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Commercial Production of Fullerenes and Carbon Nanotubes

Raouf O. Loutfya, Timothy P. Lowea, Alexander P. Moravskya and S. Katagirib

MER Corporation, Tucson Arizona USA b FIC Corporation, New York NY USA

It has been slightly over ten years since the development of a way to produce macroscopic quantities of fullerene, and the related discovery of fullerene nanotubes. As a result, over 1500 worldwide patents have been filed for the production and applications of these new materials. These applications are so wide ranging that they extend across different industries with products from additives to polymers, photoconductors, photo-resists, and bio-active agents to cosmetics. MER Corporation in Tucson, Arizona joined the ranks of fullerene enthusiasts at the beginning of its discovery by immediately licensing the Huffman–Krätschmer patents. While we are widely recognized as a producer of fullerene and nanotubes, MER has also been active in developing applications for fullerenes and nanotubes. The different applications investigated by MER will be reviewed in subsequent chapters. The overriding factor for the success of any of these applications, however, is the price of fullerenes. However, the price cannot come down markedly until large-scale applications are found. To introduce the first large-scale application an organization had to take a leap of faith and initiate the large-scale low-cost production. Mitsubishi/FIC Corporations has been a leader and pioneer in recognizing the need to support large-scale production effort to realize the fullerene and nano-technology commercialization dream. It is now our opportunity to realize the commercial applications. The present status of the scale-up production effort of fullerenes and the different nanotubes will be presented in this chapter.

1. Fullerene Production

The family of fullerenes includes the hollow cage all-carbon molecules having a convex closed-shell structure containing arbitrary numbers of hexagonal and exactly twelve pentagonal faces. They are synthesized abundantly in the carbon arc, hydrocarbon flame or field-induced hot carbon plasma and are originally embedded in the soot product. Fullerenes can be extracted from the soot due to appreciable solubility in some organic solvents. Separation of the various members of the fullerene family is accomplished by chromatography. The most stable fullerenes and have been produced in amounts of up to 23 wt % in the total harvested soot in the arc process [1], although typical technological yields are on the order of 8–15% at different production facilities. The higherorder fullerenes, of which and are the most abundant, typically make up about 2–4 wt % of the arc-produced soot. It is interesting to note that the molar ratio remains constant at 5.06 within about 1% accuracy in any carbon arc process in helium gas atmosphere, regardless of run conditions or graphite rod thickness [2]. Soon after the famous discovery of the arc process in 1990, MER Corporation was the first to offer fullerenes commercially. The mixed fullerenes that are extracted from the soot were the first product available, and after the development of chromatographic
E. (ed.,) Perspectives of Fullerene Nanolechnology, 35–46. © 2002 Kluwer Academic Publishers. Printed in Great Britain.

In the arc process. However. Guided by detailed mechanistic considerations of the carbon arc process [1]. separations on alumina with hexane eluent. purified and were offered. While the arc process is presently the most efficient means for high fullerene production rates. Alexander P. which will render the production process nearly continuous. Subsequent improvement in chromatographic methods increased the separation capacity by a factor of several hundred. Moravsky. and will make fullerene products viable alternatives to existing products that use other materials. The large-scale arc reactor developed by MER Corporation (Figure 2) has been demonstrated to be close to the optimum size and power for fullerene synthesis in an arc.Raouf O. other methods that have been investigated for fullerene synthesis may soon be 36 . by vaporization of 3-inch (~76 mm) diameter graphite rods to routinely produce over 11 wt % fullerenes soot product. Automated computercontrolled reactors (Figure 1). The scaled-up reactor (Figure 2) is currently in use for commercial fullerene production in Osaka. we have proved experimentally. in the sense that the use of the rods of larger diameter leads to a rapid reduction in fullerene yield. et al. the next logical step for increasing fullerene output will be the automation of large-scale arc reactors. which operate without any attendance for several days. and will probably remain the largest reactor in the world for a long time. that this is not the case. A further increase in vaporized rod diameter and in arc power is technically feasible but does not appear to be economically justified. Loutfy. and the output of mixed fullerenes and purified and was increased dramatically. Japan. with one graphite rod at a time being loaded and vaporized. were constructed in 1992. Further increases in fullerene production rate were expected by employing thicker graphite rods in larger. The first primitive arc reactors were operated manually. Timothy P. the scale-up of the arc process has reduced the cost of fullerenes to a level that will stimulate these new uses of fullerenes. Lowe. With several applications of fullerenes about to flourish. fullerene production in carbon arcs was generally believed to be a non-scalable process. more powerful arc reactors.

