CARBON NANOTUBES

Dr. A.Subramania Centre for Nanoscience and Technology, Pondicherry University Puducherry-605 014, India

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OVERVIEW
INTRODUCTION TYPES OF CNTs VECTOR NOTATION FOR CNT STRUCTURES SYNTHESIS OF CNTs PURIFICATION of CNTs CHARACTERIZATION OF CNTs PHYSICAL PROPERTIES OF CNTs FUNCTIONALIZATION OF CNTs CNTs REINFORCED METAL MATRIX COMPOSITES CNTs REINFORCED POLYMER COMPOSITES APPLICATIONS OF CNTs

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INTRODUCTION
CNTs are allotrope of carbon. They are nanometers in diameter and several micrometers in length.
CNTs discovered in 1991 by the Japanese electron microscopist, Sumio Iijima, while studying the arc - evaporation synthesis of fullerenes.

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TYPES OF CNTs
There are two types of nanotubes;
1) Single Walled Carbon Nanotubes (SWCNTs)

2) Multi Walled Carbon Nanotubes (MWCNTs)

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1. SWCNT
Most SWCNTs have a diameter of 2nm with a tube length of 100m, making it effectively a 1-D structure called nanowires

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2. MWCNT

MWCNTs consist of multiple layers of graphene rolled in themselves to form tube shape

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VECTOR NOTATION FOR CNT STRUCTURES

The way to find out how the carbon atoms are arranged in a molecule can be done by pair of indices (n,m), called chiral vector.
By this way, it can be identified whether the carbon atoms are arranged in a zig zag, arm chair or in a helical shape (chiral).

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1. ZIG-ZAG

If m=0, the nanotubes are called Zig zag. In which the hexagon points lies along the long axis of the tube.

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2. ARM CHAIR

If n=m, the nanotubes are called Arm chair. In which the flat side of the hexagon lies along the long axis of the tube.

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3. CHIRAL

In which the configurations lies between the two extremes.

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ZIG-ZAG

(0,0)

Ch = (10,0)

a2
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y x
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ARM CHAIR

(0,0)

a2
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y x

Ch = (10,10)

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CHIRAL

(0,0)

Ch = (10,5)

a2
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y x
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SYNTHESIS OF CNTs
Carbon nanotubes are generally produced by the following techniques 1. Arc discharge method 2. Laser ablation method 3. Chemical vapour deposition method 4. Solar beam Evaporation method 5. Solvothermal synthesis 6. Electrochemical Method
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1. Arc discharge method

In this method, an electric arc is generated in between two closely spaced graphite electrodes (<1 mm apart) under an inert atmosphere of helium or argon in the reduced pressure of 50 -700 mbar. A direct current of 50 -120A with a driving potential of 30V is used to create a high temperature plasma (>3000C) between the two electrodes. At the plasma region, the carbon electrodes sublime and condense rapidly to form CNTs and other carbonaceous by products.
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Arc discharge method

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2. Laser Ablation method

A laser source is used to generate high temperature on a carbon target. The vapourized carbon rapidly cools in a helium gas stream and forms CNTs and other carbonaceous by products.

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3. Chemical vapour deposition method (CVD) In this method, by putting a carbon source in the gas phase and using an energy source such as plasma to get a gaseous carbon molecule. Commonly used carbon sources are methane, carbon monoxide, acetylene etc. CVD carbon nanotube synthesis is essentially a two step process consisting of a catalyst preparation step followed by the actual synthesis of nanotubes. The temperature used for the synthesis of nanotubes by CVD is generally in the range of 650-900C. Typical yields for CVD are approximately 30%.
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4. Solar Beam Evaporation method

The graphite crucible is filled with a mixture of graphite powder and metallic catalysts and placed in a graphite pipe heated at its top by the sun light. The evaporated material is drawn immediately through the graphite pipe, which acts as a thermal screening by reducing radioactive loses. On its wall either MWCNT or MWCNT and SWCNT together or only SWCNT will be formed.

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5. Solvothermal method
CNTs can be synthesized solvothermally using a planar hexagonal configuration such as hexachlorobenzene as a carbon precursor. In a typical reaction, reduction of hexachlorobenzene is carried out by metallic potassium in benzene as well as in the presence of Co/Ni catalyst at 350C, resulting in the formation of MWCNTs with an average diameter of 40nm. When catalysts are not used, the reaction usually gives nanostructures, such as carbon spheres, hollow spheres and hallow cones.

