Materials

& Design
Materials and Design 28 (2007) 1477–1489
www.elsevier.com/locate/matdes

Carbon nanotubes – Production and industrial applications

Melissa Paradise 1, Tarun Goswami *

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. Specifically 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.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Single wall nanotubes; Multi-wall nanotubes; Nanometer; Chemical vapor deposition; Arc discharge; Carbon

1. Introduction the method used for fullerenes preparation. In this form,

Carbon is known to be the most versatile element that
exists on the earth. It has many different properties which
can be used in different 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 advance-
ments 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 first 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.
carbon is arranged in tubular formations on a nanoscopic
level. To observe such materials a high resolution transmis-
sion electron microscopy was used [3,4]. Carbon nanotubes
are a completely new type of carbon fibre which comprises
coaxial cylinders of graphite sheets, which range from 2 to
50 sheets [5]. The first observations Sumio made [3] were
of multi-walled nanotubes, and it was not until two years
later when single wall nanotubes were observed. Ijima along
with Ichihasi [6] used carbon electrodes with a small amount
of iron and filled the chamber around the carbon arc with
methane and argon gas which yielded the single wall carbon
nanotube. Single wall nanotubes are basically a single ful-
lerene molecule that has been stretched out so their length
is a million times its diameter [7]. Around this same time
Donald Bethune and colleagues also observed the single
wall carbon nanotube [4]. In 1996 Smalley synthesized bun-
dles of single wall carbon nanotubes for the first time [5].
The name carbon nanotube is derived from their size
which is only a few nanometers wide. By definition carbon
nanotubes are cylindrical carbon molecules with properties
that make them potentially useful in extremely small scale
electronic and mechanical applications. These tubes consist
of rolled up hexagons, 10,000 times thinner than a human
hair. Ideal nanotubes can be described as a seamless

0261-3069/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2006.03.008
1478 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489

cylinder of rolled up hexagonal networks of carbon atoms,

which is capped with half a fullerene molecule at the end
[2]. Their strength is one to two orders of magnitude and
weight six times lighter than steels. Possible applications
range from semiconductors, electronic memory, drive
products, and medical delivery systems to uses in plastics
such as automobile body panels, paint, tires and as flame
retardants in polyethylene and polypropylene [9].
Carbon nanotubes have been the focus of considerable
study because of their unusual strength along with excellent
mechanical, electrical, thermal and magnetic properties [1–
100]. Nanotechnology has been recently supported with
Nanotechnology Research and Development Act allowing
$3.7 billion over the next four years to be administered by
the National Nanotechnology Initiative with plans to cre-
ate a National Nanotechnology Program (NNP) [10] in
the United States.

2. Production of carbon nanotubes

Various methods since arc growth have been explored to

produce carbon nanotubes. Essentially nanotube structures
are all formed in the same way but the process which causes
the formation differs, Fig. 1. The first method for the pro-
duction of multi-wall carbon nanotubes was through arc
growth [14] Fig. 1(a), but most attractive method commer-
cially used is condensation–vaporization densation (CVD)
method. Under this method there are different ways to
induce the carbon vaporization such as the electric arc dis-
charge, continuous or pulsed laser ablation, or solar energy
[11] Fig. 1(b). Chemical methods have also been found to
synthesize carbon materials such as the catalytic decompo-
sition of hydrocarbons, the production by electrolysis
(Fig. 1(c)), heat treatment of a polymer, the low tempera-
ture solid pyrolysis, or the in situ catalysis [15]. Recently
a catalytic chemical vapor deposition (CCVD) has also
been experimented which may prove to be better than the Fig. 1. Schematic representation of various processes used to produce
regular CVD method [12]. Some other methods which also CNTs: (a) Electric-arc method used at the University of Montpelier
(France). (b) Schematic representation of oven laser-vaporization appa-
have been found to work in the production of carbon ratus used at Rice University (Houston, Texas, USA). (c) Electrolysis
nanotubes is the plasma torch method [13] the underwater experimental system (Brighton, UK). (d) Arc discharge and CNT
alternating current (AC) electric arc method [14] and pro- formation and transport in the sheath. (e) Arc-discharge technique. (f)
duction in a microgravity environment [8]. Laser ablation process. (g) Solar furnace from Odeillo (France). (h) Solar
experimental chamber used in Odeillo (France).
3. CVD process
concentration of methane, the size and the pretreatment of
In the CVD process growth involves heating a catalyst metallic catalyst, and the time of reaction. Many times a
material to high temperatures (500–1000 °C) in a tube fur- catalyst is added to speed up the process, to lower high pro-
nace using a hydrocarbon gas through the tube reactor duction costs, and improve the quality of the final product
over a period of time [16]. The basic mechanism in this pro- [17]. The type of carbon nanotube produced depends on the
cess is the dissociation of hydrocarbon molecules catalyzed metal catalyst used during the gas phase delivery [18]. In the
by the transition metal and saturation of carbon atoms in CVD process single wall nanotubes are found to be pro-
the metal nanoparticle [16]. Precipitation of carbon from duced at higher temperatures with a well-dispersed and sup-
the metal particle leads to the formation of tubular carbon ported metal catalyst while multi wall nanotubes are formed
solids in a sp2 structure [16]. at lower temperatures and even with the absence of a metal
The characteristics of the carbon nanotubes produced by catalyst [19], Fig. 2. To eliminate impurities formed during
CVD method depend on the working conditions such as the the process such as graphite compounds, amorphous car-
temperature and the pressure of operation, the volume and bon, fullerenes, coal and metal nanoparticles a purification
 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489 1479

