Carbon Nano-tubes (CNTs)

and Multiwall Carbon

Nanotubes (MWCNTs)

By
Soumyajit Roy
Jadavpur University
 Graphene

Carbon Nanotubes
Graphene and Carbon Nanotubes
• Graphene is atomically thin crystal of Carbon
which is stronger than steel but flexible, is
transparent for light, and conducts electricity
(gapless semiconductor).

• Carbon Nanotubes (CNT) are cylindrical

molecules with a diameter ranging from 1 nm
to a few nanometers and length up to a few
micrometers. Their structure consists of a
graphite sheet wrapped into a cylinder.
What was at the beginning?
Carbon materials Diamond and
graphite are two
allotropes of carbon:
pure forms diamond
graphite of the same
element that differ
in structure.
Allotropes of Carbon a) Diamond

b) Graphite

c) Lonsdaleite

d) - f) fullerenes
(C60, C540, C70)
(Discover in 1985)

g) Amorphous Carbon

h) Carbon Nanotube
(Discover in 1991)
 Structural Features
• Every atom in any Nanotube
is in the same chemical
environment, has the same bonds:-
• But the material can be changed from conductor
to semiconductor just by rolling it up differently.
Also, The single crystal structures can exhibit
either semiconducting or metallic behavior
depending only on the diameter
and angle of lattice.
• Strong sp2 hybridised bonds make
Graphene mechanically strong.
 Geometrical structure of NT
Properties depend on the orientation of the hexagonal network with
respect to the nanotube long axis, a property known as chirality.

In case SWNTs are ideally

perfect, their chemical
reactivity will therefore be
highly favoured at the tube
tips, at the very location of
the pentagonal rings.
 Construction of Nanotubes
• a1 , a2 primitive lattice
vectors of graphene
• Chiral vector:
c = n1 a1 + n2 a2
• n1 , n2 integers: chiral
numbers
• Mirror lines: "zig-zag
line” through the
midpoint of bonds
"armchair line” through
the atoms
• Sixfold symmetry:
0 ≤ θ < 60°
 Ways to roll a carbon sheet

Sketch of three different SWNT structures as examples for

(a) a zig-zag-type nanotube, (b) an armchair type nanotube, (c) a helical nanotube
 Properties of Nanotubes/ CNTs
• Superior stiffness and strength to all other materials
• Extraordinary electric properties
• Reported to be thermally stable in a vacuum up to 2800o C.
• Capacity to carry an electric current 1000 times better than
copper wires.
• Twice the thermal conductivity of diamonds
• Pressing or stretching nanotubes can change their electrical
properties by changing the quantum states of the electrons
in the carbon bonds
• They are either conducting or semi-conducting depending
on the their structure.
• It takes 48,000 kN·m·kg−1 (steel has max 154 kN·m·kg−1).
• Also, it is chemically resilient.
 Mechanical Properties
• Carbon nanotubes are the strongest and stiffest materials yet
discovered in terms of tensile strength and elastic modulus.
• This strength results from the covalent sp² bonds formed between
the individual carbon atoms. Because of C-C bonds, CNTs are
expected to be extremely strong along their axes and have a very
large Young’s modulus in their axial direction.
• The Young modulus value of a SWNT is estimated as high as 1Tpa to
1.8 Tpa. The high value of elastic modulus makes it suitable for the
application as probe tips of scanning microscopy.
• The modulus of a SWNT depends on the diameter and chirality.
• For MWNT, it correlates to the amount disorder in the sidewalls.
• for single wall nanotube bundles (also known as ropes), it has been
demonstrated that shearing effects due to the weak inter tube
cohesion gives significantly reduced moduli compared to individual.
 Thermal properties
• 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.
• It is predicted that carbon nanotubes will be able to
transmit up to 6000 W·m−1·K−1 at room temperature;
compare this to copper, a metal well-known for its good
thermal conductivity, which transmits 385 W·m−1·K−1.
• The temperature stability of carbon nanotubes is
estimated to be up to 2800 °C in vacuum and about 750
°C in air.
• Thermal expansion of CNTs will be largely isotropic, which
is different than conventional graphite fibers, which are
strongly anisotropic.
• It is expected that low-defect CNTs will have very low
coefficients of thermal expansion.
 Chemical Properties
• The chemical reactivity of a CNT is, compared with a graphene
sheet, enhanced as a direct result of the curvature of the CNT
surface. This curvature causes the mixing of the π and σ orbital,
which leads to hybridization between the orbitals. The degree
of hybridization becomes larger as the diameter of a SWNT
gets smaller. Hence, carbon nanotube reactivity is directly
related to the π-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. Covalent chemical modification of either
sidewalls or end caps has shown to be possible. For example,
the solubility of CNTs in different solvents can be controlled
this way.
• However, covalent attachment of molecular species to fully
sp2-bonded carbon atoms on the nanotube sidewalls proves to
be difficult. Therefore, nanotubes can be considered as usually
chemically inert.
 Limitation of Carbon Nanotubes (CNTs)
• Lack of solubility in most solvents compatible with the
biological milieu (aqueous based).
• The production of structurally and chemically reproducible
batches of CNTs with identical characteristics.
• Difficulty in maintaining high quality and minimal impurities

