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     

Nylon 66 nanofibers prepared by CO2 laser supersonic drawing

Nylon 66 nanofibers were prepared by irradiating as‐spun nylon 66 fibers with radiation from a carbon dioxide (CO₂) laser while drawing them at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through the fiber injection orifice. The fiber diameter depended on the drawing conditions used, such as laser power, chamber pressure, laser irradiation point, and fiber supply speed. A nanofiber obtained at a laser power of 20 W and a chamber pressure of 20 kPa had an average diameter of 0.337 μm and a draw ratio of 291,664, and the drawing speed in the CO₂ laser supersonic drawing was 486 m s^?1. The nanofibers showed two melting peaks at about 257 and 272°C. The lower melting peak is observed at the same temperature as that of the as‐spun fiber, whereas the higher melting peak is about 15°C higher than the lower one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40015.     

Single‐wall carbon nanotubes dispersion behavior and its effects on the morphological and mechanical properties of the electrospun nanofibers

The dispersion behavior of single‐walled carbon nanotube (SWCNT) has important effects on morphological and mechanical properties of SWCNT composite nanofibers. The relationship of the dispersion conditions with morphological and mechanical characteristics for SWCNT / polyacrylonitrile (PAN) / polyvinylpyrrolidone (PVP) composite nanofibers have been examined. The SEM and TEM analyses of the nanofibers revealed that the deformation in the nanofiber structures increases with increasing concentration of SWCNTs. Tensile results showed that only 2 wt% SWCNT loading to the electrospun composite nanofibers gave rise to 10‐fold and 3‐fold increase in the tensile modulus and tenacity of nanofiber layers, respectively. Essentially, high mechanical properties and uniform morphology of the composite nanofibers were found at SWCNT concentration of ∼2 wt% due to their stable and individual dispersion. POLYM. COMPOS., 33:1951–1959, 2012. © 2012 Society of Plastics Engineers     

Spinnability of SPPESK and its application in esterification

The electrospinning of sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) and its blend with polyether sulfone (PES) were investigated and the blend nanofibers were applied as a catalyst in esterification. Attempts to electrospin pure SPPESK resulted in electrospraying rather than electrospinning. However, a blend polymer solution of SPPESK and PES resulted in smooth electrospinning when SPPESK content was lower than 9 wt%. The geometrical properties such as fiber diameter and distribution, surface chemical properties such as inter-molecular interaction and crystalline, mechanical properties were investigated by SEM, FTIR, XRD, etc. The catalytic activities of SPPESK-PES nanofibers were measured by esterification of ethanol with acetic acid. A pseudo-homogeneous model was established to describe the kinetics of esterification with nanofiber as a catalyst. The results showed that the SPPESK-PES blend nanofiber had a high specific surface area (46.7–58.9 m²/g), good mechanical properties, good catalytic properties (ethanol conversion up to 80 % when reacted 8 h), and good forward rate constants (10.0?×?10^?3–14.6?×?10^?3 L/(mol?min)).     

Hydrophilic non-wovens made of cross-linked fully-hydrolyzed poly(vinyl alcohol) electrospun nanofibers

Fully-hydrolyzed poly (vinyl alcohol) (PVA) nanofibers were successfully electrospun from aqueous solutions of PVA in the presence of acetic acid. A continuous spinning of uniform PVA nanofibers proceeded by the addition of acetic acid due to the changes of electronic conductivity and surface tension of aqueous solution of PVA. When cross-linking agent 1 was added to aqueous solution of PVA and subsequent thermal treatment of as-spun nanofibers, chemically cross-linked PVA nanofibers were achieved to resist disintegration in contact with hot water and the tensile mechanical property of nanofiber non-wovens was greatly improved by the formation of cross-linking points. Magnetite was deposited uniformly onto the hydrophilic surface of cross-linked PVA nanofibers and the resulted nanofibers decorated with magnetite showed a magnetic responsiveness. The deposition of magnetite on the PVA nanofibers can generate self-standing magnetic non-wovens.     

