Review
Carbon fibers for composites
S. CHAND
Textile, Retail and Consumer Science, The University of Tennessee, Knoxville, USA
E-mail: subhash− chand@webtv.net
An attempt has been made to review and analyze the developments made during last few
decades in the field of high performance carbon fibers. The focus is primarily on high
technology sector, which includes aerospace and nuclear engineering or other areas, where
the large scale use of carbon fibers is driven by maximum performance and not by cost
factors. We have identified and suggested some specific areas for future research in order
to minimize the gap between theoretical and practically realized tensile strengths and other
mechanical properties of carbon fibers. ° C 2000 Kluwer Academic Publishers
been drastically reduced from hours to minutes dur- tion with SO2 instead of oxygen or air, and observed that
ing last two decades. However, the decomposition of considerable amounts of sulfur are incorporated into the
PAN during carbon fiber preparation cab be shown fiber chemical structure, as bridges between the adja-
schematically as in Fig. 1 [2]. Grassie and McGuchan cent molecular chains, producing a rigid structure. Thus
[44] observed that stabilization reaction can be initi- it has been observed that by combining low-temperature
ated by the presence of electrophilic groups, such as and high-temperature treatment with SO2 , fibers with
acids, in comonomer. Inclusion of comonomers espe- more cross-linking and a higher initial carbon content
cially methacrylic acid, itaconic acid, and acrylamide can be obtained, which gives rise to carbon fibers with
into the PAN polymer chain enhanced the rate of degra- better mechanical properties. Incorporation of certain
dation. The rate of degradation in the presence of vinyl additives, such as aminosiloxane [55] or cuprous chlo-
acetate comonomer, although significantly faster than ride [56, 57], into PAN fibers to catalyze the cyclization
that of PAN homopolymer, was much slower than in the process has been reported [37]. Different temperature
case of mathacrylic acid and acrylamide [45–47]. These profiles have also been suggested for faster stabiliza-
comonomeric initiators also serve to lower the temper- tion [58]. However, Fitzer and Muller [42] suggested
ature required for stabilization. Lower temperatures re- that different fibers have different optimum stabiliza-
sult in reduced entropic relaxation of the molecules, tion parameters. Finer fibers are considered more suit-
which translates to improved tensile properties of the able for stabilization [2].
final carbon fibers [48]. When PAN is heated in oxidiz- Generally, carbonization is done above 1200 ◦ C in
ing atmosphere, the rate of cyclization is faster and the an inert atmosphere. A nitrogen environment is gen-
final carbon product is produced in better yield and with erally used up to 2000 ◦ C and argon is used as inert
improved mechanical properties. The use of oxidizing medium above this temperature because carbon reacts
agents has also been suggested for the stabilization pro- with nitrogen at this temperature to form cyanogen [48].
cesses [49–52], but does not seem to be in industrial use. The carbon fiber yield can be enhanced by carboniz-
Raskovic and Marinkovic [53], and Raskovic et al. [54] ing oxidized PAN fibers in an atmosphere of HCl va-
investigated the stabilization of PAN fibers by oxida- pors [59]. Carbonization in HCl vapors decreases the
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amount of HCN by eliminating nitrogen as ammonia. of carbon fibers from rayon fibers is usualy very low,
It also has a marked dehydrating action and eliminates varying between 10 and 30%. A slow rate of heating
oxygen as water vapor. Consequently, carbon yield in- results in a higher yield but is less economical. The car-
creases. There is an increase in the tensile modulus and bon fiber yield and the processing rate can be markedly
strength with carbonization temperature. It has been improved by carrying out the low-temperature pyroly-
observed that the strength values peak at carbonization sis of rayon in presence of reactive atmosphere, such
temperatures of ∼ =1700 ◦ C, whereas modulus contin- as air or oxygen [64–66], chlorine [67–69], and HCl
ues to rise with carbonization/graphitization temper- valor [70, 71]. The presence of a reactive atmosphere
ature. It has been felt that increased tension exposure promotes dehydration of cellulose and inhibits the for-
