Electrospun composite nanofibers for functional applications

In this article an outline of studies conducted to date utilizing the process of electrospinning is presented. This overview for the first time focuses on research of composite nanofiber synthesis and their applications. The phenomenon of bringing materials to the nanometer scale not only improves their properties, but also creates entirely new ones. The electrospinning technique is a simple and versatile method that offers a time and cost effective production of strategic combinations of polymer and composites nanofibers useful for numerous applications highlighted in this review. The future prospects of the field are also examined.     

Electrospun cerium nitrate/polymer composite fibres: synthesis, characterization and fibre-division model

Cerium (Ⅲ) nitrate/poly(vinylpyrrolidone) (Ce(NO3)3/PVP) composite fibres have been prepared by electrospinning. After calcining the composite fibres in air at 500℃,CeO2 nanowires were obtained. The characterizations of the as-spun composite fibres and resultant nanowires have been carried out by a scanning electron microscope (SEM),an infrared spectrometer,an x-ray diffractometer and a fluorescence spectrophotometer. Interestingly,some unusual ribbon-like or twin fibres were observed besides the common fibres with circular or elliptic cross sections. We developed a fibre-division model resulting from Coulomb repulsion and solvent vaporization to interpret the formation of the ribbons or twin fibres,which has been confirmed by the SEM studies. Our results also indicate that the formation of the ribbons or twin fibres is less dependent on operation voltage and work distance.     

Ti/TiO_2包覆ZnO:Tb纳米纤维的光学性质

用电纺丝方法制备了ZnO:Tb纳米纤维.用X-射线衍射、Raman光谱对其形貌做了表征.结果显示,ZnO:Tb纳米纤维为六方纤锌矿结构,Tb掺杂对ZnO的结晶性有影响.利用表面等离激元,通过对纳米纤维表面包覆金属Ti和TiO_2,比较了其光致发光谱,得到在325 nm激发下ZnO:Tb纳米纤维中稀土发光效率低的原因是ZnO和Tb之间不能进行有效的能量传递;包覆TiO_2后能提高稀土发光效率.     

Dielectric properties of electrospun titanium compound/polymer composite nanofibres

Poly(vinylpyrrolidone)/tetrabutyl titanate (PVP/ [CH3(CH2)3O]4Ti) composite nanofibres are prepared by elec- trospinning. After calcining parts of composite nanofibres in air at 700 C, petal-like TiO2 nanostructures are obtained. The characterizations of composite nanofibres and TiO2 nanostructures are carried out by a scanning electron micro- scope, an x-ray diffractometer, and an infrared spectrometer. Electrospun nanofibres are pressed into pellets under different pressures in order to explore their dielectric properties. It is found that the dielectric constants decrease with frequency increasing. The dielectric constant of the composite nanofibre pellet increases whereas its dielectric loss tangent decreases due to the doped titanium ions compared with those of pure PVP nanofibre pellets. In addition, it is observed that the dielectric constant of the composite nanofibre pellet decreases with the increase of the pressure applied in pelletization.     

Polymer nanofibers prepared by low-voltage near-field electrospinning

Electrospinning is a straightforward method to produce micro/nanoscale fibers from polymer solutions typically using an operating voltage of 10 kV–30 kV and spinning distance of 10 cm–20 cm. In this paper, polyvinyl pyrrolidone (PVP) non-woven nanofibers with diameters of 200 nm–900 nm were prepared by low-voltage near-field electrospinning with a working voltage of less than 2.8 kV and a spinning distance of less than 10 mm. Besides the uniform fibers, beaded-fibers were also fabricated and the formation mechanism was discussed. Particularly, a series of experiments were carried out to explore the influence of processing variables on the formation of near-field electrospun PVP nanofibers, including concentration, humidity, collecting position, and spinning distance.     

Electrospun nanofibers of NiO/SiO2 composite

Composite nanofibers with a weight ratio of 30%NiO-70%SiO₂ and diameters ranging from 80 to 100 nm were successfully prepared by electrospinning a precursor mixture of polyvinyl alcohol (PVA)/silica/nickel acetate followed by calcination treatment of the electrospun polymer/inorganic composite fibers. The resulting NiO/SiO₂ composite nanofibers were characterized by TG-DTA, FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy . The results revealed that the crystalline phase of NiO nanoparticles were formed at a temperature higher than 600 °C. The SEM results show that the morphology of the fibers is affected greatly by the calcination temperature.     

Electrospun nanofibers of poly(acrylonitrile)/Eu and their photoluminescence properties

Nanofibers of poly(acrylonitrile)/Eu³⁺ were prepared by using sol-gel processing and electrospinning technique. The diameter of the nanofibers in the non-woven membranes was about 70-100 nm. The nanofibers were characterized by scanning electron microscopy (SEM), fourier transform infrared (FT-IR), and photoluminescence (PL). In our work, the PAN/Eu³⁺ hybrid nanofibers showed excellent photoluminescence properties. A possible PL mechanism was proposed accordingly. It is expected that these kind of materials would be applied in equipments such as optoelectronic nanodevices in the future.     

