CNTs synthesis

SUBMITTED TO: SUBMITTED BY:

DR. S.K. GUPTA SIR NAVEEN DIKSHIT

H.O.D. S/R: 23/15

CHEMICAL ENGINERING DEPARTMENT 3RD YEAR CH

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INDEX

 ABSTRACT 3
(1) Introduction 4

(2) History 5
(3) Methods for CNT synthesis 6
3.1 Arc discharge method 6
3.1.1 SWNTs by Arc discharge method 6
3.1.2 Arc Plasma Jet Method 8

3.2 LASER ablation method 9

3.3 Chemical Vapour Deposition 10

3.3.1 Growth mechanism 11
3.3.1A Root growth mechanism 11
3.3.1B Tip growth mechanism 11
3.3.2 New directions in CVD 12

(4) Bulk synthesis of SWNTs 13

4.1 Methane CVD 13
4.2 HiPco Method 14
4.3 CO CVD method 15
4.4 Alcohol CVD Method 16

(5) Purification Methods 16

5.1 Gas phase method 16
5.2 Liquid Phase method 17
5.3 Intercalation 17

(6) CONCLUSION 18
 References 19

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ABSTRACT

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. These
cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology,
electronics, optics and other fields of material science and technology. One of the greatest
impacts on nanoscience and nanotechnology has been made by the carbon nanotubes.

Nanotubes are members of the fullerene structural family. Their name is derived from their long,
hollow structure with the walls formed by one-atom-thick sheets of carbon called graphene.

The nanotubes can be single or multi-walled abbreviated as SWNT and MWNT respectively.
Single wall nanotube (SWNT ) consist of one cylinder. It is made of single graphene sheet rolled
up into cylinder closed by two caps (semi fullerenes). The SWNTs have diameter in the range of
0.5 -2.0 nm. The length is in the range of 50-150 μm length. The SWNTs are microporous and
the specific surface area is in the range of 1300 m2/g (outer surface). SWNTs are commonly
arranged in bundles. SWNTs have less topological defects and have better mechanical and
electro physical properties.

Multiwall (MWNT) nanotubes consist of many nested concentric SWNTs cylinders with
increasing successive radii. The concentric walls are spaced regularly at 0.34 nm similar to inter
graphene distance. The advantage of MWNT over SWNT is that the multi-shell structures of
MWNTs are stiffer than single wall hence stability is higher. Also large scale synthesis of
MWNT is possible by various methods. The most common characterization techniques of these
materials are electron microscopy, Raman spectroscopy, TGA , IR and UV-Vis.

In this report, an attempt has been made to discuss about the common preparation methods,
purification methods and growth mechanism of CNTs. Although there are many methods for the
production of CNTs the most common methods are being covered in this report thoroughly.

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(1) Introduction

Graphene is the basic structural element of carbon nanotubes. It is one-atom thick planar
sheet of (sp2) bonded carbon atoms that are densely packed in a honeycomb crystal lattice.
which is a basic building block for graphitic materials of all other dimensionalities. It can be
wrapped up into fullerenes, rolled into nanotubes or stacked into graphite.

Finite size of graphene layer has dangling bonds(the carbon present in a single graphene
layer has some unsaturation and hence possess very high energy) . Upon rolling dangling
bonds are eliminated (However there will be an increase in strain energy), but overall Energy
decreases (more stability).

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(2) HISTORY

In 1985, a confluence of events led to an unexpected and unplanned experiment with a

new kind of microscope resulting in the discovery of a new molecule made purely of
carbon.
In fact, what had been discovered was not just a single new molecule but an infinite class
of new molecules: the fullerenes. Each fullerene – C60, C70, C84, etc. – possessed the
essential characteristic of being a pure carbon cage, each atom bonded to three others as
in graphite. Unlike graphite, every fullerene has exactly 12 pentagonal faces with a
varying number of hexagonal faces .

Some fullerenes, like C60, were spheroidal in shape, and others, like C70, were oblong like
a rugby ball. Dr. Richard Smalley recognized in 1990 that, in principle, a tubular
fullerene should be possible, capped at each end, for example, by the two hemispheres of
C60, connected by a straight segment of tube, with only hexagonal units in its structure.
Millie Dresselhaus, upon hearing of this concept, dubbed these imagined objects
“buckytubes.”.

