CARBON NANOTUBES

Nanomaterial engineering

DITA FLORESYONA
OUTLINE
1. Carbon
2. Hybridized atomic orbitals
3. Allotropic forms of carbons
CARBON
Carbon's ground state configuration is 1s2 2s2 2p2 or more easily read:
Hybridized Atomic Orbitals
sp3 Hybridization
sp2 Hybridization

An energy diagram showing three degenerate sp2-hybridized atomic orbitals

An illustration of an sp2 hybridized carbon

atom.
sp Hybridization

An energy diagram showing two degenerate sp-hybridized

atomic orbitals
 ALLOTROPIC FORMS OF CARBONS
Allotropes :
Different structural modifications of an element; the atoms of the element are bonded together in a different manner.

Allotropes of carbon:
•Diamond (hardest natural mineral)
•Graphite(dry lubricant, graphene)
•Amorphous carbon (coal and soot)
•Fullerene family (C60, carbon nanotubes etc)

Diamond has a giant molecular structure. Each carbon atom is covalently bonded to four other carbon atoms. A lot of energy is
needed to separate the atoms in diamond. ... Graphite on the other hand has flat layers of carbon atoms held by weak van der Waal's
forces which makes Graphite a weak object and easily breakable.
 DISCOVERY OF CARBON C60

 1985, Robert F. Curl, … discovered a new form of carbon，

that 60 or 70 carbon atoms could cluster together to form
a cage-like molecule.

 The molecular structure resembled the pattern of a soccer

ball or the geodesic designs of Buckminster Fullerenes. Thus
the name buckyballs or fullerenes.

 Since then the discovery has led to new research in

polymers, semiconductors, and other various areas.

 Nobel Prize to their finders in 1996

 Video fullerene
FULLERENE AND CARBON NANOTUBE

C60 C70 MWCNT

SWCNT CNT
Video : Nanotube
DIAMOND, GRAPHITE, AND NANOTUBE
Diamond

The electrons within diamond are tightly held within the bonds among the carbon atoms. These electrons absorb
light in the ultraviolet region but not in the visible or infrared region.
CARBON NANOTUBES

Nanomaterial engineering

DITA FLORESYONA
OUTLINE

1. The history of carbon nanotube

2. What is carbon nanotube

3. The types of carbon nanotubes

4. The properties of carbon nanotubes

5. The synthesis of carbon nanotubes

6. The application of carbon nanotubes

The history of carbon nanotubes
HISTORY OF CARBON NANOTUBES
What is Carbon nanotubes?
➢ Carbon nanotubes (CNTs) are a new form of completely artificial crystalline carbon. In contrast with fullerenes,
which have been detected in interstellar dust, natural CNTs have never been found either in space or on Earth.

➢ A single-walled nanotube (SWNT) can also be easily imagined as a graphene sheet wound around the surface of an
invisible cylinder.

➢ The interatomic C–C distance is 1.44 Å (vs. 1.42 Å in graphite)

➢ An extremely important characteristic of the SWNTs is the helicity that describes how the graphene sheet is
rolled up around the tube axis.

➢ In the case of MWNTs, the radial spacing between two concentric cylinders is typically of about 3.4 Å
Graphene to carbon nanotube
NANOTUBE
Nanotube

A CNT can be viewed as a hollow cylinder formed by rolling graphite sheets. Bonding in nanotubes is essentially sp2.
However, the circular curvature will cause quantum confinement and – rehybridization in which three  bonds
are slightly out of plane; for compensation, the  orbital is more delocalized outside the tube. This makes nanotubes
mechanically stronger, electrically and thermally more conductive, and chemically and biologically more active than
graphite.
Types of Carbon Nanotubes
Single-walled CNTs Double-walled CNTs Multi-walled CNTs

Diameter = 1–2 nm Diameters ranging from 2 to 50 nm

inter-layer distance ~ 0.34 nm

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

Types Carbon nanotubes
Interactions between Carbon nanotubes
ONE-DIMENSIONAL TRANSPORT

 Due to their nanoscale dimensions, electron

transport in carbon nanotubes will take place
through quantum effects and will only
propagate along the axis of the tube. Because
of this special transport property, carbon
nanotubes are frequently referred to as “one-
dimensional.”
ELECTRICAL PROPERTIES OF CARBON NANOTUBES

 If the nanotube structure is armchair then the

electrical properties are metallic

 If the nanotube structure is chiral then the electrical

properties can be either semiconducting with a very
small band gap, otherwise the nanotube is a moderate
semiconductor

 In theory, metallic nanotubes can carry an electrical

current density of 4×109 A/cm2 which is more than
1,000 times greater than metals such as copper
WHY?
THERMAL PROPERTIES OF CARBON NANOTUBES

 It is predicted that carbon nanotubes will be able to transmit up to 6000 watts per meter per Kelvin
at room temperature; compare this to copper, a metal well-known for its good thermal conductivity,
which transmits 385 watts per meter per K.

 The temperature stability of carbon nanotubes is estimated to be up to 2800oC in vacuum and about
750oC in air.
DEFFECT IN CARBON NANOTUBES
THE SYNTHESIS OF CARBON NANOTUBES

Commonly used method for the synthesis of Carbon Nanotubes:

1. Arc discharge
2. Chemical vapour deposition
Arc Discharge
➢ The oldest method to produce carbon nanotubes

➢ Carbon nanotubes were first synthesized by Iijima in 1991 using Acr discharge method
Arc Discharge Setup
➢ Arc discharge is the electrical breakdown of a gas
to generate plasma.

