Production Of Carbon Nanotubes

Nyla Vaidya
B005
Index

 What is a CNT
 Structure and Special Properties
 Classification and Applications
 Synthesis
 Comparing the Synthesis methods
 Purification
 What is a CNT ?
 Carbon nanotubes (CNTs) are allotropes of carbon. A
carbon nanotube is a one-atom thick sheet of graphite
(called graphene) rolled up into a seamless cylinder with
diameter of the order of a nanometer. This results in a
nanostructure where the length-to-diameter ratio exceeds
10,000. Such cylindrical carbon molecules have novel
properties that make them potentially useful in a wide
variety of applications in mechanical, structural, thermal,
electrical & electronics, optical, biomedical and other
fields of science.

Image reference

https://www.ossila.com/products/double-walled-carb
Structure and Special Properties
 They exhibit extraordinary strength and unique electrical properties, and are
efficient conductors of heat. Their name is derived from their size, since the
diameter of a nanotube is on the order of a few nanometers (approximately
50,000 times smaller than the width of a human hair), while they can be up to
several millimeters in length.
 Structure
 The structure of a carbon nanotube is formed by a layer of carbon atoms that are bonded together in a
hexagonal (honeycomb) mesh.

 Properties
 The special nature of carbon combines with the molecular perfection of single-wall CNTs to endow them
with exceptional material properties.
Such as:
 Excellent electron field emitters Extraordinarily flexible and elastic

 Higher tensile strength Lower thermal expansion coefficient

 They are excellent conductors of thermal energy They are ideal conductors of electrical energy
Classification
 The first noticeable discovery of carbon nanotubes was reported by Ilijima in
1991, when he found layers of carbon (graphene) rolled into tubular structure in
the soot of arc discharge method. The nanotubes consisted of up to several tens
of graphitic shells (so called multi-walled carbon nanotubes) with adjacent shell
separation of 0.34 nm, diameters of 1 nm and high length/diameter ratio.

 1. Single-Walled Carbon Nanotube

 Single-Walled Carbon Nanotube is a cylinder formed with only one layer of

carbon molecules. Commonly, these have diameters ranging from 0.4 to 2 mm.
Increasing temperature results in larger-sized (wider) SWCNTs.

 2. Multi-Walled Carbon Nanotubes

 (MWCNTs) differ with SWCNTs by the number of cylindrical walls they have.
In MWCNTs, the carbon molecules form multiple concentric walls of
consequentially increasing diameters around one another.
Applications of single- walled carbon
nanotubes
 Various applications in which single walled carbon nanotubes are
useful in different industries are :
 As catalysts in several chemical reactions for better-controlled reactions and best
results

 As super-capacitors

 As nano-electrodes

 As parts of advanced sensors

 For ideal energy conversion

 As replacements for conventional lithium-battery anodes

 For storing hydrogen more efficiently

Applications of Multi- walled carbon nanotubes

 Multi-walled carbon nanotubes are strong, have better electrical and thermal conducting
capacities, and thus find broader potential in the following ways:

 The use of MWCNTs in batteries can double storage power.

 In solar cells
 In transistors
 For flat panel displays
 In case of better energy storage
 Arc Discharge
 This is one of the oldest methods of carbon nanotube production. First utilized in 1991 at NEC’s Fundamental
Research Laboratory to produce new type of finite carbon structures consisting of needle-like tubes. The tubes were
produced using an arc discharge evaporation method similar to that used for the fullerene synthesis. The carbon
needles, ranging from 4 to 30 nm in diameter and up to 1 mm in length, were grown on the negative end of the carbon
electrode used for the direct current arc-discharge evaporation of carbon.
 During the process they used a pressurized chamber filled with a gas mixture of 10 Torr methane and 40 Torr argon.
Two vertical thin electrodes were installed in the center of the chamber. The lower electrode (cathode) contained a
small piece of iron in a shallow dip made purposefully to hold iron. The arc was generated by running a DC current od
200 A at 20 V between the electrodes.
 The use of the three components, namely argon, iron and methane, was critical for the synthesis of SWNT. Carbon
soot produced as result of arc-discharge settled and nano tubes grew on the iron catalysts contained in negative
cathode. The nano-tubes had diameters of 1 nm with a broad diameter distribution between 0.7 and 1.65 nm. In a
similar process Bethune used thin electrodes with bored holes as anodes, which were filled with a mixture of pure
powdered metals (Fe, Ni or Co) (catalysts) and graphite.
 The electrodes were vaporized with a current of 95 - 105 A in 100 - 500 Torr of Helium. SWNT were also produced
by the variant of arc-technique as well. In this variant, the arc was generated between two graphite electrodes in a
reaction chamber under helium atmosphere (660 mbar). Th is method also gave large yield of carbon nanotubes.
Ebbesen and Ajayan however, reported large-scale synthesis of MWNT by a variant of the standard arc discharge
technique as well.
Arc
Discharge