In 1991, after the discovery and verification of the fullerenes, Sumio Iijima of NEC
observed multiwall nanotubes formed in a carbon arc discharge and two years later, he
and Donald Bethune at IBM independently observed single-wall nanotubes – buckytubes.
After Arc discharge method several other methods were also developed like Laser
ablation method , CVD , HiPCO and CoMoCat method.

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3)METHODS FOR SYNTHESIS OF CNTs

 Arc discharge Method

 LASER ablation method
 Chemical Vapor Deposition method(CVD)
 High pressure Carbon monoxide (HiPco) method
 CoMoCat. Method

3.1)ARC DISCHARGE METHOD:

This method was used by Iijima in 1991 for the synthesis of MWNTs. The schematic diagram is
showing the following components.

 Chamber filled with a rarefied ambient gas

 Two pure graphite rods having tip to tip clearance of 1-2 mm
 dc current supply
 When a dc arc current is supplied between two electrodes, the anode is consumed and
fullerenes is formed in the chamber soot and a part of evaporated anode gets deposited on
the cathode as cathode deposit. Iijima observed the samples from this cathode deposit by
Transmission Electron Microscopy (TEM) and he observed the existence of multi walled
nanotubes.

3.1.1) SWNTs BY ARC DISCHARGE METHOD

Two years after the discovery of MWNTs by arc discharge method The single-walled nanotubes
were synthesized in 1993 by Iijima and Ichihashi by using a Fe catalyst while a IBM group used
Co catalyst. By the arc discharge evaporation of electrodes including a magnetic catalyst, the
SWNTs were found to be formed like cotton-like soot in the chamber, not in the cathode deposit
as in the case of MWNTs. Two conclusions were drawn after few experiments were carried out.

 SWNTs were produced in the entire chamber.

 MWNTs were confined to cathode deposit only.

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  SWNTs formation requires a catalyst while MWNTs do not.
 The mass production of SWNTs was first produced by using binary metals Ni and Y in
Helium environment

Arc discharge experiment setup

Arc discharge using Ni-Y mixture in He atmosphere

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3.1.2)ARC PLASMA JET METHOD

 The mass production of cotton-like soot was enhanced by this modification.

 The electrodes were rearranged by an angle of 30 degree
 In the conventional methods about more than half of the evaporated anode becomes a
cathode deposit, which does not include SWNTs.
 Hence more than 80% of the evaporating anode becomes soot including SWNTs.
 When this soot was observed by using HRTEM, it was found that bundles of SWNTs
along with catalytic particles surrounded by thick amorphous carbon are observed.
 The removal of thick amorphous carbon from SWNTs was not easy, when attempted by
heat treatment, SWNTs were severely damaged.

schematic of modified arc discharge apparatus

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3.2)LASER ABLATION METHOD

In 1995, Smalley and co-workers produced carbon nanotubes using laser ablation technique.In
the laser ablation technique, a high power laser was used to vaporize carbon from a graphite
target at high temperature. Both MWNTs and SWNTs can be produced with this technique.

In order to generate SWNTs, metal particles as catalysts must be added to the graphite targets
similar to the arc discharge technique. The quantity and quality of produced carbon
nanotubes depend on several factors such as the amount and type of catalysts, laser power and
wavelength, temperature, pressure, type of inert gas, and the fluid dynamics near the carbon
target. The laser is focused onto a carbon targets containing 1.2 % of cobalt/nickel with 98.8 %
of graphite composite that is placed in a 1200°C quartz tube furnace under the argon atmosphere
(~500 Torr). In such technique, argon gas carries the vapors from the high temperature chamber
into a cooled collector positioned downstream. The nanotubes will self-assemble from carbon
vapors and condense on the walls of the flow tube. Carbon nanotubes produced by laser ablation
were purer (up to 90 % purity) than those produced in the arc discharge .

Schematic diagram of the laser ablation apparatus.