Fig. 1 (continued)

is needed. This is achieved by oxidative treatments in the
gaseous phase, liquid phase, acid treatment, micro filtra-
tion, thermal treatment and ultrasound methods. After
the process is complete the samples need to be characterized
further. Techniques such as Raman scattering (RS), thermal
gravimetric analysis (TGA), scanning electronic micros-
copy (SEM) and atomic force microscopy (AFM) have been
used for such characterization [15].
4. Arc method
The arc method [2], in which carbon nanotubes were dis-
covered, is carried out in low pressure He or other neutral
atmosphere (Fig. 1(a)). Seales reaction chambers and vac-
uum equipment are needed to provide the atmosphere.
The products are known to be well graphitized but there
are some problems with this method. The growth needs
to be interrupted to remove the product from the chamber
[2]. The most widely used process in producing carbon
nanotubes is the electric arc discharge method, Fig. 1(d–
e). This same process is also used in producing fullerenes.
In this method an electric arc discharge is generated
between two graphite electrodes under inert atmosphere
of helium or argon. A very high temperature is obtained
which allows the sublimation of the carbon. Two kinds
of synthesis can be performed in the arc: evaporation of
pure graphite or co-evaporation of graphite and metal
[11]. For the carbon nanotubes to be obtained, purification
1480 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489
Fig. 2. TEM micrograph of a multi-walled carbon nanotube.
by gasification with oxygen or carbon dioxide is needed
[20]. The first successful production of multi wall nano-
tubes at the gram level was developed in 1992 by Ebbesen
and Ajayan [21]. For single wall nanotubes to be obtained
a metal catalyst is needed and this first success of achieving
substantial amounts came in 1993 by Bethune coworkers
[22]. Process parameters involve small gaps between elec-
trodes (>1 mm), high current (100 A), plasma between
the electrode at about 4000 K, voltage range (30–35 V)
under specified electrode dimensions.
5. Laser ablation method
The laser ablation method is the second technique for
producing carbon nanotubes which is very useful and pow-
erful (Fig. 1(f)). This process is known to produce carbon
nanotubes with the highest quality and high purity of single
walls [23]. Laser ablation was the first technique used to
generate fullerenes in clusters. In this process, a piece of
graphite is vaporized by laser irradiation under an inert
atmosphere. This results in soot containing nanotubes
which are cooled at the walls of a quartz tube. Two kinds
of products are possible: multi walled carbon nanotubes or
single walled carbon nanotubes [11]. For this process a
purification step by gasification is also needed to eliminate
carbonaceous material. The effect of the gasification
depends on the type of reactant used [24]. The first growth
of high quality single wall nanotubes was achieved by
Smalley and coworkers [25].
6. Other methods
Another method which is still being explored is through
solar energy (Fig. 1(g–h)). It was used only for fullerene
production until 1996. In this method nanotubes are now
produced using highly concentrated sunlight from a solar
furnace. The sunlight is focused on a graphite sample and
vaporizes the carbon. Soot containing the nanotubes is then
condensed in a dark zone of a reactor, which is collected in a
filter and water cooled [11]. Carbon nanotubes can also be
produced under chemical methods. The catalytic decompo-
sition of hydrocarbons is performed in a flow furnace at
high temperatures. It results in four structural forms: amor-
phous carbon layers on the surface of the catalyst, filaments
of amorphous carbon, graphite layers covering metal parti-
cles, and multi wall carbon nanotubes. Electrolysis pro-
duces carbon nanotubes by passing an electric current in a
molten ionic salt between graphite electrodes [11].
Other methods which have been recently developed such
as the plasma torch method, was designed on the basis that
carbon nanotubes would naturally grow in any environ-
ment in which both appropriate metal atoms and carbon
atoms are present. The underwater AC electric arc method
actually combines the underwater growth with the use of
an AC controlled power supply. Using environments such
as microgravity can also help lead to better nanotubes and
production by eliminating the effects of uncontrolled buoy-
ancy [7].
Some of the methods are more effective than others but
a problem that all methods face is the ability for the carbon
nanotubes to self align. Many applications of carbon nano-
tubes require controlled growth of aligned carbon nano-
tubes with surface modification. Controlled synthesis of
well aligned nanotubes in predetermined patterns is partic-
ularly important in terms of fundamental studies and appli-
cations [26] (Fig. 3). Depending on which substrate is being
used in the CVD process two-dimensional (2D) or three-
dimensional (3D) micropatterns can be produced [26].
Self-alignment is a key technology in silicon device manu-
facturing and could benefit nanomechanical fabrication
processes because patterned layers can be produced with-
out additional lithography steps and could provide more
accurate alignment than lithography. One successful
method has been performed through the synthesis of car-
bon nanotubes in an enhanced CVD process on Si wafers
and patterned Si wafers with parallel line arrays and holes
and using Fe and CoSix as a catalyst [27]. This process suc-
cessfully produced carbon nanotubes and carbon nanorods
which were aligned and parallel to the substrate which
favors applications towards microelectronic devices [27].
7. Structure
Carbon nanotubes are built from sp2 carbon units and
consist of honeycomb lattices and are a seamless structure.
They are tubular having a diameter of a few nanometers
but lengths of many microns. MWNTs are closed graphite
tubules rolled like a graphite sheet, Fig. 2. Diameters usu-
ally range between 2 and 25 nm, and the distance between
sheets is about 0.34 nm [28], Fig. 3. single-walled carbon
nanotubes’ (SWNT) are made of a single seamlessly rolled
graphite sheet with a typical diameter of about 1.4 nm
which is similar to a buckyball (C60) [16] (Fig. 4). They
 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489 1481

