A composite polyaniline/graphene–coated polyamide6 nanofiber mat for electrochemical applications

In this study, polyamide6 (PA6) nanofiber mats were fabricated through the electrospinning process. The nanofibers were coated by polyaniline (PANI) using the in situ polymerization of aniline in the presence of graphene oxide. The composite of the PANI/graphene oxide–coated nanofiber mat was treated with hydrazine monohydrate to reduce graphene oxide to graphene, and this was followed by the reoxidation of PANI. Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), thermal gravimetric analysis (TGA), tensile strength tests, electrical conductivity measurements, cyclic voltammetry (CV), and charge/discharge measurements were conducted on the composite PA6/graphene nanofiber mats. It was found that the surface of the PA6 nanofibers was coated uniformly with the granular PANI and graphene oxide. Besides, the composite nanofibers showed good tensile and thermal properties. Their electrical conductivity and specific capacitance, when used as a separator in the cell, were 1.02 × 10^?4 S/cm and 423.28 F/g, respectively. Therefore, the composite PANI/reduced graphene oxide–coated PA6 nanofiber mats could be regarded as suitable candidates for application in energy storage devices.     

Solution‐blown nylon 6–chitosan core–shell nanofiber for highly efficient affinity adsorption

A facile spinning‐based strategy was developed to fabricate chitosan (CS) surface nanofiber‐based affinity membranes for protein adsorption. The core–shell nanofiber mat of nylon 6–CS was prepared via coaxial solution blowing process. The nanofibers have a diameter range of 60–300 nm. The core–shell structure was confirmed by transmission electron microscopy, and CS was observed as a thin layer that uniformly adhered to the core. The dye ligand of cibacron blue F3GA (CB F3GA) was further covalently immobilized on the nanofibers with a content of 425 µmol/g. The pristine and CB F3GA‐attached mats were studied in protein adsorption. High bovine serum albumin adsorption capacities of 91.9 and 219.6 mg/g were obtained for pristine and CB F3GA‐attached mats, respectively. Given its properties of high flux rate and low pressure drop, CB F3GA‐attached nylon 6–CS nanofiber mat meets the requirements of highly effective affinity membrane chromatography. Copyright © 2016 John Wiley & Sons, Ltd.     

浸润性可调的导电聚苯胺/聚丙烯腈同轴纳米纤维

聚苯胺(PANI)因其具有可调的导电性、优异的化学稳定性、简单的制备方法等特点, 在化学电源、抗静电涂层、电磁屏蔽材料、抗腐蚀、传感器等领域具有广泛的应用前景[^1~4]. 由于聚苯胺的刚性分子链使得聚苯胺几乎不溶不熔, 难以加工应用, 因此, 将导电聚合物直接制成纳米纤维一直是合成纤维界所希望的目标之一. 此外, 由于材料尺度的减小, 使纳米材料的表面与界面性质,尤其是表面浸润性变得更为突出.浸润性是固体表面的重要特征之一, 它主要由表面的化学组成和微观结构共同决定^[5,6]. 可调的浸润性在超疏水材料、药物传输、仿生材料和微流体等领域具有重要的应用价值^[7~10] , 引起人们广泛关注.     

Characterization of poly(methyl methacrylate) nanofiber mats by electrospinning process

In this study, the aim is to describe the influence of electrospinning parameters on the morphology, the water wetting property and dye adsorption property of poly(methyl methacrylate) nanofiber mats. Specifically, the effects of solution concentration, solvent type, applied voltage, distance between the electrodes and particulate reinforcement on the diameter and shape of the nanofibers were investigated. All poly(methyl methacrylate) nanofiber mats contained beaded nanofiber structures. With increasing the polymer solution concentration, the average fiber diameter also increased. Poly(methyl methacrylate) nanofiber mat electrospun from dimethylformamide solution resulted in thicker fibers when compared with the mat electrospun from acetone solution. Increasing the electric potential difference between the collector and the syringe tip did not increase the average fiber diameter. Besides increasing the distance between the electrodes resulted in a decrease in the average fiber diameter. When compared with PMMA nanofiber mat, thicker fibers were obtained with silica nanoparticles reinforced nanofiber mat. According to the water contact angle measurements, all poly(methyl methacrylate) nanofiber mats revealed hydrophobic surface property. PMMA nanofiber mat with the highest water contact angle gave rise to the highest dye adsorption capacity.     