Comparison of Carbon Nanotubes (CNTs) Properties

Material Material Young’s Tensile Strength Density
modulus (GPa) (GPa) (g/cm3 )
SWCNT 1054 150 N/A
MWCNT 1200/ 150/ 2.6 150 2.6
Steel 208 0.4 7.8
Epoxy 3.5 0.005 1.25
Wood 6 0.008 0.6
 Advantages of Nanotubes
• Extremely small and lightweight making excellent
replacement for metallic wires.
• 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 function
almost just as well as in extreme cold as they to in
extreme heat.
• Improve conductive mechanical properties of composites.
Disadvantages
• Despite all research researchers still don‟t understand how CNTs
work.
• Extremely small so are difficult to work with.
• Currently the process relatively expansive to produce the nanotubes.
• Would be expansive to implement this new technology in and
replace the older technology in all the places that we could.
• At the rate of technology has been becoming obsolete it may be a
gamble to bet on this technology
 Appliances
Applications 1. Nano Balance
• CNTs can be conjugated with various 2. Magnetic
biological molecules including drugs, Nanotubes
proteins and nucleic acid to afford 3. Nanotubes
bio-functionalities. Reinforced
Composites
• CNTs can act as antennas for radios
4. Reinforcement
and other electromagnetic devices.
armour & Other
• Conductive CNTs are used in brushes Materials.
for commercial electric motors. They 5. Reinforcement
replace traditional carbon black. Polymer.
• The CNTs improve electrical and 6. Solar storage
thermal conductivity because they 7. Hydrogen storage
stretch through the plastic matrix of 8. Thermal
the brush. Protection
9. Space Elevator
 Single Wall Nanotube SWNT
Multi Wall Nanotube MWNT

 SWNT
• Consist of just one layer of carbon
• Greater tendency to align into ordered bundles
• Used to test theory of NT properties
 MWNT
• Consist of 2 or more layers of carbon
• Tend to form unordered clumps
 Difference between SWCNT and MWCNT
SWCNT MWCNT
Single layer of graphene Multiple layers of graphene
Catalyst is required for synthesis Can be produced without catalyst
Bulk synthesis is difficult as it requires Bulk synthesis is easy
proper control over growth and
atmospheric condition
Purity is poor Purity is high
A chance of defect is more during A chance of defect is less but once
functionalization occurred it is difficult to improve.
Less accumulation in the body It has very complex structure
It can be easily twisted and is more It cannot be easily twisted
pliable
Characterization and evaluation is It has very complex structure
easy
 Methods of Production

Arc Method Chemical Vapor Deposition

Laser Ablation Hydrocarbon Flames

 Arc Method
Tends to produce MWNT
Lengths ~10 nm
Diameter d 5-30 nm
To obtain SWNT need a
metal catalyst (1% Y, 4.2% Ni)

