静电纺丝法制备聚丙烯腈/聚苯胺复合纳米纤维及其表征

利用静电纺丝技术,以聚丙烯腈(PAN)和苯胺(ANI)为前驱物,用过硫酸胺(APS)溶液在低温下缓慢氧化聚合,制备了PAN/PANI复合纳米纤维,直径约500 nm.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、X射线衍射(XRD)和激光拉曼(RAMAN)光谱仪等测试手段对材料的形貌和结构进行了表征.探讨了材料制备过程中影响纤维形貌、尺寸、均匀度的因素和PANI含量对复合纤维导电性能的影响,结果表明,PAN浓度、ANI的加入量和电压是影响纤维特性的主要因素;PANI在PAN基体中呈纳米尺寸分布,复合纳米纤维具有良好的导电性能,导电率可达10-2S/cm.     

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.     

Electrospun poly(3‐hexylthiophene)/poly(ethylene oxide)/graphene oxide composite nanofibers: effects of graphene oxide reduction

In this article, we report on the production by electrospinning of P3HT/PEO, P3HT/PEO/GO, and P3HT/PEO/rGO nanofibers in which the filler is homogeneously dispersed and parallel oriented along the fibers axis. The effect of nanofillers' presence inside nanofibers and GO reduction was studied, in order to reveal the influence of the new hierarchical structure on the electrical conductivity and mechanical properties. An in‐depth characterization of the purity and regioregularity of the starting P3HT as well as the morphology and chemical structure of GO and rGO was carried out. The morphology of the electrospun nanofibers was examined by both scanning and transmission electron microscopy. The fibrous nanocomposites are also characterized by differential scanning calorimetry to investigate their chemical structure and polymer chains arrangements. Finally, the electrical conductivity of the electrospun fibers and the elastic modulus of the single fibers are evaluated using a four‐point probe method and atomic force microscopy nanoindentation, respectively. The electrospun materials crystallinity as well as the elastic modulus increase with the addition of the nanofillers while the electrical conductivity is positively influenced by the GO reduction. Copyright © 2016 John Wiley & Sons, Ltd.     

Controlled Nanofiber Composed of Multi‐Wall Carbon Nanotube/Poly(Ethylene Oxide)

We have successfully fabricated poly(ethylene oxide) (PEO) nanofibers containing embedded multi‐wall carbon nanotubes (MWCNTs). An initial dispersion of the MWCNTs in distilled water was achieved using sodium dodecyl sulfate. Subsequently, the dispersion was decanted into a PEO solution, which enabled separation of the MWCNTs and their individual incorporation into the PEO nanofibers on subsequent electrospinning. Initially, the carbon nanotube (CNT) rods were randomly oriented, but owing to the sink‐like flow in the electrospinning wedge, they became gradually oriented along the streaming direction, in order that oriented CNTs were obtained on entering the electrospun jet. Individual MWCNTs became embedded in the nanofibers, and were mostly aligned along the fiber axis. Evidence of load transfer to the nanotubes in the composite nanofiber was observed from the field‐emission scanning electron microscopy, transmission electron microscopy and conductivity data.     

Carbon nanostructure-derived polyaniline metacomposites: electrical, dielectric, and giant magnetoresistive properties

Polyaniline (PANI) nanocomposites incorporating different loadings of graphene and various other carbon nanostructures including carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have been synthesized using a surface-initiated polymerization (SIP) method. Transmission electron microscopy (TEM) results indicate that the graphene has been exfoliated into a few layers (typically one, two, and three layers) during polymerization and has been uniformly dispersed in the PANI matrix. The graphene layer dispersion degree is quantified by a free-path spacing measurement (FPSM) method based on the TEM microstructures. The SIP method also demonstrates its feasibility for coating PANI on one-dimensional (1D) CNFs and CNTs without introducing additional surface functional groups. The effects of graphene size, loading level, and surface functionality on the electrical conductivity and dielectric permittivity of their corresponding nanocomposites have been systematically studied. The temperature-dependent conductivity behavior revealed a quasi-3D variable range hopping (VRH) electron transport mechanism for all the nanocomposites. Giant magnetoresistance (GMR) at room temperature is observed in pure PANI, which can be enhanced by the incorporation of a high loading of graphene (5%) due to the π-π stacking-induced efficient electron transport at the PANI/graphene interface. More interestingly, negative permittivity is found in each composite which can be easily tuned by adjusting the filler loading, morphology, and surface functionality.     

