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Carbon Nanofibers: A New Ultrahigh-Strength Material for Chemical

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Theoretical Foundations of Chemical Engineering, Vol. 37, No. 5, 2003, pp. 429–438.
Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 37, No. 5, 2003, pp. 460–470.
Original Russian Text Copyright © 2003 by Mordkovich.

Carbon Nanofibers:
A New Ultrahigh-Strength Material for Chemical Technology
V. Z. Mordkovich
International Center for Materials Research, 1-1 Minami-Watarida-cho, Kawasaki-ku, Kawasaki 210-0855, Japan
Received January 23, 2003

Abstract—Carbon nanofibers are described as a new ultrahigh-strength material, which is superior to both
ordinary carbon fibers and other high-strength materials. The place occupied by nanofibers in the classification
of carbon materials is shown, and an analysis is made of the relationship between the structure of a fiber and its
useful properties, in particular, the strength and tensile modulus. Studies on the synthesis of nanofibers are
reviewed. It is shown that the practically important problem of producing nanofibers of maximum possible
length must be solved by controlling the temperature conditions of the reaction. The prospects for introducing
nanofibers into the market of high-strength and heat-resistant materials are analyzed. The most likely prospect
seems to be the partial replacement of polyacrylonitrile-based fibers by nanofibers, first and foremost, in the
fields where the requirements for high strength are particularly stringent due to safety reasons.

In recent years, ultrahigh-strength carbon nanofi-
bers have made their way from scientific laboratories
into industry. These fibers constitute a web of ultrathin
monomolecular carbon fibers, each less than 0.1 µm in
diameter: hence, follows the prefix nano, which refers
to a typical diameter of several tens of nanometers.
Such fibers are characterized by an extraordinarily high
tensile modulus and tensile strength. In particular, a
fiber as thin as a human hair (i.e., 50 µm thin) with-
stands a load of 2 kg, whereas a steel wire of the same
thickness endures only 200 g. Other important proper-
ties of carbon nanofibers are their high electrical con-
ductivity, extremely high corrosion resistance, invari-
ability of mechanical properties over a very wide tem-
perature range (from cryogenic temperatures to more
than 1000°C), and excellent compatibility with living
tissues.
Carbon nanofibers are closely related to ordinary
micron-sized carbon fibers, which are widely used in
industry and are produced at an annual rate above ten
thousand tons. Ordinary carbon fibers are also a rela-
tively new material, whose properties, in particular,
strength, have been improved at least twofold over the
last decade. However, nanofibers, even at present, are
superior to ordinary fibers in many parameters and still
have room for improvement.
The purpose of this work is to report on recent
advances in the field of these new materials, to show the
place of nanofibers among other carbon fibers, and to
discuss the prospects for their use in industry.
GENERAL INFORMATION
AND CLASSIFICATION OF CARBON FIBERS
The most straightforward method for carbon fiber
production is the charring of natural or synthetic textile
fibers in the absence of air. In this way, one can process
linen, cotton, and nylon; however, practical use is made
of fibers based on viscose or polyacrylonitrile. The pro-
duction of polyacrylonitrile-based fibers (PAN fibers)
now constitutes up to 80% of the global production of
carbon fibers. The thickness of polyacrylonitrile-based
fibers is, as would be expected, on the same order as the
thickness of the initial textile fibers, i.e., no smaller than
3–5 µm. The properties of polyacrylonitrile-based
fibers depend, first and foremost, on the parameters of
charring, which is performed in several steps and
involves, as a rule, so-called stabilization in air at 200–
300°C, carbonization in an inert-gas atmosphere at
1200–1400°C, and, ultimately, high-temperature
annealing in vacuum or an inert-gas atmosphere at
2000–3000°C [1, 2].
Another important type of fibers is pitch-based
fibers, which are produced from coal-tar or petroleum
pitches. Fibers are extruded from a dense pitch through
spinnerets and are then subjected to heat treatment
according to a procedure similar to the heat treatment of
polyacrylonitrile-based fibers. Like the polyacryloni-
trile-based fiber, the typical diameter of a pitch-based
fiber is several micrometers. The properties of these
fibers are determined not so much by the heat treatment
conditions as by the properties of the raw material:
depending on the type of the pitch used, either isotropic
or anisotropic (or mesophase) fibers are produced,
whose properties differ considerably.
Lastly, the third important type of carbon fibers is
vapor-grown carbon fibers (VGCF). They were the first
to be used worldwide but were rapidly replaced by
fibers of other types. Vapor-grown carbon fibers were
produced through the pyrolysis of carbon-containing
gases (methane, ethylene, acetylene, carbon monoxide,
etc.) on a metal (most often iron) catalyst at 500–

