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     

Electric current as a control variable in the electrospinning process

In the electrospinning process submicron‐diameter polymer fibers can be produced when a high potential difference is applied to a polymer drop suspended at the tip of a capillary. The electrospinning process is affected by a wide range of parameters, because of which controlling the properties of the fibers is difficult. This is the major hurdle in the development of practical applications of electrospun fibers along with its low productivity. Here we are proposing to use the electric current in the electrospinning process to control the “quality of the fibers”. Electrospinning of a solution of polyacrylonitrile in dimethylformamide (PAN/DMF) was done by applying a programmed variable flow rate at different constant voltages. The electric current in the process was measured in real time. Four types of jet regimes were observed, electric current and the morphology of the fibers corresponding to these regimes were analyzed. A relation between the electric current, type of jet and morphology of the fibers has been established. The mechanical properties of electrospun fiber mats were also measured by a tensile testing method. POLYM. ENG. SCI. 46:954–959, 2006. © 2006 Society of Plastics Engineers     

熔体直写电纺聚己内酯纤维有序沉积工艺

目前聚合物熔体电纺技术制备的纤维大多以杂乱无序的无纺布形式存在,限制了电纺技术在组织工程支架以及机器人等需要有序结构领域的应用。本文将熔体电纺技术与三维运动平台相结合,采用自主设计的熔体电纺可控成型实验装置,对聚己内酯（PCL）进行熔体直写静电纺丝,获得了有序纤维。研究了喷头移动速度、接收距离和纺丝电压对熔体直写电纺纤维沉积形貌的影响。结果表明,纤维直径随着喷头移速、接收距离和纺丝电压的增大而减小,其中接收距离的改变对直径的影响最为显著;接收距离的增大虽然有利于纤维的细化,但是距离过大会使纤维沉积的有序性变差;当射流下落速度与喷头移动速度相匹配时,射流才能实现有序沉积;增大接收距离和纺丝电压会引起射流鞭动,需要相应地增大喷头移动速度才能实现有序沉积。     

Electrospinning of polymer melts: Phenomenological observations

Melt electrospinning is an alternative to solution electrospinning, however, melt electrospinning has typically resulted in fibers with diameters of tens of microns. In this paper we demonstrate that polypropylene fibers can be reduced from 35 ± 8 μm in diameter, to 840 ± 190 nm with a viscosity-reducing additive. Melt electrospun blends of poly(ethylene glycol)-block-poly(?-caprolactone) (PEG₄₇-b-PCL₉₅) and poly(?-caprolactone) (PCL) produced fibers with micron-scale diameters (2.0 ± 0.3 μm); this was lowered to 270 ± 100 nm by using the gap method of alignment for collection. The collected melt electrospun fibers often fused together where they touched, allowing the stabilization of relatively thick non-woven felts. The melt electrospun collection also included coiled circles and looped patterns of fibers approximately 150-250 μm in diameter. The polymer jet was visible between the collector and spinneret for particularly significant lengths, and underwent coiling and buckling instabilities close to the collector. The focused deposition of melt electrospun fibers was maintained when multiple jets were observed, with the collections from multiple jets separated by 3.8 ± 0.5 mm for a 5 cm collector gap. The frequent fusion points between melt electrospun fibers, and a reduction in diameter for the gap method of alignment, indicated that the melt electrospun fibers are still slightly molten at collection.     

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.     

