2013

Synthesis of Carbon Nanotubes -

Seminar Report by
Prasad Moruskar

Seminar Report by Prasad Moruskar,

Roll No. 31.
P.V.P.Institute of Technology, Budhgaon
15/09/2013
 A SEMINAR REPORT ON

SYNTHESIS OF CARBON NANOTUBES

Submitted in partial fulfillment of the requirements for the

Award of the degree of
BACHELOR OF ENGINEERING
In
CHEMICAL ENGINEERING

Submitted by

PRASAD.P.MORUSKAR

DEPARTMENT OF CHEMICAL ENGINEERING

PADMABHOOSHAN VASANTRAODADA PATIL INSTITUTE OF
TECHNOLOGY.
BUDHGAON (SANGLI.) 416 304
OCTOBER -2013
 PADMABHOOSHAN VASANTRAODADA PATIL INSTITUTE OF
TECHNOLOGY.
BUDHGAON (SANGLI.) 416 304
DEPARTMENT OF CHEMICAL ENGINEERING

CERTIFICATE

Certified that seminar work entitled “SYNTHESIS OF CARBON

NANOTUBES” is a bonafide work carried out in the seventh semester by
‘PRASAD.P.MORUSKAR’ in partial fulfillment for the award of Bachelor of
Engineering in “CHEMICAL ENGINEERING” from SHIVAJI UNIVERSITY
during the academic year 2013-2014.who carried out the seminar work under the
guidance of ‘Dr. MOHAN.N.PATIL’ .

Dr. PATIL.M.N Prof. PATIL.U.S DR. KOLTE.S.V

(Guide) (H.O.D.) (Principal)
 ABSTRACT
Nanotechnology is a field of applied science and technology covering
a broad range of topics. The main unifying theme is the control of matter
on a scale smaller than 1 micrometer as well as the fabrication of devices
on this same length scale. So carbon nanotubes received extensive
attention due to their nanoscale dimension and outstanding materials
properties.
Different types of carbon nanotubes can be produced in various ways.
The most common synthesis techniques are the arc discharge, the laser
ablation and the chemical vapour deposition (CVD). The nanotube
production the first two methods were utilized mainly for the production
of SWNTs while the third one produced mainly MWNTs. The principle
of CVD is the decomposition of various hydrocarbons over transition
metal supported catalyst. Single-walled (SWNT), multi-walled (MWNT)
and coiled carbon nanotubes are produced. Carbon nanotubes have been
of great interest, both from a fundamental point of view and for future
applications.
 CONTENTS
1. INTRODUTION
1.1 History
1.2 Introduction of carbon
2. WHAT ARE CARBON-NANOTUBES
2.1 Definition
3. CLASSIFICATION
3.1 Conductivity
3.2 Chirality
3.3 Layers
4. PROPERTIES
5. SYSTHESIS

5.1Arc Discharge
5.2 Laser Ablation
5.3 Chemical Vapour Deposition
6. APPLICATION
7. DRAWBACKS
8. CONCLUSION
9. REFERENCE
 1. INTRODUTION

1.1 History

Carbon nanotubes(CNTs) were firstly observed and described in 1952 by

Radushkevichand Lukyanovich1 and later in 1976 the single (or double)walled
carbon nanotubes were observed by Oberlin et al.2 In more recent history the
discovery of CNTs is attributed to Iijima as the first scientist who described the
multiwalled carbon nanotubes (MWNTs) preparation process after a random event
during the test of a new arc evaporation method for C60 carbon molecule
fabrication in 1991.
In 1993 another two separate works from Iijima et al. and Bethune et al.
describing the growth process of single walled carbon nanotubes (SWNTs). From
the discovery by Iijima’s, the CNTs have begun to be widely used in many
applications due to their unique electrical, mechanical, optical, thermal and other
properties. The application of CNTs is usually given by the CNTs structure
(number of walls, diameter, length, chiral angle, etc.), which gives them the
specific properties. The possible applications of CNTs include conductive films,
solar cells, fuel cells, super-capacitors, transistors, memories, displays, separation
membranes and filters, purification systems, sensors, clothes, etc.

1.2 Introduction of carbon

Carbon comes from a Latin word “carbo”, which is derived from s French
word “charbon”, meaning charcoal. It is the 4th most abundant chemical element
in the universe by mass, after hydrogen, helium and oxygen.

