Effect of solution properties on nanofibrous structure of electrospun poly(lactic‐co‐glycolic acid)

Electrospinning of poly(lactic‐co‐glycolic acid) (PLGA) in chloroform or 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was investigated, focusing on its solution parameters, to develop nonwoven biodegradable nanofibrous structures for tissue engineering. PLGA nanofibers were obtained by electrospinning of 15 wt % PLGA solution and the resulting average fiber diameters were varied with the range of 270–760 nm, depending on solution property. When small amounts of benzyl triethylammonium chloride (BTEAC) was added to the PLGA/chloroform solution, the average diameter was decreased from 760 to 450 nm and the fibers were densely amounted in a straight shape. In addition, the average fiber diameter (270 nm) of nanofibers electrospun from polar HFIP solvent was much smaller than that (760 nm) of nanofibers electrospun from nonpolar chloroform solvent. Therefore, it could be concluded that conductivity or dielectric constant of the PLGA solution was a major parameter affecting the morphology and diameter of the electrospun PLGA fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1214–1221, 2006     

Effect of organic solvent on morphology and mechanical properties of electrospun syndiotactic polypropylene nanofibers

We study the stress–strain behaviors of the electrospun sPP single nanofibers as well as nonwoven mats, which were electrospun from sPP solutions using two different solvents (decalin and cyclohexane) by electrospinning. The effects of organic solvents were explored on the morphologies and the mechanical properties of the corresponding electrospun sPP single nanofibers and nonwoven mats. It was found that the nature of organic solvents dramatically affected the surface morphologies, the circular and looping deposition of the electrospun sPP fibers, and the mechanical properties. The tensile strength of both electrospun sPP single nanofibers and nonwoven mats prepared from decalin-base solution was stronger than that of cyclohexane-base solution.     

A cost effective and facile approach to prepare beadless polycarbonate nanofibers with ultrafine fiber morphology

Preparing defect free nanofibers with average diameter well below 100 nm is a challenge to researchers by electrospinning technology. In the present contribution, the electrospinning method was utilized to prepare beadless polycarbonate (PC) nanofibers with average diameter 90 nm using comparatively less toxic and suitable solvents in a convenient way. Spinning PC with pure dichloromethane (DCM) and also with 1:1 mixture of DCM and N,N dimethylformamide under the same spinning parameters with varying PC concentration has very much helped to establish the effect of solvents on fiber formation. This study also proved the impact of solution concentration, viscosity, and solution conductivity on the formation of beadless ultrafine PC fibers and subsequently on the bead density and average fiber diameter. The appropriate proportion of solvents under suitable spinning parameters has helped to minimize the quantity of PC during the formation of bead free nanofibers by electrospinning. The ultrafine, uniform, and beadless morphology of the electrospun PC fibers can be utilized for various nanotechnology advancements. POLYM. ENG. SCI., 59:1799–1809, 2019. © 2019 Society of Plastics Engineers     

Effect of evaporation and solidification of the charged jet in electrospinning of poly(ethylene oxide) aqueous solution

The electrospinning process uses electrical force to produce nanofibers. A charged droplet acquires a conical shape known as the Taylor cone and then becomes unstable. A charged jet emerges from the vertex and develops a spiral path due to the electrically driven bending instability, which makes it possible, in a small space, for the jet to elongate by a large amount and produce nanofibers. Evaporation and the associated solidification were identified as important factors that affect the diameter of electrospun nanofibers. In this study, the evaporation rate and solidification of the charged jet were controlled by varying the relative humidity during electrospinning of poly(ethylene oxide) from aqueous solution. As the relative humidity increased, the solidification process became slower, allowing elongation of the charged jet to continue longer and thereby to form thinner fibers. As the relative humidity increased from 5.1% to 48.7%, the diameter of the solidified fiber decreased from 253 nm to 144 nm. As the relative humidity increased above 50%, beads formed on the thinner fibers, indicating that the capillary instability occurred before the jet solidified. The vapor concentration of solvent is an effective electrospinning process control parameter of fiber diameter that also produces a systematic change in the development of beads on the fibers.     

