Polymeric nanofibers containing solid nanoparticles prepared by electrospinning and their applications

Generally, polymer solution or sol–gel is used to produce electrospun nanofibers via the electrospinning technique. In the utilized sol–gel, the metallic precursor should be soluble in a proper solvent since it has to hydrolyze and polycondensate in the final solution; this strategy straitens the applications of the electrospinning process and limits the category of the electrospinnable materials. In this study, we are discussing electrospinning of a colloidal solution process as an alternative strategy. We have utilized many solid nanopowders and different polymers as well. All the examined colloids have been successfully electrospun. According to the SEM and FE SEM analyses for the obtained nanofiber mats, the polymeric nanofibers could imprison the small nanoparticles; however, the big size ones were observed attaching the nanofiber mats. Successfully, the proposed strategy could be exploited to prepare polymeric nanofibers incorporating metal nanoparticles which might have interesting properties compared with the pristine. For instance, PCL/Ti nanofiber mats exhibited good bioactivity compared with pristine PCL. The proposed strategy can be considered as an innovated methodology to prepare a new class of the electrospun nanofiber mats which cannot be obtained by the conventional electrospinning technique.     

Effects of Fe2+ ions on morphologies,microstructures and mechanical properties of electrospun nylon‐6 nanofibers

In this study, nylon‐6 nanofiber mats containing Fe²⁺ ions were fabricated via electrospinning. The resultant electrospun nylon‐6/FeCl₂ nanofiber mats were characterized by SEM, TEM, Fourier transform IR spectroscopy, wide angle XRD and DSC. Unique morphological features, such as spider's‐web‐like morphologies, were observed and became evident with increasing additive Fe²⁺ ions. The metastable γ form was predominant in the as‐spun nylon‐6 nanofibers. The relative intensity of such γ form gradually decreased with increasing additive Fe²⁺ ions, indicative of transformation of the crystalline structure in the electrospun nylon‐6/FeCl₂ nanofibers due to strong molecular interactions between the nylon‐6 backbone and the additive Fe²⁺ ions. The effects of additive Fe²⁺ ions on the mechanical properties of both nonwoven nanofiber mats and single nanofibers were investigated. In particular, Young's modulus of nylon‐6/FeCl₂ single nanofibers gradually increased from 1.46 to 5.26 GPa with increasing additive Fe²⁺ ions. © 2013 Society of Chemical Industry     

Novel electrospun nanofiber mats as effective catalysts for water photosplitting

Two novel photocatalysts based on ceramic materials for hydrogen production from water splitting under the solar radiation are introduced. CdS-doped and CdS–PdS-doped poly(vinyl acetate) electrospun nanofiber mats reveal good activity toward water photosplitting. The efficient ceramic nanoparticles were in situ synthesized in the polymer solution which was subjected to the electrospinning process. CdS–PdS-doped poly(vinyl acetate) nanofibers produce more hydrogen compared to the naked CdS NPs. Immobilization of the CdS and CdS–PdS nanoparticles inside the polymer nanofibers is an effective strategy to overcome the photocorrosion and toxicity problems of the CdS-based materials.     

Crosslinking assisted fabrication of ultrafine poly(vinyl alcohol)/functionalized graphene electrospun nanofibers for crystal violet adsorption

This article reports the fabrication of water‐stable electrospun mats made from water‐soluble poly(vinyl alcohol) and comprising ultrafine nanofibers for a high surface area to volume ratio as required for the adsorption of crystal violet. Acid‐catalyzed crosslinking is uniquely demonstrated as a facile strategy to improve water stability and, just as importantly, fine‐tune the nanofiber size of the electrospun mats. Amine‐functionalized graphene nanoplatelets are incorporated as an adsorption performance enhancer instead of the more widely reported graphene oxide. The functionalized graphene also facilitates fabrication of the composite electrospun mats by direct mixing of the water‐dispersible graphene with the aqueous polymer solution. The enhanced adsorption performance of the polymer nanocomposite mats is explained in detail at the molecular level, while the adsorption mechanism is supported by adsorption isotherm and related kinetic data. Moreover, the adsorbent mats can be removed from the water after use with the mat integrity still maintained. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46318.     

