Carbon nanotubes: Background

“C” 6 th atom in the periodic table. It has been found to be at least a partial
constituent in over 90 per cent of all chemicals known to man.

C60: Fullerene or C60 is soccer-ball-shaped

C60 is a molecule that consists of 60 carbon atoms, arranged as 12 pentagons and
20 hexagons. The shape is the same as that of a soccer ball.
The most striking property of the C60 molecule is its high symmetry

R. Buckminster Fuller

They vaporised graphite with a powerful laser in an atmosphere of helium gas. When they
analysed the resulting carbon clusters, they found many previously unknown carbon
molecules. These varied in size, but the most common molecule contained 60 carbon atoms.
Dr. S. Paria, NIT RKL Nanotechnology 1
Properties
Unlike graphite or diamond, fullerenes are closed–cage carbon molecules,
consisting of a number of five-membered rings and six-membered rings.
In order to make a closed cage, all the fullerene molecules should have the
formula of C20+m, where m is a integer number. For example: the structure of C60
is a truncated icosahedron, which looks like a soccer ball with 12 pentagons and
20 hexagons.
The bonds in C60 are having two different kinds. As a result, the length of a bond
in a pentagon is 1.45Å, that of a bond between pentagons is 1.40Å.
Applications:
Lubricant,
Rocket fuel
Drug delivery
Promising preliminary biological activities, such as DNA photocleavage, HIV-
Protease (HIV-P) inhibition, neuroprotection and apoptosis.

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 Carbon nanotube (CNT)

Discovery: S. Iijima in 1991

The tube like structure was produced during arc-
discharge evaporation method similar to that
used in fullerene synthesis, the needles grow at
the negative end of the electrode (Ar at 100 torr).
Each tube comprises coaxial tubes of graphite
sheets, ranging in number from 2 up to 50. Each
tube carbon atom hexagons are arranged in a
helical fashion about the needle axis.
The smallest dia (2.2 nm) corresponds roughly to
a ring of 30 carbon hexagons; this small dia
imposes strain on the planer bonds of the
hexagons and this causes two neighbouring
hexagons on the ring to meet at an angle of ~ 6º,
that for C60 is 42º.
C-C bond energy of C60 is lower that graphite,
Suggested that bending lower the BE.
(a) Five sheet, 6.7 nm dia, (b) Two
sheet, 5.5 nm dia, (c) Seven sheet, 6.5
nm dia, 2.2 ID
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 Bonding in Carbon

Bonding of Carbon atoms

↑↓ ↑↓ ↑ ↑
Six electrons present in the orbital
1S 2S 2 Px 2 Py
In ground state: 1S2 2S2 2Px1 2Py1
↑↓ ↑ ↑ ↑ ↑
In excited state: 1S2 2S1 2Px1 2Py1 2Pz1 1S 2 S 2 Px 2 Py 2 Pz

Diamond: The four valence electrons are thus equally distributed among the sp3orbitals, while
each orbital points to one of the four corners of a tetrahedron. The tetrahedral structure, together
with the highly directed charge density, give strength and stability to the σ bonds. Consequently,
all the bonds in diamond are of the same length (1.54 Å) and bond angle (109.47 o).

Diamond is the hardest known material due to σ bonds and no delocalized π bonds and also shows
electrically insulating. 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, so pure diamond appears clear to human eyes. Diamond has unusually high
thermal conductivity.

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 Bonding in Carbon

Graphite: Three outer-shell electrons of each carbon atom occupy the planar sp2 hybrid
orbital to form three in-plane σ bonds with an out-of-plane π orbital (bond). This makes
a planar hexagonal network. The bond angle is 120°
van der Waals force holds sheets of hexagonal networks parallel with each other with a
spacing of 0.34 nm. The σ bond is 0.14 nm long. An out-of-plane orbital or electron is
distributed over a graphite plane and makes it more thermally and electrically
conductive. The interaction of the loose electron with light causes graphite to appear
black. The weak van der Waals interaction among graphite sheets makes graphite soft
and hence ideal as a lubricant because the sheets are easy to glide relative to each other.

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 Bonding in Carbon

CNT: When a graphite sheet is rolled over to form a nanotube, the sp2 hybrid orbital is
deformed for rehybridization of sp2 toward sp3 orbital or σ−π bond mixing. The circular
curvature will cause quantum confinement and σ−π rehybridization in which three σ
bonds are slightly out of plane; for compensation, the π 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.
In addition, they allow topological defects such as pentagons and heptagons to be
incorporated into the hexagonal network to form capped, bent, toroidal, and helical
nanotubes whereas electrons will be localized in pentagons and heptagons because of
redistribution of electrons.
For convention, we call a nanotube defect free if it is of only hexagonal network and
defective if it also contains topological defects such as pentagon and heptagon or other
chemical and structural defects.
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 Applications
Applications:

• Materials
• Chemical and biological separation, purification, and catalysis
• Energy storage such as hydrogen storage, fuel cells, and the lithium battery
• Composites for coating, filling, and structural materials
• Devices
• Probes, sensors, and actuators for molecular imaging, sensing, and
manipulation
• Transistors, memories, logic devices, and other nanoelectronic devices
• Field emission devices for x-ray instruments, flat panel display, and other
vacuum nanoelectronic applications

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 SWNT and MWNT
A SWNT is a hollow cylinder of a graphite sheet whereas a MWNT is a group of coaxial
SWNTs. SWNT was discovered in 1993.