0040-5795/03/3705-0429$25.00 © 2003 MAIK “Nauka /Interperiodica”

430 MORDKOVICH

Table 1. Classification of carbon fibers according to the production method

Raw material Fiber Characterization of fiber
Polyacrylonitrile PAN fiber Continuous; diameter 5–20 µm; in mechanical properties: fiber
of various types
Isotropic pitch Isotropic pitch- Continuous; diameter 10–30 µm; in mechanical properties:
based fiber general-purpose fiber
Anisotropic Mesophase pitch- Continuous; diameter 10–30 µm; in mechanical properties:
mesophase pitch based fiber usually high-modulus fiber, a variety of structures
Carbon-containing gas VGCF, including Limited length; diameter 3–1000 µm; in mechanical properties:
nanofiber general-purpose fiber
Carbon-containing gas Nanofiber Limited length; diameter 1–100 nm; combination of ultrahigh strength
and ultrahigh modulu

1500°C [1, 3–5]. Fibers grown by pyrolysis can also be
subjected to additional high-temperature annealing in
vacuum or an inert-gas atmosphere at 2000–3000°C
[1]. The properties of vapor-grown carbon fibers are
determined by the growth and annealing conditions.
Vapor-grown carbon fibers, unlike pitch- and polyacry-
lonitrile-based fibers, still cannot be produced as
threads of infinite length. The length of a vapor-grown
carbon fiber is limited by the growth conditions and can
be anywhere from several micrometers to several tens
of centimeters. Thus, from the vapor-grown carbon
fibers of the current generation, only staple (discontin-
uous) rather than textile (continuous) fibers can be
obtained. This fact has naturally limited the range of
application of vapor-grown carbon fibers. Another lim-
itation had been the nonuniformity of properties, which
strongly differ from fiber to fiber, but this problem has
been successfully solved in recent years [1]. The great
advantage of vapor-grown carbon fibers is the fact that
their diameter can be arbitrarily small and limited from
below not by the thickness of the initial polymer fiber,
as in pitch- and polyacrylonitrile-based fibers, but by
the minimum theoretical diameter of a monomolecular
carbon nanotube (0.7 nm) [4–8]. Nanofibers proper are
vapor-grown carbon fibers less than 0.1 µm in diame-
ter: at such diameters, the properties of a fiber, particu-
larly its strength, change qualitatively.
The classification of carbon fibers according to the
methods by which they are produced is presented in
Table 1, which summarizes the above data and also lists
general characteristics of fibers.
STRENGTH OF CARBON FIBERS
The most important mechanical property of fibrous
materials is the tensile strength σ (Pa or kg/cm2), here-
inafter referred to simply as the strength. This parame-
ter characterizes the maximum tensile stress at which
the fiber remains unbroken. Other important mechani-
cal characteristics are Young’s modulus E (Pa) (which
determines the stiffness of a fiber during stretching) and
the ultimate strain (which is the maximum elongation
(%) at which a fiber still remains unbroken).
Conventionally, carbon fibers have been classified
according to their strength σ into high-strength (σ >
3 GPa) and ultrahigh-strength (σ > 4.5 GPa) fibers; and
according to Young’s modulus E into low-modulus (E <
100 GPa), medium-modulus (E = 200–320 GPa), high-
modulus (E > 350 GPa), and ultrahigh-modulus (E >
450 GPa) fibers [9]. This classification is rather condi-
tional and gradually becoming obsolescent. Initially,
the classification of fibers into high-strength and high-
modulus fibers was sufficient; however, over time, as
these fibers found use in the aerospace industry,
account was also taken of other parameters, such as the
ultimate strain of fibers. Moreover, polyacrylonitrile-
based fibers and vapor-grown carbon fibers were cre-
ated, which combine an ultrahigh strength with an
ultrahigh modulus. Therefore, at the present time, a
more general classification of fibers into general-pur-
pose (GP) fibers and high-performance (HP-grade)
fibers is applied. Figure 1 presents the modern classifi-
cation of carbon fibers according to their mechanical
properties.
Nanofibers are simultaneously ultrahigh-strength
and ultrahigh-modulus. The strength of nanofibers is
beyond the scale of Fig. 1 and can reach 12 GPa (and
possibly even 30 GPa); therefore, for nanofibers, a new,
superhigh-strength grade could be introduced. It is con-
ceivable that this will be done once these fibers find
application in industry. Figure 2 and Table 2 compare
the properties of different fibers, including noncarbon
ones.
As one can see from the above, the mechanical
properties of carbon fibers, even those of identical ori-
gin and equal thickness, can differ considerably from
one another. This difference is determined by differ-
ences in the fiber structure.
STRUCTURE OF CARBON FIBERS
The structure of several types of ordinary, micron-
sized fibers is schematized in Figs. 3 and 4. The elec-
tron micrographs of fibers whose structures are shown
in Fig. 3 are presented in Fig. 5. The figures show that
mesophase pitch-based fibers (Figs. 3a, 3b) consist of

