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.     

Diameter control of electrospun polyacrylonitrile/iron acetylacetonate ultrafine nanofibers

Electrospinning is the process of producing ultrafine fibers by overcoming the surface tension of a polymer solution using high voltage. In this work, the effects of both solution properties (viscosity, conductivity, and surface tension) and operational conditions (voltage, feed rate, and spinneret‐collector distance), on the structure of electrospun polyacrylonitrile nanofibers, were systematically investigated. Iron acetylacetonate was added to the electrospinning solution to control fiber diameter by selectively adjusting solution properties. It was found that, with increased salt concentration, the fiber diameter increases and then passes through a maximum due to changes in solution viscosity, conductivity, and surface tension. In addition, the fiber diameter increases with increase in voltage, feed rate, and spinneret‐collector distance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1611–1618, 2008     

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。     

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.     

A comparative study of jet formation in nozzle‐ and nozzle‐less centrifugal spinning systems

Centrifugal spinning, a recently developed approach for ultra‐fine fiber production, has attracted much attention as compared with the electrospinning, due to its high yield, no solution polarity and high‐voltage electrostatic field requirements, etc. In this study, the jet formation process and spinning parameters on jet path are explored and compared in nozzle‐ and nozzle‐less centrifugal spinning systems. For nozzle‐less centrifugal spinning, fingers are formed at the front of thin liquid film due to the theory of Rayleigh–Taylor instability. We find that the lower solution concentration and higher rotational speed favor the formation of thinner and longer fingers. Then, the critical angular velocity and initial jet velocity for nozzle‐/nozzle‐less centrifugal spinning are obtained in accordance with the balance of centrifugal force, viscous force, and surface tension. When jet leaves the spinneret, it will undergo a series of motions including necking and whipping processes, and then, a steady spiral jet path is formed with its radius getting tighter. Finally, we experimentally study the effect of rotational speed and solution concentration on jet path, which shows that the higher rotational speed results in a larger radius of jet path while the solution concentration has little effect on it. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1547–1559     

以旋转竖直铜针为收集器静电纺制备PVP螺旋型纤维绳

以竖直旋转的细铜针为接收器,聚乙烯基吡咯烷酮(PVP)/无水乙醇质量分数为10%,电压25 kV,在不同的旋转速度下纺出了PVP螺旋纤维绳.当竖直细铜针固定不转时,纺丝纤维呈松散线状结构;竖直细铜针旋转速度加快,纤维形态由松散的螺旋缠绕向紧密缠绕的趋势变化,PVP纤维在纺丝针头和接收铜丝间静电库仑引力(垂直方向),纺出纤维间的库仑斥力(水平方向),以及铜针高速旋转力(切线方向)的三重作用下,最终制得PVP螺旋微米纤维绳.用扫描电子显微镜(SEM)对其进行表征.实验结果表明,接收器旋转速度和接收距离对多螺旋结构纤维的形貌有显著影响.讨论了螺旋纤维的形成机理.     

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.     

Mass preparation of nanofibers by high pressure air‐jet split electrospinning: Effect of electric field

A novel electrospinning method using airflow, namely high pressure air‐jet split electrospinning, was proposed to fabricate polymer nanofibers with ultrahigh production rate. 7 wt % polyacrylonitrile spinning solution with a 0.157 Pa s viscosity was divided into micron size droplets by the filter screen in the front of the nozzle, and then these droplets were divided and split through high pressure airflow, which were drafted into nanofibers directly in the electric field and airflow field. In this study, the electric field distributions with different positive electrodes were simulated and their effect on fiber formation was investigated. The results show that electric field distribution and its intensity depended on electrodes area, a broader electric field distribution with a stronger intensity would bring about a larger cone angle of spraying jet region, at the same time, the contrast in the spray region enhanced. When the whole nozzle was charged, thinner fibers with about 170 nm could be prepared and the fiber production was 75.6 g/h. Compared with the conventional needle electrospinning, the throughput of nanofibers could be improved by thousands of times based on this novel electrospinning method. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 993–1001     

Nanofibers prepared by electrospinning from solutions of biobased polyamide 4

A successful preparation of polyamide 4 nanofibers via electrostatic spinning with diameters close to 100 nm is described. Polyamide 4 was prepared by the anionic ring‐opening polymerization of 2‐pyrrolidone and characterized. The effect of the system parameters (i.e., molar mass of the polymer, the solvent system) and the process parameters (i.e., the electrode‐to‐collector distance) during the electrostatic spinning have been studied. The morphology of the polyamide 4 fiber layers is given except molar mass of the polymer and the concentration of its solution primarily by the conformation of polyamide chains due to polyelectrolyte effect which was confirmed by viscosity measurements. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2203–2210     

Preparation and characterization of high‐molecular‐weight atactic poly(vinyl alcohol)/sodium alginate/silver nanocomposite by electrospinning