during graphitization generally yields fibers with better mation of tars [69, 70]. It has also been found that the
mechanical properties using any PAN precursor mate- decomposition of cellulose in the presence of flame-
rial [60]. However, this approach has significant process retardants occurs at lower temperature, at faster rate,
implications and is generally avoided. An optimum ten- and carbon yield is larger [72]. Rayon fibers are im-
sion during stabilization also leads to improvement in pregnated with flame-retardant substance from aqueous
mechanical properties of the final fibers [61–63]. solution before heat treatment. Impregnation leads to
The reactions involved in the conversion of cellulose more uniform and faster stabilization due to absence of
into carbon fibers are shown in Fig. 2 [2]. The yield diffusion related problems. The carbonization of rayon
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fibers is done usually in an inert atmosphere, although plane of aromatic rings, the carbon atoms are placed
the use of reactive atmosphere has been suggested in on a hexagonal lattice, but the corresponding atoms
the literature [70, 71]. Application of tension during on an adjacent plane may be translated by an arbi-
carbonization and graphitization improves mechanical trary displacement. Hence carbon fibers generally have
properties of the final carbon fibers [73]. only two-dimensional order referred to as ‘turbostratic’
Mesophase pitches are thermoplastic and are ren- structure [48]. Inter-plane spacing in carbon fibers,
dered infusible by a suitable oxidation treatment. As processed even at higher temperatures, is significantly
these pitches have higher softening points, the oxida- higher than that of perfect graphite. However, many
tion treatment can be carried out at a higher tempera- researchers [6, 92–94] have reported evidence of three-
ture, where diffusion and oxidation processes are faster. dimensional order in certain carbon fibers. Kumar et al.
The oxidation is generally carried out in between 250 [6] have reported that most of PAN based carbon fibers
and 300 ◦ C in electrically heated oven for about 40 min- have particulate morphology, whereas pitch based car-
utes [2]. The stabilized mesophase pitch fibers are ready bon fibers have sheet-like morphology. They also re-
for carbonization and graphitization processes at any ported that a sheet-like morphology does not necessar-
temperature, without need of high-temperature stretch- ily imply a three-dimensional order and, on the other
ing. Increasing the final heat treatment temperature re- hand, a fiber with particulate morphology can display
sults in better mechanical properties of resulting carbon three-dimensional order. Rayon based fibers show par-
fibers [2]. ticulate morphology and may have three-dimensional
Carbon fibers when used without surface treat- order. Typical scanning electron micrographs of PAN-
ment produce composites with low interlaminar shear based, pitch-based, and rayon-based carbon fibers are
strength (ILSS). This has been attributed to weak ad- shown in Figs 3–5 [6], respectively. It has been ob-
hesion and poor bonding between the fiber and ma- served that extensive graphitized small areas do exist
trix [2]. All the carbon fibers are thus given a surface even in those fibers which had never been exposed to
treatment, the exact nature of which is a trade secret. temperatures beyond 1100 ◦ C [2]. Preferential orienta-
These treatments increase the surface area and surface tion of graphitic sheets in fiber axial direction increases
acidic functional groups and thus improve bonding be- with heat treatment temperature. Orientation and size of
tween the fiber and the resin matrix [74–79]. This tends these sheets is greater on the surface than in the interior
to increase the wettability of the carbon fiber and en- of a carbon fiber [2, 6]. Modulus of the fibers increases
hances the ILSS. Surface treatments may be classified with increase in orientation [2]. Carbon fibers are sup-
into oxidative and non-oxidative treatments. Oxidation posed to have up to 20% voids elongated in fiber axial
treatments involve gas-phase oxidation, liquid-phase direction [48]. There is a transition from many small
oxidation carried out chemically [80] or electrochem- pores to fewer larger pores as heat treatment tempera-
ically [81], and catalytic oxidation. The non-oxidative ture is increased [2].
