Ince Yardimciand Yagmurcukardes 2021

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Synthesis Methods of Carbon Nanotubes
Chapter · November 2021

DOI: 10.1007/978-3-319-70614-6_52-1
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Atike Ince Yardimci and Nesli Yagmurcukardes
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
CNT Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Arc Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Laser Ablation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Sonochemical/Hydrothermal Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Liquid Phase Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Flame Synthesis of CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Plastic Pyrolysis Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Chemical Vapor Deposition (CVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Abstract
Carbon nanotubes (CNTs) with their extraordinary mechanical, electrical, and
thermal properties have built broad interest in most areas of science and engi-
neering and are utilized for many applications in the nanotechnology area. There
are many approaches for CNT synthesis. While arc discharge, laser ablation, and
chemical vapor deposition are the most common methods, lots of rarely utilized
CNT production methods were reported in the literature. In this chapter, a detailed
discussion about CNT synthesis methods with their experimental process, advan-
tages, and disadvantages are provided. Especially, the CVD method, which is the
most promising CNT synthesis method, has been reviewed with its subtypes.
CNT synthesis method directly defines the type and properties of nanotubes.
A. I. Yardimci (*)
Technology Transfer Office, Uşak University, Uşak, Turkey
e-mail: atike.yardimci@usak.edu.tr
N. Yagmurcukardes
Department of Material Science and Nanotechnology Engineering, Engineering Faculty, Uşak
University, Uşak, Turkey
© Springer Nature Switzerland AG 2021 1

J. Abraham et al. (eds.), Handbook of Carbon Nanotubes,
https://doi.org/10.1007/978-3-319-70614-6_52-1
2 A. I. Yardimci and N. Yagmurcukardes
Therefore, researchers are still working on new methods and the development of
currently used methods. Literature studies indicate that different synthesis
methods come to the fore for different features such as SWCNT or MWCNT
production, vertically aligned nanotubes, high yield synthesis, large-area synthe-
sis, etc. In this chapter, a general overview and comparison of these methods
are made.
Keywords
Carbon nanotube · Synthesis · Synthesis methods · Growth parameters · High
quality CNT
Introduction
Intensive researches in the synthesis of high-quality CNTs have been carried out
since the first discovery of CNTs using arc synthesis techniques by Iijima in 1991. To
obtain high quality and high yield of CNTs in a cost-effective way, a lot of methods
have been tried and compared to each other. In this chapter, various carbon nano-
tubes synthesis (CNTs) methods are discussed in detail with the support of current
literature. Among the discussed techniques gas-phase methods such as arc discharge,
laser ablation, and chemical vapor decomposition (CVD) are found as the most
promising methods for the synthesis of CNTs. In addition to gas-phase CNT
synthesis methods, some condensed phase synthesis methods have been developed
for carbon nanomaterial production. Molten salt systems and organic liquid systems
such as electrochemical and sonochemical methods are some examples of condensed
phase methods. Liquid phase synthesis of CNTs by applying an electrical current to a
conductive substrate in organic solvents is also an alternative method. For each CNT
synthesis technique, different process parameters such as gas flow rates, pressure,
growth time, growth temperature, catalyst type, catalyst pretreatment process, sub-
strates, carrier gases, and type of carbon precursors define the CNT growth mech-
anism and influence CNT properties.
Each CNT synthesis method has some advantages and disadvantages that add
different properties to the nanotubes, which is of paramount importance when
choosing a specific method for the preparation of CNTs with the required properties.
The most promising three synthesis methods are arc discharge, laser ablation, and
chemical vapor deposition (CVD). First CNT synthesis was carried out with the Arc
discharge method; however, in this method CNTs are found together with a large
concentration of amorphous carbon, and CNTs are not aligned. The laser ablation
method is the second method and it can provide arrays of ordered CNTs. Besides, arc
discharge and laser ablation methods require a large amount of energy as well as a
source of graphite, which makes them uneconomical processes for large-scale
production. The CVD technique is the most widespread method to produce CNTs,
which is appropriate for scaling up. This method provides low-cost CNT production
using a simple setup. Also, it enables the production of a large yield of CNTs with
Synthesis Methods of Carbon Nanotubes 3
high purity at a lower temperature compared to the previous methods. The properties
of CNTs in terms of alignment, diameter, and length could be controlled by the CVD
method. While arc discharge and laser ablation methods require a solid target and
very high temperatures to evaporate it, the CNTs obtained from both arc-discharge
and laser ablation methods are tangled and thus purification is not evident for
nanotubes synthesized by these methods. All of the CNT synthesis methods have
some advantages and disadvantages, each technique will be explained below. There
are a lot of CVD types that are determined by factors such as reactants used during
the process, maximum tolerable air leakage amount into the system, purity of the
materials used, size, shape, and properties of the substrate, and so on. Detailed
information about CVD types is provided in this chapter.
CNT Synthesis Methods
Arc Discharge
The Arc-discharge method is the first method to utilize for producing CNTs by Iijima
(Iijima et al. 1992),.MWCNTs were obtained in 1991, and SWCNTs were obtained
in 1993 firstly by this method. In this method, CNT growth carries out on carbon
electrodes by applying direct current (DC) to obtain a non-fluctuating arc, for which
closed-loop automation is utilized to adjust the gap automatically during
arc-discharge evaporation of carbon. The process occurs in an inert buffer gas
atmosphere such as argon, helium, hydrogen, nitrogen, or their mixtures in order
to avoid the oxidation of carbon at higher temperatures (Popov 2004). Utilized two
electrodes are high purity graphite electrodes; one of them (anode) contains catalysts
such as Fe, Co, Ni while the other one (cathode) is pure graphite (Iijima and
Ichihashi 1993). The anode surface is heated to a higher reaction temperature
between 3000 and 6500 K, which provides anode to vaporize and condense on
the cathode surface; therefore nanotube formation has occurred. The carbon vapors
precipitate in the gas phase and drift toward the cathode where it cools down due to
the temperature gradient. After an arc application time of few minutes, the discharge
is stopped and cathodic deposition that contains CNTs along with the soot is
collected from the walls of the chamber. The obtained product is then purified for
observation under an electron microscope to investigate its morphology.
Methane is the best gas for the growing of MWNTs (Ando 1994). However, it is
indicated that the CNTs can also be grown in the liquid nitrogen atmosphere or
water.
Another important parameter is the pressure of inert gas during the
arc-evaporation process, which has a strong influence on SWCNTs. The stability
of electric arc (Harris 2007; Arora and Sharma 2014) and the type of power supply
(Arora and Sharma 2014) also affect the morphology and quality of the CNTs. DC
arc current is applied across the electrodes in the arc-discharge method, and contin-
uous emission of electrons from the cathode bombards the anode at high velocity.
The diameter of the cathode is usually larger than that of the anode, and it results in a
lower current density of the cathode than the anode. Therefore, a high-temperature
gradient across the electrodes is observed, which sublimes the carbon precursor filled
inside the anode and results in the formation of CNTs. However, when AC arc
current is applied, the current changes periodically across the electrodes, and depo-
sition does not occur at either side of the electrodes. Other important arc discharge
parameters are growth temperature, electrode dimension, geometry, shape of elec-
trodes, and pulse duration. Especially, growth temperature directly influences the
diameter of SWCNTs, and growth temperature, type of catalyst, and carbon precur-
sor affect the diameter of MWCNTs.
This method allows the production of SWCNTs or MWCNTs easily and enables
the synthesis of carbon particles in the open air with optimum energy usage and high
reaction temperature, which provides CNTs with high crystallinity. The most impor-
tant advantage of this technique is its high efficiency and the capability to produce
CNTs in a specific area.
Laser Ablation
The laser ablation method was firstly employed to produce CNTs by Smalley’s
Group in 1995 in a double-pulse laser oven and it is mostly utilized to develop
SWCNT bundles with a narrow diameter distribution (Guo et al. 1995). The working
principle of the laser ablation method is similar to that of the arc-discharge method.
Firstly, a piece of graphite target is vaporized by utilization of various varieties of
lasers under high temperature in an inert gas atmosphere, and vaporization of carbon
gas is followed by condensation process. CNT growth temperature in this method is
nearly 1200 C and the generally used inert gases are argon, neon, or helium. At this
high temperature, a continuous or a pulsed laser is employed to vaporize the target
that is located in the center of the quartz tube furnace to produce fullerenes and
CNTs. The target also consists of a mixture of graphite and metal catalysts, such as
Fe, Co, and Ni (Yudasaka et al. 1999; Kataura et al. 2000). Bi-metallic catalysts also
could be appropriate for CNT growth by laser ablation. For materials that have high
boiling temperatures, the laser can be more suitable than the other vaporization
devices because of the energy density of the laser (Guo et al. 1995). By-products
obtained during the CNT synthesis process are α-C, graphite particles, graphitic
polyhedrons with enclosed metal particles, polyhedral, and fullerenes.
The principle of obtaining a CNT is by following these steps: Firstly, the target is
vaporized and then a cloud occurrs, which contain C, C2, C3, and rapidly catalyst
vapors are formed. With the condensation of the cloud, the small weight of carbon
molecules comes together to form a larger one. The vaporized catalysts are included
in this large molecule to prevent the closing of these carbon molecules into a cage
structure. The growth process is finalized with a SWNT. When the system is cooled
up to low temperature, this process is finished (Baddour and Briens 2005).
In literature, the pulsed arc technique and the pulsed laser technique are found to
be similar in terms of nucleation, growth mechanism, and SWCNT yields and
morphologies. In the laser ablation method, different types of lasers, pulse width,
and laser wavelength were tried to enhance the quality of nanotubes, production rate,
and consistency in the production rate. Different laser systems such as dual-laser-
pulsed system and continuous laser system were employed in many studies and
detailed investigations indicate that laser ablation method seems to be the most
reliable, environmentally friendly, and promising SWCNTs synthesis method. It
provides high purity, yield, and easy post-processing as compared to other CNT
synthesis techniques. In this method, the size of carbon agglomerates, catalyst cluster
growth mechanism, and carbon-metal catalyst interactions define nanotube proper-
ties. Other advantages of this method are: high-quality SWCNT synthesis
(MWCNTs synthesis with this method could be performed only in some special
growth conditions), diameter controllability and narrow diameter distribution, tun-
able duration of laser vaporization, and high crystallinity of the CNT (Soni et al.
2020). Besides the advantages of laser ablation, the high temperatures and using a
laser to produce CNTs make this method uneconomical compared to other CNT
synthesis methods.
Electrolysis
The capture of carbon dioxide (CO2) is an important issue because of the negative
impact of this gas on climate change. The concentration of CO2 in the atmosphere
continues to increase with fossil fuel combustion, deforestation, and massive indus-
trialization. Therefore, the conversion of CO2 is a significant topic.
In the electrolytic synthesis method of CNTs, which was developed in the
Institute of General and Inorganic Chemistry (Novoselova et al. 2006), CO2 is the
main reactant and is introduced in chloride melt under optimum parameters.
Cathodic reduction of CO2 to elemental carbon in metallic electrodes forms the
basis of the electrolysis method. By electrochemical reactions, a new condensed
carbon phase is produced on the cathode from a liquid molten salt phase containing
dissolved carbonic acid gas. CO2 indicates a low solubility in the chloride melting,
so the only possible way to increase the cathode process rate is to create an extreme
gas pressure. The only cathodic reaction product of wide current density and
potential ranges is carbon and the anodic reaction product is oxygen. CO2 is
separated into elemental carbon (C) and O2 electrochemically and the graphite
anodes utilized in this electrolysis method can react with isolated oxygen and
produce carbon dioxide. Therefore, a continuous process is provided.
If the correct combinations of electrode materials, electrolyte, temperature, and
electrical current were provided; CNTs have been obtained from CO2 by the
electrolysis method (Novoselova et al. 2008). Carbon could be converted in a
compact and stable form by the electrolysis method and carbon storage in this
form is possible.
Generally, the CNT growth process occurs by the decomposition of carbon-
containing precursor or a hydrocarbon gas on the surface of a metal catalyst such
as Fe, Ni, Co, Mo, and their oxides forms and alloys. However, in electrochemical
techniques, the most common catalysts are Ni or Ir anode and steel cathode for the
formation of carbon nanotubes or fibers. Ni erosion is assumed to be the source of