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

 CARBON NANOFIBERS: A NEW ULTRAHIGH-STRENGTH MATERIAL 431

σ, MPa σ, GPa

4 3 2

6000 4
e 15

4000 d f 3
10
1

1
b c
2000 5 6 2
5
a
7
0 200 400 600 0 200 400 600 800
E, GPa E, GPa

Fig. 1. Classification of carbon fibers according to their
mechanical properties: (a) general-purpose, (b) high-mod-
ulus, (c) ultrahigh-modulus, (d) high-strength, (e) ultra-
high-strength, and (f) high-performance fibers. The lines
represent the ultimate strains ε = (1) 0.5, (2) 1, (3) 1.5, and
(4) 2%.
Fig. 2. Comparison between the mechanical properties of
various fibers: (1) PAN and pitch carbon fibers, (2) VGCF,
(3) carbon nanofibers, (4) diamond whisker, (5) aramide
(stiff-chain polymers based on liquid-crystal polyamides of
Kevlar type), (6) high-strength polyethylene, and (7)
alloyed steel wire.

straight graphite strips or flakes aligned with the fiber
axis. At a cross section, these flakes can form various
packings: stellar, stratified, or random. Such a structure
provides for high fiber stiffness, since, along a fiber,
there are practically no elements that can be stretched;
however, the strength depends entirely on the length
of flakes, making a high strength difficult to ensure.
These observations are fully consistent with the data
in Tables 1 and 2, which show that pitch-based fiber
can be high-modulus but not high-strength.
Polyacrylonitrile-based fibers (Fig. 3c) have a more
complex structure and consist of many tubular elements
combined into a three-dimensional structure. This
structure is shown in Fig. 4 in greater detail, where open
and closed pores formed by tubular elements are well
seen. Such a structure can and does provide high
strength due to the overlap of tubular elements, but its
high stiffness is difficult to preserve solely by increas-
ing the structure density and decreasing the total pore
volume.
Vapor-grown carbon fibers (Fig. 3d) consist of many
tubes inserted into one another and, correspondingly,
have a hollow core. High-temperature annealing causes
the slightly ordered carbon layers of tubes to crystallize
into graphite flakes several micrometers in size and,
thus, transforms the round tubular elements into poly-
hedral ones (Fig. 3e). Such a structure could ensure a
high stiffness in combination with a high strength, pro-
vided that there is strong adhesion between concentric
tubes. However, this adhesion is actually weak and the
most typical failure of a vapor-grown carbon fiber can be
likened to a sword being pulled from a sheath (Fig. 6). As
a result, vapor-grown carbon fibers are characterized by
a very wide scatter in their properties and, conse-
quently, low reliability.