ZnO nanocrystallites/cellulose hybrid nanofibers fabricated by electrospinning and solvothermal techniques and their photocatalytic activity

ZnO nanocrystallites have been in situ embedded in cellulose nanofibers by a novel method that combines electrospinning and solvothermal techniques. Zn(OAc)₂/cellulose acetate (CA) precursor hybrid nanofibers with diameter in the range of 160–330 nm were first fabricated via the electrospinning technique using zinc acetate as precursor, CA as the carrier, and dimethylformamide (DMF)/acetone(2 : 1) mixture as cosolvent. The precursor nanofibers were transformed into ZnO/cellulose hybrid fibers by hydrolysis in 0.1 mol/L NaOH aqueous solution. Subsequently, these hybrid fibers were further solvothermally treated in 180°C glycerol oil bath to improve the crystallite structure of the ZnO nanoparticles containing in the nanofibers. The structure and morphology of nanofibers were characterized by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. It was found that hexagonal structured ZnO nanocrystallites with the size of ～ 30 nm were dispersed on the nanofiber surfaces and within the nanofibers with diameter of about 80 nm. The photocatalytic property of the ZnO/cellulose hybrid nanofibers toward Rhodamine (RhB) was tested under the irradiation of visible light. As a catalyst, it inherits not only the photocatalytic ability of nano‐ZnO, but also the thermal stability, good mechanical property, and solvent‐resistibility of cellulose nanofibers. The key advantages of this hybrid nanofiber over neat ZnO nanoparticles are its elasticity, dimensional stability, durability, and easy recyclability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

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.     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

气流-静电纺丝法制备P(AN-co-AA)纳米纤维的研究

用气流-静电纺丝法制备了丙烯腈-丙烯酸共聚物[P(AN-co-AA)]纳米纤维。通过扫描电镜(SEM)对纳米纤维形貌的表征,研究了聚合时丙烯酸(AA)单体的含量、溶剂种类以及工艺参数对P(AN-co-AA)纳米纤维直径和形貌的影响,得到了最佳工艺条件为:纺丝溶剂N、N-二甲基甲酰胺(DMF)、聚合单体中AA的摩尔分数比15%、P(AN-co-AA)质量分数10%、外加电压20kV、接收距离20cm,所得P(AN-co-AA)纳米纤维的平均直径为156nm。     

Characterization on oxidative stabilization of polyacrylonitrile nanofibers prepared by electrospinning

Ultrafine polyacrylonitrile (PAN) fibers, as a precursor of carbon nanofibers, with diameters in the range of 220–760 nm were obtained by electrospinning of PAN solution using N,N-dimethyl formamide (DMF) as solvent. Morphology of the nanofibers for varying concentration and applied voltage was investigated by field emission scanning electron microscopy (FESEM). The thermal properties and structural changes during the oxidative stabilization process were primarily investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Fourier transform infrared (FT-IR) and Raman spectroscopy. The nanofiber diameters increase as the applied voltage is increased and they also increase with an increase in the concentration of the polymer solution. It was also concluded that the electrospun fibers displayed a very sharp exothermic peak at 297.34 °C. A transition temperature observed by FT-IR and Raman was approximately 300 °C, which was closely consistent with the results of DSC and TGA studies. It was also found that oxidative stabilization in air was accompanied by a change in color of nanofibers webs.     

Studies on the synthesis of electrospun PAN‐Ag composite nanofibers for antibacterial application

We have successfully synthesized polyacrylonitrile (PAN) nanofibers impregnated with Ag nanoparticles by electrospinning method at room temperature. Briefly, the PAN‐Ag composite nanofibers were prepared by electrospinning PAN (10% w/v) in dimethyl formamide (DMF) solvent containing silver nitrate (AgNO₃) in the amounts of 8% by weight of PAN. The silver ions were reduced into silver particles in three different methods i.e., by refluxing the solution before electrospinning, treating with sodium borohydride (NaBH₄), as reducing agent, and heating the prepared composite nanofibers at 160°C. The prepared PAN nanofibers functionalized with Ag nanoparticles were characterized by field emission scanning electron microscopy (FESEM), SEM elemental detection X‐ray analysis (SEM‐EDAX), transmission electron microscopy (TEM), and ultraviolet‐visible spectroscopy (UV‐VIS) analytical techniques. UV‐VIS spectra analysis showed distinct absorption band at 410 nm, suggesting the formation of Ag nanoparticles. TEM micrographs confirmed homogeneous dispersion of Ag nanoparticles on the surface of PAN nanofibers, and particle diameter was found to be 5–15 nm. It was found that all the three electrospun PAN‐Ag composite nanofibers showed strong antibacterial activity toward both gram positive and gram negative bacteria. However, the antibacterial activity of PAN‐Ag composite nanofibers membrane prepared by refluxed method was most prominent against S. aureus bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of biomimetic tussah silk fibroin/chitosan composite nanofibers