(n, 0)
Ch

Chiral (n, m)

(m, m)

A carbon nanotube is based on a two-dimensional graphite sheet. The chiral vector is

defined on the hexagonal lattice as
Ch = ma1 + na2
θ = chiral angle = the angle between chiral and zigzag direction
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 Different nanotubes
“Armchair” nanotubes correspond to the configuration with no 'twist' in
the rolling. Thus, if you were to follow one of the bonds and make
alternating left and right turns at the intersections, you would eventually
come back to your starting position.

Arm chair

By rolling a graphite sheet in different directions, two typical nanotubes can be obtained:
zigzag (n, 0), armchair (m, m) and chiral (n,m) where n>m>0 by definition. In the specific
example, they are (10,0), (6,6), and (8,4) nanotubes.

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 Zigzag
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Zigzag and chiral nanotubes are metallic when (n – m) = 3q (where q is an
integer) or semiconductors in all other cases. This includes armchair tube
where n = m.

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 CNT synthesis methods

•Arc discharge synthesis

•Laser ablation synthesis
•Thermal synthesis
Chemical vapor deposition (CVD)
High-pressure carbon monoxide synthesis
Flame synthesis
Plasma-enhanced chemical vapor deposition (PECVD)

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Arc discharge synthesis
•Arc discharge synthesis uses a low-voltage (~12 to 25 V),
high-current (50 to 120 amps).
•An arc is produced across a 1-mm gap between two
graphite electrodes 5 to 20 mm in diameter. An inert gas such
as He or Ar is used as the atmosphere for the reaction, at a
pressure of 100 to 1000 torr.
Iijima produced the first MWCNTs by this method. He found
that nanotubes formed on the cathode, along with soot and
fullerenes.
Both Iijima and Bethune found that SWCNTs could only form by adding metal catalyst
to the anode; specifically, Iijima used an Fe:C anode in a methane:argon environment,
while Bethune utilized a Co:C anode with a He environment.
By tailoring the Ar:He gas ratio, the diameter of the SWCNTs formed can be controlled,
with greater Ar yielding smaller diameters.

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Laser ablation synthesis
The first large-scale (gram quantities) production
of SWCNTs was achieved in 1996 by the
Smalley group at Rice University.
The laser ablation technique uses a 1.2 at. % of cobalt/nickel with 98.8 at.% of graphite
composite target that is placed in a 1200°C quartz tube furnace with an inert atmosphere of
~500 Torr of Ar or He and vaporized with a laser pulse. A pulsed- or continuous-wave laser
can be used. Nanometer-size metal catalyst particles are formed in the plume of vaporized
graphite. The metal particles catalyze the growth of SWCNTs in the plasma plume, but
many by-products are formed at the same time. The nanotubes and by-products are
collected via condensation on a cold finger downstream from the target.

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 Mechanical properties of CNTs
Material Young's modulus Tensile Strength Density (g/cm3)
(GPa) (GPa)
Multi wall 1200 150 2.6
nanotube
Single wall 1054 75 1.3
nanotube
SWNT Bundle 563 150 1.3
Graphite (in plane) 350 2.5 2.6
Steel 208 0.4 7.8
Epoxy 3.5 0.005 1.25
Wood 16 0.008 0.6

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 Young’s modulus of SWNT and MWNT
Young’s modulus is independent of tube chirality, but dependent on tube
diameter. The highest value is from tube diameter between 1 and 2 nm, about
1 TPa.
Large tube is approaching graphite and smaller one is less mechanically
stable. When different diameters of SWNTs consist in a coaxial MWNT, the
Young’s modulus will take the highest value of a SWNT plus contributions
from coaxial intertube coupling or van der Waals force. Thus, the Young’s
modulus for MWNT is higher than a SWNT, typically 1.1 to 1.3 Tpa.
When many SWNTs are held together in a bundle or a rope, the weak van der
Waal force induces a strong shearing among the packed SWNTs. This does
not increase but decreases the Young’s modulus. It is shown experimentally
that the Young’s modulus decreases from 1 TPa to 100 GPa when the
diameter of a SWNT bundle increases from 3 nm (about 7 (10,10) SWNTs) to
20 nm.