metal catalyst particles (Novoselova et al. 2008).
The synthesized CNTs are usually MWCNTs in this method and the possibility to
obtain MWCNTs by this method is with content up to 40 vol% in the cathode
product. MWCNTs have generally curved forms and they frequently create bundles
and most of the nanotubes are partially filled with the electrolyte salt. Besides, some
different carbon phases are produced with CNTs and these phases contain nanoscale-
sized metallic impurities. Metallic impurities are placed inside and on the ends of the
CNTs. The increase of CNT percentage in the overall volume of the carbon product
was detected in the samples where the austenite phase was fixed. As a result, the
metallic phase acts as a catalyst for nanotube formation in the electrolytic synthesis
method of CNTs from molten salts.
The advantages of the electrolytic method are simple experimental set-up, con-
trollable synthesis process by the electrolysis modes, cheap raw materials, control-
lable CNT structures, and morphologies and carbon phases doping in one step by
means of optimization of electrolysis conditions and electrolytic bath composition
(Chen and Fray 2003). Synthesis of CNTs by electrolysis method is a cheap method
compared to conventional CNT synthesis methods. Considering, the disadvantages
of this method, there are two main problems with this method. First is the cracking
problem of graphite cathode during the electrolysis process and the second is the
accumulation of electrolysis products such as chlorine gas (anode), alkaline metal
(cathode), and carbon nanomaterials (cathode) in the bath. These two problems
cause instability in the process and prevent continuous performance.
Sonochemical/Hydrothermal Synthesis
The sonochemical/hydrothermal synthesis technique is an appropriate method to pro-

duce different types of carbon nanostructures such as nano-onions, nanorods, nanowires,
nanobelts, and MWCNTs. There are three important advantages of this method com-
pared to other CNT synthesis methods. Firstly, the starting materials are easy to obtain
and are stable in ambient temperature; secondly, even at low temperatures about
150–180 C, CNT growth is carried out in this method, lastly, it does not require a
hydrocarbon gas or carrier gas for the CNT growth process. For the production of
MWCNTs by sonochemical/hydrothermal method, Gogotsi et al. utilized a mixture of
polyethylene and water with a Ni catalyst, and the mixture was heated to 700–800 C
under 60–100 MPa pressure (Gogotsi et al. 2000) and both closed- and open-end
MWCNTs with the wall numbers from several to more than 100 carbon layers were
obtained. CNTs synthesized by sonochemical/hydrothermal method have a small wall
thickness and large inner core diameter, 20–800 nm. In another study, Manafi et al.
studied low temperature sonochemical/hydrothermal MWCNT synthesis using reduc-
tion of CH2Cl2 by metallic Li in the presence of Co catalyzer at a low CNT growth
temperature of about 150–160 C for 24 h. CH2Cl2, CoCl2, and metallic Li were utilized
as starting materials in 5 mol/L NaOH aqueous solution. In this study, MWCNTs with
high purity and lengths of 2–5 μm and diameters of 60 20 nm were obtained at such a
low-temperature value (Manafi et al. 2008). In this study, the starting solution was
pretreated ultrasonically and this pretreatment process provided uniform catalyst particle
distribution and this process was concluded with the formation of MWCNTs. Razali
et al. synthesized CNTs by hydrothermal method at growth temperature of 200 C
(Razali et al. 2016). They used ferrocene with sulfur to form ferrous sulfide particles that
act as the catalyst material for CNT growth. They synthesized well-graphitized nano-
tubes with a diameter range of 10–12 nm and hundreds of nanometers in length.
In general, CNTs obtained by sonochemical/hydrothermal method have wall
thickness between 7 and 25 nm and with an outer diameter of 50–150 nm. During
the CNT growth process, a mixture of CO, CO2, H2O, H2, and CH4 are sent to
the tube.
Multi-walled carbon nanocells and MWCNTs have been artificially grown in
hydrothermal fluids from amorphous carbon at temperatures below 800 C without
utilizing any metal catalysts by interconnecting multi-walls of graphitic carbon
causes the formation of carbon nanocells at 600 C (Moreno et al. 2000). The
average diameter of obtained nanocells was smaller than 100 nm, and their outer
diameters and diameter of internal cavities were in the range of 15–100 nm and
10–80 nm, respectively. Short nanotubes and nano-onions formation by hydrother-
mal synthesis were also reported in the literature from nanoporous carbon utilizing
elemental Cs at a growth temperature of 50 C. It was indicated that the synthesized
carbon nanoparticles were more ordered. At his low growth temperature some of the
obtained carbon nanostructures were nanopolyhedra, tubes, and onions. At growth
temperature 350 and 500 C, the same carbon nanostructures were found at larger
numbers compared to 50 C for elemental Cs usage (Stevens et al. 1998).
Liquid Phase Synthesis
Liquid phase synthesis of CNTs is an appropriate method to produce aligned CNTs

by applying electrical heating to a substrate in organic liquids. Zhang et al. studied
liquid phase CNT synthesis on Si substrates coated with Fe thin films (Zhang et al.
2002). The substrates were electrically heated to 500–1000 C in organic liquid and
the results indicated aligned MWCNTs growth and well-stick nanotubes on the Si
substrates by utilizing methanol and ethanol. The top ends of the obtained nanotubes
closed and some different shapes of CNTs such as a special kind of coupled CNT
containing a left hand rotated and a right hand rotated CNT with bridging chains
between these two nanotubes were also observed in microscopic studies. Therefore,
this method is appropriate especially for the synthesis of hollow MWCNTs.
CNT growth in organic liquids is based on the adsorption and decomposition of
organic radicals at the surface of catalyst material under thermodynamic equilibrium.
The liquid phase CNT synthesis experimental set-up consists of an external water-
cooled glass liquid chamber, a DC power supply utilized for the application of a
controlled current to the catalyst substrate.
After an organic liquid is filled into the chamber, an inert gas is introduced into
the chamber and the catalyst is heated to the desired CNT growth temperature, which
is generally in the range of 500–1000 C and then a constant electrical current is

