High Precision Deposition Electrospinning of nanofibers and nanofiber nonwovens

Electrospinning is known to produce nanofiber nonwovens with lateral dimensions in 10 cm up to the meter range meeting thus requirements characteristic of filter, textile or even tissue engineering applications. For particular applications other types of deposition pattern are of benefit (i) in which the deposition area is strongly limited in the lateral dimension, (ii) in which a linear deposition path is oriented along a specified direction or (iii) in which the nonwovens are deposited following a predesigned pattern. This paper reports experimental results for the High Precision Deposition Electrospinning (HPDE) approach introduced by us earlier. It is based on a syringe type die-counter electrode set-up used for conventional continuous electrospinning, the key feature being a reduction of the distance between the spinning die and the substrate from the conventional value of 10-50 cm down to the millimeter and below mm range in order to suppress the onset of bending instabilities and the corresponding spread of the deposition area. The architecture of the nonwovens is controlled in this case by buckling processes and deflections of the jet by transiently charged nanofibers on the substrate. A second important feature of the set-up is a counter electrode/substrate which can be subjected to precise motions in the deposition plane. Based on a careful optimization of the spinning parameters and a tight online control of the spinning process a deposition of individual nanofibers or nonwovens is achieved which meets all deposition requirements specified above. This opens the route towards novel applications among others in areas relying on specific surface architectures such as sensorics, microfluidics and possibly also surfaces of implants.     

Garland formation process in electrospinning

The electrospinning technique has become a widely used method to produce nanofibers. Much experimental and theoretical work has been done to investigate the electrospinning process. A typical path of a single jet of polymer solution begins with a straight segment, and then a bending instability generates coils inside a cone shaped envelope. The jet elongates and becomes thinner, and dries into a nanofiber.Polystyrene solutions with different salt concentrations were electrospun to investigate the effect of changing the electrical conductivity on the fibers that were formed. Salt increased the conductivity of the solution and smooth fibers formed. Electrospinning a polystyrene solution with salt, at relatively high voltage, caused the jet to first form bending coils with small and slowly increasing diameters. These small diameter coils were subsequently incorporated into a larger diameter bending instability coil. That is, a coil with a slender envelope cone developed first and this slender coil formed a larger bending coil with a more rapidly increasing diameter. This unusual situation produced a complicated jet path, which is called a “garland”. The coils entangled and conglutinated in flight to form a fluffy network of fibers. The conditions for the formation of garlands also provide examples of jet splitting and branching during the electrospinning process.     

Investigation of post-spinning stretching process on morphological, structural, and mechanical properties of electrospun polyacrylonitrile copolymer nanofibers

Electrospun polyacrylonitrile (PAN) copolymer nanofibers with diameters of ∼0.3 μm were prepared as highly aligned bundles. The as-electrospun nanofiber bundles were then stretched in steam at ∼100 °C into 2, 3, and 4 times of the original lengths. Subsequently, characterizations and evaluations were carried out to understand morphological, structural, and mechanical properties using SEM, 2D WAXD, polarized FT−IR, DSC, and mechanical tester; and the results were compared to those of conventional PAN copolymer microfibers. The study revealed that: (1) the macromolecules in as-electrospun nanofibers were loosely oriented along fiber axes; although such an orientation was not high, a small extent of stretching could effectively improve the orientation and increase the crystallinity; (2) most of macromolecules in the crystalline phase of as-electrospun and stretched nanofibers possessed the zig-zag conformation instead of the helical conformation; and (3) the post-spinning stretching process could substantially improve mechanical properties of the nanofiber bundles. To the best of our knowledge, this study represented the first successful attempt to stretch electrospun nanofibers; and we envisioned that the highly aligned and stretched electrospun PAN copolymer nanofibers could be an innovative type of precursor for the development of continuous nano-scale carbon fibers with superior mechanical strength.     