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3.3) CHEMICAL VAPOUR DEPOSITION

CVD is the most widely used method for the production of carbon nanotubes. During CVD, a
substrate is prepared with a layer of metal catalyst particles, most commonly nickel, cobalt, iron
or a combination. The metal nanoparticles can also be produced by other ways, including
reduction of oxides or oxides solid solutions. The substrate is heated to approximately 700 °C.
To initiate the growth of nanotubes, 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). 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 transported to the edges of
the particle, where it forms the nanotubes. The catalyst particles can stay at the tips of the
growing nanotube during growth, or remain at the nanotube base, depending on the adhesion
between the catalyst particle and the substrate. Fluidised bed reactor is the most widely used
reactor for CNT preparation. Fe, Co and Ni catalysts are mostly used for the catalytic growth of
CNT. More recently, CNTs have also been grown from metal such as Au, Ag and Cu. Catalyst
serves as nucleation sites and also promotes pyrolysis of hydrocarbons.

Schematic for carbon vapor deposition method

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3.3.1) Growth mechanism

The growth mechanism of CNTs is yet to be fully established. In general it is proposed that
hydrocarbons adsorb on metal particles and are catalytically decomposed. This results in carbon
dissolving into particle. Upon supersaturation, carbon precipitates in tubular crystalline form.
Various alternative models have been proposed and appropriate description of growth depends
on synthesis route and conditions used. Two most described models are-

3.3.1A)Root growth mechanism. When there is a strong interaction between the catalyst
clusters and substrate, the CNT grows by the root-growth mechanism. The pyrolysis of
hydrocarbons produces the carbon atoms which are extremely mobile on metal surfaces and
rapidly diffuse over and through the metal particles. The graphite precipitates around the catalyst
particles and cylindrical structures are formed in a nested fashion from the catalyst particle, with
the catalyst particle at the root. The growth of the nanotubes stops when the catalyst particles are
completely covered with layers of carbon.

3.3.1B)Tip growth mechanism The tip growth mechanism is observed when the
interaction between metal catalyst clusters and substrate is weak. Due to the weak interaction, the
catalyst particles are lifted off the substrate by the cylindrical structures formed below it. While,
the carbon nanotube base remains anchored to the substrate, the tip carrying the catalyst particle
grows toward the region of higher feed gas concentration. The tip growth stops when the catalyst
particle is covered with carbon layers .

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3.3.2) New Directions in the Chemical Vapour Deposition

As for the fact that CVD is such a promising method for the production of carbon nanotubes,
there is an ongoing research in this field. Some new methods were developed.

CVD-method allows the pretreatment of the substrate surface which can lead to impressive,
controlled multi-walled and single-walled nanotubes architectures. Multi-walled nanotubes self-
assemble into aligned structures because of the Van der Waals interaction between the single
tubes. The substrates are catalytically patterned by the photolitography which enables selective
deposition of the catalyst and consequently selective and controlled growth of carbon nanotubes.

Photolithography also termed optical lithography or UV lithography, is a process used in

microfabrication to pattern parts of a thin film or the bulk of a substrate. It uses light to transfer a
geometric pattern from a photomask to a light-sensitive chemical "photoresist", or simply
"resist," on the substrate.

During CVD growth, the outer walls of the tubes interact with their neighbours via van der
Waals forces, forming a rigid bundle which grows perpendicularly to the substrate.

In 2004 Iijima introduced another modification, the super-growth CVD or water-assisted CVD .
Here, the activity and lifetime of the catalyst are enhanced by addition of water into the CVD
reactor. With this method dense, well-aligned "forests", perpendicular to the substrate with
heights up to 2.5 mm can be produced.

With the low temperature CVD that was firstly reported in 2006 tungsten filament increases the
decomposition of the precursor gases. Single-walled nanotubes were observed at temperatures as
low as 350°C.

In 2007 a high-efficiency CVD-method based on hydrocarbon gas camphor (C10H16O) was

demonstrated.

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4) Bulk Synthesis of SWNTs

Over the last few years, several methods have been developed that have the potential for
industrial-scale preparation of nanotubes. All of them are based on CVD methods. Among these
methods, four different approaches have been shown to be the most promising:

 Methane CVD
 HiPCO
 CO CVD
 Alcohol CVD.