applied through the catalyst substrate. As a result of the application of the electric
current, gas bubbles are formed and flow upward from the catalyst substrate surface,
and they condense at the top of the liquid. During this process, the water-cooled
system provides control in such a way that the temperature of the organic liquid in
the chamber is lower than the boiling point. To measure the temperature of the
catalyst substrate, an optical pyrometer is utilized.
Catalyst-free CNT growth is also possible in liquid phase synthesis. Yamagiwa
et al. studied simple preheating effects by using stainless steel substrates and
obtained highly pure and aligned CNT arrays from ethanol without the addition of
a catalyst or its precursor (Yamagiwa et al. 2016). Their results indicated that
preheating temperature influenced directly the morphologies of the MWCNTs.
Besides, since no catalysts are used during production in this method, there are no
metal nanoparticle impurities on the walls of the nanotubes afterward and it is not
necessary to purify CNTs.
Alcohols such as methanol and ethanol are frequently utilized as the organic
liquid in liquid phase CNT synthesis. Especially CNTs produced with methanol
indicate a high purity and perfect alignment (Yamagiwa et al. 2007). However, if
ethanol is utilized in the synthesis, the liquid-phase method is also one of the most
environmentally friendly methods for aligned CNT arrays synthesis. The main
advantages of liquid phase synthesis methods are the simple production process,
low cost, and a one-step process, which does not require a vacuum process or
catalyst preparation step.
Flame Synthesis of CNTs
The main challenge in CNT synthesis is to obtain a high yield of products with a high
crystalline structure. The scaled-up and reliable production of CNTs offers a wide
range of possibilities to synthesize CNT for various applications such as memory
devices, MEMs/NEMs, hydrogen storage, electrochemical actuators, and sensor
applications. Especially, for CNT synthesis with metal catalysts, furnace methods
have some important advantages. Chemical vapor deposition (CVD) is the dominant
method to produce CNTs because of its high efficiency. However, these methods do
not allow large-scale synthesis on large surfaces; these processes require a lot of
energy and long processing times. Flames are utilized for the production of solid
black and printing ink. This method is useful for growing to determine the rate of
growth as well as the structure of CNTs. The production of CNTs with flames is
similar to the CVD method.
Flames are scalable and are commercially used for the production of solid carbon
forms such as carbon black and printing ink. This method is useful to grow to
determine the development rate and also the structure of CNTs. CNTs develop in a
similar way as the CVD method. Flame synthesis of CNTs, which is an alternative
method to provide large area synthesis with elevated process temperatures and the
hydrocarbon reactant for the synthesis of a metal catalyst supported CNTs, is an
autothermal process in which it can maintain the temperature to achieve the desired
production parameters. The evaporated catalyst can be injected into a flame (Vander
Wal 2000). The use of flame creates a suitable environment to allow various carbon
forms to be synthesized at nano-level at the same time. Large substrates could be
covered readily by a flame restoring of multiple flame sources. This method provides
a controllable residence time within the desired flame region as well. Besides these
advantages, the diffusion flame generally utilizes a complicated burner with some
other apparatus, and in addition, gaseous fuels must be stored safely and carefully.
In this method, a transition metal precursor is dispersed within a support matrix
such as Al, Si, or TiO or a mixture of these materials. A thinner oxide layer is an
advantage; it provides great dispersion and the small size of metal nanoparticles. As
a hydrocarbon source, diffusion flame synthesis of CNTs utilizes nitrogen diluted
acetylene (C2H2), ethylene (C2H4), methane (CH4), or ethanol (C2H5OH), etc., as
hydrocarbon sources with an oxidizer to create a gas mixture that includes carbon
dioxide (CO2), water vapor (H2O), carbon monoxide (CO), hydrogen (H2) saturated
and unsaturated hydrocarbons (C2H2, C2H4, C2H6), and radicals (Rathinavel et al.
2021).
Establishing and maintaining the precise balance between the optimized carbon
supply and flame temperature in the flame synthesis of CNTs is very important.
Oversupply of carbon causes amorphous carbon formation. The complex rela-
tionship between fuel, oxidizer, and temperature in the combustion process, along
with other important parameters in CNT synthesis such as catalyst type and compo-
sition are parameters that are still being studied by researchers.
Plastic Pyrolysis Method
Today, the continuous increase of plastic wastes is a major environmental problem.

This has led to an increase in studies on the recycling of plastic waste. Traditional
recycling methods were tried to solve this waste problem; however, low-cost
products were obtained and so these methods were not economically viable. Poly-
propylene, polystyrene, and polyethylene make up the majority of plastic waste.
Therefore, the recycling of plastic waste for producing high-quality products such as
CNTs is a good way to be used in commercial and industrial applications. The plastic
pyrolysis method is utilized to synthesize CNTs from plastic wastes. Abul-Enein
et al. studied the pyrolysis of different plastic wastes such as low- and high-density
polyethylene, polypropylene, polyethylene terephthalate, and polystyrene for pro-
ducing MWCNTs using a two-step process (Aboul-Enein et al. 2018). The first step
was the cracking of plastic wastes to produce hydrocarbon gases at a temperature of
700 C and the second step was the decomposition of hydrocarbon gases that were
decomposed on the surface of the Ni-Mo/Al2O3 catalyst to form CNTs at a growth
temperature of 650 C. The results indicated that thermal degradation of the wastes
provided the synthesis of different products including hydrocarbon gases, liquid, and
char. The yield of the gas products depends on the type of plastic waste. Low density
polyethylene and polypropylene gave the largest yields among the plastic wastes and
the smallest value was revealed for polystyrene. This method allows to produce
MWCNTs and the yield of nanotubes was related to the amount of gas produced. As
expected, the highest yield of MWCNTs was obtained by utilizing low density
polyethylene and polypropylene wastes and the obtained MWCNTs for these two
plastic waste showed the highest quality and purity among the used plastics in
Raman spectra while polyethylene terephthalate and polystyrene were found not to
be appropriate for CNT formation.
The most frequently used catalyst materials for CNT growth from waste polymers
are Ni and its bimetallic catalyst forms, for example, Ni/Zn, Ni/Ca, Ni/Mg, Ni/Ce,
Ni/Al, Ni/Mo/Mg. In general, the metal particles are impregnated in the surface of
catalyst support material such as alumina, silica, or magnesia and the interaction
between catalyst nanoparticles and support material is significant for the growth
process. Increasing amounts of metals impregnated on the support surface results in
a decrease in the inner diameter of CNT, as well as the ratio of different metals is also
an important CNT growth parameter. It was also found that the filamentous carbon
production was higher using polyethylene than polypropylene or polystyrene.
Besides, waste plastics and hydrocarbon gases, pyrolysis oils also could be utilized
for CNT synthesis. Pyrolysis oil could be obtained from a printed circuit board and
CNTs could be prepared through pyrolysis oil-based resin (Borsodi et al. 2016).
During CNT production with plastic pyrolysis, as a by-product hydrogen production
is also provided.
As conclusion, plastic pyrolysis is an important CNT synthesis method because
the formation of CNTs from waste plastics provides resource conservation and
environmental protection.
Chemical Vapor Deposition (CVD)
Chemical vapor deposition (CVD) is a widely used material processing technology

whereby solid materials are formed on a heated substrate by a chemical reaction of
vapor precursors in the form of a thin film, powder, or single crystal. It is possible to
obtain a wide range of material properties by varying experimental conditions such
as substrate type, substrate temperature, the composition of the reaction gas mixture,
and total gas flow pressure. CVD technology has many advantages over other vapor
deposition techniques. For example, the reaction can be controlled in such a way that
deposition may occur only in certain regions of substrate or material that may cover a
rough surface relatively uniform with high quality. Another advantage of CVD is
that source materials are flown into chambers from external reservoirs that can be
refilled without contamination of the growth environment. Deposition requires low
vacuum levels and has more tolerance for precision in the process conditions,
making it a popular technology for electronics and, optoelectronics, surface modi-
fication, and biological applications. However, CVD generally requires high tem-
peratures and highly toxic source gases, which need great attention during the
operation. But still, its benefits predominate these problems for microelectronic
fabrications.
The type of the CVD system is determined by factors such as reactants used
during the process, maximum tolerable air leakage amount into the system, purity of
the materials used, size, shape, and properties of the substrate, and so on. To achieve
high-quality thin films, parameters such as temperature, substrate type, pressure in
the chamber, gas flow amount, and concentration are essential parameters. There-
fore, suitable CVD equipment is required. Several designs are possible to satisfy the
needs of the researchers including heating methods, gas flow controls, loading type
of substrate, etc. A CVD system is constructed basically in three main modules:
reaction gas delivery system, a reactor with gas flow components and exhaust system
with pressure controllers, and vacuum pumps.
During the CVD processing high-pressure, toxic, flammable, and explosive gas,
liquid, and solid precursors are used. Therefore, it is essential to design safe and
precisely controlled systems. The gaseous reactants are stored in high-pressure gas
bottles with fitted metal regulators to control the outlet pressure. Valves and metal
gasket seals are used in the connection of gas pipes to the inlet part of the reaction
chamber. Mass flow controllers are used in controlling the gas flow rate according to
a set flow rate sent as an electric signal without being affected by conditions and gas
pressure fluctuations. While liquid precursors are introduced by heating them above
the boiling temperature, solid source precursors are dissolved in a suitable solvent or
sublimated into the gas phase. The main degradation problem in CVD processes is
contaminations caused by reactions between gasses and the materials of gas delivery
systems and by air leakage. The contamination level in the process may be improved
by using purified reactants, obtaining a low air leak rate by improving vacuum levels
at connection parts, and using degassed vacuum seal O-rings, using nonreactive
carrier gasses during vaporization, checking the material-gas compatibility.
The geometry and the type of reaction chambers are varied due to the type of
process and the sample characteristics such as size, shape, and number. Reaction
chambers may be designed as horizontally (Fig. 1a) or vertically (Fig. 1b) (Huang
et al. 2020; Sun et al. 2021). The quartz tube is a widely used reaction chamber due
to its resistance to high temperatures and to rapid temperature changes. Metal flanges
are used to connect gas inlets and outlets to quartz tubes with cooling components.
The substrate is usually placed at the middle part of the chamber close to thermo-
couples by using a quartz or graphite sample holder. Targeted deposition character-
istics such as thickness, composition, and structure are strongly dependent on the
sample holder configuration and optimized experimental conditions. To have repro-
ducible products, it is important to have precise control on annealing ramping rate,
gas flow rate, gas composition, temperature, pressure, and cooling rate.
There exist various techniques for heating the substrates. Conductive substrates
may be heated by resistive heating or radiofrequency induction heating whereas
nonconductive substrates are heated by optical heating with tungsten filaments or
lasers, thermal radiation heating. The shape and the type of materials that exist in the
substrate have an influence on the heat transfer mechanism.
The temperature measuring systems and heating components are essential for
thermal CVD processes. The widely used heating measurement devices are thermo-
couples. They are usually placed between the quartz tube and the heating zone.
Fig. 1 Schematic diagram of a typical (a) horizontal and (b) vertical chemical vapor deposition
system (CVD) with reactor chambers, gas delivery systems, vacuum systems, energy systems, and
control systems. (Reprinted with permission from (Saeed et al. 2020; Huang et al. 2020))
There are many types of thermocouples, each with its characteristics varied by
temperature range, durability, vibration resistance, chemical resistance, and compat-
ibility. Type J, K, T, and E thermocouples are the most common types of thermo-
couples called “Base Metal.” Type R, S, and B thermocouples are “Noble Metal”
thermocouples that are used in applications where higher temperatures are required.
Catalytic CVD (CCVD)

