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Materials and Design 28 (2007) 14771489
www.elsevier.com/locate/matdes
Department of Mechanical Engineering, The T.J. Small College of Engineering, Ohio Northern University, Ada, OH 45810, United States
Received 8 August 2005; accepted 10 March 2006
Available online 5 May 2006
Abstract
Carbon nanotubes are discussed in this paper from the time of their discovery to present day applications. Specically the production
methods, properties and industrial applications of carbon nanotubes are reviewed. Production methods include classical approaches such
as the arc method, chemical vapor deposition, laser ablation, and electric arc discharge along with new methods which are being tested
such as through solar energy, plasma and microgravity environments. The electrical and mechanical properties and actual structure of
carbon nanotubes are discussed in detail. Both current applications of carbon nanotubes along with potential uses are also elucidated in
this review. The data has been compiled from open literature to comment on trends in behavior of the carbon nanotubes.
2006 Elsevier Ltd. All rights reserved.
Keywords: Single wall nanotubes; Multi-wall nanotubes; Nanometer; Chemical vapor deposition; Arc discharge; Carbon
1. Introduction
Carbon is known to be the most versatile element that
exists on the earth. It has many dierent properties which
can be used in dierent ways depending on how the carbon
atoms are arranged. For more than 6000 years carbon has
been used for the reduction of metal oxides. Carbon in the
form of graphite was discovered in 1779, and 10 years later
in the form of a diamond. It was then determined that both
of these forms belong to a family of chemical elements. It
was not until about 200 years later that the next advancements in carbon took place. In 1985 Kroto, Smalley and
Curl2 discovered fullerenes [1]. A few years later the carbon
nanotube was discovered.
Carbon nanotubes (CNT) were rst discovered in 1991,
by Sumio Iijima,3 in fullerene soot [2,3]. It was a product
of the carbon-arc discharge method, which is similar to
*
Corresponding author. Tel.: +1 419 772 2385; fax: +1 419 772 2404.
E-mail address: t-goswami@onu.edu (T. Goswami).
1
Junior student in the Department of Mechanical Engineering Ohio
Northern University, 45810, United States.
2
Recipients of 1996 Nobel Prize in Chemistry for the discovery of
fullerenes.
3
Recipient of 2002 Benjamin Franklin medal in Physics for his work on
carbon nanotubes.
0261-3069/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2006.03.008
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3. CVD process
In the CVD process growth involves heating a catalyst
material to high temperatures (5001000 C) in a tube furnace using a hydrocarbon gas through the tube reactor
over a period of time [16]. The basic mechanism in this process is the dissociation of hydrocarbon molecules catalyzed
by the transition metal and saturation of carbon atoms in
the metal nanoparticle [16]. Precipitation of carbon from
the metal particle leads to the formation of tubular carbon
solids in a sp2 structure [16].
The characteristics of the carbon nanotubes produced by
CVD method depend on the working conditions such as the
temperature and the pressure of operation, the volume and
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Fig. 1 (continued)
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Fig. 3. Micrographs showing carbon nanotubes (a) macrograph of carbon nanotubes, (b) scanning electron micrographs of CNTs at 10,000 and 20,000
magnication, (c) aligned carbon nanotubes.
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Table 1
Mechanical properties of carbon nanotubes [5]
Material
Youngs modulus
(GPa)
Tensile strength
(GPa)
Density
(g/cm3)
1054
1200
208
3.5
16
150
150
0.4
0.005
0.008
2.6
7.8
1.25
0.6
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9. Applications
Carbon nanotubes have attracted a great deal of attention world wide with their unique properties which are
leading to many promising applications. Potential practical
applications have been reported such as chemical sensors
[40], eld emission materials [41], catalyst support [42],
electronic devices [43], high sensitivity nanobalance for
nanoscopic particles [43], nanotweezers [44], reinforcements in high performance composites, and as nanoprobes
in meteorology and biomedical and chemical investigations, anode for lithium ion in batteries [45], nanoelectronic
devices [46], supercapacitors [47] and hydrogen storage
[48]. New applications are likely in the diamond industry
since experiments have shown the conversion of carbon
nanotubes to diamond under high pressure and high temperatures with the presence of a certain catalyst [49]. These
are just a few possibilities that are currently being explored.
As research continues, new applications will also develop.
10. Composites
Given the mechanical properties that have been reported
on carbon nanotubes, an entire new class of composite materials may be possible with the use of carbon nanotubes. The
rst commercially recognized use for multi wall nanotubes
was electrically conducting components in polymer composites [50]. The matrices used in carbon nanotubes incorporated into composites can improve the electrical properties
which can act as a polymer, metal, or metal oxide [14]. Carbon nanotube metal or metal oxide composites have been
made to improve electrical conductivity. For applications
in polymer nanocomposites the elastic and fracture properties of carbon nanotubes must be understood along with
interactions at the nanotube matrix interface. The performance of carbon nanotubes in a polymer or ceramic matrix
is well above traditional llers such as carbon black or ultra
ne metal powders [51]. The major dierence from conventional ber-reinforced composites in that the scale is narrowed down to nanometers instead of micrometers [33].
Large similarities between mechanical properties of a
polymer lm and a SWNT matrix exist in that both have
high viscoelasticity that can be evaluated using a nanoindentor [52]. It would be dicult to replace all carbon bers
in their uses since there has been so much work done with
them. It is better for carbon nanotube research to look to a
new market rather replace the old. The great novelty with
carbon nanotubes is that they can achieve high stiness
along with high strength [34]. Also studies have shown that
carbon nanotubes do perform as reinforcing elements with
polymer [53], ceramic [54] and metallic matrices [55], but
without alignment their performance in terms of strength
and stiness fall short of traditional carbon bers.