The allotropes of carbon are the different molecular configuration that pure
carbon can take. Allotropes of carbon include Diamond, Graphite, Amorphous
carbon, Fullerences, carbon–nanotubes, carbon-nanobuds, Glassy carbon and
Chaoite.
 2. WHAT ARE CARBON-NANOTUBES?

Carbon –nanotubes (CNTs) are allotropes of carbon. These are extremely

thin hollow cylinders made of carbon atoms.
A carbon nanotubes is a one –atom thick sheet of graphite (called grapheme) rolled
up into a seamless cylinder with diameter of the order of a nanometer. This result
in a nanostructure where the length-to-diameter ratio exceeds 10,000.

Fig.1 Wrapping of graphene sheet.

The fullerenes are a family of carbon

allotropes. They are molecules composed entirely
of carbon, in form of a hollow sphere, ellipsoid or
tube. Cylinder fullerenes are called Carbon
nanotubes or buckytubes. Fullerenes are similar
in structure to graphite .A nanotubes is cylinder,
with at least one end typically capped with a
hemisphere of the buckyballs structure. Their
name is derived from their size, since the diameter
of a nanotube is of the order of few nanometers
(approx. 10,000 to 50,000 times smaller than the
width of a human hair), while they can be up to
several millimeters in length.

Fig 2. Nanotubes structure

 3. CLASSIFICATION

Based on Conductivity:
 Metallic
 Semiconducting
 Based on Chirality:
 Zigzag
 Armchair
 Chiral
Based on Layers:
 Single walled nanotubes (SWNT)
 Multi walled nanotubes (MWNT)

3.1Classification based on Conductivity

The conductance of a carbon-nanotube is mainly affected by its chirality

(amount of twist in the tube).Twisting is found to transform the metallic nanotube
to a semiconducting one with a band-gap that varies with the twist angle as shown
below. Carbon nanotube display either metallic or semiconducting properties. Both
large, multiwalled nanotubes (MWNTs), with many concentric carbon shell, and
bundles or ropes of aligned single-walled nanotubes(SWNTs)are complex
composite conductors that incorporate many weakly coupled nanotubes that each
have a different electronic structure. Carbon nanotubes exhibit several
technologically important characteristics Metallic nanotubes can carry extremely
large current densities; semiconducting nanotubes can be electrically switched on
and off as field-effect transistors (FETs).

3.2 Classification based on Chirality:

CNTs based on their chirality are classified as Zig-Zag, Armchair and

Chiral. Nanotubes form different types, which can be describe by the chiral vector
(n,m), where n and m are integers of the vector equation C=n â1 + m â2 and  is a
chiral angle.
 The chiral vector is determined as shown in the fig.3. Consider graphene
sheet for chiral construction as per chiral vector.

Fig.3 Chiral construction

If C lies along the zigzag line (n,0) such as (1,0),(4,0)(12,0)etc. or if chiral angle
 = 0 then the tube is called as “Zigzag” type.

If C lies along the Armchair line (n,m) =(n,n) such as (1,1),(4,4)(6,6)etc. or if

chiral angle  = 30 then the tube is called as “Armchair” type.

If C lies along the Chiral line (n,m) such as (5,3),(6,4)(12,7)etc. or if chiral angle
0<  < 30 then the tube is called as “Chiral” type.(Fig.4)

Fig .4

Structural
nanotubes
Zigzag Armchair Chiral
The values of n and m determine the chirality or twist of the nanotube. The
chirality is turn affects the conductance of nanotube, it’s density. it’s lattice
structure ,and other properties. A SWNT is considered metallic, if n-m is a
divisible by 3, otherwise the nanotube is a semiconductor, i.e.

If (n-m)/3=0, the tube is metallic.

If (n-m)/3=0, the tube is semiconductor.

3.3 Classification based on layers:

Single-walled nanotubes

SWNTs have one shell of carbon atoms in a hexagonal arrangement. Most SWNTs
have a diameter of close to 1 nanometer with a tube length that can be many
thousands of times longer up to few centimeters have been produced.

The structure of a SWNTs can be conceptualized by wrapping a one-atom-thick

layer of graphite called graphene into a seamless cylinder shown in Fig 1.the way
the graphene sheet is wrapped is represented by a pair of indices (n,m)called the
chiral vector.