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.     

静电纺丝制备Eu(BA)3phen/PANI/PVP光电双功能复合纳米纤维及其性能

采用静电纺丝技术将聚苯胺(PANI)和稀土配合物Eu(BA)3phen掺杂到高分子材料聚乙烯吡咯烷酮(PVP)中, 制备出新型的具有光电双功能的Eu(BA)3phen/PANI/PVP复合纳米纤维. 采用扫描电子显微镜、 X射线能量色散谱仪、 荧光光谱仪及宽频介电松弛谱仪对样品进行了表征. 实验结果表明, 复合纳米纤维直径为(270±31) nm. 在275 nm紫外光激发下, Eu(BA)3phen/PANI/PVP复合纳米纤维发射出主峰位于580, 594和617 nm的红光, 对应于Eu3+的 5D0→7F0, 5D0→7F1和5D0→7F2跃迁. 当m[Eu(BA)3phen]:m(PANI):m(PVP)=15:10:100 时, 复合纳米纤维的荧光发射最强. 复合纤维的电导率随PANI含量的增大而升高. 在m(PANI):m(PVP)=50:100时, 其电导率在高频(106 Hz)下达到1.5×10-6 S/cm.     

Atmospheric plasma treatment of pre‐electrospinning polymer solution: A feasible method to improve electrospinnability

The electrospinnability of polyethylene oxide (PEO) was manipulated by atmospheric plasma treatment of pre‐electrospinning solutions. Conductivity, viscosity, and surface tension of PEO solutions increased after plasma treatment, and the plasma effect remained longer when the solution concentrate increased. Both untreated and treated solutions were then electrospun, and the morphology of the resultant nanofibers was observed by SEM. Atmospheric plasma treatment improved the electrospinnability of PEO solutions and led to less beads and finer diameter distribution in the resultant nanofibers. Additionally, plasma treatment of the pre‐electrospinning solutions affected the crystal structure of resultant nanofibers. These results suggest that atmospheric plasma treatment is a feasible approach to improve the electrospinnability of polymer solutions and can used to control the structure of electrospun nanofibers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Electrospinning of composite nanofibers based on chitosan,poly(ethylene oxide), and chitin nanofibrils

Composite chitosan nanofibers containing 20 wt % chitin nanofibrils and 10 wt % PEO are obtained via the electrospinning method. Additions of 0.5–20.0 wt % chitin nanofibrils into chitosan solutions with concentrations of 3–7 wt % in acetic acid (70 vol %) insignificantly increase the electrical conductivity, surface-tension coefficient, and viscosity of these mixed solutions. Decreases in the viscosities of chitosan solutions containing chitin nanofibrils with increases in shear rate provide evidence for the structuring of solutions and the orientation of chitosan macromolecules and chitin nanofibrils in the shear flow. The effects of shear stress and a high-voltage electric field on chitosan solutions containing chitin nanofibrils and PEO result in a decrease in the imperfection of composite nanofibers. The introduction of chitin nanofibrils allows the content of PEO in the composite nanofibers to be reduced.     