For industrial applications as composites large quantities of nanotubes will be needed. It has been found that
the best method for high quantity and low cost production
of nanotubes is provided through the CVD method. Cost
factors also lead more to the use of multi wall nanotubes
rather than single wall nanotubes [50]. Incorporating nanotubes into plastics can lead to a dramatically increased
modulus of elasticity and strength in structural materials.
The main problem still lies in producing the nanotubes so
they are uniformly dispersed, achieving nanotube-matrix
adhesion providing stress transfer and intra bundle sliding
in single wall nanotubes [50]. Promising results have been
observed by Biercuk and others to overcome these problems by increasing Vickers hardness with single wall nanotubes and increasing the modulus of elasticity and breaking
stress in polystyrene using multiwall nanotubes [56].
Nanotube reinforced composites have already been successfully created. Experiments on a fully integrated nanotube composite using single wall nanotubes demonstrated
dramatic enhancement of mechanical properties. To produce these composites a reaction of terminal diamines with
alkycarboxl groups attached to single wall nanotubes in the
course of dicarboxxlic acid acyl peroxide treatment was
needed. The ultimate strength and shear modulus increased
from 30% to 70% with only the addition of 14 wt% of single wall nanotubes. The strain to failure also increased
showing an increase in toughness [57] (Fig. 9).
Rubber compounds reinforced by nanotubes are potential applications in tire industry. By replacing the carbon
black with carbon nanotubes improved skid resistance
and reduced abrasion of the tire have been found in experimental results [58]. Carbon nanotubes may provide a safer,
faster, and eventually cheaper transportation [59] in the
future. Although expectations of carbon nanotubes are very
high for their use in composites there has been some speculation against the results they produce when mixed with
some polymers and plastics. Carbon nanotubes themselves
are superior conductors by themselves but they may not
exhibit the same level of conductivity when integrated into
other materials [60]. Experiments have shown the conductivity to increase thermal conductivity by two or threefold
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Fig. 10. Use of a MWNT as an AFM tip At the center of the vapor grown
carbon ber (VGCF) is a MWNT which forms the tip. The VGCF
provides a convenient and robust technique for mounting the MWNT
probe for use in a scanning probe instrument [66].
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Table 2
Threshold electrical eld values for dierent materials for a 10 mA/cm2
current density [66]
Material
Mo tips
Si tips
p-type semiconducting diamond
Undoped, defective CVD diamond
Amorphous diamond
Cs-coated diamond
Graphite powder (<1 mm size)
Nanostructured diamonda
Carbon nanotubesb
50100
50100
130
30120
2040
2030
17
35 (unstable >30 mA/cm2)
13 (stable at 1 A/cm2)
a
b
Heat-treated in H plasma.
Random SWNT lm.
tron emissive materials should have low threshold emission elds and should be stable at high current density [66]
(Table 2). Carbon nanotubes posses the right combination
of properties: nanometer size diameter, structural integrity,
high electrical conductivity, and chemical stability that
make good electron emitters [79]. The rst eld emission
from carbon nanotubes was performed in 1995 by Rinzler
from single isolated multi wall nanotubes [80] and by multi
wall nanotube lm by de Heer [81]. Research on electronic
devices has since focused primarily on the use of single
and multi wall carbon nanotubes as eld emission electron
sources [82] for at panel displays [83], lamps [84], gas discharge tubes providing surge protection [85], and X-ray
[86] and microwave generators [87]. A potential applied
between a nanotube coated surface and an anode creates
high electric elds which is a result of a small radius of the
nanober tip and the length of the nanober [50]. The local
elds cause electrons to tunnel from the nanotube tip to the
tunnel. This process of nanotube tip electron emission differs from that of bulk metals because it arises from discrete
energy states instead of continuous electronic bands and its
behavior depends on the nanotube tip structure, single wall
nanotubes [88] or multi wall nanotubes [84] (Fig. 11).
Fig. 11. Left: Schematic of a prototype eld emission display using carbon nanotubes. Right: A prototype 4.5_ eld emission display fabricated by
Samsung using carbon nanotubes (image provided by Dr. W. Choi of Samsung Advanced Institute of Technologies).
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Table 3
Hydrogen storage of carbon nanotubes to other carbon materials [66]
Flat panel displays are one of the more lucrative applications of carbon nanotubes but are also the most technically complex. Nanotubes are at an advantage over liquid
crystal displays since they have low power consumption,
high brightness, a wide viewing angle, a fast response rate
and a wide operating system [50]. In the actual process electric elds direct the eld-emitted electrons toward the
anode where phosphorus produces light for the at panel
display [50]. Prototype matrix-addressable diode at panel
displays have been constructed at Northwestern University
[66]. One demonstration consists of nanotube-epoxy stripes
on the cathode glass plate and phosphor coated indium-tinoxide (ITO) stripes on the anode plate [89]. Pixels are then
formed at the intersection of the cathode and anode stripes.
Pulses of 150 V are switched among anode and cathode
stripes to produce an image [66].
Material
Max. wt%
H2 T (K)
P (MPa)
510
4
11.26
67.55
53.68
4.52
0.4
20
14
14
5.0
8.25
4.2
133
300
298
298
298
298
298773
473673
473674
<313
<313
80
300
0.040
0.040
11.35
11.35
11.35
11.35
0.101
0.101
0.101
0.101
0.101
7.18
10.1
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[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[98]
[99]
[100]
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