• The carbon arc discharge method, initially used for producing C60
fullerenes, is the most common and perhaps easiest way to produce CNTs,
as it is rather simple.
• However, it is a technique that produces a complex mixture of components,
and requires further purification to separate the CNTs from the soot and the
residual catalytic metals present in the crude product.
• This method creates CNTs through arc-vaporization of two carbon rods
placed end to end in an enclosure that is usually filled with inert gas at low
pressure. The discharge vaporizes the surface of one of the carbon
electrodes, and forms a small rod-shaped deposit on the other electrode.
 Arc Method (contd.)
• Carbon Nanotubes Arc Discharge Production Method
• Producing CNTs in high yield depends on the uniformity of the
plasma arc, and the temperature of the deposit forming on the
carbon electrode.
• Hipco method is an arc method synthesis method carried out
under high pressure and was developed at Rice University to
create high quality single-walled carbon nanotubes (SWCNT)
from the gas-phase reaction of iron carbonyl with high-pressure
carbon monoxide gas.
• Iron pentacarbonyl is used to produce iron nanoparticles that
provide a nucleation surface for the transformation of carbon
monoxide into carbon during the growth of the nanotubes.
• Synthesis produces high quality materials but only in the
milligrams range and isn’t commercially scale-able.
 Laser Ablation
• In 1996 CNTs were first
synthesized using a dual-
pulsed laser and achieved
yields of >70wt% purity.
Samples were prepared by
laser vaporization of graphite
rods with a 50:50 catalyst
mixture of Cobalt and Nickel at
1200oC in flowing argon, • The use of two successive laser
followed by heat treatment in pulses minimizes the amount of
a vacuum at 1000oC to remove carbon deposited as soot.
the C60 and other fullerenes. • The second laser pulse breaks up
• The initial laser vaporization the larger particles ablated by
pulse was followed by a the first one, and feeds them
second pulse, to vaporize the into the growing nanotube
target more uniformly. structure.
 Laser Methods (contd.)
• The material produced by this method appears as a mat of “ropes”,
10-20nm in diameter and up to 100um or more in length
• By varying the growth temperature, the catalyst composition, and other
process parameters, the average nanotube diameter and size distribution
can be varied.
• Arc-discharge and laser vaporization are currently the principal methods
for obtaining small quantities of high quality CNTs. However, both
methods suffer from drawbacks.
• The first is that both methods involve evaporating the carbon source, so it
has been unclear how to scale up production to the industrial level using
these approaches.
• The second issue relates to the fact that vaporization methods grow CNTs
in highly tangled forms, mixed with unwanted forms of carbon and/or
metal species.
• The CNTs thus produced are difficult to purify, manipulate, and assemble
for building nanotube-device architectures for practical applications.
 Catalyzed Chemical Vapor Deposition
Catalyst at 500-1000oC
Catalysts typically
transition-metal
nanoparticles on porous
Al2O3 (large surface area)
SWNT d~1.4nm,

• Each rope is found to consist primarily of a bundle of single walled

nanotubes, aligned along a common axis.
• Undoubtedly the most common method of carbon nanotubes synthesis,
catalyzed chemical vapor deposition of hydrocarbons over a metal
catalyst is a classical method that has been used to produce various
carbon materials such as carbon fibers and filaments for over 20 years.
• Large amounts of CNTs can be formed by catalytic CVD of acetylene over
Cobalt and iron catalysts supported on silica or zeolite.
 Catalyzed Chemical Vapor Deposition (contd.)
• The carbon deposition activity seems to relate to the cobalt content of
the catalyst, whereas the CNTs’ selectivity seems to be a function of
the pH in catalyst preparation.
• Fullerenes and bundles of single walled nanotubes were also found
among the multi walled nanotubes produced on the carbon/zeolite
catalyst.
• Supported catalysts such as iron, cobalt, and nickel, containing either a
single metal or a mixture of metals, seem to induce the growth of
isolated single walled nanotubes or single walled nanotubes bundles in
the ethylene atmosphere.
• The production of single walled nanotubes, as well as double-walled
CNTs, on molybdenum and molybdenum-iron alloy catalysts has also
been demonstrated.
• Methane has also been used as a carbon source. In particular it has
been used to obtain ‘nanotube chips’ containing isolated single walled
nanotubes at controlled locations.
 Hydrocarbon Flames
• In flame synthesis, combustion
of a portion of the
hydrocarbon gas provides the
elevated temperature
required, with the remaining
fuel conveniently serving as
the required hydrocarbon
reagent.
• Hence the flame constitutes an
efficient source of both energy
and hydrocarbon raw material.
Combustion synthesis has been • CNTs can also be produced by
shown to be scalable for high- Electrolysis, Use of Solar
volume commercial Energy, Heat Treatment of a
production. Polymer, and Low-
Temperature Solid Pyrolysis.
Purification and Functionalization of CNTs
• The carbon nanotubes could be contaminated with catalyst
particles, carbon clusters and smaller fullerenes (C60 /C70).
There are several techniques for purification:
(1) removal of the catalyst by acidic treatment (+ sonication),
thermal oxidation or magnetic separation (Fe);
(2) removing of small fullerenes by micro filtration or extraction
with CS2; and (3) removal of other carbonaceous impurities by
thermal oxidation, selective functionalization of nanotubes or
by annealing.
• Also, for CNTs it is very important to be pretreated and
functionalized before they are applied.
• In order to make the dispersion in liquids easier, it is necessary
to physically or chemically attach certain molecules, i.e.
functional groups, to the carbon nanotubes.
• Methods for functionalizing are cutting, oxidation, wrapping
etc. For biological purposes, carbon nanotubes can be
functionalized with lipids, proteins or biotins.
Nanofluids
 Nanofluid
Definition Properties
• A nanofluid is a fluid containing • High Thermal conductivity
nanometer-sized particles, called • higher heat transfer rate
nanoparticles. These fluids are • Viscosity of the Nanofluid
engineered colloidal suspensions of increases with an increase in the
nanoparticles in a base fluid. particle volume concentration
• The nanoparticles used in • Increases Thermal conductivity
nanofluids are typically made of and decreases viscosity with
metals, oxides, carbides, or carbon increase in temperature.
nanotubes. • Adding nanoparticles in a base
• Nanofluids are suspensions of solid fluid will increase the specific
particles having size of 1100 nm in heat capacity of the fluid.
a liquid which is mainly a heat
transfer fluid.

