Professional Documents
Culture Documents
Carbon nanotubes (CNTs) are now well into their teenage years. Early on, theoretical predictions and experimental data showed that CNTs possess chemical and mechanical properties that exceed those of many other materials. This has triggered intense research into CNTs. A variety of production methods for CNTs have been developed; chemical modification, functionalization, filling, and doping have been achieved; and manipulation, separation, and characterization of individual CNTs is now possible. Today, products containing CNTs range from tennis rackets and golf clubs to vehicle fenders, X-ray tubes, and Li ion batteries. Breakthroughs for CNT-based technologies are anticipated in the areas of nanoelectronics, biotechnology, and materials science. In this article, I review the current situation in CNT production and highlight the importance of clean CNT material for the success of future applications.
Nicole Grobert Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK E-mail: nicole.grobert@materials.oxford.ac.uk
Carbon fibers and filaments have been studied for over 100 years. Hughes and Chambers1, and Schtzenberger and Schtzenberger2 reported the growth of filamentous carbon in 1889 and 1890, respectively. In the early 1950s, Radushkevich and Lukyanovich3 published a report on hollow carbon fibers (Fig. 1). Since then, the demand by the space and aerospace industry for stronger, lightweight materials with improved mechanical properties has led to substantial progress in the production and characterization of carbon filaments and hollow carbon fibers.
28
REVIEW
Fig. 1 Low-resolution transmission electron micrograph depicting three hollow carbon fibers at MAG 20 000. These fibers were first reported by Radushkevich and Lukyanovich in 1950. (Adapted and reprinted with permission from3.)
Fig. 3 Simulated images of a DWNT in a SWNT bundle and a SWNT in a DWNT bundle. To avoid misinterpretation of such complicated transmission electron micrograph images, the authors suggest analyzing the cross section of the nanotubes and bundles. If possible, TEM images should be combined with image simulations and other characterization methods, e.g. Raman spectroscopy. (Adapted and reprinted with permission from5. 2006 Elsevier.)
Fig. 2 First viewgraph of what today is called SWNT or DWNT. Based on this image, it is difficult to determine the exact number of walls. (Adapted and reprinted with permission from4. 1976 Elsevier.)
Fig. 4 Typical scanning electron micrograph of the carbon filaments often observed during metal dusting processes. (Scale bar = 2 m.)
whether the nanotube in Fig. 2 consists of one or two concentric graphene cylinders (Fig. 3)4,5. The carbon fiber community then was familiar with filament-like structures and did not pay further attention to smaller-scale objects like the CNTs observed by Endo et al.4. Instead, research focused on generating carbon fibers from polymer-based precursors using rayon, polyacrylonitrile (PAN), or mesophase pitch. Graphitic nanofibers were also encountered by the catalysis community and steel industry. Here, carbon nanofibers were, and still are, considered unwanted byproducts causing poisoning6 of metal catalyst particles or damage to reactor walls in furnaces7. This process is also known as metal dusting or corrosion (Fig. 4)8-10. Yet the paper entitled Helical microtubules of graphitic carbon published by Iijima in 199111 caused an unprecedented change in carbon science. Iijima was fascinated by the Krtschmer-Huffman paper on the lab-scale production of C60
12.
in Richmond, Virginia and one month later he published his paper in Nature11. A combination of factors was responsible for the tremendous impact of Iijimas paper and for the attention that these graphitic nanofibers continue to attract today14. 15 years later, the number of publications related to CNTs is still increasing exponentially.
by the Krtschmer-Huffman method provided by Ando12,13 using a high-resolution transmission electron microscope (HRTEM). In 1990, Iijima presented images of carbon nanotubes (Fig. 5) at a meeting
29
REVIEW
(a)
(b)
(c)
Fig. 6 Models of three atomically perfect SWNT structures. Fig. 5 Iijimas TEM micrographs of three MWNTs consisting of three, five, and seven concentric graphene shells. (Adapted and reprinted with permission from11. 1991 Nature Publishing Group.)
devices, has yet to be achieved. One of the key limiting factors is the unavailability of clean materials. As discussed in the following sections, current growth methods are insufficient for the controlled production of CNTs with uniform structure and uniform properties.