Nanofibrous polyaniline thin film prepared by plasma‐induced polymerization technique for detection of NO2 gas

A nanofibrous polyaniline (PANI) thin film was fabricated using plasma‐induced polymerization method and explored its application in the fabrication of NO₂ gas sensor. The effects of substrate position, pressure, and the number of plasma pulses on the PANI film growth rate were monitored and an optimum condition for the PANI thin film preparation was established. The resulting PANI film was characterized with UV–visible spectrophotometer, FTIR, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The PANI thin film possessed nanofibers with a diameter ranging from 15 to 20 nm. The NO₂ gas sensing behavior was studied by measuring the change in electrical conductivity of PANI film with respect to NO₂ gas concentration and exposure time. The optimized sensor exhibited a sensitivity factor of 206 with a response time of 23 sec. The NO₂ gas sensor using nanofibrous PANI thin film as sensing probe showed a linear current response to the NO₂ gas concentration in the range of 10–100 ppm. Copyright © 2009 John Wiley & Sons, Ltd.     

静电纺丝技术制备Tb（BA）3phen/PANI/PVP光电双功能复合纳米纤维

采用静电纺丝技术将聚苯胺(PANI)和稀土配合物[Tb(BA)3phen]掺杂到高分子材料(PVP)中,制备出一类新型的具有光电双功能的Tb(BA)3phen/PANI/PVP复合纳米纤维.用扫描电子显微镜(SEM)、X射线能量色散谱仪(EDS)、荧光光谱仪及宽频介电松弛谱仪对样品进行了表征.结果表明,复合纳米纤维直径为(331±43)nm.在276 nm紫外光激发下,Tb(BA)3phen/PANI/PVP复合纳米纤维发射出主峰位于491,547和585 nm的绿光,对应Tb3+的5D4→7F6,5D4→7F5和5D4→7F4跃迁.当Tb(BA)3phen∶PANI∶PVP的质量比为15∶10∶100时,复合纳米纤维的荧光发射最强,其电导率随PANI含量的增大而升高,在PANI∶PVP为50%(wt%)时,其电导率在高频(106Hz)下达1.531×10-6S/cm.     

Fabrication,characterization, and drug release study of vitamin C–loaded alginate/polyethylene oxide nanofibers for the treatment of a skin disorder

Pigmented purpuric dermatosis (PPD) is a skin disorder mainly seen in the lower limbs. The nanofibrous web has been shown to be an appropriate alternative for the treatment of skin diseases as a drug delivery vehicle. In this study, sodium alginate (SA)/polyethylene oxide (PEO) nanofibers containing vitamin C (VC) were fabricated using both blended electrospinning and core/shell electrospinning. The resultant nanofibers were characterized using Fourier transform infrared spectroscopy and scanning electron microscopy. Enhancing the VC content resulted in increasing the nanofibers diameter. Also, the degradation rate and drug release were investigated. Drug release was evaluated using the in vitro dissolution and permeation method. The degradation rate and the drug release of the core/shell nanofibers were found to be lower than those of the blended nanofibers. The drug release of the extended nanofibers followed a different pattern, indicating that the extension of the nanofibers could be a promising way to control the drug release.     

静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维

以聚丙烯腈(PAN)为载体基质、 以铕-聚乙二醇(Eu-PEG)和铽-聚乙二醇(Tb-PEG)为相变荧光材料, 加入掺杂的导电聚苯胺(PANI), 采用静电纺丝技术制得Tb-PEG+Eu-PEG/PANI/PAN复合纤维. 采用扫描电子显微镜(SEM)、 荧光光谱(FL) 仪、 差示扫描量热(DSC)仪及宽频介电松驰谱(BDS)仪等方法对相变荧光导电复合纤维的性能进行分析. 研究结果表明, 复合纤维具备良好的荧光、 相变及导电性能. 在294 nm紫外光激发下, 通过调节Tb-PEG和Eu-PEG的质量比可调节复合纤维的发光强度和颜色, 同时复合纤维的相变温度在5467 ℃之间. 复合纤维的电导率达到10^-6 S/cm, 随着PANI含量的增加, 电导率和介电常数增加. 通过调节Tb-PEG, Eu-PEG和PANI的比例及PEG的分子量, 可以实现复合纤维荧光、 导电及相变性能的可控调整.     

