A novel method of selecting solvents for polymer electrospinning

The selection of a desirable solvent or solvent system as the carrier of a particular polymer is fundamental for the optimisation of electrospinning. Solvent selection is pivotal in determining the critical minimum solution concentration to allow the transition from electrospraying to electrospinning, thereby significantly affecting solution spinnability and the morphology of the electrospun fibres. 28 solvents diversely positioned on the Teas graph were studied for their solubility and electrospinnability for making polymethylsilsesquioxane (PMSQ) solutions. The results are combined and mapped on the Teas graph using different colour codes. Based on this new spinnability-solubility map, various solvent systems for PMSQ are methodically developed. Solvents are selected to produce binary solvent systems that have solvent parameters close to a good single solvent for electrospinning of the polymer solution. This work shows that solvents of high solubility do not necessarily produce solutions good for electrospinning. Polymethylsilsesquioxane solutions of the same concentration in solvents of partial solubility showed better spinnability than solutions in solvents of high solubility. A methanol-propanol binary solvent system produced electrospun fibres with high surface porosity, showing that high volatility and high vapour pressure difference among solvents mixed can induce phase separation in electrospinning. It is noteworthy that the binary solvent system mixing 2-nitropropane (high solubility) and dimethylsulphoxide (non-solvent), neither of which exhibited high volatility, also produced highly porous electrospun fibres. This demonstrates that phase separation can be induced by solubility difference in the electrospun polymer solution.     

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.     

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     

Control of structure and morphology of highly aligned PLLA ultrafine fibers via linear-jet electrospinning

In this work, poly(l-lactic acid) (PLLA) ultrafine fibers with different morphology and structure were fabricated by a novel linear-jet electrospinning method which relies on a conventional electrospinning set-up with continuous rotating drum. To control the morphology and structure of PLLA electrospun fibers, different solution systems and electrospinning conditions were investigated. Two PLLA solution systems (PLLA/DMF/CH₂Cl₂ and PLLA/CH₂Cl₂) with different concentration and conductivity were used for the electrospinning and their influences on the formation of the linear electrospinning jet were discussed. Two types of collecting patterns with aligned buckling and linear structure were achieved under the linear electrospinning jet. Highly aligned PLLA electrospun fibers with porous surface could be formed by using the highly volatile solvent CH₂Cl₂. Here, it should be emphasized that the diameter and surface porosity of such highly aligned PLLA electrospun fibers can be fine tuned by varying the winding velocity. The results of SEM images and polarized FTIR investigations verified that the as-spun PLLA porous surface fibers were highly aligned and molecularly oriented, leading to the enhanced mechanical performance as compared to the non-woven PLLA electrospun fibers.     

The effects of processing variables on electrospun poly(ethylene glycol) fibrous hydrogels formed from the thiol-norbornene click reaction

Electrospinning has been used to create scaffolds with tunable micro/nano architecture, stiffness, and porosity to mimic native extracellular matrix. This study investigated the effects of electrospinning parameters and hydrogel formulation (solvent and crosslinker type) on the architecture and properties of fibrous poly(ethylene glycol) (PEG) hydrogels formed from a photoclick thiol-norbornene reaction. Fibrous hydrogels were prepared using hydrogel precursors (four-arm PEG norbornene and multi-thiol crosslinker), sacrificial poly(ethylene oxide) (PEO, 400 kDa), and photoinitiator (I2959) in either 2,2-triflouroethanol (TFE) or water. Three thiol crosslinkers- 2,2′-(ethylenedioxy)diethanethiol (EDT), pentaerythritol tetrakis(3mercaptopropionate) (PTMP), and PEG dithiol (PEGDT)- were investigated. Fibrous PEG networks with uniform fibers were produced at applied voltages of 10 or 12 kV for TFE and 16 kV for water. Fiber diameters of electrospun hydrogels were largely affected by the solvent when combined with PEO concentration and ranged from 0.5 to 3.5 mm in dry state. While the effect of crosslinker type on fiber diameter, morphology, and porosity of the fibrous hydrogel was minimal, it did modulate its shear modulus. To this end, this study provides the groundwork for selecting processing parameters to achieve desired properties of fibrous PEG thiol-norbornene hydrogels for intended tissue engineering applications ranging from neural, cardiovascular to musculoskeletal.     