Enhancement of the mechanical properties and thermostability of poly(vinyl alcohol) nanofibers by the incorporation of sodium chloride

The mechanical properties and thermostability of poly(vinyl alcohol) (PVA) nanofiber mats have been obviously improved by the incorporation of sodium chloride (NaCl). The tensile properties including tensile strength and modulus of membranes with an addition of 1.0 wt % NaCl increased from 2.51 to 4.22 MPa and 33.0 to 176.30 MPa, respectively, more than 160 and 700% of those of the electrospun pure PVA membranes. Moreover, thermogravimetric analysis showed that the initial decomposition temperature (T_i) and the half decomposing temperature (T_50%) of PVA nanofibers with the addition of NaCl were at least 26 and 59 °C higher than that of pure PVA nanofibers, respectively, indicating a strong interaction between the PVA and the salt ions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45981.     

Cobalt/copper-decorated carbon nanofibers as novel non-precious electrocatalyst for methanol electrooxidation

In this study, Co/Cu-decorated carbon nanofibers are introduced as novel electrocatalyst for methanol oxidation. The introduced nanofibers have been prepared based on graphitization of poly(vinyl alcohol) which has high carbon content compared to many polymer precursors for carbon nanofiber synthesis. Typically, calcination in argon atmosphere of electrospun nanofibers composed of cobalt acetate tetrahydrate, copper acetate monohydrate, and poly(vinyl alcohol) leads to form carbon nanofibers decorated by CoCu nanoparticles. The graphitization of the poly(vinyl alcohol) has been enhanced due to presence of cobalt which acts as effective catalyst. The physicochemical characterization affirmed that the metallic nanoparticles are sheathed by thin crystalline graphite layer. Investigation of the electrocatalytic activity of the introduced nanofibers toward methanol oxidation indicates good performance, as the corresponding onset potential was small compared to many reported materials; 310 mV (vs. Ag/AgCl electrode) and a current density of 12 mA/cm² was obtained. Moreover, due to the graphite shield, good stability was observed. Overall, the introduced study opens new avenue for cheap and stable transition metals-based nanostructures as non-precious catalysts for fuel cell applications.     

ITO electrode modified by self-assembling multilayer film of polyoxometallate on poly(vinyl alcohol) nanofibers and its electrocatalytic behavior

Poly(vinyl alcohol) (PVA) nanofiber mats were collected on indium tin oxide (ITO) substrate by electrospinning method. A multilayer film composed of α-[P₂W₁₈O₆₂]⁶⁻ (abbr. P₂W₁₈), a polyoxometallate (POM) anion, and poly(diallymethylammonium chloride) (abbr. PDDA) was fabricated by layer-by-layer (LBL) self-assembly technique on the PVA/ITO electrode. The PDDA/P₂W₁₈ multilayer film could be unselectively or selectively deposited on the PVA/ITO electrode via changing the amount of PVA nanofibers on the ITO substrate. The scanning electron microscope (SEM) images showed that when the electrospun time was short the PDDA/P₂W₁₈ multilayer film was unselectively deposited on PVA nanofiber mats because the amount of PVA nanofibers was too little to cover most of the ITO substrate. However, when the electrospun time was long enough, the PDDA/P₂W₁₈ multilayer film was selectively deposited on PVA nanofiber mats because of the larger surface area and higher surface energy of PVA nanofibers in comparison with the flat ITO substrate. Growth process of the multilayer film was determined by cyclic voltammetry (CV). Electrocatalytic effects of the PDDA/P₂W₁₈ multilayer film unselectively and selectively deposited on the PVA/ITO electrode on NO₂⁻ were observed.     

Interior synthesizing of ZnO nanoflakes inside nylon‐6 electrospun nanofibers

Doping of the polymeric electrospun nanofibers by metal oxides nanoparticles is usually performed by electrospinning of a colloidal solution containing the metal oxide nanoparticles. Besides the economical aspects, electrospinning of colloids is not efficient compared with spinning of sol–gels, moreover well attachment of the solid nanoparticles is not guaranteed. In this study, reduction of zinc acetate could be performed inside the nylon‐6 electrospun nanofibers; so polymeric nanofibers embedding ZnO nanoflakes were obtained. Typically, zinc acetate/nylon‐6 electrospun nanofibers were treated hydrothermally at 150°C for 1 h. Besides the utilized characterization techniques, PL study affirmed formation of ZnO. The produced nanofibers showed a good antibacterial activity which improves with increasing ZnO content. Overall, the present study opens new avenue to synthesize hybrid nanofibers by a facile procedure. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions

