Synthesis of Carbon Nanotubes
I Polina Shifrina
12.05.2011
This handout briefly summarizes the production methods of carbon nanotubes.
1. Introduction
Carbon nanostructures like fullerenes, graphene and nan~tubes ~re . of great
interest for the current research as well as for future industrial applications. The
reason for this is that the band gap of single-walled carbon nanotubes (SWNTs) can
vary from zero to about 2 eV and hence their electrical conductivity can be the one
of a metal or the semiconductor. Moreover, the carbon nanotubes market is steadily
growing and thus effective and cheap solutions for the production of high quality
carbon nanotubes are needed. To the best of my knowledge, the main focus in the
current research lays on exploring the effective production methods for single-
walled carbon nanotubes (SWNTs) because of their unique physical and chemical
pr~perties and hence their potential electronic application. (!) ((};J
This handout presents different synthesis methods like arc aischargeJADJ;r~
ablation@ehemical vapour deposition (CVD) as well as some of the more recent
methods 1«orking with high pressure of the carbon monoxide or some unique
catalytic mixture. The production methods are ex lained and their advantages and-
disadvanta es examined. actual production of✓.c...?rb~nanotubes contains e
T.P-~
following steps ynthesis,~urification@hspectio~nd~ckaging. Although this
handout concentrates on the synthesis, the other factors should not be completely
neglected as they contribute significantly to the production costs.
2. Growth Mechanism
To begin with , I shortly explain the general growth mechanism of carbon nanotubes
that is basically common for different growth methods.
First of all, the exact way in which nanotubes are formed is not completely
I/ · understood . One distinguishes
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Support first, a round or pear-shaped
precursor for the formation of
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nanotubes is formed on the surface
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' of the metal catalyst. Second, the
I carbon diffuses on the sides of the
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SYNTHESIS OF CNTs by various
methods
1. Arc discharge Method
• During the arc Dischare Method CNTs was first time used by Sumio
I ----
Ii j ima in 1991.
• Nanotubes were initially discovered using this technique so it is the
most widely-used method of nanotube synthesis,
• Carbon contained in the negative electrode sublimates because of
the high discharge temperatures forming Nanotubes.
I • Yield for this method is up to 30 percent by weight,
' P!J)duces both single- and multi-walled nanotubes with lengths of up to ~O S0 /jJIYJ
micrometers with few structural defects.
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Fig 1 Synthesis of CNTs by Arc Discharge Method
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2. CVD Nlethod
Commercial method for production of carbon nanotubes
• Substrate is prepared with a layer of metal catal st articles( commonly
nickel,__f_obalt, iron, or a combination)
• Diameters of the nanotubes depends on the size of the metal particles
• Two gases are bled into the reactor:
✓ a process gas (such as ammonia, nitrogen or hydrogen) and
✓ a carbon-containing gas (such as acetylene, ethylene, ethanol or
methane)
• This can be controlled by patterned (or masked) depositio~al,
anneali~, or by plasma etching of a metal layer•
• Sub~ rate is now heated to ~ 700°C which initiate the growth of
nanotubes ,
• Nanotubes grow at the sites of the metal catalyst_;_ the carbon-containing
gas is broken apart at the surface of the catalyst particle, and the carbon is
J. transported to the edges of the particle, where it forms the nanotubes.
Catalyst particles can stay at the tips of the growing nanotube during the
growth proc!_Ss, or remain at the nanotube base, depending on the adhesion
between the catalyst particle and the substrate <
✓ · One issue in this synthesis route is the removal of the catal st su wort via
f-icbea-'7Y1an acid treatment, which sometimes could destroy the original structure of
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the carbon nanotubes. However~ alternative catal~ t [Link] that ar~
soluble in water have raven effective for nanotube growth.
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Fig:2 Synthesis of CNTs by CVD method
4 THE
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3. Laser ablation Method
• Developed by Dr. Richard Smalley and co-workers at Rice University
• Pulsed-laser vaporizes a graphite target in a high-temperature re~
which has inert gas • lo:N,· t~af:J;.,+ ,,.,,·,a~ w ,-,i, S'6 :ro ~ J~ooi ·
• Nanotubes develop on the cooler surfaces of the reactor as the vaporized
carbon condenses ·
-
• Water-cooled surface may be included in the system to collect the
nanotubes .
• The laser ablation method yields around 70% -.,,JjJ
• Produces primarily single-walled carbon nanotubes with a controllable
-----
diameter determined b the reaction tern erature · -
J:-- • ore expensive than either arc discharge or chemical vapor deposition
• However, the length of MWNT produced through laser ablation is
mu0 shorter than that produced by arc discharge method. Therefore, this
method does not seem adequate for the synthesis of MWNT. The diameter
1
v distribution of SWNTs made by this method is roughly between 1.0 and 1.6 *
nm. Because _of the good quality of nanotubes produced by this method,
scientists are trying to scale up laser ablation. However, the results are not
yet as good as for the arc-discharge method, but they are still promising.
quartz tube
graphite target with (diameter 20 mm)
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pressure control
argon gas input
wilh rnass now control l!IJlllll~;i.4,,1~ deposited soot
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hot zone of 190 mm length
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Fig 3 Synthesis of CNTs by Laser Ablation Method
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Fig 3 Synthesis of CNTs by Laser Ablation Method
Applications of CNTs
• Multipurpose innovative carriers for drug delivery and diagnostic
applications •
• Biosensors, composite materials, molecular electronics .
• Delivery of drugs, antigens and genes .
• Functionalized CNTs with high solubility and low toxicity as drug carriers.
• High loading capacity of drug in double functionalized carbon nanotube. -
• They can be used as lubrican_!:, or glidants in tablet manufacturing due to
nanosize and sliding nature of graphite layers bound with Van der Waals
forces.
• Carrier for Drug delivery: Carbon nanohorns (CNHs) are the spherical
aggregates of CNTs with irregular horn like shape. Research studies have
pr_?ved CNTs and CNHs as a potential carrier for drug delivery s_ystem.
• In Genetic Engineering: lln genetic engineering, CNTs and CNHs are
used to manJpulate genes and atoms in the development of bio imag_ing
genomes, proteomics and ti~sue engineering.
• Biomedical applications.
• Artificial implants: Normally body shows rejection reaction for implants
with the post administration pain but, miniature sized nanotubes and
nanohorns get attached with other proteins and amino acids avoiding
rejection. Also, they can be used as implants in the form of artificial joints
without host rejection reaction.
• Preservative: Carbon nanotubes and nanohorns are antioxidant in nature.
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,,- Hence, they are used to preserve drugs formulations
prone to oxidation .
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• As catalyst: Nanohorns offer large surface area and hence, the catalyst at
molecular level can be incorporated into nanotubes in large amount
. As Biosensors: CNTs act as sensing materials in pressure, flow, thermal,
gas, optical, mass, position, stress, strain, chemical, and biological sensors.
Reference:
[11 International Journal of Engineering Research and General Science
Volume 2, Issue 4, June-July, 2014 . Carbon Nanotubes: A Review on
Synthesis, Properties and Applicationsl7l
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Self-cleaning action:
The most prominent application of
nanotechnology in the household
is self-cleaning or "easy-to-clean"
surfaces on ceramics or glasses.
Nano ceramic partides have
improved the smoothness and
heat resistance of common
household equipment such as the
flat iron.
Water rolls off the surface taking
duct or contaminant along with.
• For a superhydrophobic surface, it must exhibit Contact Angle greater
than1500 and the contact angle hysterisis must also be low.
• That contact angle measure by using instrument contact angle meter
or goniometer.
