Carbon bundles

Aligned multiwall CNT arrays were synthesized as a basis for a microstructured catalyst, which was then tested in the Fischer-Tropsch reaction in a microchannel reactor [269]. Fabrication of such a structured catalyst first involved MOCVD of a thin but dense A1203 film on a FeCrAlY foam to enhance the adhesion between the catalyst and the metal substrate. Then, multiwall CNTs were deposited uniformly on the substrate by controlled catalytic decomposition of ethene. Coating the outer surfaces of the nanotube bundles with an active catalyst layer results in a unique hierarchical structure with small interstitial spaces between the carbon bundles. The microstructured catalyst was characterized by the excellent thermal conductivity inherent to CNTs, and heat could be efficiently removed from the catalytically active sites during the exothermic Fischer-Tropsch synthesis. 

An HT fiber composite was found to be dimensionally and structurally unstable well below the maximum fiber processing temperature of 1400 C. The fiber shrank (the frozen in process stress relaxes) at temperatures as low as 850°C. The shrinkage of the fiber bundle embedded in phenolic resin during the carbonization process was influenced by matrix shrinkage stresses and pyrolysis products. Above 1000°C, the HTA carbon fiber in carbon-carbon bundles continuously changed its structure. After heat treatment at a temperature of 2800°C, the structure (lattice distance, orientation of the crystallites, crystallite size) was very similar to that of HM fibers. 

Zhou et al [163] also measured the tensile properties of carbonized PAN yarns. The 1000°C carbonized bundle had a tensile strength of 325 15 MPa and a modulus of 40 4 GPa. These values increased to 542 45 and 58 6 GPa, respectively, with the increase of the final graphitization temperature to 2200°C. The values are measured for the bundle which can differ from the properties of single fibers to a great extent. 

Metal dusting corrosion of 304 SS at 550°C for 160 hours showing filamentous carbon bundles on the surface, regions of localized corrosion filled with carbon deposit, regions protected by Cr-rich surface oxide, and M7C3 carbides in the alloy subsurface (adapted from ref. 16). 

Optical and SEM images of the metal dusting of 35/45 alloy after 160 hours of corrosion at 650°C showing carbon bundles on the surface, localized corrosion regions filled with carbon deposit, alloy surface protected by Cr-rich oxide film, and filamentous carbon in the carbon bundles. 

Inorganic membranes (29,36) are generaUy more stable than their polymeric counterparts. Mechanical property data have not been definitive for good comparisons. IndustriaUy, tube bundle and honeycomb constmctions predominate with surface areas 20 to 200 m. Cross-flow is generaUy the preferred mode of operation. Packing densities are greater than 1000 /m. Porous ceramics, sintered metal, and metal oxides on porous carbon support... 

Galvanic corrosion can be controlled by the use of sacrificial anodes. This is a common method of controlling corrosion in heat exchangers with Admiralty tube bundles and carbon steel tube sheets and channel heads. The anodes are bolted direcdy to the steel and protect a limited area around the anode. Proper placement of sacrificial anodes is a precise science. 

Fibrous Composites. These composites consist of fibers in a matrix. The fibers may be short or discontinuous and randomly arranged continuous filaments arranged parallel to each other in the form of woven rovings (coUections of bundles of continuous filaments) or braided (8). In the case of chopped strand mat the random arrangement is planar. In whisker (needle-shaped crystals or filaments of carbon and ceramics) reinforced materials the arrangement is usually three-dimensional and the resulting composites are macroscopically homogeneous. 

If I ever have to design an amine plant I will know, for example, that the temperature of the lean amine solution entering the absorber should be about 10°F higher than the inlet gas temperature to prevent hydrocarbon condensation and subsequent foaming, that the reboiler tube bundle should be placed on a slide about six inches above the bottom of the shell to provide good circulation, that about two percent of the total circulating flow should pass through the carbon towers, and many other necessary requirements. 

Early transport measurements on individual multi-wall nanotubes [187] were carried out on nanotubes with too large an outer diameter to be sensitive to ID quantum effects. Furthermore, contributions from the inner constituent shells which may not make electrical contact with the current source complicate the interpretation of the transport results, and in some cases the measurements were not made at low enough temperatures to be sensitive to 1D effects. Early transport measurements on multiple ropes (arrays) of single-wall armchair carbon nanotubes [188], addressed general issues such as the temperature dependence of the resistivity of nanotube bundles, each containing many single-wall nanotubes with a distribution of diameters d/ and chiral angles 6. Their results confirmed the theoretical prediction that many of the individual nanotubes are metallic. 