Chitosan bicomponent fibers were prepared via the electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions with different concentrations. With a 4% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were lower than 80/20, electrospinning nanofibers could be obtained. With a 90% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were less than 95/5, good nanofibers could be electrospun. The average diameter of the nanofibers gradually decreased, and its distribution became narrower as the poly(vinyl alcohol) concentration increased. Chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions could be electrospun at various concentrations by the adjustment of the chitosan and poly(vinyl alcohol) concentrations. The effects of the viscosity and conductivity of the blend solution on the morphologies of the fiber mats were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5692–5697, 2006     

Morphology enhancement of TiO2/PVP composite nanofibers based on solution viscosity and processing parameters of electrospinning method

In this work, different sol solutions with various titanium tetraisopropoxide (TIP)/glacial acetic acid ratios in 2‐propanol with 5 wt % poly(vinyl pyrrolidone) (PVP) (M_w = 360,000 g/mol) were prepared and electrospun. Composition of the prepared sols and as‐spun TiO₂/PVP nanofibers were determined by Fourier transform infrared and Raman spectroscopy methods. Morphology of the electrospun TiO₂/PVP nanofibers was studied by scanning electron microscopy and transmission electron microscopy (TEM) techniques. Rheometry measurements of the sol solutions showed decrease of viscosity upon the addition of TIP to the polymer solutions with constant polymer and acid concentrations. The sol solution having the lowest viscosity (at shear rate 10 s^?1) but the highest TIP/glacial acetic acid ratio showed beaded nanofibers morphology when electrospun under 10 and 12 kV applied voltage while injection rate, needle tip to collector distance, and needle gauge were kept constant. However, smooth electrospun TiO₂/PVP composite nanofibers with the average nanofibers diameters (148 ± 79 nm) were achieved under the same condition when applied voltage increased to 15 kV. TEM micrographs of the electrospun TiO₂/PVP nanofiber showed that the TiO₂ particles with continuous structure are formed at the middle of the nanofiber and distributed along its axis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46337.     

Electrospun CdS–TiO2 doped carbon nanofibers for visible-light-induced photocatalytic hydrolysis of ammonia borane

CdS/TiO₂ NPs-decorated carbon nanofibers were introduced as a novel photocatalyst working under visible light radiation for the effective hydrolytic dehydrogenation of ammonia borane. Calcination of electrospun nanofiber mats composed of titanium tetraisopropoxide, poly (vinyl pyrrolidone) (PVP), and cadmium acetate dihydrate with a few drops of ammonium sulfide in argon atmosphere at 850 °C led to the production of CdS–TiO₂ decorated carbon nanofibers. As-synthesized nanocomposite exhibited a strong photocatalytic activity for catalytic hydrolysis of ammonia–borane. The favorable electrons-transfer properties, better dispersion, high surface area, and adsorption property are the main features of nanocomposites that exhibit high catalytic efficiency.     

Mechanical properties of polymer nanofibers revealed by interaction with streams of air

Electrospun nanofibers were captured directly between two steel rods that functioned as the “grips” of the tensile testing apparatus. Tension was applied to the selected nanofiber by displacing one of the grips at controlled rates or in steps. The stress was revealed by the deflection of a nanofiber, caused by the drag force from a broad stream of air, which flowed perpendicular to the fiber at a known velocity. The deflected position and shape of the nanofiber was observed with a light arrangement optimized to produce bright glints that were photographed with a camcorder. Image analysis of the catenary shapes of the nanofibers was combined with scanning electron microscopy measurements of the diameter of the ends of the tested fibers to evaluate the mechanical properties.Measurements of properties, including tensile strength, tensile modulus and elongation-to-break, of thin electrospun fibers were obtained on six chemically different polymers: nylon 6, poly(ethylene oxide), polyvinylpyrrolidone, poly(2-ethyl-2-oxazoline), Tecoflex^® and Tecophilic^® polyurethanes. To the best of our knowledge, this is the first report of tensile data on single polyvinylpyrrolidone and poly(2-ethyl-2-oxazoline) nanofibers. These soft nanofibers with low strain to break rarely survive the sample loading procedures where single fiber manipulation is involved. This method complements difficult mechanical measurements of polymer nanofibers and low strength microfibers made on miniature mechanical testing devices. Mechanical hysteresis curves were attained that show the recoverable and non-recoverable tensile deformation of PEO, nylon and Tecophilic^® polyurethane fibers.     

