Applications of electrospun nanofibers for electronic devices

In recent decades, electrospinning of nanofibers has progressed very rapidly in both scientific and technological aspects, and electrospun nanofibers have shown enormous potential for various applications. In particular, electrospun nanofibers have significantly enhanced the application performance of many electronic devices, such as solar cells, mechanical-to-electric energy harvesters, rechargeable batteries, supercapacitors, sensors, field-effect transistors, diodes, photodetectors, and electrochromic devices. This chapter provides a comprehensive summary on the recent progress in the application of electrospun nanofibers in electronic devices.

Aligned nanofibers from polypyrrole/graphene as electrodes for regeneration of optic nerve via electrical stimulation

The damage of optic nerve will cause permanent visual field loss and irreversible ocular diseases, such as glaucoma. The damage of optic nerve is mainly derived from the atrophy, apoptosis or death of retinal ganglion cells (RGCs). Though some progress has been achieved on electronic retinal implants that can electrically stimulate undamaged parts of RGCs or retina to transfer signals, stimulated self-repair/regeneration of RGCs has not been realized yet. The key challenge for development of electrically stimulated regeneration of RGCs is the selection of stimulation electrodes with a sufficient safe charge injection limit (Q(inj), i.e., electrochemical capacitance). Most traditional electrodes tend to have low Q(inj) values. Herein, we synthesized polypyrrole functionalized graphene (PPy-G) via a facile but efficient polymerization-enhanced ball milling method for the first time. This technique could not only efficiently introduce electron-acceptor nitrogen to enhance capacitance, but also remain a conductive platform-the π-π conjugated carbon plane for charge transportation. PPy-G based aligned nanofibers were subsequently fabricated for guided growth and electrical stimulation (ES) of RGCs. Significantly enhanced viability, neurite outgrowth and antiaging ability of RGCs were observed after ES, suggesting possibilities for regeneration of optic nerve via ES on the suitable nanoelectrodes.

Layer-by-layer structured membranes of silk fibroin and polyethylenimine on electrospun silk fibroin nanofibers

Self-assembled silk fibroin (SF)-polyethylenimine (PEI) multilayered films were fabricated on ethanol treated electrospun SF nanofibrous substrates via the electrostatic layer-by-layer (LBL) adsorption. The film coated membranes were characterized using scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectrophotometer (XPS). The SEM images showed that the multilayers of SF-PEI were formed on the surface of the ethanol treated SF nanofibres. The characteristics such as the fiber shape and porous structure were well maintained as the number of the coated SF-PEI bilayers was less than five. However, obvious adhesive substances and blocked pores were observed on the surface of the fibers as the number of bilayers of SF-PEI increased to six. Furthermore, the obvious core-shell structures were observed by TEM. The thickness of five SF-PEI bilayers was approximately 80nm. Additionally, the XPS results also revealed that the SF-PEI multilayer composite membranes formed. The adsorption mainly depended on a simple electrostatic interaction between the layers of SF and PEI. These SF-PEI multilayer assembled nanofibrous membranes could be a promising material for use as a sensor, gene delivery agent and scaffolds.

Effects of MWNT nanofillers on structures and properties of PVA electrospun nanofibres

In this study, we have electrospun poly(vinyl alcohol)(PVA) nanofibres and PVA composite nanofibres containing multi-wall carbon nanotubes (MWNTs) (4.5 wt%), and examined the effect of the carbon nanotubes and the PVA morphology change induced by post-spinning treatments on the tensile properties, surface hydrophilicity and thermal stability of the nanofibres. Through differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD) characterizations, we have observed that the presence of the carbon nanotubes nucleated crystallization of PVA in the MWNTs/PVA composite nanofibres, and hence considerably improved the fibre tensile strength. Also, the presence of carbon nanotubes in PVA reduced the fibre diameter and the surface hydrophilicity of the nanofibre mat. The MWNTs/PVA composite nanofibres and the neat PVA nanofibres responded differently to post-spinning treatments, such as soaking in methanol and crosslinking with glutaric dialdehyde, with the purpose of increasing PVA crystallinity and establishing a crosslinked PVA network, respectively. The presence of carbon nanotubes reduced the PVA crystallization rate during the methanol treatment, but prevented the decrease of crystallinity induced by the crosslinking reaction. In comparison with the crosslinking reaction, the methanol treatment resulted in better improvement in the fibre tensile strength and less reduction in the tensile strain. In addition, the presence of carbon nanotubes reduced the onset decomposition temperature of the composite nanofibres, but stabilized the thermal degradation for the post-spinning treated nanofibres. The MWNTs/PVA composite nanofibres treated by both methanol and crosslinking reaction gave the largest improvement in the fibre tensile strength, water contact angle and thermal stability.