Effects of the spin line temperature profile and melt index of poly(propylene) on melt‐electrospinning

Effects of the spin line temperature and melt index of polymer on fiber formation by the melt‐electrospinning process have been studied. Employing four levels of primary heating temperatures and two levels of secondary heating temperatures provided the necessary temperature profiles. Cooling time was altered through variation in tip‐to‐collector distance. Effects of the polymer melt index were also investigated using two types of poly(propylene) with different melt index values. Changes in diameter and structure of the electrospun fibers were then observed using scanning electron microscopy and differential scanning calorimetry. It is worth to note that providing enough cooling time in the spin line is effective in producing finer fibers. However, introducing the higher heating temperature in the spin line adversely affected fibrous shape formation. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

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     

The effects of processing parameters on the morphology of PLA/PEG melt electrospun fibers

Electrospinning of a polymer melt is an ideal technique to produce highly porous nanofibrous or microfibrous scaffolds appropriate for biomedical applications. In recent decades, melt electrospinning has been known as an eco‐friendly procedure as it eliminates the cytotoxic effects of the solvents used in solution electrospinning. In this work, the effects of spinning conditions such as temperature, applied voltage, nozzle to collector distance and collector type as well as polyethylene glycol (PEG) concentration on the diameter of melt electrospun polylactic acid (PLA)/PEG fibers were studied. The thermal stability of PLA/PEG blends was monitored through TGA and rheometry. Morphological investigations were carried out via optical and scanning electron microscopy. Based on the results, blends were almost stable over the temperature range of melt electrospinning (170 ? 230 °C) and a short spinning time of 5 min. To obtain non‐woven meshes with uniform fiber morphologies, experimental parameters were optimized using ANOVA. While increasing the temperature, applied voltage and PEG content resulted in thinner fibers, PEG concentration was the most influential factor on the fiber diameter. In addition, a nozzle to collector distance of 10 cm was found to be the most suitable for preparing uniform non‐woven PLA/PEG meshes. At higher PEG concentrations, alterations in the collector distance did not affect the uniformity of fibers, although at lower distances vigorous bending instabilities due to polarity augmentation and viscosity reduction resulted in curly fibrous meshes. Finally, the finest and submicron scale fibers were obtained through melt electrospinning of PLA/PEG (70/30) blend collected on a metallic frame. © 2017 Society of Chemical Industry     

Morphology,structure, and properties of metal oxide/polymer nanocomposite electrospun mats

Adding nanoparticles into polymer solutions before electrospinning creates unique hierarchical morphologies dispersed throughout small diameter nanoparticle‐polymeric fibers. Effects of polymer composition, nanoparticle (NP) type, loading, and electrospinning voltage conditions were studied. As examples, indium, iron, and titanium oxide engineered nanoparticles (NPs) were dispersed into polyvinylpyrrolidone or polystyrene and electrospun. NP loadings below 5 wt % did not affect critical voltage required for Taylor cone formation, whereas higher NP loadings require higher critical voltages. Polymeric fiber thickness and macroscopic morphology is not impacted by up to 5 wt % NP loadings, and NP dispersion throughout the fibers were similar to their dispersion in initial polymer suspension. NP loadings above 5 wt % increased viscosity, which decrease subsequent fiber diameter. Experiments in water containing inorganic and organic pollutants in water demonstrate that the polymer is largely nonporous. This work enables design of multifunctional nanomaterial‐polymer composite fibers for wide‐ranging applications such as water and air treatment. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43811.     

The morphology of electrospun polystyrene fibers

Electrospinning is a process of electrostatic fiber formation which uses electrical forces to produce polymer nanofibers from polymer solution. The electrospinning system consists of a syringe feeder system, a collector system, and a high power supplier. The important parameters in the morphology of electrospun polystyrene fibers are concentration, applied voltage, and solvent properties. Higher concentrations of the polymer solution form thicker fibers and fewer beads. When the concentration is 7 wt%, electrospun fibers have an average diameter of 340 nm, but as the concentration of PS increases to 17 wt%, the fiber diameter gradually thickens to 3,610 nm. The fiber morphology under different solvent mixture ratios and solvent mixtures has also been studied.     