Fig. 3. Micrographs showing carbon nanotubes (a) macrograph of carbon nanotubes, (b) scanning electron micrographs of CNTs at 10,000 and 20,000
magnification, (c) aligned carbon nanotubes.

have a tendency to form in bundles which are parallel in
contact and consist of tens to hundreds of nanotubes [29].
Depending on how the grapheme walls of the nanotube
are rolled together they can result in an armchair, zigzag or
chiral shapes (Fig. 5). These groups are distinguished by
their unit cells which are determined by the chiral vector
given by the equation: C h ¼ n^ a1 þ m^ a2 where ^
a1 and ^a2
are unit vectors in the two-dimensional hexagonal lattice,
and n and m are integers. Another important parameter
is the chiral angle, which is the angle between Ch and ^a1
(Fig. 6). When n = m and the chiral angle is 30 degrees it
is known as an armchair type. When m or n are zero and
the chiral angle is equal to zero the nanotube is known as
zigzag. Chiral nanotubes are therefore when the chiral
angles are between 0° and 30°. The diameter is found by
€ 2 2 1=2
the equation d t ¼ ðO3=pÞa cc ðm þ mn þ n Þ , where ac–c
is the distance between neighboring carbon atoms in the
flat sheet. The phase difference is known to be 2P, where,
for example, 10 hexagons are around the circumference
of a zigzag type, the 11th would collide with the first when
it comes around the circumference once [30].
The chiral angles along with diameter determine the
properties of the nanotube. Studies of optical properties
of nanotubes show that in most cases they act as semi
1482 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489
Fig. 4. Structures of (a) diamond, graphite, and fullerene (from R.E.
Smalley), (b) a single-wall helical carbon nanotube [3].
Fig. 5. Illustrations of the atomic structure of (a) an armchair and (b) a
ziz-zag nanotube [33].
conductors but in a few rare cases they act as metallic. This
metallic behavior only happens when n  m = 3L and
L = 0, resulting in the (HOMO–LUMO) fundamental
gap being 0.0 eV. The electronic properties are a result of
the electrons being normal to the nanotube axis. While act-
ing as a semi conductor the fundamental gap was found to
be 0.5 eV, which was a function of the diameter which
causes them to exist as ropes in their native state [30].
The energy gap is found by Egap = 2y0acc/d, where y0 is
the C–C tight bonding overlap energy (2.7 ± 0.1 eV), acc
is the nearest neighbor C–C distance (0.142 nm), and d is
the diameter. Studies also showed that a small gap would
exist because of P/r bonding orbital and P*/r* anti-bond-
ing orbital at the Fermi level. The Fermi energy is the high-
Fig. 6. Schematic diagram showing how a hexagonal sheet of graphite is
‘rolled’ to form a carbon nanotube [33].
est occupied orbital, has finite density neighboring carbon
atoms in the flat sheet. The phase difference is known to
be 2P, levels for a metallic tube and zero for a semiconduc-
tor. The density state occurs at sharp peaks as the energy
level is increased [4].
8. Properties
Carbon nanotubes are unique nanostructures which are
known to have remarkable electronic and mechanical
properties. These characteristics have sparked great interest
in their possible uses for nano-electronic and nano-
mechanical devices. Properties of carbon nanotubes can
also be expanded to thermal and optical properties as well.
Carbon nanotubes are predicted to have high stiffness and
axial strength as a result of the carbon–carbon sp2 bonding
[31]. Studies exploring the elastic response, inelastic behav-
ior and buckling yield strength and fracture need to be con-
ducted to find practical uses of the nanotubes.
The mechanical properties of a solid must ultimately
depend on the strength of its interatomic bonds. With
knowledge of known properties of crystal graphite the
mechanical properties of carbon nanotubes can be pre-
dicted with some confidence [32]. Experimental and theo-
retical results have shown an elastic modulus of greater
than 1 TPa (that of a diamond is 1.2 TPa) and have
reported strengths 10–100 times higher than the strongest
steel at a fraction of the weight [33]. It has been predicted
that carbon nanotubes have the highest Young’s modulus
of all different types of composite tubes such as BN, BC3,
BC2N, C3N4, CN, etc. [34] (Table 1). The definition of
Young’s modulus involves the second derivative of the
energy with respect to the applied stress/strain. In general,
the strength of the chemical bonds determines the actual
value of Young’s modulus and smaller diameters result in
a smaller Young’s modulus. However, in tests conducted
on carbon nanotubes show that little dependence exists
on the diameter of the tube with Young’s modulus, which
does help to hypothesize that carbon nanotubes do possess
the highest Young’s modulus which is expected around
 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489
Table 1
Mechanical properties of carbon nanotubes [5]
Material Young’s modulus Tensile strength
(GPa) (GPa)
Single wall nanotube 1054 150
Multi wall nanotube 1200 150
Steel 208 0.4
Epoxy 3.5 0.005
Wood 16 0.008
1 TPa [35]. Experiments conducted have resulted in tensile
strengths in the range from 11 to 63 GPa, with dependence
on the outer shell diameter, which is not far from the the-
oretical yield strength of 100 GPa.
Due to high in-plane tensile strength of graphite, both
single and multi wall carbon nanotubes, are expected to
have large bending constants since they mostly depend on
Young’s modulus. The nanotube has been found to be very
flexible. It can be elongated, twisted, flattened, or bent into
circles before fracturing. Simulations conducted by Bern-
holc and colleagues indicate it can regain their original
shape. Their ‘kink-like’ ridges allow the structure to relax
elastically while under compression, unlike carbon fibers
