Fabrication and electrical characterization of electrospun polyacrylonitrile‐derived carbon nanofibers

Carbon nanofibers were produced from a polyacrylonitrile/N,N‐dimethylformamide precursor solution by an electrospinning process and later pyrolysis at temperatures ranging from 500 to 1100°C in an N₂ atmosphere for about 1 h. The morphological structure of the nanofibers was studied with scanning electron microscopy. Scanning electron microscopy images of carbonized polyacrylonitrile nanofibers without a gold coating showed that the carbonized polyacrylonitrile nanofibers possessed electrical properties. The thermal behavior of the nanofibers was studied with thermogravimetric analysis. An indirect four‐point‐probe method was used for the measurement of the conductivity of nanofiber mats. The conductivity increased sharply with the pyrolysis temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of electrospun ultrafine polyamide‐6 nanofibers

We report on the preparation and characterization of ultrafine polyamide‐6 nanofibers by the electrospinning technique. The effect of electrospinning on the formation of ultrafine polyamide‐6 nanofiber structure was examined. The morphological and structural characterizations and thermal properties of the ultrafine polyamide‐6 nanofibers were investigated in comparison with bulk polyamide‐6 pellets. In order to accurately characterize the ultrafine polyamide‐6 nanofiber structure by direct identification of mass resolved components, we performed matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry. Field emission scanning electron microscopy images revealed the presence of ultrafine polyamide‐6 nanofibers bound between the main fibers. The diameter of the polyamide‐6 nanofibers was observed to be in the range 75–110 nm, whereas the ultrafine structures consisted of regularly distributed very fine nanofibers with diameters of about 9–28 nm. The MALDI‐TOF spectra showed the presence of protonated and sodiated ions that were assigned to polyamide‐6 chains. Copyright © 2011 Society of Chemical Industry     

Non‐ionic surfactants for enhancing electrospinability and for the preparation of electrospun nanofibers

BACKGROUND: Electrospinning is widely used to produce nanofibers; however, not every polymer can be electrospun into nanofibers. To enhance electrospinability, much effort has been made in designing new apparatus, such as vibration‐electrospinning, magneto‐electrospinning and bubble‐electrospinning. RESULTS: A representative non‐ionic surfactant, TritonR X‐100, is used to enhance electrospinability. The surfactant is added to an electrospun poly(vinyl pyrrolidone) polymer solution, and a dramatic reduction in surface tension is observed. As a result, a moderate voltage is needed to produce fine nanofibers, which are commonly observed during the conventional electrospinning procedure only at elevated voltage. CONCLUSION: The novel strategy produces smaller nanofibers than those obtained without surfactants, and the minimum threshold voltage is much decreased. Copyright © 2008 Society of Chemical Industry     

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

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

Studies on the synthesis of electrospun PAN‐Ag composite nanofibers for antibacterial application

We have successfully synthesized polyacrylonitrile (PAN) nanofibers impregnated with Ag nanoparticles by electrospinning method at room temperature. Briefly, the PAN‐Ag composite nanofibers were prepared by electrospinning PAN (10% w/v) in dimethyl formamide (DMF) solvent containing silver nitrate (AgNO₃) in the amounts of 8% by weight of PAN. The silver ions were reduced into silver particles in three different methods i.e., by refluxing the solution before electrospinning, treating with sodium borohydride (NaBH₄), as reducing agent, and heating the prepared composite nanofibers at 160°C. The prepared PAN nanofibers functionalized with Ag nanoparticles were characterized by field emission scanning electron microscopy (FESEM), SEM elemental detection X‐ray analysis (SEM‐EDAX), transmission electron microscopy (TEM), and ultraviolet‐visible spectroscopy (UV‐VIS) analytical techniques. UV‐VIS spectra analysis showed distinct absorption band at 410 nm, suggesting the formation of Ag nanoparticles. TEM micrographs confirmed homogeneous dispersion of Ag nanoparticles on the surface of PAN nanofibers, and particle diameter was found to be 5–15 nm. It was found that all the three electrospun PAN‐Ag composite nanofibers showed strong antibacterial activity toward both gram positive and gram negative bacteria. However, the antibacterial activity of PAN‐Ag composite nanofibers membrane prepared by refluxed method was most prominent against S. aureus bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Interior synthesizing of ZnO nanoflakes inside nylon‐6 electrospun nanofibers

