Carbon nanotubes (CNTs) have exceptional mechanical, electrical, and thermal properties compared with those of commercialized high-performance fibers. For use in the form of fabrics that can maintain such properties, individual CNTs should be held together in fibers or made into yarns twisted out of the fibers. Typical methods that are used for such purposes include (a) surfactant-based coagulation spinning, which injects a polymeric binder between CNTs to form fibers; (b) liquid-crystalline spinning, which uses the nature of CNTs to form liquid crystals under certain conditions; (c) direct spinning, which can produce CNT fibers or yarns at the same time as synthesis by introducing a carbon source into a vertical furnace; and (d) forest spinning, which draws and twists CNTs grown vertically on a substrate. However, it is difficult for those CNT fibers to express the excellent properties of individual CNTs as they are. As solutions to this problem, post-treatment processes are under development for improving the production process of CNT fibers or enhancing their properties. This paper discusses the recent methods of fabricating CNT fibers and examines some post-treatment processes for property enhancement and their applications.
Methanol as a carbon source in chemical vapor deposition (CVD) graphene has an advantage over methane and hydrogen in that we can avoid optimizing an etching reagent condition. Since methanol itself can easily decompose into hydrocarbon and water (an etching reagent) at high temperatures [1], the pressure and the temperature of methanol are the only parameters we have to handle. In this study, synthetic conditions for highly crystalline and large area graphene have been optimized by adjusting pressure and temperature; the effect of each parameter was analyzed systematically by Raman, scanning electron microscope, transmission electron microscope, atomic force microscope, four-point-probe measurement, and UV-Vis. Defect density of graphene, represented by D/G ratio in Raman, decreased with increasing temperature and decreasing pressure; it negatively affected electrical conductivity. From our process and various analyses, methanol CVD growth for graphene has been found to be a safe, cheap, easy, and simple method to produce high quality, large area, and continuous graphene films.
Orange peel (OP) exhibits a sorption capacity towards anionic dyes such as reactive blue 19 (RB19). Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant was used to modify the surface nature of OP to enhance its adsorption capacity for anionic dyes from an aqueous solution. Four adsorbents were investigated: the OP, sodium hydroxide-treated OP (SOP), CTAB-modified OP and CTAB-modified SOP. The physical and chemical properties of these sorbents were determined using nitrogen adsorption at 77 K and by scanning electron microscope and Fourier transform infrared spectroscopy techniques. The adsorption of the RB19 dye was assessed with these sorbents at different solution pH levels and temperatures. The effect of the contact time was considered to determine the order and rate constants of the adsorption process. The adsorption data were analyzed considering the Freundlich, Langmuir, Elovich and Tempkin models. The adsorption of RB19 by the assessed sorbents is of the chemisorption type following pseudo-first-order kinetics. CTAB modification brought about a significant increase in RB19 adsorption, which was ascribed to the grafting of the sorbent with a cationic surfactant.
Graphite oxide (GO) was produced using the modified Hummer's method. Poly(p-phenylene sulfide) (PPS)/reduced graphite oxide (RGO) composites were prepared by in situ polymerization method. The electrical conductivity of the PPS/RGO composites was no more than 82 S/m. It was found that as GO content increased in the PPS/RGO composites, the crystallization temperature and electrical conductivity of the composites increased and the percolation threshold value was at 5-8 wt% of GO content.
Polyacetylene (PA) films with vertically aligned fibril morphology were synthesized in homeotropic nematic liquid crystal (N-LC) solvent by using a magnetic field of 5 Tesla as an external perturbation. Scanning electron microscope (SEM) photographs indicated that the lengths of fibrils from the substrate were 5-35μm, depending on polymerization time. Carbonization was carried out using iodine-doped PA film and a morphology-retaining carbonization method. From the SEM results, we confirmed that the vertical morphology of the PA remains unchanged even after carbonization at 800℃. The weight loss of the films due to carbonization at 800℃ is about 20% of the weight of the film before iodine doping. It is expected that vertically aligned carbon might be a precursor for preparing vertical graphite materials, which materials could be useful for electrochemical energy storage and cell electrodes.
