CONTENTS

1. INTRODUCTION

2. HISTORY

3. DISCOVERY

4. CLASSIFICATION OF CARBON NANOTUBES

5. SYNTHESIS OF CARBON NANOTUBES

6. MILESTONES IN CNT EVOLUTION

7. PROPERTIES OF CNT’S

8. ADVANTAGES

9. DISADVANTAGES

10. APPLICATIONS

11. CHALLENGES

12. CONCLUSION

13. REFRENCES

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1. INTRODUCTION
Carbon nanotubes (CNTs) take the form of cylindrical carbon molecules and have novel
properties that make them potentially useful in a wide variety of applications in nanotechnology,
electronics, optics, and other fields of materials science. They exhibit extraordinary strength and
unique electrical properties, and are efficient conductors of heat. Inorganic nanotubes have also
been synthesized.

Manufacturing a nanotube is dependent on applied quantum chemistry, specifically, orbital

hybridization. Nanotubes are composed entirely of sp2 bonds, similar to those of graphite. This
bonding structure, stronger than the sp3 bonds found in diamond, provides the molecules with
their unique strength. Nanotubes naturally align themselves into "ropes" held together by Van
der Waals forces. Under high pressure, nanotubes can merge together, trading some sp2 bonds
for sp3 bonds, giving great possibility for producing strong, unlimited-length wires through high-
pressure nanotube linking.

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes
have been constructed with length-to-diameter ratio of up to 132,000,000:1, significantly larger
than for any other material. These cylindrical carbon molecules have unusual properties, which
are valuable for nanotechnology, electronics, optics and other fields of materials science and
technology. In particular, owing to their extraordinary thermal conductivity and mechanical and
electrical properties, carbon nanotubes find applications as additives to various structural
materials. For instance, nanotubes form a tiny portion of the material(s) in some (primarily
carbon fiber) baseball bats, golf clubs, or car parts.

Nanotubes are members of the fullerene structural family. Their name is derived from their long,
hollow structure with the walls formed by one-atom-thick sheets of carbon, called graphene.
These sheets are rolled at specific and discrete ("chiral") angles and the combination of the
rolling angle and radius decides the nanotube properties; for example, whether the individual
nanotube shell is a metal or semiconductor.

Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi-walled nanotubes

(MWNTs). Individual nanotubes naturally align themselves into "ropes" held together by van der
Waals forces, more specifically, pi-stacking.
Applied quantum chemistry, specifically, orbital hybridization best describes chemical bonding
in nanotubes. The chemical bonding of nanotubes is composed entirely of sp2 bonds, similar to
those of graphite. These bonds, which are stronger than the sp3 bonds found in alkanes and
diamond, provide nanotubes with their unique strength.

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2. HISTORY
In 1952 L. V. Radushkevich and V. M. Lukyanovich published clear images of 50 nanometer
diameter tubes made of carbon in the Soviet Journal of Physical Chemistry. This discovery was
largely unnoticed, as the article was published in the Russian language, and Western scientists'
access to Soviet press was limited during the Cold War. It is likely that carbon nanotubes were
produced before this date, but the invention of the transmission electron microscope (TEM)
allowed direct visualization of these structures.
Carbon nanotubes have been produced and observed under a variety of conditions prior to 1991.
A paper by Oberlin, Endo, and Koyama published in 1976 clearly showed hollow carbon fibers
with nanometer-scale diameters using a vapor-growth technique. Additionally, the authors show
a TEM image of a nanotube consisting of a single wall of graphene. Later, Endo has referred to
this image as a single-walled nanotube.
In 1979, John Abrahamson presented evidence of carbon nanotubes at the 14th Biennial
Conference of Carbon at Pennsylvania State University. The conference paper described carbon
nanotubes as carbon fibers that were produced on carbon anodes during arc discharge. A
characterization of these fibers was given as well as hypotheses for their growth in a nitrogen
atmosphere at low pressures.
In 1981, a group of Soviet scientists published the results of chemical and structural
characterization of carbon nanoparticles produced by a thermocatalytical disproportionation of
carbon monoxide. Using TEM images and XRD patterns, the authors suggested that their
“carbon multi-layer tubular crystals” were formed by rolling graphene layers into cylinders.
They speculated that by rolling graphene layers into a cylinder, many different arrangements of
graphene hexagonal nets are possible. They suggested two possibilities of such arrangements:
circular arrangement (armchair nanotube) and a spiral, helical arrangement (chiral tube).