which fracture easily [4].
The unique elastic and inelastic properties have brought
about more studies on the durability of carbon nanotubes.
For single wall nanotubes simulations of deformations
showed that each shape change corresponded directly to
an abrupt release in energy and a singularity in the
stress/strain curve. The nanotubes were found to have an
extremely large breaking strain which decreased with tem-
perature. However, it was concluded single wall nanotubes
were subject to buckling under high pressure, which is
responsible for the pressure induced abnormalities of vibra-
tion modes and electrical resistivity (Fig. 7). The elastic
modulus, Poisson’s ratio and bulk modulus were all found
to be directly affected by the tubes radius. A max bulk
modulus was found to be 38 GPa with samples having a
radius of 0.6 nm. For multi-wall nanotubes the properties
were a little more complicated to calculate. An empirical
lattice dynamics model was used, which showed that
multi-wall nanotubes were insensitive to parameters such
as the chirality, tube radius, and the number of layers.
Thermal properties including specific heat and thermal
conductivity of carbon nanotubes are determined primarily
by the phonons [31]. A phonon is a quantum acoustic
energy similar to the photon. Phonons are a result of lattice
vibrations observed in the Raman spectra [4]. Especially at
low temperatures the phonon contribution to these quanti-
ties dominates and is due to the acoustic phonons. The
measurements of thermoelectric power of nanotube sys-
tems give direct information for the type of carriers and
conductivity mechanisms.
Theoretical and experimental results show superior elec-
trical properties of carbon nanotubes. They can produce
electric current carrying capacity 1000 times higher than cop-
per wires [36]. For 1D systems cylindrical surface, transla-
1483
Density
(g/cm3)
2.6
7.8
1.25
0.6
Fig. 7. TEM micrograph and computer simulation of nanotube buckling
[33].
tional symmetry with a screw axis could affect the
electronic structures and related properties. The electronic
capabilities possessed by carbon nanotubes are seen to arise
predominately from interlayer interactions, rather than from
interlayer interactions between multilayers within a single
carbon nanotube or between different nanotubes [37].
These optical properties have proved to be especially
unique with capabilities of acting as either a metallic or
semiconductor, which depends on tubule diameter and chi-
ral angle. Studies have shown that metallic conduction can
be achieved without introduction of doping effects. For
semiconducting nanotubes the band gaps have been found
to be proportional to a fraction of the diameter and with-
out relation to the tubule chirality [37]. The I-tight-binding
model within the zone folding scheme shows, one third of
carbon nanotubes are found to be metallic while two thirds
are semiconducting, depending on their indices [31]. Calcu-
lations based on the use of r and P bands, due to curva-
ture induced mixing of these bands, are used to predict
that some metallic nanotubes are very-small-band-gap
semiconducting nanotubes [38] (Fig. 8). The symmetry of
the structures basically relates all the calculations in both
single and multi-wall carbon nanotubes. Electronic proper-
ties of bundles of single wall nanotubes can be derived,
assuming the intertube interactions are not strong enough
to change the band structure. Broken symmetry caused
by interactions between tubes in a bundle create a pseudo-
gap of about 0.2 and 0.1 eV [39]. This pseudogap, which is
created can modify electronic properties such as semimetal-
like temperature dependence of the electrical conductivity
and a finite gap in the infrared absorption spectrum is pre-
dicted [31].
1484 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489
Fig. 8. Band-gap values vs. nanotube diameters define nanotubes as
metallic or semiconducting [5].
9. Applications
Carbon nanotubes have attracted a great deal of atten-
tion world wide with their unique properties which are
leading to many promising applications. Potential practical
applications have been reported such as chemical sensors
[40], field emission materials [41], catalyst support [42],
electronic devices [43], high sensitivity nanobalance for
nanoscopic particles [43], nanotweezers [44], reinforce-
ments in high performance composites, and as nanoprobes
in meteorology and biomedical and chemical investiga-
tions, 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 tem-
peratures 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 mate-
rials may be possible with the use of carbon nanotubes. The
first commercially recognized use for multi wall nanotubes
was electrically conducting components in polymer compos-
ites [50]. The matrices used in carbon nanotubes incorpo-
rated into composites can improve the electrical properties
which can act as a polymer, metal, or metal oxide [14]. Car-
bon nanotube metal or metal oxide composites have been
made to improve electrical conductivity. For applications
in polymer nanocomposites the elastic and fracture proper-
ties of carbon nanotubes must be understood along with
interactions at the nanotube matrix interface. The perfor-
mance of carbon nanotubes in a polymer or ceramic matrix
is well above traditional fillers such as carbon black or ultra
fine metal powders [51]. The major difference from conven-
tional fiber-reinforced composites in that the scale is nar-
rowed down to nanometers instead of micrometers [33].
Large similarities between mechanical properties of a
polymer film and a SWNT matrix exist in that both have
high viscoelasticity that can be evaluated using a nanoin-
dentor [52]. It would be difficult to replace all carbon fibers