CNTs may exhibit extraordinary aspect ratios. SWNTs are found to grow up to several centimeters long15, i.e. 109 times their diameter. MWNTs exhibit lengths of up to a centimeter16 and have diameters from 5-100 nm. CNT properties are strongly dependent on their structure, e.g. for typical diameters, all armchair SWNTs and one-third of all zigzag nanotubes are metallic, the rest are semiconducting17. Extraordinary mechanical properties of SWNTs were predicted shortly after their discovery18. Doping of CNTs can be used to tune their electronic response19. Several accounts have shown that CNTs can act as field-effect transistors20 or that vertically aligned CNTs are ideal candidates for low-resistance interconnects21,22 (Figs. 7a and b). These properties make CNTs attractive for applications in nanoelectronics20 and quantum computing23, as gas sensors24-26, or fillers in polymer27, ceramic28,29, or metal30 composites31. Today, numerous spin-off companies offer CNTs at competitive prices, and more and more products containing CNTs are becoming available. However, no currently available CNT-based application makes use of the properties of individual nanotubes. To date, all commercial CNTbased applications rely on the bulk properties of CNT ensembles. The much anticipated breakthrough of individual CNTs, e.g. in electronic
Table 1 Variation of Youngs modulus and tensile strength found for different carbon nanotubes. Author
Treacy et al.102 Krishnan et al.103 Wong et al.104 Salvetat et al.105 Salvetat et al.106 Yu et al.107 Demczyk et al.108 Bacon109 Edie et al.110
Nanotube type
MWNTARC SWNTLSR MWNTARC MWNTARC MWNTCVD
Method
thermal vibrations (TEM) thermal vibrations (TEM) AFM AFM AFM AFM (dual cantilevers) TEM (tension)
30
REVIEW
(a)
in the chamber as a fluffy web-like material37. Ando13 showed that the arc evaporation of a graphite rod with a pure Fe catalyst in conjunction with a hydrogen and inert gas mixture may be used for growing macroscopic SWNT nets of up to 20-30 cm in length. Replacing He by H2 results in MWNTs with a very thin innermost tube of <0.4 nm13. The length of the MWNTs can be increased by introducing B into the anode38,39. Boron also appears to favor the formation of zigzag MWNTs38,39. Loiseau and others40-43 have shown that the insertion of metals or their carbides yields filled MWNTs. As a rule of thumb, arc-discharge MWNTs are typically 20 m long and have a diameter of around 10 nm. The number of walls is limited to ~20-30. MWNTs produced by this method are highly crystalline and exhibit fewer defects than MWNTs produced by other methods. SWNTs produced by the same method occur in bundles37. Their diameter ranges from 1-2 nm. It remains difficult to measure the SWNT length accurately because of the entanglement of the SWNT bundles. The SWNTs in
(b)
Fig. 7 (a) Model of Infineons vertical carbon nanotube transistor. (b) PECVDgrown carbon fibers, ~1 m in diameter, used as interconnects in experiments (Part (a) courtesy of G. Duesberg. Part (b) adapted and reprinted with permission from www.ipt.arc.nasa.gov/Graphics/interconnects_2.jpg.)
the bundles exhibit a collection of different chiralities. Arc-discharge MWNT and SWNT samples commonly contain substantial amounts of byproducts such as amorphous carbon and polyhedral carbon. In SWNTs samples, encapsulated metal catalyst particles are also present.
commercial suppliers. Therefore, a detailed characterization of the CNT material is not available, because companies and labs specializing in CNT synthesis often do not have access to or cannot afford detailed and time consuming structural characterization of each CNT batch. Often, only the first samples produced using a new process are studied in detail. Subsequent batches are assumed to exhibit similar features. Unfortunately, this approach is unsuitable for CNT evaluation because small fluctuations in synthesis conditions can change the structure of CNTs dramatically.
31
REVIEW
(a)
(c)
(b)
(d)
Fig. 10 SEM image of carbon nanocoils generated by pyrolysis of melamine over Co-oxide substrates.
