The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibers

Electrospinning is a simple method of producing nanofibers by introducing electric field into the polymer solutions. We report an experimental investigation on the influence of processing parameters and solution properties on the structural morphology and average fiber diameter of electrospun poly ethylene oxide (PEO) polymer solution. Experimental trials have been conducted to investigate the effect of solution parameters, such as concentration, molecular weight, addition of polyelectrolyte in PEO solution, solvent effect, as well as governing parameter, such as applied voltage. The concentration of the aqueous PEO solution has shown noteworthy influence on the fiber diameter and structural morphology of electrospun nanofibers. At lower concentrations of PEO polymer solution, the fibers showed irregular morphology with large variations in fiber diameter, whereas at higher concentrations, the nanofibers with regular morphology and on average uniform fiber diameter were obtained. We find that the addition of polyelectrolytes, such as sodium salt of Poly acrylic acid (PAA) and Poly allylamine hydrochloride (PAH), increases the conductivity of PEO solutions and thereby decreases the bead formation in electrospun nanofibers. The increase in applied voltage has been found to affect the structural morphology of nanofiber while the addition of ethanol in PEO solution diminishes the bead defects. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Process Optimization and Empirical Modeling for Electrospun Poly(D,L‐lactide) Fibers using Response Surface Methodology

Summary: Ultrafine fibers were spun from poly(D ,L ‐lactide) (PDLA) solution using a homemade electrospinning set‐up. Fibers with diameter ranging from 350 to 1 900 nm were obtained. Morphologies of fibers and distribution of fiber diameters were investigated varying concentration and applied voltage by scanning electron microscopy (SEM). Average fiber diameter and distribution were determined from about 100 measurements of the random fibers with an image analyzer (SemAfore 5.0, JEOL). A more systematic understanding of process parameters of the electrospinning was obtained and a quantitative relationship between electrospinning parameters and average fiber diameter was established by response surface methodology (RSM). It was concluded that the concentration of polymer solution played an important role in the diameter of fibers and standard deviation of fiber diameter. Lower concentration tended to facilitate the formation of bead‐on‐string structures. Fiber diameter tended to increase with polymer concentration and decrease with applied voltage. Fibers with lower variation in diameter can be obtained at lower concentration regardless of applied voltage. Fibers with uniform diameter and lower variation in diameter can be obtained at higher concentration and higher applied voltage. Process conditions for electrospinning of PDLA could be chosen according to the model in this study.

Contour plots of average fiber diameter as a function of concentration and applied voltage.     

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.     

Electrospinning of aqueous lignin/poly(ethylene oxide) complexes

Microfibers of kraft lignin blended with poly(ethylene oxide) (PEO) were produced by electrospinning of the solution of lignin and high molecular weight poly(ethylene oxide) (PEO) in alkaline water. Interactions between lignin and PEO in alkaline aqueous solutions create association complexes, which increases the viscosity of the solution. The effect of polymer concentration, PEO molecular weight, and storage time of solution before spinning on the morphology of the fibers was studied. It showed that after one day the viscosity dropped and fiber diameter decreased. Results from the solutions in alkaline water and N,N‐dimethylformamide (DMF) with different polymer concentrations were compared. The 7 wt % of (Lignin/PEO: 95/5 wt/wt) in alkaline aqueous solution was successfully spun and the ratio of PEO in lignin/PEO mixture could be further reduced. In comparison, higher concentrations were needed to prepare a spinning solution in DMF and fiber diameters were in a much smaller range. The final target of spinning lignin is to produce carbonized fibers. Fibers spun from aqueous solutions had lower PEO content, which is a big advantage for the carbonization process as it reduces the challenges regarding melting of the fibers or void creation during carbonization. Furthermore, the larger diameter of these fibers inhibits disintegration of the carbonized fibers, which happens due to the mass loss during the process. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41260.     

静电纺丝制备MWNTs/PVA/PEO复合超细纤维

采用硝酸对多壁碳纳米管(MWNTs)进行纯化处理,利用表面活性剂十二烷基磺酸钠(SDS)或聚乙烯醇(PVA)对纯化后的MWNTs进行了表面修饰,将修饰后的MWNTs添加到PVA和聚氧化乙烯(PEO)共混水溶液中,通过静电纺丝制备了MWNTs/PVA/PEO复合超细纤维。结果表明:PVA修饰的MWNTs比SDS修饰的MWNTs在PVA/PEO纺丝液中有更好的分散稳定性。随MWNTs添加量的增加,纤维的平均直径减小;当添加PVA修饰的MWNTs质量分数为0.53%时,纤维平均直径达368 nm,且纤维表面光滑、分布均匀。     