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 stiffness
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 stiffness fall short of traditional carbon fibers.
For industrial applications as composites large quanti-
ties 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 nano-
tubes 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 prob-
lems by increasing Vickers hardness with single wall nano-
tubes and increasing the modulus of elasticity and breaking
stress in polystyrene using multiwall nanotubes [56].
Nanotube reinforced composites have already been suc-
cessfully created. Experiments on a fully integrated nano-
tube composite using single wall nanotubes demonstrated
dramatic enhancement of mechanical properties. To pro-
duce 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 1–4 wt% of sin-
gle wall nanotubes. The strain to failure also increased
showing an increase in toughness [57] (Fig. 9).
Rubber compounds reinforced by nanotubes are poten-
tial 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 exper-
imental 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 specu-
lation 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 conduc-
tivity to increase thermal conductivity by two or threefold
 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489
Fig. 9. Presence of 5 wt% multi wall carbon nanotubes results in a steeper
slope in the stress–strain curve [66].
when it should have been close to 50 fold [60]. The problem
is that carbon nanotubes vibrate at much higher frequencies
than the atoms in surrounding material which causes the
resistance to be so high the thermal conductivity is limited
[60]. Inducing stronger bonds between the nanotube and
other material might help in solving the problem [60]. The
use of carbon nanotubes to improve materials will be inves-
tigated in the future as production increases and applicabil-
ity in industrial settings become possible.
11. Sensors and probes
Carbon nanotubes have proved to have some advanta-
ges for sensing applications. Their small size with larger
surface; high sensitivity, fast response and good reversibil-
ity at room temperature enable them as a gas molecule sen-
sor [61]; enhanced electron transfer when used as electrodes
in electrochemical reactions [62]; and easy protein immobi-
lization with retention of activity as potential biosensors
[62] are among some of the desirable applications. Studies
have shown that surface modification performed on
aligned carbon nanotubes even furthers the sensitivity of
nanotube sensors [25]. The main advantage of these sensors
are the nanscopic size of the nanotube sensing element and
the corresponding nanoscopic size of the material required
for a response [50]. The mechanical robustness of the nano-
tubes and the low buckling force increase the probe life
along and minimizes damage during repeated hard crashes
into substrates [49]. The cylindrical shape and small tube
diameter also allow for imaging in narrow deep crevices
and improve resolution in comparison to conventional
nanoprobes, especially for high sample feature heights [63].
Electronic properties suggest carbon nanotubes will be
able to mediate electron transfer reactions with electro active
species in a solution when used as electrode material [64].
This leads to the idea that carbon nanotube based electrodes
can be used in miniature chemical sensing [65]. Electrode
materials with carbon nanotubes resulted in better behavior
than traditional carbon electrodes including good conduct-
ing ability and high chemical stability [29]. The electrical
1485
resistivity of single wall nanotubes have been found to
change sensitively on exposure to gaseous ambients contain-
ing NO2 , NH3 , and O2. By monitoring this change the pres-
ence of gases could be detected. Results showed are at least
an order of magnitude faster than those currently available
and that they could be operated at room temperature or at
higher temperatures for sensing applications [66]. This sens-
ing application is now being researched for its use on auto-
motive tires. A tiny sensor would be able to monitor and
report tire pressure to the driver while being able to with-
stand extreme temperature and vibrations [58].
Since multi wall nanotubes are conducting they can be
used as scanning probes on microscope tips in instruments
such as a scanning tunneling microscope (STM), atomic
force microscope (AFM) and electrostatic force micro-
scopes (Fig. 10). With their ultra high sensitivity, high res-
olution electron microscopes which have sub-nanoscale
accuracy have the ability to obtain information on the
atomic arrangement, element identification and electronic
structure of nanocarbon materials [67]. Nanotubes tips
can also be used for high resolution imaging or as active
tools for surface manipulation. On an AFM tip they can
be controlled like tweezers to pick up and release nanoscale
structures [68]. Nanoscopic tweezers have been made that
are driven by the electrostatic interaction between two
nanotubes on a probe tip [69].
Studies have shown the reversible bending of nanotubes
can be used to alter their conduction. Optimal designs such
as the zigzag and armchair nanotubes were observed to
have a difference in mechanical response at large bending
and the current passing through metallic structures
decreasing at larger bending angles as the semiconductor
increases [70]. The correspondence between mechanical
response and electronic transport has been proven poten-
tial applications of nanotubes in such applications as
nano-electro-mechanical sensors and even switches [71].
Fig. 10. Use of a MWNT as an AFM tip At the center of the vapor grown
carbon fiber (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].
1486 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489