Disk-electrospinning of PVA nanofibres

In this study, we demonstrated that a thin aluminium disk can be used as nozzle to electrospin PVA nanofibres on a large-scale. A schematic of this electrospinning system and a SEM image of as-spun PVA nanofibers are shown in Figure 1. The lower part of the disk is inside a bath containing the polymer solution, which is connected to a high voltage powder supply. During electrospinning, the disk rotates and picks up a thin layer of electrically charged PVA solution. A large number of fibres are then electrospun simultaneously from two sides of tile disk and deposited on the electrode collector.
With the small prototype unit we used, the fibre production rate can be as high as 6.0 which is about 270 times higher than that of a corresponding normal needle electrospinning system (0.022g/hr). The effects of appliedb voltage, the distance between the disk nozzle and collector, and PVA concentration on the fibre morphology were examined. The dependency of fibre diameter on the PVA concentration showed a similar trend to that for a conventional electrospinning system using a syringe needle nozzle, but the diameter distribution was wider for the disk electrospun fibres in this study.
The profiles of electric field strength in disk electrospinning showed considerable dependence on the disk thickness, with a thin disk exhibiting similar electric field profile to
that of a needle electrospinning system, but a thick disk (cylinder) exhibiting levelled electric field between the disk and the collector. PVA nanofibres electrospun from disk electrospinning were compared to that electrospun from syringe needle and metal cylinder nozzles.

Needleless electrospinning. I. A comparison of cylinder and disk nozzles

In this study, we demonstrated the needleless electrospinning of poly(vinyl alcohol) (PVA) nanofibers with two nozzles, a rotating disk and a cylinder, and examined the effect of the nozzle shape on the electrospinning process and resultant fiber morphology. The disk nozzle needed a relatively low applied voltage to initiate fiber formation, and the fibers were mainly formed on the top disk edge. Also, the PVA concentration had little influence on the disk electrospinning process (up to 11 wt %). In comparison, the cylinder electrospinning showed a higher dependence on the applied voltage and polymer concentration. The fibers were initiated from the cylinder ends first and then from the entire cylinder surface only if the applied voltage were increased to a certain level. With the same polymer solution, the critical voltage needed to generate nanofibers from the disk nozzle was lower than that needed to generate nanofibers from the cylinder. Both electrospinning systems could produce uniform nanofibers, but the fibers produced from the disk nozzle were finer than those from the cylinder when the operating conditions were the same. A thin disk (8 cm in diameter and 2 mm thick) could produce nanofibers at a rate similar to that of a cylinder of the same diameter but 100 times wider (i.e., 20 cm long). Finite element analysis of electric field profiles of the nozzles revealed a concentrated electric field on the disk edge. For the cylinder nozzle, an uneven distribution of the electric field intensity profile along the nozzle surface was observed. The field lines were mainly concentrated on the cylinder ends, with a much lower electric field intensity formed in the middle surface area. At the same applied voltage, the electric field intensity on the disk edge was much higher than that on the cylinder end. These differences in the electric field intensity profiles could explain the differences in the fiber fineness and rate of the nanofibers produced from these two nozzles. These findings will benefit the design and further development of large-scale electrospinning systems for the mass production of nanofibers for advanced applications.

Electrospun nanofibres

This research contributes new knowledge to fundamental understanding and applications of nanofibre materials made by the electrospinning technique. An innovative method was developed to visualise the fibre thinning, and the nanofibres with improved mechanical properties and controlled surface wettability were prepared. These nanofibres have shown significant potential in wound dressing application.

Electrospinning of polymers for functional nanofibres

Nanofibres have wide applications in energy, environment and medical areas. This project examined new needleless electrospinning technologies for mass production of nanofibres. Functional nanofibres with side-by-side and core-sheath structures have been prepared and their properties have been elucidated.

Preparation and characterization on cellulose nanofiber film

In this study, cellulose nanofibers were obtained from wood pulp using a chemo-mechanical method and thin films were made of these cellulose nanofibers. The morphology of the films was studied by scanning electron microscopy (SEM). SEM image analysis revealed that the films were composed of cellulose nanofibers with an average diameter of around 32 nm. Other properties were also characterized, including the degree of crystallinity by X-ray diffraction, chemical bonding by infrared attenuated total reflectance analysis, and thermal properties by differential scanning calorimetry. The foldable, strong, and optically translucent cellulose nanofiber films thus obtained have many potential applications as micro/nano electronic devices, biosensors and filtration media, etc.

Needleless electrospinning of nanofibrous structures

In this study, different wire coils have been used as electrodes for needless electrospinning. Very thin and uniform nanofibres have been produced, and the fibre productivity is much higher than existing electrospinning systems.