Densifying and strengthening of electrospun polyacrylonitrile‐based nanofibers by uniaxial two‐step stretching

The effects of alignment of polyacrylonitrile (PAN) nanofibers and a two‐step drawing process on the mechanical properties of the fibers were evaluated in the current study. The alignment was achieved using a high‐speed collector in electrospinning synthesis of the nanofibers. Under optimal two‐step drawing conditions (e.g., hot‐water and hot‐air stretching), the PAN nanofiber felts exhibited large improvements in both alignment and molecular chain‐orientation. Large increase in crystallinity, crystallite size, and molecular chain orientation were observed with increasing draw ratio. Optimally, stretched PAN‐based nanofibers exhibited 5.3 times higher tensile strength and 6.7 times higher tensile modulus than those of the pristine one. In addition, bulk density of the drawn PAN nanofibers increased from 0.19 to 0.33 g/cm³. Our results show that fully extended and oriented polymer chains are critical in achieving the highest mechanical properties of the electrospun PAN nanofibers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43945.     

Dispersion of soybean stock‐based nanofiber in a plastic matrix

The focus of this work is the study of the dispersion mechanism of soybean stock‐based nanofibers in a plastic matrix. The cellulose nanofibers were extracted from soybean stock by chemo‐mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 and 100 nm and lengths of thousands of nanometers. These nanofibers were characterized by atomic force microscopy and transmission electron microscopy. X‐ray diffraction studies showed that the soybean stock nanofibers had a relative percentage crystallinity of about 48%. Selective chemical treatments increased the cellulose content of soybean stock nanofibers from 41 to 61%. The matrix polymers used in this project were poly(vinyl alcohol) (PVA) and polyethylene (PE). The mechanical properties of nanofiber‐reinforced PVA film demonstrated a 4‐ to 5‐fold increase in tensile strength, as compared to the untreated fiber‐blend‐PVA film. One of the problems encountered in the use of nanoreinforcements lies in the difficulty in ensuring good dispersion of the filler in the composite material. Improved dispersion level of nanofibers within a thermoplastic was achieved by adding ethylene‐acrylic oligomer emulsion as a dispersant. In the solid phase of nanofiber‐blend‐PE composites, the compression‐molded samples showed that improved mechanical properties were achieved with coated nanofibers. Copyright © 2006 Society of Chemical Industry     

Spider-net within the N6, PVA and PU electrospun nanofiber mats using salt addition: Novel strategy in the electrospinning process

Electrospun nanofibers are promising candidates in the nanotechnological applications due to the advantages of the nanofibrous morphology. Therefore, many attempts were reported to modify the electrospun mats to gain more beneficial properties. In the present study, we are introducing a strategy to synthesize electrospun polymeric nanofiber mats containing spider-net binding the main nanofibers. Addition with long stirring time of a metallic salt having tendency to ionize rather than formation of sol–gel in the host polymer solution reveals to synthesize a spider-net within the electrospun nanofibers of the utilized polymer. Nylon6, polyurethane and poly(vinyl alcohol) have been utilized; NaCl, KBr, CaCl₂ and H₂PtCl₆ have been added to the polymeric solutions. In the case of nylon6 and poly(vinyl alcohol), addition of the inorganic salts resulted in the formation of multi-layers spider-network within the electrospun nanofibers mats. The synthesized spider-nets were almost independent on the nature of the salt; the optimum salt concentration was 1.5 wt%. The metallic acid led to form trivial spider-nets within both of nylon6 and poly(vinyl alcohol) nanofibers. In a case of polyurethane, few spider-nets were formed after salt addition due to the low polarity of the utilized solvents. According to TEM analysis, the synthesized spider-net consisted of joints; the later issued from the main nanofibers at Taylor's cone zone. The spider-net improved the mechanical properties and the wetability of the nylon6 nanofiber mats, accordingly a mat having amphiphilic feature has been prepared.     

In situ transmission electron microscope tensile testing reveals structure–property relationships in carbon nanofibers

Tensile tests were performed on carbon nanofibers in situ a transmission electron microscope (TEM) using a microelectromechanical system (MEMS) tensile testing device. The carbon nanofibers tested in this study were produced via the electrospinning of polyacrylonitrile (PAN) into fibers, which are subsequently stabilized in an oxygen environment at 270 °C and carbonized in nitrogen at 800 °C. To investigate the relationship between the fiber molecular structure, diameter, and mechanical properties, nanofibers with diameters ranging from ∼100 to 300 nm were mounted onto a MEMS device using nanomanipulation inside the chamber of a Scanning Electron Microscope, and subsequently tested in tension in situ a TEM. The results show the dependence of strength and modulus on diameter, with a maximum modulus of 262 GPa and strength of 7.3 GPa measured for a 108 nm diameter fiber. In particular, through TEM evaluation of the structure of each individual nanofiber immediately prior to testing, we elucidate a dependence of mechanical properties on the molecular orientation of the graphitic structure: the strength and stiffness of the fibers increases with a higher degree of orientation of the 0 0 2 graphitic planes along the fiber axis, which coincides with decreasing fiber diameter.     

