Electrospinning of thermoplastic polyurethane microfibers and nanofibers from polymer solution and melt

Electrospinning technique was used to produce ultrafine fibers from thermoplastic polyurethane (TPU). A direct comparison between melt and solution electrospinning of TPU was provided for the evaluation of process–structure relationship. It was found that the deposition rate of melt electrospinning (0.6 g h^?1) is four times higher than that of solution electrospinning (0.125 g h^?1) for TPU under the same processing condition. However, the average fiber diameters of solution electrospun TPUs (220–280 nm) were much lower than those of melt electrospun TPUs (4–8 μm). The effect of processing variables including collection distance and electric field strength on the electrospun fiber diameter and morphology was also studied. The findings indicate that increasing the electric field strength yielded more electrical forces acting on polymer jet and resulted in a decrease in fiber diameter as a result of more fiber drawing in both solution and melt electrospun fibers. It was also demonstrated that increasing the collection distance led to an improvement in the solidification of melt electrospun fibers and thus less fused fibers were obtained. Finally, a close investigation of fiber structures revealed that melt electrospun TPU fibers had smooth surface, whereas solution electrospun TPU fibers showed high intensity of cracks on the fiber surface. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrospinning of poly(hydroxybutyrate‐co‐hydroxyvalerate) fibrous tissue engineering scaffolds in two different electric fields

Poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) was electrospun into ultrafine fibrous nonwoven mats. Different from the conventional electrospinning process, which involves a positively charged conductive needle and a grounded fiber collector (i.e., positive voltage (PV) electrospinning), pseudo‐negative voltage (NV) electrospinning, which adopted a setup such that the needle was grounded and the fiber collector was positively charged, was investigated for making ultrafine PHBV fibers. For pseudo‐NV electrospinning, the effects of various electrospinning parameters on fiber morphology and diameter were assessed systematically. The average diameters of PHBV fibers electrospun via pseudo‐NVs were compared with those of PHBV fibers electrospun via PVs. With either PV electrospinning or pseudo‐NV electrospinning, the average diameters of electrospun fibers ranged between 500 nm and 4 μm, and they could be controlled by varying the electrospinning parameters. The scientific significance and technological implication of fiber formation by PV electrospinning and pseudo‐NV electrospinning in the field of tissue engineering were discussed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

静电纺超细相变纤维的研究进展

相变纤维(PCF)已被广泛研究并用作高性能非织造布和涂料。随着纤维制造技术的发展,静电纺超细PCF已经被开发和研究。综述了静电纺丝技术对超细(亚微米)PCF的研究和发展状况。讨论了使用长链脂肪烃(或石蜡)、聚乙二醇、脂肪酸(及其共晶体)和其它固液相变材料(PCM)作为潜热储存材料的静电纺超细PCF的形态、组成和热性质,为制造具有所需热物理性质的超细PCF提供指导。     

气流辅助聚合物熔体微分电纺流道优化设计

为进一步降低熔体微分电纺的纤维直径,使其达到纳米尺度,在现有直线狭缝电纺喷头的基础上设计了可以使高速气流汇聚的“V”形风道,通过高速气流对熔体微分射流进行二次牵伸细化。采用实验研究和数值模拟相结合的方法,以射流间距和喷头端电场强度为指标,研究了“V”形风道结构、材质对电纺微分射流的影响。研究结果表明,风道结构会不可避免地削弱喷头端的电场强度、降低射流的效率。增加风刀与喷头尖端的头端凸出量以及采用不导电的聚醚醚酮作为风刀材质都可以有效地降低风刀对射流效率的影响,而风道的宽度对喷头端电场强度影响不大。在优化的风刀结构和材质的基础上,成功制备了平均直径为825 nm的熔体电纺超细纤维。研究证实在气流辅助牵伸的作用下,直线狭缝电纺能够实现熔体电纺超细纤维的批量制备。     

Wire Melt Electrospinning of Thin Polymeric Fibers via Strong Electrostatic Field Gradients

