Review Articles

Carbon Letters Vol. 14, No. 3, 131-144 (2013)

Carbon nanotubes–properties and applications: a review

Khalid Saeed Ibrahim♠
Department of Chemistry, University of Malakand, Khyber Pakhtunkhwa, Pakistan

Article Info Abstract

Received 2 May 2013 The carbon nanotube (CNT) represents one of the most unique inventions in the field of nan-
Accepted 12 July 2013 otechnology. CNTs have been studied closely over the last two decades by many researchers
around the world due to their great potential in different fields. CNTs are rolled graphene
*Corresponding Author with SP2 hybridization. The important aspects of CNTs are their light weight, small size with
E-mail: [email protected] a high aspect ratio, good tensile strength, and good conducting characteristics, which make
them useful as fillers in different materials such as polymers, metallic surfaces and ceramics.
CNTs also have potential applications in the field of nanotechnology, nanomedicine, tran-
sistors, actuators, sensors, membranes, and capacitors. There are various techniques which
can be used for the synthesis of CNTs. These include the arc-discharge method, chemical
Open Access
vaporize deposition (CVD), the laser ablation method, and the sol gel method. CNTs can be
DOI: http://dx.doi.org/ single-walled, double-walled and multi-walled. CNTs have unique mechanical, electrical
DOI:10.5714/CL.2013.14.3.131 and optical properties, all of which have been extensively studied. The present review is
This is an Open Access article distributed focused on the synthesis, functionalization, properties and applications of CNTs. The toxic
under the terms of the Creative Commons effect of CNTs is also presented in a summarized form.
Attribution Non-Commercial License
(http://creativecommons.org/licenses/
by-nc/3.0/) which permits unrestricted Key words: carbon nanotube, synthesis, functionalization, toxic effect of CNTs
non-commercial use, distribution, and
reproduction in any medium, provided
the original work is properly cited.

1. Introduction

In recent years, much research has focused on nanotechnology and nanocomposites. Re-
searchers select specific filler and introduce it into a specific polymer to achieve a specific
composite with modified properties. If the filler is a nano material, the composite is termed a
nanocomposite [1]. Nanotechnology brings evolutionary changes to everyday life.

VOL. 14 NO. 3 July 31 2013

pISSN: 1976-4251
eISSN: 2233-4998
1.1 Nanotechnology

The word “nano” is from the Greek, meaning dwarf (small); scientific treatment at the
REVIEWS
Carbon nanotubes–properties and applications: a review
nano level (atomic level) with the help of special scientific instruments is known as nano-
technology, which has become a well-known field in the last three decades [2]. The word
Khalid Saeed Ibrahim
Graphene growth from polymers
Hong-Kyu Seo and Tae-Woo Lee
Preparation of needle coke from petroleum by-products
Humala Paulus Halim, Ji Sun Im and Chul Wee Lee

“nanotechnology” was coined by Norio Taniguchi in 1974, in Japan. He stated that, “nan-
Contact resistance in graphene channel transistors
Seung Min Song and Byung Jin Cho
carbonlett.org

otechnology mainly consists of the processing steps of the separation, consolidation and
deformation of materials by one atom or one molecule [3]. Nanotechnology is a vast field
which explores many facts about the structures and properties of materials.

1.2 Carbon nanotubes (CNTs)

KCS Korean Carbon Society

CNTs, also called buckytubes, are cylindrical carbon molecules with unique properties that
http://carbonlett.org make them potentially useful in a wide variety of applications. These include applications in
pISSN: 1976-4251 nano-electronics, optics, and materials applications. CNTs exhibit extraordinary strength as
eISSN: 2233-4998 well as unique electrical, mechanical and thermal properties. CNTs are the members of the
fullerene family, which was discovered by Kroto et al. [4] in 1985. Buckyballs are spheri-
Copyright © Korean Carbon Society cal fullerenes, whereas CNTs are cylindrical, with at least one end typically capped with a

131
Carbon Letters Vol. 14, No. 3, 131-144 (2013)

Fig. 2. Single-walled carbon nanotubes, surface and internal view. Re-

printed from Saether et al. [11] permission from Elsevier.

Fig. 1. (a) Formation of graphene derivatives. (b) Graphene sheet. (c)

Graphene sheets rolled into carbon nanotubes. Reprinted from Geim and Fig. 3. Double-walled carbon nanotubes. Reprinted from Pichler [12]
Novoselov [9] with permission from Nature Publishing Group and Shab- with permission from Nature Publishing Group.
nam et al. [10] with permission from Elsevier.