treatments involve deposition of more active forms of PAN based carbon fibers have higher tensile and
carbon, such as the highly effective whiskerization, the compressive strength than pitch based carbon fibers,
deposition of pyrolytic carbon [82, 83], or the grafting because PAN based fibers have particle-like structure
of the polymers on the carbon fiber surface [84]. Carbon and smaller crystals as compared to sheet-like structure
fibers can also be plasma treated to improve bonding be- and larger crystals in pitch based fibers [5, 95–98]. The
tween the fiber and matrix. Liquid phase oxidation treat- cross-sectional structure of carbon fibers also plays an
ments are milder, very effective and are preferred [2]. important role in determining compressive properties of
Although whiskerization treatment gives excellent re- carbon fibers. Endo [99] and Hayes et al. [95] studied
sults, it is not commercially used because it is expensive compressive behavior of two different pitch-based car-
and difficult to carry out precisely. It also needs to be bon fibers and proposed that fibers with a folded-radial
understood that many times a weak interface is desired texture show higher compressive strength than fibers
between fiber and a brittle matrix to improve toughness with flat-layer structure. The two structures have been
of the composite [84]. A weak and elastic interface pro- reproduced in Fig. 6 [95]. Knibbs [100] identified three
vides better crack resistance [85, 87]. Though, a strong different types of structures for PAN carbon fibers pre-
interface between fiber and a ductile matrix results in pared under different processing conditions. The three
improvement in tensile strength, compressive strength, structures are schematically represented in Fig. 7 [2].
and yield strength of the composite [80, 88–90]. Zhu Transverse structure of the final carbon fibers depends
et al. [85] overcame this limitation of interface by using very much upon the type of spinning process used, tem-
bone-shaped fibers with enlarged ends in conjunction perature of spinning, the shape of spinneret, the use of
with weak interface, in short fiber composites. stirrer and its shape [2, 101]. However, the structure is
independent of heat treatment temperature [2].
It has been found that compressive strength increase
2.4. Fiber morphology and mechanical with decrease in crystallite size, orientation, density,
properties and with increase in inter-planar spacing and void con-
Perfect graphite has three-dimensional periodicity and tent [102–105]. Crystal anisotropy, as measured by
belongs to the hexagonal crystal system. However, L c L b /L a , where L a , L b , L c are crystal sizes parallel to
Johnson [91] reported that face centered cubic sequence fiber axis in graphitic plane, perpendicular to fiber axis
is also observed. In carbon fibers, within each basal in graphitic plane, and perpendicular to graphitic plane,
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Figure 3 Scanning electron micrographs of PAN-based carbon fibers [6]: (a) low and (b) high magnification.
Figure 4 Scanning electron micrographs of pitch-based carbon fibers [6]: (a) low and (b) high magnification.
respectively, provides the best correlation so far with creased [107]. Compressive strength is considered to be
carbon fiber compressive strength [6]. Compressive well related to shear modulus between the basal planes
strength of the fibers has been found to decrease with [97, 98]. Surface and sizing treatments are usually nec-
increase in modulus for both pitch and PAN based fibers essary to realize higher compressive strengths in carbon
[6, 95]. Though, up to a carbonization temperature of fiber composites [108, 109]. However, it has been ob-
1500 ◦ C, compressive strength, tensile strength, and served that surface and sizing treatments are more effec-
tensile modulus show similar tendency [106]. For both tive in tension than in compression, whereas the effect
pitch and PAN based fibers, the same modulus fibers can of fiber morphology is more prominent in compression
have different compressive strengths [6]. For a given than in tension [110, 111]. Miwa et al. [112] studied
modulus compressive strength may be improved if de- the effect of fiber diameter on compressive strength of
sired orientation may be achieved along with smaller the fibers and reported that compressive strength in-
crystal size. High-modulus fibers fail in shear mode creases with decreasing diameter but remains almost
while low-modulus fibers fail in buckling mode [6, 95]. unchanged at a diameter range smaller than 10 µm. This
With boron-ion implantation, the carbon fiber compres- improvement may be due to statistically less number of
sive strength and torsional modulus increased by up to flaws and more uniform structure in smaller diameter
25% and 50%, respectively, while the crystal size de- fibers [87].
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Figure 5 Scanning electron micrographs of rayon-based carbon fibers [6]: (a) low and (b) high magnification.
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4. Precursor molecules should have high degree of 22. Idem., Am. Chem. Soc. Div. Org. Coat. Plast. Chem. Prepr. 31
order, orientation and flatness [149, 150]. (1971) 415.
23. Monsanto Co., US Patent no. 3549307 (Dec. 22, 1970).
5. Simple release of non-carbon atoms and easy cy-
24. Celanese Corp., US Patent no. 3547584 (Dec. 15, 1970).
clization [48, 149]; e.g., nitrogen and oxygen atoms 25. J . E C O N O M Y and R . Y . L I N , Appl. Polym. Symp. 29 (1976)
should be a part of side groups rather than of main 199.
chain. 26. H . M . E Z E K I E L and R . G . S P A I N , J. Polym. Sci. 19C (1967)
6. Precursor should have a high molecular weight 249.
27. R . G . B O U R D E A U and F . S . G A L A S S O , Am. Ceram. Soc.
[33].