Toluene sensing properties of SnO2-ZnO hollow nanofibers fabricated from single capillary electrospinning

SnO₂-ZnO hollow nanofibers were fabricated through a facile single capillary electrospinning technology. The structure and toluene sensing properties of the hollow fibers were investigated. The results indicated that the fibers possess a hollow structure, a rough porous surface after being annealed at 600 °C and the diameters are in the range of 80-160 nm. A sensor fabricated from these fibers exhibits considerable sensitivity and good stability against toluene at 190 °C, which can be attributed to the special 1D hollow structure and the promoting effect of the SnO₂/ZnO heterojunction. The formation mechanism and toluene sensing mechanism of SnO₂-ZnO hollow nanofibers were also discussed.     

Electrospinning fabrication of rime-like NiO nanowires/nanofibers hierarchical architectures and their photocatalytic properties

Rime-like NiO Nanowires/nanofibers hierarchical architectures have been fabricated employing a co-precipitation reaction and electrospinning method. The synthesized hierarchical structure was characterized using SEM, XRD and BET analysis methods. The effects of growth temperature and reaction time on the morphologies of the as-prepared structures were investigated by SEM characterization and a possible mechanism for the formation of NiO hierarchical structures is proposed. Based on the nitrogen adsorption and desorption measurements, the BET surface area of the as-obtained sample is 61.0 m²/g and the pore sizes of ca. 5.0 nm. The catalytic efficiency of the NiO nanomaterials developed was evaluated by the photocatalytic degradation of acetaldehyde. In comparison with sphere-like and fiber-like structures, the NiO hierarchical structures show an excellent ability to rapidly acetaldehyde pollutant, which may be attributed to its unique hierarchical and porous surface structures.     

Electrospun one-dimensional graphitic carbon nitride-coated carbon hybrid nanofibers (GCN/CNFs) for photoelectrochemical applications

Coupling of graphitic carbon nitride (GCN) with electrospun carbon nanofibers (CNFs) enhanced the photoelectrochemical (PEC) performance of a pristine GCN photoanode. Polyacrylonitrile (PAN) was electrospun to form fibers that were then carbonized to form one-dimensional (1D) CNFs, which were then used to fabricate the GCN structure. The optimum GCN/CNFs hybrid structure was obtained by controlling the amount of GCN precursors (urea/thiourea). The surface morphology of the hybrid structure revealed the coating of GCN on the CNFs. Additionally, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction confirmed the phases of the GCN/CNFs hybrids. PEC results showed a higher photocurrent of 3 μA for the hybrid compared with that of 1 μA for the pristine GCN. The high photocurrent for the hybrid structures indicated the formation of heterojunctions that resulted from a lower recombination rate of charge carriers. Moreover, UTh_0.075 (0.075 g of urea and 0.075 g of thiourea) hybrid sample showed the highest performance of hydrogen generation with its numerical value of 437 μmol/g, compared to those of UTh_0.1(0.1 g of urea and 0.1 g of thiourea) and UTh_0.05 (0.05 g of urea and 0.05 g of thiourea) composite samples. This higher hydrogen production could be explained again with successful formation of heterojunctions between GCN and CNFs. Overall, we report a new approach for obtaining 1D hybrid structures, having better PEC performance than that of pristine GCN. These hybrids could potentially be used in energy-related devices.     

Production of nanofibers by electrospinning under pressurized CO2

Electrospinning is one of the simple technical methods for the production of polymer nanoparticles and nanofibers. Various polymers have been successfully electrospun into ultrafine particles and fibers in recent years mostly in solvent solution and some in melt form. In this work, near- and supercritical CO₂ were used as media for this process. At these conditions, the solubility can be tuned by controlling the temperature and pressure. Therefore, it is possible to form particles and fibers within a thermodynamic window where the biopolymer has been softened, but not dissolved. The experiments were conducted by using electrospinning under pressurized CO₂ system at pressures of ～ 8.0 MPa and temperature of 313 K to produce several polymers fibers. Polyvinylpyrrolidone was used as the starting material. During the electrospinning process, the applied voltage was 10–17 kV and the distance of nozzle and collector was 8 cm. The concentration of polymer solution was 4 wt%. The morphology- and structure-produced fibers were observed by scanning electron microscopy. The results showed that temperature and pressure affected the morphology of fibers produced by electrospinning in pressurized CO₂. This suggests that the thermal behavior of the polymer can be optimized by adjusting the polymer through the adjustment of pressure and temperature by using CO₂ as a solvent.     