hemisphere with the buckyball structure. The name CNT derives

from the size, as the diameter of a nanotube is on the order of
a few nanometers. Iijima [5] first synthesized multi-walled car-
bon nanotubes (MWNTs) in 1991 using a simple arc-evaporation
method. However, CNTs were discovered long before research-
ers even imagined that carbon may exist in such a diverse allo-
tropic form. In 1952, Radushkevich and Lukyanovich [6] report-
ed the discovery of “worm-like” carbon formations. These were
observed during their study of the soot formed by the decomposi-
tion of carbon monoxide (CO) on iron particles at 600°C. On the Fig. 4. Multi-walled carbon nanotubes. Reprinted from Dresselhaus et
basis of many experiments and transmission electron microscope al. [14] with permission from Elsevier.
(TEM) images and other characterization techniques, the authors
concluded that the formed product consisted of long filamentary
or needle-like carbon crystals with diameters of about 50 nm. 1.4.1. Single-walled CNTs
The discovery of nanotubes passed almost unnoticed due to lack Single-walled CNTs (SWCNTs) are made of a single gra-
of attention to the field of nanotechnology at that time, like a phene sheet rolled upon itself with a diameter of 1–2 nm
number of other areas before and after [7]. (Fig. 2). The length can vary depending on the preparation
methods.
1.3 Structure of CNTs
1.4.2. Double-walled CNTs
CNTs, also known as tubular fullerenes, are cylindrical gra- These nanotubes are made of two concentric carbon nano-
phene sheets of sp2-bonded carbon atoms. In CNTs the graphene tubes in which the outer tube encloses the inner tube, as shown
sheet is rolled upon itself to form different allotropes of carbon, in Fig. 3.
including graphite, fullerenes and CNTs [8].
1.4.3. Multi-walled CNTs
1.4 Types of CNTs MWNTs consist of multiple layers of graphene rolled upon
itself with diameters ranging from 2 to 50 nm depending on the
CNTs can be divided into three categories on the basis of the number of graphene tubes. These tubes have an approximate
number of tubes present in the CNTs. These are described below. inter-layer distance of 0.34 nm [13].

DOI: http://dx.doi.org/10.5714/CL.2013.14.3.131 132

 Carbon nanotube-properties & applications

2.2. Laser ablation

In 1996, Thess et al. [20] reduced h i g h yields (>70%)

of CNTs by means of the laser ablation of graphite rods with
small amounts of Ni and Co at 1,200°C.
In this method, the graphite target is bombarded with laser
light. The tube grows until too many catalyst atoms aggregate
on the end of the nanotube. The large particles either detach or
become over-coated with sufficient amounts of carbon to poison
the catalysis. This allows the tube to terminate with a fullerene-
like tip or with a catalyst particle.

2.3. Chemical vapor deposition

In the above synthetic techniques, two major problems re-

Fig. 5. Different types of carbon nanotubes on the basis of chirality. Ah- main, i.e., the realization of both large-scale production and
mad et al. [16] with permission from Elsevier. ordered synthesis [21]. However, in 1996, a CVD was dis-
covered for nanotube synthesis [22,23]. This method is ca-
pable of controlling the growth direction on the substrate and
1.4.4. Types on the basis of chirality synthesizing a large quantity of nanotubes [22]. During this
Chirality is a very important factor in determining the electri- process, a mixture of hydrocarbon gas, acetylene, methane or
cal properties of CNTs. On the basis of chirality, there are three ethylene and nitrogen is introduced into the reaction chamber.
types of CNTs, i.e., chiral, armchair, and zigzag [15]. These During the reaction, nanotubes are formed on the substrate by
three types are shown in Fig. 5. the decomposition of the hydrocarbon at temperatures 700°C–
900°C at atmospheric pressure [23]. This technique has two
major benefits. The nanotubes are obtained at a much lower
2. Synthesis of CNTs temperature, although at a lower quality, and the catalyst can
be deposited over the substrate, which allows CNTs to adopt
CNTs can be prepared by various methods, such as the arc- well-organized structures.
discharge method, chemical vapor deposition (CVD), and laser
ablation. 2.4. Vapor-phase growth

