. Herein, we present a novel and simple centrifugal spinning technology that extrudes nanofibers from polymer solutions by using a high-speed rotary and perforated spinneret. Polyacrylonitrile (PAN) nanofibers were prepared by selectively varying parameters that can affect solution intrinsic properties and operational conditions. The resultant PAN nanofibers were characterized by SEM, and XRD. The correlation between fiber morphology and processing conditions was established. Results demonstrated that the fiber morphology can be easily manipulated by controlling the spinning parameters and the centrifugal spinning process is a facile approach for fabricating polymer nanofibers in a large-scale and low-cost fashion.     

丙烯腈-衣康酸基纳米纤维纱线的热稳定及碳化研究

碳纳米纤维主要以聚丙烯腈(PAN)作为前驱体,通过纺丝、热稳定、碳化等后处理工艺制备而得.但是,PAN基纳米纤维取向度低、致密性差,热稳定后环化度低,碳化后导电性差等缺点阻碍其在高性能碳纳米纤维领域的发展.因此,在PAN分子链中引入衣康酸(IA),通过溶液聚合法合成了P(AN-co-IA)共聚物并通过静电纺丝法制备了P...     

Polysulfone nanofibers prepared by electrospinning and gas/jet-electrospinning

Polysulfone nanofibers were prepared by electrospinning. The electrospinning equipment was designed in a new way, wherein the spinneret was combined with a gas jet device. The intrinsic viscosity of the used polysulfone was 0.197 dL/g in dimethyl acetamide, which was also the solvent in electrospinning. The gas used in this gas jet/electrostatic spinning was nitrogen. The relationship between the process parameters and the average diameter of polysulfone nanofibers was investigated. The main process parameters studied in this work were the voltage, the flow rate of the spinning fluid, the distance between the spinneret and the nanofiber collector and the temperature in the spinning chamber. The other important factors determining the nanometer diameter were the spinning fluid properties including its viscosity, surface tension and electrical conductivity. The average diameter and the diameter distribution of electrospinning nanofibers were measured experimentally by using scanning electron microscopy. The diameter of polysulfone nanofibers prepared by the gas jet/electrostatic spinning was in the range 50–500 nm. It was found that the diameter of nanofibers mainly depended on high voltage, the gap between the spinneret and the collector and the concentration of polymer solutions. It is concluded that the gas-jet/electrospinning is a better method than the conventional electrospinning, in that it makes the nanofibers finer and more uniform and exhibits higher efficiency in the process of electrospinning. __________ Translated from Acta Polymerica Sinica, 2005, (5) (in Chinese)     

聚丙烯腈纳米纤维的再细化

通过电纺丝法研究了溶剂种类、溶液浓度、纺丝倾斜角、聚合物分子量对纳米纤维形态和直径的影响,寻找到最佳工艺条件,并得到了平均直径为20nm的超细纤维.     

Characterization of poly(methyl methacrylate) nanofiber mats by electrospinning process

In this study, the aim is to describe the influence of electrospinning parameters on the morphology, the water wetting property and dye adsorption property of poly(methyl methacrylate) nanofiber mats. Specifically, the effects of solution concentration, solvent type, applied voltage, distance between the electrodes and particulate reinforcement on the diameter and shape of the nanofibers were investigated. All poly(methyl methacrylate) nanofiber mats contained beaded nanofiber structures. With increasing the polymer solution concentration, the average fiber diameter also increased. Poly(methyl methacrylate) nanofiber mat electrospun from dimethylformamide solution resulted in thicker fibers when compared with the mat electrospun from acetone solution. Increasing the electric potential difference between the collector and the syringe tip did not increase the average fiber diameter. Besides increasing the distance between the electrodes resulted in a decrease in the average fiber diameter. When compared with PMMA nanofiber mat, thicker fibers were obtained with silica nanoparticles reinforced nanofiber mat. According to the water contact angle measurements, all poly(methyl methacrylate) nanofiber mats revealed hydrophobic surface property. PMMA nanofiber mat with the highest water contact angle gave rise to the highest dye adsorption capacity.     

Liquid crystal fibers produced by using electrospinning technique

This paper investigates the electrospinning process of liquid crystalline polysiloxane with cholesterol as side chain (LCPC) and the influence on the morphology of the formed fibers by mixing LCPC solution with small-molecule liquid crystal, triethylamine, and poly(ethylene oxide)(PEO). The mechanical properties of single fibers were characterized by a novel approach. The results indicate that, under appropriate conditions, fine liquid crystal fibers can be obtained and the preferable mechanical properties can be achieved, especially after annealing. WXRD was used to investigate the orientation of polymer molecules in the formed fibers, suggesting that strong interaction exists between LCPC and PEO molecule in the resulting composite fibers, and polymer molecular tends to arrange regularly during electrospinning processing. This research work provides a new and facile method of using electrospinning to prepare liquid crystal fibers, which would be useful for designing the related high-performance materials.     