Bull. 55 (1976) 785.
28. G . S . B H A T and R . S C H W A N K E , J. Thermal Anal. 49 (1997)
It has been emphasized that any significant improve- 399.
ment is most likely to be led by synthesis of new precur- 29. J . M . A U G L , AD Report 780430/5 GA, 1974, p. 37.
30. US Patent no. 3635675 (Jan. 18, 1972).
sor materials that can cause increase in lateral –C–C– 31. ICI Ltd., British Patent no. 1283714 (Aug. 2, 1972).
bonding sequences while maintaining a high axial ori- 32. E . A . B O U C H E R , R . N . C O O P E R and D . H . E V E R E T T ,
entational order in the carbon fibers [151]. Carbon 8 (1970) 597.
33. G . M . J E N K I N S and K . K A W A M U R A , “Polymeric Carbons”
(Cambridge University Press, London, 1976) p. 11.
34. German Patent no. 1246510 (Aug. 3, 1967).
4. Concluding remarks 35. S . N A T E S A N and G . S . B H A T , in Extended Abstracts of 23rd
A considerable progress has been made in the past in Biennial Conference on Carbon (American Carbon Society, 1997)
establishing the fundamental material-process interac- p. 422.
36. R . B . M A T H U R , O . P . B A H L , V . K . M A T T A and K . C .
tions in the field of high performance carbon fibers. N A G P A L , in Proceedings of Seminar on Carbon Fibers and Their
However, a significant degree of discrepancy still ex- Applications (Indian Carbon Society, 1986) p. 57.
ists especially with regard to tensile and compressive 37. W . W A T T , in Proceedings of 3rd Conference on Industrial Car-
strengths of carbon fibers. There is need of a different bons and Graphite (Society of Chemical Industry, London, 1971)
and more comprehensive approach for the development p. 471.
38. W . G . H A R L A N D , M . W . K I N G and L . N . P H I L L I P S ,
of carbon fibers used in high technology sector. Based British Patent no. 1431883 (1976).
upon our current knowledge of the process and related 39. O . P . B A H L , R . B . M A T H U R and T . L . D H A M I ,
topics, suggestions made in the paper for future research J. Mater. Sci. Eng. 13 (1985) 105.
seem to be very much plausible. Therefore, integrated 40. K . H . C U P P and D . E . S T U E Z , US Patent no. 3592595 (1971).
efforts may be made in these and other possible direc- 41. R . M O R E T O N , in Proceedings of 3rd Conference on Industrial
Carbon and Graphite (Society of Chemical Industry, London, 1971)
tions in order to reduce the existing gap between the- p. 472.
oretical and practically realized tensile strengths, and 42. E . F I T Z E R and T . M U L L E R , in Extended Abstracts of 15th
also improve compressive behavior of carbon fibers. Biennial Conference on Carbon (Philadelphia, 1981) p. 312.
43. R . M O R E T O N , “Carbon Fibers—Their Composites and Appli-
cations” (The Plastics Institute, London, 1971) paper 12.
44. N . G R A S S I E and R . M cG U C H A N , Eur. Polymer J. 8 (1972)
References 257.
1. W . S . S M I T H , “Engineered Materials Handbook-Vol. 1” (ASM 45. G . T . S I V Y and M . M . C O L E M A N , Carbon 19 (1981) 127.
International, Ohio, 1987) p. 49. 46. M . M . C O L E M A N and G . T . S I V Y , ibid. 19 (1981) 133.
2. J . B . D O N N E T and R . C . B A N S A L , “Carbon Fibers” (Marcel 47. G . T . S I V Y and M . M . C O L E M A N , ibid. 19 (1981) 137.
Dekker, Inc., New York, 1990). 48. S . D A M O D A R A N , P . D E S A I and A . S . A B H I R A M A N ,
3. National Materials Advisory Board: Committee Report, “High Per- J. Text. Inst. 81 (1990) 384.
formance Synthetic Fibers for Composites” (National Academy 49. O . P . B A H L and L . M . M A N O C H A , Angew. Makromol.