Tussah silk fibroin (TSF)/chitosan (CS) composite nanofibers were prepared to mimic extracellular matrix by electrospinning with hexafluoroisopropanol (HFIP) as a solvent. The viscosity and conductivity of TSF/CS blend solution were analyzed and the morphology, secondary structure, and thermal property of TSF/CS composite fibers were investigated by SEM, ¹³C CP/MAS-NMR, X-ray diffraction, and DSC Techniques. The electrospinnability of TSF solution was improved significantly by adding 10 wt% CS, and morphology of electrospun TSF nanofibers changed from flat strip to cylindrical. At the same time, the average fiber diameters decreased from 542 to 312 nm, accompanying by an obvious improvement in fiber diameter uniformity. However, when the CS content in blend solution was more than 15 wt%, the diameter of electrospun TSF/CS nanofibers appeared to be polarized which can be attributed to phase separation of the two components in composite nanofibers. Blending 10 wt% CS did not change the conformation of TSF in TSF/CS composite nanofibers, and TSF in composite nanofibers at various composition ratios had mainly taken the α-helix structure. The thermal decomposition temperature of electrospun TSF/CS composite nanofibers decreased with the increase of CS content due to the lower decomposition temperature of CS. To study the cytocompatibility and cell behavior on the TSF/CS nanofibers, human renal mesangial cells were seeded onto electrospun TSF/CS composite nanofibers. Results indicated that the addition of CS promoted cell attachment and spreading on TSF nanofibers significantly, suggesting that electrospun TSF/CS composite nanofibers could be a candidate scaffold for tissue engineering.     

明胶超细纤维成形研究

以去离子水为溶剂,采用静电纺丝工艺制备明胶超细纤维。系统探讨了温度、浓度及电纺工艺参数对明胶电纺纤维成形的影响。结果表明：纺丝环境温度的升高有利于获得平均直径较小的纤维;随着明胶溶液质量分数从25％下降到15％,所得明胶纤维平均直径从266．5nm下降到167．7nm,其直径分布也逐渐变窄;随着静电纺丝电压升高,所得纤维直径降低;改变静电纺丝接收距离,所得的纤维直径及其分布均无太大变化。考察了纺丝液中的离子对明胶电纺纤维形貌的影响,发现随着添加的NaGl浓度的增大（0．01～0．5mol／L）,所得明胶纤维的直径呈线性增加（196～390nm）,与纯明胶电纺相比,离子的加入使所得纤维直径分布变宽。     

Preparation and characterization of potassium sodium niobate nanofibers by electrospinning

In this work, we describe the electrospinning of (K,Na)NbO₃ fibers and the effect of calcination temperature on the final phase composition. The envisaged application is for the fabrication of ferroelectric sensor hybrid materials. A solution of potassium acetate, sodium methoxide, and niobium ethoxide dissolved in methanol, acetylacetone, and acetic acid was mixed with polyvinylpyrrolidone (PVP) dissolved in methanol, producing a viscous solution for electrospinning. Confirmation that the proposed equation on the average diameter of fibers produced from high viscosity solutions was larger than that of a lower viscosity solution was made. A scanning electron microscopy (SEM) study showed the fibers to be cylindrical, smooth with diameters of around 400 nm and an aspect ratio >1000. The electrospun fibers were calcined from 700°C to 1050°C observing the fiber morphology. With increasing calcining temperature, the grain size increased. The calcined (K,Na)NbO₃ nanofibers were brittle and generally found to display the “necklace effect.”     