3. DISCOVERY
They were discovered In 1991 by the Japanese electron microscopist SUMIO IIJIMA NEC
Laboratory in Tsukuba-- used high-resolution transmission electron microscopy to observe
carbon nanotubes, And into the awareness of the scientific community. Iijima's discovery of
multi-walled carbon nanotubes in the insoluble material of arc-burned graphite rods in 1991 and
Mintmire, Dunlap, and White's independent prediction that if single-walled carbon nanotubes
could be made, then they would exhibit remarkable conducting properties helped create the
initial buzz that is now associated with carbon nanotubes. Nanotube research accelerated greatly
following the independent discoveries by Bethune at IBM and Iijima at NEC of single-walled
carbon nanotubes and methods to specifically produce them by adding transition-metal catalysts
to the carbon in an arc discharge. The arc discharge technique was well-known to produce the
famed Buckminster fullerene on a preparative scale, and these results appeared to extend the run
of accidental discoveries relating to fullerenes. The original observation of fullerenes in mass
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spectrometry was not anticipated, and the first mass-production technique by Krätschmer and
Huffman was used for several years before realizing that it produced fullerenes.

4. CLASSIFICATION OF CARBON NANOTUBES

Carbon nanotubes are mainly classified into two:-

1. Single-walled Nanotubes (SWNTS)

2. Multi-walled Nanotubes (MWNTS)

4.1 SINGLE-WALLED NANOTUBES (SWNTS)

 A single-walled carbon nanotube (SWNT) may be thought of as a single atomic layer

thick sheet of graphite (called graphene) rolled into a seamless cylinder.

 Most single-walled nanotubes (SWNT) have a diameter of close to 1 nanometre, with a

tube length that can be many millions of times longer.

 Single-walled nanotubes are an important variety of carbon nanotube because they

exhibit electric properties that are not shared by the multi-walled carbon nanotube
(MWNT) variants.

Single walled CNTS (Graphical Representation)

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4.2 MULTI-WALLED NANOTUBES (MWNT)

1. Multi-walled nanotubes (MWNT) consist of multiple rolled layers (concentric tubes) of

graphite.

2. There are two models which can be used to describe the structures of multi-walled
nanotubes.

3. In the Russian Doll model, sheets of graphite are arranged in concentric cylinders.

4. In the Parchment model, a single sheet of graphite is rolled in around itself, resembling a
scroll of parchment or a rolled newspaper. (The Russian Doll structure is observed more
commonly).

5. The telescopic motion ability of inner shells and their unique mechanical properties will
permit the use of multi-walled nanotubes as main movable arms in coming Nano
mechanical devices.

Multi Walled CNTS

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4.3 OTHER CARBON NANOTUBE STRUCTURES

Torus:-
Carbon nanotube bent into a torus (doughnut shape).Nanotori are predicted to have many unique
properties, such as magnetic moments 1000 times larger than previously expected for certain
specific radii. Properties such as magnetic moment, thermal stability, etc. vary widely depending
on radius of the torus and radius of the tube.

Nanobud:-
Carbon Nanobuds are a newly created material combining two previously discovered allotropes
of carbon: carbon nanotubes and fullerenes. In this new material, fullerene-like "buds" are
covalently bonded to the outer sidewalls of the underlying carbon. They are good field emitters.
In composite materials, the attached fullerene molecules may function as molecular anchors
preventing slipping of the nanotubes, thus improving the composite’s mechanical properties.

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GRAPHENATED CARBON NANOTUBES (G-CNTS):-
Graphenated CNTs are a relatively new hybrid that combines graphitic foliates grown along the
sidewalls of multi walled or bamboo style CNTs use in super capacitor applications.

PEAPOD:-

A Carbon peapod is a novel hybrid carbon material which traps fullerene inside a carbon
nanotube.

CUP-STACKED CARBON NANOTUBES:-


CSCNTs exhibit semiconducting behaviors due to the stacking microstructure of graphene
layers.

NITROGEN DOPED CARBON NANOTUBES:-

N-doping provides defects in the walls of CNT's allowing for Li ions to diffuse into inter-wall
space. It also increases capacity by providing more favorable bind of N-doped sites. N-CNT's are
also much more reactive to metal oxide nanoparticle deposition which can further enhance
storage capacity, especially in anode materials for Li-ion batteries. However Boron doped
nanotubes have been shown to make batteries with triple capacity.

