Carbon filament

The acconunodation coefficient for Kr on a carbon filament is determined experimentally as follows. The electrically heated filament at temperature 72 is stretched down the center of a cylindrical cell containing Kr gas at 7. Gas molecules hitting the filament cool it, and to maintain its temperature a resistance heating of Q cal sec cm is needed. Derive from simple gas kinetic theory the expression... 

Dust Inhalation. During processing, fine carbon filaments (5—10 p.m in diameter) may break and be circulated in the air as a carbon dust that can be inhaled by operators. Studies (71) show the fibers are too large to represent a respiratory health risk however they often create discomfort, and a protective mask is recommended when working in areas where carbon fiber dust is present. 

Regarding a historical perspective on carbon nanotubes, very small diameter (less than 10 nm) carbon filaments were observed in the 1970 s through synthesis of vapor grown carbon fibers prepared by the decomposition of benzene at 1100°C in the presence of Fe catalyst particles of 10 nm diameter [11, 12]. However, no detailed systematic studies of such very thin filaments were reported in these early years, and it was not until lijima s observation of carbon nanotubes by high resolution transmission electron microscopy (HRTEM) that the carbon nanotube field was seriously launched. A direct stimulus to the systematic study of carbon filaments of very small diameters came from the discovery of fullerenes by Kroto, Smalley, and coworkers [1], The realization that the terminations of the carbon nanotubes were fullerene-like caps or hemispheres explained why the smallest diameter carbon nanotube observed would be the same as the diameter of the Ceo molecule, though theoretical predictions suggest that nanotubes arc more stable than fullerenes of the same radius [13]. The lijima observation heralded the entry of many scientists into the field of carbon nanotubes, stimulated especially by the un-... 

Fig. 1. Carbon filaments grown after acetylene decomposition at 973 K for 5 hours on (a) Co(2.5%)-graphite (b) Fe-graphite (c) Ni-graphite (d) Cu graphite.

Fig. 5. Acetylene decomposition on Co-HY (973 K, 30 minutes) (a) encapsulated metal particle (b) carbon filaments (A) and tubules of small diameters (B) on the surface of the catalyst.

Kohle,/. coal charcoal carbon, kohlebeheizt, a. heated with coal, coal-fired. Kohle-chemie, /. coal(tar) chemistry, -druck, m. Photog.) carbon print, -fadenlampe, /. carbon-filament lamp, -feuerung, /. heating with coal coal furnace, kohlefrei, a. carbon-free. 

Fluorescence Spectroscopy with a Carbon Filament Atom Reservoir". Anal. Chlm. Acta (1969), 27-41. 

The activity and stability of catalysts for methane-carbon dioxide reforming depend subtly upon the support and the active metal. Methane decomposes to carbon and hydrogen, forming carbon on the oxide support and the metal. Carbon on the metal is reactive and can be oxidized to CO by oxygen from dissociatively adsorbed COj. For noble metals this reaction is fast, leading to low coke accumulation on the metal particles The rate of carbon formation on the support is proportional to the concentration of Lewis acid sites. This carbon is non reactive and may cover the Pt particles causing catalyst deactivation. Hence, the combination of Pt with a support low in acid sites, such as ZrO, is well suited for long term stable operation. For non-noble metals such as Ni, the rate of CH4 dissociation exceeds the rate of oxidation drastically and carbon forms rapidly on the metal in the form of filaments. The rate of carbon filament formation is proportional to the particle size of Ni Below a critical Ni particle size (d<2 nm), formation of carbon slowed down dramatically Well dispersed Ni supported on ZrO is thus a viable alternative to the noble metal based materials. 

In contrast to the Pt catalysts discussed above, Ni based catalysts (i.e., also when supported on ZrO usually form coke at such a rapid rate that most fixed bed reactors are completely blocked after a few minutes time on stream (see Fig. 8) [16], The coke formed with the Ni catalysts is filamentous. The Ni particle remaining at the tip of the filament hardly deactivates as the coke formed on its surface seems to be transported through the metal particle into the carbon fibre, but the drastic increase in volume causes reactor plugging and prevents use of the still active catalyst (see Fig. 8). The TEM photographs indicate that the carbon filaments have similar diameters to those of the Ni particles. 

As the metal particle size decreases the filament diameter should also decrease. It has been shown that the surface energy of thirmer filaments is larger and hence the filaments are less stable (11,17-18). Also the proportion of the Ni(l 11) planes, which readily cause carbon formation, is lower in smaller Ni particles (19). Therefore, even though the reasons are diverse, in practice the carbon filament formation ceases with catalysts containing smaller Ni particles. Consequently, well dispersed Ni catalysts prepared by deposition precipitation of Ni (average metal particle size below 2-3 nm) were stable for 50 hours on stream and exhibited no filamentous coke [16]. 

Schematic representation of carbon filaments of different structure produced by metal-catalyzed decomposition of methane, (a) Platelet structure, (b) "herringbone" structure, and (c) ribbon structure. MP denotes a nanosized metal particle.

TEM images of carbon filaments produced by decomposition of NG over Fe(10 wt%)/Al203 catalyst at 850°C. (a) Carbon filaments with embedded iron nanoparticles, (inset b) high-resolution TEM image of the wall of a carbon filament, and (c) = an iron nanoparticle encapsulated in carbon layers at the tip of a carbon filament. 

A series of kinetic studies on the carbon filament formation by methane decomposition over Ni catalysts was reported by Snoeck et al. [116]. The authors derived a rigorous kinetic model for the formation of the filamentous carbon and hydrogen by methane cracking. The model includes the following steps ... 

The rigorous kinetic modeling with the incorporation of the diffusion step allows explaining the deactivation of the carbon filament growth and the influence of the affinity for carbon formation on the nucleation of the filamentous carbon. 

Snoeck, J., Froment, G., and Fowles, M., Kinetic study of the carbon filament formation by methane cracking on a nickel catalyst, /. Catal., 169, 250,1997. 

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