Multi -walled nanotubes

MWNTs consist of multiple concentrically nested carbon tubes i.e consist of

multiple layers of graphite rolled in on themselves to form a tube shape. Shown
in Fig below

Fig 5.Multi-walled nanotubes (MWNT)

 4. PROPERTIES

Size: C-nanotubes are extremely thin hollow cylinders made of carbon atom. There
size range from about 0.6 to 1.8 nanometers in diameter.

Density: 1.33 to 1.40 gram per cubic centimeter. To make a comparison,

Aluminum has a density of 2.7 gram per cubic centimeter.

Resilence: C-nanotubes can be bent at large angle and restraightened without

damage.

Strength: C-nanotubes are of the Strongest and Stiffest materials known, in terms
of tensile strength and elastic modulus respectively. SWNTs have an average
tensile strength of about 45 GPa. In comparison, high carbon-steel has a tensile
strength of 1.2 GPa.

Chemical reactivity: The chemical reactivity of a CNT is, compared with a

graphene sheet, enhanced as a direct result of the curvature of the CNT surface.
Carbon nanotube reactivity is directly related to the pi-orbital mismatch caused by
an increased curvature. Therefore, a distinction must be made between the sidewall
and the end caps of a nanotube. For the same reason, a smaller nanotube diameter
results in increased reactivity. SWNTs are stable up to 750◦C in air and up to∼
1,500–1,800 ◦C in inert atmosphere.

Kinetic: Multiwalled c-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 nanotubes shell
thus creating an atomically prefect linear or rotational bearing. So this property has
been utilized to create the world's smallest rotational motor.

Fig 6. smallest rotational motor

Thermal: All nanotubes are expected to be very good thermal conductors along
the tube, exhibiting a property known as “ballistic conduction”, but good insulators
laterally to the tube axis. The c-nanotube will be able to transmit heat up to 6000
W·m−1·K−1 at room temperature compare to Cu. The temperature stability is
estimated to be up to 2800oC in vacuum and about 750oC in air.

Electrical: Depending on their chiral vector, carbon nanotubes with a small

diameter are either semi-conducting or metallic. Because of the symmetry and
unique electronic structure of graphene, the structure of a nanotube strongly affects
its electronic properties.
For a given (n, m) nanotube, if n-m is a multiple of 3, then the nanotube is
metallic, otherwise the nanotube is a semiconductor. Thus all armchair (n=m)
nanotubes are metallic, and nanotube (5, 0), (6, 4), (9, 1), etc.are semiconductor.
In theory, metallic nanotube can have electrical current density more than 1,000
times greater than metals such as Ag and Cu.

Current carrying capacity: The current carrying capacity of SWNTs is estimated

at 1 billion amperes/cm2. Copper wires burn out at about 1 million amperes/cm2.
 5. SYSTHESIS
Techniques have been developed to produce nanotubes in sizeable
quantities, including arc discharge, laser ablation and chemical vapour deposition
(CVD). Most of these processes take place in vacuum or with process gases.
Large quantities of nanotubes can be synthesized by these methods; advance in
catalysis and continuous growth processes are making CNTs more commercially
viable.

 Arc Discharge
Nanotubes were observed in 1991 in the carbon soot of graphite electrodes
during an arc discharge, by using a current of 100 amps, that was intended to
produce fullerenes. Because nanotubes were initially discovered using this
technique. It has been the most widely used method of nanotube synthesis.

The carbon arc discharge method, initially used for producing C60 fullerenes,
is the most common and perhaps easiest way to produce carbon nanotubes as it is
rather simple to undertake. However, it is a technique that produces a mixture of
components and requires separating nanotubes form the soot and the catalytic
metal present in the crude product.

This method creates nanotubes through arc-vaporization of two carbon rods

placed end to end separated by approximately 1mm, in an enclosure that is usually
filled with inert gas (helium, argon ) at low pressure (between 50 and 700 mbar).
Recently it is possible to create nanotubes with the arc method in liquid nitrogen.

Fig 7. Arc discharge

 A direct current of 50 to100 A driven by approximately 20 V creates a high
temperature discharge vaporizes one of the carbon rods and forms a small rod
shaped deposit on the other rod. Producing nanotubes in high yield depends on the
uniformity of the plasma arc and the temperature of the deposit form on the carbon
electrode.