Growth of carbon nanofibers on activated carbon fiber fabrics

Activated carbon fiber fabrics, an excellent adsorbent, were used as catalyst supports to grow carbon nanofibers. Because of the microporous structure of the activated carbon fibers, the catalysts could be distributed uniformly on the carbon surface. Based on this concept, the carbon nanofibers can be grown directly on the activated carbon fiber fabrics. We demonstrate that carbon nanofibers with a diameter between 20 and 50 nm for most of the fibers can be synthesized uniformly and densely on activated carbon fiber fabrics, impregnated by nickel nitrate catalyst precursor, using catalytic chemical vapor deposition. Although the carbon nanofibers are not straight with a crooked morphology, they form a three-dimensional network structure. Structure characterizations by TEM and XRD indicate that the carbon nanofibers have a turbostratic graphite structure and the graphite layers are stacked with a herringbone structure.     

Mechanical and structural characterization of electrospun PAN-derived carbon nanofibers

The mechanical and structural properties of individual electrospun PAN-derived carbon nanofibers are presented. EELS spectra of the carbonized nanofibers shows the C atoms to be partitioned into ∼80% sp² bonds and ∼20% sp³ bonds which agrees with the observed structural disorder in the fibers. TEM images show a skin-core structure for the fiber cross-section. The skin region contains layered planes oriented predominantly parallel to the surface, but there are some crystallites in the skin region misoriented with respect to the fiber long axis. Microcombustion analysis showed 89.5% carbon, 3.9% nitrogen, 3.08% oxygen and 0.33% hydrogen. Mechanical testing was performed on individual carbonized nanofibers a few microns in length and hundreds of nanometers in diameter. The bending modulus was measured by a mechanical resonance method and the average modulus was 63 GPa. The measured fracture strengths were analyzed using a Weibull statistical distribution. The Weibull fracture stress fit to this statistical distribution was 0.64 GPa with a failure probability of 63%.     

Interpretation and use of glints from an electrospinning jet of polymer solutions

Optical observations of jets provide information useful for control of electrospinning of polymer solutions. Combinations of videography, stereography, and methods for illumination of the multiple coils of an electrospinning jet path, that depend on bright glints of reflected light from the jet, recorded quantitative information about the location, vector velocity, and rotation of selected segments of the jet. New bending coils were observed to form at rates of 200–1560 turns per second. This bending frequency decreased as the capillary number of the solutions increased. The polarization of light, in glints reflected at Brewster's angle, allows measurement of the index of refraction of the fluid jet, in flight. Asymmetric illumination of an electrospinning jet made both the handedness and changes in handedness of the electrical bending coils apparent to visual observation and in 2-dimensional images. Evidence was found, in the form of polarized ribbon-like glint traces, for the occurrence of undulations on the surface of some jets.     

Oxygen reduction reaction properties of carbon nanofibers: Effect of metal purification

Carbon nanofibers (CNFs) are grown on metal catalysts and electrochemical treatment is used to remove the metal catalyst residuals from the as-grown CNFs. For comparison, the CNFs are also purified by a chemical method and a thermal method. The oxygen reduction reaction (ORR) properties of CNFs purified by these three methods are examined by cyclic voltammetry. CNFs treated by the electrochemical method have a more positive ORR onset reduction potential and peak potential compared with those treated by chemical and thermal methods, and this is because the microstructures of CNFs are less changed by electrochemical method. However, they have a lower electrochemical capacity and ORR peak current than those treated by the chemical method. Cyclic voltammetric measurements at different scan rates confirm that the oxygen reductions on CNFs treated by electrochemical and chemical methods are controlled by diffusion, while on CNFs treated by thermal method is partially influenced by diffusion.     

Preparation of carbon nanofibers/carbon foam monolithic composite from coal liquefaction residue

Carbon nanofibers/carbon foam composites that are made by growing carbon nanofibers (CNFs) on the surface of a carbon foam (CF) have been prepared from coal liquefaction residues (CLR) by a procedure involving supercritical foaming, oxidization, carbonization, and catalytic chemical vapour deposition (CCVD) treatment. These new carbon/carbon composites were examined using SEM, TEM and XRD. The results show that the as-made CF has a structure with cell sizes of 300-600 μm. X-ray diffraction studies show that iron-containing contaminates are present in the CLR. However, these species may act as a catalyst in the CCVD process as established in the literature. After the CCVD treatment, the cell walls of CF are covered by highly compacted CNFs that have external diameters of about 100 nm and lengths of several tens of micrometers. This work may open a new way for direct and effective utilization of the CLR.     