Table 2. Properties of some typical carbon fibers

Isotropic Mesophase
Characteristic PAN fiber VGCF Nanofiber
pitch-based fiber pitch-based fiber
Diameter, µm 14.5 6.5 10 5–8 0.05
Density, g/cm3 1.57 1.81 2.0 2.0 2.1
Tensile strength, MPa 600 2500 2100 4000 12000
Young’s modulus, GPa 30 300 520 300 600
Resistivity, Ω cm 5 × 103 800 500 50 20

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

432
(a)
(d)
Fig. 3. Structure of carbon fibers: (a) mesophase pitch-based fiber with stellar packing at cross section, (b) mesophase pitch-based
fiber with stratified packing at cross section, (c) PAN fiber, (d) VGCF, (e) VGCF after annealing at 3000°C.
Nanofibers, like micron-sized vapor-grown carbon
fibers, have a tubular structure. However, the difference
between them is not only in their respective scales but
also in the fact that tubes constituting a nanofiber are
monomolecular objects, rather than a “papier-máché”
of graphite flakes.
Fig. 4. Structure of high-strength PAN fiber [10].
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
MORDKOVICH
(b) (c)
(e)
Figure 7 shows how a carbon tube is formed from a
graphite sheet (a). The graphite sheet is rolled up so that
the upper and lower edges coincide to form a cylinder
(b). This is accompanied by a shift due to which a band
of carbon hexagons is inserted into the tube (c) to form
a coil around it. If the sheet is rolled up in other direc-
tions, tubes of different diameter and motif will be pro-
duced. Owing to a high strength and the conjugation of
bonds in a graphite sheet, this sheet is a single planar
molecule with an extraordinarily high tensile modulus
(1000 Gpa) and high tensile strength (20 Gpa) [5, 6].
However, in graphite crystals, individual sheets are
bonded to one another by very weak van der Waals
forces; as a result, the graphite is extremely brittle and
breaks down at a shear stress of only 0.48 MPa [5, 6].
A tube (nanotube) rolled up from a graphite sheet inher-
its the high mechanical properties of the sheet and,
simultaneously, acquires all the advantages of any tubu-
lar structure. A defectless carbon nanotube has a tensile
modulus of 1800 GPa and a strength no lower than
30 GPa, which is a record of a sorts and even exceeds
the parameters of single-crystal diamond whiskers (see
Fig. 2). The closer a nanofiber structure is to the
described ideal model, the fewer the number of defects;
and the longer an individual fiber, the closer the fiber
strength to the above remarkably high values.
It has long been known that a decrease in the diam-
eter of a vapor-grown carbon fiber causes gradual
improvement in mechanical properties. As the fiber
diameter approaches the threshold value 1 µm, which
characterizes the transition from a fiber to a nanofiber,
this tendency becomes more and more noticeable. In
particular, Fig. 8 illustrates the results of an early study
[11] where such a tendency is clearly exhibited: there is
a wide scatter of data for different samples, which is
characteristic of vapor-grown carbon fibers.
Nanofibers can consist of nanotubes with one to
one-hundred tubular monomolecular layers (walls).
Vol. 37 No. 5 2003
 CARBON NANOFIBERS: A NEW ULTRAHIGH-STRENGTH MATERIAL 433

(a) 2 µm (b) 2 µm (c)

(d) 1 µm (e)

Fig. 5. Electron micrographs [5] of fibers shown in Fig. 3: (a) mesophase pitch-based fiber with stellar packing at cross section, (b)
mesophase pitch-based fiber with stratified packing at cross section, (c) PAN fiber, (d) VGCF, (e) VGCF after annealing at 3000°C.