Production and Characterization of Zirconia (ZrO2) Ceramic Nanofibers by Using Electrospun Poly(Vinyl Alcohol)/Zirconium Acetate Nanofibers as a Precursor

Zirconia (ZrO₂) inorganic ceramic nanofibers were produced using electrospinning of the poly(vinyl alcohol)/zirconium acetate as a precursor followed by calcinating and sintering to decompose the polymer and turn the metal salt (zirconium acetate) into the metal oxide. Characterization of the nanofibers, including polymer thermal decomposition, chemical and crystal structure, phase transformations, and fiber morphology were investigated by simultaneous thermal analysis (STA), thermomechanical analysis (TMA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM). The results showed that the polymer decomposition started at 250°C and zirconia nanofibers with different phases (tetragonal and monoclinic) were obtained by the calcination of the precursor nanofibers at various temperatures between 500°C and 1100°C. The initially crystallized zirconia phase, which formed at 500°C, was tetragonal and with increasing calcination temperature, zirconia nanofibers with increasing amount of monoclinic phase were formed. Consequently, at 1100°C, the tetragonal phase disappeared and was transformed to the monoclinic phase of the zirconia completely. Increasing the calcination temperature caused the fiber average diameter decrease and grain growth took place due to the removal of the polymer and organic groups; neighboring grains sintered to each other and formed fibers with a high aspect ratio. At 1100°C the grains size was about the same as the fiber diameter.     

Synthesis of SnO2/ZnO composite nanofibers by electrospinning method and study of its ethanol sensing properties

In this paper, we report the synthesis of SnO₂/ZnO composite nanofibers via electrospinning method. Polyvinyl alcohol (PVA)/zinc acetate/stannous chloride nanofibers were electrospun using a solution containing PVA, zinc acetate and stannous chloride in distilled-water followed by calcination at 650 °C for 2 h, obtaining the related composite nanofibers. The nanofibers were characterized by simultaneous thermal analysis (STA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and Fourier Transform Infrared spectroscopy (FTIR). Ethanol sensing of the nanofibers showed a good and desirable sensing behavior such as high sensitivity, quick response and recovery times.     

Electrospun polymer nanofibers coated with metal oxides by liquid phase deposition

Polyacrylonitrile fibers were electrospun yielding diameters in the range of 50 to 200 nm. These nanofibers were then immersed in an aqueous coating solution to deposit a continuous film of titanium dioxide on the surface. In order to shorten the coating time and optimize the metal oxide layer thickness, the fibers were surface functionalized by immersion in sodium hydroxide to have carboxylic acid groups. Polyelectrolytes were electrostatically adsorbed to some of the functionalized fiber surface samples prior to metal oxide deposition. The metal oxide nucleation density was compared after three hours for nanofibers with a cationic surface, an anionic surface, a carboxylic acid surface, and an untreated surface. Fibers with the carboxylic acid surface exhibited the highest nucleation density, which led to the shortest coating time. Such polymer-metal oxide nanoscale composite structures are expected to be of great utility in a number of applications, including sensors, photovoltaic cells, and catalytic surfaces.     

Surface functionalization, morphology and thermal properties of polyamide6/O-MMT composite nanofibers by Fe2O3 sputter coating

In the present work, the pure polyamide6 (PA6) nanofiber and PA6/organically modified montmorillonite (O-MMT) composite nanofiber were firstly prepared by a facile compounding process with electrospinning, and then coated by nanosize Fe₂O₃ using magnetron sputter technique. The effects of Fe₂O₃ sputter coating on structures, surface morphology and thermal stability were characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), atomic force microscope (AFM) and thermogravimetric analyses (TGA), respectively. The SEM images showed that the diameters of composite nanofiber were decreased with the loadings of O-MMT and the nanosize Fe₂O₃ is well coated on the surface of the homogeneous and cylindrical nanofibers. The XPS spectra reflected the chemical features of the deposited nanostructures. The EDX confirmed the presence of the O-MMT and Fe₂O₃ in the fibers. The AFM observation revealed that there was a remarkable difference in the surface morphology of composite nanofiber before and after sputter coating. The TGA analysis indicated the barrier effects of silicate clay layers and catalysis effects of Fe₂O₃ improved thermal stability properties of the composite nanofiber.     