A novel method for a high‐strength electrospun meta‐aramid nanofiber by microwave treatment

Electrospun nanofibers have attracted great attention as potential reinforcements in composite application due to their high specific surface area, high porosity, and versatility. Because the electrospun nanofibers exhibit relatively low mechanical strength due to low crystallinity and random alignment, many researchers have tried to enhance the mechanical strength through various approaches, such as heat treatment and fiber orientation control. These methods, however, are difficult to control and require the use of high temperatures and sophisticated apparatuses, and high costs. In this study, we investigate a novel microwave technique to fabricate high‐strength electrospun meta‐aramid nanofiber mats. To optimize the microwave irradiation conditions, the electrospun nanofiber was treated at varying levels of moisture and for different irradiation times. Field emission scanning electron microscopy was used to observe the surface morphology of the electrospun nanofiber mats at the different irradiation times. The changes in the crystallinity and thermal properties were investigated using X‐ray diffraction and thermogravimetric analysis measurements. Tensile tests were performed to measure the mechanical strength of the meta‐aramid nanofiber mats with respect to each parameter. As a result, any residual solvents and salts were removed, and the degree of crystallization was dramatically increased by microwave irradiation under wet conditions. These effects led to a 2.8‐fold increase in the tensile strength of the nanofiber mats compared with an untreated mat. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 807–814     

Electrospinning of polyurethane/organically modified montmorillonite nanocomposites

Polyurethane/organically modified montmorillonite (PU/O‐MMT) nanocomposites were electrospun and the effect of O‐MMT on the morphology and physical properties of the PU/O‐MMT nanofiber mats were investigated for the first time. The average diameters of the PU/O‐MMT nanofibers were ranged from 150 to 410 nm. The conductivities of the PU/O‐MMT solutions were linearly increased with increasing the content of O‐MMT, which caused a decrease in the average diameters of the PU/O‐MMT nanofibers. The as‐electrospun PU and PU/O‐MMT nanofibers were not microphase separated. The exfoliated MMT layers were well distributed within the PU/O‐MMT nanofibers and oriented along the fiber axis. When the PU/O‐MMT nanofibers were annealed, the exfoliated MMT layers hindered the microphase separation of the PU. The electrospinning of PU/O‐MMT nanocomposites resulted in PU nanofiber mats with improved Young's modulus and tensile strength. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3171–3177, 2005     

Electrospun Polyaniline/Poly(ethylene oxide) Composite Nanofibers Based Gas Sensor

Camphor‐10‐sulfonic acid (HCSA) doped polyaniline (PANI)/poly(ethylene oxide) (PEO) composite nanofibers with different compositions (12 to 52 wt.% of PANI) were synthesized by an electrospinning method and their properties including optical, electrical and sensing were systematically investigated. FT‐IR shows that an increase of IR absorbance ratios of aromatic C? C stretching vibration of benzenoid rings of PANI to C? O? C symmetric vibrational modes of PEO confirmed that the PANI content in nanofiber mats increased proportionally with increase in PANI content in electrospinning solution. The band gap of PANI was determined to be 2.5 eV using UV‐Vis spectroscopy. The electrical conductivities of the nanofibers increased with an increase in the PANI content in the nanofibers. Additionally, the sensitivity toward NH₃ increased as the PANI content increased, but branched nanofibers reduced sensing response. The humidity sensitivity changed from positive to negative as the PANI content increased. The electron transport mechanism was studied by measuring the temperature dependence electrical resistivity. The negative temperature coefficient of resistance revealed a semiconducting behavior for the PANI/PEO nanofibers. The activation energy, calculated by Arrhenius plot, increased as the PANI content decreased. The power law indicated that electrons were being transported in a three dimensional matrix, and the longer hopping distance required more hopping energy for electron transport.     

Enhancement of conductivity by diameter control of polyimide-based electrospun carbon nanofibers

Oxydianiline-pyromellitic dianhydride poly(amic acid) (ODA-PMDA PAA) was polymerized with a catalyst support of triethyl amine for controlling molecular weight. This polymer was used for electrospinning in the preparation of PAA nanofibers, a precursor of carbon nanofibers. Here the amount of catalyst and concentration of PAA solution were optimized to produce polyimide-based carbon nanofibers approximately 80 nm in diameter. The effects of molecular weight of PAA, bias voltage, and spinning rate on the morphology of electrospun PAA and polyimide nanofibers have been evaluated. We showed that the conductivity of the carbon nanofiber mat decreased with increasing nanofiber diameter, where the conductivity of polyimide-based carbon nanofiber mat was much higher than those of other types of carbon nanofiber mat. The key ingredient to increase conductivity in a carbon nanofiber mat was found to be the number of cross junctions between nanofibers.     

