Carbon nanotubes

Old and New Forms of Carbon

1779 was graphite discovered by Scheele
Ten years later Lavoisier realized that carbon belongs to the family of chemical
elements.
He identified diamond with another allotropic form of carbon.
At ambient pressure hexagonal graphite is the most stable carbon allotrope.
Conclusively at temperatures around 3000C poorly ordered carbons are usually
converted to well-ordered graphite materials
The conversion of graphite to diamond requires high pressure, as the density of
diamond (3.514gcm-3) is higher than that of graphite (2.26 g cm-3)

GRAPHITIC CARBONS
There are three different kinds of possible orientation for the graphene sheets:
(i) Plane orientation-graphite flakes, pyrolytic graphites;
(ii) Axial orientation (co-axial, radial) and graphite fibres; and
(iii) Point orientation (concentric, radial)-mesophase carbon microbeads, carbon
spherules

Fullerenes
The discovery of the fullerenes by Kroto, Smalley and Curl in 1985 - Nobel Prize
Award for Chemistry in 1996.
In 1990 Krgtschmer and Huffman
Fullerenes derivatives can be divided into three groups: endohedral compounds,
exohedral compounds and heterofullerenes

Endohedral
In endohedral fullerene compounds at least one atom or ion is located inside the
cage.
At least four principally different methods for the preparation of endohedrals have
been described:
(i) co-evaporization of carbon and metals or metaloxides (laser, arc vaporization);
(ii) Heating of fullerene material with gases under pressure (window mechanism);
(iii) Defined opening and closing of the fullerene cage by chemical reactions (not
yet achieved); and
(iv) Ion bombardment of fullerenes and fullerene films (comparatively high yield in
case of alkalimetal ions)

Exohedral
Covalent bonding, Intercalation

Heterofulllerenes
The discovery of fullerenes in 1985 by Curl, Kroto, and Smalley culminated in their
Nobel Prize in 1996.
Fullerenes, or Buckminsterfullerenes, are named after Buckminster
C60, contains 20 hexagonal faces and 12 pentagonal faces just like a soccer ball
and possess perfect icosahedral symmetry
Ijima in 1991 discovered carbon nanotubes that
conduct heat more than Copper
conduct electricity more than diamond
has stiffness much more than steel
has strength more than Titanium
is lighter than feather
can be a insulator or conductor just
based on geometry

Carbon nanotubes are fullerene-related structures which consist of graphene

cylinders closed at either end with caps containing pentagonal rings
CNTs can span 23,000 miles without failing due to its own weight.
CNTs are 100 times stronger than steel.
Many times stiffer than any known material
Conducts heat better than diamond
Can be a conductor or insulator without any doping
Lighter than feather

This is a nanoscopic structure made of carbon atoms in the shape of a hollow

cylinder. The cylinders are typically closed at their ends by semi-fullerene-like
structures. There are three types of carbon nanotubes:

Armchair,
Zig-zag and
Chiral (helical) nanotubes.

Fig. 1. Schematic diagram showing how a hexagonal sheet of graphite is rolled to form a carbon nanotube E.T. Thostenson et al

Two important consequences derive from the SWNT structure as described above:
1. 65 = 30 atoms at each tip are involved in pentagonal rings (considering that
adjacent pentagons are unlikely) In case SWNTs are ideally perfect, their chemical
reactivity will therefore be highly favored at the tube tips, at the very location of the
pentagonal rings.
2. Though carbon atoms are involved in aromatic rings, the C=C bond angles are no
longer planar as they should ideally be. This means that the hybridization of carbon
atoms is no longer pure sp2 but get some percentage of the sp3 character, in a
proportion that increases as the tube radius of curvature decreases.