The chemical vapor deposition is based on the decomposition of hydrocarbons in the
presence of a suitable transition metal catalyst. For obtaining CNTs with high purity
on a large scale, the CVD method is a confidential synthesis method. During the
synthesis of CNTs, catalysts may be introduced in the form of gas particulates or as
solid precursors. The morphology and the growth yield of the nanotubes are directly
related to the type of the selected metallic catalyst. As the catalyst plays a critical role
in the nucleation and the growth of CNTs, a large number of studies focused on the
catalyst type, preparation, composition, morphology, and size to figure out its
influence on the growth of CNTs.
The most popular catalysts for catalytic CVD synthesis of CNTs are Fe, Ni, and
Co transition metals due to their high carbon solubility and easy carbon diffusion.
The catalytic activity of Fe, Co, and Fe/Co on alumina or silica supports is inves-
tigated and the best yield of MWNTs was obtained at 7008 C on alumina synthe-
sized from hydrolysis of aluminum isopropoxide with the mixture of Fe and Co
(Nagaraju et al. 2002). The catalytic activity of Fe, Co, and Ni transition metals are
compared using laser-treated vanadium plates as catalytic supports in the decompo-
sition of acetylene at 7208 C. While CNTs with high density and small diameters
(10–15 nm) were obtained with an iron catalyst, on nickel and cobalt catalysts
carbon sources resulted in amorphous or fiber-like material. Lee et al. also studied
the effect of the same catalysts (Ni, Fe, and Co) and it is revealed that nanotube
growth rate is directly related with catalyst type and highest rate obtained with nickel
catalyst whereas the best crystallinity is obtained over an iron catalyst (Lee et al.
2002). It is possible to produce well-aligned, highly pure MWCNTs with tungsten-
based catalysts.
Nonmetallic catalysts are also studied in the synthesis of CNTs. Well-aligned
CNTs with high density are synthesized using magnetic fluids of magnetite nano-
particles that spin-coated on Si substrates. In addition, uniform distribution of
particles obtained by mixing the magnetic fluid with PVA gave the opportunity to
control nanoparticle density.
To increase the productivity of the catalysts, some preparation routes may be
applied. For example, Kong et al. patterned catalytic islands on Si wafers (Kong
et al. 1998). The dispersion amount of the catalyst material directly influences the
efficiency of the catalyst. While well-dispersed particles resulted in narrow-sized
CNTs, large particles or aggregates failed in nanotube growth. SEM and TEM
images of a MWCNT sample are displayed in Fig. 2.
Fig. 2 TEM and SEM images of MWCNTs grown on Co-Mo/MgO catalyst by CCVD method
Floating Catalyst Chemical Vapor Deposition (FCCVD)

Large-scale production of CNTs with optimized properties that are comparable to the
individual CNT remained a challenge for a long time. Floating catalyst chemical
vapor deposition (FCCVD) is the most scalable technique with mass production, low
cost, high purity, and ease of fabrication. In the FCCVD technique, a catalyst is
injected into the gas phase with the carbon source. During the growth, the first
catalyst decomposes into small nanoparticles, which then collapse with each other to
form bigger particles in size, then the coating of sulfur appears on nanoparticles and
the growth process of CNTs is started. Sulfur has a significant role in stabilizing the
growing edge of CNTs by removing blocking groups. In FCCVD, various hydro-
carbon sources may be used in the growth of CNTs and their chemical structure and
pyrolysis temperature directly affect the morphology of the product. For example, in
the study of Gspann et al., toluene and methane hydrocarbon sources were com-
pared, and results revealed that CNTs synthesized by toluene were stronger and purer
than CNTs that were synthesized by methane (Gspann et al. 2014). The carrier gas
flow rate has an impact on the retention time, which is the total time required for
catalyst nanoparticles to collide to form bigger-sized nanoparticles and the growth of
CNTs occurs. While the low flow rate leads to a larger diameter of catalyst nano-
particles, the higher flow rate results in a smaller diameter.
In the FCCVD technique, metallocenes are widely used catalyst sources. A
metallocene is composed of two cyclopentadienyl anions (Cp-ring) bound to a
central metal atom that is in the oxidation state II. Ferrocene is the most popular
organometallic compound due to its low cost, low toxicity, and good stability under
ambient conditions.
Alcohol Catalyst Chemical Vapor Deposition (ACCVD)

In the alcohol catalyst chemical vapor deposition (ACCVD) technique, alcohol is
used as a carbon source molecule. It is easier to control ACCVD as solid carbon
formation is less with alcohol frame when compared to hydrocarbon flame.
Low-cost and easier scale-up productions of SWNTs are possible with ACCVD
due to its lower reaction temperatures (lower than 600 C) and higher purity features.
The low reaction temperature in ACCVD also enables the direct growth of CNTs on
patterned semiconductor substrates. Cobalt films with a thickness of 1 nm are widely
used catalysts for CNT synthesis using ethanol supported on aluminum oxide films.
Aligned CNTs with heights of up to hundreds of micrometers, in high quality and
high purity, is possible. Murakami et al. performed ACCVD on quartz substrates
using Co and Mo catalysts and obtained vertically aligned SWCNTs (VA- SWCNTs)
with a thickness of ~1 μm (Murakami et al. 2004). The thickness of the VA-SWNTs
increased up to 20 μm by adding a small amount of C2H2 to ethanol; however, the
diameters of the SWCNTs exceed 1 nm even with the usage of Al2O3 buffer layers or
Mo cocatalysts. Pt- group metal catalysts are also studied in the growth of SWCNTs
by ACCVD and it was investigated that diameters of SWCNTs decreased with
decreasing growth temperature, but vertical growth was not achieved. Vertical
alignment was obtained by ACCVD with an Ir catalyst in a cold-wall CVD system.
The length of SWCNTs increased with increasing growth time and the thickness of
VA-SWCNT reached 5 μm. Additionally, the diameters of the SWCNTs were

measured between 0.8 and 1.1 nm, which is much smaller than CNTs grown with
Fe and Co catalysts.
Thermal CVD
The thermal CVD technique generally requires high temperatures (~ 800 to
2000 C), which may be obtained by resistance heating, induced high-frequency
heating, radiant heating, hot plate heating, etc. Thermal CVD may be categorized
according to how heat is supplied to the substrates: hot-wall and cold-wall. Both can
be designed either horizontally or vertically. The horizontal reactor is the most
common one where the substrates may be placed horizontally, vertically, or with
any tilt angle according to the gas flow. The vertical reactor is advantageous in terms
of material uniformity and growth rate.
A hot-wall reactor is surrounded by a tube furnace that is often heated by
resistance elements. The walls of the reactor and the substrates all have the same
temperature. As the growth takes place on substrate, by the time the walls of the
reactor may be coated with materials. Thus, contamination may be a risk for purity
with the reaction of formerly grown material and vapor. In some cases, substrates
may be loaded vertically to reduce particle contamination and increase the loading
capacity. Hot-wall reactors have the main advantage of more precise temperature
control.
In a cold-wall reactor, only the substrate is heated, and therefore, the reactor wall
remains cold. This structure gives the opportunity for rapid heating and cooling.
Heating in cold-wall CVD may be provided by resistance, hot plates, or induction.
The cold-wall CVD will be discussed in more detail in further sections.
In the thermal CVD method, catalyst-coated substrate is placed in a thermally
heated atmosphere. During the exposure of one or more hydrocarbon precursor
gases, CNTs are formed by reaction or decomposition on the substrate. Vertically
aligned CNTs on Co/Ni patterned and pretreated Si substrates were synthesized
using C2H2 precursor with the 15–40 sccm flow rate for 10–20 min. at 800–900 C
(Murakami et al. 2004). The same technique was used to obtain aligned bamboo-
shaped CNTs on Fe-coated Si substrates (Lee and Park 2000). Tripathi et al. used
Al2O3 substrates to grow CNTs by the only decomposition of C2H2 at 800 C,
without using any catalyst and the diameter distribution of CNTs were between
6–8 nm (Tripathi et al. 2014). Aligned and Fe-Co alloy-filled MWCNTs was
synthesized on Si substrates by pyrolysis of ferrocene/cobaltocene mixture at
980 C. The diameters of encapsulated metal nanowires were measured as
10–20 nm with a length of up to a few micrometers.
Rapid thermal chemical vapor deposition (RTCVD) is a type of thermal CVD
method where a rapidly heated substrate is exposed to precursors. The infrared lamps
are used for rapid heating and cooling. Here, the typical duration of growth is much
less compared to normal thermal CVD. After heating lamps are energized, the
irradiation passes through the tube and is absorbed by the substrate only. Thus, its
surroundings have remained at room temperature.
RTCVD was used to synthesize SWCNTs and MWCNTs on Ni/Al2O3 substrates

