Influence of monomeric concentration on mechanical and electrical properties of poly(styrene-co-acrylonitrile) and poly(styrene-co-acrylonitrile/acrylic acid) yarns electrospun

Two series of copolymers were synthesized by emulsion polymerization: poly(styrene-co-acrylonitrile) P(S:AN) and P(S:AN-acrylic acid) P(S:AN-AA). The monomeric concentrations in both series were: 0:100, 20:80, 40:60, 50:50 (wt%:wt%), and 1 wt% of AA. The copolymers were dissolved in N,N-dimethylformamide (4–10 wt%) and were electrospun. Polymeric yarns were collected using a blade collector. The synthesized and fabricated materials were characterized by known techniques. Mechanical and electrical properties of polymeric yarns indicated a dependence of monomeric concentration. Elastic modulus increases as acrylonitrile concentration increases (up to 30 MPa). Yarns were submitted to degradation process into saline solution, where the acrylic acid content kept a constant elastic modulus at long times. The electrical current into yarns was higher when the concentration is 50:50 wt%:wt% (1.2 mA). The cytotoxicity results showed a cell viability close to 100% for yarns without AA.     

Preparation of nonwoven mats of electrospun poly(lactic acid)/polyaniline blend nanofibers: A new approach

The preparation of nonwoven mats of electrospun poly(lactic acid)/polyaniline (PANI) blend nanofibers faces some critical challenges that will be addressed in the present work. The challenges are in achieving high and adjustable content of PANI while keeping the spinnable solution nonagglomerated with no need to further filtration that might lead to wrong estimation of PANI content in the mat. We report an unprecedented content of 40% wt of PANI that is achieved using a new two‐step procedure. It is based on: (1) the preparation of the spinnable solution from a friable nonagglomerated and readily dispersible PANI: ‐TSA powder and (2) the use of an optimized mixture of ‐cresol/dichloromethane. The obtained nanofiber mats are characterized by FTIR and UV–vis spectroscopy. The morphology and the thermal stability of the nanofibers are investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The amorphous structure of the nanofibers is verified using XRD measurements. The DC‐conductivity of these blend nanofibers is found to be far larger than the published DC‐conductivity values for blend nanofibers of PANI with PLLA or with other polymers. This is attributed to the high content of PANI in the blend and to the role played by ‐cresol as a secondary dopant. The investigation of the aging effect on the DC‐conductivity reveals an exponential decrease with a characteristic time of weeks. The electrical impedance spectroscopy (EIS) shows a pure ohmic behavior of the blend mat. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43687.     

Optical sensor based on fluorescent PMMA/PFO electrospun nanofibers for monitoring volatile organic compounds

The development of polymeric materials with superior electrical and/or optical properties is highly demanded for designing optical gas sensors, where conjugated polymers play an important role due to their π‐electron conjugation. However, usually the low processability and high cost of these materials hinder technological applications. Here we report on a simple route to develop highly fluorescent electrospun nanofibers of poly(methyl methacrylate) (PMMA) containing low contents of polyfluorene (PFO). The PMMA_PFO nanofibers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis, while the luminescence properties changes were evaluated by exposing the PMMA_PFO nanofibers to distinct volatile organic compounds (VOCs) including ethanol, toluene, tetrahydrofuran, acetone, dichloromethane, and chloroform. The changes in luminescence properties, specifically fluorescence quenching, of PMMA_PFO nanofibers were analyzed in terms of conformational changes from glassy‐phase to β‐phase of PFO when the nanofibers were exposed to the VOCs. The developed nanostructured platform showed a suitable response to detect chloroform, with linear responses in the concentration range from 10 to 300 ppm and from 350 to 500 ppm and limits of detection of 47.9 and 15.4 ppm, respectively. The results suggest the PMMA_PFO electrospun nanofibers are highly potential materials for optical gas sensor applications based on luminescence quenching. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46128.     

A method for scale‐up of co‐electrospun nanofibers via flat core‐shell structure spinneret

An approach to the scale‐up of co‐electrospinning via a flat core‐shell structure spinneret has been developed in this study. The spinneret with a flat surface involves shell‐holes and core‐needles. Electric field simulation reveals that the flat core‐shell spinneret configuration creates a more uniform electric field gradient. Experimental study shows that in comparison with the conventional needle co‐electrospinning, core‐shell nanofibers produced by this new designed setup are finer and of better morphology. Composite nanofibers with special morphologies can be fabricated by modifying the structure of this spinneret. The production rate of the core‐shell nanofibers can be enhanced by increasing the hole and needle number of the spinneret. This novel design is expected to provide a promising method towards the massive production of core‐shell nanofibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41027.     