Optimization of Electrospun Polyacrylonitrile/Poly(Vinylidene Fluoride) Nanofiber Diameter Using the Response Surface Method

Electrospinning of polyacrylonitrile/poly(vinylidene fluoride) (PAN/PVdF) was applied using Box–Benkhen experimental design to obtain a quantitative relationship between selected electrospinning parameters (namely applied voltage, solution concentration, and PVdF composition) and nanofiber diameter and standard deviation of nanofiber diameter. Important parameters in the model were determined by analysis of variance (ANOVA). The model was consequently used to find the optimal conditions that yield the minimum PAN/PVdF nanofiber diameter. The morphology and nanofiber diameter were investigated by field emission scanning electron microscopy (FESM). The range of produced nanofiber diameters was from 116 to 379 nm. It was concluded that the nanofiber diameter tended to increase with solution concentration and decrease with PVdF composition. The applied voltage had no significant effect on the nanofiber diameters. Nanofibers with smaller standard deviation in diameter could be obtained at lower solution concentrations and higher PVdF composition. The model predicted the minimum nanofiber diameter of 114 nm when the applied voltage was set at 19.7 kV, solution concentration set at 14.07 wt%, and the PVdF composition set at 58.78 wt%.     

Magnetic nanofibers with core (Fe3O4 nanoparticle suspension)/sheath (poly ethylene terephthalate) structure fabricated by coaxial electrospinning

One-dimensional magnetic nanostructures have recently attracted much attention because of their intriguing properties that are not realized by their bulk or particle form. These nanostructures are potentially useful for the application to ultrahigh-density data storages, sensors and bulletproof vest. The magnetic particles in magnetic nanofibers of blend types cannot fully align along the external magnetic field because magnetic particles are arrested in solid polymer matrix. To improve the mobility of magnetic particles, we used magneto-rheological fluid (MRF), which has the good mobility and dispersibility. Superparamagnetic core/sheath composite nanofibers were obtained with MRF and poly (ethylene terephthalate) (PET) solution via a coaxial electrospinning technique. Coaxial electrospinning is suited for fabricating core/sheath nanofibers encapsulating MRF materials within a polymer sheath. The magnetic nanoparticles in MRF were dispersed within core part of the nanofibers. The core/sheath magnetic composite nanofibers exhibited superparamagnetic behavior at room temperature and the magnetic nanoparticles in MRF well responded to an applied magnetic field. Also, the mechanical properties of the nanofiber were improved in the magnetic field. This study aimed to fabricate core/sheath magnetic composite nanofibers using coaxial electrospinning and characterize the magnetic as well as mechanical properties of composite nanofibers.     

Preparation of PSFO and LPSFO nanofibers by electrospinning and their electronic transport and magnetic properties

Pr_0.5Sr_0.5FeO₃ (PSFO) and La_0.25Pr_0.25Sr_0.5FeO₃ (LPSFO) nanofibers are prepared by electrospinning followed by calcination, and their morphologies, microstructures, electronic transports, and magnetic properties are studied systematically. The temperature-dependent resistance curves of PSFO and LPSFO nanofibers are measured in a temperature range from 300 K to 10 K. With the temperature lowering, the resistance increases gradually and then decreases sharply due to the occurrence of ferromagnetic metal phase. The metal-insulator transition temperatures are about 110 K and 180 K for PSFO and LPSFO nanofibers, respectively. The electronic conduction behavior above the transition temperature can be described by one-dimensional Mott's variable-range hopping (VRH) model. The hysteresis loops and the field-cooled (FC) and zero-field-cooled (ZFC) curves show that both PSFO nanofiber and LPSFO nanofiber exhibit ferromagnetism. Although the doping of La reduces the overall magnetization intensity of the material, it increases the ferromagnetic ratio of the system, which may improve the performance of LPSFO in solid oxide fuel cell.     

Fabrication and Optimization of Poly(vinyl alcohol)/Zirconium Acetate Electrospun Nanofibers Using Taguchi Experimental Design

This paper presents an investigation regarding poly(vinyl alcohol)/zirconium acetate (organic–inorganic) (PVA/Zrace) nanofibers prepared by electrospinning which could be used as a precursor for fabricating ceramic metal oxide nanofibers. The effect of some processing variables, including polymer solution concentration, tip to collector distance and applied voltage of electrospinning, and the amount of Zrace and their interactions, on the diameter of the nanofibers were studied. Taguchi experimental design and a statistical analysis (ANOVA) were employed and the relationship between experimental conditions and yield levels determined. It was concluded that to obtain a narrow diameter distribution as well as maximum fiber fineness, a polymer concentration of 10 wt%, tip to collector distance of 18 cm and applied voltage of 20 kV variables were the optimum. Furthermore, it was also concluded that the ratio of Zrace (6 g) to PVA solution (10% wt) played an important role for achieving the minimum fiber diameter. Under these optimum conditions, the diameters of the electrospun composite fibers ranged from 86 nm to 381 nm with a diameter average of 193 nm. The experiments were done with Qualitek-4 software with “smaller is better” as the quality characteristics. The optimized conditions showed an improvement in the fibers diameter distribution and the average fibers diameter showed good resemblance with the result predicted using the Taguchi method and the Qualitek-4 software. The ANOVA results showed that all factors had significant effects on the fibers diameter and distribution, but the effect of PVA concentration and zirconium acetate were more significant than the other factors.