Nanofluids are dilute liquid suspensions of nanoparticles with at least one of

their principal dimensions smaller than 100 nm. From previous investigations,
nanofluids have been found to possess enhanced thermophysical properties
such as thermal conductivity, thermal diffusivity, viscosity and convective heat
transfer coefficients compared to those of base fluids like oil or water
 Application of Nanofluids
• They exhibit excellent thermophysical  Heat Transfer Applications
properties like high thermal conductivity, • Industrial Cooling Applications
thermal diffusivity, convective heat transfer • Smart Fluids
coefficient, and viscosity compared to the • Nuclear Reactors
corresponding base fluids. • Extraction of Geothermal Power
• The nanoparticles used in nanofluids are and Other Energy Sources
mainly nanoparticles of metals, metal oxides,  Automotive Applications
carbides, and carbon nanotubes. • Nanofluid Coolant
• The most common base fluids in which these • Nanofluid in Fuel
nanoparticles are dispersed are water, • Brake and Other Vehicular
Nanofluids
ethylene glycol, and oil. These nanofluids are
 Electronic Applications
useful in applications that involve heat
• Cooling of Microchips
transfer like microelectronics, fuel cells, and
• Microscale Fluidic Applications
pharmaceutical processes due to their
 Biomedical Applications
possession of outstanding thermal properties.
• Nanodrug Delivery
• There has been a wide application of fluids in • Cancer Theraupetics
heat exchanging phenomenon. Fluids like oil, • Cryopreservation
water, etc. are convenient sources of exchange • Nanocryosurgery
of energy in many industrial processes. • Sensing and Imaging
 Nanofluids in Heat Transfer Applications
 Industrial Cooling Applications  Nuclear Reactors
• A wide range of applications of nanofluids have • Feasibility of
been found in the fields of Power Plants, nanofluids in nuclear
Electronics, Automotive, and Nuclear applications by
Engineering where efficient heat dissipation and improving the
improved heat transfer are required. performance of any
• Nanofluids had the ability to enhance heat water-cooled nuclear
transfer without the requirement of large system that is heat
pumping power. removal limited.
• High thermal conductivities provided by • Possible applications
nanofluids even at low concentration of include pressurized
nanoparticles. water reactor (PWR)
• Thermal conductivity is a very important primary coolant,
property of nanofluid for the study of convective standby safety systems,
heat transfer of any fluid, because the accelerator targets,
conductivity of particles is more than the fluid. plasma divertors, and
so forth.
https://journals.sagepub.com/doi/full/10.1155/2010/519659
 Nanofluids in Heat Transfer Applications
 Extraction of Geothermal Power and Other Energy Sources
• When extracting energy from the earth's crust that varies in
length between 5 to 10 km and temperature
between 500oC and 1000oC, nanofluids can be employed to
cool the pipes exposed to such high temperatures.
• When drilling, nanofluids can serve in cooling the machinery
and equipment working in high friction and high
temperature environment. As a “fluid superconductor,”
nanofluids could be used as a working fluid to extract energy
from the earth core and processed in a PWR power plant
system producing large amounts of work energy.
 Cooling of Microchips
• A principal limitation on developing smaller microchips is the
rapid heat dissipation. However, nanofluids can be used for
liquid cooling of computer processors due to their high
thermal conductivity.
 Nanofluid in Automobile
 Nanofluid Coolant in Automobile
• The use of nanofluids as coolants would allow for smaller size and better
positioning of the radiators. Owing to the fact that there would be less fluid
due to the higher efficiency, coolant pumps could be shrunk and truck
engines could be operated at higher temperatures allowing for more
horsepower while still meeting stringent emission standards.
• The application of nanofluid also contributed to a reduction of friction and
wear, reducing parasitic losses, operation of components such as pumps
and compressors, and subsequently leading to more fuel savings.
 Nanofluid in Fuel
• The aluminum nanoparticles, produced using a plasma arc system, are
covered with thin layers of aluminum oxide, owing to the high oxidation
activity of pure aluminum, thus creating a larger contact surface area with
water and allowing for increased decomposition of hydrogen from water
during the combustion process. During this combustion process, the
alumina acts as a catalyst and the aluminum nanoparticles then serve to
decompose the water to yield more hydrogen. It was shown that the
combustion of diesel fuel mixed with aqueous aluminum nanofluid
increased the total combustion heat while decreasing the concentration of
smoke and nitrous oxide in the exhaust emission from the diesel engine.