MWNTs produced by CVD, in particular, differs significantly from MWNTs generated by arc discharge (MWNTARC). For example, CVDgrown MWNTs (MWNTCVD) are usually less crystalline and exhibit many more defects than MWNTARC. Therefore, MWNTCVD are less straight than MWNTARC (Figs. 9c and d). In some instances, depending on the catalyst, spiral growth can be observed (Fig. 10) 64,68-70. CVD is probably the most versatile production method for CNTs, especially for generating doped CNTs, e.g. with B, N, or both19,54,63,64,68,71-76. MWNTCVD can reach a centimeter in length and usually possess larger diameters of up to 100 nm. The number of walls in MWNTCVD can vary from three to >100. MWNTCVD usually grow perpendicular to the substrate; therefore their length is relatively easy to measure (Figs. 8c and 11). The CNT and carbon-fiber communities are still debating at what diameter CNTs should still be called CNTs and from what diameter the structures are carbon nanofibers.
as ropes or bundles consisting of several individual SWNTs. Byproducts such as amorphous carbon or encapsulated metal catalyst particles are also present. The laser-ablation technique favors the growth of SWNTs; MWNTs are usually not generated with this method. The quality, length, diameter, and chirality distribution of the material are believed to be comparable with those of SWNTs grown by arc discharge.
Electrolysis
Electrolysis is a less common method for CNT production. To date, it is the only condensed phase method for generating CNTs, and was developed by Hsu et al. in 199577,78. MWNTs are formed when a current is passed through two graphite electrodes immersed in molten
32
REVIEW
using the information provided. Fig. 13 shows images of MWNT samples from the webpages of four different companies. While all four samples are sold as MWNTs, it is obvious that the morphology of the CNT material is very different. In addition, the micrographs are taken using different microscopy techniques, e.g. TEM and scanning electron microscopy (SEM), and at different magnifications. To illustrate that a single electron microscopy image is not enough for CNT characterization, I show TEM and SEM images of one sample labeled SWNTCVD at a range of magnifications (Figs. 14 and 15). At higher magnification, the TEM image depicts double- and tripleFig. 12 Typical TEM viewgraph of an electrolytically produced MWNT sample. (Adapted and reprinted with permission from78. 1995 Nature Publishing Group.)
walled nanotubes. Thus, the sample, although labeled SWNTCVD, is in fact a collection of SWNTs, DWNTs, MWNTs, metal catalyst particles, and soot, as can be seen clearly at lower magnification. SEM images taken at lower magnification reveal that the SWNTCVD material occurs as large agglomerates rather than individual nanotubes. Therefore, providing only a single micrograph at a given magnification
ionic salts, such as LiCl at 600C. After electrolysis, the carbonaceous material is extracted by dissolving the ionic salt in distilled water and separating the dispersion by filtration. The material produced contains MWNTs, carbon-encapsulated metal particles from the salt ions, amorphous carbon, and carbon filaments (Fig. 12)77. Adding less than 1 wt.% of other salts, such as SnCl2 or PbCl2, results in the formation of metal nanowires coated with amorphous carbon77,79,80. So far, only the generation of MWNTs (MWNTELE) has been reported. The formation of SWNTs via electrolysis has not been observed. MWNTELE possess diameters of 10-20 nm, consist of only a few walls, e.g. 10-15, and are estimated to be >500 nm long. MWNTELE occur predominantly in entangled bundles also containing amorphous carbon, spheroidal carbon particles, and metal-encapsulated particles. Several other production methods for CNTs have been reported. These processes are often based on earlier concepts and the number of publications constitutes a minor contribution to the literature. To summarize, the structure and properties of CNTs are highly sensitive to the production method and synthesis parameters such as temperature, reactor size, gas flow and pressure, precursors, etc. For example, MWNTARC are highly crystalline, have few defects, and are straight, whereas MWNTCVD are longer, exhibit larger diameters, are highly defective, and are not straight. Defects influence not only the electronic structure but also the mechanical properties81. This may help to understand why the Youngs modulus of MWNTCVD is orders of magnitude smaller than the Youngs modulus of MWNTARC (Table 1).
Fig. 13 Four randomly chosen images of different nanotube samples labeled MWNTs from supporting information provided by the supplier.