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

Influence of lactic acid on degradation and biocompatibility of electrospun poly(ε‐caprolactone) fibers

Electrospinning of a poly(ε‐caprolactone) (PCL)/lactic acid (LA) blend was investigated to fabricate electrospun PCL fibers with improved biodegradability and biocompatibility for biomedical applications. Simple blending of PCL solution with various amounts of LA was used for electrospinning, and the physicochemical properties of the as‐fabricated mat were evaluated using various techniques. Scanning electron microscopy showed that fiber diameter decreased with increasing amount of LA. Fourier transform infrared spectroscopy and thermogravimetric analysis also revealed that LA was successfully incorporated in PCL fibers. The presence of LA can accelerate the biodegradation of PCL fibers and enhance the hydrophilicity of a membrane. The adhesion, viability and proliferation properties of osteoblast cells on the PCL/LA composite fibers were analyzed using in vitro cell compatibility tests which showed that LA can increase the cell compatibility of PCL fibers. Additionally, subsequent conversion of LA into calcium lactate by neutralization with calcium base can provide Ca²⁺ ions on the fiber surface to promote the nucleation of CaPO₄ particles. © 2013 Society of Chemical Industry     

Effects of mechanical force on crystalline structure of electrospun poly(1‐butene) membranes

Fibrous poly(1‐butene) membranes were prepared from solutions using mixed solvents via electrospinning. The electrospun fibrous poly(1‐butene) membranes were stretched at elongations of 8, 16 and 24%, respectively. Scanning electron microscopy and stress–strain analysis showed that the deformation was elastic at an elongation of 8%, while plastic deformation occurred above 16%. The crystalline transformation induced by mechanical stretching was investigated using wide‐angle X‐ray diffraction. The poly(1‐butene) membrane stretched at 24% exhibited decreased diffraction intensity at 2θ = 11.8° and 18.3°, corresponding to the (200) and (213) crystalline reflections, indicating that crystalline transformation from metastable form II to either stable form I or I′ occurred due to mechanical stretching. Copyright © 2011 Society of Chemical Industry     

Morphology of electrospun nylon‐6 nanofibers as a function of molecular weight and processing parameters

In the present study, the morphology and mechanical properties of nylon‐6 nanofibers were investigated as a function of molecular weight (30,000, 50,000, and 63,000 g/mol) and electrospinning process conditions (solution concentration, voltage, tip‐to‐collector distance, and flow rate). Scanning electron micrographs (SEM) of nylon‐6 nanofibers showed that the diameter of the electrospun fiber increased with increasing molecular weight and solution concentration. An increase in molecular weight increases the density of chain entanglements (in solution) at the same polymer concentration; hence, the minimum concentration to produce nanofibers was lower for the highest molecular weight nylon‐6. The morphology of electrospun fibers also depended on tip‐to‐collector distance and applied voltage concentration of polymer solution as observed from the SEM images. Trends in fiber diameter and diameter distribution are discussed for each processing variable. Mechanical properties of electrospun nonwoven mats showed an increase in tensile strength and modulus as a function of increasing molecular weight. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(ϵ‐caprolactone)‐functionalized carbon nanofibers by surface‐initiated ring‐opening polymerization