Fabrication of Electrically Conducting Polypyrrole‐Poly(ethylene oxide) Composite Nanofibers

Summary: Electrically conducting polypyrrole‐poly(ethylene oxide) (PPy‐PEO) composite nanofibers are fabricated via a two‐step process. First, FeCl₃‐containing PEO nanofibers are produced by electrospinning. Second, the PEO‐FeCl₃ electrospun fibers are exposed to pyrrole vapor for the synthesis of polypyrrole. The vapor phase polymerization occurs through the diffusion of pyrrole monomer into the nanofibers. The collected non‐woven fiber mat is composed of 96 ± 30 nm diameter PPy‐PEO nanofibers. FT‐IR, XPS, and conductivity measurements confirm polypyrrole synthesis in the nanofiber.

An SEM image of the PPy‐PEO composite nanofibers. The scale bar in the image is 500 nm.     

Solution Blowing of Poly（dimethylsiloxane）/Nylon 6 Nanofiber Mats for Protective Applications

A new strategy was developed to fabricate superhydrophobic nylon 6 nanofibers, in which the blend solutions of poly(dimethylsiloxane)(PDMS) prepolymer and nylon 6 was spun using an innovative solution blowing process, and then the PDMS prepolymer contianning nanofibers were cured to obtain PDMS/nylon 6 nanofiber mats. Morphology, surface composition, non-wetting property and protective performance were investigated. The results showed that the addition of PDMS prepolymer improved the spinnability of the spinning solutions, and the PDMS/nylon 6 nanofibers had smooth surfaces and diameters from 100 nm to 350 nm. The presence of PDMS effectively enhanced the hydrophobicity of the nanofiber mats, showing water contact angles of 132° to 161° for PDMS contents of 1 wt% to 3 wt%. The PDMS/nylon 6 mats also possessed excellent protective and transport properties. The results indicated the potential application of the novel nanofiber mats in protective clothing.     

Fabrication of collagen immobilized electrospun poly (vinyl alcohol) scaffolds

In the development of tissue engineering scaffolds, the interactions between material surface and cells play crucial roles. The biomimetic 3‐D scaffolds absolutely provide better results for fulfilling requirements such as porosity, interconnectivity, cell attachment and proliferation. In this study, 3‐D electrospun scaffolds were prepared by using an electrospinning technique. Photo cross‐linkable polyvinyl alcohol was used as a polymeric matrix. During the electrospinning, the nanofibers were cross‐linked with in situ ultraviolet radiation. The crosslinked polymer fibers were achieved in a simple process at a single step. Nanofiber surface was modified with collagen by a chemical approach. The chemical structures were proven by attentuated total reflectance Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. The surface morphology of the nanofibers was characterized by scanning electron microscope (SEM). Morphological investigations show that the resulting nanofibrous matrix has uniform morphology with a diameter of 220–250 nm. In vitro attachment and growth of 3T3 mouse fibroblasts and human umbilical vein endothelial cells (ECV304) cells on polyvinyl alcohol‐based nanofiber mats were also investigated. Cell attachment, proliferation, and methylthiazole tetrazolium cytotoxicity assays indicated good cell viability throughout the culture time, which was also confirmed by SEM analysis. Copyright © 2015 John Wiley & Sons, Ltd.     

Morphology studies of polyaniline lengthy nanofibers formed via dimers copolymerization approach

In this paper, two different aniline dimers, N-phenyl-1,2-phenylenediamine (2-PPD) and N-phenyl-1,4-phenylenediamine (4-PPD) were used as starting monomers in polyaniline (PANI) synthesis. It was found that 2-PPD dimer alone produced only an amorphous PANI oligomer with a flaky morphology, while the 4-PPD provided either linear nanofiber or a spaghetti-like hollow nanofiber structures comprising of worm-like fibril subunits. By adjusting the molar fed ratio of 4-PPD to 2-PPD in the copolymerization, long PANI nanofibers with length up to tens of microns, bundled together by single PANI fibrils with diameter ca. 3-5 nm, was formed. A possible formation mechanism was proposed taking account of the reactivity difference at positions 4 and 2 on the 4-PPD and 2-PPD, respectively.     