33
REVIEW
advanced significantly and the quality of catalytically grown CNTs has improved steadily so that large quantities of fairly clean CNTs can now be produced. However, structural control has yet to be achieved. One needs to be able to reproduce CNT material independent of the person carrying out the experiment and the specifics of the setup. This can only be achieved by understanding the growth of CNTs as a function of the precursor and catalyst materials, experimental parameters such as gas flow, pressure, and temperature, and production method. High-throughput synthesis using a combinatorial approach to catalyst selection88-90, in conjunction with structural characterization
Fig. 15 SEM images of a CNT sample taken at different magnifications. The sample was labelled as SWNTs by the supplier. At lower magnification it becomes apparent that the nanotube material occurs is large agglomerates rather than individual nanotubes.
of the catalyst particles and in situ electron microscopy studies91-97, are essential to create a better understanding of CNT growth. Although in situ investigations combined with density functional theory calculations have suggested that CNT growth catalyzed by Ni particles is a surface-diffusion-based process94,96, there is still a lack of consistent atomic-scale data98,99 on nanotube formation for other transition metals commonly used for nanotube growth. Furthermore, it is still unclear whether carbon dissolves and diffuses through the metal catalyst particle and then precipitates as a carbon filament, or whether carbon diffuses on the surface of the catalyst particle, or whether bulk and surface diffusion compete. Therefore, synergetic experimental-theoretical studies are essential for the clarification of growth mechanisms that currently are still based on models originally postulated for carbon fibers in the 1970s5,100. The findings of classical catalysis and metal corrosion studies ought to be revisited as a focus for current investigations. At the same time, unspecific descriptions of CNT samples need to be replaced by a standardized nomenclature. The abbreviation MWNT alone is insufficient to describe sample quality. Since there is a clear difference in CNT samples produced via different methods, the description ought to at least include the production method, e.g. MWNTARC for MWNTs grown by arc discharge, or MWNTCVD for those generated using CVD.
is insufficient to characterize the material. It is not possible to judge the quality of the commercial material discussed above from the information provided by the companies. Structural specifications are often descriptive rather than factual. Samples, for instance, are named split MWNTs, short MWNTs, long MWNTs, curly MWNTs, or similar. Furthermore, the information provided for different samples varies. Sometimes TEM, SEM, and Raman data is available, other samples are characterized by different techniques, such as atomic force microscopy, and BET surface area, or field-emission measurements. As a result of poor sample quality and lack of consistent characterization information, a number of labs have developed purification and separation techniques to obtain clean nanotube material and to select nanotubes of specific characteristics82,83. However, such purification methods often also remove large parts of the nanotubes themselves. For example, oxidation of MWNTs grown by arc discharge reduces the sample by 99%84. Other methods, such as acid treatment or surfactants may damage or functionalize the nanotube surface, and hence may also alter their properties85. Therefore, in order to be able to provide researchers with specific CNT material, one first has to characterize the samples carefully. A minimum characterization must include the electron microscopic analysis of material at different length scales including SEM, TEM, and analytical methods. The production method, including the catalyst employed, needs to be stated. From the micrographs, approximate CNT content, typical length and diameter, as well as distribution of length and diameter should be specified. For SWNTs, chirality distributions should be made available using optical spectroscopy methods86. Oxidation resistance data would provide information on the crystallinity of CNTs, e.g. the higher their oxidation resistance, the less defects are present. Therefore, a standardized characterization protocol is vital in order to compare samples objectively87.
Summary
The demand for uniform CNTs entails two major challenges that need to be overcome. One is the reproducibility of specific CNT material and the second is the transition from lab- to large-scale production. For this, it is indispensable to establish clear characterization patterns87 and a standard description of real CNT material.
Acknowledgments
I would like to thank the Royal Society for financial support.