4.1 METHANE CVD

Methane CVD was developed by Dai’s group at Stanford; they first reported the synthesis of
bulk amounts of SWNTs by CVD from methane at 900°C.43 A systematic study of the catalyst
leads to the conclusion that the best catalyst for their process is an Fe/Mo bimetallic catalyst
supported on an Al2O3-SiO2 hybrid material.

The Al2O3-SiO2 hybrid exhibits both strong metal-support interaction from Al2O3 and better
structural stability than either Al2O3 or SiO2 alone at temperatures as high as 900°C. The
catalyst has a surface area of almost 200 m2 /g and a mesopore volume of 0.8 mL/g.

Several groups used other hydrocarbons and catalysts to prepare SWNTs. For example, one
group prepared SWNTs using an extremely small amount of C2H4 diluted by Ar and an
Fe/Mo bimetallic catalyst with an Al2O3 support. Both single and double-walled nanotubes were
observed for reaction temperatures from 700°C to 850°C. However, methane is still the most
common gas used to prepare SWNTs.

It has been shown that when different catalysts are used, the optimal reaction conditions are
different. Unfortunately, there is no available systematic theory that can explain all of the
experimental observations.

Clearly, more systematic studies are needed in this research field to provide a better
understanding of the general growth mechanism and to explain all of the experimental
observations.

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4.2) HiPco Method

HiPCO stands for high-pressure catalytic decomposition of carbon monoxide. It is a method used
to prepare SWNTs, using high-pressure CO as the carbon source. The catalysts used in a HiPCO
process are formed in the gas phase from a volatile organometallic catalyst precursor introduced
into the reactor. The organometallic species decompose at high temperature, forming metal
clusters on which SWNTs nucleate and grow.

The HiPco process was originally developed by Smalley’s research group at Rice University. In
this procedure, high-pressure (30–100 atm) and high temperature (1050°C) CO with Fe(CO)5 as
a catalyst precursor produced high-quality SWNTs at a rate of approximately 450 mg/h. The
product consists of entangled SWNT bundles interspersed with Fe nanoparticle.

Schematic of HiPco method

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4.3) CO CVD METHOD

CO was actually the first feed gas used for the growth of SWNTs. Dai et al. performed the first
CVD synthesis of SWNTs by Mo-catalyzed disproportionation of CO at 1200°C in 1996. It was
reported that most of the resulting SWNTs had catalytic particles attached to the ends, indicating
that the growth of SWNTs was catalyzed by preformed nanoparticles. However, due to safety
reasons related to the use of CO, reports on the growth of SWNTs using CO are limited, as
compared with other feed gases. However, the use of CO as a feed gas does offer certain
advantages over hydrocarbons. An important advance in the CO CVD method that makes it
potentially commercial is the development of the CoMoCat process by Resasco’s group at the
University of Oklahoma, who used Co-Mo bimetallic catalysts and a fluidized bed CVD reactor
to produce a large quantity of SWNTs. Even more interesting, it was found that the SWNTs
produced by their process have very narrow diameter and chirality distributions.

Schematic of a CoMoCat Method

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4.4) Alcohol CVD

The most recent addition to the family of CVD methods for SWNT production is the alcohol
CVD method. Maruyama et al. recently reported the synthesis of high purity SWNT using
alcohols such as methanol and ethanol as a carbon source. The synthesis temperature is 700–
800°C. The catalyst used in the method is a bimetallic (Fe-Co) catalyst supported on a zeolite.
TEM and SEM showed that the products are very clean SWNTs without any amorphous carbon
coating. It is hypothesized that the OH radical formed at high temperature from alcohols can
remove the amorphous carbon efficiently during nanotube growth, leaving only pure SWNTs as a
product. If proven to be scalable, alcohols may become a better carbon source for industrial-scale
synthesis of SWNTs because of their wide availability and their ease in handling and storage, as
compared with methane and carbon monoxide.