Study of the effect of rutile/anatase TiO2 nanoparticles synthesized by hydrothermal route in electrospun PVA/TiO2 nanocomposites

Mixed rutile–anatase TiO₂ nanoparticles were synthesized by hydrothermal treatment under acidic conditions and incorporated into poly(vinyl alcohol) (PVA). These nanocomposites were electrospun to produce nanofibers of PVA/TiO₂, which were characterized by scanning electron microscopy, transmission electron microscopy, X‐ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The photocatalytic degradation of Rhodamine B and degradation of the polymer by UV‐C lamps were also investigated. The results showed that TiO₂ nanoparticles did not change the morphology and thermal behavior of the nanofiber polymer, but were effective in modifying the UV absorption of PVA without reducing its stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and antibacterial activity of PET/chitosan nanofibrous mats using an electrospinning technique

The nanofiber deposition method, by electrospinning, was employed to introduce antibacterial activity and biocompatibility to the surface of poly (ethylene terephthalate) (PET) textiles. The polymer blends of PET and chitosan were electrospun on to the PET micro‐nonwoven mats for biomedical applications. The PET/chitosan nanofibers were evenly deposited on to the surface, and the diameter of the nanofibers was in the range between 500 and 800 nm. The surface of the nanofibers was characterized using SEM, ESCA, AFM, and ATR‐FTIR. The wettability of the PET nanofibers was significantly enhanced by the incorporation of chitosan. The antibacterial activity of the samples was evaluated utilizing the colony counting method against Staphylococcus aureus and Klebsiella pneumoniae. The results indicated that the PET/chitosan nanofiber mats showed a significantly higher growth inhibition rate compared with the PET nanofiber control. In addition, the fibroblast cells adhered better to the PET/chitosan nanofibers than to the PET nanofibers mats, suggesting better tissue compatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fabrication and Antibacterial Activity of Electrospun Nylon 6 Nanofibers Grafted With 2-Substituted Vinylimidazoles

The authors present the fabrication of electrospun nanofibers with antimicrobial properties by the UV-initiated grafting (photo-grafting) of 2-substituted vinylimidazoles onto nylon 6 nanofibers. The characterization was performed using IR spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM-EDX). The antimicrobial properties of the grafted electrospun nylon 6 nanofibers were evaluated against Escherichia coli and Staphylococcus aureus as model challenge microorganisms, using the dynamic shake flask method. All the grafted electrospun nylon 6 nanofibers exhibited excellent growth reduction of E. coli (99.94–99.99%) and S. aureus (99.55–99.99%). The electrospun nylon 6 nanofiber composites could be used twice before a decrease in antibacterial activity was observed. The study showed that electrospun nylon 6 nanofiber composites possess a potential for use to control pathogens in water.     

Effects of hard and soft components on the structure formation,crystallization behavior and mechanical properties of electrospun poly(l-lactic acid) nanofibers

The effects of multi-wall carbon nanotubes (MWCNTs) and poly(ethylene oxide) (PEO) on the structure formation, morphology, crystallization behavior and mechanical property of electrospun poly (l-lactic acid) (PLLA) nanofiber mats were investigated by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC) and mechanical test. If incorporate hard filler, MWCNTs into electrospun PLLA nanofiber, the crystallinity, chain orientation, and crystallization behaviors were almost not influenced by the MWCNTs content owing to the MWCNTs mainly acted as impeding the crystal growth and chain diffusion. If incorporate small content of soft and miscible component, PEO (10 wt%) into the electrospun PLLA and PLLA/MWCNTs nanofibers, the crystallinity and crystallization rate of PLLA in nanofibers were obviously enhanced. The synergistic effect of PEO and MWCNTs in PLLA nanofibers was observed during melt-crystallization behaviors of PLLA/MWCNTs fibers. Based on those results, we found that the chain mobility is an important factor to influence the structure formation and crystallization behaviors in the electrospun nanofibers. Our results indicated that the structure and properties of electrospun nanofibers could be optimized by compounding with hard inorganic filler and soft polymer components.     