Aligned multi-wall carbon nanotubes are now being Table 2

used for the development of an amperometric biosensor Threshold electrical field values for different materials for a 10 mA/cm2
current density [66]
[70]. Electrodes modified with carbon nanotubes are used
for the immobilization of enzymes and other redox pro- Material Threshold electrical field (V/m)
teins on the ends of aligned nanotube arrays [72], on the Mo tips 50–100
walls of carbon nanotubes [73] and inside nanotubes [74]. Si tips 50–100
p-type semiconducting diamond 130
It has been shown that small proteins can be entrapped Undoped, defective CVD diamond 30–120
into the inner channel of opened carbon nanotubes by sim- Amorphous diamond 20–40
ple absorption [75]. Azamaian et al. [73] demonstrated the Cs-coated diamond 20–30
principal where glucose oxidase was absorbed along the Graphite powder (<1 mm size) 17
length of carbon nanotubes and randomly distributed on Nanostructured diamonda 3–5 (unstable >30 mA/cm2)
Carbon nanotubesb 1–3 (stable at 1 A/cm2)
a glassy carbon electrode. The key in this design is the
a
establishment of electron transfer between enzyme active Heat-treated in H plasma.
b
Random SWNT film.
site and electrochemical conducer [71]. Small surface area
leads to constraints on enzyme loading [76]. Carbon nano-
tubes posses the high surface area needed along with the tron emissive materials should have low threshold emis-
structure dependant metallic character to promote electron sion fields and should be stable at high current density [66]
transfer reactions at low potentials [77]. Based on results, (Table 2). Carbon nanotubes posses the right combination
chemical etching was proven to be most efficient when of properties: nanometer size diameter, structural integrity,
opening carbon nanotubes and allowing the entrance of high electrical conductivity, and chemical stability that
the enzyme at the inner shell [71]. make good electron emitters [79]. The first field emission
Basic electronic properties of semiconducting carbon from carbon nanotubes was performed in 1995 by Rinzler
nanotubes change when placed in a magnetic field [78]. from single isolated multi wall nanotubes [80] and by multi
The ‘‘band gap’’ shrank which is unique among known wall nanotube film by de Heer [81]. Research on electronic
materials [78]. Nanotubes band gaps are comparable with devices has since focused primarily on the use of single
silicon and gallium arsenide which are currently the main- and multi wall carbon nanotubes as field emission electron
stays of the computer industry because their narrow band sources [82] for flat panel displays [83], lamps [84], gas dis-
gaps correspond with how much electricity it takes to flip charge tubes providing surge protection [85], and X-ray
a transistor from ‘on to off’ [78]. With the possibility of car- [86] and microwave generators [87]. A potential applied
bon nanotubes band gap disappearing all together in the between a nanotube coated surface and an anode creates
presence of stronger magnetic fields, they could take over high electric fields which is a result of a small radius of the
the roles of silicon and gallium arsenide potentially revolu- nanofiber tip and the length of the nanofiber [50]. The local
tionizing the computer industry [78]. fields cause electrons to tunnel from the nanotube tip to the
tunnel. This process of nanotube tip electron emission dif-
12. Field emission devices fers from that of bulk metals because it arises from discrete
energy states instead of continuous electronic bands and its
Field emission is a quantum effect when compared to behavior depends on the nanotube tip structure, single wall
thermionic emission. For technological applications, elec- nanotubes [88] or multi wall nanotubes [84] (Fig. 11).

Fig. 11. Left: Schematic of a prototype field emission display using carbon nanotubes. Right: A prototype 4.5_ field emission display fabricated by
Samsung using carbon nanotubes (image provided by Dr. W. Choi of Samsung Advanced Institute of Technologies).
 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489 1487