High‐molecular‐weight poly(vinyl alcohol) (PVA)/sodium alginate (SA)/ silver nanocomposite was successfully prepared via electrospinning technique. Water‐based colloidal silver in a PVA/SA blend solution was directly mixing without any chemical and structural modifications into PVA/SA matrix to form an organic‐metallic nanocomposite. The effect of the addition of silver colloidal solution on the PVA/SA/silver nanocomposite was investigated through a series of experiments varying molecular weight of PVA and electrospinning processing parameters such as concentration of PVA solution, PVA/SA blend ratio, applied voltage, and tip‐to‐collector distance. In the case of PVA with number‐average degree of polymerization of 1700, by increasing the amount of SA in spinning solution, the morphology was changed from fine uniform fiber to beaded fiber or bead‐on‐string fiber structure. Increase of the amount of silver colloidal solution resulted in higher charge density on the surface of ejected jet during spinning, thus more electric charges carried by the electrospinning jet. As the charge density increased, the diameter of the nanocomposites became smaller. Transmission electron microscopy images showed that the dense silver nanoparticles were well separately dispersed in PVA/SA matrix. Energy‐disperse X‐ray analysis indicated that carbon, oxygen, natrium, and silver were the principle element of PVA/SA/silver nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1916–1926, 2009     

Electrospinning Process of Thermo-sensitive Poly(N-isopropylacrylamide) /poly (2-acrylamido-2-methylpropanesulfonic acid) Nanofibers

Poly (N-isopropylacrylamide)/poly (2-acrylamido-2-methylpropanesulfonic acid) (PNIPAAm/PAMPS) nanofibers was prepared using the electrospinning technique. The electrospinning process parameters such as solution concentration, voltage, receiver distance and flow rate were determined by the orthogonal experiments. The appropriate electrospinning parameters were 7.0% of solution concentration, 10.0 kV of voltage, 20 cm of distance and 3.1 μL·min^?1 of flow rate, respectively. The major factor affecting the nanofibers diameter was the solution concentration and the diameter increased with the solution concentration. The Fourier-transform infrared spectroscopy (FTIR) was conducted to characterize the structure of the components for electrospinning. Scanning electron microscopy (SEM) was taken to observe the morphology, and the contact angle (CA) measuring was carried out to determine the wettability of the nanofibers with temperatures. The results of SEM observation showed that the surfaces of nanofibers were smooth with uniform fibrous diameters and without the formation of beads. The CA detections showed that the electrospun PNIPAAm/PAMPS nanofibers exhibited thermo-sensitivity of hydrophilicity at 20°C and hydrophobicity at 40°C.     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Crimped polymer nanofibres by air-driven electrospinning

Electrospinning is a well-known process for producing sub-micron scale polymer filaments through an electrostatic field. This paper presents a very simple “confined” air-driven electrospinning system, in which polyamide nanofibres are produced in the form of continuous crimped filaments. The reported system consists of a vertical cylinder with a weak tangential air-flow feeding from the top, placed between the capillary source electrode and the grounded target collector. The air-flow drives the polymer jet inside the electrostatic field, curls up the filament and reduces the deposition area on the collector surface. Numerical evaluations of both the electrostatic field and the air-flow path within the chamber are reported. The proposed configuration has been successfully tested electrospinning a solution of polyamide-6 in formic acid, varying the applied voltage and the distance between the electrodes. SEM observations of the electrospun fibres revealed that a large amount of crimped nanofibres was produced free from bead defects.     

Fabrication and characterization of zein-based nanofibrous scaffolds by an electrospinning method

Electrospun zein membranes were prepared using DMF as solvent. By changing the solution concentration, the electrospinning voltage and the distance between the spinneret and collector, nanofibrous meshes without bead defects could be obtained. In order to improve the mechanical strength of the hydrated zein meshes, core-shell-structured nanofibrous membranes with PCL as the core material and zein forming the shell were prepared by coaxial electrospinning. The core-shell structure of the composite fibers was confirmed by SEM characterization of the fibers, either extracted with chloroform to remove the inner PCL, or elongated to expose their cross-section. The composition and average diameter of the composite fibers could be modulated by the feed rate of the inner PCL solution. It was found that the core-shell fibrous membranes have similar wettability to the electrospun zein mesh. The presence of PCL in the fibers could significantly improve the mechanical properties of the zein membrane.     

无针式静电纺丝喷头几何形状对电场分布规律的影响机理

根据射流的质量守恒、 电荷守恒和动量守恒分析稳态射流的运动过程, 建立了控制方程组; 应用有限元分析软件COMSOL Multiphysics 5.0建立3种无针式喷头模型, 分析其外部电场的分布规律. 研究发现, 在由典型圆柱体喷头到增加辅助电极的阶梯轴喷头的几何形状变化过程中, 电场强度分布受两侧添加的辅助电极角度和增加回转体数量及回转体直径的影响, 通过设计, 电场被逐步优化. 对无针式静电纺丝装置的生产效率及纤维质量的提高具有重要意义.     