REFERENCES
1. Hughes, T. V., and Chambers, C. R., US Patent 405480, (1889) 2. Schtzenberger P. S. L., C. R. Acad. Sci. (1890) 111, 774 3. Radushkevich, L. V., and Lukyanovich, V. M., Zurn. Fisc. Chim. (1952) 26, 88 4. Oberlin, A., et al., J. Cryst. Growth (1976) 32, 335
34
REVIEW
5. Hayashi, T., et al., Carbon (2006) 44, 1130 6. De Jong, K. P., and Geus, J. W., Catal. Rev. (2000) 42, 481 7. Brand, U. J., et al., Practical Metallography-Praktische Metallographie (1999) 36, 406 8. Zeng, Z., and Natesan, K., Chem. Mater. (2005) 17, 3794 9. Bernst, R., et al., Materials And Corrosion-Werkstoffe Und Korrosion (2006) 57, 724 10. Toh, C. H., et al., Materials At High Temperatures (2003) 20, 527 11. Iijima, S., Nature (1991) 354, 56 12. Krtschmer, W., et al., Nature (1990) 347, 354 13. Ando, Y., and Zhao, X. L., New Diamond Frontier Carbon Technol. (2006) 16, 123 14. Monthioux, M., and Kuznetsov, V. L., Carbon (2006) 44, 1621 15. Zhu, H. W., et al., Science (2002) 296, 884 16. Wang, H., et al., Appl. Phys. Lett. (2006) 88, 213111 17. Hamada, N., et al., Phys. Rev. Lett. (1992) 68, 1579 18. Tersoff, J., and Ruoff, R. S., Phys. Rev. Lett. (1994) 73, 676 19. Burch, H. J., et al., Appl. Phys. Lett. (2006) 89, 143110 20. Avouris, P., and Chen, J., Materials Today (2006) 9 (10), 46 21. Hoenlein, W., et al., Microelectron. Eng. (2006) 83, 619 22. Kreupl, F., et al., Microelectron. Eng. (2002) 64, 399 23. Khlobystov, A. N., et al., J. Mater. Chem. (2004) 14, 2852 24. Wongwiriyapan, W., et al., Nanotechnology (2006) 17, 4424 25. Kong, J., et al., Science (2000) 287, 622 26. Modi, A., et al., Nature (2003) 424, 171 27. Coleman, J. N., et al., Carbon (2006) 44, 1624 28. Thostenson, E. T., et al., J. Phys. D: Appl. Phys. (2005) 38, 3962 29. Poyato, R., et al., Nanotechnology (2006) 17, 1770 30. Kim, K. T., et al., Mater. Sci. Eng., A (2006) 430, 27 31. Harris, P. J. F., Int. Mater. Rev. (2004) 49, 31 32. Fahlman, B. D., Curr. Org. Chem. (2006) 10, 1021 33. Sato, H., and Hata, K., New Diamond Frontier Carbon Technol. (2006) 16, 163 34. Bell, M. S., et al., Carbon: The Future Material For Advanced Technology Applications, Messina, G., et al. (eds.), Springer-Verlag, Berlin (2006) 100, 77 35. Terranova, M. L., et al., Chemical Vapor Deposition (2006) 12, 315 36. Ebbesen, T. W., and Ajayan, P. M., Nature (1992) 358, 220 37. Journet, C., et al., Nature (1997) 388, 756 38. Blase, X., et al., Phys. Rev. Lett. (1999) 83, 5078 39. Li, L.-J., et al., Carbon (2006) 44, 2752 40. Wang, Z. Y., et al., Prog. Chem. (2006) 18, 563 41. Loiseau, A., and Willaime, F., Appl. Surf. Sci. (2000) 164, 227 42. Demoncy, N., et al., Eur. Phys. J. B (1998) 4, 147 43. Loiseau, A., and Pascard, H., Chem. Phys. Lett. (1996) 256, 246 44. Dillon, A. C., et al., Chem. Phys. Lett. (2000) 316, 13 45. Braidy, N., et al., Chem. Phys. Lett. (2002) 354, 88 46. Scott, C. D., et al., Appl. Phys. A (2001) 72, 573 47. Guo, T., et al., Chem. Phys. Lett. (1995) 243, 49 48. Endo, M., CHEMTECH (1988) 18, 568 49. Grobert, N., et al., Chem. Commun. (2001), 471 50. Nasibulin, A. G., et al., J. Nanoparticle Res. (2006) 8, 465 51. Ku, B. K., et al., Nanotechnology (2006) 17, 3613 52. Pinault, M., et al., Nano Lett. (2005) 5, 2394 53. Mayne, M., et al., Chem. Phys. Lett. (2001) 338, 101 54. Reyes-Reyes, M., et al., Chem. Phys. Lett. (2004) 396, 167 55. Kamalakaran, R., et al., Carbon (2003) 41, 2737 56. Kondo, D., et al., Chem. Phys. Lett. (2006) 422, 481 57. Zhong, G. F., et al., Jpn. J. Appl. Phys. (2005) 44, 1558 58. Kiselev, N. A., et al., Carbon (2006) 44, 2289