Polyaniline nanofibers for In situ MAO‐catalyzed polymerization of ethylene

In this work electro‐conductive polyaniline nanofibers (PAni‐nanofibers) were prepared via interfacial methodology. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that the synthesized PAni‐nanofibers present high aspect ratio with an average diameter of 80 nm, while they exhibit high conductivity (DC conductivity values: 4.19 ± 0.21 S cm^?1). After specific treatment to remove moisture and remaining trapped HCl from PAni‐nanofibers, it was possible to prepare promising polyethylene (PE)/PAni composites by in situ polymerization of ethylene using bis(cyclopentadienyl) zirconium(IV) dichloride (Cp₂ZrCl₂) and methylaluminoxane (MAO) as catalytic system. More precisely, various contents of PAni‐nanofibers (from 0.2 to 7 wt %) were successfully incorporated in the in situ produced PE/PAni nanocomposites. PAni‐nanofibers were found to affect significantly the crystallization of the polyolefinic matrix while preserving its thermal stability. Preliminary measurements of electric properties showed PAni‐nanofibres are able to bring electro‐conductive properties to the in situ polymerized PE/PAni composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41197.     

Room temperature CO sensing by polyaniline/Co3O4 nanocomposite

Polyaniline/cobalt oxide (PANI/Co₃O₄) nanocomposites have been investigated for their sensitivity towards carbon monoxide (CO) gas at room temperature. The Co₃O₄ nanoparticles were prepared by ultrasound assisted coprecipitation method and then incorporated into the PANI matrix. Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy, powder X‐ray diffraction, and field emission scanning electron microscopy have been used to characterize the nanomaterials. The PANI/Co₃O₄ nanocomposite sensors were found to be highly selective to CO gas at room temperature. A significantly high response of 0.81 has been obtained for 75 ppm CO concentration with a response time of 40 s. Based on the observations of the sensing study, a mechanism for CO sensing by the nanocomposite has been proposed. Influence of humidity on the sensor response towards CO has also been studied and the results presented. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44115.     

Functionalization of electrospun nanofibers of natural cotton cellulose by cerium dioxide nanoparticles for ultraviolet protection

Nanofibers of natural cotton cellulose with a degree of polymerization above 10,000 were prepared by electrospinning; they were then functionalized with a rare‐earth nano‐oxide material of cerium dioxide (CeO₂) by means of the hydrothermal method to obtain the designated properties. The morphology, structure, and properties of the as‐obtained nanocomposite fibers were characterized by scanning electron microscopy, transmission electron microscopy, energy‐dispersive spectroscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, and ultraviolet (UV)–visible spectrophotometry. The results show that hydrothermally grown CeO₂ nanoparticles exhibited a polycrystalline cubic fluorite structure and could be dispersed uniformly on the surface of the cellulose nanofiber. The strong interface and electrostatic interactions between the nanoparticles and nanofibers effectively prevented nanoparticle fall‐off. The modified natural cotton cellulose nanofibers showed excellent protection against UV radiation because of the function of the CeO₂ particles. Such cellulose nanocomposite materials could have potential applications in UV protection for data‐storage or memory devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1524–1529, 2013     

Preparation and hemocompatibility of electrospun O‐carboxymethyl chitosan/PVA nanofibers

Chitosan was deacetylated and carboxymethylated to prepare O‐carboxymethyl chitosan (CMC) for further electrospinning. CMC was characterized using FTIR, NMR, and chemical titration, indicating a degree of carboxymethylation of 51.4%. CMC was electrospun together with poly(vinyl alcohol) (PVA) to prepare membranes composed of nanofibers. The electrospinning conditions were optimized. The CMC/PVA membrane obtained at the conditions of 15.2 g/mL CMC 50 mL, 8 g/mL PVA 5 mL, 25 kV, and a distance of 23 cm, had nanofibers without beads, with diameters of 70–200 nm. The mats were crosslinked by glutaraldehyde before platelet adhesion measurement. The nanofibrous structure remained after crosslinking while the wettability decreased. CMC/PVA mats with higher CMC amount and fewer beads, had fewer adherent platelets and less platelets aggregation showing better hemocompatibility. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43565.     