Mechanical property enhancement of non‐bonding electrospun mats via adhesive

In the present study, the effect of adhesive on the morphology of different electrospun polymeric mats was investigated. The modification of two polymers, poly(methyl methacrylate) and poly(vinyl chloride), was carried out by blending the polymers with different amounts of poly(butyl acrylate) (PBA) adhesive to investigate the effect of different amounts of adhesive with heat hardener in hybrid mats. The introduction of various concentrations of PBA into different polymer solutions led to the formation of point‐bonded electrospun fibrous mats. Scanning electron microscopy images indicated that point‐bonded polymer/adhesive fibers were uniformly distributed throughout the mats. Fourier transform infrared spectrometry, contact angle measurements and thermogravimetric analysis were used to study the different properties of the hybrid mats. The tensile strength of the blended fibrous electrospun mats was increased effectively. This enhancement of the mechanical properties of the mats due to the presence of adhesive increases the number of potential applications of the electrospun mats, especially for mechanically weak polymers. Copyright © 2012 Society of Chemical Industry     

Electrospinning and crosslinking of zein nanofiber mats

Electrospinning processing can be applied to fabricate fibrous polymer mats composed of fibers whose diameters range from several microns down to 100 nm or less. In this article, we describe how electrospinning was used to produce zein nanofiber mats and combined with crosslinking to improve the mechanical properties of the as‐spun mats. Aqueous ethanol solutions of zein were electrospun, and nanoparticles, nanofiber mats, or ribbonlike nanofiber mats were obtained. The effects of the electrospinning solvent and zein concentration on the morphology of the as‐spun nanofiber mats were investigated by scanning electron microscopy. The results showed that the morphologies of the electrospun products exhibited a zein‐dependent concentration. Optimizing conditions for zein produced nanofibers with a diameter of about 500 nm with fewer beads or ribbonlike nanofibers with a diameter of approximately 1–6 μm. Zein nanofiber mats were crosslinked by hexamethylene diisocyanate (HDI). The tensile strength of the crosslinked electrospun zein nanofiber mats was increased significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:380–385, 2007     

Electrospinning fabrication and characterization of poly(vinyl alcohol)/waterborne polyurethane nanofiber membranes in aqueous solution

Poly(vinyl alcohol) (PVA)/waterborne polyurethane (WBPU) nanofiber mats were prepared using electrospinning method with aqueous solutions. Scanning electron microscopy (SEM), X‐ray diffraction (XRD), thermal gravimetric analyzer (TGA), and tensile strength testing machine (ZWICK) were used to characterize the morphology and properties of the PVA/WBPU nanofiber mats. The results showed that the morphologies of PVA/WBPU nanofiber mats changed with the total solid concentration and the mass ratio of PVA/WBPU in the spinning solution. The tensile strength and thermal stability of the fibers could be significantly affected by the WBPU contents. The electrospun PVA/WBPU membranes showed higher water uptake, which would have potential applications in wound dressings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Bis-GMA/TEGDMA Dental Composites Reinforced with Electrospun Nylon 6 Nanocomposite Nanofibers Containing Highly Aligned Fibrillar Silicate Single Crystals

The objective of this research was to study the reinforcement of electrospun nylon 6/fibrillar silicate nanocomposite nanofibers on Bis-GMA/TEGDMA dental composites. The hypothesis was that the uniform distribution of nano-scaled and highly aligned fibrillar silicate single crystals into electrospun nylon 6 nanofibers would improve the mechanical properties of the resulting nanocomposite nanofibers, and would lead to the effective reinforcement of dental composites. The nylon 6/fibrillar silicate nanocomposite nanofibers were crystalline, structurally oriented and had an average diameter of approximately 250 nm. To relatively well distribute nanofibers in dental composites, the nanofiber containing composite powders with a particle structure similar to that in interpenetration networks were prepared first, and then used to make the dental composites. The results indicated that small mass fractions (1% and 2%) of nanofiber impregnation improved the mechanical properties substantially, while larger mass factions (4% and 8%) of nanofiber impregnation resulted in less desired mechanical properties.