2.1. Arc-discharge method This is a relatively new technique and a modified form
of CVD. The main difference is that the CNTs are syn-
In 1991, Iijima [5] reported the existence of a new tabular- thesized directly from the reaction gas and catalytic metal
shaped species, now called CNTs. The tubes were produced us- in the chamber without a substrate [24]. Two furnaces are
ing an arc-discharge evaporation method similar to that used for placed inside the reaction chamber. The catalyst used in
fullerene synthesis in the past. Carbon needles with diameters this case is ferrocene. Vaporization of catalytic carbon is
ranging from 4 to 30 nm and lengths up to 1 mm were grown on maintained at a relatively low temperature in the first fur-
the negative end (cathode) of a carbon electrode by means of the nace. Fine catalytic particles are formed here and when
direct current (DC) arc-discharge evaporation of carbon in an they reach the second furnace, and the decomposed car-
argon-filled vessel (100 torr). Ebbesen and Ajayan [17] reported bons are absorbed in this catalyst by diffusion, where they
the large-scale synthesis of MWNTs by this method. are converted into CNTs.
The arc-discharge assembly includes two vertical thin
electrodes installed in the center of the chamber. The lower 2.5. Flame synthesis method
electrode (cathode) has a shallow dip to hold a small piece
of iron during the evaporation phase. The arc-discharge c a n Another method by which CNTs can be prepared is the
b e generated by running a DC current of 200 A at 20 flame synthesis method. In this method, hydrocarbon flames
V between the two electrodes. The use of the three compo- are utilized. These flames assist with the initiation and
nents, argon, iron and methane, is critical for the synthesis growth of CNTs. Gases such as CO, CH4, C2H2, C2H4, and
of SWNTs. In the arc-discharge synthesis of nanotubes, C2H6, which are present in the post-flame area, are rich
Bethune et al. [18] used as anodes thin electrodes with bored sources of carbon. The reaction is exothermic and chemical
holes which were filled with a mixture of pure powdered energy released in the form of heat in the flame supports
metals (Fe, Ni or Co) and graphite. The electrodes were endothermic carbon deposition reactions. Catalysts are also
vaporized with a relatively low current of 95–105 A at 100– required to provide reaction sites for the deposition of solid
500 Torr in a He atmosphere. Large quantities of CNTs were black carbon. CNTs grow in the same manner as in CVD.
generated u s i n g t h i s technique by Journet et al. [19]. The If an appropriate catalyst and flame and reaction conditions
arc was generated between two graphite electrodes in a reac- are provided, large amounts of CNTs can be gained com-
tor under a helium atmosphere (660 mbar). mercially [25].

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Carbon Letters Vol. 14, No. 3, 131-144 (2013)

2.6. Recent trends in the synthesis of CNTs quasi-ballistic [42]. CNTs, due to their electronic nature, can be
used in transistors and other switching applications in advanced
A recent nebulized spray pyrolysis method has also been used electronics [43]. The most recent application of nanotubes was
for the synthesis of MWNTs. A nebulized spray, the key factor as an emitter. The important aspect of CNT emitters is that the
in this method, is generated by a special ultrasonic atomizer. emission can be obtained at a lower threshold voltage [44].
MWNTs with fairly uniform diameters in aligned bundles have CNTs can also be used in sensors, micron-scale on-chip triodes
been obtained via this technique. Using an ultrasonic nebulizer, at a high frequency (>200 MHz), vacuum microelectronics, and
ferrocene (catalyst) and ethanol (as solvent and carbon source) for X-ray generation [45,46].
are sprayed into a tubular furnace at a fixed temperature of
800°C under an argon flow of 1 L/min. Ethanol is used as a sol- 3.2. Mechanical properties of CNTs
vent as well as a carbon source due to its non-polluting nature,
low cost, harmless byproducts (e.g., CO), and ease of handling. CNTs are considering as the strongest materials in nature
High growth of MWNTs on a surface can be produced. The ad- at this point. The literature suggests that CNTs are very strong
vantage of using a nebulized spray is the ease of scaling into an materials, especially in the axial direction [47]. The Young’s
industrial-scale process, as the reactants are fed into the furnace modulus ranges from 270 to 950 GPa, while the tensile
continuously [26]. strength is also very high, in the range of 11–63 GPa. Several
reports have shown that in the radial direction, CNTs are rather
soft [48]. The first TEM observation of radial elasticity showed