Press, Washington, D.C., 1992) p. 54. Chem. 48 (1975) 145.
4. T . O H S A W A , M . M I W A and M . K A W A D E , J. Appl. Polym. 50. L . M . M A N O C H A , O . P . B A H L and G . C . J A I N , ibid. 67
Sci. 39 (1990) 1733. (1975) 11.
5. H . S H I N O H A R A , T . S A T O and F . S A I T O , J. Mater. Sci. 28 51. O . P . B A H L and L . M . M A N O C H A , Fiber Sci. Tech. 9
(1993) 6611. (1976) 77.
6. S . K U M A R , D . P . A N D E R S O N and A . S . C R A S T O , ibid. 52. Idem., Carbon 13 (1975) 297.
28 (1993) 423. 53. V . R A S K O V I C and S . M A R I N K O V I C , ibid. 16 (1978) 351.
7. M . A . S T E I N B E R G , Scientific American 255 (1986) 67. 54. V . R A S K O V I C , I . D E Z A R O V and S . M A R I N K O V I C ,
8. T . E D I S O N , US Patent no. 223898 (Jan. 1880). in Proceedings of 2nd International Carbon Conference (Baden-
9. R . B A C O N and M . M . T A N G , Carbon 2 (1964) 211. Baden, 1976) p. 121.
10. Idem., ibid. 2 (1964) 220. 55. Japan Exlan Co. Ltd., British Patent no. 1499085 (1978).
11. E . F I T Z E R , ibid. 27 (1989) 621. 56. J . P . R I G G S , US Patent no. 3656882 (1972).
12. J . E C O N O M Y and L . W O H R E R , in Proceedings of 2nd Shirley 57. J . B . R O B I N , US Patent no. 3416874 (1968).
International Seminar (Shirley Institute, Manchester, England, 58. Great Lakes Carbon Corp., US Patent no. 4279612 (1981).
Sept. 1970). 59. S H I N D O , “Carbon Fibers—Their Composites and Applications”
13. R . Y . L I N and J . E C O N O M Y , Am. Chem. Soc. Div. Org. Coat. (The Plastics Institute, London, 1971) p. 18.
Plast. Chem. Prepr. 31 (1971) 403. 60. D . J . O ’N E I L , J. Polymer. Mater. 7 (1979) 203.
14. K . K A W A M U R A and G . M . J E N K I N S , J. Mater. Sci. 7 (1972) 61. T . I S H I K A W A , R . M A K I and M . M O R I S H I T A , in Proceed-
1099. ings of 161st National Meeting (American Chemical Society, Los
15. British Patent no. 1228910 (April 21, 1971). Angeles, 1971) p. 400.
16. US Patent no. 3856593 (Oct. 24, 1974). 62. J . W . J O H N S O N and W . W A T T , Appl. Polym. Symp. 9
17. US Patent no. 3903220 (Sept. 2, 1975). (1969) 215.
18. British Patent no. 1406378 (Sept. 17, 1975). 63. W . W A T T and J . W . J O H N S O N , in Proceedings of 3rd Con-
19. German Patent no. 2315144 (Oct. 11, 1973). ference on Industrial Carbons and Graphite (Society of Chemical
20. British Patent no. 1274963 (May 17, 1973). Industry, London, 1971) p. 417.
21. H . M . E Z E K I E L , Appl. Polym. Symp. 9 (1969) 315. 64. S . L . S T R O N G , Am. Chem. Soc. Div. Org. Coat. Plast. Chem.
1311
Prepr. 31 (1971) 426. H . S U N A G O , ibid. 28 (1993) 1611.
65. R . B A C O N , W . A . S C H A L A M A N and S . L . S T R O N G , 97. M . G . N O R T H O L T , L . H . V E L D H U I Z E N and H .
Unpublished Technical Report (1959) in “Chemistry and Physics J A N S E N , in Proceedings of 20th Biennial Conference on Car-
of Carbon Vol. 9,” edited by Jr. P. L. Walker and P. L. Thrower bon (American Carbon Society, 1991) p. 222.
(Marcel Dekker, New York, 1973) p. 12. 98. V . R . M E H T A and S . K U M A R , J. Mater. Sci. 29 (1994) 3658.