Figure 9 presents a transmission electron micrograph of hydrogen to form metallic iron (Fig. 10b). Lastly, iron-
a nanofiber. Parallel dark strips are clearly seen, which containing organometallic compounds can be intro-
are shadows of individual monomolecular tubes. A duced directly into the reactor: their decomposition
black, electron-opaque spot at the end of fibers is a cat- results in the deposition of iron particles onto a sub-
alyst crystal on which the fibers had grown.
strate placed into the reactor beforehand (Fig. 10c).
With the method for growing fibers in a gas flow
METHODS FOR PRODUCING VAPOR-GROWN (Fig. 11), a carbon-containing gas must be supple-
CARBON FIBERS
mented with a volatile iron compound, e.g., iron carbo-
Methods for producing nanofibers are, by and large, nyl, although ferrocene Fe(C5H5)2 (proposed by Endo
the same as methods for manufacturing ordinary vapor- [14]) is used more often. Another method for introduc-
grown carbon fibers. A carbon-containing gas (meth- ing a catalyst into the reaction zone during fiber growth
ane, ethylene, acetylene, carbon monoxide, or benzene
or ethanol vapor) is decomposed on a metal (iron- in a gas flow involves the injection of a suspension of a
based) catalyst at 500–1500°C [1, 3–5]. The carbon- fine iron powder in an organic solvent directly into the
containing component is usually mixed with hydrogen. reactor.
Manufacturers usually do not divulge details of the pro-
cess; however, the main principles of the process are
described in sufficient detail, as they have been worked
out over the last twenty years at several competing sci-
entific centers [4, 5, 11–23]. The largest contribution
was made by the Endo Laboratory, Shinshu University,
Japan [4, 5, 12–15].
The process is performed by one of two methods
whereby fibers are grown either on a substrate (Fig. 10)
or in a gas flow (Fig. 11). In the method for growing
fibers on a substrate (Fig. 10), a catalyst must be
applied on a graphite or ceramic substrate. For this pur-
pose, the substrate is painted with an iron paint, which
is a suspension of fine iron powder in an organic sol-
vent, whereupon the solvent is removed by evaporation 10 µm
(Fig. 10a). Another method of catalyst application is the
spraying of a solution of iron compounds (nitrates, fer-
rocene, etc.) onto a substrate with the subsequent
decomposition of these compounds by heating in Fig. 6. Typical rupture of VGCF under load [11].

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

434 MORDKOVICH

(a) (b)

(c)

Fig. 7. Scheme of the formation of a monomolecular carbon tube by rolling up a graphite sheet [6].

In all of the cases, a catalyst particle is trapped by a An advantage of the method of growing fibers on a
growing fiber and, eventually, each fiber ends with a substrate is the fact that the length of fibers grown by
metal microcrystal cap. Fiber growth on a substrate and this method (up to several tens of centimeters) is much
in a gas flow is schematized in Fig. 12. larger than the fiber length (several millimeters)
achieved by the method of growing fibers in a gas flow.
However, the process is not continuous and this is a
large drawback.
σ, GPa
(a) The purity of the gas mainly affects catalyst activity.
3 The presence of water vapor at a concentration of sev-
eral tens of ppm (or higher) decreases the reaction yield
2 and the fiber length. Purification is particularly impor-
tant if the carrier gas is not hydrogen but rather the
1 products of the steam-air reforming of methane (67%
CO, 1.2% H2, 16% CO2, 15% N2, 0.2% O2, and 0.6%
0 10 20 30
d, µm
E, GPa 10 nm
(b)
300

200

100

0 10 20 30
d, µm

Fig. 8. (a) Strength and (b) the tensile modulus of VGCF

versus fiber diameter. Fig. 9. Transmission electron micrograph of a nanofiber.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

 CARBON NANOFIBERS: A NEW ULTRAHIGH-STRENGTH MATERIAL 435

(a)
Suspension
of Fe Spraying CxHy
particles and drying
H2

Substrate
Furnace

(b)

Solution Application CxHy

of Fe and drying
salt
H2

Substrate Furnace

(c)

OMC CxHy
H2
Fe H2
Fe
Substrate

Furnace Furnace

Fig. 10. Schemes of the growth of VGCF on a substrate: (a) a catalyst is applied as a suspension of a fine iron powder in a solvent,
(b) a catalyst is applied as a solution of iron compounds, and (c) iron-containing organometallic compounds (OMC) are introduced
immediately into the reactor [14].