Higher‐order structural analysis of nylon‐66 nanofibers prepared by carbon dioxide laser supersonic drawing and exhibiting near‐equilibrium melting temperature

Extended chains and/or extended chain crystals (ECC) are important structures for improving the mechanical properties of polymer fibers. ECC have so far been produced using specially prepared materials or manufacturing methods. In our study on the production of nanofibers by carbon dioxide (CO₂) laser supersonic drawing, we succeeded in producing nylon‐66 nanofibers having a high melting point near the equilibrium melting point (T_m⁰). Two melting points (T_m) of 260 and 276°C were observed for the nanofibers, with the latter temperature being close to the T_m⁰ (280°C) of nylon‐66. A nanofiber that was heat treated at 279°C for 10 min displayed a large stacked lamellar structure with an average crystal thickness of 140 nm. That value was close to the average molecular chain length of 212 nm, which was calculated from the average molecular weight of the nanofibers. It was inferred from these results that ECC corresponding to the average molecular chain length were present in the nanofibers. The CO₂ laser supersonic drawing process is applicable to general purpose thermoplastic polymers and uses a simple drawing system. It is expected that this drawing method will help to improve the fundamental performance of general purpose polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40361.     

Magnetic‐field‐assisted electrospinning highly aligned composite nanofibers containing well‐aligned multiwalled carbon nanotubes

Composite nanofiber meshes of well‐aligned polyacrylonitrile (PAN)/polyvinylpyrrolidone (PVP) nanofibers containing multiwalled carbon nanotubes (MWCNTs) were successfully fabricated by a magnetic‐field‐assisted electrospinning (MFAES) technology, which was confirmed to be a favorable method for preparation of aligned composite nanofibers in this article. The MFAES experiments showed that the diameters of composite nanofibers decreased first and then increased with the increase of voltage and MWCNTs content. With the increase of voltage, the degree of alignment of the composite nanofibers decreased, whereas it increased with increasing MWCNTs concentration. Transmission electron microscopy observation showed that MWCNTs were parallel and oriented along the axes of the nanofibers under the low concentration. A maximum enhancement of 178% in tensile strength was manifested by adding 2 wt % MWCNTs in well‐aligned composite nanofibers. In addition, the storage modulus of PAN/PVP/MWCNTs composite nanofibers was significantly higher than that of the PAN/PVP nanofibers. Besides, due to the highly ordered alignment structure, the composite nanofiber meshes showed large anisotropic surface resistance, that is, the surface resistance of the composite nanofiber films along the fiber axis was about 10 times smaller than that perpendicular to the axis direction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41995.     

Novel core‐sheath antimicrobial nanofibrous mats

The poor mechanical properties of electrospun materials remain one of the major hindrances toward their practical application. In this study, we report the synthesis of core‐sheath nanofibrous mats to enhance the mechanical properties of an antimicrobial polymer nanofiber for application in filter media. This objective was achieved via coaxial electrospinning of poly[styrene‐co‐N‐(N′,N′‐dimethyl‐3‐aminopropyl)maleimide] as the sheath which is an antimicrobial polymer and nylon 6 polymer for the core which is well reported for exceptional mechanical properties. Extensive characterization of these fibers was performed using scanning electron microscopy, scanning transmission electron microscopy, confocal fluorescence microscopy as well as attenuated total reflectance Fourier transform spectroscopy to provide evidence of the core‐sheath morphology. Antimicrobial evaluation was also carried out on the fabricated fibers via the live/dead fluorescence technique. This was done to determine if the poly[styrene‐co‐N‐(N′,N′‐dimethyl‐3‐aminopropyl)maleimide] retained its antimicrobial activity. The fibers were found to be effective against the Gram‐positive Staphylococcus aureus (ATCC25925) and Gram‐negative Pseudomonas aeruginosa (ATCC27853). Subsequent tensile testing and filtration experiments provided evidence that the incorporation of the nylon core improved mechanical properties of the nanofiber mats. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46303.     