66. R . B A C O N , W . A . S C H A L A M A N and S . L . S T R O N G , 99. M . E N D O , ibid. 23 (1988) 853.
Unpublished Technical Report (1968) in “Chemistry and Physics 100. R . H . K N I B B S , J. Microsc. 94 (1971) 273.
of Carbon Vol. 9,” edited by Jr. P. L. Walker and P. L. Thrower 101. M. S. DRESSELHAUS, G. DRESSELHAUS, K.
(Marcel Dekker, New York, 1973) p. 12. S U G I H A R A , I . L . S P A I N and H . A . G O L D B E R G ,
67. J . V . D U F F Y , J. Appl. Polym. Sci. 15 (1971) 715. “Graphite Fibers and Filaments” (Springer-Verlag, Berlin, 1988)
68. S . L . M A D R O S K Y , V . E . H A R T and S . J . S T R A U S S , p. 12.
J. Res. Natl. Bur. Stand. 56 (1956) 343. 102. S . K U M A R , W . W . A D A M S and T . E . H E L M I N I A K ,
69. R . O . M A Y E R , D . R . E C K E R and W . J . S P R Y , US Patent J. Reinf. Plast. 7 (1988) 108.
no. 3333926 (1967). 103. S . K U M A R and T . E . H E L M I N I A K , in “The Materials Sci-
70. S H I N D O , Y . N A K A N I S H I and I . S E M A , Appl. Polym. Symp. ence and Engineering of Rigid Rod Polymers, Vol. 134,” edited
9 (1969) 271. by W. W. Adams, R. K. Eby and D. E. McLemore (MRS, Pitts-
71. S H I N D O , US Patent no. 3529934 (1970). burgh, 1989) Materials Research Society Symposium Proceedings,
72. W . A . R E E V E S , R . M . D E R K I N S , B . P I C C O L O and p. 363.
G . L . D R A K E , Text. Res. J. 40 (1970) 223. 104. A . C R A S T O and D . P . A N D E R S O N , Proc. Amer. Soc. Comp.
73. R . B A C O N , in “Chemistry and Physics of Carbon Vol. 9,” edited 5 (1990) 809.
by Jr. P. L. Walker and P. L. Thrower (Marcel Dekker, New York, 105. D . P . A N D E R S O N and S . K U M A R , in Proceedings of Annual
1973) p. 1. Technical Conference (Society of Plastics Engineers, May 1990)
74. L . W E I T Z S A C K E R and L . T . D R Z A L , in Proceedings of p. 1248.
ANTEC’96 (Society of Plastics Engineers, Brookfield, CT, 1996) 106. J. HAO, S. DAMODARAN, A. S. ABHIRAMAN,
p. 3656. P . D E S A I and S . K U M A R , in Proceedings of Materials Re-
75. M . S H E R W O O D , J. Electron Spectroscopy and Related Phe- search Society Symposium (MRS, Pittsburgh, 1993) p. 135.
nomena 81 (Sept. 1996) 319. 107. Y. MATSUHISA, M. WASHIYAMA, T. HIRAMATSU,
76. L . W E I T Z S A C K E R , X . M I N G and L . T . D R Z A L , Surface H . F U J I N A and G . K A T A G I R I , in Proceedings of 20th Bi-
and Interface Analysis 25 (Feb. 1997) 53. ennial Conference on Carbon (American Carbon Society, 1991)
77. H . J . J A C O B A S C H , K . G R U N D K E , P . U H L M A N N , F . p. 226.
S I M O N and E . M A E D E R , Composite Interfaces 3 (1996) 293. 108. M . M I W A , A . T A K E N O , Y . M O R I , T . Y O K O I and
78. R . C . B A N S A L and P . C H H A B R A , Indian J. Chem. 20A A . W A T A N A B E , J. Mater. Sci. 31 (1996) p. 2957.
(1981) 449. 109. W . G W O M E I , Polymer J. 29 (1997) 705.
79. E . F I T Z E R and R . W E I S S , in Intern. Symp. Society of Plastics 110. M . M I W A . Y . M O R I and A . T A K E N O , ibid. 33 (1998) 2013.