H2O), as proposed in the literature [17, 18]. The gas
composition can affect the fiber thickness and structure.
In particular, fibers with a nontubular structure can
form [23]. The effect of gas composition on the struc-
ture of the product is best illustrated by the effect of a
small amount of phosphorus impurity [21, 22]. It was
shown [21] that the pyrolysis of acetylene containing
phosphorus impurity (under some conditions, sulfur
impurity) gives rise to coiled nanofibers, which are a
peculiar kind of microscopic springs. Such fibers are
not high-strength but, in their elasticity, are close to
ordinary rubber. An electron micrograph of coiled
nanofibers is presented in Fig. 13.
The particle size of the catalyst has a substantial
effect on both the yield and rate of the reaction, as well
as fiber thickness. It was established that, for fiber
growth to be efficient, the diameter of a catalyst particle
must be no larger than 20 nm. The average rate of fiber
growth on a catalyst with particles of 10–20 nm is
1 mm/min, whereas the rate of increase in thickness is
1–2 nm/min [1].
It was found that the lengthening and thickening of
fibers do not take place simultaneously. This is illus-
trated in Fig. 14, which shows the dynamics of the
length and diameter of fibers in the course of the pro-
cess by the example of pyrolysis of benzene vapor on
an iron catalyst [15]. In the general case, lengthening
requires a lower temperature. An increase in the tem-
perature of the process and a decrease in the catalyst
activity cause the fibers to thicken, thereby transform-
ing them from nanofibers into ordinary micron-sized
vapor-grown carbon fibers.
Thus, the practically important problem of growing
nanofibers of the maximum possible length is to be
solved by controlling the temperature conditions of the
reaction and by ensuring higher catalyst stability. This
prevents thickening of nanofibers (their transformation
into micron-sized fibers) and prolongs the growth stage
and, consequently, increases the fiber length.
PROSPECTS FOR INDUSTRIAL USE
The prospects for using ultrahigh-strength carbon
nanofibers are mainly related to the fields where ordi-
nary high-strength carbon fibers have been imple-
mented in recent decades. The price of nanofibers, as

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

436 MORDKOVICH

(a)
Suspension of Fe
in benzene

(b)
Furnace

H2
OMC

CxHy

Fibers

H2

Fig. 11. Schemes of the growth of VGCF in a gas flow: (a) a catalyst is introduced into the reactor as a suspension in a liquid hydro-
carbon and (b) volatile organometallic compounds (OMC) are used [14].

Fiber
(a) growth Fiber
Formation Carbon thickening
of catalyst Carbon film
particle deposition growth

Substrate
(b)

Ferrocene

Catalyst particle

Carbon transport

Fiber growth

Fiber thickening

Fig. 12. Models of the growth of VGCF [1], including nanofibers, (a) on a substrate and (b) in a gas flow.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

 CARBON NANOFIBERS: A NEW ULTRAHIGH-STRENGTH MATERIAL 437

T, °C
(a)
1100

1050 Activation Thickening

Growth
1000
1 2 3 t, h

l, mm d, µm
70 (b)
25
3 µm 60

50 1 20
Fig. 13. Electron micrograph of coiled nanofibers forming
“carbon rubber.”
40 15
2
well as polyacrylonitrile-based fibers of high-perfor-
mance grade, is $1000–5000 US per kilogram. There is 30
10
a prospect for a decrease in this price to $40–50 US per
kilogram (this is the price of general-purpose fibers). 20
This price is substantially higher than the price of the 5
main competing materials (see Fig. 2), namely, high- 10
strength aramide fibers and high-strength polyethylene,
and is incomparable to the price of textile fiberglass. 0 0
The production processes of these fibers differ corre- 1 2 3 t, h
spondingly: the annual production of textile fiberglass
as of 2001 has reached 1 million tons [24], whereas the Fig. 14. Dynamics of (a) the substrate temperature T and (b)
(1) the length l and (2) diameter of VGCF in the course of
annual production of carbon fibers as of 2001 has the growth process during pyrolysis of benzene vapor on an
reached 10000 tons [2]. The world market for carbon iron catalyst [15].
fibers has increased over the last twenty years by an
average of 5% annually (see Table 3). It is easy to
understand why, in terms of price, the markets for car- Cords and laminates based on carbon fibers are used
bon fibers and fiberglass are approximately identical; a to handle the longitudinal forces of bending, centrally
further increase in production together with an increase compressed, and noncentrally compressed elements:
in the fraction of ultrahigh-strength carbon fibers can flat and ribbed slabs, crossbars, beams, girder elements,
take place only through a decrease in the price of car- etc. Special jackets with bidirectional fibers are used to
bon fibers, for which there are reserves.
Inside the existing market of carbon fibers, the par- Table 3. Annual production (t) of carbon fibers of all types [2]
tial replacement of polyacrylonitrile-based fibers by
nanofibers holds the greatest promise, first and fore- EU Other
Year USA Japan Total
most, in the fields where requirements for high strength countries counties
are particularly stringent and due to safety reasons. 1981 550 140 290 50 1030
Among such fields are the aerospace and sport indus-
tries, which require strong carbon plastics and carbon– 1982 600 220 470 150 1440
carbon composites, and also civil engineering, espe- 1983 800 270 500 350 1920
cially in regions of permafrost, seismic activity, etc., 1984 1200 450 560 560 2770
where ultrahigh-strength carbon fibers are used as a 1985 1650 580 600 400 3230
corrosion-resistant jacketing of bridge supports, traffic
overpasses, high-rise buildings, and other construc- 1986 1920 690 620 500 3730
tions. Such a jacketing decreases the risk of destruction 1987 2300 830 650 600 4380
due to bending and shear loads by a factor of several 1988 2600 1000 700 700 5000
tens. In particular, Japan enacted a program of recon- 1989 3000 1200 770 800 5770
struction of all bridges and traffic overpasses and rein-
forcement of all supports with carbon fibers (and begin- 1990 3500 1450 850 900 6700
ning in 2001, with ultrahigh-strength carbon fibers). 2000 5500 2800 1200 1200 10700