3. Properties that Vander Waal’s forces can deform two adjacent nanotubes
[49]. Later, nano-indentations with an atomic force microscope
CNTs reportedly have extremely high surface areas, large (AFM) were performed by different groups of researchers to
aspect ratios, and remarkably high mechanical strength. The measure the radial elasticity of MWNTs quantitatively, and tap-
tensile strength of CNTs is 100 times greater than that of steel, ping/contact mode AFM was recently used to examine SWNTs
and the electrical and thermal conductivities approach those of [50-52]. The results showed that CNTs are in fact very soft in
copper [27,28]. These unique properties make CNTs good can- the radial direction. The radial direction elasticity of CNTs is
didates as fillers in different polymers and ceramics to realize important, especially for the formation of CNT nanocomposites
desirable consumer products [29,30]. It has also been predicted and their mechanical properties, in which embedded tubes are
that CNT-based field-effect transistors (FETs) will soon supplant subjected to large deformation in the transverse direction when
their silicon-based analog counterparts [31]. CNTs are also good a load is applied to a composite structure. Because the carbon-
incorporating agents due to their unique electrical, mechanical carbon bonds observed in graphite are among the strongest in
and thermal properties. nature, CNTs have excellent potential as they are the stiffest
and toughest structure ever synthesized by scientists. Studying
3.1. Electronic nature of CNTs CNTs under TEM has shown that these materials are flexible
and do not break upon bending [53-57]. Earlier theoretical cal-
CNTs show electrical properties in chiral forms. Researchers culations were carried out to predict the mechanical properties
have demonstrated that CNTs exhibit unique conductive proper- of CNTs [58-60]. The first attempt to determine the Young’s
ties. These results were the first to suggest that geometric differ- modulus for individual MWNTs was performed by Treacy et
ences such as defects, chirality, different diameters and the de- al. [28], who measured the amplitudes of thermal vibrations
gree of crystallinity of the tubular structure greatly influence the in CNTs under TEM. They demonstrated that nanotubes pos-
electronic properties of CNTs [32,33]. SWNTs are metals with sess an average Young’s modulus of Y = 1–1.8 TPa, which is
resistivities that range from 0.34 × 10–4 to 1.0 × 10–4 ohm·cm extremely high compared to commercially available carbon fi-
[27]. Considering the bonding of the carbon atoms in CNTs, bers (Y ≥ 800 GPa). Various research groups performed direct
arranged in a hexagonal lattice, each carbon atom is covalently measurements of the bending forces of MWNTs as a function
bonded to three neighbor carbons via sp2 molecular orbitals. of the displacement inside an AFM. The values for the Young’s
Thus, the fourth valence electron remains free in each unit, and modulus were found to be between 0.32 and 1.47 TPa [61-
these free electrons are delocalized over all atoms and contribute 70]. Falvo et al. [61] observed that MWNTs could be bent at
to the electrical nature of CNTs. Thus, CNTs can be conducting sharp angles without undergoing any structural fracturing us-
or semi-conducting types depending on the type of chirality [25- ing an AFM tip. Endo et al. [62] observed that while breaking
37] Semiconducting SWNTs are usually in the form of p-type vapor-grown CNTs in liquid nitrogen, an inner tubule could
semiconductors [38]. MWNTs are composed of many tubes of survive this pressure. Zhu et al. [63] applied high pressures (50
SWNTs and therefore are not likely to be strictly one-dimensional GPa) at room temperature, using shock waves, to arc-discharge
conductors. A pseudo-gap was observed in I –V measurements, MWNTs and noted that the tubes do not break but collapse;
which attributes to its conducting nature [39]. that is, the outer shells transform into curled graphene domains
From the above discussion, we note that the electrical proper- while the inner cores display structural defects. More theoreti-
ties of both SWNTs and MWNTs have been relatively well cal work on the mechanical properties of CNTs was carried out
explored. This area has been a field of great interest since the by Sinnot et al. [70], who found that SWNTs could exhibit a
last decade [40,41]. SWNTs, due to the ballistic nature of elec- Young’s modulus as high as that of diamond. Yakobson [71]
tron transport, can be described as quantum wires. On the other and Ru [72] proposed a mechanism of CNT transformation un-
hand, transport in MWNTs is found to be fairly diffusive or der uniaxial tension, leading to pentagon-heptagon defects in