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6.Electrochemical method
A simple electrochemical process is used to synthesis CNTs at room temperature, without the presence of any metal catalysts and can be directly deposited onto a suitable substrate. In this electrochemical approach, 1 vol. % of acetonitrile (CH3CN) in deionised water is used as the electrolyte, the deposition will take place at room temperature under the lower voltage of 16-20 V between the substrate (tin-oxide coated glass) and counter electrode (graphite). The growth of the film deposition on the substrate was monitored by scanning electron microscopy at an interval of 1hr till the formation of carbon nanotubes, after a deposition period of 4 hrs. The carbon film obtained at intermediate duration was found to be in its amorphous phase, which subsequently converted into carbon nanotubes.
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Mechanism
CH3+ radicals generated from acetonitrile in the electrochemical process giving rice to the formation of amorphous carbon in the form of very small clusters with unsaturated bonds. The dehydrogenation of carbon from CH3+ radicals can be predicted thro the following reaction;

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SEM microstructures of the films on tin-oxide coated glass deposited for (a) t=1 h (b) t=2 h (c) t=3 h and (d) t=4 h

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PURIFICATION of CNTs
CNTs prepared by various methods contain impurities such as amorphous carbon, smaller fullerenes and metal catalyst etc. These impurities will interfere with most of the desired properties of the CNTs. Hence, purification process is required for the synthesized nanotubes. The purification process generally consists of six steps

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PURIFICATION of CNTs

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1.Thermal Oxidation

Oxidation treatment is a good way to remove carbonaceous impurities or to clear the metal surface at 300C in air

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2. Acid treatment In general, the acid treatment will remove the metal particles. When a treatment is in HNO3, the acid has an effect on the metal catalyst and not on the SWCNTs. If a treatment is in HCl, the acid has a little effect on the SWCNTs.
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3. Ultrasonication

In this, particles are separated due to ultrasonic vibrations.

Agglomerates of different nanoparticles will be forced to vibrate and will become more dispersed is highly dependable on the surfactant, solvent and reagent used.

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4. Magnetic purification
In this method, ferromagnetic particles are removed from their graphitic shells.
The SWCNTs suspension containing inorganic nanoparticles, mainly ZrO2. These particles are then trapped with permanent magnetic poles. After, a subsequent chemical treatment, a high purity SWCNTs will be obtained.

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5. Microfiltration
Microfiltration is based on size of the particles

SWCNTs are trapped in a filter, and the other nanoparticles such as metal catalyst, fullerene etc. are passing through the filter.

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6. Annealing
Due to high temperatures (600-1000C) in vacuum, most of the defects created in the earlier steps can be removed in the CNTs. When using high temperature vacuum treatment (1600C), the metal will be melted and can also be removed.

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CHARACTERIZATION OF CNTs

There are several techniques to characterize the CNTs. Among them, XRD, SEM/TEM and Raman Spectroscopy studies are important.

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SEM
SEM study has been extensively used to study CNTs and its alignment.

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TEM
TEM study allowing for the assessment of detailed structures.
We can find the diameter of the CNTs accurately and also the interspacing between the different walls of the MWCNT.

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PHYSICAL PROPERTIES OF CNTs

CNTs have some incredible physical properties and they are given below;
Mechanical properties Electrical properties Thermal properties Optical properties

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1. Mechanical properties CNTs are the strongest and stiffest materials due to its C-C bond strength. Youngs modulus of individual SWCNT and MWCNT are measured as 1054 GPa (1.054 TPa) and 1200 GPa (1.200 TPa), respectively from the amplitude of thermally driven vibrations observed in the TEM. AFM can also be used to measure the mechanical properties of individual CNTs The tensile strength of CNT is about 150 GPa. High strength steel alloys break at about 0.4 GPa. Thus carbon nanotubes are about 30-40times stronger than steel.
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Mechanical properties

A) AFM image of a SWNT bundle adhered on the alumina ultrafiltration membrane, leading to a clamped beam configuration for mechanical testing.

(B) Schematic representation of the measurement technique. The AFM applies a load, F, to the portion of nanotube with a suspended length of L and the maximum deflection d at the center of the beam is directly measured from the topographic image, along with L and the diameter of the tube.

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2. Electrical properties
CNTs have the most interesting property that they are metallic or semiconducting, depending on the diameter and chirality of the tube. Chirality refers to how the tubes are rolled with respect to the direction of its (n,m) vector in the graphene plane, where n, m are two integers. A metallic NT is obtained when the difference n-m is a multiple of 3. If the difference is not a multiple of 3, a semiconducting NT is obtained. In theory, metallic NTs can have an electric current density more than 1000 times greater than metals such as silver and copper. They have extremely low electrical resistance. It is an excellent material for high current applications.
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3. Thermal properties
Along the tube axes, CNTs have excellent thermal conductivity to the tune of ~6000 Wm-1K-1 at room temperature. On the other hand , copper has an excellent conductor of heat is valued at 385 W m-1K-1. However, along the diameter of the tube, CNTs are insulating.
The thermal stability of CNTs is very high (Ca. 3100 K in vacuum. But, in presence of oxygen, CNTs are easily oxidized at ~ 900K.
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4. Optical properties

Metallic tubes of any other metals have no band gas (0.0 eV). But semiconductor CNTs have a band gap that is a function of the diameter and its band gap energy ranges from 0.4 to 0.7 eV.

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FUNCTIONALIZATION OF CNTs
CNTs have to be functionalized in order to acquire additional physical-chemical properties. Its unique properties make it desirable for different applications.

Functionalization of CNTs changing some of the graphite properties to make CNTs soluble in different media or attaching different groups or even inorganic particles for further utilization of modified nanotubes. Functionalization of CNTs can be done as follows;
Exohedral (outside) Functionalization Endohedral (inside) Functionalization
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1. Exohedral (outside) Functionalization Meaning that the attachment of different groups or compounds to the sidewall of the nanotube. This can be achieved by covalent attachment.