by thermal decomposition of C2H2/H2 at 600 C. It is concluded that CNT growth
was the result of a liquid metastable: dissolution of carbon, its oversaturation,
and diffusion. In another study, catalysts were placed inside the pores of AlPO4-5
and L-type zeolites, and CNTs were synthesized at 800 C with the mixture of CH4
and H2 in RTCVD system (Martin et al. 2008). The effect of vacuum and H2
pretreatment of catalyst on growth morphology of carbon structures was examined.
Plasma-Enhanced CVD (PECVD)

The plasma-enhanced CVD (PECVD) was first emerged due to the need for micro-
electronic processing. High substrate temperatures at thermal CVD was a serious
problem for photoresist used patterned wafers. Therefore, PECVD allows to process
with lower wafer temperatures between room temperature to 100 C in IC manu-
facturing. The low temperature is possible with PECVD because highly energetic
electrons are used to create glow discharge plasma. In this type of plasma, the
temperature of electrons is higher than the temperature of ions, which provides
maintenance of discharge plasma at low temperatures. Precursor gas decomposition
is provided by these high-energy electrons by transferring their energy into a gas
mixture. As a result of this interaction, reactive radicals, ions, neutral atoms, and
molecules, and other exciting species are produced, some of which interact with the
substrate for either etching or deposition process. Since the high energy of electrons
is mostly transferred for chemical reactions, the gas itself is stayed cooler, and
growth occurs on substrates at lower temperatures compared to temperatures in
conventional CVD systems.
Plasma-enhanced CNT growth has several advantages over thermal growth. For
example, CNTs can be easily aligned or even free-standing SWCNTs may be formed
due to the presence of an electric field. The modification of the nucleation process is
also possible with the present electric field. Additionally, narrow chirality distribu-
tions are observed through CNTs produced by PECVD.
The rectors of PECVDs are classified according to the type of plasma source that
is used to generate the gas discharge of feedstock. DC-PECVD uses DC power to
achieve glow discharge plasma between the anode and the cathode that are fixed
parallel to each other inside the reactor. Plasma and the strong electric field are
produced with the applied negative DC voltage to the cathode.
In the study of Tanemura et al., DC-PECVD of aligned CNTs on Co/Ni-coated
tungsten wires with mixtures of C2H2 and NH3 were optimized (Tanemura et al.
2001). The effects of wire temperature, wire diameter, gas pressure, and sample bias
were investigated. It is concluded that alignment of CNTs strongly depends on the
catalyst and its support material and the sample bias affects the morphology of
CNTs. Free-standing single CNT arrays were grown on Ni dot arrays by PECVD and
it is revealed that vertical alignment was directly dependent on the location of the
catalyst metals. VACNTs were grown on Ni-coated SiO2/Si substrate at low tem-
perature (120 C) enabling the growth of CNTs onto substrates such as plastics and
sensitive nanoelectronic devices that cannot sustain high temperatures.
It is important to mention that as DC sources use high power to accelerate the

ions, the high applied voltage may lead to substrate damage due to the strong ion
bombardment in the DC-PECVD process.
Oxygen-Assisted CVD
CVD is the most popular and reliable method for carbon nanostructure growth.
However, in CVD processes, the low carbon diffusion rate results in the passivation
of catalyst, and amorphous carbon formation has occurred on the surface of the
catalyst. This is the main result of poisoning the carbon nanostructures formed at low
temperatures. On the other hand, studies revealed that moderate concentration of
oxygen, air, and water with the precursor gases improve the catalytic activity and
help to remove the amorphous carbon layer leaving the pure carbon nanostructure at
the growth temperature.
High-purity SWCNTs were grown by cobalt nanoparticles with small diameters
by using oxygen-assisted CVD. Various precursor gases such as CH4, H2, and C2H4
were introduced into chamber at 900 C growth temperature. With the small amount
of oxygen flow, amorphous carbons and residual catalysts are evacuated from the
chamber. It was concluded that high purity SWCNTs without any distinct defect
were obtained by the oxygen-assisted CVD process. Besides dramatic increment in
the purity, small amount of oxygen also increased the yield of the CNTs.
In the study of Chou et al. carbon materials, i.e., CNTs, multilayer graphene
(MLG), double-layer graphene (DLG), and single-layer graphene (SLG) on a Ni foil
substrate were synthesized by oxygen-assisted CVD at ultralow pressure (20 mTorr)
(Chou et al. 2015). Although oxygen seems to be undesirable in carbon nanomaterial
synthesis, this study showed that the growth of NTs, MLG, DLG, and SLG can be
maintained by adjusting oxygen concentration during the CVD process. Oxygen
assessment also provides an easy way to control the layer of grown graphene.
The effects of hydrogen and oxygen on the synthesis of CNTs by the CVD
method were discussed in the study of Zhang et al. (2005). In hydrocarbon-based
growth, highly reactive hydrogen species were damaging the formation of sp2-like
SWNTs in a diameter-dependent manner, and with the addition of the oxygen, H
species were purified and precise control over the C-H ratio was provided for SWNT
growth.
The oxygen assistance in field emission treatment improved the uniformity of
CNT pixel arrays. The addition of oxygen gas during the field emission process
improved the uniformity of emission area and the brightness of a CNT pixel array by
83% and 90%, respectively. Emission stability was preserved during the process.
These phenomena were explained with the oxidation of highly emitting CNTs
resulted in burning out. As a result, emitting CNTs with high current were removed
and more emitting CNTs with weak current were excited at a higher field, leading to
a balanced emission from each pixel in the array.
Water-Assisted CVD
In 1996, it was revealed that a water sonication of raw CNTs made by the
arc-discharge technique was an effective method for purifying SWCNTs. Based on
this information, Hata et al. firstly reported the water-assisted CVD technique used in
the synthesis of vertically aligned CNT growth in millimeter scale (Hata et al. 2004).
During the CVD process, a small amount of water (~ 20–500 ppm) was added into
the feedstock and above 99.98% carbon purity was achieved. The assistance of water
in CNT synthesis enhances the activity and the lifetime of the catalyst. The effect of
water in the selectivity of SWCNTs over multi-walled nanotubes was confirmed and
in the following studies, nanocatalyst stability through CO2/H2O mixtures was
discussed. As a result, it was clarified that as a kinetic process, the water-generated
surface-bound hydroxyl species might prevent the growth of the particle leading to
an effective growth yield and improved overall control over CNT self-dispersion.
Water-assisted CVD growth of vertically aligned SWCNTs is also called “super
growth.” Water vapors of 20–500 ppm are passed through the reaction chamber by
flowing carrier gas mixtures such as Ar or He with H2 through a water bubbler. The
bubbler principle is rather simple and robust. The water is stored inside a stainless
steel canister (bubbler), and an inert carrier gas such as Ar or N2, is passed through
the liquid to bubble. The precursor vapor saturates the atmosphere in the bubbler and
the vapor then enters into the heated substrate surface. The delivery of reactants
depends on the temperature of the bubbler, the carrier gas flow rate, and the pressure
over the surface of the liquid. Generally, ethylene or acetylene is used as carbon
precursor along with various catalysts i.e. Fe, Al/Fe, Al2O3/Fe, Al2O3/Co.
Wu et al. reported the one-step water-assisted CVD growth of metal oxide
nanosheets/carbon nanotubes (CNTs) composites and helical CNTs were grown
with the CVD growth process that prolonged to 1 h. The typical fishbone type
CNTs were also observed by HRTEM (Wu et al. 2019). The CVD process was
carried at the atmosphere pressure and as carrier gases, H2 and Ar, as a carbon
precursor methane and as a metal catalyst ferrocene (0.05 g) were used. The reactor
was heated to the desired temperature in the range 1020–1100 C at a ramp rate of
25.5–27.5 C/min under an ambient flow rate of Ar (30 sccm).
Microwave Plasma-Enhanced CVD (MPECVD)