Electrospinning of uniform polystyrene fibers: The effect of solvent conductivity

By means of the electrospinning technique, micron- and nanofibers can be obtained from polymer solutions under a very high electrical field. A special challenge is to produce bead-free uniform fibers since any minor changes in the electrospinning parameters such as slight variations in the polymer solutions and/or electrospinning experimental parameters may result in significant variations in the final nanofiber morphology. Furthermore, it is often not trivial at all to obtain reproducible uniform electrospun nanofibers for the optimized electrospinning conditions. Here we report that the conductivity of the solvent is the key factor for the reproducible electrospinning of uniform polystyrene (PS) fibers from dimethylformamide (DMF) solutions. It is shown that even slight changes in the conductivity of the DMF solutions can greatly affect the morphology of the resulting electrospun PS fibers. Here, we have carried out a thorough and systematic study on the effect of solution conductivity on the electrospinning of bead-free polystyrene (PS) fibers when dimethylformamide (DMF) was used as the solvent. Interestingly, we found out that different grades of solvent as-received (DMF) from various suppliers have slightly different solution conductivities. Consequently, the polymer solutions prepared with the same PS concentration have different conductivities, which are shown to have significant changes on the morphology of the PS fibers resulting in beaded or bead-free uniform fibers when electrospun under the identical electrospinning conditions. Such as, bead-free PS fibers were obtained from PS solutions in the range of 20% (w/v) through 30% (w/v) depending on the DMF grade used. In brief, it was observed that solutions with a higher conductivity yielded bead-free fibers from lower polymer concentrations, which confirms that the solution conductivity plays a very significant role in producing bead-free uniform PS fibers.     

Conductive chitosan/multi walled carbon nanotubes electrospun nanofiber feasibility

The current study focuses on the electrospinning of chitosan (CHT)/multi walled carbon nanotubes (MWNTs) composite nanofiber using a highly stable dispersion. The acetic acid (1–100%) and trifluoroacetic acid/dichloromethane (TFA/DCM 70: 30) was tested as solvent, and the TFA/DCM (70 : 30) is most preferred for fiber formation process with acceptable electrospinnability. Moreover, a new protocol was used to establish proper technique for preparation of electrospinning solution. FT-IR spectroscopy utilized to infer the extent of interaction between CHT polymer chain and MWNT filaments. A quite simple technique was employed to show the stability of electrospinning solution before nanofiber formation process. Scanning electronic microscope (SEM) was employed to show the influence of spinning parameters on surface morphology of electrospun fiber. Under optimized condition, homogeneous and beadfree CHT/MWNTs nanofibers and known physical characteristics were prepared. The formation of conducting nanofibers based on CHT nanocomposites can be considered as a significant improvement in electrospinning of CHT/CNT dispersion. The direct outcome of the current study includes the homogeneous CHT/MWNTs nanofibers with an average diameter of 275 nm and a conductivity of 9×10⁻⁵ S/cm. These results are extremely important for further investigation regarding biomedical applications.     

Electrospun PLA/PCL fibers with tubular nanoclay: Morphological and structural analysis

Biodegradable polymers are good candidates for a wide range of applications in tissue engineering and drug delivery because of their biocompatibility, their degradation, mechanical properties, and offer a sustained release of encapsulated drugs. The electrospun polymer nanofibrous materials can be used as carriers for hydrophobic and hydrophilic drugs. This research work focused on poly(lactic acid) (PLA) and blends of PLA with poly (ε‐caprolactone) (PCL) that are reinforced with different concentrations of halloysite nanotubes (HNTs) and various cosolvents for electrospinning including chloroform : acetone, chloroform : methanol, and dichloromethane (DCM) : N,N, dimethylformamide (DFM). The fibers produced from the DCM : DMF system without HNTs were more uniform resulting in smaller fiber diameters as compared to the chloroform: methanol system due to the increased solution conductivity. The addition of HNT nanoparticles produced electrospun fibers with large diameters because the viscosity of the solution increased. Cosolvent was important in determining fiber diameters because it strongly influenced the solution viscosity and conductivity. HNTs had relatively small impact on the growth of a crystalline morphology in PCL–HNT composites. The solvent mixture of chloroform : methanol was better for PLA‐based systems since PLA was found to have slightly higher crystallinity and larger enthalpy value indicating the improved structural orderness in the PLA polymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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 electrospun ethylene vinyl alcohol copolymer (EVOH) fibres on the structure,morphology, and properties of poly(lactic acid) (PLA)