DOI: http://dx.doi.org/10.5714/CL.2013.14.3.131 134

 Carbon nanotube-properties & applications

these tubes under high stress. Guanghua et al. [73] also showed
theoretically that the mechanical properties of SWNTs are
mainly dependent on the diameter. They estimated the theo-
retical Young’s modulus of nanotubes, of »1 nm diameter, is in
the range of 0.6–0.7 TPa. Hernandez et al. [74] also obtained
theoretical values of the Young’s modulus which were in close
agreement with those obtained experimentally for MWNTs
(1–1.2 TPa). They also reported that the increase in diameter
is proportional to the enhancement of the mechanical proper-
ties and that if the diameter is increased to a certain value, the
Young`s moduli of the tubes approach those of planar graphite.
Yu et al. [47,50] measured the Young’s modulus of individual Fig. 6. Most common types of functionalization. CNT, carbon nanotube.
Reprinted from Hirsch [84] with permission from Wiley-VCH Verlag GmbH.
SWNTs, reporting values between 320 and 1470 GPa and de-
termining a breaking strength of SWNTs on the perimeter of
each rope ranging from 13 to 52 GPa.

3.3. Thermal properties of CNTs

As rolled graphitic structures, CNTs are of great importance

and interest not only for their electronic and mechanical prop-
erties, but also for their thermal properties. Although their size
is very small, the quantum effects are important and the low-
temperature specific heat and thermal conductivity show direct
evidence of the 1-D quantization of the phonon band structure
in CNTs [56,70,75]. The incorporation of pristine and function- Fig. 7. Mechanism of carbon nanotube dispersion with the help of a sur-
alized nanotubes to different materials can double the thermal factant. Reprinted from Vaisman et al. [90] with permission from Elsevier.
conductivity for a loading of only 1%, showing that nanotube
composite materials may be useful for thermal management
applications in industries. Kim et al. [76] measured the thermal 4.1. Non-covalent functionalization
conductivity of individual MWNTs and found it to be 3,000
W/K (higher than that of graphite) at room temperature. Beside This type of functionalization is based on Van der Waal’s
this they also determined that the value is two orders higher than forces. Beside these forces, hydrophobic or Pi-Pi interactions
the magnitude those obtained for bulk MWNTs. A similar study have also been reported. Non-covalent functionalization is im-
was carried for SWNTs, with this result being greater than 200 portant and interesting because it does not damage or modify
W/m K for SWNTs [77]. There are several factors which influ- the CNTs structure to a great extent. In solution beside van-der
ence the thermal properties such as the number of phonon-active Waal’s forces some other forces are also involved, which render
modes, the length of the free path for the phonons, and boundary the efficiency of this type of functionalization. Some common
surface scattering [77-79]. These properties also depend on the examples of this type of functionalization include use of surfac-
atomic arrangement, the diameter and length of the tubes, the tant, especially with SWNTs, CNT wrapping, and non-covalent
number of structural defects and the morphology, as well as the protein interactions [84].
presence of impurities in the CNTs [80-82].
4.2. Covalent functionalization