Surface Functionalization of PEO Nanofibers Using a TiO2 Suspension as Sheath Fluid in a Modified Coaxial Electrospinning Process

Convenient and integration fabrication process is a key issue for the application of functional nanofibers. A surface functionalization method was developed based on coaxial electrospinning to produce ultraviolet(UV) protection nanofibers. The titanium dioxide(TiO₂) nanoparticles suspension was delivered through the shell channel of the coaxial spinneret, by which the aggregation of TiO₂ nanoparticles was overcome and the distribution uniformity on the surface of polyethylene oxide(PEO) nanofiber was obtained. With the content of TiO₂ increasing from 0 to 3%(mass fraction), the average diameter of nanofibers increased from (380±30) nm to (480±100) nm. The surface functionalization can be realized during the electrospinning process to gain PEO/TiO₂ composite nanofibers directly. The uniform distribution of TiO₂ nanoparticles on the surface of nanofibers enhanced the UV absorption and resistance performance. The maximum UV protection factor(UPF) value of composite nanofibers reaches 2751. This work presented a novel surface-functionalized way for the preparation of composite nanofiber, which has great application potential in the field of micro/nano system integration fabrication.     

Sol-Gel Co-Electrospun LiNiO2 Hollow Nanofibers

Using a coaxial capillary spinneret electrospinning technique combined with the sol-gel method, the nickelic xerogel hollow nanofibers first were prepared and the polycrystalline LiNiO₂ hollow nanofibers were obtained after sintering. The obtained hollow nanofibers were about 500 nm to 4 µm in outer diameter, and were made up of 20 ～ 30 nm nanocrystals. The xerogel hollow nanofibers and those calcined at different temperatures were characterized by thermogravimetric (TG) analysis, Fourier transform infrared (FTIR) spectrum, x-ray diffractometry (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).     

Characterization of gelatin nanofibers electrospun using ethanol/formic acid/water as a solvent

Gelatin nanofibers were prepared via electrospinning using aqueous solutions of formic acid and ethanol as the solvent instead of cytotoxic solvents. The resulting mat was further crosslinked with glutaraldehyde (GTA). The influence of the storing time on the viscosity and gel point of the solution was investigated. The gelatin nanofibers were examined using a field emission scanning electron microscope (FESEM) for the fiber size and morphology. The lowest diameter of gelatin fiber (85 nm, without beads) was achieved when the gelatin concentration was 20 wt% and electrospinning was conducted with a voltage of 20 kV over a distance of 10 cm at ambient temperature. The results from differential scanning calorimetry (DSC) showed that the softening temperature of gelatin nanofibers crosslinked with GTA was elevated. In addition, GTA‐crosslinked gelatin nanofibers exhibited cell compatibility for mouse mesangial cells (CRL 1927). Copyright © 2008 John Wiley & Sons, Ltd.     

Design of a novel co‐electrospinning system with flat spinneret for producing helical nanofibers

A kind of biomimetic fibers of helical structures at nanoscale has attracted increasing interest. In this study, a novel co‐electrospinning setup with a designed flat spinneret, used for the fabrication of helical nanofibers, is reported in this study. Poly(m‐phenylene isophthalamide) (Nomex) and Thermoplastic polyurethane (TPU) are chosen as the two components in co‐electrospinning. To display the efficiency for producing helical fibers, a generally used core–shell needle spinneret is used for comparison. The effect of the uniformity of electric field distribution created by these two types of spinnerets on the jet motion and the resultant helical fibers is developed, with systematical simulation and experimental research. The results showed that the co‐electrospinning system with the newly designed flat spinneret can produce helical nanofibers efficiently. Compared with the needle spinneret, the flat spinneret created more uniform electric field, leading to better morphology and structure of the resultant helical fibers. In addition, an approach to achieve the scale‐up of this co‐electrospinning system is developed. This novel design is expected to provide a promising method to fabricate nanofiber materials with helical structures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1496–1505     

Electrospinning process using field‐controllable electrodes

For the production of uniaxially oriented nanofibers and a three‐dimensional, biodegradable scaffold consisting of nanosized fibers, an electrospinning process was modified with a cylindrical auxiliary electrode that was connected to a spinning nozzle to stabilize the initially spun solution and a parallel‐plate electrode as a collector generating an alternating‐current electric field for collecting spun jets. With the complex electric field in the electrospinning process, biodegradable poly(ε‐caprolactone) nanofibers were stacked on a thin, dielectric substrate covering the electrode according to a predetermined design. The degree of orientation of spun nanofibers to the field direction of a target electrode was highly dependent on the applied frequency and field strength of the target electrode. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1426–1433, 2006