The effect of ethylene content and of the concentration of the solution used for electrospinning on the morphology of electrospun poly ethylene vinyl alcohol (EVOH) fibre was studied. Also, poly(lactic acid) (PLA) filled with electrospun EVOH fibres was investigated. Good interfacial adhesion between PLA and EVOH fibres was obtained with smaller diameter fibres. The effect of electrospun fibres resulted in disrupted lamellar morphology and also decreased the degree of crystallinity related to the semicrystalline framework. Surface roughness was calculated using atomic force microscopy (AFM). Surface roughness increased with the increase in fibre diameters. The rheology experiments revealed that electrospun EVOH fibres enhance the storage modulus of PLA composites while having low crystallinity. EVOH fibres showed the capacity of tuning the degradation behaviour. The good interfacial morphology between PLA and smaller diameter fibres slowed down the degradation rate, whereas composites with larger diameter fibres, due to poor interfacial adhesion showed faster degradation rate than the other compositions, because large EVOH fibres afford channels by which NaOH solution can easily penetrate throughout the composite material. The incorporation of EVOH fibres into PLA matrix allowed obtaining materials with increased storage modulus and also showed viability to tune the degradation behaviour of PLA based products.     

Electrospinning short polymer micro-fibres with average aspect ratios in the range of 10–200

Ultra fine short fibres have a variety of applications. Short aligned fibres or a mixture of short and long fibres can reinforce brittle materials, alter the appearance, texture and durability of synthetic fibres, and adjust the strength, toughness and stiffness of a composite material. Among electrospun products, short fibres are usually produced by secondary processing of continuous as-spun fibres. However, this is not entirely straightforward or cost-effective due to the efficiency of the secondary process and the relatively low tensile strength of the electrospun ultrafine fibres. Besides, sub-micrometre size fibres with an average aspect ratio (AR) <200 have not been directly produced without further processing by changing collector geometry in electrospinning. Using a model polymer, polymethylsilsesquioxane (PMSQ), short micro-fibres with 10 < AR < 200 were electrospun directly in this work, i.e. without the need for a secondary process. The AR and particularly fibre length were shown to be strongly influenced by the solvent system used for electrospinning and the molecular weight ([`(M<sub>w</sub>)] \overline {{M_w}} ) of the polymer. When using PMSQ1 ([`(M_w)] \overline {{M_w}} =7500) in methanol instead of acetone, short fibres with AR <200 were produced instead of continuous fibres. Moreover, when [`(M_w)] \overline {{M_w}} of the polymer was decreased from 7500 (PMSQ1) to 4300 (PMSQ2), with all other conditions kept constant, significant reduction in the AR of the as-spun fibres was observed. Short fibres with average AR of 15 were produced from PMSQ2 solution in 3:2 v/v dimethylsulphoxide:2-nitropropane. The average AR of short fibres spun from PMSQ2 solution in 2:3 v/v methanol:propanol was 31. Also PMSQ1 in both of the above-mentioned binary solvent systems produced long continuous fibres with AR >3000 under the same spinning conditions.     

Electrospinning and characterisation of ceria doped yttria fibres

Abstract

Homogeneous inorganic-organic composite fibres were produced using electrospinning technique from alcoholic solutions containing polyvinyl butyral and precursors of yttrium and cerium ions. Upon heat treatment, ceria and yttria doped ceria fibres retaining the original morphological features observed in the as spun composition were obtained. X-ray diffraction was used to identify the crystalline phases of the final products. Scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and Brunauer-Emmett-Teller analysis were used to study the ceramic phase formation and the evolution of morphological features of the fibres. Thus, several micrometres long, uniform ceria and yttria doped ceria fibres of high phase purity were produced. The CeO₂ and the CeO₂ with Y₂O₃ fibres presented average diameter that ranged from 19 to 25?μm, and the distribution of specific surface ranged from 33 to 43?m²?g^?1.     

Comparisons between silk fibroin nonwoven electrospun fabrics using aqueous and formic acid solutions

The objective of this study is to compare the spinnability, morphology, structure, mechanical properties, and cell compatibility of the silk fibroin nanofiber nonwoven electrospun fabrics using aqueous (AQ) solution and formic acid (FA) solution. The lower limit concentration was 5?wt% and 3?wt% of AQ solution and FA solution for electrospinning, respectively. The fiber diameter of electrospun fabric using FA solution was larger than that using aqueous solution at the same concentration. The secondary structure contents of silk fabrics were same between AQ and FA solutions. FA was remained in silk nanofibers, and the remained FA could be neutralized. Young’s modulus and cell adhesion on electrospun fabric using FA was lower than that using AQ solution. On the contrary, lower cell proliferation rate on electrospun fabric using FA was kept even after neutralization.     

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     

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.     