non-conductive carbon or hydrocarbon gas could be used as starting material. A new highly efficient process may be just around the corner. but it has too low a specific production rate to ever reach the fullerene output level available with a scaled-up arc process. The field-induced high-intensity plasmas are an attractive alternative to the arc process. MWNTs are an all-carbon fullerene structure composed of concentric nested graphene cylinders forming an average misorientation angle of 0° to the tube axis. The flame technique possesses the potentially important advantage of being an exothermic process. In conclusion. and that many opportunities are not yet explored.Commercial Production of Fullerenes and Carbon Nanotubes adapted for commercial production. provided their undesirable properties such as low inherent yield and specific production rate. 2. The hundreds of kilowatt continuous power lasers are prohibitively expensive to be used for fullerene production. inexpensive powder. high operating cost and/or high capital expenditure are obviated.1. To become competitive to the arc process. it becomes obvious that fullerenes can be produced by virtually any process capable of generating and appropriate curing of carbon vapor. Other known techniques. Synthesis of Carbon Nanotubes (MWNTs. SWNTs and DWNTs) and Vapor-Grown Carbon Fibers (VGCFs) by the Arc and CVD Techniques Arc-Grown MWNTs 2. these alternative techniques would have to make use of their potential to be operated continuously at a level of hundreds of kilowatts useful power per production unit. such as the use of low-pressure hydrocarbon flames or laser vaporization of carbon have only a slight chance of becoming competitive on a large scale. MER is undertaking technical feasibility studies for this method. mainly because of technical difficulties. and are found in the core material of the 37 . Arc-grown MWNTs are produced without metal catalysts. and product collection could be automated and continuous.

The thermal conductivity along the length of the tube is ~1500 W/mK. The aspect ratio is around 100. orientation. and it has proven useful as a conductive additive 38 . and is most commonly 2 nm. with 15 nm as the average. quality and content in cathode deposits [3. and the resistivity is 2.Raouf O. which contains few nanotubes. the optimized conditions for MWNT production give approximately 40 wt % MWNTs in the soft core material of the cathode deposit. Timothy P. deposit that is formed on the cathode during vaporization of the anode. The measured tensile strength is 11–63 GPa for the outer layer of the MWNT. Alexander P. The cathode deposit core is a soft. black fibrous material that is easily separated from the fused carbon shell. Lowe. TEM examination of representative samples show the major contaminants to be multi-layer polyhedral particles (MPPs) and various kinds of graphitic particles. Their distribution. 4] depend primarily on the radial temperature distribution within the arc gap. and both ends are capped. Scaled-up production of arc-grown MWNTs MWNTs can be regarded as a useful by-product of fullerene synthesis in the arc. et al. The inner diameter is in the 1–4 nm range. They therefore have high mechanical. Moravsky. MER/FIC offers the separated core material on a kilogram scale. which in turn is defined by the operating conditions of the arc reactor. Loutfy.1. They typically have outer diameters in the range of 3–50 nm. thermal and electrical conductivity. A transmission electron microscopy (TEM) image of arc-grown MWNTs is shown in Figure 3.1. Arc-produced MWNTs are perfectly straight and have few defects. The Young’s modulus of MWNT is calculated to be ~1000–1500 GPa and has been measured at 1000–3700 GPa. While limited amounts of MWNTs are found in the cathode deposits produced during fullerene production.

the purification process also opens the ends of many of the MWNTs. While the larger-scale reactors have been found to produce lower yield products than small-scale reactors. 39 . among many other uses under development. as electron emitters in electron guns. 2. Catalytic MWNTs abound in structural defects. MWNTs of more than 95% purity have been obtained in research scale samples (Figure 4) by purification of the cathode deposit core material using a procedure which decomposes the graphitic carbon and MPP contaminants. depending on the amount of defects).Commercial Production of Fullerenes and Carbon Nanotubes for plastics.2. Therefore their mechanical strength and conductive properties are lower than those of arc-produced MWNTs (sometimes by several orders of magnitude. Coincidentally. Catalytic MWNTs MWNTs are also produced by catalytic pyrolysis of hydrocarbons over metals (catalytic CVD method). resulting in bends and kinks between straight segments. and may foster research into effective ways to fill MWNTs with useful materials. but are usually much longer CCVD-grown tubes are often capped with a metal nanoparticle at the growing end. Catalytic MWNTs are preferable to arc-produced MWNTs when high aspect ratio is more important than high structural strength or high conductivity. The laboratory-scale process has proven to be scalable with the production of arcgrown MWNTs in a large-scale reactor built by MER. and as probe tips in atomic-force microscopy. This procedure has clear potential for scale-up to process arc-grown MWNT. Catalytically grown MWNTs are of about the same outer and inner diameters (3–70 nm and 2–10 nm) as arc-grown nanotubes. and may contain metal inclusions in the inner channel.