In this study, reduced graphene oxide/polyimide (r-GO/PI) composite films, which showed significant enhancement in their electrical conductivity, were successfully fabricated. GO was prepared from graphite using a modified Hummers method. The GO was used as a nanofiller material for the preparation of r-GO/PI composites by in-situ polymerization. An addition of 20 wt% of GO led to a significant decrease in the volume resistivity of composite films by less than nine orders of magnitude compared to that of pure PI films due to the electrical percolation networks of reduced GO created during imidization within the films. A tensile test indicated that the Young's modulus of the r-GO/PI composite film containing 20 wt% GO increased drastically from 2.3 GPa to 4.4 GPa, which was an improvement of approximately 84% compared to that of pure PI film. In addition, the corresponding tensile strength was found to have decreased only by 12%, from 113 MPa to 99 MPa.
Poly(vinylidene chloride) (PVDC)-derived nanoporous carbons were prepared by various activation methods: heat-treatment under an inert atmosphere, steam activation, and potassium hydroxide (KOH) activation at 873, 1073, and 1273 K. The pore structures of PVDC-derived nanoporous carbons were characterized by the N2 adsorption technique at 77 K. Heat treatment in an inert atmosphere increased the specific surface area and micropore volume with elevating temperature, while the average micropore width near 0.65 nm was not significantly changed, reflecting the characteristic pore structure of ultramicroporous carbon. Steam activation for PVDC at 873 and 1073 K also yielded ultramicroporosity. On the other hand, the steam activated sample at 1273 K had a wider average micropore width of 1.48 nm, correlating with a supermicropore. The KOH activation increased the micropore volume with elevating temperature, which is accompanied by enlargement of the average micropore width from 0.67 to 1.12 nm. The average pore widths of KOH-activated samples were strongly governed by the activation temperature. We expect that these approaches can be utilized to simply control the porosity of PVDC-derived nanoporous carbons.
A fabrication method to improve the processability of thermoplastic carbon nanotube (CNT) mat composites was investigated by using in-situ polymerizable and low viscous cyclic butylene terephthalate oligomers. The electrical conductivity of the CNT mat composites strongly depended on the compression pressure, and the trend can be explained in terms of two cases, low and high compression pressure, respectively. High CNT mat content in the CNT mat composites and the surface of the CNT mat composites with fully contacted CNTs was achieved under high compression pressure, and direct contact between four probes and the surface of the CNT mat composites with fully contacted CNTs gave resistance of 2.1Ω. In this study the maximum electrical conductivity of the CNT mat composites, obtained under a maximum applied compression pressure of 27 MPa, was 11 904 S m-1, where the weight fraction of the CNT mat was 36.5%.
Dielectrophoretic filtering and alignment of single-walled carbon nanotubes (SWCNTs) were tested using deuterium oxide as a solvent. A solution of deuterium oxide-SWCNTs was dropped on top of a silicon chip and an ac electric field was applied between pre-defined electrodes. Deuterium oxide was found to be a better solvent than hydrogen oxide for the dielectrophoresis process with higher efficiency of filtering. This was demonstrated by comparing Raman spectra measured on the initial solution with those measured on the filtered solution. We found that the aligned nanotubes along the electric field were not deposited on the substrate but suspended in solution, forming chain-like structures along the field lines. This so-called pearl chain formation of CNTs was verified by electrical measurements through the aligned tubes. The solution was frozen in liquid nitrogen prior to the electrical measurements to maintain the chain formation. The current-voltage characteristics for the sample demonstrate the existence of conduction channels in the solution, which are associated with the SWCNT chain structures.
Nanoporous non-woven carbon fibers for a gas sensor were prepared from a pitch/polyacrylonitrile (PAN) mixed solution through an electrospinning process and their gas-sensing properties were investigated. In order to create nanoscale pores, magnesium oxide (MgO) powders were added as a pore-forming agent during the mixing of these carbon precursors. The prepared nanoporous carbon fibers derived from the MgO pore-forming agent were characterized by scanning electron microscopy (SEM), N2-adsorption isotherms, and a gas-sensing analysis. The SEM images showed that the MgO powders affected the viscosity of the pitch/PAN solution, which led to the production of beaded fibers. The specific surface area of carbon fibers increased from 2.0 to 763.2m2/g when using this method. The template method therefore improved the porous structure, which allows for more efficient gas adsorption. The sensing ability and the response time for the NO gas adsorption were improved by the increased surface area and micropore fraction. In conclusion, the carbon fibers with high micropore fractions created through the use of MgO as a pore-forming agent exhibited improved NO gas sensitivity.