掺杂羧基化碳纳米管的纳米碳纤维前驱体的制备及表征

为获得结构完整、 性能优良的纳米碳纤维前驱体, 采用静电纺丝法制备了掺杂羧基化多壁碳纳米管(MWCNTs)的聚丙烯腈(PAN)纳米纤维. 用扫描电子显微镜、 偏振红外光谱、 透射电子显微镜、 拉曼光谱及拉伸性能测试等对杂化纳米纤维的微观结构和力学性能进行了研究, 分析了MWCNTs含量的影响. 实验结果表明, 5%(质量分数)的MWCNTs掺杂量为杂化纳米纤维直径的突变点, 且MWCNTs的加入有利于PAN分子链的取向, MWCNTs在PAN纤维中大体上沿纤维轴向取向分布. 3%MWCNTs/PAN杂化纳米纤维的拉伸强度和拉伸模量分别达到88.6 MPa和3.21 GPa.     

Optical birefringence and molecular orientation of electrospun polycaprolactone fibers by polarizing-interference microscopy

The potential of polarizing-interference Pluta microscope for determination of optical birefringence of individual nanofibers formed by electrospinning was shown. This technique can be applied for measurements of fiber birefringence, practically at diameter above 300 nm. The molecular orientation of individual polycaprolactone (PCL) nanofibers was determined from birefringence assuming the same orientation of both phases, crystal and amorphous. The molecular orientation was determined using DSC crystallinity, crystal intrinsic birefringence calculated for the first time for PCL from bond polarizabilities as well as estimated value of amorphous intrinsic birefringence. Our results indicate that the birefringence and thus molecular orientation are strongly inhomogeneous along the nanofibers, reflecting a complex nature of forces acting during electrospinning process. The average molecular orientation is weak if any, being dependent together with fiber thickness and crystallinity on electrospinning parameters, like applied voltage, concentration and type of solvent. The obtained results indicate that the average molecular orientation displays similar dependence on applied voltage as fiber diameter. Relatively low melting temperature of electrospun nanofibers suggests low crystal size and/or high concentration of defects in crystals. This observation corresponds with low crystallinity and molecular orientation, indicating together relatively low degree of crystal ordering due to high rate of cooling and solvent evaporation during electrospinning, limiting thus crystallization process.     

The fabrication of photosensitive self-assembly Au nanoparticles embedded in silica nanofibers by electrospinning

In this study, we demonstrated a simple, efficient, and low-cost method to fabricate large-area self-assembly Au nanoparticles (AuNPs) encapsulated within silica nanofibers (Au/SiO₂). The method is based on electrospinning and thermal decomposition of hybrid nanofibers prepared from the solution of tetraethylorthosilicate (TEOS), polyvinylpyrrolidone (PVP) and AuNPs. This study employed the electrospinning technique for the first time as a successful method for preparing a self-organized AuNP peapod chain in a silica nanofiber matrix, under mild conditions. It has the advantage of easily controlling the diameters of the silica nanofibers as well as the concentration of the AuNPs in the spinning solution. The Au/SiO₂ hybrid nanofibers fabricated by this method exhibited an obvious photoelectric response under the illumination wavelength around the Au/SiO₂ nanofibers surface plasmon resonance (SPR) absorption band, whereas no photoelectric response was observed for the pure silica fibers. The excellent characteristics of photoelectric response suggest that the electrospinning technique has a great potential for large-scale fabrication of functional nanofiber devices. The ability of coupling light responses into the nanosystems dependent on metallic nanoparticle SPR opens up new prospects for the construction of nanoscale waveguiding devices, sensors and optoelectronics.     