et al.2.2. A true continuous process for catalytic MWNT production has been recently developed at MER Corporation. by varying the process parameters. which is two orders of magnitude longer than the arc-produced MWNTs. The length and diameter of the mass-produced catalytic MWNTs can be controlled over a very wide range. while the tube diameter is about the same in both products. can be employed. large area (up to uniform arrays of MWNTs are grown that are perfectly aligned normal to a flat support (Figure 5). 2. It has been demonstrated that conductive supports.2.1. Alexander P. Loutfy. Timothy P. like n-doped silicon wafers. Scaled-up production of MWNTs by the catalytic pyrolysis of hydrocarbons At MER. Synthesis of large arrays of aligned MWNTs by CVD using a floating catalyst In a system similar to the one where catalytic MWNTs are synthesized. a scaled-up version of a reported process [5] that employs the pyrolytic decomposition of xylenes over a ‘floating’ ferrocene-derived catalyst produces nearly pure MWNTs.Raouf O. and it was shown that there is good electrical contact between the MWNTs and the support. The thickness of the layer of aligned MWNTs 40 . 100nm–l mm and respectively. 2. A straightforward treatment to remove iron catalyst nanoparticles yields a product that is nearly 100% MWNTs. The length of these catalytic tubes can reach 1 mm. Moravsky. as opposed to arc-produced tubes that have a fairly stable size distribution independent of arc conditions. with small amounts of residual iron catalyst. Lowe.

The diameter and surface density of fibers produced are controlled by the method of catalyst preparation and by the process parameters. and they generally possess less orderly structured outer layers. although these tubes can be much thicker than arc-grown MWNTs (a few micrometers in diameter) due to sidewall growth. The average misorientation angle between a graphene plane and the tube axis can be in the range Accordingly. the cone angle may vary between 0 and 180°. With the cone is transformed into a cylinder and VGCFs are referred to as MWNTs. Vapor-grown carbon fibers (VGCFs) The vapor-grown carbon fibers (VGCFs) are near axially symmetric lamellar structures composed of conical-shaped graphene-sheet-based elements. Multiple exposed edges appear on the outer walls of the VGCFs.2. since their mechanical and conductive properties are poor compared to those of carbon nanotubes and polymer-based carbon fibers. which can be removed by treatment with a mineral acid. The edges can also bind transition metal ions. the angle can vary within a layer in the radial direction. A ‘herring-bone’-type structure comprises either intact cones or truncated cones having flat or convex caps.2.4. 2. In real ‘herring-bone’ and CLNT structures. If the cap is absent. 41 . The latter extreme corresponds to a ‘platelet’-type structure. These are the most promising areas for VGCF applications. a hollow internal cavity is formed and the structure is considered to be a conical layer nanotube (CLNT). and the linear density of edges increases with increasing The many exposed edges make VGCFs good candidates for intercalation of the interlayer spaces with small molecules or ions. but are much better adapted to the adsorption and release of chemicals from between the graphene layers. These practically pure VGCFs are typically up to ten times thicker (20–200 nm in diameter) than concentric MWNTs. Under certain conditions some MWNTs are produced as a component of aligned arrays whose major composition is ‘herring-bone’ VGCFs.Commercial Production of Fullerenes and Carbon Nanotubes can be varied from a few micrometers to one millimeter. and the layers may comprise various defects and discontinuities. making VGCFs a promising catalyst support. with surface density of tubes of approximately 30 billion per Aligned MWNT arrays on conductive supports with the tube ends free of iron catalyst particles have also been produced. matching to the shape of the metal catalyst particle from which it formed. which is similar to the microwave plasma CCVD technique that was first reported in [7]. so they may find use in gas storage or Li-ion electrochemical cells. 2. They are less conductive than MWNTs. ideally composed of a stack of flat graphene sheets. The growing ends of as-produced VGCFs contain nickel or iron microparticles depending on the catalyst employed. RF plasma-assisted CVD synthesis of aligned arrays of VGCFs Perfectly aligned arrays (Figure 6) of VGCFs with ‘herring-bone’ internal structure have been deposited normal to the surface of electrically conducting supports by the RF plasma-assisted CCVD method [6].3.