5) PURIFICATION METHODS

Purification of CNTs generally refers to the separation of CNTs from other entities, such as
carbon nanoparticles, amorphous carbon, residual catalyst, and other unwanted species. 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 with
varying degrees of success are

 gas-phase
 liquid-phase
 intercalation method

5.1) Gas Phase

The first successful technique for purification of nanotubes was developed by Thomas Ebbesen
and coworkers. Following the demonstration that nanotubes could be selectively attached by
oxidizing gases these workers realized that nanoparticles, with their defect rich structures might
be oxidized more readily than the relatively perfect nanotubes. They found that a significant
relative enrichment of nanotubes could be achieved this way, but only at the expense of losing the
majority of the original sample.

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5.2) Liquid Phase The current liquid-phase purification procedure follows certain essential
steps:

 preliminary filtration- to get rid of large graphite particles

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

5.3) Intercalation

An alternative approach to purifying multi walled nanotubes was introduced in 1994 by a

Japanese research group. This technique made use of the fact that nanoparticles and other
graphitic contaminants have relatively “open” structures and can therefore be more readily
intercalated with a variety of materials that can close nanotubes.

By intercalating with copper chloride, and then reducing this to metallic copper, the research
group was able to preferentially oxidize the nanoparticles away, using copper as an oxidation
catalyst. Since 1994, this has become a popular method for purification of nanotubes.

The first stage is to immerse the crude cathodic deposit in a molten copper chloride and
potassium chloride mixture at 400°C and leave it for one week. The product of this treatment,
which contains intercalated nanoparticles and graphitic fragments, is then washed in ion
exchanged water to remove excess copper chloride and potassium chloride. In order to reduce
the intercalated copper chloride-potassium chloride metal, the washed product is slowly heated
to 500°C in a mixture of Helium and hydrogen and held at this temperature for 1 hour.

Finally, the material is oxidized in flowing air at a rate of 10°C/min to a temperature of 555°C.
Samples of cathodic soot which have been treated this way consist almost entirely of nanotubes.
A disadvantage of this method is that some amount of nanotubes are inevitably lost in the
oxidation stage, and the final material may be contaminated with residues of intercalates. A
similar purification technique involves intercalation with bromine followed by oxidation.

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6) CONCLUSION

Carbon nanotubes clearly constitute a fascinating class of materials exhibiting a variety of novel
properties. Synthesis is the key issue of CNT research. There has been wide variety of techniques
for synthesizing CNTs. In this article, the different synthesis methods of CNTs have been
reviewed. The CNTs (single and multi-walled) are produced by three main techniques, arc
discharge, laser vaporization and chemical vapor deposition. Over the last few years, several
methods have been developed that have the potential for industrial-scale preparation of nanotubes.
All of them are based on CVD methods. Among these methods, four different approaches have
been shown to be the most promising were methane CVD, CO CVD, HiPco Method and Alcohol
CVD.

The CNTs from the arc discharge are often covered with amorphous carbon, which contains
metallic particles in the case of metal-carbon co-evaporation. With the laser vaporization method,
CNTs are very clean i.e. less covered with amorphous carbon.

Catalytic CVD is an extremely versatile technique for the production of CNTs. One major
advantage of the CVD approach is that CNTs can be made continuously, which could provide a
very good way to synthesize large quantities of CNTs under relatively controlled conditions.

A variety of hydrocarbons, catalyst and catalyst supports have been used successfully by various
groups worldwide to synthesize CNTs. Many investigations into the properties of CNTs and their
potential applications require clean and uniform CNTs that contain no impurities. A number of
purification methods have been developed to date. Care should be taken when the technique is
chosen, as the effect on the entire sample will also depend on the composition and the amount of
the sample. The CVD technique can also be adopted for the controlled growth of CNTs at
particular sites on a substrate for various applications. Due to the great potential of CNTs, it is
clear that novel technologies will emerge in the near future.

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7) REFERENCES

wikipedia

Nptel course CO-ORDINATED BY : IIT GUWAHATI

Synthesis of CNT by arc discharge method: Yoshinori Ando* and Xinluo Zhao

Meijo university JAPAN

www.mrs.org/publications/bulletin

R.E. Smalley and B.I. Yakobson, Solid State

Commun. 107 (1998) p. 597.

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