Electrospinning of Poly(Hydroxybutyrate-co-hydroxyvalerate) Fibrous Scaffolds for Tissue Engineering Applications: Effects of Electrospinning Parameters and Solution Properties

Electrospinning, a technology capable of fabricating ultrafine fibers (microfibers and nanofibers), has been investigated by various research groups for the production of fibrous biopolymer membranes for potential medical applications. In this study, poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), a natural, biocompatible, and biodegradable polymer, was successfully electrospun to form nonwoven fibrous mats. The effects of different electrospinning parameters (solution feeding rate, applied voltage, working distance and needle size) and polymer solution properties (concentration, viscosity and conductivity) on fiber diameter and morphology were systematically studied and causes for these effects are discussed. The formation of beaded fibers was investigated and the mechanism presented. It was shown that by varying electrospinning parameters within the processing window that was determined in this study, the diameter of electrospun PHBV fibers could be adjusted from a few hundred nanometers to a few microns, which are in the desirable range for constructing “biomimicking” fibrous scaffolds for tissue engineering applications.     

Wettability Improvement of Poly (Butylene Terephthalate) Nanofibrous Mats Prepared via Electrospinning by Blending With Regenerated Silk Fibroin

Poly (butylene terephthalate) (PBT)/regenerated silk fibroin (RSF) blend electrospun nanofibrous mats were manufactured to combine the excellent mechanical behavior of PBT with the extraordinary hydrophilic property of RSF. A 1:1 mixture of trifluoroacetic acid (TFA) and dichloromethane (DCM) was adopted as the solvents for PBT and RSF with 20% (w/v) PBT and 16 wt% RSF solutions being mixed in various proportions for electrospinning. The morphology, crystallization, Fourier transform infrared (FTIR) spectra, surface roughness, contact angle, and wetting time of the electrospun blended materials were studied. When the weight ratio of RSF was larger than 50%, a water drop on the surface of the electrospun mat was completely permeated within 300 s or less. Besides the chemical influence of the amino and carboxy groups in RSF, the physical characteristics of the RSF in the blend electrospun mats, such as random coil structure, lower crystallinity, rougher surface than PBT, etc., were a partial reason for the improvement of wettability. The blend nanofibrous mats may be especially applicable in biomedical fields.     

Polymer nanofibers prepared by low-voltage near-field electrospinning

Electrospinning is a straightforward method to produce micro/nanoscale fibers from polymer solutions typically using an operating voltage of 10 kV–30 kV and spinning distance of 10 cm–20 cm. In this paper, polyvinyl pyrrolidone (PVP) non-woven nanofibers with diameters of 200 nm–900 nm were prepared by low-voltage near-field electrospinning with a working voltage of less than 2.8 kV and a spinning distance of less than 10 mm. Besides the uniform fibers, beaded-fibers were also fabricated and the formation mechanism was discussed. Particularly, a series of experiments were carried out to explore the influence of processing variables on the formation of near-field electrospun PVP nanofibers, including concentration, humidity, collecting position, and spinning distance.     

Fabrication and Optimization of Poly(vinyl alcohol)/Zirconium Acetate Electrospun Nanofibers Using Taguchi Experimental Design

This paper presents an investigation regarding poly(vinyl alcohol)/zirconium acetate (organic–inorganic) (PVA/Zrace) nanofibers prepared by electrospinning which could be used as a precursor for fabricating ceramic metal oxide nanofibers. The effect of some processing variables, including polymer solution concentration, tip to collector distance and applied voltage of electrospinning, and the amount of Zrace and their interactions, on the diameter of the nanofibers were studied. Taguchi experimental design and a statistical analysis (ANOVA) were employed and the relationship between experimental conditions and yield levels determined. It was concluded that to obtain a narrow diameter distribution as well as maximum fiber fineness, a polymer concentration of 10 wt%, tip to collector distance of 18 cm and applied voltage of 20 kV variables were the optimum. Furthermore, it was also concluded that the ratio of Zrace (6 g) to PVA solution (10% wt) played an important role for achieving the minimum fiber diameter. Under these optimum conditions, the diameters of the electrospun composite fibers ranged from 86 nm to 381 nm with a diameter average of 193 nm. The experiments were done with Qualitek-4 software with “smaller is better” as the quality characteristics. The optimized conditions showed an improvement in the fibers diameter distribution and the average fibers diameter showed good resemblance with the result predicted using the Taguchi method and the Qualitek-4 software. The ANOVA results showed that all factors had significant effects on the fibers diameter and distribution, but the effect of PVA concentration and zirconium acetate were more significant than the other factors.     