Alexander P.Raouf O. Lowe.5.3. laser or catalytic CVD process is in the range 1–5 nm. Loutfy. The aspect ratio can be as large as Figure 8 is a TEM micrograph of arcgrown SWNTs. and can be controlled by experimental conditions. Scaled-up arc synthesis of SWNTs The laboratory-scale synthesis of SWNTs in the arc using Ni/Co based catalyst has been subjected to an extensive set of mechanistic studies [9].3. 2. leading to the consistent 42 .1. Bulk production of VGCFs with abundant random exposed edges Randomly oriented pure VGCFs of ‘herring-bone’ and ‘platelet’ internal structure (Figure 7) are obtained at MER Corporation in bulk quantities (kg) by the catalytic pyrolysis of a mixture of ethylene or carbon monoxide with hydrogen over an ironcopper catalyst.2. SWNTs made by any of the synthetic methods are essentially defect-free structures that possess outstanding mechanical and conductive properties. Single-walled carbon nanotube (SWNT) SWNTs are a fullerene structure made of a graphene sheet rolled into a seamless cylinder having carbon caps on both ends. The tubes are highly elastic and are always buckled or kinked rather than broken if bent. Theoretical estimates predict 1200–1700 GPa for the value of the Young’s modulus and 3000 W/m K for the axial thermal conductivity. 2. The metallic type of SWNTs possess a very low resistivity of both by theoretical estimates and direct measurements. Moravsky. 2. This process is described in detail in [8]. et al. Timothy P. The diameter of SWNTs produced by the arc.

As in the scale-up of fullerene production by increasing the diameter of the reactant rod. However. there is a general consensus that yield will decrease as the rod diameter increases. research at MER has determined that 25 mm diameter rods packed with the Ni/Co based catalyst can be used to increase production with a minimal decrease in yield.Commercial Production of Fullerenes and Carbon Nanotubes production of SWNT product with 40 vol % yield of SWNTs. An efficient purification 43 .

which could have special applications. The outer diameter of DWNTs is in the range of 2–5 nm. et al. The tubes are highly elastic and buckle at bending. The control of SWNT properties has proven to be difficult. The inter-wall distance (~0. Loutfy. while the inner diameter is 1–4 nm. they are typically found in a less curved and tangled state. and since they are stiffer than SWNTs. the scale-up of the purification process will make these materials valuable. Timothy P.Raouf O. but more experimentation is required to define the effects. with modifications to the catalysts and atmosphere employed [10]. Lowe. Moravsky. provided they are produced in abundance at low cost. A sulfur-promoted Fe/Co/Ni-based catalyst was recently found [10] that is capable of producing more than 60 wt % yield of SWNTs with very large diameter (about 4.39 nm) is slightly larger than the distance in MWNTs. The procedure enables ~30% recovery of pure tubes even from low-yield SWNT starting materials. Therefore. The length of DWNTs can reach DWNTs are produced in a carbon arc in a technique that is similar to SWNT production. depending on the synthesis conditions. The outer and inner walls of a tube are defect-free graphene sheets.0 nm on the average). and the tube probably has similar high mechanical strength and conductive properties to those found in SWNTs. Double-walled carbon nanotubes (DWNTs) DWNTs are a fullerene structure made of two nested graphene cylinders with both cylinders capped at the ends (see Figure 10). Alexander P. The 44 . Further optimization of the synthesis parameters and consequent scaling-up of the process are expected to finally give much more efficient production of these high-yield thick tubes. procedure employed at present at MER yields research quantities (~10g per month) of more than 90 wt % pure SWNTs (Figure 9).4. Variation of arc conditions and/or catalyst composition has some effect on the tube parameters. 2.

High-resolution TEM (HRTEM) analysis of typical samples has shown that the ratio of DWNT/SWNT is higher than 30 and the yield of DWNTs in as-produced fibrous material exceeds 70 wt %. the limiting factors for the commercialization of the fullerenes-based materials is now finding the right (killer) applications.1. In Chaps. 22–29 some of the MER/FIC applications development efforts are described. Scale-up production of many of these products was accomplished. Conclusion Different methods were investigated experimentally and theoretically to produce fullerenes and various types of nanotubes (SWNT. 45 . lithium batteries and other technologies. and arc-DWNT).8 nm [10].Commercial Production of Fullerenes and Carbon Nanotubes values for mechanical strength. arc-MWNT. VG-MWNT. 3. CVD-aligned MWNT.2 to 4.4. hydrogen storage. Selective synthesis of DWNTs in the arc Selective synthesis of double-walled carbon nanotubes (DWNT) is efficiently accomplished using a slight variation in the same Fe/Co/Ni catalyst composition and preparation procedure used for SWNTs [10]. Accordingly. The scaling-up of this arc synthesis method is underway to make DWNTs available for extensive research work on anticipated applications in cold field emission. and the size distribution is sharply peaked at 3. 2. The outer diameter of these DWNTs ranges from 3.9 nm. Scale-up schemes for all other materials are underway. thermal and electrical conductivity for DWNTs are not yet defined.

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