Engineers, University of Leige, 1983. 111. N. S. BROYLES, K. N. E. VERGHESE, R. M. DAVIS,
80. L . I B A R R A , A . M A C I A S and E . P A L M A , J. Appl. Polym. J . J . L E S K O and J . S . R I F F L E , in Proceedings of ANTEC’98
Sci. 61 (1996) 2447. (Society of Plastics Engineers, Brookfield, CT, 1998) p. 2240.
81. M . D E L A M A R , G . D E S A R M O T , O . F A G E B A U M E , 112. M . M I W A , Y . L I U , H . T S U Z U K I , A . T A K E N O and
R . H I T M I , J . P I N S O N and J . M . S A V E A N T , Carbon 35 A . W A T A N A B E , J. Mater. Sci. 31 (1996) 499.
(1997) 801. 113. G . A . C O O P E R and R . M . M A Y E R , ibid. 6 (1971) 60.
82. Z . K U N , W . Y U K I N G and Z . B E N L I A N , in Transactions of 114. W . S . W I L L I A M S , D . A . S T E F F E N S and R . B A C O N ,
Nonferrous Metals Society of China-English Edition, 1997, Vol. J. Appl. Phys. 41 (1970) 4893.
7, No. 3, p. 86. 115. M . S T E W A R T and M . F E U G H E L M A N , J. Mater. Sci. 8 (1973)
83. H I R O S H I , N . T E T S U J I , S . H I R O S H I , A . F U J I O and 1119.
O . M A S A T O S H I , J. Nuclear Sci. Tech. 32 (1995) 369. 116. R . A . C O Y L E , L . M . G I L L I N and B . J . W I C K S , Nature
84. Z . A N N A , W . X U Q I N and L . S H I J I N , J. East China Univ. 226 (1970) 257.
Sci. Tech. 20 (1994) 485. 117. C . N . T Y S O N , J. Phys. D.: Appl. Phys. 8 (1975) 749.
85. Y . T . Z H U , J . A . V A L D E Z , N . S H I , M . L . L A V A T O , 118. H . K . B O W A N , Scientific American 255 (Oct. 1986) 169.
M . G . S T O U T , S . J . Z H O U , W . R . B L U M E N T H A L and 119. J . W . J O H N S O N , Appl. Polym. Symp. 9 (1969) 229.
T . C . L O W E , in Proceedings of International Symposium on 120. J . W . J O H N S O N and D . J . T H O R N E , Carbon 7 (1969) 659.
Processing of Metals and Advanced Materials (Minerals, Metals 121. E . F I T Z E R , K . G E I G L and L . M A N O C H A , in Proceedings of
& Materials Society, San Antonio, Texas, 1998) p. 251. 5th International Conference on Industrial Carbons and Graphite
86. S . H . J A O and F . J . M cG A R R Y , in Proceedings of 22nd In- (Society of Chemical Industry, London, 1978) p. 405.
ternational SAMPE Technical Conference (SAMPE, Covina, CA, 122. P . E H R B U R G E R , J . J . H E R Q U E and J . B . D O N N E T , in
1990) p. 455. Proceedings of ACS Symposium on Petroleum Derived Carbons
87. T . W . C H O U , R . L . M cC U L L O U G H and R . B . P I P E S , (American Chemical Society, Washington, D.C., 1975) p. 324.
Scientific American 255 (Oct. 1986) 193. 123. S . A L L E N , G . C O O P E R and R . M A Y E R , Nature 224 (1969)
88. S . H . G A R D N E R , R . M . D A V I S and K . L . R E I F S N I D E R , 684.
in Proceedings of ANTEC’98 (Society of Plastics Engineers, 124. B . F . J O N E S and I . D . P E G G S , ibid. 239 (1972) 95.
Brookfield, CT, 1998) p. 1546. 125. J . W . S . H E A R L E and R . G R E E R , Textile Progress 2 (1970) 1.
89. Y . K A T S U T O S H I , S . S Y O U I C H I , H . T O S H I H I R O and 126. K . H I S A T A N I , K . O K A J I M A and K . K A M I D E , Polymer J.
I . T O H R U , J. Japan Inst. Metals 59 (1995) p. 1108. 28 (1996) 99.
90. B . D . A G A R W A L and L . J . B R O U T M A N , “Analysis and 127. P . J . G O O D H E W , A . J . C L A R K E and J . E . B A I L E Y ,
Performance of Fiber Composites” (John Wiley & Sons, Inc., New J. Materials Sci. Eng. 17 (1975) 3.