Morphology of electrospun nylon‐6 nanofibers as a function of molecular weight and processing parameters

In the present study, the morphology and mechanical properties of nylon‐6 nanofibers were investigated as a function of molecular weight (30,000, 50,000, and 63,000 g/mol) and electrospinning process conditions (solution concentration, voltage, tip‐to‐collector distance, and flow rate). Scanning electron micrographs (SEM) of nylon‐6 nanofibers showed that the diameter of the electrospun fiber increased with increasing molecular weight and solution concentration. An increase in molecular weight increases the density of chain entanglements (in solution) at the same polymer concentration; hence, the minimum concentration to produce nanofibers was lower for the highest molecular weight nylon‐6. The morphology of electrospun fibers also depended on tip‐to‐collector distance and applied voltage concentration of polymer solution as observed from the SEM images. Trends in fiber diameter and diameter distribution are discussed for each processing variable. Mechanical properties of electrospun nonwoven mats showed an increase in tensile strength and modulus as a function of increasing molecular weight. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of poly(ether sulfone) nanofibers by gas‐jet/electrospinning

Poly(ether sulfone) (PES) nanofibers were prepared by the gas‐jet/electrospinning of its solutions in N,N‐dimethylformamide (DMF). The gas used in this gas‐jet/electrospinning process was nitrogen. The morphology of the PES nanofibers was investigated with scanning electron microscopy. The process parameters studied in this work included the concentration of the polymer solution, the applied voltage, the tip–collector distance (TCD), the inner diameter of the needle, and the gas flow rate. It was found from experimental results that the average diameter of the electrospun PES fibers depended strongly on these process parameters. A decrease in the polymer concentration in the spinning solutions resulted in the formation of nanofibers with a smaller diameter. The use of an 18 wt % polymer solution yielded PES nanofibers with an average diameter of about 80 nm. However, a morphology of mixed bead fibers was formed when the concentration of PES in DMF was below 20 wt % during gas‐jet/electrospinning. Uniform PES nanofibers with an average diameter of about 200 nm were prepared by this electrospinning with the following optimal process parameters: the concentration of PES in DMF was 25 wt %, the applied voltage was 28.8 kV, the gas flow was 10.0 L/min, the inner diameter of the needle was 0.24 mm, the TCD was 20 cm, and the flow rate was 6.0 mL/h. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Corona discharge from electrospinning jet of poly(ethylene oxide) solution

Corona discharges from electrospinning jets were observed and photographed at the tip of the Taylor cone, and in a cylindrical region around the jet, a few millimeters below the tip. The corona discharge was also faintly visible to a dark adapted eye. At the position at which the cylindrical corona discharge became apparent, typical conditions were a jet diameter of 30 μm, an applied potential of 12 kV, and a calculated radial electric field of 400 kV/cm, The calculated electric field required to create a corona in air around a metal wire of the same diameter, calculated from Peek's empirical formula, was only about 200 kV/cm. The cross sectional shape of some segments of the electrospun fibers had two or three lobes. The lobes often separated, and formed smaller fibers.     

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     

The thermal effects on electrospinning of polylactic acid melts

We demonstrate that melt electrospinning can be a feasible way to produce sub-micron scale polylactic acid (PLA) fibers in this paper. This solvent-free approach to produce sub-micron scale fibers is more environmentally benign than common solution electrospinning processes, and has a potential to increase the production rate significantly. Our experimental results show that temperatures at the spinneret and in the spinning region are critical to produce sub-micron sized fibers: a high-speed photographic investigation reveals that when spinning temperature is below glass transition temperature, whipping of the jet is suppressed by fast solidification in the spinning region, leading to a larger jet diameter. Both thermal and mechanical degradations of PLA in melt electrospinning can be significant but no change in chemical composition is found. Due to rapid solidification, melt electrospun PLA fibers are mostly amorphous, and the small presence of β crystals is noted in the sub-micron scale PLA fibers by XRD studies. The highly oriented structure of PLA fibers gives rise to cold crystallization at around 95 °C, and the degree of crystallinity of fibers increases with increasing the degree of annealing. Finally, PLA nanofibers have directly been electrospun onto cellulose filter media, and a drastic enhancement in collection efficiency of sub-micron sized dust particles is presented. Melt electrospun PLA nanofiber mats with no residual solvent may serve as better filter media and tissue scaffolds than those obtained from solution electrospinning processes.     