4. Dispersion of CNTs In this type of functionalization, the desired groups are at-
tached onto the sidewall or tips of the CNTs permanently in an
One of the problems associated with CNTs is the agglomera- irreversible manner. Various chemical groups such as carboxyl-
tion of these tubes due to weaker intermolecular forces, leading ic, p-aminobenzoic acid, fluorine, added dichloro-carbon groups
to difficulty in their dispersion in different polymeric mediums are attached to the surface or at the ends of the CNTs [85-88].
and even in various solvents. The functionalization of CNTs is The advantages of chemical functionalization are that it can be
carried out to overcome their agglomeration and bundle forma- attached covalently with polymeric materials and dispersed well
tion, which also enhances their dispersion in polymeric materi- in different solvents. The main disadvantage of the chemical
als and solvents. Thus, the purification or functionalization of function is the production of defects on CNTs. Various methods
CNTs is very important to enhance their degrees of reactivity of the functionalization of CNTs are shown in Fig. 6.
and homogenous dispersion. Purification removes unwanted
particles that remain after the synthesis process, while function- 4.3. Dispersion of CNTs using surfactants
alization introduces a specific functional group onto the side
chains or ends of the CNTs [83]. Different methods are used The use of surfactants has also been reported for the purpose
by researchers for the functionalization and dispersion of CNTs. of CNT dispersion in polymeric materials [89]. Some impor-
These include the following: tant surfactants such as polyethylene glycol, sodium dodecyl

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Carbon Letters Vol. 14, No. 3, 131-144 (2013)

Fig. 9. Applications of CNTs.

gy conversion devices, field-emission devices, hydrogen storage

Fig. 8. Functionalization of carbon nanotubes. Reprinted from Wu et al.
[87] with permission from The Royal Society of Chemistry.
devices, and semiconductor devices [93,94]. Wastewater treat-
ment by CNTs is also a rapidly growing field for those who are
interested in adsorption studies [95]. The major problem associ-
sulfate, and dodecyl-benzene sodium sulfonate are commonly ated with CNTs is their high cost and nonrenewable characteris-
use for the reduction of the aggregative tendency of CNTs in tic. At present, special efforts are in progress to develop certain
water and other related solvents. It was proposed that the pres- preparation methods for CNTs which minimize their cost. Some
ence of benzene rings is responsible for the high dispersive ef- of the very important and promising applications of CNTs are
ficiency of CNTs. The p-stacking interactions of benzene rings discussed below in detail.
onto the CNT surfaces are believed to increase the adsorption
ratio of surfactants. It was also determined that besides aromatic 5.1. CNTs as fillers
groups, naphthenic (saturated rings) groups also provide good
surfactant-tube affinity. Fig. 7 show the mechanism by which the The use of CNTs as fillers in different materials to form nano-
surfactant micelles overcome the weaker Van der Waal’s forces. composites is one of the most developed fields in nanotechnol-
ogy. Many researchers working in the field of nanocomposites
4.4. Physical dispersion by ultrasonication have attempted to use CNTs as a filler. The main idea for incor-
porating CNTs into different polymeric and other materials is
Physical dispersion is also an important way to decrease the to improve the properties of these materials. By doing so, the
agglomeration tendency of CNTs. Sonication provides certain mechanical, electrical and thermal properties are improved to al-
vibrational energies to agglomerated CNTs, overcoming the at- most an ideal range. Garcia-Gutierrez et al. [96] prepared Melt-
tractive forces within the nanomaterials and becoming dispersed processed injected molded polybutylene terephthalate (PBT)/
within a solvent or polymeric material. Fig. 8 shows different SWNTs nanocomposites and presented that SWNTs effect
approaches for the functionalization of CNTs. the polymer orientation during shearing and also template the
crystallization behavior of PBT. Soichia et al. [97] found that
the tensile modulus and yield strength increased with an addi-
5. Applications of CNTs tion of SWNT loading in a SWNTs/polyimide nanocomposite.
With good dispersion, they showed that the mechanical prop-
Nanotechnology is one of the latest and the most developed erties of polyimide were enhanced. Bhattacharyya et al. [98]
technologies, presenting many advantages and benefits for new prepared melt-mixed styrene maleic anhydride (SMA) encap-
materials with significantly improved properties. Nanotechnol- sulated SWNTs with a polyamide-12 (PA12) matrix in a coni-
ogy can be used in different applications in various fields, in- cal twin-screw extruder. The process of encapsulation by the
cluding nano-medicine, energy, the environment, and in sensors SMA copolymer leads to a greater dispersion of SWNT and thus
[91]. Although the fields of nanotechnology are vast and new enhances the interfacial adhesion between the PA12 and SMA-
materials come into use regularly, the potential of CNTs is most modified SWNT. This leads to enhanced mechanical properties
promising. Since their discovery by Iijima [5] in 1991, CNTs are of the formed product. Saeed and Park [99] prepared MWNT/
the most rapidly growing nanomaterials in the field of nanotech- nylon nanocomposites by in situ bulk polymerization. They used
nology due to their various applications. Many investigators and pristine MWNTs (P-MWNTs) and purified acid-treated MWNTs
researchers have dedicated much effort to the creation of novel (A-MWNT) as a reinforcing material and studied the mechani-
properties and to expanding the number of novel applications in cal, thermal, electrical, and rheological properties as well as the
diverse fields, from materials science, medicine, electronics and structural morphology and crystallization temperature via vari-
energy storage, with many studies focusing on nanotechnology ous techniques and compared the properties of both P-MWNT/
and the use of CNTs as fillers [92]. More attractive applications nylon and A-PMWNT/nylon nanocomposites. It was concluded
of CNTs can be achieved through the use of CNTs for applica- that A-MWNTs can be well dispersed in nylon as compared
tions that require conductivity and a high absorption capacity to P-MWNTs due to the presence of functional groups on the
and for the creation of high-strength composites, fuel cells, ener- A-MWNTs. The crystallization temperature increased with