Chemical treatments for improving adhesion between electrospun nanofibers and fabrics

Nanofiber‐coated fabrics have potential uses in filters and protective clothing. One major challenge is to ensure good adhesion of nanofibers to the fabrics achieving satisfactory durability against abrasion for practical use. This work is aimed to study adhesion mechanisms and their improvement between nanofibers and textile substrates; to achieve this goal cotton fabrics were treated with an alkali solution, while nylon fabrics were treated with ethanol. Adhesion of polyamide‐6 electrospun nanofiber layer to fabrics was evaluated by means of a peeling test. Treated fabrics showed improved bonding towards nanofibers: adhesion energy was ～0.58 J m^?2 for both untreated fabrics, and after treatments increased to 0.93 and 0.86 J m^?2 for cotton and nylon ones, respectively. Optical observations revealed that nanofibers deposited on fabrics are mainly linked to external protruding fibers (i.e., fabric hairiness). Therefore, surface hairiness seems to be the critical factor limiting adhesion. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39766.     

Sea‐island polyurethane/polycarbonate composite nanofiber fabricated through electrospinning

Sea‐island polyurethane (PU)/polycarbonate (PC) composite nanofibers were obtained through electrospinning of partially miscible PU and PC in 3 : 7 (v/v) N,N‐dimethylformamide (DMF) and tetrahydrofuran (THF) mixture solvent. Their structures, mechanical, and thermal properties were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric (TG), and differential scanning calorimetry (DSC). The structures and morphologies of the nanofibers were influenced by composition ratio in the binary mixtures. The pure PC nanofiber was brittle and easy to break. With increasing the PU content in the PU/PC composite nanofibers, PU component not only facilitated the electrospinning of PC but improved the mechanical properties of PU/PC nanofibrous mats. In a series of nanofibrous mats with varied PU/PC composition ratios, PU/PC 70/30 showed excellent tensile strength of 9.60 Mpa and Young's modulus of 55 Mpa. After selective removal of PC component in PU/PC composite nanofibers by washing with acetone, the residual PU maintained fiber morphology. However, the residual PU nanofiber became irregular and contained elongated indents and ridges along the fiber surface. PU/PC composite fibers showed sea‐island nanofiber structure due to phase separation in the spinning solution and in the course of electrospinning. At PC content below 30%, the PC domains were small and evenly dispersed in the composite nanofibers. As PC content was over 50%, the PC phases became large elongated aggregates dispersed in the composite nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of continuous nanofiber yarn using novel multi‐nozzle bubble electrospinning

A novel multi‐nozzle bubble electrospinning apparatus, including spinning unit, metering pump, constant flow pump, metal funnel and yarn winder, was designed for the preparation of continuous twisted polyacrylonitrile nanofiber yarns, and the principle of nanofiber yarn spinning was studied. An innovative spinning unit consisting of nozzle and air chamber was used to improve the production of nanofibers. Double conjugate electrospinning was developed using two pairs of oppositely charged spinning units to neutralize the charges. The effects of applied voltage, air flow rate, overall solution flow rate and funnel rotary speed on the fiber diameter, production rate and mechanical properties of the nanofiber yarns were analyzed. Nanofibers could be aggregated stably and bundled continuously, then twisted into nanofiber yarns uniformly at an applied voltage of 34 kV, air flow rate of 1200 mL min^?1 and overall solution flow rate of 32 mL h^?1. With an increase in the funnel rotary speed, the twist angle of the nanofiber yarns gradually increased when the take‐up speed was constant. The yarn tensile strength and elongation at break showed an increasing trend with increasing twist angle. Nanofiber yarns obtained using this novel method could be produced at a rate from 2.189 to 3.227 g h^?1 with yarn diameters ranging from 200 to 386 µm. Nanofiber yarns with a twist angle of 49.7° showed a tensile strength of 0.592 cN dtex^?1 and an elongation at break of 65.7%. © 2013 Society of Chemical Industry     

Conjugate electrospinning of continuous nanofiber yarn of poly(L‐lactide)/nanotricalcium phosphate nanocomposite