Surface-functionalized electrospun carbon nanofiber mats as an innovative type of protein adsorption/purification medium with high capacity and high throughput

Due to recent advances in the production of biotherapeutics, high capacity, high throughput adsorption media for efficient and economic separation of these medically important products are in great demand. One option that has been evaluated extensively is membrane/mat adsorption. While these media allow for rapid adsorption (due to the decreased internal diffusion) and high throughput processing (due to the open porous structure), they often suffer from low capacity and poor enrichment factors. Herein, we report the fabrication, characterization, and protein adsorption evaluation of an innovative type of membrane/mat adsorption media based on electrospun carbon nanofibers. By surface-functionalization of these nanofibers with a weak acid cation-exchange ligand, the capacity was doubled for binding a model protein (i.e., lysozyme) compared to commercial products; and the capacity value was over 200 mg lysozyme per gram of adsorption media. Meanwhile, the thin nanofibers (having diameters of ~300 nm) along with open pores among nanofibers in the mats (having sizes of ~10-15 μm) allowed for higher operating flow rates and lower pressure drops. Furthermore, the incorporation of higher ligand density and the addition of a non-ionic surfactant (i.e., Triton X-305) into the adsorption buffer eliminated the non-specific binding of a competing protein (bovine serum albumin). In combination, this study suggested that electrospun carbon nanofiber adsorption media would provide a promising alternative to packed resin beds for bioseparations.     

Plasma-Electrospinning Hybrid Process and Plasma Pretreatment to Improve Adhesive Properties of Nanofibers on Fabric Surface

Electrospun nanofiber mats are inherently weak, and hence they are often deposited on mechanically-strong substrates such as porous woven fabrics that can provide good structural support without altering the nanofiber characteristics. One major challenge of this approach is to ensure good adhesion of nanofiber mats onto the substrates and to achieve satisfactory durability of nanofiber mats against flexion and abrasion during practical use. In this work, Nylon 6 nanofibers were deposited on plasma-pretreated woven fabric substrates through a new plasma-electrospinning hybrid process with the objective of improving adhesion between nanofibers and fabric substrates. The as-prepared Nylon 6 nanofiber-deposited woven fabrics were evaluated for adhesion strength and durability of nanofiber mats by carrying out peel strength and flex resistance tests. The test results showed significant improvement in the adhesion of nanofiber mats on woven fabric substrates. The nanofiber-deposited woven fabrics also exhibited good resistance to damage under repetitive flexion. X-Ray photoelectron spectroscopy and water contact angle analyses were conducted to study the plasma effect on the nanofibers and substrate fabric, and the results suggested that both the plasma pretreatment and plasma-electrospinning hybrid process introduced radicals, increased oxygen contents, and led to the formation of active chemical sites on the nanofiber and substrate surfaces. These active sites helped in creating crosslinking bonds between substrate fabric and electrospun nanofibers, which in turn increased the adhesion properties. The work demonstrates that the plasma-electrospinning hybrid process of nanofiber mats is a promising method to prepare durable functional materials.     

Processing and characterization of oriented electrospun poly(vinylidene fluoride) mats

Mats of highly oriented poly(vinylidene fluoride) nanofibers were electrospun by means of a conventional electrospinning equipment; the orientation, however, was obtained using a disk collector rotating at a speed of 4000 rpm and a device that reduced the influence of air displacement during nanofiber orientation. Thermal transitions of the mats were determined by differential scanning calorimetry, the predominant crystalline phase by Fourier transform infrared spectroscopy and wide‐angle X‐ray scattering and the nanofiber orientation and morphology by scanning electron microscopy. Relative permittivity, loss index, stable remnant polarization, and coercive field of the mats were also determined and compared with those obtained for a mat electrospun at 2000 rpm and an oriented commercial film. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 000: 000–000, 2012     

静电纺丝制备荧光导电双功能复合纳米纤维及其表征

采用静电纺丝技术将导电聚苯胺(PANI)和铕/铽稀土配合物掺杂到高分子基质聚乙烯吡咯烷酮(PVP)中,制备出荧光导电复合纳米纤维。用扫描电镜(SEM)、荧光光谱仪(FL)、宽频介电松驰谱仪对荧光导电复合纳米纤维的性能进行分析,结果显示,在270nm紫外光激发下,铕系列与铽系列复合纳米纤维分别发出红光和绿光。同时,复合纳米纤维的电导率可以达到1.18×10~(-6) S/cm,两种复合纳米纤维同时具有优异的荧光性能及良好的导电功能。     

Coaxial Electrospinning Method for the Preparation of TiO2@CdS/PVA Composite Nanofiber Mat and Investigation on its Photodegradation Catalysis

TiO₂/PVA composite nanofiber mat was prepared via an electrospinning technology. SH‐TiO₂‐SiO₂ hybrid particles and PVA solution were injected through a coaxial syringe, yielding a composite nanofiber mat. The as‐prepared SH‐TiO₂‐SiO₂/PVA composite nanofiber mat was immersed in Cd²⁺ cation solution and S^2? anion solution in turn. Thus, yellow TiO₂@CdS/PVA composite nanofiber mats were prepared. By adjusting the number of times a mat was immersed in the Cd²⁺ and S^2? solutions, different amounts of CdS particles attaching to the mats were obtained. Both SH‐TiO₂‐SiO₂/PVA and TiO₂@CdS/PVA composite nanofiber mats were employed to catalyze the photodegradation of a model dye, methylene blue. The photodegradation performance could be greatly enhanced by the introduction of CdS particles anchoring onto TiO₂ particles. The photodegradation efficiency reached 99.2% within 180 min. Also, the nanofiber mat could be recycled and reused at least 10 times. The photodegradation efficiency of TiO₂@CdS/PVA composite nanofiber mats remained 68.8% for 10 cycles.     