Effect of Blend Ratio and Draw Ratio on the Mechanical Properties of PET/PP Blended Conjugate Fibers

This study analyzes the influence of blend ratio and draw ratio on the fiber properties of blend fibers composed of poly (ethylene terephthalate), or PET, and polypropylene, or PP, (hereafter referred to as PET/PP conjugate fibers). For a comparison, PET and poly (butylene terephthalate), or PBT blends, (hereafter referred to as PET/PBT conjugate fibers) are also investigated. Various blend ratios of fibers are melt spun and drawn in a multistep drawing method. The conjugate fibers are evaluated using tenacity, Young's modulus, wide-angle X-ray diffraction, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) tests. The results show that multistep drawing using a lower first-step draw ratio provides a higher tenacity and Young's modulus. Furthermore, when the blend ratio is 75/25 in a PET/PP conjugate fiber and 50/50 in a PET/PBT conjugate fiber, the polymer components undergo a phase inversion phenomenon. A PP sub-micron (10^?1 ～ 10⁰ micron) fiber of about 0.0001 ～ 0.00017 tex in fineness, or about 0.4 ～ 0.5 micron in diameter, can be obtained when PET/PP conjugate fiber is treated with a 25% NaOH aqueous solution by weight. However, A PBT sub-micron fiber cannot be achieved using a PET/PBT conjugate fiber.     

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     

Nanodroplet formation and exclusive homogenously nucleated crystallization in confined electrospun immiscible polymer blend fibers of polystyrene and poly(ethylene oxide)

By utilizing electrospun blend fibers of polystyrene (PS) and poly(ethylene oxide) (PEO) with diameters in sub-microns, nanodroplets of the minor component (PEO) were obtained by annealing the blend fibers above the glass transition temperature (T_g) of the matrix polymer (PS), as a result of the Rayleigh-Plateau instability in the melt. However, direct thermal annealing of the PS/PEO blend fibers led to poor Rayleigh breakup of the PEO fibers in the PS matrix, and fractionated crystallization with both homogeneous and heterogeneous nucleation was observed, probably due to a broad size distribution of PEO particles. On the contrary, after confining the PS/PEO blend fibers with a high T_g polymer, poly(4-tert-butyl styrene) (P4tBS, T_g ∼ 143 °C), well-defined Rayleigh breakup of the PEO fiber was achieved by annealing the P4tBS-coated PS/PEO blend fibers at 150 °C. Consequently, exclusive homogeneously nucleated PEO crystallization was observed at −20 °C. This report could provide a universal method to achieve nano-sized droplets for the study of nanoconfinement effect by utilizing electrospun immiscible polymer blend fibers without addition of any compabitilizers.     

聚醚砜的静电纺丝研究

采用聚醚砜(PES)的良溶剂二甲基甲酰胺(DMF)和非良溶剂丙酮(AC)为共溶剂体系,研究了溶剂组成、纺丝成形条件对静电纺丝PES纤维的形貌及纤维直径的影响。结果表明:DMF/AC的配比对于静电纺丝PES纤维形貌具有直接的调控作用,随着DMF/AC混合溶剂中AC用量的增加,纤维平均直径变大,纤维毡中串珠数目明显减少,纤维均一性变好;随着纺丝液浓度的升高,纺丝电压的增大,纤维的平均直径变大;接收距离的变化对纤维平均直径影响不大;PES最佳纺丝工艺条件为纺丝溶液质量分数13%,纺丝电压15 kV,接收距离10 cm,mDMF/mAC为8.5/1.5,在此条件下,可以获得纤维平均直径为96 nm的PES纤维毡。     

The novel alginate/N‐succinyl‐chitosan antibacterial blend fibers

Alginate/ N‐Succinyl‐chitosan (SCS) blend fibers, prepared by spinning their mixture solution through a viscose‐type spinneret into a coagulating bath containing aqueous CaCl₂, were studied for structure and properties with the aid of infrared spectroscopy (IR) and X‐ray diffraction (XRD). The results indicated a good miscibility between alginate and SCS, because of the strong interaction from the intermolecular hydrogen bonds. The best values of the dry tensile strength and breaking elongation were obtained when SCS content was 30 wt %. The wet tensile strength decreased with the increase of SCS content, and the wet breaking elongation achieved maximum value when the SCS content was 30 wt %. Introduction of SCS in the blend fiber improved water‐retention properties of blend fiber compared to pure alginate fiber. Antibacterial fibers, obtained by treating the fibers with aqueous solution of silver nitrate, exhibited good antibacterial activity to Staphylococcus aureus. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PEO酸——新型的聚酯纤维抗静电改性剂