Effects of surfactants on the microstructures of electrospun polyacrylonitrile nanofibers and their carbonized analogs

In this study, the influence of surfactants on the processability of electrospun polyacrylonitrile (PAN) nanofibers and their carbonized analogs was investigated. The surfactants employed in this effort are Triton X‐100 (nonionic surfactant, SF‐N), sodium dodecyl sulfate (SDS) (anionic surfactant, SF‐A), and hexadecyltrimethylammonium bromide (HDTMAB) (cationic surfactant, SF‐C). Interactions between electrospun PAN and the surfactants, reflected in effects on as‐spun and carbonized nanofiber morphologies and microstructures, were explored. The results show that uniform nanofibers are obtained when cationic and anionic surfactants (surfactant free and nonionic surfactants) are utilized in the preparation of electrospun PAN. In contrast, a bead‐on‐a‐string morphology results when the aniconic and cationic surfactants are present, and defect structure is enhanced with cationic surfactant addition. Moreover, fiber breakage is observed when the nonionic surfactant Triton X‐100 is employed for electrospinning. After carbonizaition, the PAN polymers were observed to have less ordered structures with addition of any type of surfactant used for electrospinning and the disorder becomes more pronounced when the anionic surfactant is utilized. Owing to the fact that microstructure defects create midband gap states that enable more electrons to be emitted from the fiber, an enhancement of electron emission is observed for PAN electrospun in the presence of the anionic surfactant. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3726–3735, 2013     

Recent progress in interfacial toughening and damage self‐healing of polymer composites based on electrospun and solution‐blown nanofibers: An overview

In this article, we provide an overview of recent progress in toughening and damage self‐healing of polymer–matrix composites (PMCs) reinforced with electrospun or solution‐blown nanofibers at interfaces with an emphasis on the innovative processing techniques and toughening and damage self‐healing characterization. Because of their in‐plane fiber architecture and layered structure, high‐performance laminated PMCs typically carry low interfacial strengths and interlaminar fracture toughnesses in contrast to their very high in‐plane mechanical properties. Delamination is commonly observed in these composite structures. Continuous polymer and polymer‐derived carbon nanofibers produced by electrospinning, solution blowing, and other recently developed techniques can be incorporated into the ultrathin resin‐rich interlayers (with thicknesses of a few to dozens of micrometers) of these high‐performance PMCs to form nanofiber‐reinforced interlayers with enhanced interlaminar fracture toughnesses. When incorporated with core–shell healing‐agent‐loaded nanofibers, these nanofiber‐richened interlayers can yield unique interfacial damage self‐healing. Recent experimental investigations in these topics are reviewed and compared, and recently developed techniques for the scalable, continuous fabrication of advanced nanofibers for interfacial toughening and damage self‐healing of PMCs are discussed. Developments in the near future in this field are foreseen. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2225–2237, 2013     

Carbonized electrospun polyacrylonitrile nanofibers as highly sensitive sensors in structural health monitoring of composite structures

Electrospun polyacrylonitrile (PAN) nanofibers were stabilized at 280°C for 1 h in an ambient condition, and then carbonized at 850°C in inert argon gas for additional 1 h in order to fabricate highly pure carbonous nanofibers for the development of highly sensitive sensors in structural health monitoring (SHM) of composite aircraft and wind turbines. This study manifests the real‐time strain response of the carbonized PAN nanofibers under various tensile loadings. The prepared carbon nanofibers were placed on top of the carbon fiber pre‐preg composite as a single layer. Using a hand lay‐up method, and then co‐cured with the pre‐preg composites in a vacuum oven following the curing cycle of the composite. The electric wires were connected to the top surface of the composite panels where the cohesively bonded conductive nanofibers were placed prior to the tensile and compression loadings in the grips of the tensile unit. The test results clearly showed that the carbonized electrospun PAN nanofibers on the carbon fiber composites were remarkably performed well. Even the small strain rates (e.g., 0.020% strain) on the composite panels were easily detected through voltage and resistance changes of the panels. The change in voltage can be mainly attributed to the breakage/deformation of the conductive network of the carbonized PAN nanofibers under the loadings. The primary goal of the present study is to develop a cost‐effective, lightweight, and flexible strain sensor for the SHM of composite aircraft and wind turbines. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43235.     