Here, a novel melt electrospinning method to produce few‐micron and nanometer thick fibers is presented, in which a polymer‐coated wire with a sharp tip is used as the polymer source. The polymer coating is melted via Joule heating of the source wire and extracted toward the target via electrostatic forces. The high viscosity and low charge density of polymer melts lower their stretchability in melt. The method relies on confining the Taylor cone and reducing initial jet diameter via concentrated electrostatic fields as a means to reduce the diameter of fibers. As a result, the initial jet diameter and the final fiber diameter are reduced by an order of magnitude of three to ten times, respectively, using wire melt electrospinning compared to syringe‐ and edge‐based electrospinning. The fiber diameter melt electrospun via this novel method is 1.0 ± 0.9 µm, considerably thinner than conventional melt electrospinning techniques. The generation of thin fibers are explained in terms of the electrostatic field around the wire tip, as obtained from finite element analysis (FEA), which controls the size and shape of the melt electrospun jet.     

The mechanism of the controlled deposition of electrospun fibers

The controlled deposition of electrospun fibers means that the electrospun fibers can be collected in a limited and specified area and can present better applications in the fields of medical treatment, garment making, and 3D printing. In order to study the mechanism of the controlled deposition of electrospun fibers, simulation and experimental methods were used. Specifically, in the electrospinning experiment, circular copper sheets of different diameters were used as collectors. The effect of different collector areas on the morphology of fiber deposition was discussed. The electric field distribution of electrospinning with different specifications of collectors was simulated correspondingly. The experimental results show that, as compared to the traditional large flat collector, the area where the electrospun fibers are deposited is significantly reduced when a smaller circular copper plate was used as a collector. The smaller the area of the collector, the more the fibers tend to deposit at the center area of the collector, and the more likely the morphology of the product formed by the fiber deposition to exhibit a center protrusion shape. The controlled deposition of the electrospun fiber technology can provide more opportunities for the application of the electrospinning technology.     

Poly(lactide) nanofibers produced by a melt‐electrospinning system with a laser melting device

A new melt‐electrospinning system equipped with a CO₂‐laser melting device was developed. Rod‐like samples were prepared from poly(lactide) pellets, and then fibers were produced from the samples using the new system. The effects of producing conditions on the fiber diameter were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were obtained: (i) in a special case, fibers having an average fiber diameter smaller than 1 μm could be obtained using the system developed; (ii) the fiber diameter could be decreased with increased laser output power, but the physical properties of the fibers such as the melting point and the molecular weight were decreased; and (iii) the electrospun fibers exhibited an amorphous state, and the annealed fibers exhibited an isotropic crystal orientation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1640–1645, 2007     

Morphologies and crystal structures of styrene–acrylonitrile/isotactic polypropylene ultrafine fibers fabricated by melt electrospinning

Ultrafine fibers or fiber web is an attractive material for its high aspect ratio or porous structure which is welcomed in various applications. In this study, ultrafine fibers (5–10 μm) of styrene–acrylonitrile (SAN) copolymer/isotactic polypropylene (iPP) blends were produced by melt electrospinning, SAN acted as a polymeric nucleating agent (PNA) in iPP fibers. Wide‐angle X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and polarized optical microscopy were used to investigate the morphologies and the crystal structures of SAN/iPP electrospun fibers. The results showed that SAN/iPP melt formed microfibers with different morphologies and crystallinities through electrostatic stretching. The morphological distribution of SAN in iPP fibers depended on the SAN content, and the distribution influenced its nucleating activity and the final crystal structure of SAN/iPP electrospun fibers. After annealing treatment, the molecular chains of iPP in the confined SAN/iPP microfibers disorientated and rearranged, leading to the formation of a mixture of α‐ and γ‐crystal forms. The relative amount of the γ‐crystal form depended on PNA's concentration, annealing temperature and annealing time. Melt electrospun iPP fibers prepared in this study were collected as fiber webs that can be used for protective clothing material, filtration media, reinforcement for composites, and so on. POLYM. ENG. SCI., 53:2674–2682, 2013. © 2013 Society of Plastics Engineers     