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 37 No. 5 2003

438 MORDKOVICH
reinforce constructions operating in a complex stressed
state: columns, pillars, crossbars of skeleton construc-
tions; such jackets are also used to take on transverse
and shear forces, etc. [25].
The mechanical and processing properties of car-
bon-fiber materials are opening up wide possibilities
for the repair, reinforcement, and restoration of build-
ings and objects made from concrete, reinforced con-
crete, stone, and wood, i.e., industrial buildings, reser-
voirs, bunkers, tower silos and water-cooling towers,
oil platforms, retaining walls, bridges, pipes, tunnels,
hydraulic and port facilities, etc. In Russia, a number of
projects in Moscow and Novorossiisk have been imple-
mented by the S&P Clever Reinforcement Company
AG (Switzerland) through its distributor, ZAO Triada-
Holding. Although global production of ultrahigh-
strength fibers is mainly concentrated in Japan (Toray
and Mitsubishi), Russian manufacturers of polyacry-
lonitrile-based fibers are also present in the market, in
particular, the Chelyabinsk Electrode Plant and the
Federal State Unitary Research Institute of Graphite-
Based Construction Materials (NIIGrafit), Moscow.
Along with their high strength, carbon nanofibers
also have a number of other useful properties which
distinguish these materials from ordinary carbon fibers
[4, 5]. Other important fields for their application are
carbon–lithium batteries for computers and mobile
phones (only Japanese manufacturers provide an
annual production of 30 million devices), start capaci-
tors for electronic devices, electrically conducting plas-
tic composites, and, lastly, biomaterials.
At present, carbon nanofiber technology is being
implemented by only two manufacturers, the Japanese
companies Showa Denko and Mitsubishi. Production
began in 2001 and now ranges from several hundred
kilograms, by Showa Denko, to 10 t, by Mitsubishi. The
carbon nanofibers produced are used in construction in
seismic regions and in the production of carbon–lith-
ium batteries for mobile phones, start capacitors for
electronic devices, and electrically conducting Teflon–
carbon tape.
REFERENCES
1. Inagaki, M., New Carbons: Control of Structure and
Functions, Oxford: Elsevier, Sci., 2002.
2. Sciences of Carbon Materials, Marsh, H. Ed., Alicante:
Univ. di Alicante, 2000.
3. Baker, R.T.K. and Harris, P.S., The Formation of Fila-
mentous Carbon, Chemistry and Physics of Carbon,
Walker, P.L. and Thrower, P.A., Eds., New York: Marcel
Dekker, 1978, p. 83.
4. Carbon Nanotubes, Endo, M., Ed., Oxford: Pergamon,
1996.
5. Carbon Nanotubes: Preparation and Properties, Ebbe-
sen, T.W., Ed., New York: CRC, 1997.
6. Dresselhaus, M.S., Dresselhaus, G., and Eklund, P.C.,
Science of Fullerenes and Carbon Nanotubes, London:
Academic, 1996.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
View publication stats