The deposition processes carried at too high temperatures are unsuitable for elec-
tronic device fabrication as most connections are made of materials like alumina,
which have melting points below 700 C. These challenges forced scientists to
explore alternative deposition techniques carried at low temperatures. At low pres-
sures, microwave plasma is a kind of low-temperature plasma due to the non-
equilibrium state between electrons and other heavy particles full of active species.
Therefore, microwave-plasma-enhanced chemical vapor deposition (MPECVD) is a
good candidate for low-temperature synthesis processes of carbon nanostructures.
Okai et al. synthesized CNTs on Ni and Fe-Ni-Cr alloy substrates along with
methane and hydrogen gases by MEPCVD and investigated their structures. The
total gas pressure was maintained at 250–300 Pa and growth was carried for
30–60 min under 10–20 sccm methane/80–90 sccm hydrogen gas mixture flow.
Plasma was generated by a 2.45 GHz microwave generator with 500 W power, and
the growth temperature was measured as 650 C at the sample stage. A negative
voltage was applied to the substrates during the process. TEM results showed that
CNTs had a piled-cone structure with metal particles on top by determining the
diameter of nanotubes. The diameters of CNTs were ranged between 60 nm and
80 nm. Additionally, in the case of Ni substrates, metal particles were composed of
Ni; and in the case of Fe-Ni-Cr alloy substrates, they were composed of both Fe and
Ni metals (Okai et al. 2000).
The vertically aligned CNTs were grown on sputtered Ni-coated Si substrates by
using MEPCVD at 700 C with gas mixtures of CH4 (~20%) and H2 (~80%). The
applied microwave power and the pressure during the growth of CNTs were 400 W
and 10 Torr, respectively. The growth time of CNTs was maintained for 5 min. The
results revealed that the diameter, growth rate, and density of CNTs are directly
related to the grain size and morphology of the Ni films, which may be altered by the
rf power density during the rf magnetron sputtering process. The diameters of CNTs
were varied between 10 nm and 35 nm. The growth rate and the density of CNTs
increased with decreasing rf power density. The effect of microwave plasma on the
alignment of CNTs was investigated by Bower et al. and it was shown that nanotubes
were always aligned normal to the local substrate surface (Bower et al. 2000). The
alignment was induced by the electric field applied on the substrate surface due to the
plasma ambient. When the plasma source was switched off, the plasma-grown
straight nanotubes and thermally grown curly nanotubes were formed without any
alignment. During the plasma process, CNTs were grown at a significantly high rate
of 100 nm/s, which gave the opportunity for large-scale production of CNTs. The
catalyst synthesis of CNTs using CH4–CO2 precursors was carried successfully by
MPECVD. As catalysts Fe, Ti, and Fe/Ti nanoparticles were used and a significant
difference in morphologies in carbon deposition was observed between Fe and
Ti. By optimizing the growth parameters of precursors, a high yield of vertically
aligned CNTs was obtained on Fe-deposited substrate. On the other hand, Ti was
found unsuitable as a catalyst for CNT production. Vertically aligned MWCNTs
were synthesized on Fe-deposited Si substrate at low temperatures below 330 C by
MPECVD using CH4 and CO2 gas mixture. The DC bias voltage was varied from
150 V to 200 V, at 300 W microwave power, at 1.3–2.0 kPa range of total gas
pressure, and substrate temperatures were measured between 300 C and 350 C.
The diameter of MWCNTs was measured as about 15 nm and the highest yield of
about 50% was obtained at low temperatures (below 330 C) by MPECVD with an
optimized rate of CH4/CO2 gas mixture (Chen et al. 2002).
Radiofrequency CVD (RF-CVD)

Radiofrequency CVD (RF-CVD) uses RF power to generate plasma. Power of
13.56 MHz is supplied to the reactor by an impedance network between the supply
and the plasma. The RF discharges are still dynamic at sub-Torr pressure levels and
the bias voltage measured on the electrode smaller than the bias voltage of DC
discharges. RF plasma discharges are divided into two categories due to the method
of coupling the power supply. In capacitively coupled plasma (CCP) system, elec-
trode configuration is like that of DC-PECVD system but uses RF power supply. In
an inductively coupled plasma (ICP) system, a coil is placed outside of the reactor
and RF power is generated to the inside of the reactor by forming a coil through a
dielectric window (Sengupta 2018). The CCP RF-PECVD system is used in the
synthesis of vertically aligned carbon nanofibers at 560 C with Ni catalyst on Si
substrates. Nanofibers were observed as “herring-bone” and “bamboo-lie” struc-
tures. ICP RF-PECVD was used in the growth of bamboo-like CNTs with repeating
arrowhead shapes. Aligned MWCNTs fully filled with Fe, Co, and Ni nanoparticles
were synthesized by ICP RF-PECVD using nanowires (Fe, Co, and Ni) as catalysts.
The length of the nanowires was 420 20 nm, which is suitable for the formation of
a fully filled structure of CNTs. The significant effect of the type of catalyst on the
alignment and the crystallinity of CNTs were observed. While the CNTs catalyzed
by Ni and Fe have better alignment and a higher degree of graphitization, those from
Co show a little curled character in the tips and somewhat tangle between CNTs.
SWCNTs were grown by a home-built radiofrequency (RF,13.56 MHz) 4-in.
remote PECVD system at 600 C. The nanotubes were of high quality and
high-performance field effect transistors were obtained by RF-PECVD nanotubes.
Electrical characterization revealed that nearly 90% of the nanotubes were semi-
conductors and thus highly preferential growth of semiconducting over metallic
tubes were achieved in the PECVD process.
Hot-Filament CVD (HFCVD)

The hot-filament CVD (HFCVD) system is composed of heated coiled wire that
decomposes the precursors, and deposition takes place on a substrate placed near the
filament at lower temperatures. A typical HFCVD system used in CNTs growth is
shown in Fig. 3. The first HFCVD technique was used in 1979 to produce amor-
phous silicon films with low substrate temperatures under silane gas flow and a high
Fig. 3 Schematic diagram of

the hot-filament-enhanced
chemical vapor. Deposition
system used in the deposition
of MWCNT growth.
(Reprinted with permission
from (Ono et al. 2004),
© Copyright (2004) The
Japan Society of Applied
Physics)
deposition rate was achieved. During the HFCVD processing, various types of metal
filaments such as tungsten, tantalum, and rhenium are resistively heated and their
temperatures are maintained at 1800–2300 C. The filament temperature plays a
critical role in the production as it influences the type and quality of the grown
carbon materials. While little or no diamond structure is observed at filament
temperatures below 1800 C, higher temperatures up to 2300 C results in higher
growth rates and high-quality polycrystalline diamonds. However, the higher the
filament temperature, the faster the filaments become carburized and brittle. It is
important to select a suitable filament that can resist processing temperatures. The
substrate temperature, which is determined by the residence time, mobility of
reactant molecules, and radicals absorbed at the substrate surface, is also critical
for the synthesis of the target material. The residence time is inversely proportional
to the total gas mass flow rate in the reactor with laminar flow. In the HFCVD
chamber, the substrate temperature is essentially affected by the filament temperature
and its power, distance to the filament, and total pressure. Thus, precise temperature
control of the substrate is needed to optimize the growth parameters and quality of
the product materials.
CNTs were grown by HFCVD on Cu substrates with the substrate temperature of
900 C and passing 2.0% methane in the hydrogen gas mixture. The gas mixture of
100 sccm was flown through the reactor and activated by a heated Re filament placed
at 8 mm above the substrate. The temperature range of the resistively heated filament
was measured between 2300 and 2500 C. It was revealed that bamboo-shaped
CNTs were obtained with diameters of 50–100 nm at variable lengths. Well-aligned
bamboo-shaped CNTs by HFCVD were grown on Ni film-coated Si substrate using
C2H4/NH3 precursors with a flow rate of 25/100 sccm. Diameter-controlled growth
of SWCNTs was achieved by using Fe catalyst and C2H2 as precursor at 590 C.
Aligned CNTs on Inconel sheets were grown by HFCVD with a gas mixture of CH4
and H2 and optimum alignment was achieved at the bias of 2500 V. Hot filament
effects on vertically aligned CNT growth were investigated with respect to precursor
composition, filament temperature, and filament types. Mixtures of CH4 and H2
gases were used as precursors. It was revealed that growth rate increased with the
increasing concentration of CH4 in the mixture and independent of filament type and
temperature. Carbon filament was used to synthesize SWCNTs and MWCNTs with
C2H2 and H2 mixture on silica-supported Fe-Co catalysts. It was found that forma-
tion of the SWCNTs was favored at low C2H2 concentration and low ambient
pressure. The planarly configurated vertically aligned CNTs with 48 μm length
and micropatterned array with 36 μm lengthened CNTs on Al substrates were
produced using CH4 as precursors (Sengupta 2018).
Fluidized-Bed CVD (FBCVD)