Image reference
https://www.scirp.org/html/5470.html
Laser Methods
 In the laser ablation process, a pulsed laser is made to strike at graphite target in a high temperature
reactor in the presence of inert gas such as helium which vaporizes a graphite targets. The nanotubes
develop on the cooler surfaces of the reactor, as the vaporized carbon condenses. A water-cooled
surface is also included in the most practical systems to collect the nanotubes.

 This method was first discovered by Smally and co-workers at Rice University in 1995. At the
time of discovery, they were studying the effect of laser impingement on metals. They
produced high yields (>70%) of Single walled Carbon Nanotubes by laser ablation of graphite
rods containing small amounts of Ni and Co at 1200˚C. In this method two-step laser ablation was
used. Initial laser vaporization pulse was followed by second pulse to vaporise target more rapidly.

 The two-step process minimizes the amount of carbon deposited as soot. Tubes grow in this
method on catalysts atoms and continued to grow until too many catalyst atoms aggregate at the
end of the tube. The tubes produced by this method are in the form of mat of ropes 10 - 20 nm in
diameter and up to 100 micron or more in length. By varying temperature, catalyst composition and
other process parameters average diameter and length of carbon nanotube could be varied.
Laser
Methods

Image reference
https://www.researchgate.net/
figure/Schematic-diagram-of-
CNT-formation-progress-by-l
aser-ablation-method_fig2_33
3854738
Comparing the Synthesis methods
 Arc-discharge and laser vaporization are
currently the principal methods for
obtaining small quantities of high quality
CNTs.

 Both methods involve evaporating the

carbon source, so it has been unclear
how to scale up production to the
industrial level using these methods.

 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

manipulate, purify, and assemble for
building nanotube-device architectures
for practical applications. 
Purification

 Purification of CNTs generally is the separation of CNTs from other entities.

 The classic chemical techniques for purification have been tried, but they have not been
found to be effective in removing the undesirable impurities.

 Three basic methods have been used so far, namely gas-phase, liquid-phase, and
intercalation methods and more recently, plasma purification.
Gas Phase Carbon
Nanotubes
 nanotubes could be selectively attached by oxidizing gases

 They found that a significant relative enrichment of nanotubes could be achieved this way, but at the
expense of losing the majority of the original sample. 

 A new gas-phase method has been developed at the NASA Glenn Research Center to purify gram-scale
quantities of single-wall CNTs.

 This is a modification of a gas-phase purification technique uses a combination of high-temperature

oxidations and repeated extractions with nitric and hydrochloric acid.

 This improved procedure significantly reduces the amount of impurities, increasing their stability
significantly.
Liquid Phase Carbon Nanotubes

 The current liquid-phase purification procedure follows certain essential steps:

 preliminary filtration

 dissolution- to remove fullerenes (in organic solvents) and catalyst particles (in concentrated acids)

 centrifugal separation

 microfiltration

 chromatography to either separate multi walled nanotubes and unwanted nanoparticles or single walled nanotubes
and the amorphous carbon impurities.

 It is important to keep the CNTs well-separated in solution, so the CNTs are typically dispersed using a surfactant
prior to the last stage of separation.
References
Websites (Information) and papers
 https://www.cheaptubes.com/carbon-nanotubes-history-and-production-methods-2/#purific
ation
 https://www.techopedia.com/definition/3145/carbon-nanotube-cnt
 https://www.scirp.org/html/5470.html
Papers
 https://www.researchgate.net/publication/333854738_Carbon_Nanotube_Based_Fiber_Sup
ercapacitor_as_Wearable_Energy_Storage
 https://www.researchgate.net/figure/Schematic-diagram-of-CNT-formation-progress-by-las
er-ablation-method_fig2_333854738
 https://www.rigaku.com/vacuum/app11-nanotube.php
 https://www.ossila.com/products/double-walled-carbon-nanotubes