Fig. 23. Experimental room temperature Raman spectrum from a sample consisting primarily of bundles or ropes of single-wall nanotubes with diameters near that of the (10,10) nanotube. The excitation laser wavelength is 514.5 nm. The inset shows the lineshape analysis of the vibrational modes near 1580 cm . SWNT refers to singlewall carbon nanotubes [195].

Clearly, not all forms of earbon material, nor all the possible applieations thereof, are diseussed in this book. However, the applieation of earbon materials in many advaneed teehnologies are reported here. Carbon has played an important role in mankind s teehnologieal and soeial development. In the form of charcoal it was an essential ingredient of gunpowder The industrial revolution of the IS and 9 eenturies was powered by steam raised from the burning of eoal New applieations of earbon materials wiU surely be developed in the future. For example, the reeently diseovered earbon nanostruetures based on C q (closed eage moleeules, tubes and tube bundles), may be the foundation of a new and signifieant applieations area based on their superior meehanieal properties, and novel eleetronie properties. 

Inspired by experimental observations on bundles of carbon nanotubes, calculations of the electronic structure have also been carried out on arrays of (6,6) armchair nanotubes to determine the crystalline structure of the arrays, the relative orientation of adjacent nanotubes, and the optimal spacing between them. Figure 5 shows one tetragonal and two hexagonal arrays that were considered, with space group symmetries P42/mmc P6/mmni Dh,), and P6/mcc... 

Modifications of the conduction properties of semiconducting carbon nanotubes by B (p-type) and N ( -type) substitutional doping has also been dis-cussed[3l] and, in addition, electronic modifications by filling the capillaries of the tubes have also been proposed[32]. Exohedral doping of the space between nanotubes in a tubule bundle could provide yet an-... 

No superconductivity has yet been found in carbon nanotubes or nanotube arrays. Despite the prediction that ID electronic systems cannot support supercon-ductivity[33,34], it is not clear that such theories are applicable to carbon nanotubes, which are tubular with a hollow core and have several unit cells around the circumference. Doping of nanotube bundles by the insertion of alkali metal dopants between the tubules could lead to superconductivity. The doping of individual tubules may provide another possible approach to superconductivity for carbon nanotube systems. 

Fig. 2a. Bundles and individual single-layer carbon nanotubes bridge across a gap in a carbon film.

Fig. 5. STM image of a long bundle of carbon nanolubes. The bundle is partially broken in a small area in the upper left part of the image. Single lubes on the flat graphite surface are also displayed.

C.-H. Kiang e o/.[33] reported that the singlelayered coiled lubes were obtained by co-vaporizing cobalt with carbon in an arc fullerene generator. A single-layered helical structure with radii of curvature as small as 20 nm was seen. These helically coiled forms lend to bundle together. In the soot obtained with sulfur-containing anodes, they also found the 1.3-nm diameter lube coil around the 3.6 nm tube (see Fig. 14). This kind of structure was theoretically proposed in ref. [14]. 

Song et al. [16] reported results relative to a four-point resistivity measurement on a large bundle of carbon nanotubes (60 um diameter and 350 tm in length between the two potential contacts). They explained their resistivity, magnetoresistance, and Hall effect results in terms of a conductor that could be modeled as a semimetal. Figures 4 (a) and (b) show the magnetic field dependence they observed on the high- and low-temperature MR, respectively. 

Work on the production and oxidation of SWNT samples at SRI and other laboratories has led to the observation of very long bundles of these tubes, as can be seen in Fig. 2. In the cleanup and removal of the amorphous carbon in the original sample, the SWNTs self-assemble into aligned cable structures due to van der Waals forces. These structures are akin to the SW nanotube crystals discussed by Tersoff and Ruoff they show that van der Waals forces can flatten tubes of diameter larger than 2.5 nm into a hexagonal cross-sectional lattice or honeycomb structure[17]. 

Fig, 6. EEL spectra of bundle of four SWCNTs, MWCNT and graphite in the energy ranges (a) from 0 to 45 eV (plasmon region) and (b) from 280 to 300 eV (carbon K-edge) (modified from ref. 14). 

The interpretation of thermoelectric power data in most materials is a delicate job and this is particularly true for the case of carbons and graphites. In the case of SWCNTs the data are not consistent with those calculated from the known band structure which leads to much smaller values than observed. Hone et al. [11] suggest from their data that they may indicate that the predicted electron-hole symmetry of metallic CNTs is broken when they are assembled into bundles (ropes). 

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