Effects of solvents on the morphology and conductivity of poly(3,4‐ethylenedioxythiophene):Poly(styrenesulfonate) nanofibers

In this study, the effect of solvents on the morphology and conductivity of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS) nanofibers is investigated. Conductive PEDOT:PSS nanofibers are electrospun by dissolving a fiber‐forming polymer, polyvinyl alcohol, in an aqueous dispersion of PEDOT:PSS. The conductivity of PEDOT:PSS nanofibers is enhanced 15‐fold by addition of DMSO and almost 30‐fold by addition of ethylene glycol to the spinning dopes. This improvement is attributed to the change in the conformation of the PEDOT chains from the coiled benzoid to the extended coil quinoid structure as confirmed by Raman spectroscopy, X‐ray diffraction, and differential scanning calorimetry. Scanning electron microscopy images show that less beady and more uniform fiber morphology could be obtained by incorporation of ethylene glycol in the spinning dopes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40305.     

Polypyrrole-coated fiber-scaffolds: Concurrent linear actuation and sensing

Conducting polymers such as polypyrrole (PPy) can be deposited on various substrates to obtain conductive electroactive coatings. While electrochemical coatings are generally considered to be more effective, chemical coatings are more industrially suitable, especially on complex substrates. In this work, we aimed to explore the electro-chemo-mechanical response of conductive fiber scaffolds (CFS) prepared by coating PPy (chemically) on glucose-gelatin nanofibre scaffolds. Electroactivity was readily observed in both aqueous and propylene carbonate solutions of lithium bis(trifluoromethanesulfonyl)imide, with mainly anion activity in both cases. A higher actuation response was achieved in the aqueous solutions with strain in the range of 1.2% and stress in the range of 3 kPa. Under both cyclic voltammetry and square wave potential steps driving, stable actuation for over 100 cycles was maintained. In addition to actuation, the CFS samples exhibited concurrent sensory properties, in sensing current densities and mechanical load. The PPy-coated CFS material functioning as both an actuator and a sensor is envisaged to have potential applications in smart materials, soft robotics or e-skin. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48533.     

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.     

Characteristics and 3D formation of PVA and PEO electrospun nanofibers with embedded urea

The behavior of electrospun polyvinyl alcohol (PVA) and polyethylene oxide (PEO) nanofibers embedded with urea is studied as a function of various process parameters. Our results show that three‐dimensional nanofiber networks can be obtained when high concentrations of urea in the solution are used during electrospinning. The nanofibers are characterized using both scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). The stability of the nanofiber as a function of electric field has also been studied. The successful formation of three‐dimensional nanofiber networks can open new trends toward applications in fertilizers containing nanofibers in the nanoagricultural field. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39840.     

Surface modification of electrospun chitosan nanofibrous mats for antibacterial activity

Chitosan (CS) blended with poly(ethylene oxide) (PEO) was electrospun into nanofibrous mats. The spinning solution of 6.7 : 0.3 (% w/v) of CS : PEO was dissolved in a 70 : 30 (v/v) trifluoroacetic acid/dichloromethane solution. The obtained fibers were smooth without beads on their surfaces and average diameter of the fiber was 272 ± 56 nm. N‐(2‐hydroxyl) propyl‐3‐trimethyl ammonium chitosan chloride (HTACC) and N‐benzyl‐N,N‐dimethyl chitosan iodide (QBzCS) were each prepared from the CS/PEO mats. They were identified by Fourier‐transform infrared and X‐ray photoelectron spectroscopy and degree of swelling in water. Both quaternized electrospun chitosan mats exhibited superior antibacterial activity to the unmodified electrospun CS/PEO against Staphylococcus aureus and Escherichia coli at short contact times. After 4 h of contact, the reduction of both bacterial strains by CS/PEO, HTACC, and QBzCS was equal at about 99–100%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40981.     

Piezoelectric properties of PVDF-conjugated polymer nanofibers

This study presents the development and characterization of PVDF-conjugated polymer nanofiber-based systems. Five different conducting polymers (CPs) were synthesized successfully and used to create the nanofiber systems. The CPs used are polyaniline (PANI), polypyrrole (PPY), polyindole (PIN), polyanthranilic acid (PANA), and polycarbazole (PCZ). Nanofiber systems were produced utilizing the Forcespinning® technique. The nanofiber systems were developed by mechanical stretching. No electrical field or post-process poling was used in the nanofiber systems. The morphology, structure, electrochemical and piezoelectric performance was characterized. All of the nanofiber PVDF/CP systems displayed higher piezoelectric performance than the fine fiber PVDF systems. The PVDF/PPY nanofiber system displays the highest piezoelectric performance of 15.56 V. The piezoelectric performance of the PVDF/CP nanofiber systems favors potential for an attractive source of energy where highly flexible membranes could be used in power actuators, sensors and portable, and wireless devices to mention some.     