Effects of some electrospinning parameters on morphology of natural silk‐based nanofibers

Natural silk, from Bombyx mori solutions were electrospun into nanofibers, with diameters ranged from 60 to 7000 nm. The effects of electrospinning temperature, solution concentration and electric field on the formation nanofibers were studied. Optical and scanning electron microscope were used to study the morphology and diameter of electrospun nanofibers. It was observed that the nanofibers became flattened with ribbon‐like shape with increasing the electrospinning temperature. The nanofiber diameter increases with the increase in the concentration of silk solution at all electrospinning temperature. With increasing the voltage of electric field at 50°C, morphology of the nanofibers changes from ribbon‐like structure to circular cross section. Referring to the literature the probable mechanism responsible for the change of morphology is pointed out. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

气流-静电纺丝法制备聚对苯二甲酸乙二酯纳米纤维

采用50%苯酚和50%1,1,2,2-四氯乙烷的混合溶液为溶剂,通过气流-静电纺丝法制备了聚对苯二甲酸乙二酯(PET)纳米纤维。利用扫描电镜(SEM),研究了聚合物分子质量、溶液浓度、电压、接收距离(喷丝孔到接收板的距离)对电纺纤维形态结构的影响。结果表明:随着聚合物分子质量和溶液浓度增加,纤维平均直径也随之增加;纤维平均直径随电压的增加而减小;随接收距离的增加,纤维平均直径先减小后增加。最佳工艺条件为:聚合物特性黏度为0.818 dL/g,溶液质量分数为15%,电压为32 kV,接收距离为23 cm,所得PET电纺纳米纤维平均直径为85 nm。     

Electrospinning of solvent‐resistant nanofibers based on poly(acrylonitrile‐co‐glycidyl methacrylate)

This article reports on the preparation of novel solvent‐resistant nanofibers by electrospinning of poly(acrylonitrile‐co‐glycidyl methacrylate) (PANGMA) and subsequent chemical crosslinking. PANGMA nanofibers with diameters ranging from 200 to 600 nm were generated by electrospinning different solutions of PANGMA dissolved in N,N‐dimethylformamide. Different additives were added to reduce the fiber diameter and improve the morphology of the nanofibers. The as‐spun PANGMA nanofibers were crosslinked with 27 wt % aqueous ammonia solution at 50°C for 3 h to gain the solvent resistance. Swelling tests indicated that the crosslinked nanofibers swelled in several solvents but were not dissolved. The weight loss of all the crosslinked nanofibrous mats immersed in solvents for more than 72 h was very low. The characterization by electron microscopy revealed that the nanofibrous mats maintained their structure. This was also confirmed by the results of the pore size measurements. These novel nanofibers are considered to have a great potential as supports for the immobilization of homogeneous catalysts and enzymes. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrospinning of polycaprolactone nanofibers using H2O as benign additive in polycaprolactone/glacial acetic acid solution

Considerable efforts have been devoted to the production of polycaprolactone (PCL) nanofibrous structures by electrospinning. However, some toxic solvents have often been used to achieve bead‐free nanofibers. At present, a benign solvent such as glacial acetic acid (GAC) only leads to beaded or microscale fibers. Therefore a study is done to extend the electrospinnability of the PCL/GAC system by the addition of H₂O. The solution properties of conductivity, viscosity, and surface tension were altered by the addition of H₂O, especially increasing the conductivity and viscosity. These properties essential to electrospinning could remain stable for 6 h when the H₂O content was less than or equal to 9 vol %. Then ultrafine PCL fibers with diameters from 188 to 200 nm, 10 times smaller than when dissolved in pure GAC, were electrospun from solutions of PCL with concentrations in the range of 17 to 20 wt % with H₂O content at 9 vol %. Finally, the crystallinity and crystallite size of the resulting fibers were smaller than that of raw PCL pellets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45578.     

Nanofibers from recycle waste expanded polystyrene using natural solvent

Summary A new recycling technique has been developed. In this method, EPS (expanded polystyrene), generally called Styrofoam, is dissolved with natural solvent, d-limonene and electrospun. This method can economically produce the nanofibers. The electrospinning process produces a nonwoven mat of long polymer fibers with diameters in the range of 10–500 nm and high surface areas per unit mass. PS (Polystyrene) polymer dissolved in different solvents such as THF (Tetrahydrofuran), DMF (Dimethylformaide), and DMAc (Dimethylacetamide) etc. may all be electrospun into nanofibers. These solvents cause environmental problem and difficulty of process handling. Natural solvent, d-limonene is used for dissolving PS. PS nanofibers are produced with PS solution using d-Limonene. This paper describes the use of polystyrene (PS) nanofibers electrospun from recycled EPS solution dissolved in d-limonene. The electrospun polystyrene nanofiber diameters vary from 300 to 900 nm, with an average diameter of about 700 nm.     

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.