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 Carbon nanotube-properties & applications

an increase in the ratio of MWNTs in nylon. Prashantha et al. Beguin [112] showed that CNTs could be used in Li ion batter-
[100] prepared MWNTs and polypropylene (MWNT/PP) and ies. According to these authors, a high irreversible capacity is
MWNTs and polypropylene-grafted maleic anhydride (MWNT/ possible for CNTs. Meunier et al. [113] carried out calculations
PP-g-MA) nanocomposites and studied the rheological, me- to determine the charging and discharging phenomenon in Li+
chanical, and morphological properties of these nanocompos- batteries. They suggested that by damaging the surface of the
ites with various compositions of MWNTs using a range of SWNT materials chemically or mechanically, one can increase
techniques. They reported that MWNTs have better dispersion the electrochemical storage of these batteries. On the basis of
in PP-g-MA as compared to PP, and reported that MWNTs and such possibilities, many electronics companies have begun to
PP-g-MA have good adhesion and strong interfacial strength as use carbon nanofibers and nanotubes as the electrodes in Li+ bat-
compared to MWNTs/PP because the MWNTs/PP-g-MA have teries to enhance their storage capacity and lifetimes.
high mechanical properties and an improved rheological per-
colation threshold. Zhang et al. [101] fabricated poly (adipic 5.4. CNTs in supercapacitors and actuators
acid-hexamethylene diamine) (PA66) and F-MWNTs. Amino-
MWNTs were used in the fabrication process, and the disper- Due to their large surface area as well as their high electrical
sion of A-MWNTs was increased in formic acid (HCOOH) after conductivity, CNTs are excellent materials for use in electro-
PA66 functionalization. The PA66 materials were grafted onto chemical devices [107]. Niu et al. [114] and Ma et al. [115] were
the surface of A-MWNTs. It was concluded that the chain length the first to demonstrate that with sheet electrodes of pyrolyti-
of the PA decreased with an addition of A-MWNTs, the thermal cally grown MWNTs, it is possible to achieve very high specific
decomposition temperature of the PA-MWNTs were higher than capacitances in individual cells in devices containing 38 wt% of
that of the pure PA66 composite, and the storage modulus was H2SO4 as the electrolyte. The cells could reach power densities
improved with an addition of A-MWNTs. that exceeded 8,000 W/kg. Recently, a similar study was carried
out by Frackowiak and Beguin [112] and Ma et al. [115], who
5.2. In electronic devices as field-emission demonstrated that MWNT-polypyrrole composites are able to
sources reach specific capacitances of 163 F/g. CNT supercapacitors are
used in applications to devices that require high power capabili-
CNTs can be used in electric devices as field-emission sourc- ties and higher storage capacities. The power densities approach
es. This can be done when a potential is applied between the 20 kW/kg at energy densities of 7 Wh/kg [112]. CNT-embedded
CNT surface and the anode. Electrons are easily emitted from supercapacitors can be used to provide fast acceleration and to
their tips due to the curvature present in the CNTs in the form store braking energy electrically for hybrid electric vehicles. Ac-
of pentagons [102,103] or due to the presence of oxidized tips tuators are important devices, but the problem associated with
[104,105]. With this principle, CNTs can be used for the fabri- them is that their efficiency decreases with an increase in the
cation of multiple electronic devices [104], including flat-panel temperature. Therefore, CNT-modified actuators were prepared
displays, intense light sources, bright lamps [93,106,107], and by several researchers. These work at relatively low voltages
X-ray sources [46,108]. Although CNTs are good emitters, and at temperatures as high as 350oC [116]. For example, the
nanocomposites of CNTs are also excellent electron-emission maximum stress observed in SWNT actuators was 26 MPa
surfaces which are vacuum stable [109]. There are many advan- [117]. This value is comparable to that of natural muscles, as it
tages when using CNTs as an electron emitter. These include is 100 times larger than the value for natural muscle [103].
long lifetimes of the components, stable field-emission over
prolonged time periods, low emission threshold potentials, the 5.5. Sensors
absence of the need for an ultra-high vacuum, and high current
densities. It has been reported that large current densities as high Sensors are important detecting devices that are now widely
as 4 A/cm2 [107] can be achieved. used in different fields. The efficiency of biosensors and molecu-
lar sensors can be enhanced by attaching CNTs onto them. With
5.3. Batteries (Lithium ions batteries) chemical force microscopy techniques, Wong et al. [118] were
the first to demonstrate that it is possible to sense functional
Lithium (Li) is a useful element, as it offers unique proper- chemical groups attached onto the ends of CNTs. Thus, it is pos-
ties due to its lowest electronegativity and because electrons sible to construct various types of sensors containing nanotube
are easily donated from Li. Thus, it is the best candidate for the composite pellets, which are very sensitive to gases and which
fabrication of lightweight and efficient batteries. However, de- can be used to monitor leaks in chemical plants. Collins et al.
spite the above advantages, the high reactivity of Li limits its [119] reported after working in a similar field that SWNTs are
applicability, as the metal loses its efficiency. This problem can extremely sensitive to air and vacuum conditions by noting large
be solved by the combining an application of CNTs and Li by in- variations in the electrical resistance levels of their SWNT sam-
tercalating Li ions within CNTs. This enables Li+ ions to migrate ples. They also added that MWNTs can be used as efficient sen-
from a graphitic anode to the cathode. A separating medium is sors for NH3, H2O, CO2 and CO. Varghese et al. [120] detected
required between the anode and cathode, usually polyolefin. changes in the resistance and capacitance levels of CNTs when
The theoretical Li storage capacity is expected to be 372 mAh/g the environment was slightly modified. In 2002, highly sensitive
when intercalated with CNTs. The charge and discharge phe- and fast-responsive microwave-resonant sensors were prepared
nomena in these batteries are controlled by the Li+ intercalation for detecting NH3 using either SWNTs or MWNTs [121]. In ad-
and de-intercalation rates [110,111]. Recently, Frackowiak and dition to gas sensing, CNTs and its composites can be used as