Poly(Butylene Terephthalate)/Single Wall Carbon Nanotubes Composite Nanofibers by Electrospinning

Poly(buthylene terephthalate)(PBT)/single wall carbon nanotubes (SWCNTs) composite nanofibers were prepared by electrospinning. The effect of carbon nanotubes on the morphology, crystallization, and mechanical properties of the electrospun composite nanofibers were investigated by SEM, DSC, and tensile testing, respectively. SEM observations indicated that the presence of SWCNTs resulted in finer nanofibers for lower loading; however, a broader distribution, especially for the higher diameter ranges was found for nanofibers with higher amounts of carbon nanotubes. SWCNTs accelerated crystallization and acted as a nucleating agent; the degree of crystallinity increased with increasing content of SWCNTs, followed by a moderate decrease at higher content. Specific tensile strength and modulus of the PBT/SWCNTs composite nanofibers mats were higher than that of neat PBT nanofibers mat. However, the elongation at break of composite nanofibers mats was lower than that of the neat PBT nanofibers mat.     

Two-nozzle electrospinning of (MWNT/PU)/PU nanofibrous composite mat with improved mechanical and thermal properties

Composite nanofibrous mat composed of neat polyurethane (PU) and multiwalled carbon nanotubes/polyurethane (MWNT/PU) nanofibers have been fabricated by one-step angled two-nozzle electrospinning. The morphological, thermal, and mechanical properties of the electrospun nanofibers were evaluated. The diameters of electrospun neat PU and composite nanofibers ranged from 239 to 1058 nm. The two-nozzle electrospun (MWNT/PU)/PU composite nanofibers showed curly, and randomly-oriented fibers with interfiber bonding, and were generally bigger in size than single-nozzle electrospun nanofibers. The tensile strength of the neat PU composite nanofiber mat obtained from two-nozzle electrospinning was 25% higher than that obtained from neat PU single-nozzle electrospinning. The incorporation of MWNTs in the composite nanofiber increased the tensile strength by as much as 64% without reducing elongation, made the composite nanofiber more thermally stable, and improved the melting zone. The present results showed that side-by-side angled two-nozzle electrospinning can improve the quality of the electrospun nanofibers that could have potential application in different fields such as filtration, protective clothing and tissue engineering.     

Predicting Polymorphism of Electrospun Polyvinylidene Fluoride Membranes by Their Morphologies

Although electrospinning of polyvinylidene fluoride (PVDF) has been studied for more than 10 years, the crystalline phase differentiation of the electrospun mats is still normally through the combination of different characterization techniques, and the relationship between polymorphism and morphology of the fibers in electrospun PVDF membranes has never been reported. Here, we show their close relationships by conducting room-temperature electrospinning experiments on various polymer/solvent systems. The electrospun membranes full of bead-free fibers have a very high fraction of β-phase, F(β), over 90%, and high orientation, whereas the membranes comprising beads and/or a large number of beaded fibers most often result in a low fraction of β-phase (F(β) normally below 50%) and low orientation. On the other hand, electrospun membranes consisting of both bead-free fibers and a very limited number of beaded fibers showed a medium high fraction of β-phase, F(β) more than 70% but less than 90%. These findings suggest the feasibility of intuitively predicting the crystalline phase of electrospun PVDF membranes directly by their morphologies, which is obviously simple, inexpensive and convenient for future investigations.     

Production of nanofibers by electrospinning under pressurized CO2

Electrospinning is one of the simple technical methods for the production of polymer nanoparticles and nanofibers. Various polymers have been successfully electrospun into ultrafine particles and fibers in recent years mostly in solvent solution and some in melt form. In this work, near- and supercritical CO₂ were used as media for this process. At these conditions, the solubility can be tuned by controlling the temperature and pressure. Therefore, it is possible to form particles and fibers within a thermodynamic window where the biopolymer has been softened, but not dissolved. The experiments were conducted by using electrospinning under pressurized CO₂ system at pressures of ～ 8.0 MPa and temperature of 313 K to produce several polymers fibers. Polyvinylpyrrolidone was used as the starting material. During the electrospinning process, the applied voltage was 10–17 kV and the distance of nozzle and collector was 8 cm. The concentration of polymer solution was 4 wt%. The morphology- and structure-produced fibers were observed by scanning electron microscopy. The results showed that temperature and pressure affected the morphology of fibers produced by electrospinning in pressurized CO₂. This suggests that the thermal behavior of the polymer can be optimized by adjusting the polymer through the adjustment of pressure and temperature by using CO₂ as a solvent.     