Solid Carbon Source-Based Production Techniques for Carbon Nanotubes

Laser ablation, solar energy,
Electric arc
A high temperature (1,000K < T < 6,000 K) medium and the fact that the carbon
source originates from the erosion of solid graphite.
Laser vaporization of graphite was actually the very first method to demonstrate
the existence of fullerenes, including the most popular one

Laser Ablation

Electric-Art Method Experimental Devices

The principle of this technique is to vaporize
carbon in the presence of catalysts (iron, nickel,
cobalt, yttrium, boron, gadolinium, and so forth)
under reduced atmosphere of inert gas (argon or
helium). After the triggering of the arc between
two electrodes, a plasma is formed consisting of
the mixture of carbon vapor, the rare gas (helium
or argon), and the vapors of catalysts.
Two types of anodes can be utilized as soon as
catalysts need to be introduced: (1) graphite
anodes in which a coaxial hole is drilled several
centimeters in length and in which catalyst and
graphite powders are mixed; (2) graphite anodes
in which the catalysts are homogeneously

Template-based synthesis

Schematic illustration of the experimental procedure used generate metal

nanotubes that are characterized by co-axial, multiple walls; (A,C) template
engaged replacement reaction between Ag and HAuCl4 and (B) electroless
plating of Ag note that the cross-sections and side surfaces of the tubular
nanostructure are determined by the template

(b) laservaporization
apparatus

(a) Electric-arc method

(c) Electrolysis experimental system

(d) Arc discharge

(e) Arc-discharge technique.

(g) Solar furnace

(f) Laser ablation process.

Arc discharge synthesis uses

a low-voltage (~12 to 25 V), highcurrent (50 to 120 amps) power
supply (an arc welder can be used)

(e) Arc-discharge technique.

1.2 at. % of cobalt/nickel with 98.8 at.%
of graphite composite target that is
placed in a 1200C quartz tube furnace
with an inert atmosphere of ~500 Torr
of Ar or He and vaporized with a laser
pulse.
(f) Laser ablation process.

c) Chemical Vapor Deposition:

Hydrocarbon + Fe/Co/Ni catalyst CNT
Steps:
Dissociation of hydrocarbon.
Dissolution and saturation
of C atoms in metal nanoparticle.
Precipitation of Carbon.

Chemical vapor deposition

Choice of catalyst material?

Base Growth Mode or Tip Growth Mode?
Metal support interactions
Flame synthesis
a hydrocarbon flame composed of ~10%
ethylene or acetylene with Fe or Co
(cobaltacene, ferrocene, cobalt
acetylacetonate) particles interspersed and
diluted in H2 and either He or Ar was
ignited

(h) Solar experimental chamber

three types of mechanism have been put forward, which could be labeled gas, solid
and liquid.
GAS

SOLID

nucleation and growth occur as a

result of direct condensation from the
vapour, or plasma, phase.

form on the cathode as a result

of a solid state transformation.
liquid

nanotubes nucleate within globules

of liquid carbon deposited onto the
cathode.
Vapour phase growth
nucleation and growth occurred as a result of direct condensation from the vapour,
or plasma, phase.
nanotubes and nanoparticles form in the region of the arc next to the cathode
surface.

Liquid phase growth

liquid carbon globules to be ejected from the anode
Initially, because of the high vapour pressure of liquid carbon, the
surface of a globule will evaporatively cool very rapidly.

Solid phase growth

carbon in the vapour phase (consisting largely of C2 species) condenses
onto the cathode as a fullerene soot-like material.
This condensed carbon then experiences extremely high temperatures
as the arcing process continues, resulting in the formation firstly of
nanotube seeds and then of multiwalled nanotubes.

Schematic illustration of the solid

phase growth model for
multiwalled carbon nanotubes.
(a) Electron bombardment from
cathode causes heating of
anode surface, and evaporation
of C2 and other species. These
rapidly coalesce into fullerene
soot fragments.
(b) Some of the fullerene soot
condenses onto the cathode,
with the remainder being
deposited on the walls of the
vessel.
(c), (d), (e) Enlarged views of
interior of cathodic deposit,
showing transformation of
fullerene soot into firstly openended seed structures and
then multiwalled nanotubes and
nanoparticles.