Fundamental study of crystallization,orientation, and electrical conductivity of electrospun PET/carbon nanotube nanofibers

The morphology, structure, and properties of polyethylene terephthalate (PET)/Carbon Nanotubes (CNT) conductive nanoweb were studied in this article. Nanocomposite nanofibers were obtained through electrospinning of PET solutions in trifluoroacetic acid (TFA)/dichloromethane (DCM) containing different concentrations and types of CNTs. Electrical conductivity measurements on nanofiber mats showed an electrical percolation threshold around 2 wt % multi‐wall carbon nanotubes (MWCNT). The morphological analysis results showed smoother nanofibers with less bead structures development when using a rotating drum collector especially at high concentrations of CNTs. From crystallographic measurements, a higher degree of crystallinity was observed with increasing CNT concentrations above electrical percolation. Spectroscopy results showed that both PET and CNT orientation increased with the level of alignment of the nanofibers when the nanotube concentration was below the electrical percolation threshold; while the orientation factor was reduced for aligned nanofibers with higher content in CNT. Considerable enhancement in mechanical properties, especially tensile modulus, was found in aligned nanofibers; at least six times higher than the modulus of random nanofibers at concentrations below percolation. The effect of alignment on the mechanical properties was less important at higher concentrations of CNTs, above the percolation threshold. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2052–2064, 2010     

静电纺丝法和气流-静电纺丝法制备聚砜纳米纤维

应用电纺法制备了聚砜纳米纤维.设计了一种新型的气流静电纺丝装置,其特点是在喷丝头上添加了喷气组件.电纺过程中所用聚砜的特性粘数为0.97dLg,溶剂为二甲基乙酰胺,载气为氮气.研究了聚砜纳米纤维的平均直径与过程参数之间的关系.研究表明影响聚砜纳米纤维的平均直径的主要因素为电压、纺丝液的流速、喷丝头与收集器之间的距离、操作温度以及纺丝液的性质(如粘度、表面张力和电导率).纳米纤维的平均直径和直径分布用扫描电镜表征.应用这种气流静电纺丝法制备的纳米纤维的直径范围是50～500nm.所得纳米纤维的直径依赖于电压、喷丝头与收集器之间的距离以及喷丝液的浓度.结果表明,采用气流静电纺丝不仅能制备较细而且均匀的纳米纤维,而且产量更高.     

Influence of solvents properties on morphology of electrospun polyurethane nanofiber mats

Segmented polyurethane (SPU) nanofiber mats were prepared by electrospinning technique using the combination of four different solvents viz. tetrahydrofuran, N,N′‐dimethyl formamide, N,N′‐dimethyl acetamide, and dimethyl sulfoxide. Morphology of the electrospun nanofibers was examined by field emission scanning electron microscope. Experimental results revealed that the morphologies of polyurethane nanofiber mats have been changed significantly with the solvent selection for the electrospinning. It was observed that the diameters and morphology of the SPU nanofibers were influenced greatly by the use of combination of solvents. The uniform polyurethane nanofibers without beads or curls could be prepared by electrospinning through the selection of combination of good conductive and good volatile solvent viz. 7.5 wt/v% of SPU in N,N′‐dimethyl formamide/tetrahydrofuran (30 : 70 v/v) solutions at 20 kV applied voltages and volume flow rate of 1 ml/min. On the basis of the results obtained from this investigation, it has been established that solvent selection is one of the driving factors for controlling the morphology of the polyurethane electrospun nanofiber mats. The well‐controlled morphology of electrospun polyurethane nanofiber mats could be useful for many potential industrial applications such as in biomedical, smart textiles, nanofiltration, and sensors. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrospinning fabrication of partially crystalline bisphenol A polycarbonate nanofibers: Effects on conformation, crystallinity, and mechanical properties

The application of an electrostatic and centrifugal field (1800 rpm) in a novel electrospinning process was shown to improve the degree of uniaxial alignment in polymer nanofibers and to enhance orientational order in polymer chains, producing bisphenol A polycarbonate (BPAPC) nanofibers with superior mechanical properties. High-speed videography showed that the additional centrifugal field effectively removed electrical bending instability and promoted molecular orientation during the electrospinning process. Infrared spectroscopic (IR) characterization revealed that the fraction of trans–trans conformers in BPAPC nanofibers reached 67% under optimal electrospinning conditions (25 kV and 1800 rpm at 25 °C). Modulated differential scanning calorimetry (MDSC) and wide-angle X-ray diffraction (WXRD) assays showed that a degree of crystallinity of 6.5% could be achieved. Moreover, two crystal phases at angles of 2θ = 17.3° and 21.9° were produced in BPAPC nanofibers. The elastic modulus of BPAPC nanofibers with a crystallinity of 6.5% was 7.11 and 5.13 GPa, as measured via atomic force microscopy (AFM) and nanoindenter (NI) experiments, respectively. These results demonstrated that the mechanical behavior of BPAPC nanofibers could be improved by conducting the proposed electrospinning technique. Moreover, BPAPC nanofibers produced through the proposed method could be potentially applied for the reinforcement of composites.