Poly(ɛ-caprolactone) Electrospun Scaffolds Filled with Nanoparticles. Production and Optimization According to Taguchi's Methodology

Polycaprolactone (PCL) scaffolds were produced by electrospinning. Polymeric solutions in a mix of dichloromethane (DCM) and dimethylformamide were electrospun to form fibers in the sub-micron range. Physical properties of the PCL solutions were characterized with respect to density, viscosity, conductivity and surface tension. Processing was optimized following Taguchi's methodology to select the set of processing parameters that resulted in producing fibers with the smallest diameters, minimum number of defects and with the narrowest distribution of fiber diameter. Morphology of electrospun fibers was qualitatively and quantitatively analyzed for the different sets of processing parameters. The optimum conditions found to electrospun PCL were used to process PCL solutions containing nanoparticles of hydroxyapatite (HA) or bioactive glass (BG). Bioactivity of nanocomposite electrospun membranes in simulated body fluid (SBF) was analyzed and biological response was tested by assessing proliferation and viability of MT3C3-E1 preosteoblasts cultured on PCL and its nanocomposite membranes.     

Elaboration and characterization of magnetic nanocomposite fibers by electrospinning

We describe a simple method based on the electrospinning process to prepare heterogeneous hybrid submicronic fibers with magnetic behavior, consisting of Co nanoparticles embedded in a polyacrylonitrile (PAN) polymer. Quantity and anisotropy of magnetic nanoparticles are key parameters to improve the specific magnetic properties of fibers. We notably show that for higher Co nanoparticles concentration, their lower dispersity into the resulting fibers lead to dipolar interactions that become demagnetizing. The structural and morphological properties of Co nanodisks and of the resulting nanocomposite fibers are investigated by SEM, TEM, and EDX. The magnetic properties of the hybrid electrospun fibers have been evaluated with a SQUID magnetometer.     

A direct-electrospinning process by combined electric field and air-blowing system for nanofibrous wound-dressings

An electrospinning process has been introduced to fabricate micro/nanofiber membranes having high porosity and specific surface area. When constantly/uniformly depositing the micro/nanofiber membrane on a target, the electrospun fibers require flushing out of the high charge and excessive remaining solvent built up, since these factors can interrupt the constant deposition rate of the electrospun fibers on substrates. These limitations can be overcome with a direct-electrospinning process, which can lower the charges of the electrospun fibers through a window of guiding electrodes and remaining solvent of the electrospun fibers during the spinning process by an air-blowing system. Because of the reduced charge accumulation of the electrospun fibers, the micro/nanofibers can be deposited on any kind of target, which may be a conductive or a non-conductive material. The fabricated membrane had a dramatically reduced charge, remaining solvent concentration, sufficient tensile modulus, and small pore-size distribution. To observe the possibility as a biomedical wound-dressing material, a bacteria-shielding test of the fabricated membrane was conducted. PACS 47.65.-d; 81.16.-c; 81.07.-b; 61.41.+e; 87.85.J-     

Electrospinning of polyacrylonitrile fibers from ionic liquid solution

We developed a temperature-controlled electrospinning apparatus specially for the polymers/IL system with high viscosity and surface tension and investigated the electrospinning of polyacrylonitrile (PAN)/1-butyl-3-methyl-imidazolium bromide ([BMIM][Br]) solutions. The rheological behaviors, surface tensions and conductivities of PAN/[BMIM]/[Br] solutions at different temperatures indicated that appropriately increasing the temperature is beneficial to their spinnability. It is also shown that PAN/[BMIM]/[Br] with a concentration of 3 wt%, 4 wt% and 5 wt% can be electrospun to fibers by increasing their temperatures to 70°C, 75°C or 85°C, respectively. A rotating drum composed of a dacron mesh was used as a collector in order to avoid the contraction of the wet fibers. This present study provides an alternative method for electrospinning polymer fibers.     