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5. SYNTHESIS OF CARBON NANOTUBES
Techniques have been developed to produce nanotubes, including arc discharge, laser ablation
and chemical vapor deposition (CVD). Most of these processes take place in vacuum or with
process gases. CVD growth of CNTs can take place in vacuum or at atmospheric pressure. Large
quantities of nanotubes can be synthesized by these methods; advances in catalysis and
continuous growth processes are making CNTs more commercially viable.

SWNTs and MWNTs are usually made by carbon-arc discharge, laser ablation of carbon, or
chemical vapor deposition (typically on catalytic particle). Nanotube diameters range from 0.4
to 3 nm for SWNTs and from 1.4 to at least 100 nm for MWNTs. Nanotube properties can thus
be tuned by changing the diameter. Unfortunately, SWNTs are presently produced only on a
small scale and are extremely expensive. All currently known synthesis methods for SWNTs
result in major concentrations of impurities. These impurities are typically removed by acid
treatment, which introduces other impurities, can degrade nanotube length and perfection, and
adds to nanotube cost.

MWNTs produced catalytically by gas-phase pyrolysis, like the Hyperion nanotubes, have high
defect densities compared to those produced by the more expensive carbon- arc process.

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5.1 ARC DISCHARGE METHOD

CNT production requires 3 elements,

 Carbon feed

 Metal catalyst

 Heat

The nanotubes were initially discovered using this technique; it has been the most widely-
used method of nanotube synthesis.

 Two Graphite electrodes placed in an inert Helium atmosphere.

 When DC current is passed anode is consumed and material forms on cathode.

 For SWNT mixed metal catalyst is inserted into anode.

 Pure iron catalyst + Hydrogen-inert gas mixture gives 20 to 30cm long tube.

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5.2 LASER ABLATION

 In the laser ablation process, a pulsed laser vaporizes a graphite target in a high-
temperature reactor while an inert gas is bled into the chamber.

 Nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon
condenses.

 A water-cooled surface may be included in the system to collect the nanotubes.

 The laser ablation method yields around 70% and produces primarily single-walled
carbon nanotubes with a controllable diameter determined by the reaction
temperature.

 It is more expensive than either arc discharge or chemical vapor deposition.

LASER ABLATION METHOD

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5.3 CHEMICAL VAPOR DEPOSITION (CVD)

 During CVD, a substrate is prepared with a layer of metal catalyst articles

most commonly nickel, cobalt, iron, or a combination.

 The diameters of the nanotubes that are to be grown are related to the size of the
metal particles.

 The substrate is heated to approximately 700°c.

 To initiate the growth of nanotubes, two gases are bled into the reactor a process gas
(such as ammonia, nitrogen or hydrogen) and a carbon-containing gas (such as
acetylene, ethylene, ethanol or methane).

 Nanotubes grow at the sites of the metal catalyst.

 The carbon-containing gas is broken apart at the surface of the catalyst particle, and
the carbon is transported to the edges of the particle, where it forms the nanotubes.

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6. MILESTONES IN CNT EVOLUTION
The observation of the longest carbon nanotubes (18.5 cm long) was reported in 2009. These
nanotubes were grown on Si substrates using an improved chemical vapor deposition (CVD)
method and represent electrically uniform arrays of single-walled carbon nanotubes.

The shortest carbon nanotube is the organic compound cycloparaphenylene, which was
synthesized in early 2009.

The thinnest carbon nanotube is armchair (2,2) CNT with a diameter of 3 Å. This nanotube was
grown inside a multi-walled carbon nanotube. Assigning of carbon nanotube type was done by
combination of high-resolution transmission electron microscopy (HRTEM), Raman
spectroscopy and density functional theory (DFT) calculations
.
The thinnest freestanding single-walled carbon nanotube is about 4.3 Å in diameter. Researchers
suggested that it can be either (5,1) or (4,2) SWCNT, but exact type of carbon nanotube remains
questionable. (3,3), (4,3) and (5,1) carbon nanotubes (all about 4 Å in diameter) were
unambiguously identified using more precise aberration-corrected high-resolution transmission
electron microscopy. However, they were found inside of double-walled carbon nanotubes.