Porous Electrospun PES/PEG Ultrafine Fibers for the Removal of Endocrine Disruptors

In this work, porous polyethersulfone (PES)/polyethylene glycol (PEG) ultrafine fibers were prepared via electrospinning technique, and then were used to removing endocrine disrupters from their aqueous solutions. The surface and the internal structures of PES/PEG ultrafine fibers were characterized by scanning electron microscopy (SEM) and the result showed that they were both porous. The porous electrospun PES/PEG ultrafine fibers can remove endocrine disrupters such as biphenyl A (BPA) and biphenyl (BP) effectively. Compared with pure PES ultrafine fibers, PES/PEG ultrafine fibers showed larger adsorption capacity and faster kinetics of uptaking target species. The hydrophilic properties and the porosity of porous PES/PEG ultrafine fibers can be controlled by adding hydrophilic materials such as polyethylene glycol (PEG), which can improve the adsorption properties of porous PES/PEG ultrafine fibers significantly. The results showed that porous electrospun PES/PEG ultrafine fibers had the potential to be used in environmental application and water treatment.     

静电纺丝聚合物加工技术及其应用

电纺丝是一种使带电荷的聚合物溶液或熔体在静电场中射流来制备聚合物超细纤维的加工方法。电纺纤维织物的空隙率高、比表面积大、构架织物的直径处于纳米级别。综述了电纺丝技术的发展以及过程参数对电纺丝织物的影响。介绍了最新研究的许多新颖纤维品种、它们的微观形貌、制备方法以及不同纳米纤维在不同领域中的应用。     

Implication of stable jet length in electrospinning for collecting well-aligned ultrafine PLLA fibers

Stable jet based electrospinning (SJES) has recently emerged as a straight-forward approach for the continuous fabrication of well-aligned ultrafine fibers and fiber assemblies. This article reports on the influences of some pivotal solution parameters including solvent, polymer molecular weight, and concentration on the formation of a stable jet length (SJL) in electrospinning of a biodegradable polymer, poly(l-lactide acid) (PLLA). Our results reveal that enhanced critical SJL can be achieved at lower solvent dielectric constant and higher viscoelasticity of solutions contributed by the molecular weight and concentration, beneficial for achieving higher degree of fiber alignment. Moreover, hierarchical orderliness including the macroscopic fiber alignment, the elongation along the fiber direction of microscopic pores on the fiber surface and the molecular orientation within the electrospun PLLA fibers, can be modulated by the SJL. The molecular orientation and crystallinity of the aligned PLLA fibers from SJES increased with increasing the SJLs. Also, the measured tensile properties data suggest a positive trend associated with the SJL. This study thus allows establishing a solid correlation of SJL with respect to the macroscopic alignment, internal molecular structural development, and mechanical performance of the electrospun ultrafine PLLA fibers pertaining to the SJES.     

Structural properties and superhydrophobicity of electrospun polypropylene fibers from solution and melt

Isotactic polypropylene (iPP) has successfully been electrospun from both solution and melt using an elevated temperature setup. First, PP nanofibers with two different average diameters (0.8 μm and 9.6 μm) were obtained via electrospinning of iPP in decalin, and the effect of deformation and solidification on the morphological and structural features of the resulting fibers was studied. Secondly, melt electrospun PP fibers with two different average diameters were also fabricated to compare the structures with those of solution electrospun PP fibers. DSC and XRD results show that β form crystals which can increase the impact strength and toughness of electrospun fibers are present in sub-micron scale PP fibers from solution, while fibers from melt mostly show α form crystals. The annealed fibers have changed their morphological forms into α and γ crystal forms. Finally, it is observed that electrospun PP fiber webs both from solution and melt exhibit superhydrophobicity with a water contact angle about 151° which is substantially higher than those of a commercial PP non-woven web and a compression molded PP film, 104° and 112°, respectively. Such superior hydrophobicity was observed for all PP electrospun fibers and it was not altered by the processing scheme (solution or melt) or fiber diameter (sub-micron or micron). Enhanced hydrophobicity of electrospun PP fiber webs contribute to excellent barrier performance without losing permeability when they are applied to protective clothing.     