Investigation of Effect of Electrospinning Parameters on the Morphology of Polyacrylonitrile/Polymethylmethacrylate Nanofibers: A Box–Behnken-Based Study

Polyacrylonitrile (PAN)- and polymethylmethacrylate (PMMA)-blended nanofibers produced using electrospinning and mat morphology were studied. The response surface method was exploited to optimize the diameter and its standard deviation of electrospun PAN/PMMA non-woven membranes. The diameter and its standard deviation were related to the solution concentration, applied voltage, and PMMA composition. The morphology of nanofibers was studied by means of field emission scanning electron microscopy. The importance of parameters and their interactions was investigated through the analysis of variance. The nanofibers' diameter increased with solution concentration and decreased with applied voltage. The data showed that the diameter of nanofibers decreased up to 50% with PMMA composition, and then increased with further increase of PMMA composition. Some important interactions between the parameters were detected.     

Formation of high aspect ratio polyamide-6 nanofibers via electrically induced double layer during electrospinning

In the present study, the formation of high aspect ratio nanofibers in polyamide-6 was investigated as a function of applied voltage ranging from 15 to 25 kV using electrospinning technique. All other experimental parameters were kept constant. The electrospun polyamide-6 nanofibers were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF). FE-SEM images of polyamide-6 nanofibers showed that the diameter of the electrospun fiber was decreased with increasing applied voltage. At the critical applied voltage, the polymer solution was completely ionized to form the dense high aspect ratio nanofibers in between the main nanofibers. The diameter of the polyamide-6 nanofibers was observed to be in the range of 75-110 nm, whereas the high aspect ratio structures consisted of regularly distributed very fine nanofibers with diameters of about 9-28 nm. Trends in fiber diameter and diameter distribution were discussed for the high aspect ratio nanofibers. TEM results revealed that the formation of double layers in polyamide-6 nanofibers and then split-up into ultrafine fibers. The electrically induced double layer in combination with the polyelectrolytic nature of solution is proposed as the suitable mechanisms for the formation of high aspect ratio nanofibers in polyamide-6.     

Electrospinning Instabilities in the Drop Formation and Multi-Jet Ejection Part I: Various Concentrations of PVA (Polyvinyl Alcohol) Polymer Solution

The electrospinning technique has attracted significant research attention because of its various potential applications and simplicity of manufacturing fibers of diameter from several micrometers to nanometer range. However, the methods for controlling the shape, structure, and uniformity of electrospun fibers have not yet been fully investigated. In this research electrospinning instabilities, such as cyclical electrospinning fluctuation and multi-jet ejections, which are closely related to the corresponding nanofiber deposition, were investigated for various polymer solution concentrations. The cyclical electrospinning fluctuation was evaluated with an image analysis program integrated with an image acquisition system that we developed. Two different drop size fluctuations of the cyclical process of the drop formation were observed.     

Effect of carbon nanotubes dispersion on morphology, internal structure and thermal stability of electrospun poly(vinyl alcohol)/carbon nanotubes nanofibers

The current work reports the effect of multi walled carbon nanotubes and single walled carbon nanotubes dispersion on morphological, structural and thermal degradation of electrospun poly(vinyl alcohol) (PVA)/carbon nanotubes (CNTs) dispersed in sodium dodecyl sulfate (SDS) (PVA/CNTs–SDS) composites nanofibers. (PVA/CNTs–SDS) nanocomposites fibers were elaborated using the traditional electrospinning process to disperse and align CNTs into the fibers, especially for low CNTs loading fraction: 0.3 and 0.7 wt%. The morphology of the electrospun fibers was studied using the scanning electronic microscopy. The average diameter of the fibers changes significantly after the incorporation of the CNTs in the PVA. Furthermore, Fourier transform infrared spectroscopy elucidated the effect of CNTs on the crystallization of the PVA which was confirmed by X-ray diffraction analysis. Thermogravimetric analysis showed that the thermal stability of the composite fibers depends on the loading fraction and on the type of carbon nanotubes.     