采用三种不同分子量的 PEO 酸(M_n=8400,3300,1000)为抗静电改性剂,以2%,5%(质量)的配比与 PET 切片共混,进行熔融纺丝,制得 PET-PEO 酸共混纤维.研究发现,改性体系具有良好的可纺性和拉伸性能.改性纤维的特性粘数和机械力学性能与纯 PET 相比,略有降低,而抗静电性能有了明显改善,且随着 PEO 酸分子量的增加而提高.PEO 酸的抗静电效果是由于它的高吸湿性 PEO 链与活性末端羧基共同作用的结果.     

Artificial neural networks modeling of electrospinning of polyethylene oxide from aqueous acid acetic solution

The artificial neural networks (ANNs) were used to provide a model for investigating the relationships of the electrospinning parameters with the diameter of polyethylene oxide (PEO) nanofibers from acid acetic aqueous solution. The effects of four parameters including PEO concentration, acetic acid concentration, applied voltage, and temperature of the electrospinning media on the nanofibers mean diameter were investigated. To train, test, and valid the model, three datasets of the input variables with random values were prepared and the mean diameters obtained were taken as the output for the network. The datasets were analyzed by ANNs software and the correlation coefficient, R-squared (R²), between the predicted values of the nanofibers mean diameter and actual amount were obtained. The results demonstrate the capability of the ANNs model for predicting the nanofibers diameter. The 3-D plots generated from the model show complex and nonlinear relationships between the parameters and nanofibers diameter. From the model, increasing the PEO concentration above a critical point leads to a sharp increase in the nanofibers mean diameter. The effects of applied voltage and temperature are mainly dependent on the PEO concentration. The acetic acid concentration, in general shows a direct relation with the nanofibers mean diameter. The plots also show that to produce nanofibers with the lowest diameter, both the PEO concentration and AcOH concentration should be at lowest values regardless the applied voltage and temperature. In contrast, highest nanofibers diameters are obtained when the PEO concentration and AcOH concentration are at their high values. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effects of solution properties and polyelectrolyte on electrospinning of ultrafine poly(ethylene oxide) fibers

The effects of solution properties and polyelectrolyte on the electrospinning of poly(ethylene oxide) (PEO) solutions were investigated. Ultrafine PEO fibers without beads were electrospun from 3, 4, 7 and 7 wt% PEO solutions in chloroform, ethanol, (dimethylformamide) DMF and water, respectively. At these concentrations, the values of [η]C were ∼10 for all solutions. The average diameters of PEO fibers were ranged from 0.36 to 1.96 μm. The higher the dielectric constant of solvent was, the thinner PEO fiber was. The average diameters of electrospun PEO fibers from PEO/water solutions were decreased and their distributions were narrowed by adding 0.1 wt% poly(allylamine hydrochloride) (PAH) and poly(acrylic acid sodium salt) (PAA) due to the increased charge density in solutions. The addition of PAH and PAA lowered the minimum concentration for electrospinning of a PEO/water solution to 6 wt%.     

Electrospinning of polycarbonate urethane biomaterials

Polycarbonate urethane (PCU) nano-fibers were fabricated via electrospinning using N,N- dimethylformamide (DMF) and tetrahydrofuran (THF) as the mixed solvent. The effect of volume ratios of DMF and THF in the mixed solvent on the fiber structures was investigated. The results show that nano-fibers with a narrow diameter distribution and a few defects were obtained when mixed solvent with the appropriate volume ratio of DMF and THF as 1∶1. When the proportion of DMF was more than 75% in the mixed solvent, it was easy to form many beaded fibers. The applied voltage in the electrospinning process has a significant influence on the morphology of fibers. When the electric voltage was set between 22 and 32 kV, the average diameters of the fibers were found between 420 and 570 nm. Scanning electron microscopy (SEM) images showed that fiber diameter and structural morphology of the electrospun PCU membranes are a function of the polymer solution concentration. When the concentration of PCU solution was 6.0 wt-%, a beaded-fiber microstructure was obtained. With increasing the concentration of PCU solutions above 6.0 wt-%, beaded fiber decreased and finally disappeared. However, when the PCU concentration was over 14.0 wt-%, the average diameter of fibers became large, closed to 2 μm, because of the high solution viscosity. The average diameter of nanofibers increased linearly with increasing the volume flow rate of the PCU solution (10.0 wt-%) when the applied voltage was 24 kV. The results show that the morphology of PCU fibers could be controlled by electrospinning parameters, such as solution concentration, electric voltage and flow rate.     