The fluidized-bed CVD (FBCVD) system is designed to inject a fluidizing gas with
suitable gas or vapor precursor. As the heterogeneous powder catalysts are used, the
gases penetrate through the powder and react to form thin films or nanomaterials on
the surface. In the FBCVD, gas/solid contact is optimized and there is no thermal
gradient. Therefore, optimal mass and heat transfer is achieved in the reaction zone.
It is also a user-friendly system that flexible operating parameters such as precursor

concentration, gas mixture, and temperature can be easily applied. It is possible to
work in either batch or continuous mode. These properties make FBCVD an
attractive tool for the homogeneous and selective production of carbon nano-
materials. In the early 2000s, the first studies in FBCVD growth of MWCNTs and
graphite nanofibers were carried out and nowadays this technique is used for the
synthesis of SWCNTs.
In a typical FBCVD system, a reactor is attached within a high-temperature
furnace, which is maintained at suitable temperature, pressure, and gas flow ratios.
The processing parameters are controlled by a data logging system (Fig. 4) (See and
Harris 2007).
Fig. 4 Sketch of a typical fluidized-bed CVD reactor setup. (Reprinted with permission from (See
and Harris 2007). © Copyright (2007) American Chemical Society)
One-step preparation of highly dispersed metal-supported catalysts followed by

synthesis of CNTs was achieved using FBCVD. This combined process helps to
eliminate drying, calcination, and reduction problems and thus reduces the aggrega-
tion or crystalline size increase of supported metal nanoparticles. Mass production of
CNTs was achieved by FBCVD using CaCo3 as a soluble support material and
similar qualities were obtained through MWCNTs.
Three-walled CNTs with a diameter of 6–10 nm and a length of 0.4 mm with
99 wt.% purities were synthesized by FBCVD using acetylene as a precursor.
Catalysts were initially immobilized on ceramic beads and CNT growth occurred.
Then CNTs and beads were separated by switching gases at a fixed temperature.
MWCNTs were produced from H2–C2H4 mixtures on Fe-SiO catalysts by FBCVD.
The parameters of catalyst preparation, the residence time, the run duration, the
temperature, precursor concentration, and the amount of metal deposited on the
support were studied and optimized. Homogeneously deposited CNTs with diame-
ters of 10–20 nm were achieved (Venegoni et al. 2002).
Fixed-Bed CVD (FBCVD)

In the production of CNTs, the FB-CVD technique offers numerous advantages such
as an optimized gas/solid contact compared to fixed-bed reactors and the absence of
any thermal gradient so that optimal mass and heat transfer are reached in the
reaction zone (Lee et al. 2002). This is also a flexible process in terms of operating
conditions and parameters. In the production of CNTs, the FB-CVD technique offers
numerous advantages such as an optimized gas/solid contact compared to fixed-bed
reactors, and the absence of any thermal gradient so that optimal mass and heat
transfer are reached in the reaction zone (Lee et al. 2002). The fixed-bed CVD
process is the most traditional and simplest technique for the synthesis of CNTs. It
usually uses a crossflow setup employed inside a horizontal furnace. The catalyst
amount should be kept at less than 1 g as the boat-shaped quartz holder has a fixed
surface area. Increasing the catalyst amount would only increase the bed depth
resulting in diffusion limitation and decrease the catalyst activity. In the study of
Zeng et al., the same amount of catalyst was used in a single and two quartz boats in
order to investigate the effect of the doubled contact area of the catalyst with the
same amount (Zeng et al. 2002). As a result, sufficient mixing was achieved to
eliminate diffusion limitations and CNTs yield increased over three times.
Cold-Wall CVD
The type of the reactor is defined according to size, shape, and the number of
substrates based on the selected process. In the cold-wall reactor, heat is only applied
to the substrate and its mounting fixture. Therefore, the walls of the reactor remain
unheated and no deposition occurs on the walls. This also eliminates the risks of
contamination. Temperature gradient near the substrate may affect the uniformity of
the thickness and the microstructure but cold-wall reactors are frequently used in
microelectronic fabrication due to their flexibility, cleanliness, high deposition rates,
and fast cooling rates.
Generally, in cold-wall CVD, substrates are mounted on a graphite holder and a

tube with a radiofrequency coil surrounds it. As graphite is partially conductive, it
absorbs radiofrequency from the coil. As a result, electron currents are induced in the
graphite to heat the substrate uniformly.
Aligned CNTs were synthesized on porous alumina substrates using ethanol as
precursor and Co-Mo as catalysts. Two types of CVD synthesis methods were used
to compare the effects: conventional thermal CVD and cold-wall CVD. While in
conventional CVD frontward carrying gas flow direction was used, in cold-wall
tangential flow direction was used toward the substrate. High density CNTs aligned
perpendicular to the substrate were achieved with cold-wall reactor due to the
precursor flow directed frontally.
Mu et al. enhanced the cold-wall CVD reactor by adding a top heater similar to
that in hot-wall CVD. Therefore, a more uniform temperature profile during the
growth was achieved and precursor gas flow was preheated before its projection onto
the catalyst. As a result, horizontally aligned SWCNTs were deposited directly on
quartz by cold-wall CVD, which is a very promising application for the fabrication
of future nanoelectronic devices (Mu et al. 2016).
Electron Cyclotron Resonance CVD (ECR-CVD)

Electron cyclotron resonance (ECR) plasma sources are used for a variety of material
processing applications such as synthesis of carbon nanomaterials, etching, and
deposition of semiconductors. ECR sources operate at low neutral gas pressures.
At low pressures, ion collisions in the substrate sheaths are reduced for anisotropic
etching of increasingly high aspect ratio features in integrated circuits. ECR sources
can operate in high ion density, which implies higher ion flux-driven processing
rates. Due to the low plasma potential of ECR plasma sources (15–30 eV), there is no
need for any substrate biasing.
The ECR-CVD method is widely used in the synthesis of CNTs due to its
advantages of high dissociation percentage of the precursor gases, high and uniform
distribution of plasma energy, enabling large-area film production. Aligned hydro-
genated amorphous CNTs were grown on porous anodic alumina by ECR-CVRD
using acetylene and argon as precursor gases. The composite film with the aligned
hydrogenated CNTs is prepared with a large area with advantages of high plasma
density at low temperatures, less ionic damage, high deposition rate, and
contamination-free growth. The pore size of anodic alumina can be adjusted to
control the diameter size in the range of 30–230 nm. In order to use CNTs as
connectors in microelectronic device technologies, the large-area horizontally
aligned CNTs on 4-inch Si substrates were synthesized by ECR-CVD with CH4
and H2 precursor gases and Co catalysts. It is possible to obtain vertical and
horizontal alignment of CNTs by manipulating the electric field applied on the
substrate and thus adjusting the flow direction of gases (Hsu et al. 2002).
Polymer Pyrolysis CVD (PP-CVD)

In the polymer pyrolysis CVD (PP-CVD) method, carbon precursor gases are
produced by the pyrolysis of polymers such as Polyethylene Glycol (PEG). In situ
growth of uniform CNT/Al composite powders by the catalytic pyrolysis of PEG and
Al nanoflake powders is possible. Al nanoflakes were chosen as the matrix due to
their large surface area, which is very helpful and increases the amount of homoge-
neously dispersed CNTs on the Al surface. As PEG has a low decomposition
temperature, it can be easily cross-linked with citric acid to form a uniform film on
the Al nanoflake surfaces. Their results revealed that the as-grown graphitic CNTs
were homogeneously dispersed on Al nanoflakes and CNT/Al composites’ com-
pressive strength of 380 MPa can be achieved.
The homogeneously dispersed CNTs in Al nanoflakes were also synthesized with
PEG as a precursor and cobalt nitrate as a catalyst by PP-CVD. During the pro-
cessing, parameters such as synthesis temperature, residence time, and mass ratio of
PEG to citric acid to cobalt nitrate were optimized. The PP-CVD process used to
synthesize CNT/Al composite powders consists of three main steps: preparation of
precursor solution, adsorption of precursor film on Al nanoflakes, and polymer
pyrolysis CVD growth of CNTs on Al nanoflakes. These steps are shown graphically
in Fig. 5. It is obvious that the structure, size, and amount of CNTs strongly depend
on the synthesis parameters. Additionally, the batch reaction mode and the lower
synthesis temperature, as 600 C, make the CVD method a safe and easy way to
scale up the synthesis of CNT/Al composite powders for industrial production.
The different growth temperatures of CNT-reinforced aluminum composite pow-
der prepared by PP-CVD were analyzed. The morphologies, structure, phase com-
position, and elemental content of the synthesized CNT-Al composite powders were
Fig. 5 Diagrams of polymer pyrolysis CVD process for the synthesis of CNT/Al composite
powders: (a) impregnation of Al nanoflakes in a precursor solution, (b) CNT growth on Al
nanoflakes within a closed batch reactor, and (c) the two-step heat treatment regime for CNT
growth. (Reprinted with permission from (Tang et al. 2013))
investigated. The highest crystallinity of CNTs was obtained at 600 C with a

reinforcement content of 7 wt%. The powder manufactured in this investigation
has excellent potential to be used in powder metallurgy, cold spraying of CNT-Al
composite coatings, and additive manufacturing of composite free-forms.
Direct Liquid Injection CVD (DLI-CVD)