Carbon nanofibers as potential materials for catalysts support,a mini-review on recent advances and future perspective

The element carbon has been used as an active catalyst as well as a catalyst support. This dual nature of carbon has been attributed to its characteristics such as high porosity, large surface area, excellent electron conductivity and chemical inert nature. Besides, the availability of different forms of carbon like graphene, activated carbon, carbon nanotubes and carbon nanofibers have provided carbon a versatile material to be used for different applications. Carbon has been widely used in different applications like electrical, bio-electrochemical, dry cells, electrodes and as a lubricant. However, in the last decades, the catalytic applications of carbon materials especially carbon nanotubes and carbon nanofibers have gained tremendous attention of the researchers worldwide. Carbon nanofibers, in particular due to thier excellent catalytic support profile like, high surface area, thermal stability and its 3D access to the reacting molecules, have been utilized for different chemical reactions. Metal supported on carbon nanofibers have been observed with better activities as compared to the traditional supported counterparts for the several reactions. This mini-review attempts to document the role of carbon nanofibers and their catalytic support profile for the some common chemical processes. The mini-review also suggests about the future innovations and research work for carbon nanofibers as potential future catalysts support.     

Chemical vapor deposition derived ultralong SiC nanofibers: structural characterization and growth mechanism

In this study, the ultralong SiC nanofibers (SiC NFs) were synthesized through the sol–gel method assisted the chemical vapor deposition technique. The scanning electron microscope, transmission electron microscopy, X-ray diffraction, Raman, Fourier transform infrared, and X-ray photoelectron spectroscopy techniques were systematically employed to investigate the microstructure, morphology, and phase composition of the as-prepared products. The results demonstrated that the as-obtained products were β-SiC nanofibers with face-centered cubic crystal structure. Meanwhile, the ultralong SiC NFs present an average diameter of about 18 nm and a length up to several hundreds of micrometers and grew along the [1 1 1] direction with a planar stacking faults. In addition, we also investigated the formation mechanism and growth process of the ultralong SiC NFs. The successful preparation of such ultralong SiC NFs provides new idea for fabricating of other silicon-based ultralong nanofibers.     

The graphitization of carbon nanofibers produced by catalytic decomposition of methane: Synergetic effect of the inherent Ni and Si

The catalytic effect of the inherent Ni and Si on the graphitization of carbon nanofibers produced by catalytic decomposition of methane is reported. The participation of the inherent Ni and Si metals as co-catalysts in the graphitization of the carbon nanofibers through the formation of Ni₂Si and SiC was inferred. Taking advantage of this catalytic effect, graphite materials showing structural characteristics comparable to oil-derived graphites which are employed in several industrial applications have been prepared from the carbon nanofibers. Unlike SiC which is further descomposed to graphite, the role of Ni₂Si remains unclear. At the CNFs heat treatment temperatures employed, Ni₂Si is in a liquid state where the carbon can be dissolved to form a supersaturated solution from which the SiC can be produced by segregation, thus being an intermediate stage in the catalytic graphitization of the carbon nanofibers. Further work are currently in progress to go insight this issue.     

The use of Weber number to predict morphology in the electrospinning of poly(ethylene oxide) nanofibers

In the electrospinning of polymer nanofibers, an electrically driven jet of polymer solution travels to a grounded target to be collected. The morphology of the resulting nanofibers can be manipulated through process parameters, though little work has been done to correlate electrospinning parameters with those of the free‐jet flow of pure liquids. This is essential when the nanofibers hold entrained beaded structures indicative of jet breakup. The effects of applied voltage and solution concentration on the fiber morphology of electrospun aqueous solutions of poly(ethylene oxide) were investigated. Solution concentrations of 4–8 wt % were used along with voltages of 4.5–11 kV to produce nanofibers with and without entrained beads. It was determined that the calculated Weber number for each condition correlated well with the resulting morphology. These results may suggest that Weber number may also be used to predict nanofibers morphology in the electrospinning of other polymer systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Active polymer nanofibers for photonics,electronics, energy generation and micromechanics