Inter-bonded fibrous matrics for 3D tissue engineering scaffolds

This thesis established a stable three-dimensional fibrous tissue scaffold that has controlled pore structure and inter-bonded fibrous structure, and also examined the effects of the 3D fibrous matrices and functional surfaces including nano-scale topography, bioactive CaP coating and antibacterial treatment on the cell growth begaviour for tissue engineering application.

A new way to nanostructure hydrogels : electrospun thermo-responsive islands-in-the-sea nanofibres

Islands-in-the-sea nanofibres are a very interesting system: one polymer (islands) is distributed in fibrillar domains within a second polymer (sea). This fibre geometry is often used in microfiber technologies to obtain very fine fibers, by removing the “sea” polymer. This geometry also allows to combine two polymers with very different properties. In this work this geometry is introduced applied to electrospun hydrogel nanofibers, in a novel fashion, and as a way to improve and stabilize the hydrogel nanofibers. Thermo-responsive islands-in-the-sea nanofibers are here produced by electrospinning solutions of a hydrogel-forming thermo-responsive polymer (crosslinked poly(N-isopropylacrylamide), PNIPAM) and a reinforcing polymer (polyetherketone cardo, PEK-c). The two polymers are thermodynamically incompatible in solution and phase separation takes place, which allows the instant formation of islands-in-the-sea nanofibers upon electrospinning. PNIPAM was then crosslinked post-spinning using an oligomeric silsesquioxane. The formed nanocomposite nanofibers showed intrinsic nanostructure, where the fibril-like PNIPAM domains are intimately adjacent to the strong PEK-c domains. Upon contacting with water, the hydrogel domains became instantly highly swollen, while the PEK-c domains did not. As a result, very wrinkly, swollen fibers were obtained, with increased capillary action, as demonstrated through confocal microscopy. The composite nanofibers in water showed excellent swelling ratios and very fast responses to temperature variations (of the order of 1 second) with morphological and optical effects: variations in fiber-diameter were accompanied by optical transitions: transparent-opaque. The produced hydrogel nanofibers also presented improved mechanical properties (even with small amounts of PEK-c), when compared to their crosslinked-PNIPAM-only nanofibers. It will be also shown how these materials can be used as optical actuators and smart hydrogel platforms with tuneable contact angle and morphology. In brief, this work aims to demonstrate a new platform technology which can be applied to several hydrogel systems, to achieve hydrogel-based composites with new and improved properties, while retaining (and improving) the main properties of the hydrogel. Here this was demonstrated by showing that the composite materials showed thermo-responsiveness, and enhanced transition kinetics.

Production of green nanomaterials

While our awareness towards sustainable society and environment grows, the importance of ‘green’ materials and manufacturing is gaining significant recognition. We have demonstrated that naturally-occurring fibers as renewable raw materials can be converted into nanoparticles and nano fibers using simple top-down methods without introducing hazardous chemicals. This new class of green nanomaterials will have a wide range of environmental and biomedical applications owing to the inherent biocompatible, biodegradable and carbon-neutral nature.

Needleless electrospinning and direct electrospinning of nanofiber yarns

Electrospinning is a simple, but efficient and versatile, technology to produce polymeric nanofibers for widely diverse applications in both textile and non-textile areas [1]. This technique has been shown many advantages such as universality in processing polymeric materials, eases of controlling the fiber diameter and functionalizing nanofibers through adjusting solution composition for electrospinning, and flexibility to generate fibrous membranes of various geometries. Although the novel applications of electrospun nanofibers have been extensively explored [2], the technology development for mass electrospinning of nanofibers has been hampered.

Electrospinning of continuous nanofiber bundles and twisted nanofiber yarns

Spinning is a prehistoric technology in which endless filaments, shorter fibers or twisted fibers are put together to produce yarns that serve as key element to assemble multifarious structural designs for diverse functions. Electrospinning has been regarded as the most effective and versatile technology to produce nanofibers with controlled fiber morphology, dimension and functional components from various polymeric materials (Dersch et al., 2007, Frenot and Chronakis, 2003, Schreuder-Gibson et al., 2002). However, most electrospun fibers are produced in the form of randomly-oriented nonwoven fiber mats (Doshi and Reneker, 1995, Madhavamoorthi, 2005). The relatively low mechanical strength and difficulty in tailoring the fibrous structure have restricted their applications. With the rapid development in nanoscience and nanotechnology, yarns composed of nanofibers may uncover new opportunities for development of well-defined three dimensional nano fibrous architectures. This chapter focuses on recent research and advancement in electrospinning of nanofiber bundles and nanofiber yarns. The preparation, morphology, mechanical properties and potential applications of these fibrous materials are discussed in details.