7. PROPERTIES OF CARBON NANOTUBES

Strength:-

Carbon nanotubes are the strongest, flexible and stiffest materials yet discovered in terms of tensile
strength and elastic modulus respectively.

This strength results from the covalent sp2 bonds formed between the individual carbon atoms
(which is stronger than the sp3 bonds found in Diamond & Alkenes).

CNTs are not nearly as strong under compression. Because of their hollow structure and high aspect
ratio, they tend to undergo buckling when placed under compressive, torsional or bending stress.

Hardness:-
The hardness (152 Gpa) and bulk modulus (462–546) of carbon nanotubes are greater than
diamond, which is considered the hardest material. (that of diamond is 150GPa & 420GPa).

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Kinetic Property:-
Multi-walled nanotubes, multiple concentric nanotubes precisely nested within one another; exhibit
a striking telescoping property whereby an inner nanotube core may slide, almost without friction,
within its outer nanotube shell thus creating an atomically perfect linear or rotational bearing, the
precise positioning of atoms to create useful machines.

Electrical Properties:-

Because of the symmetry and unique electronic structure of graphene, the structure of a nanotube
strongly affects its electrical properties.-Very high current carrying capacity.

Thermal Conductivity:-
All nanotubes are expected to be very good thermal conductors along the tube. ( Measurements
show that a SWNT has a room-temperature thermal conductivity more than copper.)

EM Wave absorption:-
Current military push for radar absorbing materials (RAM) to better the stealth
characteristics of aircraft and other military vehicles. (There has been some research on
filling MWNTs with metals, such as Fe, Ni, Co, etc., to increase the absorption
effectiveness of MWNTs in the microwave regime).

Thermal properties:-
All nanotubes are expected to be very good thermal conductors along the tube, but good
insulators laterally to the tube axis. (Measurements show that a SWNT has a room-
temperature thermal conductivity along its axis of about 3500 W·m −1·K−1, compare this
to copper, a metal well known for its good thermal conductivity, which transmits 385
W·m−1·K−1).

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 COMPARISON OF MECHANICAL PROPERTIES

Fiber material Specific Density Young's modulus(Tpa) Strength (Gpa) Strain at break(%)

Carbon 1.3 – 2 1 10 – 60 10
Nanotube
HS Steel 7.8 0.2 4.1 <10

Carbon fiber- 1.7 – 2 0.2 – 0.6 1.7 – 5 0.3 – 2.4

PAN
Carbon fiber- 2 – 2.2 0.4 – 0.96 2.2 – 3.3 0.27 – 0.6
Pitch
E/s-Glass 2.5 0.07 – 0.08 2.4 – 4.5 4.8

Kevlar-49 1.4 0.13 3.6 – 4.1 2.8

PROPERTIES OF CONDUCTIVE MATERIALS

Material Thermal conductivity Electrical conductivity

Carbon Nanotube > 3000 10^6 – 10^7

Copper 400 6 x 10^7

Carbon fiber-Pitch 1000 2 - 8.5 x 10^6

Carbon fiber-PAN 8 - 105 6.5 - 14 x 10^6

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DEFECTS:-

Toxicity:-
Under some conditions, nanotubes can cross membrane barriers, which suggests that if raw
materials reach the organs they can induce harmful effects such as inflammatory and fibrotic
reactions.

Crystallographic defect:-

As with any material, the existence of a crystallographic defect affects the material
properties. Defects can occur in the form of atomic vacancies.

8. ADVANTAGES
 Extremely small and lightweight.

 Resources required to produce them are plentiful, and many can be made with only a
small amount of material.

 Are resistant to temperature changes, meaning they function almost just as well in
extreme cold as they do in extreme heat.

 Improves conductive, mechanical, and flame barrier properties of plastics and

composites.

 Enables clean, bulk micromachining and assembly of components.

 Improves conductive, mechanical, and flame barrier properties of plastics and

composites.

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9. DISADVANTAGES
 Despite all the research, scientists still don't understand exactly how they work.

 Extremely small, so are difficult to work with.

 Currently, the process is relatively expensive to produce the nanotubes.

 Would be expensive to implement this new technology in and replace the older technology
in all the places that we could.

 At the rate our technology has been becoming obsolete, it may be a gamble to bet on
this technology.