Active polymer nanofibers for opto- and nano-electronics benefit from low cost and versatile fabrication processes and exhibit an unequaled flexibility in terms of chemical composition, physical properties and achievable functionality. For these reasons, they have rapidly emerged as powerful tool for nanotechnologies and as building blocks of a wide range of devices. Both bottom up and top down nanofabrication concepts were developed to produce nanofibers made of conjugated or other functional polymers and blends. This article summarizes and reviews the chemico-physical and functional requirements for polymer nanofibers to be used in opto- and nanoelectronics, as well as recent advances in various promising device architectures, such as light emitting and photovoltaic devices, photodetectors, field-effect transistors, piezo- and thermoelectric generators, and actuators. The outlook of functional polymer nanofibers and of devices based on them is also outlined and discussed.     

Barb formation in electrospinning: Experimental and theoretical investigations

PVA nanofibers electrospun from solutions with relatively low polymer concentrations (below 8 wt%) tend to be no longer smooth, but display barbs which occur regularly spaced along the nanofiber length. Such structures are of interest for a number of technical applications, since they affect the fiber packing, pore sizes and the internal surfaces in the nanofiber nonwovens. This paper reports both, experimental and theoretical results, allowing to elucidate the mechanism responsible for barb formation. It is found that barb formation can be explained theoretically in terms of a relatively slow charge relaxation within the jet compared to the development of the secondary electrically driven instabilities which locally deform the jet surface. Both, the electric conductivity of polymer solutions and their viscoelasticity, are key parameters controlling the competition between charge relaxation and rate of growth of capillary and electrically driven, secondary, localized perturbations of the jet surface and thus barb formation. In this paper a nonlinear theoretical model is proposed that is able to mimic the main morphological trends recorded in the experiments.     

Mechanistic study of cobalt catalyzed growth of carbon nanofibers in a confined space by plasma-assisted chemical vapor deposition

Carbon nanofibers (CNFs) were grown in the porous anodic aluminum oxide (AAO) thin film grown on the Si wafer by electron cyclotron resonance chemical vapor deposition using cobalt as the catalyst. A larger Co particle electrodeposited in the AAO pore channel produced vertically aligned CNFs with a tube diameter in compliance with the pore size of the AAO template. On the other hand, a smaller Co particle resulted in CNF growth with a nonuniform distribution of the tube diameter and a sparse tube density. Amorphous carbon residue produced under the plasma-assisted CNF growth condition seemed to play an essential role leading to the observation. A growth mechanism is proposed to delineate the volume effect of the electrodeposited Co catalyst on the CNF growth confined in pore channels of the AAO template.     

Differences between carbon nanofibers produced using Fe and Ni catalysts in a floating catalyst reactor

Carbon nanofibers were produced by the catalytic CVD process by the floating catalyst method, in semi-industrial systems at temperatures above 1350 K. Iron-derived carbon nanofibers were produced from natural gas and xylene, using ferrocene as catalyst source, yielding a thickened submicron vapor grown carbon fibers with a core of multi-wall nanotubes. For the production of Ni derived nanofibers, natural gas was used as the carbon feedstock, and the Ni was added in a nickel compound solution. When no sulfur is used, only soot was obtained, but when sulfur is added to the reactive feedstock, a highly graphitic and very nice stacked-cup-type nanofibers with no free-CVD thickened layer were produced. TEM-EDS analysis confirms that this type of stacked-cup carbon nanofiber is produced only with a partially molten catalyst and methane as hydrocarbon source. In fact, very few fibers have either a particle tip at the end or trapped metal particle inside the wide hollow core of this type of produced carbon material.     