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The elastic response of a nanotube to deformation is also very remarkable. Most hard
materials fail with a strain of 1% or less due to propagation of dislocations and defects.
Both theory and experiment show that CNTs can sustain up to 15% tensile strain before
fracture. Thus the tensile strength of individual nanotube can be as high as 150 GPa,
assuming 1 TPa for Young’s modulus (E = Tensile Stress/Tensile strain = σ/εε; Tensile
strength is the ultimate tensile stress before breaking) .

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 Practical example
Unique ability of gecko’s to climb walls and hang from ceilings

How??

Vacuum principle??

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 Van der Waals force
•They are relatively long ranged compared to other atomic or
molecular level forces (range is 0.2 nm to over 10 nm).

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 van der Waals force
Article in Nature: Adhesive force of a single gecko foot-hair. Kellar Autumn, Yiching
A. Liang, S. Tonia Hsieh, Wolfgang Zesch Wai Pang Chan, Thomas W. Kenny,
Ronald Fearing, Robert J. Full, Nature, 405, 681-685, 2000.
Setae:
Setae
•Gecko’s foot has ~500,000 hair or
•Setae of each 30-130µ
µm and ~ 5
µm dia.
•5000 setae/mm-2
Spatulae:
•Branches of 100-1000 hair Seta Spatulae
•Length 0.2-0.5 µm
•Spatula shaped ending
•10-20 µN force/seta
Gecko can produce 10 -100 N/100 mm2 pad area or 0.1 Nmm-2
Each seta produce 0.1/5000 = 20 µN force

Spatula radius = 2 µm, adhesion distance D ~ 0.3 nm

Spatulae force (S-P) = -AR/6D2 , A = Hamakar constant = 10-19 J
Spatulae force = 0.4 µN
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Setal force = 0.4 × (100-1000) = 40-400 µN
 Force of single seta

(a) After an initial push towards the surface the parallel adhesive force to the surface
increased until the setal began to slide off the edge of the sensor
(b) Setal force parallel to the surface increased with the perpendicular preloading force
Maximum parallel force was observed if the seta was allowed to slide ~ 5 µm.
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 Force of single seta
Consider spatula is a curved segment of sphere (R=2 µm) and is separated by a
small distance. Flat surface were van der Waals forces become significant
atomic gap distance (D = 0.3 nm)
Spatulae force (S-P) = -AR/6D2 , A = Hamakar constant = 10-19 J
Spatulae force = 0.4 µN
Setal force = 0.4 × (100-1000) = 40-400 µN

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Dr. S. Paria, NIT RKL Nanotechnology 23
 Applications
September 2005 / Volume 2 / Issue 9 / ISSN 1744-1560 / CTHEC2 / www.rsc.org/chemicaltechnology

1. B. Yurdumakan, N. R. Raravikar, P. M. Ajayan, A. Dhinojwala, Synthetic gecko foot-

hairs from multiwalled carbon nanotubes. Chem Comm, 3799-3801, 2005.
2. H. Lee, B. P. Lee, P. B. Messersmith, A reversible wet/dry adhesive inspired by
mussels and geckos. Nature 488, 338-342, 2007.
3. L. Ge, S. Sethi, L. Gi, P. M. Ajayan, A. Dhinojwala, Carbon nanotube-based synthetic
gecko tapes. PNAS 104, 10792-10795, 2007.
Dr. S. Paria, NIT RKL Nanotechnology 24
 Dry adhesive tape
Normal viscoelastic tape:
•Rarely hang heavy objects on wall
•Stickiness is time- and rate dependent
•Do not work under vacuum (Space applications, for climbing of robots)

Carbonnanotube based “Gecko tape”

•Comparable shear stress on hydrophilic &
hydrophobic surface
•Shear force supported by the gecko tape is
very stable & time independent
• Visco elastic tape is stronger than gecko
when measured for a short period of time

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Force for peeling the tape of 500µ
µm and 0.16 m cm2

Angle (o) Force (N.m)

45 16
30 20
10 96

θ > 10 decreased breaking of CNT

Detachment energy depend on surface energy of the surface

Detachment energy = G = F(1-cosθ θ)/width
At 45 O, G = 5 J/m2 for mica and 2.2 J/m2 for teflon
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Dr. S. Paria, NIT RKL Nanotechnology 27
 Nanotube Molecular Wires as Chemical
Sensors
Sensing gas molecules is critical to environmental monitoring, control of
chemical processes, space missions, and agricultural and medical applications.

Upon exposure to gaseous molecules such as NO2 or NH3, the electrical

resistance of a semiconducting SWNT is found to dramatically increase or
decrease. This serves as the basis for nanotube molecular sensors.
The nanotube sensors exhibit a fast response and a substantially higher
sensitivity than that of existing solid-state sensors at room temperature. Sensor
reversibility is achieved by slow recovery under ambient conditions or by
heating to high temperatures.

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