Fabrication and formation mechanism of closed-loop fibers by electrospinning with a tip collector

Electrospun nanofibers with designed or controlled structures have drawn much attention. In this study, we report an interesting new closed-loop structure in individual cerium nitrate/polyvinyl alcohol(Ce(NO_3)_3/PVA) and Na Cl/PVA fibers,which are fabricated by electrospinning with a nail collector. The electrospinning parameters such as voltage and Ce(NO_3)_3(or Na Cl) concentration are examined for the formation of the closed-loop structure. The results suggest that the increase of the spinning voltage or addition of Ce(NO_3)_3(or Na Cl) is favorable for the formation of the closed-loop structure, and the increase of loop numbers and the decrease of loop size. Further analyses indicate that the formation mechanism of the closed-loop fibers can be predominantly attributed to the Coulomb repulsion in the charged jets.     

Synthesis,characterization and mechanical properties of nylon–silver composite nanofibers prepared by electrospinning

Silver (Ag) nanoparticles (∼3 nm) were synthesized using silver nitrate as the starting precursor, ethylene glycol as solvent and poly (N-vinylpyrrolidone) (PVP) introduced as a capping agent. These nano-Ag particles were reinforced in nylon matrix by electrospinning of nylon-6/Ag solution in 2,2,2-trifluoroethanol and composite nanofibrous membranes were synthesized. The effects of solution concentration and relative humidity (RH) on the resultant fibrous membranes were studied. Scanning electron microscopy and Transmission electron microscopy was used to study the size and morphology of the fibers. It was observed that concentration and RH could be used to modulate the fiber diameter. Tensile test was used to evaluate the mechanical property of these electrospun composite membranes. The composite membranes showed higher strength (approx. 2–3 times increase in strength) compare to as synthesized nylon fibers.     

Influence of morphology on the emissive properties of dye-doped PVP nanofibers produced by electrospinning

Dye-doped polymer micro- and nanofibers with tailored light emission properties have great potential for applications in optical, optoelectronic, or photonic devices. In this study, these types of structures were obtained by electrospinning rhodamine 6 G-doped polyvinylpyrrolidone (PVP) using a polymer solution of 10% (mass) concentration in ethanol. Polymer nanofibers with different morphologies (smooth and beaded) and diameters of about 500 nm were obtained using different electrospinning conditions with the same solutions. Fluorescence optical microscopy observations showed that the dye was distributed uniformly in the doped PVP nanofibers. Different shifts were observed when we compared the wavelength of the dye emission band peak of the smooth nanofibers (566 nm) and the wavelength of the dye emission band peak of the beaded fibers (561.5 nm) produced by electrospinning in different conditions with the wavelength of the emission band peak for transparent thin films produced by spin coating (558 nm) using the same polymer solution. This demonstrates that it is possible to tune the optical properties of electrospun dye-doped polymer nanofibers simply by modifying the morphology of the material, i.e., the parameters of the electrospinning process.     

Multi-response analysis in the material characterisation of electrospun poly (lactic acid)/halloysite nanotube composite fibres based on Taguchi design of experiments: fibre diameter, non-intercalation and nucleation effects

Poly (lactic acid) (PLA)/halloysite nanotube (HNT) composite fibres were prepared by using a simple and versatile electrospinning technique. The systematic approach via Taguchi design of experiments (DoE) was implemented to investigate factorial effects of applied voltage, feed rate of solution, collector distance and HNT concentration on the fibre diameter, HNT non-intercalation and nucleation effects. The HNT intercalation level, composite fibre morphology, their associated fibre diameter and thermal properties were evaluated by means of X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), imaging analysis and differential scanning calorimetry (DSC), respectively. HNT non-intercalation phenomenon appears to be manifested as reflected by the minimal shift of XRD peaks for all electrospun PLA/HNT composite fibres. The smaller-fibre-diameter characteristic was found to be sequentially associated with the feed rate of solution, collector distance and applied voltage. The glass transition temperature (T _g) and melting temperature (T _m) are not highly affected by varying the material and electrospinning parameters. However, as the indicator of the nucleation effect, the crystallisation temperature (T _c) of PLA/HNT composite fibres is predominantly impacted by HNT concentration and applied voltage. It is evident that HNT’s nucleating agent role is confirmed when embedded with HNTs to accelerate the cold crystallisation of composite fibres. Taguchi DoE method has been found to be an effective approach to statistically optimise critical parameters used in electrospinning in order to effectively tailor the resulting physical features and thermal properties of PLA/HNT composite fibres.