7. Eletskii, A.V., Carbon Nanotubes, Usp. Fiz. Nauk, 1997,
vol. 167, no. 9, p. 945.
8. Rakov, E.G., Nanotubes of Inorganic Substances, Zh.
Neorg. Khim., 1999, vol. 44, no. 11, p. 1827.
9. Zelenskii, E.S., Kuperman, A.M., Gorbatkina, Yu.A.,
et al., Reinforced Plastics: Modern Construction Materi-
als, Ross. Khim. Zh., 2001, vol. 44, no. 2, p. 56.
10. Guigon, M., Oberlin, A., and Desarmot, G., Microtex-
ture and Structure of Some High-Modulus, PAN-Base
Carbon Fibers, Fibre Sci. Tech., 1984, vol. 20, p. 177.
11. Tibbetts, G.G. and Beetz, C.P., Mechanical Properties of
Vapor-Grown Carbon Fibers, J. Phys. D: Appl. Phys.,
1987, vol. 20, p. 292.
12. Oberlin, A., Endo, M., and Koyama, T., Filamentous
Growth of Carbon through Benzene Decomposition,
J. Cryst. Growth, 1976, vol. 32, p. 335.
13. Endo, M., Vapor-Grown Carbon Fibers, Ph.D. Thesis,
Nagoya: Nagoya Univ., 1978.
14. Endo, M. and Sikata, M., Tanso faiba (Carbon Fibers),
Oio Butsuri, 1985, vol. 54, p. 507.
15. Endo, M., Oberlin, A., and Koyama, T., Structure and
Growth Mechanism of Vapor-Grown Carbon Fibers,
Jpn. J. Appl. Phys., Part 1, 1977, vol. 16, p. 1519.
16. Katsuki, H., Matsunaga, K., Egashira, M., and Kawa-
sumi, S., Formation of Carbon Fibers from Naphthalene
on Some Sulfur-Containing Substrates, Carbon, 1981,
vol. 9, p. 148.
17. Ishioka, M., Okada, T., and Matsubara, K., Formation of
Vapor-Grown Carbon Fibers in Carbon Monoxide–Car-
bon Dioxide–Hydrogen Mixtures: I. Influence of Carrier
Gas Composition, Carbon, 1992, vol. 30, p. 859.
18. Ishioka, M., Okada, T., and Matsubara, K., Formation of
Vapor-Grown Carbon Fibers in Carbon Monoxide–Car-
bon Dioxide–Hydrogen Mixtures: II. Influence of Cata-
lyst, Carbon, 1992, vol. 30, p. 975.
19. Tibbetts, G.G., Lengths of Carbon Fibers Grown from
Iron Catalyst Particles in Natural Gas, J. Cryst. Growth,
1985, vol. 73, p. 431.
20. Egashira, M., Katsuki, H., Khayasi, K., and Kawa-
sumi, S., Sekubai-no tanso faiba (Catalytic Carbon
Fibers), Sekiyu Gakkai Si, 1983, vol. 26, p. 247.
21. Motojima, S., Hasegawa, I., Kagiya, S., et al., Vapor
Phase Preparation of Micro-Coiled Carbon Fibers by
Metal Powder Catalyzed Pyrolysis of Acetylene Con-
taining a Small Amount of Phosphorus Impurity, Car-
bon, 1995, vol. 33, p. 1167.
22. Motojima, S., Ivanaga, H., and Varadan, V.K., Kabon
maikuro koiru (Carbon Microcoils), Homen, 1998,
vol. 36, p. 140.
23. Soneda, Y. and Inagaki, M., Formation and Graphitiza-
tion of Vapor-Grown Carbon Fibers, Z. Anorg. Allg.
Chem, 1992, vol. 610, p. 157.
24. Imamutdinov, I. and Perekhodtsev, G., Dirty Glass
Effect, Ekspert, October 8, 2001, no. 37.
25. Seible, F., Priestley, N., and Innamorato, D., Earthquake
Retrofit of Bridge Columns with Continuous Carbon
Fiber Jackets. Report No. ACTT-95/08, Report to Cal-
trans, Division of Structures, Prepared under the
ARPA/TRP Program Agreement No. MDA 972-94-3-
0030, San Diego: Univ. Calif., 1998.
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