静电纺丝技术及其应用

静电纺丝是一种新技术,它可制备出直径为纳米级的丝,最小直径可至1纳米。介绍了电纺丝制备原理、设备、影响纤维性能的主要工艺参数,综述了静电纺丝技术应用的最新进展,如制备长度无限可控的微米／纳米管子、超净纳米过滤材料等。     

Melt electrospinning from poly(L‐lactide) rods coated with poly(ethylene‐co‐vinyl alcohol)

Rodlike poly(L ‐lactide) (PLLA) samples coated with poly(ethylene‐co‐vinyl alcohol) (EVOH) were made. Fibers were produced from these rodlike samples by using a melt electrospinning system equipped with a laser irradiating device, and the effects of EVOH content and the processing parameters of the melt electrospinning on fiber diameters were investigated. We also studied the fiber formation mechanism from the rods during the laser melt electrospinning process. The following conclusions were reached: (i) coating of EVOH on PLLA rods has a remarkable effect on decreasing fiber diameter from 3 μm to around 1 μm; (ii) increases in the electric field strength and temperature of spinning space decrease the average diameter of fibers produced from pure PLLA rods, and longer collector distance leads to lager PLLA fiber diameter; and (iii) the migration of PLLA component from the core to the surface of electrospun fibers takes place during the fiber formation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of TPU micro/nanofibers by a laser melt‐electrospinning system

Laser melt electrospinning is a novel technology to fabricate scaffolds in the tissue engineering applications. The melt electrospinning is much safer than the conventional solution electrospinning due to without solvent effect. In this study, thermoplastic polyurethane (TPU) micro/nanofibers were successfully prepared by using this method. The effects of laser current and applied voltage on the fibers morphologies were investigated by scanning electron microscopy. The thermal behaviors and crystallization conditions of the TPU under different states were demonstrated by differential scanning calorimetry and X‐ray diffraction analysis. The mechanical property and the specific surface area of the TPU fibers membranes were also studied. All the analysis results showed that the effects of laser current and applied voltage on the average fiber diameter were complicated, the average fiber diameter ranging from 1.70 to 2.53 µm; the TPU is not an easily crystallized material; the electrospun fibers exhibited an amorphous phase; the average elongation at break laser of the electrospun TPU fiber membranes is about 134%; the average tensile strength is about 1.02 MPa and the specific surface area of the electrospun TPU fiber membrane is about 199 m²/g. POLYM. ENG. SCI., 54:1412–1417, 2014. © 2013 Society of Plastics Engineers     

Effect of applied voltage on diameter and morphology of ultrafine fibers in bubble electrospinning

A novel electrospinning process, bubble electrospinning, was used to produce porous nonwoven fibrous mats, of which the fiber diameter can range from nano‐ to microscales. The deformation of a charged bubble, from which multiple jets were ejected, was observed using a high‐speed motion camera. The effects of different applied voltages on diameter, morphology, and structure of bubble‐electrospun ultrafine fibers were theoretically analyzed and then experimentally validated by scanning electron microscopy and atomic force microscopy. The results showed that the average diameter of fibers increased with the increase of the applied voltage in bubble electrospinning, which is quite different from that in traditional electrospinning process under the similar conditions. The number of beaded fibers decreased with increasing applied voltage. Additionally, the crystallinities of polyvinylpyrrolidone ultrafine fibers obtained in this process were higher than that of polyvinylpyrrolidone powders. The production rate of bubble electrospinning was higher than that of the traditional electrospinning. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrospinning functional nanoscale fibers: a perspective for the future

Over the past decade, electrospinning has grown from a small niche process to a widely used fiber formation technique. Applying a strong electric potential on a polymer solution or melt produces nanoscale fibers. These nanofibers form non‐woven textile mats, oriented fibrous bundles and even three‐dimensional structured scaffolds, all with large surface areas and high porosity. Major applications of electrospun membranes include tissue engineering, controlled drug delivery, sensing, separations, filtration, catalysis and nanowires. This perspective article highlights many recent advances in electrospun fibers for functional applications, with an emphasis on the advantages and proposed technologies for these non‐woven fibrous scaffolds. Copyright © 2007 Society of Chemical Industry     