59. Flahaut, E., Chem. Commun. (2003), 1442 60. Park, D., et al., Carbon (2003) 41, 1025 61. Kuang, M. H., et al., Appl. Phys. Lett. (2000) 76, 1255 62. Sunden, E., et al., J. Vac. Sci. Technol., B (2006) 24, 1947 63. Terrones, M., et al., Nature (1997) 388, 52 64. Grobert, N., et al., Appl. Phys. A (2000) 70, 175 65. Chen, M. Y., et al., J. Electrochem. Soc. (2006) 153, C747 66. Kim, H. S., et al., On The Convergence Of Bio-Information-, Environmental-, Energy-, Space- And Nano-Technologies, Pts 1 & 2 (2005) 277-279, 950 67. Kim, J., et al., J. Appl. Phys. (2001) 90, 2591 68. Grobert, N., DPhil Thesis, University of Sussex, UK, (2000) 69. Amelinckx, S., et al., Science (1994) 265, 635 70. Lau, K. T., et al., Compos. B - Eng. (2006) 37, 437 71. Wang, W. L., et al., J. Am. Chem. Soc. (2006) 128, 6530 72. Ewels, C. P., and Glerup, M., J. Nanosci. Nanotechnol. (2005) 5, 1345 73. Lozano-Castell, D., et al., Carbon (2004) 42, 2223 74. Terrones, M., et al., Carbon (2002) 40, 1665 75. Trasobares, S., et al., J. Chem. Phys. (2002) 116, 8966 76. Trasobares, S., et al., Eur. Phys. J. B (2001) 22, 117 77. Hsu, W. K., et al., Chem. Phys. Lett. (1996) 262, 161 78. Hsu, W. K., et al., Nature (1995) 377, 687 79. Hsu, W. K., et al., Chem. Mater. (1999) 11, 1747 80. Hsu, W. K., et al., Chem. Phys. Lett. (1999) 301, 159 81. Yu, M.-F. J. Eng. Mater. Technol. (2004) 126, 271 82. Bonard, J.-M., et al., Adv. Mater. (1997) 9, 827 83. Liu, X. M., et al., Curr. Appl. Phys. (2006) 6, 427 84. Ebbesen, T. W., et al., Nature (1994) 367, 519 85. Banerjee, S., and Wong, S. S., J. Phys. Chem. B (2002) 106, 12144 86. Bachilo, S. M., et al., Science (2002) 298, 2361 87. Grobert, N., et al., (2006), in preparation 88. Noda, S., et al., Carbon (2006) 44, 1414 89. Noda, S., et al., Appl. Phys. Lett. (2005) 86, 173106 90. Kakehi, K., et al., Chem. Phys. Lett. (2006) 428, 381 91. Sharma, R., and Iqbal, Z., Appl. Phys. Lett. (2004) 84, 990 92. Hansen, P. L., et al., Adv. Catal. (2006) 50, 77 93. Sehested, J., et al., Appl. Catal., A (2006) 309, 237 94. Abild-Pedersen, F., et al., Phys. Rev. B (2006) 73, 115419 95. Helveg, S., and Hansen, P. L., Catalysis Today (2006) 111, 68 96. Helveg, S., et al., Nature (2004) 427, 426 97. Sharma, R., J. Mater. Res. (2005) 20, 1695 98. Raty, J.-Y., et al., Phys. Rev. Lett. (2005) 95, 096103 99. Amara, H., et al., Phys. Rev. B (2006) 73, 113404 100. Dresselhaus, M. S., et al., Graphite Fibers and Filaments. Springer-Verlag, Berlin (1988) 5 101. Terrones, M., et al., Nanotubes: A revolution in materials science and electronics. In Fullerenes And Related Structures, Hirsch, A (ed.), Springer-Verlag, Berlin (1999) 199, 189 102. Treacy, M. M. J., et al., Nature (1996) 381, 678 103. Krishnan, A., et al., Phys. Rev. B (1998) 58, 14013 104. Wong, E. W., et al., Science (1997) 277, 1971 105. Salvetat, J.-P., et al., Appl. Phys. A (1999) 69, 255 106. Salvetat, J.-P., et al., Adv. Mater. (1999) 11, 161 107. Yu, M.-F., et al., Science (2000) 287, 637 108. Demczyk, B. G., et al., Mater. Sci. Eng., A (2002) 334, 173 109. Bacon, R., J. Appl. Phys. (1960) 31, 283 110. Edie, D. D., McHugh, J. J., In Carbon materials for Advanced Technologies, Burchill, T., (ed.), Pergammon, Amsterdam, (1999), 134
35