Surface‐treated and multilayered poly(ε‐caprolactone) nanofiber webs exhibiting enhanced hydrophilicity

To improve the hydrophilic properties of poly(ε‐caprolactone) (PCL) nano/microfiber webs for tissue engineering scaffolds, PCL webs of various structures were fabricated by electrospinning with single or double nozzles connected to an auxiliary electrode. Surface‐modified and layered PCL fiber webs were made by including water‐soluble poly(ethylene oxide) (PEO) in the PCL electrospinning solution (single‐nozzle method) or by electrospinning of alternating PCL and PEO solutions using two nozzles (double‐nozzle method), respectively. When the PEO component within the resulting webs was removed by dissolution with distilled water, the remnant PCL webs exhibited two distinct structures. Those made by the single‐nozzle method consisted of nanofibers with high surface roughness, whereas those made by the double‐nozzle method consisted of stacked layers of PCL nanofibers. Both types of structured PCL web showed improved hydrophilicity characteristics compared with those of nanofiber webs generated from a pure PCL solution using a typical electrospinning process. Cell culturing and scanning electron microscopy showed that the interactions between human dermal fibroblasts and the structured PCL scaffolds were very favorable. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2038–2045, 2007     

Electrospinning preparation and mechanical properties of PVA/HNTs composite nanofibers

In this paper, the PVA/HNTs composite nanofibers with well‐enhanced mechanical properties were successfully prepared by electrospinning technique. The structure and properties of the composite nanofibers were characterized by TEM, XRD, FT‐IR, and DSC. The results indicated that the highly oriented and dispersed HNTs wrapped in polymer matrix were achieved by inducing function during electrospinning processing. The mechanical properties of the PVA/HNTs composite nanofibers depended on HNTs content were investigated, which showed 72.4% increase in tensile strength at optimal filling content. Copyright © 2016 John Wiley & Sons, Ltd.     

Graphene oxide sheet–polyaniline nanohybrids for enhanced photovoltaic performance of dye‐sensitized solar cells

In this study, photovoltaic (PV) properties of dye‐sensitized solar cells (DSSCs) incorporated with graphene oxide nanosheet‐polyaniline (GOS‐PANI) nanohybrid/poly(ethylene oxide) (PEO) blend gel electrolytes were investigated. Chemical structure and composition of GOS‐PANI nanohybrids were characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy. The images of transmission electron microscopy revealed that PANI nanorods were anchored to the single‐layered GOS for the GOS‐PANI nanohybrids. Ionic conductivities of the GOS‐PANI/PEO–based gel electrolytes were measured using a conductivity meter. The electrochemical catalytic activities of the GOS‐PANI nanohybrids were determined through cyclic voltammetry. These GOS‐PANI nanohybrids were served as the extended electron transfer materials and catalyst for the electrochemical reduction of I₃^?. Due to the enhancement of the ionic conductivity and electrochemical catalytic activity of the gel electrolyte, better PV performance was observed for the DSSCs based on the GOS‐PANI containing electrolytes as compared to the pristine PEO electrolyte‐based DSSC sample. Moreover, PV performances of the GOS‐PANI/PEO–based DSSCs were closely related to the PANI content of GOS‐PANI nanohybrids. The highest photo‐energy conversion efficiency (5.63%) was obtained for an optimized GOS‐PANI/PEO (5:95, w/w) blend gel electrolyte‐based DSSC sample. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 321–332     

Synthesis of polyaniline/multiwall carbon nanotube composite via inverse emulsion polymerization