➢ The chamber consists of two electrodes which

are mounted horizontally or vertically; one of
which (anode) is filled with powdered carbon
precursor along with the catalyst and the other
electrode (cathode)

➢ The chamber is filled with a gas or submerged

inside a liquid environment.

➢ The arc current generates plasma of very high

temperature ~4000–6000 K, which sublimes the
carbon precursor filled inside the anode

➢ The carbon vapours aggregate in the gas phase

and drift towards the cathode where it cools
down due to the temperature gradient.
The electric current applied results in resistive heating
Growth mechanism of carbon nanotubes in arc dischaerge

➢ The gas ionizes into electrons and ions and results in hot plasma formation between the electrodes.

➢ The electrons are ejected from cathode hit the anode at high velocity and sputter the carbon precursor filled at
the centre of the anode. The high temperature resulting from resistive heating results in sublimation of carbon
precursor and converts them into carbon vapours.The carbon vapours are decomposed in carbon ions.

➢ The carbon vapours aggregate to form viscous carbon clusters and drift towards the cathode, which is cooler as
compared to anode.

The typical yield of nanotubes obtained in arc discharge is 20 – 50 mg/ min per synthesis
Carbon precursors in arc discharge
Gas used in arc discharge
Role of catalyst
➢ Usually metal → Ex: Ni, Fe, Co, Cr

➢ The metal should have low boiling temperature and high evaporation rate to act as a good catalyst in nanotube
formation

➢ On application of arc current, the metal atoms vaporize along with the carbon precursor

➢ The metal particles agglomerate with carbon vapours and nucleate at arc reactor walls.

➢ There is no established reason for deposition of SWNTs on walls of chamber instead of cathode and is an open
area for investigation.

➢ The catalyst favours the growth of SWNTs than MWNTs

Role of catalyst
Catalytic chemical vapour deposition

➢ Requires the presence of a gaseous phase containing ‘activated’ carbon (molecules, clusters).
➢ Commonly used gaseous carbon sources include methane, acetylene and carbon monoxide, but also liquid
hydrocarbons, alcohols, or carbon clusters deriving from solid carbon forms can be used.

➢ Two-step process consisting: - catalyst preparation step followed by the actual synthesis of the nanotubes

➢ Transition metal catalysts: Ni, Fe, or Co → preferential growth of single- rather than multiwalled nanotubes

➢ The dimensions of the catalyst are very critical: large particles can produce MWNTs

➢ The catalyst can be either in solid form, supported on a previously coated substrate
Catalytic chemical vapour deposition

➢ in thermal CVD the catalyst has a strong effect on the growth rate and on the final nanotube yield

➢ Oriented nanotube films (20–35 nm thick) were deposited using a mixture of acetylene and nitrogen
on flat Si substrates coated with iron oxide clusters

➢ The CNT diameters are often found to be dependent on the film thickness or on the particle size.
➢ As an example, using substrates coated by a metal film with a thickness of 13 and 27 nm, the
diameter distribution resulted in the ranges 30–40 and 100–200 nm, respectively
Catalytic chemical vapour deposition
The steps in catalytic chemical vapour deposition

1. Preparation of metal nanoparticles on a substrate.

2. The substrate is then placed in a furnace and

3. Hydrocarbon gas or CO is let into the furnace and

carbon deposition occurs by catalytic
decomposition of the hydrocarbon molecules on
the metal nanoparticles by temperatures ranging
roughly from 500 to 1200 C
Catalytic chemical vapour deposition
Roles of catalysts in catalytic chemical vapour deposition

➢ To decompose the hydrocarbon molecules

➢ In many cases, hydrocarbon molecules will decompose without forming CNT

➢ One may easily concede that the role of the catalyst is more complex than only hydrocarbon decomposition.

➢ But what happens exactly at the catalyst during the growth process? Why are transition metals appropriate for
CNT growth?
Catalytic chemical vapour deposition
Roles of catalysts in catalytic chemical vapour
deposition

➢ Nanoparticles exhibit a very high surface energy per atom.

The carbon in excess present during CVD process could
solve this energetic problem by assembling a graphene cap
on the particle surface with its edges strongly chemisorbed
to the metal

➢ chemical interactions between the transition metal 3d

electrons and the p carbon electrons
Arc discharge vs CVD
APPLICATION OF CARBON NANOTUBES

Carbon Nanotubes Properties

•CNTs have high thermal conductivity

•CNTs have high electrical conductivity
•CNTs are very elastic ~18% elongation to failure
•CNTs have very high tensile strength
•CNTs are highly flexible — can be bent considerably without damage
•CNTs have a low thermal expansion coefficient
•CNTs are good electron field emitters
 BIOSENSOR
A biosensor is a bioanalytical device consisting of 2 components a bioreceptor and a transducer.
The bioreceptor is a biomolecule that recognizes the target analyte whereas the transducer
converts the recognition event into a measurable signal.
Support for catalysts in fuel cells
Improve the hydrogen
storage capacity