Carbon nanofibers (CNFs) were covalently functionalized with biodegradable poly(?‐caprolactone) (PCL) by in situ ring‐opening polymerization (ROP) of ?‐caprolactone in the presence of stannous octoate. Surface oxidation treatment of the pristine CNFs afforded carboxylic CNFs (CNF‐COOH). Reaction of CNF‐COOH with excess thionyl chloride (SOCl₂) and glycol produced hydroxyl‐functionalized CNFs (CNF‐OH). Using CNF‐OH as macroinitiator, PCL was covalently grafted from the surfaces of CNFs by ROP, in either the presence or absence of sacrificial initiator, butanol. The grafted PCL content was achieved as high as 64.2 wt %, and can be controlled to some extent by adjusting the feed ratio of monomer to CNF‐OH. The resulting products were characterized by FTIR, NMR, Raman spectroscopy, TGA, DSC, SEM, TEM, HRTEM, and XRD. Core–shell nanostructures were observed under HRTEM for the PCL‐functionalized CNFs because of the thorough grafting. The PCL‐grafted CNFs showed different melting and crystallization behaviors from the mechanical mixture of PCL and CNF‐OH. This approach to PCL‐functionalized CNFs opens an avenue for the synthesis, modification, and application of CNF‐based nanomaterials and biomaterials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Co‐electrospun composite nanofibers of blends of poly[(amino acid ester)phosphazene] and gelatin

Electrospinning is known as a simple and effective fabrication method to produce polymeric nanofibers suitable for biomedical applications. Many synthesized and natural polymers have been electrospun and reported in the literature; however, there is little information on the electrospinning of poly[(amino acid ester)phosphazene] and its blends with gelatin. Composite nanofibers were made by co‐dissolving poly[(alaninoethyl ester)_0.67(glycinoethyl ester)_0.33phosphazene] (PAGP) and gelatin in trifluoroethanol and co‐electrospinning. The co‐electrospun composite nanofibers from different mixing ratios (0, 10, 30, 50, 70 and 90 wt%) of gelatin to PAGP consisted of nanoscale fibers with a mean diameter ranging from approximately 300 nm to 1 µm. An increase in gelatin in the solution resulted in an increase of average fiber diameter. Transmission electron microscopy and energy dispersive X‐ray spectrometry measurements showed that gelatin core/PAGP shell nanofibers were formed when the content of gelatin in the hybrid was below 50 wt%, but homogeneous PAGP/gelatin composite nanofibers were obtained as the mixing ratios of gelatin to PAGP were increased up to 70 and 90 wt%. The study suggests that the interaction between gelatin and PAGP could help to stabilize PAGP/gelatin composite fibrous membranes in aqueous medium and improve the hydrophilicity of pure PAGP nanofibers. Copyright © 2009 Society of Chemical Industry     

Covalent immobilization of β‐galactosidase onto electrospun nanofibers of poly (AN‐co‐MMA) copolymer

Immobilization of β‐galactosidase in poly (acrylonitrile‐co‐methyl methacrylate) poly (AN‐co‐MMA) Nanofibers was studied by electrospinning, and a spacer‐arm i.e., (Polyethyleneimine (PEI)) was covalently attached by the reaction of carbonyl groups of Poly (AN‐co‐MMA) nanofibers. β‐galactosidase was then covalently immobilized through the spacer‐arm of the Poly (AN‐co‐MMA) nanofibers by using glutaraldehyde (GA) as a coupling agent. Nanofibers mode of interaction was proven by FTIR and thermal gravimetric analysis and supported by morphological changes recognized through SEM examination. Factors affecting the modification process such as PEI concentration, reaction time, and reaction temperature have been studied. Its influence on the amount of coupled PEI was consequently correlated to the changes of the catalytic activity and the retained activity of immobilized enzyme, the main parameters judging the success of the immobilization process. Evidences of Poly (AN‐co‐MMA) nanofibers modification were extracted from morphological changes recognized through SEM examination. The maximum activity (V_max) and michaelis constant (K_m) of immobilized enzyme were found to be 8.8 μmole/min mg protein and 236.7 mM, respectively. Stabilities of the immobilized β‐galactosidase were obviously improved. The optimum temperature for β‐galactosidase immobilized on the spacer‐arm attached nanofiber was 5°C higher than that of the free enzyme and was also significantly broader. The immobilized β‐galactosidase had better resistance to temperature inactivation than did the free form. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Some fascinating phenomena in electrospinning processes and applications of electrospun nanofibers