The yield for this method is up to 30 % by weight and it produce both

single- and multiwall nanotubes, however they are quite short (50 microns).

 Drawback

a) If both of the electrodes are made of graphite.

b) More work to separate CNTs from its undesirable by-products.
c) 4000 °C which is an extremely high temperature.
d) Electric arc method good for scientific study but not for industrial
use.

 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 chamber. The 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.

Fig 8. Laser Ablation

 This method has a yield of around 70% and produce primarily SWNTs with
a controllable diameter determined by the reaction temperature.

 Drawback

a) Costly Technique.
b) High power requirement.

 Chemical Vapour Deposition (CVD)

CVD carbon nanotube synthesis is essentially a two-step process consisting
of a catalyst preparation step followed by the actual synthesis of the nanotube. The
catalyst is generally prepared by deposition of a transition metal (Co, Ni, Fe) onto
a substrate (SiO2, Zeolite, MCM, Metal Oxide, Al2O3) at temperature
650–1000 oC and then using different sources of carbon (CH4C2H2, C2H4, CO) for
decomposition of carbon, finally the products are purified by different methods.

Fig 9.CVD Fig 10.Deposition of nanotubes

Typical yield for CVD are approximately 30 %. At the moment, laser

ablation method produces the cleanest material, but the costs are still rather high.
Arc discharge can produce grams of low purity nanotubes. The CVD technique is
still under development but preliminary results look promising, as do prospects of
large scale CVD.
 6. APPLICATION
“The Next Big Thing Is Really Small”
Many potential applications have been proposed for carbon nanotubes
includes

Conductive and high-strength composites;

Energy storage and Energy conversion devices;

Chemicals sensors;

Field emission display and radiation sources;

Hydrogen storage media;

Nanometer-sized semiconductor devices;

Probes & interconnects;

Fuel cell;

Portable X-ray machines;

Strong fabric;

Artificial muscles;

Components of cars and spacecraft;

Electrochemical supercapacitors;

Transistors;

Nanowires;

Membranes for Desalination;

Electro-mechanical system.
 7. DRAWBACKS

Nanotube cost, polydispersity in nanotube type, and limitation in

processing and assembly methods are important barriers for some
application of single-walled nanotubes.

Problems like purification, separation of carbon nanotubes, control

over nanotube length, nanotube aggregates, low budget as well as high
contact resistance.

Carbon nanotubes are quite popular now for their prospective

electrical, thermal, and even selective-chemistry application.
Accordingly their use will be limited until large quantities of there
nanomaterials can produced.

However, many technological hurdles need to be overcome before

large-scale application reaches the marketplace.
 8. CONCLUSION

Nanotubes appear destined to open up a host of new practical

applications and help improve our understanding of basic physics at the
nanometer scale.
Carbon nanotubes could play a pivotal role in this upcoming
revolution of their remarkable structure, electrical and mechanical
properties can be exploited.
The remarkable properties of carbon nanotubes may allow them
to play crucial role in the relentless drive toward miniaturization at the
nanometer scale.
Some future application of carbon nanotubes looks very promising.
All we need are better production techniques for large amount of
purified nanotubes that have to found in the near future. Nanotubes
promises to open up a way to new application that might be cheaper,
lower in weight with better efficiency.
REFERENCE

 Synthesis of carbon nanotubes

(Indian Academy of Sciences Vol. 68, —Jan2007 pp. 51–60)
 Methods for carbon nanotubes synthesis
(The Royal Society of Chemistry 2011 Pp.15872–15884)
 NANOTUBES WHITE PAPER
(CMP CIENTIFICA JAN-2003)
 The Wondrous World of Carbon Nanotubes
(Eindhoven University of Technology Feb 2003)
 Synthesis Methods of Carbon Nanotubes and Related Materials
(Received: 26 February 2010; www.mdpi.com/journal/materials).
 www.europhysicsnews.com/full/09/article3/article3.html
 Synthesis of single- and multi-wall carbon nanotubes
(Applied Physics A Materials Science & Processing, pp 11–22 (1998))
 Synthesis and characterization of carbon nanotubes, Hongjun Gao.
(PP 139–144 Received 1 December 2003)
 Synthesis of nano-carbon, KALPANA AWASTHI, RAJESH KUMAR.
(Bull. Mater. Sci., Vol.34, No.4, July 2011, pp. 607–614. Indian Academy of
Sciences)