Economical conductive graphite-filled polymer composites via adjustable segregated structures: Construction,low percolation threshold,and positive temperature coefficient effect

The economical graphite-filled thermoplastic urethane/ultra-high molecular weight polyethylene (TPU/UHMWPE) composites with the segregated structure were constructed by the combination of mechanical crushing and melt blending method. The low percolation threshold of 1.89 wt% graphite in the adjustable segregated composites was obtained and high electrical conductivity was about 10⁻¹ S m⁻¹ at 10 wt% graphite loadings owing to the formation of three-dimensional conductive networks. Moreover, when the graphite loadings were over the percolation threshold, the remarkable positive temperature coefficient (PTC) effect of electrical resistivity for TPU/UHMWPE-Graphite composites were achieved, originating from the combined thermal motion of TPU and UHMWPE. Meanwhile, the outstanding repeatability of PTC effects was obtained after 5-time cycles. Therefore, economical conductive polymer composites were still the promising field in the practical application of PTC materials.     

Electrosynthesis,characterization, and application of poly(3,4‐ethylenedioxythiophene) derivative with a chloromethyl functionality

Poly(2‐chloromethyl‐2,3‐dihydrothieno[3,4‐b][1,4]dioxine), a chloromethyl functionalized poly(3,4‐ethylenedioxythiophene) derivative (PEDOT‐MeCl), was synthesized electrochemically via the potentiostatic polymerization of its monomer in dichloromethane solution containing suitable tetrabutylammonium tetrafluoroborate, then it was used for the characterization of film properties and the fabrication of electrochemical sensor. The properties of the resulting PEDOT‐MeCl film were characterized by different methods such as cyclic voltammetry, electrochemical impedance spectroscopy, Fourier transform infrared and ultraviolet–visible techniques, scanning electron microscope, and thermogravimetric analysis. The PEDOT‐MeCl film displayed a good reversible redox activity, remarkable capacitance properties, good thermal stability, rough, and porous structure, especially fluorescent spectra indicated that PEDOT‐MeCl was a blue‐emitter with maximum emission centered at 396 and 398 nm. Finally, the PEDOT‐MeCl film was employed for the fabrication of the sensing electrode, and dopamine was chosen as a model analyte for the application of the electrochemical sensor. Results indicated that the PEDOT‐MeCl film as sensing interface was feasible, and studies of these film properties were very beneficial for studying properties and applications of other poly(3,4‐ethylenedioxythiophene) derivative films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2660–2670, 2013     

A comprehensive study on Plantago ovata/PVA biocompatible nanofibers: Fabrication,characterization, and biological assessment

In this study, a biocompatible nanofiber is fabricated using Plantago ovata mucilage (POM) combined with polyvinyl alcohol (PVA), which is considered as a non-toxic polymer. High quality nanofibers were produced by controlling the electrospinning parameters after selecting an appropriate solvent for the POM/PVA combination (12% PVA and 3% POM). Electrospinning parameters, including high voltage, distance from collector to tip, feed rate and POM to PVA proportion were optimized following preparation of an aqueous POM/PVA solution. Using the results of scanning electron microscopy, the optimized electrospinning conditions for producing POM/PVA nanofibers were determined (high voltage = 18 kV, distance = 15 cm, feed rate = 0.125 ml/hr, PMM/PVA = 50/50) and uniform nanofibers with an average diameter of 250 nm were produced. The POM/PVA nanofiber sample was evaluated by determining the mechanical strength, characterization of produced nanofiber morphology, and investigating the cell viability by applying MTT assay. The bands for both POM and PVA from FTIR results showed that the samples remained stable. The tensile strength results showed that blending POM with PVA solution enhanced the Young's modulus by factor of 3.2 (0.2 MPa to 0.64 MPa). The MTT analysis on POM/PVA cell lines proved that the produced nanofiber considerably enabled the cellular proliferation. Enhancement in these analysis indicated how POM-based nanofibers is a promising scaffold for cell culture, drug delivery systems and food additives.