137 http://carbonlett.org
Carbon Letters Vol. 14, No. 3, 131-144 (2013)

sensitive environmental pressure sensors [122]. Wood and Wag- show clear advance regarding the use of nanotubes in current
ner noted that CNTs are very sensitive to liquid immersion or technologies, and it is clear that in the near future, further ad-
polymer-embedding processes, as the nanotubes slightly deform vances will be achieved.
in the presence of different liquid media [123].
5.8. Electronic devices using CNTs
5.6. Gas and hydrogen storage
CNTs are important nanomaterials that can be used in elec-
Due to their hollow cylindrical nature, CNTs can act as ef- tronic devices to improve the properties of these devices. Tans
ficient gas and metal containers. It has been found that many et al. [38] fabricated a three-terminal switch-able device based
important chemical species, such as metals, metal carbides, and upon SWNTs. The SWNT molecule was semiconducting and
oxides, can be introduced into CNT core by different methods, connected to metal nanoelectrodes. The performance at a low
including (a) chemical treatments, arc-discharge methods, solid- capacitance level was excellent. The major problem associated
state reactions and electrochemical techniques [124]. However, with nanotubes is the difficulty in manipulating them; thus, an-
the major issues pertaining to these techniques are related to the other method was devised to control the length and the elec-
fact that CNTs are not able to encapsulate gaseous substances. tronic properties of individual nanotubes by STM nanostruc-
Recent studies have revealed that H2 and Ar can be stored in turing [140]. Postma et al. [141] described that crossings and
SWNTs [125,126] and MWNTs [127], respectively. Terrones bends with SWNTs could be generated by means of AFM. This
et al. [128] demonstrated experimentally that it is possible to technique allows us to cut nanotubes into shorter sections using
introduce gaseous nitrogen inside MWNTs using a single-step controlled voltages applied at the STM tips and to fabricate tiny
process. They also reported that MWNTs can be loaded via the nanotube devices that could be useful for the future construction
spray pyrolysis of ferrocene and benzyl amine solutions. Similar of molecular machinery, nano-scale circuits and other nanoelec-
work was carried out by Trasobares et al. [129], but they used a tric materials [140,142]. There are many examples of experi-
powder pyrolysis of ferrocene and camphor under an ammonia mental evidence indicating that CNTs can carry current densities
atmosphere. The storage of different chemical species in CNTs of 109 A/cm2; these values are much lower than those observed
may be advantageous for the fabrication of fuel cells for use in metals (105 A/cm2) [112]. Bachtold et al. [143] and Huang et
mainly to power electric vehicles. Unfortunately, there is some al. [144] demonstrated for the very first time the fabrication of
controversy regarding the high-pressure storage of hydrogen. It field-effect transistors that exhibit a high favorable gain, a large
is important to emphasize that the hydrogen storage capacity of on-off ratio and room-temperature operation. The researchers
CNTs ranges from 0.1 to 66 wt % [130,131]. Hirscher et al. [132] showed that one-, two- and three-transistor circuits exhibit a
proved that the influence of impurities (coming from the CNT range of digital logic operations. Examples include an inverter, a
synthesis methods) may be responsible for reported previously logic NOR, a static random-access memory cell, and an AC ring
results showing uptake levels as high as 7%. From a theoretical oscillator. A Harvard group in a similar way produced crossed
point of view, density functional theory has been used to cal- nanowire p-n junctions and junction arrays that were configured
culate the H2 storage capacity in CNTs. Different mechanisms as key OR and NOR logic-gate structures, showing substantial
by which CNTs possibly adsorb hydrogen molecules were pro- gain. They can be used for the development of novel computer
posed, including chemisorption, adsorption at interstitial sites, technologies in the near future. Derycke et al. [145] demonstrat-
and the swelling of the nanotube array [133-135]. ed that CNTs can be used as a FET. The researchers also showed
The above situations clearly show that CNTs may not be the that pristine CNTs always behave as p-type transistors, whereas
best material for storing hydrogen, but additional experiments doped-nanotubes act as n-type devices. Both types could be in-
and further calculations should be carried out in order to clarify tegrated to fabricate voltage inverters [139]. Javey et al. [146]
these results [136]. The adsorption of other gases such as He, demonstrated that it is possible to generate logic rings as well as
NH3, N2, and SF6 in CNTs as well as carbon foams, was recently NOR and OR logic gates using arrays of p- and n-type nanotube
achieved by Tanaka et al. [137]. FETs, as it is difficult to control the chirality of the tubes with
the electronic properties. Collins et al. [147] demonstrated that
5.7. Scanning probe tips it is possible to peel the outer layers of arc-discharged-produced
MWNTs until the desired electronic properties of the outer shell
Scanning probe tips are of great importance as they can be are obtained. However, controlled growth in order to achieve
used to obtain images with better resolutions. If a MWNT-bound selective chiralities needs to be investigated and exploited for
scanning probe is used instead of a normal probe, it becomes pos- more electrical applications. Blase et al. [148] also worked with
sible to obtain a better image resolution as compared to earlier a similar hypothesis and demonstrated that the electronic prop-
results [138]. Presently, Seiko Instruments and Daiken Chemical erties of CNTs can be utilized within polymeric materials to re-
Company are attempting to commercialize these probes. Chemi- alize desired electrical applications.
cally modified nanotube tips can be used as sensors for detecting
specific chemical and/or biological groups [125]. These sensors 5.9. Medical applications of CNTs
are important to detect added or even illegal substances. Kim
and Lieber [139] determined experimentally that it is possible to Given the increased profits associated with medical tech-
fabricate nanotube tweezers by attaching two nanotubes onto a nology related to gene therapy, cancer treatments, and innova-
probe tip. This nano-tool operates according to the electrostatic tive new answers for life-threatening diseases, the science of
interactions between two carbon cylinders. These achievements nanomedicine has become the most rapidly growing field. The

DOI: http://dx.doi.org/10.5714/CL.2013.14.3.131 138

 Carbon nanotube-properties & applications

unique properties and characteristics of CNTs enable scientists are needed if composite materials are to be fabricated. It is
to develop new areas in nanomedicine. SWNTs and MWNTs highly likely that low-cost gas sensors, nanotube fabrics, novel
have already proven their potential to serve as safer and effec- catalytic supports, three-dimensional composite materials, heat
tive alternatives to previous drug delivery methods. They can exchangers, biological microfilters, and virus inhibitors will be
pass through membranes, carrying therapeutic drugs, vaccines, produced using CNTs in the future. It was also reported that the
and nucleic acids deep into the cell to the substrate targets. They nanotube functionalization methods which disperse CNTs well
serve as ideal non-toxic vehicles, which in some cases, increase lead to less toxic CNTs than pristine CNTs.
the solubility of the drug, resulting in greater efficiency and
safety. Overall, recent studies of CNTs have shown a very prom-
ising future for them in medicine [149]. References

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