Electrospinning has the unique ability to produce ultrathin fibers from a rich variety of materials that include polymers, inorganic or organic compounds and blends. With the enormous increase of research interest in electrospun nanofibers, there is a strong need for a comprehensive review of electrospinning in a systematic fashion. This article presents some fascinating phenomena associated with the remarkable features of nanofibers in electrospinning processes and new progress in applications of electrospun nanofibers. Copyright © 2007 Society of Chemical Industry     

Preparation of antimicrobial poly(ϵ‐caprolactone) electrospun nanofibers containing silver‐loaded zirconium phosphate nanoparticles

Antimicrobial nanofibers of poly(?‐caprolactone) (PCL) were prepared by electrospinning of a PCL solution with small amounts of silver‐loaded zirconium phosphate nanoparticles (nanoAgZ) for potential use in wound dressing applications. The electrospun nanoAgZ‐containing PCL nanofibers were characterized using field emission scanning electron microscopy, energy dispersive X‐ray spectrum (EDX), X‐ray diffraction analysis (XRD), antimicrobial tests, and biocompatibility tests. The SEM, EDX, and XRD investigations of the electrospun fibers confirmed that silver‐containing nanoparticles were incorporated and well dispersed in smooth and beadless PCL nanofibers. The results of the antimicrobial tests showed that these fibers have maintained the strong killing abilities of Ag⁺ existed in the nanoAgZ against the tested bacteria strains and discoloration has not been observed for the nanofibers. To test the biocompatibility of nanofibers as potential wound dressings, primary human dermal fibroblasts (HDFs) were cultured on the nanofibrous mats. The cultured cells were evaluated in terms of cell proliferation and morphology. The results indicated that the cells attached and proliferated as continuous layers on the nanoAgZ‐containing nanofibers and maintained the healthy morphology of HDFs. The earlier results suggested that nanoAgZ‐containing fibers may be expected to be a novel material for potential wound dressing applications because of the significant bacteriostatic activities and good biocompatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electrospinning of cellulose‐based nanofibers

Cellulose derivatives of carboxymethyl cellulose sodium salt (CMC), hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), and enzymatically treated cellulose have been electrospun, and the microstructure of the resulting nanofibers has been analyzed by scanning electron microscopy (SEM). Before electrospinning, the solutions were characterized by viscometry and surface tension measurements, and the results were correlated with spinnability. Four different CMC derivatives, varying in molecular weight (M_w), degree of substitution (DS), and substitution pattern, have been electrospun in mixtures with poly(ethylene oxide) (PEO), and nanofibers of various characteristics have formed. The CMC‐based nanostructures, i.e., the nonwoven sheet and individual nanofibers, proved to be independent of M_w and DS but largely dependent on the substitution pattern. The nonwoven sheets varied in homogeneity, and beads appeared on the individual fibers. Depending on the chemical nature of the CMC, the extraction of PEO resulted in pure CMC nanostructures of varying appearance, indicating that the distribution of PEO and CMC in the nanofibers also varied. Two different HPMC derivatives, varying in DS, were electrospun into nanofibers. Homogeneous nonwoven sheets based on nanofibers of similar appearance are formed, independent of the substitution content of the HPMC sample. Preliminary fibers were obtained from enzymatically treated cellulose in a solvent system based on lithium chloride dissolved in dimethyl acetamide (LiCl: DMAc). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1473–1482, 2007     

静电纺特殊结构纳米纤维的研究现状

纳米级纤维具有优良的机械性能和高比表面积等特性.以静电纺特殊结构纳米纤维为研究对象,根据其表观形态分别介绍了一维特殊结构纳米纤维、二维特殊结构纳米纤维膜、三维结构纳米纤维气凝胶等,并阐述了各种结构的形成机理.总结了近年来国内外采用静电纺丝技术制备特殊结构纳米纤维的调控方法,如改变溶液性质(溶液浓度、黏度、表面张力、电导...     