Tailoring the grooved texture of electrospun polystyrene nanofibers by controlling the solvent system and relative humidity

In this study, we have successfully fabricated electrospun polystyrene (PS) nanofibers having a diameter of 326 ± 50 nm with a parallel grooved texture using a mixed solvent of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). We discovered that solvent system, solution concentration, and relative humidity were the three key factors to the formation of grooved texture and the diameter of nanofibers. We demonstrated that grooved nanofibers with desired properties (e.g., different numbers of grooves, widths between two adjacent grooves, and depths of grooves) could be electrospun under certain conditions. When THF/DMF ratio was higher than 2:1, the formation mechanism of single grooved texture should be attributed to the formation of voids on the jet surface at the early stage of electrospinning and subsequent elongation and solidification of the voids into a line surface structure. When THF/DMF ratio was 1:1, the formation mechanism of grooved texture should be ascribed to the formation of wrinkled surface on the jet surface at the early stage of electrospinning and subsequent elongation into a grooved texture. Such findings can serve as guidelines for the preparation of grooved nanofibers with desired secondary morphology.     

聚乳酸纤维的静电纺丝及其形态结构研究

采用二氯甲烷为溶剂,以滚筒为收集装置,利用静电纺丝法制备了聚乳酸纳米纤维。分析了溶液体系和滚筒转速对纤维形态结构的影响。结果表明:在质量分数相同的条件下,采用相对分子质量较大的聚乳酸切片所纺纤维直径细而均匀;质量分数增加时,电纺丝产品由一些高分子微/纳米液滴渐变为成形较好、珠状较少的平滑纤维,其平均纤维直径先增加后减小;控制收集滚筒的转速在一定范围内,可以获得排列取向较好的纤维。     

Multifunctional porous membranes with antibacterial properties

Abstract

The paper describes the results of research on obtaining porous membranes produced from polylactide fibers (PLA) by electrospinning, additionally modified with gentamicin antibiotic (GM) at the stage of preparing a spinning solution to provide bactericidal properties. Both solid (1^oPNF) and porous (2^oPNF 3^oPNF) polymer fibers were obtained, and the control of fiber porosity was achieved using various solvent systems: dichloromethane (DCM), dimethylformamide (DMF), chloroform (CHL) and dimethyl sulfoxide (DMSO). Three types of fibers differing in morphology (fiber diameter) and mean pore size were obtained. Physicochemical properties of porous and solid drug-containing fibers were examined, determining their surface free energy (SFE) and wetting angle (CA), and the effectiveness of modification with the drug was confirmed in spectroscopic studies (FTIR-ATR). Antibacterial activity of the prepared drug-modified nonwovens was confirmed by the disk diffusion method against Gram-negative Escherichia coli bacteria strain. The results of tests have shown that depending on the type of solvents used at the electrospinning stage, porous fibers can be obtained from polylactide. The addition of gentamicin affected antibacterial properties, and the pore size determined the rate of drug release monitored by the ion coupled plasma method (ICP).     

The influence of solvent type and polymer concentration on the physical properties of solid state polymerized PA66 nanofiber yarn

We investigated the effects of two different solvent types and three solution concentrations on the electrospinning of solid state polymerized polyamide 66 (SSP PA66) nanofiber yarns. Nanofiber yarns were electrospun from SSP PA66 solutions in formic acid and formic acid/chloroform (3/1), using two oppositely metallic spinnerets system. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to characterize the morphology and properties of the nanofibrous yarns. Experimental results show that adding chloroform to formic acid as a binary solvent increases viscosity of polymer solution and the nanofibers diameter significantly. XRD patterns reveal that the presence of chloroform affects the crystallinity and the mechanical properties of the produced nanofibrous yarns. PA66 nanofiber yarn from 10 wt % formic acid/chloroform (3/1) solution was successfully electrospun with strength and modulus of 120.16 MPa and 1216.27 MPa respectively. It is also shown that the solution concentration has a significant effect on the modulus of the nanofibers yarns. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrospinning of Novel Poly(ester amide)s

Novel PEAs derived from 1,4‐butanediol, dimethyl adipate and a preformed α,ω‐amino alcohol were synthesised and successfully electrospun from solution. The effects of increasing the ratio of amide/ester groups in the copolymer, polymer concentration, solvent mixtures and applied voltage on fibre morphology and diameter were investigated. The obtained fibres (diameter 180–450 nm) were randomly oriented. The fibre quality and homogeneity increased with increasing amide concentration. The solvent mixture CHCl₃/HCOOH gave the best electrospinning results. The ultra‐fine fibres were characterised using SEM, DSC and FT‐IR, showing that the electrospun fibres are amorphous as compared to the pristine samples. These fibres are potential candidates for use as scaffolds in tissue engineering.