Facile Fabrication of Porous ZnS and ZnO Films by Coaxial Electrospinning for Highly Efficient Photodegradation of Organic Dyes

Porous ZnS and ZnO nano‐crystal films were fabricated via a three‐step procedure. First, Zn(CH₃COO)₂/Silk Fibroin nanofiber mats were prepared by coaxial electrospinning. Second, Zn(CH₃COO)₂/Silk Fibroin mats were immersed in NaS solution to react with S²⁻ to obtain ZnS/Silk Fibroin nanofiber mats. Finally, ZnO porous films were prepared by calcination of ZnS/Silk Fibroin composite mat at 600°C in air atmosphere. When ZnS/Silk Fibroin mats were calcinated in nitrogen, ZnS/Carbon composite mats were obtained accordingly. The resulting porous films were fully characterized. The ZnO porous films were the aggregation of ZnO nano‐crystal with hexagonal wurtzite structure. The seize of ZnO was estimated in the range of 10–20 nm. Both of the ZnS and ZnO nano‐crystal films exhibited high photocatalytic activities for the photodegradation of Methylene blue and Rhodamine B. It was also found that ZnO porous films are better than ZnS/Carbon nanofiber mats. In addition, photocatalysis of a real wastewater sample from a printing and dyeing company was conducted. The ZnO porous films exhibited excellent performance to treat the real samples. Moreover, the porous ZnO nano‐crystal photocatalyst could easily be recycled without notable loss of catalysis ability.     

Influence of solvents properties on morphology of electrospun polyurethane nanofiber mats

Segmented polyurethane (SPU) nanofiber mats were prepared by electrospinning technique using the combination of four different solvents viz. tetrahydrofuran, N,N′‐dimethyl formamide, N,N′‐dimethyl acetamide, and dimethyl sulfoxide. Morphology of the electrospun nanofibers was examined by field emission scanning electron microscope. Experimental results revealed that the morphologies of polyurethane nanofiber mats have been changed significantly with the solvent selection for the electrospinning. It was observed that the diameters and morphology of the SPU nanofibers were influenced greatly by the use of combination of solvents. The uniform polyurethane nanofibers without beads or curls could be prepared by electrospinning through the selection of combination of good conductive and good volatile solvent viz. 7.5 wt/v% of SPU in N,N′‐dimethyl formamide/tetrahydrofuran (30 : 70 v/v) solutions at 20 kV applied voltages and volume flow rate of 1 ml/min. On the basis of the results obtained from this investigation, it has been established that solvent selection is one of the driving factors for controlling the morphology of the polyurethane electrospun nanofiber mats. The well‐controlled morphology of electrospun polyurethane nanofiber mats could be useful for many potential industrial applications such as in biomedical, smart textiles, nanofiltration, and sensors. Copyright © 2013 John Wiley & Sons, Ltd.     

UV-protection and photocatalytic properties of electrospun polyacrylonitrile nanofibrous mats coated with TiO<Subscript>2</Subscript> nanofilm via sol–gel

UV radiation causes serious damage to skin, and a protective system capable of absorbing or reflecting UV radiation is required to protect skin. This paper describes the UV protection and photocatalytic properties of TiO₂ nanofilm coated electrospun polyacrylonitrile (PAN) nanofibrous mats with various nanofiber diameter and area density. The mats were coated by sol–gel process. The results of this research showed that sol–gel is capable of coating porous nanofibrous mats with a weight increase as low as 0.8%. The TiO₂ nanofilm coated on the nanofibrous mats has a considerable effect on its UV protection. The UV protection factor (UPF) of the mats increases with decreasing nanofiber diameter. In fact decreasing the diameter of nanofibers of the TiO₂ nanofilm coated PAN nanofibrous mats increases their photocatalytic activity. Moreover, this research showed that TiO₂ nanofilm produced through sol–gel process on the PAN nanofibers has a crystalline structure. The UPF of the nanofibrous mat coated with a TiO₂ nanofilm via sol–gel process can be classified as excellent.