The composite of polyaniline (PANI) and multiwall carbon nanotube carboxylated through acid treatment (c‐MWCNT) was synthesized by chemical oxidative polymerization in an inverse emulsion system. The resultant composites were compared with products from aqueous emulsion polymerization to observe the improvements in electrical conductivity, structural properties, and thermal stability obtained by this synthetic method. Prior to the inverse emulsion polymerization, MWCNT was treated with a strong acid mixture to be functionalized with carboxylic acid groups. Carboxylic acid groups on surfaces induced selective dispersibility between polar and nonpolar solvents because of the increase of hydrophilicity. As the content of c‐MWCNT was increased, the electrical conductivity was increased by a charge transport function from the intrinsic electrical conductivity of MWCNT and the formation of a highly ordered dense structure of PANI molecules on the surface of c‐MWCNT. The images observed with electron spectroscopy showed the capping of c‐MWCNT with PANI. The growth of additional ordered structures of PANI/c‐MWCNT composite, which was observed through wide‐angle X‐ray diffraction patterns, supported the capping by PANI. It was observed that the doping of the composite had a significant relationship with the concentration of dodecylbenzenesulfonic acid (DBSA). The thermal stability of PANI composite was improved by the addition of c‐MWCNT; this was thought to be related with structure ordering by inverse emulsion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2255–2266, 2008     

Enhanced orientation of PEO polymer chains induced by nanoclays in electrospun PEO/clay composite nanofibers

Polymer fibers composed of poly(ethylene oxide) (PEO) and nanoclay were fabricated by electrospinning. The morphology of the composite nanofibers was characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), which showed aligned nanoclays in the fibers. Polarized Fourier transform infrared (FT-IR) spectroscopy revealed that the PEO chains in the composite fibers exhibit a higher degree of orientation than that in PEO nanofibers containing no nanoclay. It is believed that spatial confinement is present in the electrospun nanofibers, which results in the enforcement of the mutual restriction. The anisotropic hierarchical nanostructure may have potential applications in optics, mechanical materials, and biomedical materials for cell culture.     

Characterization and electrical transport properties of polyaniline and multiwall carbon nanotube composites

Polyaniline/multiwalled carbon nanotube (PANI/MWNT) composites were prepared by in situ polymerization. Scanning electron microscope, X‐ray diffraction, Fourier transform infrared, Uv‐Visible spectroscopy, Fluorescence spectrophotometry were done to characterize the PANI/MWNT composites. Thermal stability was measured by thermogravimetry analysis. The thermal stability of PANI/MWNT composites becomes higher than PANI. Electrical transport properties of different PANI/MWNT composites were investigated in the temperature range 77 ≤ T ≤ 300 K with and without magnetic field up to 1 T. The dc resistivity of PANI/MWNT composites shows different behavior compared to the sample without MWNT. The room temperature dc magnetoconductivity of the samples is negative; however, its sign changes to positive by lowering the temperature, which has been explained by hopping type charge transport. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1767–1775, 2010     

Single-walled carbon nanotubes embedded in oriented polymeric nanofibers by electrospinning

The electrospinning process was used successfully to embed single-walled carbon nanotubes (SWCNTs) in a poly(ethylene oxide) (PEO) matrix, forming composite nanofibers. Initial dispersion of SWCNTs in water was achieved by the use of an amphiphilic alternating copolymer of styrene and sodium maleate. The resulting dispersions were stable, having a dark, smooth, ink-like appearance. For electrospinning, the dispersions were mixed with PEO solution in an ethanol/water mixture. The distribution and conformation of the nanotubes in the nanofibers were studied by transmission electron microscopy (TEM). Oxygen plasma etching was used to expose the nanotubes within the nanofibers to facilitate direct observation. Nanotube alignment within the nanofibers was shown to depend strongly on the quality of the initial dispersions. Well-dispersed and separated nanotubes were embedded in a straight and aligned form, while entangled nonseparated nanotubes were incorporated as dense aggregates. X-ray diffraction demonstrated a high degree of orientation of the PEO crystals in the electrospun nanofibers with embedded SWCNTs. This result is in pronounced distinction to the detrimental effect of incorporation of multiwalled carbon nanotubes on polymer orientation in electrospun nanofibers, as reported previously.