10. APPLICATIONS

 Micro-electronics / semiconductor
 Conducting Composites
 Artificial muscles
 Super capacitors
• Batteries

• Field emission flat panel displays

• Field Effect transistors and Single electron transistors

• Nano electronics

• Nano balance

• Data storage

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 • Magnetic nanotube

• Nano gear

• Space Elevator

• Nanotube actuator

• Molecular Quantum wires

• Hydrogen Storage

• Noble radioactive gas storage

• Solar storage

• Electromagnetic shielding

• Thermal protection

• Nanotube reinforced composites

• Reinforcement of armor and other material

• Reinforcement of polymer

• Fly wheels

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 11. CHALLENGES

The greatness of a single-walled nanotube is that it is a macro-molecule and a crystal at the same
time. The dimensions correspond to extensions of fullerene molecules and the structure can be
reduced to a unit-cell picture, as in the case of perfect crystals. A new predictable (in terms of
atomic structure–property relations) carbon fiber was born. The last decade of research has
shown that indeed the physical properties of nanotubes are remarkable, as elaborated in the
various chapters of this book. A carbon nanotube is an extremely versatile material: it is one of
the strongest materials, yet highly elastic, highly conducting, small in size, but stable, and quite
robust in most chemically harsh environments. It is hard to think of another material that can
compete with nanotubes in versatility.

There are also general challenges that face the development of nanotubes into functional devices
and structures. First of all, the growth mechanism of nanotubes, similar to that of fullerenes, has
remained a mystery .With this handicap; it is not really possible yet to grow these structures in a
controlled way. Especially for electronic applications, which rely on the electronic structure of
nanotubes, this inability to select the size and helicity of nanotubes during growth remains a
drawback. More so, many predictions of device applicability are based on joining Nano-tubes via
the incorporation of topological defects in their lattices. There is no controllable way, as of yet,
of making connections between nanotubes. Some recent reports, however, suggest the possibility
of constructing these interconnected Structures by electron irradiation and by template mediated
growth and manipulation.

For bulk applications, such as fillers in composites, where the atomic structure (helicity) has a
much smaller impact on the resulting properties, the quantities of nanotubes that can be
manufactured still falls far short of what industry would need. There are no available techniques
that can produce nanotubes of reasonable purity and quality in kilogram quantities. The industry
would need tonnage quantities of nanotubes for such applications.

Another challenge is in the manipulation of nanotubes. Nano-technology is in its infancy and the
revolution that is unfolding in this .eld relies strongly on the ability to manipulate structures at
the atomic scale. This will remain a major challenge in this field, among several others.

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 12. CONCLUSION

Nanotubes appear destined to open up a host of new practical applications and help improve our
understanding of basic physics at the nonmetric scale.

Nanotechnology is predicted to spark a series of industrial revolutions in the next two decades that
will transform our lives to a far greater extent than silicon microelectronics did in the 20 th century.
Carbon nanotubes could play a pivotal role in this upcoming revolution if their remarkable structural,
electrical and mechanical properties can be exploited.

The remarkable properties of carbon nanotubes may allow them to play a crucial role in the relentless
drive towards miniaturization scale.

Lack of commercially feasible synthesis and purification methods is the main reason that carbon
nanotubes are still not widely used nowadays. At the moment, nanotubes are too expensive and
cannot be produced selectively. Some of the already known and upcoming techniques look
promising for economically feasible production of purified carbon nanotubes.

Some future applications of carbon nanotubes look very promising. All we need are better production
technique for large amounts of purified nanotubes that have to be found in the near future. Nanotube
promises to open up a way to new applications that might be cheaper, lower in weight and have a
better efficiency

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 BIBLIOGRAPHY

[1] WWW.PA.MSU.EDU/CMP/CSC/NANOTUBE.HTML

[2]Individual single-wall carbon nanotubes as quantum wires, SJ Tans, M H Devoret, H Dai, A

Thess, R E Smalley, L J Geerligs and C Dekker,Nature,386,474

[3]Defects in Carbon Nanotub by J.charlier (2003)

[4]T. Guo, P. Nikolaev, A. Thess, D.T. Colbert, R.E. Smalley, “Catalytic growth of single-walled
nanotubes by laser vaporization.”

[5] Ming Su, Bo Zheng, Jie Liu, “A scalable CVD method for the synthesis of single-walled carbon
nanotubes with high catalyst productivity.”

[6] Meo, S.B.; Andrews R. (2001). "Carbon Nanotubes: Synthesis, Properties, and Applications".
Crit. Rev. Solid State Mater. Sci.

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