13. Flat panel displays Table 3

Hydrogen storage of carbon nanotubes to other carbon materials [66]
Flat panel displays are one of the more lucrative appli- Material Max. wt% H2 T (K) P (MPa)
cations of carbon nanotubes but are also the most techni- SWNTs (low purity) 5–10 133 0.040
cally complex. Nanotubes are at an advantage over liquid SWNTs (high purity) 4 300 0.040
crystal displays since they have low power consumption, GNFs (tubular) 11.26 298 11.35
GNFs (herringbone) 67.55 298 11.35
high brightness, a wide viewing angle, a fast response rate GNS (platelet) 53.68 298 11.35
and a wide operating system [50]. In the actual process elec- Graphite 4.52 298 11.35
tric fields direct the field-emitted electrons toward the GNFs 0.4 298–773 0.101
anode where phosphorus produces light for the flat panel Li-GNFs 20 473–673 0.101
display [50]. Prototype matrix-addressable diode flat panel Li-graphites 14 473–674 0.101
K-GNFs 14 <313 0.101
displays have been constructed at Northwestern University K-graphite 5.0 <313 0.101
[66]. One demonstration consists of nanotube-epoxy stripes SWNTs (high purity) 8.25 80 7.18
on the cathode glass plate and phosphor coated indium-tin- SWNTs (50% pure) 4.2 300 10.1
oxide (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 gen storage in these materials. The main ways to store
stripes to produce an image [66]. hydrogen is by metal hybrids, cryo-absorption, and by
the gas phase in metal hybrids [66]. Due to carbon nano-
14. Nanotube-based lamps tubes cylindrical shape and geometry, and nanometer –
scale diameters, it has been predicted that they will be able
Nanotube-based lamps are similar to displays compris- to store liquid as gas in the inner cores through capillary
ing of a nanotube-coated surface opposing a phosphor- effect improving metal hybrid batteries [94].
coated substrate, but they are less technically challenging
and require less investment [50]. With lifetimes expected 16. Electrochemical devices
in excess of 8000 h they can look to replace environmen-
tally problematic mercury-based fluorescent lamps used Carbon nanotubes have been studied for their potential
in stadium style displays [84]. Nanotube-based gas dis- uses as electrodes for devices that use electrochemical dou-
charge tubes might also find commercial use in protecting ble layer charge injection because of their high electro-
telecommunications networks from power surges [85]. chemically accessible surface area of porous nanotube
Another application arises if a metal target is used to arrays combined with high electric conductivity [50].
replace the phosphorescent screen at the anode. This causes Examples of such applications include ‘‘Supercapacitors’’
the accelerating voltage to increase producing X-rays which have capacitances much larger than ordinary dielec-
instead of light [50]. The compact geometry of the nano- tric based capacitor and electrochemical actuators which
tube based X-ray lead to potential uses for X-ray endo- may potentially be used in robots [50]. The capacitance
scopes and medical exploration [50]. for an electrochemical device depends on the separation
between the charge on the electrode and countercharge in
15. Energy storage the electrolyte. Since this distance is about a nanometer
for nanotubes in electrodes compared to a micrometer in
Graphite, carbonaceous materials and carbon fiber elec- ordinary dielectric capacitors, extremely large capacitances
trodes have been used for decades in fuel cells, batteries result from the high nanotube surface are accessible to the
and several other electrochemical applications [90]. Carbon electrolyte [50]. The use of nanotubes as electrodes in lith-
nanotubes are now being considered for energy storage ium batteries is a possibility because of the high reversible
and production because of their small dimensions, a smooth component of storage capacity at high discharge rates [50].