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     

Fabrication of gelatin/chitosan nanofibrous scaffold: process optimization and empirical modeling

Electrospinning is a very useful technique for producing polymeric nanofibers by applying electrostatic forces. This study reports on the modeling and optimization of the electrospinning process of gelatin/chitosan, using response surface methodology. The individual and the interaction effects of the gelatin/chitosan blend ratio (50/50, 60/40 and 70/30), applied voltage (20, 25 and 30 kV) and feeding rate (0.2, 0.4 and 0.6 mL h^?1) on the mean fiber diameter and standard deviation of the fiber diameter were investigated on optimization section, using scanning electron microscopy. To fabricate the nanofibrous gelatin/chitosan blend, trifluoroacetic acid/dichloromethane was selected as the solvent system. The model obtained for the mean fiber diameter has a quadratic relationship with applied voltage and feeding rate. The interaction between applied voltage and flow rate were found significant but the interactions of blend ratio and flow rate and also blend ratio and applied voltage were negligible. A quadratic relationship was obtained for applied voltage and flow rate with standard deviation of the fiber diameter and there was no interaction between the parameters in the model. The optimum condition for electrospinning of gelatin/chitosan was also introduced using the model obtained in this study. Scanning electron micrographs of human dermal fibroblast cells on the nanofibrous structures show good attachment and proliferation on the fabricated scaffold surface. Electrospun gelatin/chitosan nanofibrous mats have great potential for use as a scaffold for skin tissue engineering. © 2014 Society of Chemical Industry     

亲水性多孔聚丙烯腈纤维的研究

将聚丙烯腈(PAN)与聚氧化乙烯(PEO)共混后湿法纺丝,经水洗后处理,制成具有不同微孔结构的改性PAN纤维,然后在NaOH溶液中水解,得到亲水性多孔PAN纤维(HM-PAN)。借助红外光谱和扫描电镜表征了HM-PAN的化学结构和形貌;讨论了HM-PAN的亲水性能和力学性能。结果表明:相同水解条件下,随PEO含量增大,HM-PAN中引入的亲水基团增多,表面形成的孔穴加深、数量增多,纤维的亲水性能提高;在相同PEO含量下,通过控制水解时间、HM-PAN的孔隙结构及亲水基团数量,可以提高HM-PAN对水分的吸收及转移性能。PEO质量分数为10%的HM-PAN试样的平衡吸水倍率可高达10.48 g/g,最大芯吸高度为13.5 cm,保水率高达98.1%。HM-PAN中微孔产生的应力集中以及大分子排列规整性的破坏,导致纤维的力学性能有所下降,而水解时张力的施加可有效降低其下降幅度。     

Development of a gel spinning process for high‐strength poly(ethylene oxide) fibers

This article describes a new gel‐spinning process for making high‐strength poly(ethylene oxide) (PEO) fibers. The PEO gel‐spinning process was enabled through an oligomer/polymer blend in place of conventional organic solvents, and the gelation and solvent‐like properties were investigated. A 92/8 wt% poly(ethylene glycol)/PEO gel exhibited a melting temperature around 45°C and was highly stretchable at room temperature. Some salient features of a gel‐spun PEO fiber with a draw ratio of 60 are tensile strength at break = 0.66 ± 0.04 GPa, Young's modulus = 4.3 ± 0.1 GPa, and a toughness corresponding to 117 MJ/m³. These numbers are significantly higher than those previously reported. Wide‐angle x‐ray diffraction of the high‐strength fibers showed good molecular orientation along the fiber direction. The results also demonstrate the potential of further improvement of mechanical properties. POLYM. ENG. SCI., 54:2839–2847, 2014. © 2014 Society of Plastics Engineers     

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     

静电纺工艺参数对SEBS纤维形貌和直径的影响

通过静电纺丝,将苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)溶解于四氢呋喃(THF)中的纺丝液制备成SEBS纤维,探索了纺丝液质量分数、纺丝电压和接收距离对纤维形貌及直径的影响。通过扫描电镜观察SEBS纤维的形貌以及Photoshop软件测量了SEBS纤维的直径。结果表明,纺丝液质量分数为25%、纺丝电压为10 kV、接收距离为15 cm时,纤维成型性良好,平均直径为9.7727μm;纤维直径随着电压的增大而减少,随着接收距离的增大而先减小后增大。