Synthesis of ultrafine poly(styrene‐maleic anhydride) and polystyrene fibers by electrospinning

Fiber formation from atactic polystyrene (aPS) and alternating poly(styrene‐maleic anhydride) (PSMA) synthesized by free radical polymerization (AIBN, 90°C, 4 h) were investigated by electrospinning from various solutions. aPS was soluble in dimethylformamide (DMF), tetrahydrofuran (THF), toluene, styrene, and benzene, whereas PSMA was soluble in acetone, DMF, THF, dimethylsulfoxide (DMSO), ethyl acetate, and methanol. aPS fibers could be electrospun from 15 to 20% DMF and 20% THF solutions, but not from styrene nor toluene. PSMA, on the other hand, could be efficiently electrospun into fibers from DMF and DMSO at 20 and 25%, respectively. Few PSMA fibers were, however, produced from acetone, THF, or ethyl acetate solutions. Results showed that solvent properties and polymer–solvent miscibility strongly influenced the fiber formation from electrospinning. The addition of solvents, such as THF, generally improved the fiber uniformity and reduced fiber sizes for both polymers. The nonsolvents, however, had opposing effects on the two polymers, i.e., significantly reducing PSMA fiber diameters to 200 to 300 nm, creating larger and irregularly shaped aPS fibers. The ability to incorporate the styrene monomer and divinylbenzene crosslinker in aPS fibers as well as to hydrolyze PSMA fibers with diluted NaOH solutions demonstrated potential for post‐electrospinning reactions and modification of these ultrafine fibers for reactive support materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of novel ultrafine fibers based on DNA and poly(ethylene oxide) by electrospinning from aqueous solutions

Novel DNA/Polyethyleneoxide (PEO) electrospun fibers were obtained from aqueous solution. Key solution properties related to electrospinning: conductivity, surface tension and viscosity were determined. The ionic conductivity of the solution increased significantly with the addition of DNA and only slightly with increasing amounts of PEO; the surface tension decreased with the addition of PEO; the viscosity increased with the addition of either DNA or PEO. It was found that solutions containing both DNA and PEO had ideal properties for electrospinning. The use of these solutions resulted in the formation of ultrafine fibrous mats with fiber diameters of 50–250 nm. It was also found that the average diameter of electrospun fibers decreased with decreased feed rate, increased tip-to-collector distance and increase in the potential employed during electrospinning.     

An investigation into the influence of electrospinning parameters on the diameter and alignment of poly(hydroxybutyrate‐co‐hydroxyvalerate) fibers

Electrospinning is an effective technology for the fabrication of ultrafine fibers, which can be the basic component of a tissue engineering scaffold. In tissue engineering, because cells seeded on fibrous scaffolds with varying fiber diameters and morphologies exhibit different responses, it is critical to control these characteristics of electrospun fibers. The diameter and morphology of electrospun fibers can be influenced by many processing parameters (e.g., electrospinning voltage, needle inner diameter, solution feeding rate, rotational speed of the fiber‐collecting cylinder, and working distance) and solution properties (polymer solution concentration and conductivity). In this study, a factorial design approach was used to systematically investigate the degree of influence of each of these parameters on fiber diameter, degree of fiber alignment, and their possible synergetic effects, using a natural biodegradable polymer, poly(hydroxybutyrate‐co‐hydroxyvalerate), for the electrospinning experiments. It was found that the solution concentration invoked the highest main effect on fiber diameter, whereas both rotational speed of the fiber‐collecting cylinder and addition of a conductivity‐enhancing salt could significantly affect the degree of fiber alignment. By carefully controlling the electrospinning parameters and solution properties, fibrous scaffolds of desired characteristics could be made to meet the requirements of different tissue engineering applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011