The continuous nanofiber yarns of poly(L ‐lactide) (PLLA)/nano‐β‐tricalcium phosphate (n‐TCP) composite are prepared from oppositely charged electrospun nanofibers by conjugate electrospinning with coupled spinnerets. The morphology and mechanical properties of PLLA/n‐TCP nanofiber yarns are characterized by scanning electron microscope, transmission electron microscope, and electronic fiber strength tester. The results show that PLLA/n‐TCP nanofibers are aligned well along the longitudinal axis of the yarn, and the concentration of PLLA plays a significant role on the diameter of the nanofibers. The thicker yarn of PLLA/n‐TCP composite with the weight ratio of 10/1 has been produced by multiple conjugate electrospinning using three pairs of spinnerets, and the yarn has tensile strength of 0.31cN/dtex. A preliminary study of cell biocompatibility suggests that PLLA/n‐TCP nanofiber yarns may be useable scaffold materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Processing and properties of poly(p-phenylene benzobisthiazole)/nylon fibers

Composite fibers of poly(p-phenylene benzobisthiazole) (PBT) with nylons were spun from dilute acid solutions. The effects of wet-stretching, heat treatment time, tension, and temperature on the tensile properties are reported. Nylon 6,6 and nylon 6 at several molecular weights were studied. Moduli of 40 GPa and tensile strengths of 375 MPa were achieved for 30/70 PBT/nylon composites. Heat treatment of the nylon/PBT fibers at 160–225°C for 12–19 h increased the tensile modulus by 20–50% and the tensile strength by a smaller amount. At the same time, the intrinsic viscosity of the nylons increased as much as 100%, indicating the solid-state polymerization of the nylon. The largest tensile modulus attained is less than half the theoretical value predicted by a linear “rule of mixtures” as might be expected for an oriented molecular composite. Although differential scanning calorimetry shows a melting transition at temperatures 5–10°C higher than the pure nylons, the composite does not flow at temperatures above this transition. Sulfuric acid dissolves most of the nylon, but does not destroy the mechanical integrity of the fibers; differential scanning calorimetry indicates that the remaining fiber contains little or no nylon. The results are consistent with a microstructure consisting of a microfibrillar network of PBT, surrounded by a separate nylon phase.     

Crosslinked,electrospun chitosan–poly(ethylene oxide) nanofiber mats

Mechanical characterization of nanofiber mats is an underexplored area in biomaterial engineering. In this study, a chitosan–poly(ethylene oxide) copolymer blend was electrospun and crosslinked with glutaraldehyde (GA) for various time periods. The tensile and compressive mechanical integrity of the nanofibers was analyzed with increasing exposure to vapor crosslinking. Solubility, scanning electron microscopy characterization, Fourier transform infrared, uniaxial tensile tests, and nanoindentation analyses were used to identify these trends. The mechanical studies confirmed that the GA vapor crosslinking increased the stiffness and decreased the ductility of the electrospun mats. Increased exposure time to crosslinking led to changes in the mat surface color and resistance to dissolution. Scanning electron microscopy fiber counts verified that exposure to GA vapor crosslinking increased the average fiber diameter. By the use of vapor phase deposition, mechanical properties continued to change throughout the study. The crosslinking exposure time could be chosen to accommodate in vivo mechanical loading. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties of individual electrospun polymer-nanotube composite nanofibers

Singlewalled carbon nanotube/polyvinylalcohol composite nanofibers were electro-spun onto a silicon surface pre-patterned with trenches. These nanofibers were prepared with different loadings of SWCNTs and had radii between 20 and 40 nm. Individual fiber sections were pinned across the trenches and laterally loaded by an AFM tip to yield mechanical response curves. A simple model was exploited to extract the tensile mechanical properties from the lateral force-displacement data. Depending on the fiber composition, the tensile modulus was found to be between 3 and 85 GPa. In addition we have prepared fibers with tensile strength of up to 2.6 GPa. Such optimised fibers break at strains of ∼4% and exhibit toughness of up to 27 MJ/m³.     

Preparation and characterization of graphene oxide/poly(vinyl alcohol) composite nanofibers via electrospinning

Graphene oxide (GO) was well dispersed in poly(vinyl alcohol) (PVA) diluted aqueous solution, and then the mixture was electrospun into GO/PVA composite nanofibers. Electron microscopy and Raman spectroscopy on the as‐prepared and calcined samples confirm the uniform distribution of GO sheets in the nanofibers. The thermal and mechanical properties of the nanofibers vary considerably with different GO filler contents. The decomposition temperatures of the GO/PVA composite nanofiber dropped by 38–50°C compared with pure PVA. A very small loading of 0.02 wt % GO increases the tensile strength of the nanofibers by 42 times. A porous 3D structure was realized by postcalcining nanofibers in H₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013