York, 1990) p. 319. 128. M . M I N A G A W A , K . M I Y A N O and T . M O R I T A , Macro-
91. W . J O H N S O N , “Strong Fibers” (Elsevier, Amsterdam, 1985) molecules 22 (1989) 2054.
p. 389. 129. Y . I N O U E and A . N I S H I O K A , Polymer J. 3 (1972) 149.
92. A . F O U R D E U X , R . P E R R E T and W . R U L A N D , J. Appl. 130. K . M A T S U Z A K I , T . U R Y U , M . O K A D A and H . S H I R O K I ,
Cryst. (1968) 252. J. Polym. Sci. 6 (1968) 1475.
93. B . J . W I C K S and R . A . C O Y L E , J. Mater. Sci. 11 (1976) 376. 131. K . K A M I D E , H . O N O and K . H I S A T A N I , Polymer J. 24
94. W . K O W B E L , E . H I P P O and N . M U R D I C , Carbon 27 (1989) (1992) 917.
219. 132. H . O N O , K . H I S A T A N I and K . K A M I D E , ibid. 25 (1993)
95. G . J . H A Y E S , D . D . E D I E and J . M . K E N N E D Y , 245.
J. Mater. Sci. 28 (1993) 3247. 133. Y . N A K A N O , K . H I S A T A N I and K . K A M I D E , Polym. Int.
96. M . F U R U Y A M A , M . H I G U C H I , K . K U B O M U R A and 34 (1994) 397.
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134. Idem., ibid. 35 (1994) 207. 144. D . C . P R E V O R S E K and H . B . C H I N , in Proceedings of 24th
135. Idem., ibid. 35 (1994) 249. SAPME Technical Conference (Toronto, Canada, 1992) p. 307.
136. H . O N O and K . H I S A T A N I , Asahi Chemical Co., Ltd., 145. H . K . B E R N A R D , Scientific American 255 (1986) 158.
Japanese Patent no. 03068607 A2 910325. 146. B . G . F R U S H O U R and R . S . K N O R R , “Handbook of Fiber
137. G . M . J E N K I N S , “Chemistry and Physics of Carbon Fibers, Chemistry” (Marcel Dekker, Inc., New York, 1998) p. 870.
Vol. 11” (1973) p. 189. 147. J . E . S H E L B Y , “Handbook of Gas Diffusion in Solids and
138. F . P . B U N D Y , H . M . S T R O N G and R . H . W E N T D O R F , Melts” (ASM International, Ohio, 1996) p. 133.
“Chemistry and Physics of Carbon Fibers, Vol. 10” (1972) p. 213. 148. H . T O S H I M A , T . N A I T O , T . H I N O and K . M U R A K A M I ,
139. I . A . S . E D W A R D S , “Introduction to Carbon Science” (But- Tonen Corp., US Patent no. 5395607 (March 1995).
terworth & Co. Ltd., London, 1989) p. 4. 149. M . I N A G A K I , K . I . S A K A M O T O and Y . H I S H I Y A M A ,
140. D . V . F E D O S E E V , V . L . B U K H O V E T S , I . G . J. Mater. Res. 6 (1991) 1108.
V A R S H A V S K A Y A , A . V . L A V R E N T ’E V and B . V . 150. M . I N A G A K I , T . I B U K I and T . T A K E I C H I , J. Appl. Polym.
D E R J A G U I N , Carbon 21 (1983) 237. Sci. 44 (1992) 521.
141. D . V . F E D O S E E V , I . G . V A R S H A V S K A Y A , A . V . 151. A . S . A B H I R A M A N , P . D E S A I and B . W A D E , “Processing,
L A V R E N T ’E V and B . V . D E R J A G U I N , Powder Technology Fabrication, and Manufacturing of Composite Materials” (Ameri-
44 (1985) 125. can Society of Mechanical Engineers, 1992) p. 1.
142. M . A L A M , T . D E B R O Y , R . R O Y and E . B R E V A L , Carbon
27 (1989) 289.
143. J . D O N N E T and A . V O E T , “Carbon Black” (Marcel Dekker, Received 12 February
Inc., New York, 1976) p. 87. and accepted 21 September 1999
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