Melt‐electrospinning of poly(ethylene terephthalate) and polyalirate

Rodlike polymer samples were made from three kinds of poly(ethylene terephthalate) (PET) pellets with different intrinsic viscosities (IV), and from polyalirate (Vectra) pellets. PET and Vectra fibers were produced using a melt‐electrospinning system equipped with a CO₂‐laser melting device from these rodlike samples. The effects of IV value and laser output power on the fiber diameter of PET were investigated. Furthermore, the effect of the laser output power on the fiber diameter of Vectra was investigated. The crystal orientation of these produced fibers was also investigated by X‐ray photographs. The following conclusions were reached: (i) the diameter of PET fiber decreases with increasing laser output power; (ii) the minimum average diameter of PET fibers is scarcely influenced by the value of IV; (iii) the electrospun PET fibers show isotropic crystal orientation; (iv) fibers having an average fiber diameter smaller than 1 μm cannot be obtained from PET and Vectra using the system developed; and (v) preferred liquid crystal orientation can be seen in electrospun Vectra fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Pressure control system for electrospinning process

Electrospinning is used to produce micro‐ and nano‐sized synthetic fibers through the use of electrostatic forces. Commercially, viable production of fibers requires high throughput of uniform fibers that are free of defects. To achieve greater control over the process variables that affect the fiber formation, a scalable closed loop control system that can maintain a constant pressure at the capillary tip was designed and tested. Two sensing technologies, infrared and ultrasonic, were used and compared for their ability to detect the height of polymer solution in the electrospinning fluid container. The air pressure above the solution was measured with a pressure transducer and adjusted through a controllable syringe pump. The closed loop electrospinning system was successful at controlling and maintaining a constant pressure at the capillary tip to within 2% of the specified pressure continuously. The controlled pressure at the capillary tip showed a strong correlation to fiber diameter and uniformity for polydimethylsiloxane‐based polyurethane/DMF‐based fibers. However the control system was less effective to control fiber diameter for polyethylene oxide/Water‐based fibers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Morphology transition in electrospinning polymers by a dual‐capillary system

An experimental investigation of the fiber morphology change of fibers prepared by a dual‐capillary electrospinning system, operated in the cone‐jet mode, was carried out for poly(vinyl acetate) polymers of three molecular weights. The substrate morphology of the electrospun poly(vinyl acetate) could be changed significantly when the polymer's molecular weight, concentration, solvent, and outer liquid flow rate were varied. The onset of bead‐to‐fiber transition was determined by the critical chain overlap concentration. For solutions with a high concentration, the fiber diameter and surface were significantly affected by the physical properties of the solvents. To produce fibers of small diameter, electrospinning with a higher conductivity solution was desirable. On the other hand, a high‐conductivity solution needed to be avoided to keep the fiber uniform in diameter and smooth on the surface. The comparison of electrospun fibers produced by both single‐capillary and dual‐capillary systems was also addressed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Needleless Electrospinning from a Tube with an Embedded Wire Loop

Enhancing the production rate while maintaining control in electrospinning has been a challenge for years. This work proposes a novel spinneret from a tube with a single wire loop embedded in its one end. With the feeding of solution precisely controlled and the spinning process stablized, multiple polymer jets can be continuously generated from the wire loop. The as‐spun fibers show nanofibrous structure and its fiber diameter is greatly affected by the applied voltage and polymer concentration. As compared to needle electrospinning, the wire loop spinneret generates a stronger electric field with a larger spinnable area due to its special geometrical structure and a higher applied voltage it is connected to. Slightly coarser nanofibers are fabricated as compared to the nanofibers from needle electrospinning and the production rate is as high as 0.48 g h^?1.     

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