Index to Volume 31

Carbon nanofibers (diameter range, 3–100 nm; length range, 0.1–1000 µm) have been known for a long time as a nuisance that often emerges during catalytic conversion of carbon-containing gases. The recent outburst of interest in these graphitic materials originates from their potential for unique applications as well as their chemical similarity to fullerenes and carbon nanotubes. In this review, we focus on the growth of nanofibers using metallic particles as a catalyst to precipitate the graphitic carbon. First, we summarize some of the earlier literature that has contributed greatly to understand the nucleation and growth of carbon nanofibers and nanotubes. Thereafter, we describe in detail recent progress to control the fiber surface structure, texture, and growth into mechanically strong agglomerates. It is argued that carbon nanofibers are unique high-surface-area materials (?200 m²/g) that can expose exclusively either basal graphite planes or edge planes. Subsequently, we will present the recently explored applications of carbon nanofibers: polymer additives, gas storage materials, and catalyst supports. The latter application is described in detail. It is shown that the graphite surface structure and the lyophilicity play a crucial role during metal emplacement and catalytic use in liquid-phase catalysis. A case in point is fiber-supported Pd catalysts for nitrobenzene hydrogenation. Finally, we summarize issues with respect to the large-scale production of carbon nanofibers, including production cost estimates and research items to be dealt with in future work.     

Local chemical vapor deposition of carbon nanofibers from photoresist

The addition of nanofeatures to carbon microelectromechanical system (C-MEMS) structures would greatly increase surface area and enhance their performance in miniature batteries, super-capacitors, electrochemical and biological sensors. Negative photoresist posts were patterned on a Au/Ti contact layer by photolithography. After pyrolyzing the photoresist patterns to carbon patterns, graphitic nanofibers were observed near the contact layer. The incorporation of carbon nanofibers in C-MEMS structures via a simple pyrolysis of modified photoresist was investigated. Both experimental results considered to consist of a local chemical vapor deposition mechanism. The method represents a novel, elegant and inexpensive way to equip carbon microfeatures with nanostructures, in a process that could possibly be scaled up to the mass production of many electronic and biological devices.     

Carbon nanostructures produced by CCVD with induction heating

The catalytic chemical vapor deposition (CCVD) method in which the outer furnace is replaced by the high frequency induction heating (IH) has been used for synthesis of carbon nanostructures. Using different catalysts, various types of carbon nanofibers were obtained, with the absence of the catalyst particles at their tip as a common characteristic. The IH mode combined with the CCVD method seems attractive for the synthesis of carbon nanostructures, allowing a significant decrease of energy consumption and of the overall reaction time as compared with the heating mode with outer furnace.     

Nanocomposites of poly(ether ether ketone) with carbon nanofibers: Effects of dispersion and thermo-oxidative degradation on development of linear viscoelasticity and crystallinity

Poly(ether ether ketone), PEEK, is a widely used engineering plastic that is especially suitable for high temperature applications. Compounding of PEEK with carbon nanofibers, CNF, has the potential of enhancing its mechanical and thermal properties further, even at relatively low CNF concentrations. However, such enhancements can be compromised by myriad factors, some of which are elucidated in this study. Considering that the dispersion of the CNF into any high molecular weight polymer is a challenge, two different processing methods, i.e., melt and solution processing were used to prepare PEEK nanocomposites with low aspect ratio carbon nanofibers. The linear viscoelastic material functions of PEEK nanocomposites in the solid and molten states were characterized as indirect indicators of the dispersion state of the nanofibers and suggested that the dispersion of nanofibers into PEEK becomes difficult at increasing CNF concentrations for both solution and melt processing methods. Furthermore, the time-dependence of the linear viscoelastic material functions of the PEEK/CNF nanocomposites at 360-400 °C indicated that PEEK undergoes thermo-oxidative cross-linking under typical melt processing conditions, thus preventing better dispersion by progressive increases of the mixing time and specific energy input during melt processing. The crystallization behavior of PEEK is also affected by the presence of CNF and degree of cross-linking, with the rate of crystallization decreasing with increasing degree of cross-linking and upon the incorporation of CNFs both for the solution and melt processed PEEK nanocomposites.