In direct liquid injection CVD (DLI-CVD) reactors, liquid delivery units are used to
provide carbon sources for the deposition of carbon nanomaterials. It is easier to
control precise liquid flow rate rather than that of powders. In some cases, the liquid
is vaporized in an evaporation unit and reaches to the substrate in a vapor phase
while in other cases it reaches the substrate in a liquid phase and vaporized prior to
decomposition. If the precursor is in the liquid droplet form on a substrate, the
deposition method is named a spray or aerosol pyrolysis. The essential advantage of
DLI-CVD is using the precursors with low thermal stability and low vapor pressure
due to keeping the solution under pressure at room temperature. Additionally, it is
possible to dissolve powder precursors in a solvent to be used in DLI-CVD. The
bubbler technology can be used as a liquid delivery system. This system is preferred
as vapor pressures are optimal, not too high, or too low.
CNTs were synthesized by DIL-CVD using polyoxometalate cluster as a catalyst
and ethanol or toluene as precursors. Although the purity of CNTs was higher at
higher temperatures, the maximum CNT yield was obtained at 900 C with fast
solution injection rates. Toluene precursor is more efficient at 800 C. The MWCNTs
were synthesized by DIL-CVD using ethanol as precursor gas and Co nanoparticles
as catalysts at 750 C growth temperature. The nanotubular structure was grown
throughout the surface and the minimum crystallite size was measured as 14 nm. The
grown CNTs were then processed to be used as CO2 sensor, which achieved
ultrasensitive detection of CO2 gas at room temperature.
Template-Based CVD
The template-based CVD is a popular technique in CNT synthesis where the
formation of CNTs occurs by depositing carbon on a sacrificial template and thermal
decomposition of precursor gases. Appropriate template selection through templates,
such as glass capillaries and anodized aluminum oxide (AAO) membranes, enables
the precise control of outer diameter size, length of the tubes, and other structural
properties. Like other CVD methods, in the template-based CVD, several parameters
have an effect on grown CNTs. These variables include the type, geometry, and
dimensions of the template, relative size, and location of the template in the furnace,
type of precursor gases, gas concentration and flow rate, and growth temperature and
time. The significant effects of the deposition time, synthesis temperature, and flow
rate of the precursor gas on the wall thickness, deposited carbon mass, and carbon
morphology were investigated. The different types of CNTs were fabricated on an
anodized AAO template with acetylene precursor by using catalytic CVD. It was
revealed that the structure of CNTs directly depends on the quality of catalyst
deposition in the pores, the pore diameter of the AAO template, and the size of the
metallic catalyst.
In Table 1 the formation of various kinds of CNTs are listed regarding the
different CVD synthesis methods and different reaction conditions.
Conclusion
In conclusion, CNTs with their excellent mechanical, electrical, and chemical prop-
erties find use in different applications. Some of them are actuators, electronics,
biotechnology and biomedical, microwave absorption, filtering, and composite
materials. High efficiency and high-quality nanotube production is of great impor-
tance for all these applications.
Each method indicates different advantages and disadvantages. For example, arc
discharge and laser ablation methods provide single-walled and high crystalline
CNT production. However, these methods consume a lot of energy for nanotube
production and are not suitable for high-efficiency production. Another CNT syn-
thesis method is electrolysis, which allows a controllable synthesis process by the
electrolysis modes, cheap MWCNT production, controllable CNT morphologies,
and carbon phases doping in one step. However, the cracking problem of graphite
cathode during the electrolysis process and accumulation of electrolysis products
cause instability in the process and prevent continuous performance for this method.
The sonochemical/hydrothermal synthesis technique is a suitable method to produce
different types of carbon nanostructures such as nano-onions, nanorods, nanowires,
nanobelts, and MWCNTs. In this method, the starting materials are easy to obtain
and are stable in ambient temperature, and even at low temperatures about
150–180 C CNT synthesis could be carried out, and there is no need a hydrocarbon
gas or carrier gas for the CNT growth process in sonochemical/hydrothermal
synthesis of CNTs. The liquid phase CNT synthesis method is appropriate especially
for the synthesis of aligned CNT arrays MWCNTs and it has a simple one-step
production process and does not require a vacuum environment or catalyst prepara-
tion step. Besides, it is an environmentally friendly CNT synthesis method.
The flame synthesis method is emerging as an alternative to furnace methods.
While furnace methods do not allow large-scale synthesis on large surfaces because
of the requirement of a lot of energy and long processing times, the flame synthesis
method is suitable for large surface MWCNT synthesis. The plastic pyrolysis method
is another method to utilize for the synthesis of CNTs from plastic wastes such as
polypropylene, polystyrene, and polyethylene. With the flame synthesis method,
MWCNTs production is possible and this method works similar to the catalytic CVD
method and it is an important method in terms of environmental protection and
recycling of waste. CVD method is based on the decomposition of hydrocarbons in
the presence of a suitable transition metal catalyst. For obtaining CNTs with high
purity on a large scale, the CVD method is a confidential synthesis method and
capable of both SWCNT and MWCNT production with high crystallinity and high
yield. It is a low-cost method compared to other methods suitable for SWCNT
production.
28
Table 1 Summary of studies on CNT synthesis with different types of CVD

Method Product Characteristics C Source Catalyst References
Thermal CVD Vertically aligned CNTs Length: 5 μm Acetylene Co/Ni Lee et al. (1999)
diameter: 200 nm
Thermal CVD Aligned CNTs Bamboo-shaped Acetylene Fe-coated Si substrates Lee et al. (2000)
Thermal CVD CNTs Diameter: 6–8 nm Acetylene Al2O3 substrates Tripathi et al.
without catalyst (2014)
DC-PECVD Aligned CNTs Length: 5 μm Acetylene, ammonia Co/Ni-coated tungsten Tanemura et al.
diameter: wires (2001)
20–130 nm
Oxygen-assisted MWCNTs Diameter: 3 nm Acetylene Ni foil substrates Chou et al. (2015)
CVD
Water-assisted Vertically aligned Length: 2.5 mm Ethylene Fe, Al/Fe, Hata et al. (2004)
CVD SWCNTs Al2O3/Fe, Al2O3/Co on Si
wafer
Water-assisted MONs/CNTs composites Outer diameter: Methane Ferrocene Wu et al. (2019)
CVD 25 nm
Wall thickness:
6 nm
Microwave- Piled cone structured Diameter: Methane Ni and Fe-Ni-Cr alloy Okai et al. (2000)
PECVD 60–80 nm substrates
Microwave- Vertically aligned CNT Diameter: Methane Ni-coated Si substrates Bower et al.
PECVD 10–35 nm (2000)
Microwave- Vertically aligned MWCNTs Diameter: 15 nm Methane-carbon Fe-deposited Si substrate Chen et al. (2002)
PECVD yield: 50% dioxide
Radiofrequency Aligned, bamboo-like, arrowhead Length: Methane-nitrogen Fe, Co, Ni nanoparticles Sengupta (2018)
CVD shape 420 20 nm
Hot-filament CVD Bamboo-shaped CNTs Diameter: Methane in hydrogen Cu substrates Sengupta (2018)
50–100 nm
A. I. Yardimci and N. Yagmurcukardes
Hot-filament CVD Aligned bamboo-shaped Length: 10 μm Ethylene-ammonia Ni-coated Si substrate Sengupta (2018)
diameter:
20–80 nm
Fluidized-bed Multi-walled CNTs Diameter: Ethylene-hydrogen Fe-SiO2 Venegoni et al.
CVD 10–20 nm (2002)
Fixed-Bed CVD Multi-walled CNTs Diameter: Acethylene-hydrogen Fe–Ni, Ni, and Fe Zeng et al. (2002)
9–30 nm
ECR-CVD Vertically and horizontally Length: 3–350 μm Methane-hydrogen Co Hsu et al. (2002)
aligned CNTs
Polymer pyrolysis CNT/Al composite powders Length: Polyethylene Glycol Cobalt nitrate Tang et al. (2013)
CVD 200–800 nm (PEG)
diameter:
10–20 nm
29
Overall, various nanotubes synthesis methods have been developed since the
discovery of CNTs in 1991, and among these methods, CVD is currently the most
widely used method.
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Synthesis Methods of Carbon Nanotubes

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CNT Synthesis Methods

formation of carbon nanotubes or ﬁbers. Ni erosion is assumed to be the source of

The sonochemical/hydrothermal synthesis technique is an appropriate method to pro-

Liquid Phase Synthesis

Liquid phase synthesis of CNTs is an appropriate method to produce aligned CNTs

is generally in the range of 500–1000  C and then a constant electrical current is

Flame Synthesis of CNTs

Plastic Pyrolysis Method

Today, the continuous increase of plastic wastes is a major environmental problem.

Chemical Vapor Deposition (CVD)

Chemical vapor deposition (CVD) is a widely used material processing technology

Catalytic CVD (CCVD)

Floating Catalyst Chemical Vapor Deposition (FCCVD)

Alcohol Catalyst Chemical Vapor Deposition (ACCVD)

VA-SWCNT reached 5 μm. Additionally, the diameters of the SWCNTs were

RTCVD was used to synthesize SWCNTs and MWCNTs on Ni/Al2O3 substrates

Plasma-Enhanced CVD (PECVD)

It is important to mention that as DC sources use high power to accelerate the

Microwave Plasma-Enhanced CVD (MPECVD)

Radiofrequency CVD (RF-CVD)

Hot-Filament CVD (HFCVD)

Fig. 3 Schematic diagram of

Fluidized-Bed CVD (FBCVD)

It is also a user-friendly system that ﬂexible operating parameters such as precursor

One-step preparation of highly dispersed metal-supported catalysts followed by

Fixed-Bed CVD (FBCVD)

Generally, in cold-wall CVD, substrates are mounted on a graphite holder and a

Electron Cyclotron Resonance CVD (ECR-CVD)

Polymer Pyrolysis CVD (PP-CVD)

investigated. The highest crystallinity of CNTs was obtained at 600  C with a

Direct Liquid Injection CVD (DLI-CVD)

Table 1 Summary of studies on CNT synthesis with different types of CVD

Tang J, Fan G, Li Z, Li X, Xu R, Li Y et al (2013) Synthesis of carbon nanotube/aluminium

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is generally in the range of 500–1000 C and then a constant electrical current is

investigated. The highest crystallinity of CNTs was obtained at 600 C with a