Scanning electron micrographs of multiwalled carbon nanotubes

produced by heat-treating carbon black. (a) Tubes with one free
end and the other end terminating in carbon black, (b) tubes with
apparent Y-branches (arrowed

Defects in carbon nanotubes (CNT)

Point defects such as vacancies
Topological defects caused by forming pentagons and heptagons e.g. 5-7-7-5 defect
Hybridization defects caused due to fictionalization
Mechanical properties
Changes in stiffness observed.
Stiffness decrease with topological defects and increase
with functionalization
Defect generation and growth observed during plastic deformation
and fracture of nanotubes
Composite properties improved with chemical bonding between
matrix and nanotube
Electrical properties
Topological defects required to join metallic and semi-conducting
CNTs
Formation of Y-junctions
Other applications
Hydrogen storage, sensors etc

Topological defects can be formed in carbon nanotubes (CNTs) during processing or

subsequent loadings.
Presence of defects reduces the stiffness of the SWNT.
Multiple defects either occurring in close proximity (interacting) or otherwise (non-interacting)
can cause different levels of stiffness reductions.

Issues:

Figure (9,0) carbon nanotube with (a) a

single 5-7-7-5 defect, (b) two 5-7-7-5
interacting defects along the length of
the tube (c) two 5-7-7-5 interacting
defects along the circumference of the
tube

Effects of defects on elastic and also

inelastic properties (strength, stiffness
and elastic to plastic transition and
failure)
Role of chirality, diameters and location
of single and multiple interacting/noninteracting defects and their effect on
properties
Aligned defects in single/multi-walled
CNTs and their effect on mechanical
properties and hydrogen storage
Interaction of defects and
functionalization in load transfer
Origin of defects as a function of
combined thermal and mechanical load
application

Chemical functionalizations

There are also several chemical functionalizations which we briefly mention in the following :
1.Amidation Formation of Carbon Nanotube-Acyl Amides
2.Fluorination of Nanotubes
3.Chlorination of Carbon Nanotubes
4.Bromination of MWCNTs
5.Hydrogenation of Carbon Nanotubes.
6.Addition of Radicals
7.Addition of Nucleophilic Carbenes
8.Sidewall Functionalization through Electrophilic Addition
9.Addition of Nitrenes
10.Nucleophilic Cyclopropanation
11.Azomethine Ylides .
12.Diels-Alder Reaction
13.Sidewall Osmylation of Individual SWCNTs
14.Aryl Diazonium Chemistry
15.Electrochemical Functionalization
16.Cathodic Coupling
17.Anodic Coupling

Some applications of Carbon Nanotubes include the following

Micro-electronics /
semiconductors
Conducting Composites
Controlled Drug
Delivery/release
Artificial muscles
Supercapacitors
Batteries
Field emission flat panel
displays
Field Effect transistors and
Single electron transistors
Nano lithography
Nano electronics
Doping
Nano balance
Nano tweezers
Data storage
Magnetic nanotube
Nanogear

Nanotube actuator
Molecular Quantum wires
Hydrogen Storage
Noble radioactive gas storage
Solar storage
Waste recycling
Electromagnetic shielding
Dialysis Filters
Thermal protection
Nanotube reinforced composites
Reinforcement of armour and other materials
Reinforcement of polymer
Avionics
Collision-protection materials
Fly wheels"

Future Uses of CNTs

Nano-Electronics
Nanotubes can be conducting or insulating depending on their properties
Diameter, length, chirality/twist, and number of walls
Joining multiple nanotubes together to make nanoscale diodes
Max Current Density: 10^13 A/cm^2
Hydrogen Storage
Interest in hydrogen as a fuel has grown dramatically since 1990. However,
hydrogen storage technologies must be significantly advanced if a hydrogen
based energy system is to be established.
Nanotubes have been long heralded as potentially useful for hydrogen storage to
meet energy densities at values of 6.5wt% set by DOE.
Issues:
Mechanism of hydrogen adsorption: is it a purely physical or chemical interaction or is it
somewhere in between.
Optimize a given carbon adsorbent system: simulation of different parameters such as
temperature, pressure, diameter and chirality.
Simulation of adsorption considering nanotube with defects , disorder, diameter polydispersity,
and functionlization.
Simulation of adsorption of Li-doped nanotube