Development,optimization, and characterization of electrospun poly(lactic acid) nanofibers containing multi‐walled carbon nanotubes

Electrospinning of poly (L ‐D ‐lactic acid) (PLA) was investigated with the addition of multi‐walled carbon nanotubes (MWNT) for development of a scaffold for tissue engineering. Through this experiment, it was determined that the optimal concentration of PLA with weight average molecular weight (M_w) 250,000 g/mol is ～20 wt % as indicated by scanning electron microscopy. This concentration produces fibers with no beading or film formation. The preferred solvent system is a combination of chloroform and dimethyl formamide to alleviate the volatile action of chloroform. The optimum processing parameters for PLA are an electric field of 1 kV/cm which was determined by a surface response plot to minimize fiber diameter based on the applied voltage, working distance, and addition of MWNT. Fourier Transform infrared spectroscopy has indicated the removal of the solvent system. With the addition of MWNT, the fiber diameter was drastically reduced by 70% to form fibers with a mean diameter of 700 nm. This is believed to be due to an increased surface charge density for the MWNT/polymer solution. Transmission electron microscopy validated the alignment of the MWNT within the fibers. MWNT loading exhibited an increase in the conductance of the scaffold and the tensile modulus at an optimal loading level of 0.25 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Improved catalytic activity by catalase immobilization using γ‐cyclodextrin and electrospun PCL nanofibers

Nanofibrous structures are promising for biocatalyst immobilization due to their large surface area which facilitates the enzyme attachment, stability, ease of separation, and fine porous structure. There is limited research available on the change in enzyme activity following interaction with cyclodextrin. In this study, catalase enzyme was immobilized into nanofibrous structures by various techniques, with and without γ‐CD addition, and the enzymatic activity of catalase was evaluated. In addition, catalase‐γ‐CD complex containing PEO polymer solution was electrospun in between PCL nanofibrous layers as a newly developed technique. The enzyme immobilized nanofibrous structures were characterized by SEM, XRD, and FT‐IR analysis methods. Among all the activity tests, best enzyme activity was recorded with catalase‐γ‐CD physical mixture encapsulated PCL nanofibrous layers. Moreover, the test results indicated that the use of cyclodextrin in immobilization process considerably improves the catalytic activity of the enzyme. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44404.     

Pd负载电纺碳纳米纤维的制备及其催化活性

Pd纳米粒子负载的碳纳米纤维是催化Sonogahira偶合反应的良好催化剂,其高长径比使之易于从反应混合物中过滤分离;金属纳米粒子与碳纤维间的强相瓦作用使其具有良好的多次重复使用性.通过电纺丝技术和碳化技术制备了Pd金属纳米粒子负载的电纺碳纳米纤维,透射电镜观察显示最终碳化温度及在该温度下的停留时间是影响钯纳米粒子尺寸及其在纤维中分布的主要因素.并通过所得复合纳米纤维对Sonogahira偶合反应的催化活性研究,发现475～575℃这一温度范围是制备具有良好催化活性的金属钯纳米粒子负载的碳纳米纤维的最佳的碳化温度段.     

Properties of electrospun poly(vinyl alcohol) hydrogel nanofibers crosslinked with 1,2,3,4‐butanetetracarboxylic acid

ABSTRACT: Electrospun nanofibrous hydrogel membranes have been gaining significant importance due to the combination of unique physical properties of nanofibers and biocompatibility of hydrogels. Thus, they are considered as potential candidates for medical textile applications. This study deals with electrospinning of poly(vinyl alcohol) (PVA) hydrogel nanofibrous membranes. The chemical crosslinking of PVA with proportionate quantities of 1,2,3,4 butanetetracarboxylic acid (BTCA) was undertaken to form hydrogel structures. Cross‐linked membranes were characterized by scanning electron microscopy, FT‐IR and thermogravimetric analysis, water swelling, and durability tests. FT‐IR analysis demonstrated the formation of ester linkages between PVA and BTCA and thermogravimetric analysis showed that crosslinking improved the thermal stability of the nanofibrous structure. Furthermore, the results indicated that crosslinking with BTCA improved water stability of PVA membranes and the nanofibrous structure was preserved after water treatment. It is envisaged that use of BTCA as a cross‐linker to form hydrogel nanofibers could be a practical and a promising method for medical textile applications, especially for wound dressings given its nontoxicity and immiscibility with polymer solutions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013