surface topology, and perfect surface specificity since only The reversible capacity reported with single wall nanotubes
the graphite planes are exposed in their structure [66]. The is 1000 mA h/g compared to 372 mA h/g for graphite [95]
efficiency of the fuel cells is determined by the rate of electron and 708 mA h/g for ball milled graphite [79].
transfer at carbon electrodes, which has been shown by sev-
eral experiments to be fastest on carbon nanotubes [91]. 17. Nanometer-sized electronic devices
The area of hydrogen storage is one of the most active
studies involving energy storage yet also the most contro- Recent advances have led to the idea that nanotubes will
versial. Extremely high and reversible hydrogen storage be useful for downsizing circuit dimensions. Presently, cur-
has been reported in materials containing single wall nano- rent-induced electromigration causes conventional metal
tubes [92] along with graphite nanofibers fibers [93] which wires interconnects to fail when the diameter becomes too
has attracted interest both in industry along with the aca- small [50]. The covalently bonded structure of carbon nano-
demic world (Table 3). The problem remains, however, in tubes militates against similar breakdown of nanotube wires
a lack of understanding of the basic mechanisms of hydro- and because of ballistic transport the intrinsic resistance of
1488 M. Paradise, T. Goswami / Materials and Design 28 (2007) 1477–1489
the nanotube should essentially vanish [50]. Experimental
results have shown that metallic single wall nanotubes can
carry up to 109 A/cm2 compared to current densities for
normal metals being only 105 A/cm2 [96].
The research of field effect transistors (NT-FETs) aims
to replace source drain channel structure with a nanotube.
Transistors assembled with carbon nanotubes may or may
not work however depending on whether the chosen nano-
tube is semiconducting or metallic, which the operator has
no control over [50]. It might be possible to peel back layers
from multi-wall nanotubes to achieve desired properties
but advances in microlithography are still needed to perfect
this reduction method. Recent developments have focused
the media attention to nanotube nanoelectronic applica-
tions [50]. Crossed single wall nanotubes have been used
in producing three and four-terminal electronic devices
[97] along with nonvolatile memory that functions like a
electromechanical relay [98]. Nanotube transistors [99]
have also been reported using integrated nanotubes which
may lead to large scale integration. Patterned growth of
carbon nanotubes on silicon wafers [100] may prove to
be the step needed to integrate nanotubes into electronics.
18. Conclusions
Carbon nanotubes may have only recently caught the
attention of the world but many advances have been made
since their discovery about a decade ago. They are unique
nanostructures that display the desirable properties of any
other known material. The techniques of production have
also come a long way but still have some room to be more
efficient and cost effective. They have amazing electronic
and mechanical properties which lead to incredible forms
of strength, and conductivity. Due to these qualities the
field of applications is almost endless. From reinforcements
in composites, sensors and probes, energy storage, electro-
chemical devices and nanometer sized electronics carbon
nanotubes could revolutionize the world.
Acknowledgements
One of the authors (T.G.) acknowledge Mr. Tom
Hughes of Applied Science Inc. for providing insights on
this subject and data. Mr. David Bennett assisted with
the illustrations. This research was a part of summer re-
search experience for undergraduates funded by Ohio
Northern University.
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