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First is the functionalization via end and defect-side chemistry.

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The second is functionalization through side wall by treating nanotubes in an oxidizing environment For example, in a mixture of concentrated HNO3 and H2SO4, the oxygen containing groups such as COOH, -C=O and OH introduced at the ends and side walls of the tubes. These groups can serve as starting points for further functionalization of the nanotubes.

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 Other popular chemical functionalization of CNTs are; Fluorine functionalized multiwalled nanotubes, which achieves a high degree of functionalization by replacing fluorine with other functional groups.

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Amidation of CNTs can be done on the already carboxyl functionalized nanotubes via treatment in SOCl2 followed by octadecylamine.

Schematic of one type of chemical sidewall functionalization of SWNTs.

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Third class of functionalization of nanotubes is the noncovalent exohedral functionalization.

For example, wrapping nanotubes in polymers, piptides or surfactants.

The advantage of this method is that it does not destroy the electronic structure of the nanotubes.

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Solvent free covalent functionalization of CNTs.

In this, nanotubes are mixed with various anilines and isoamyl nitrite or sodium nitrite to produce nanotubes with covalently attached different chemical groups.

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2. Endohedral (inside) Functionalization Meaning that nanotubes are functionalized by filling them with different nanoparticles. This can be achieved by Filling of CNTs with colloidal suspensions followed by evaporation of the carrier liquid. CNTs are filled with some compounds, which react under particular thermal or chemical conditions and produce nanoparticles, which are trapped in the nanotubes.

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Applications of functionalized CNTs

Any functionalization of CNTs is made to change properties such as solubility, conductivity, magnetism etc., thus making it applicable for various applications. Usually all manipulations are made with the outer walls of CNTs.
The nanotubes functionalized with metallic nanoparticles can be used in building nanodevices, sensors for medicine, nanooptoelectronics, scanning tips for atomic force microscopes (AFM) etc.,

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CNTs REINFORCED METAL MATRIX COMPOSITES

CNTs reinforced metal matrix composites are prepared thro a variety of processing techniques such as plasma spraying, ion implantation, thermal vapour deposition, mechanical alloying and sintering (or) hot pressing etc., are very tedious and expensive. Hence, electrodeposition techniques can be used to prepare CNT reinforced metal matrix composites. CNT reinforced metal-matrix composites can be obtained by electrodeposition and Electroless deposition processes. The objective of adding fibrous reinforcement such as CNT is two fold; 1. To increase the tensile strength and 2. To increase the elastic modulus of the composite. Due to these effects, the CNTs have a higher stiffness and strength compared to the metal matrix.
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1. Mechanical properties
The critical issues in mechanical properties MM-CNT composites are the homogeneous distribution of CNTs in the metal matrix, and the interfacial reaction and booking with the matrix to work as an effective reinforcement. For example, in the case of Ni/Ni alloy CNTs composite coatings, the maximum improvement in the hardness was 44% by the addition of 2 vol% of CNT in the composite coating deposited by electroless method. In the case of Ti-Ni- shape memory alloy with 4.5 wt% of CNT, improves the hardness 200%.

Elastic modulus
Improvement in the elastic modulus of the composite is a result of the large tensile modulus of 350 970 GPa of CNTs.
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2. Wear and friction properties

Wear properties are more critical for coatings. For example, in the case of Ni CNTs, Cu CNTs electrodeposited coatings, a decrease in the coefficient of friction (COF) and increase in the wear resistance was observed.

The decrease in COF is due to the lubricating nature of CNTs.

The improved wear resistance is due to preventing the surface roughness of the matrix by CNTs . Deng et al have reported a maximum of 83% decrease in the wear and 60% decrease in COF for electroless Ni-P-CNTs coating containing 2 vol. % of CNTs.
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3. Corrosion properties Electrodeposited coatings are more prone to corrosion due to the presence of pores and voids. All the composite coatings with CNTs addition have shown an increase in the corrosion resistance. Chen et al have measured the corrosion rate of the composites to be 5 times lower than the Ni-coatings. This is due to the chemical inertness of the CNTs that helps in forming a passive layer on the coating surface. And also CNTs help to filling up voids and pores of electrodeposited coatings leaving no place for the initiation of localized corrosion.
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Applications of CNTs-reinforced MMCs

Industry
Automobile Industry

Application
Break shoes, Piston rings, Gears

Property Desired
High strength, Wear resistance, Good thermal conductivity, Low density.

Aerospace Industry
Space Industry

Aircraft brakes, Landing gears

High gain antenna boom, Structural radiators Light weight bicycles, Tennis and badminton rackets Micro-beams, Micro-gears Anodes, Anode coatings, Hydrogen storage materials

Good wear resistance, Good thermal conductivity, Low density, High strength .
Low density, High strength, Low coefficient of thermal expansion, Good electrical coductivity. High strength, High elastic modulus. High elastic modulus, High surface area. Large surface area, High CD, Reduced response time, Increased H2 adsorption - desorption rate.

Sports Industry MEMS and Sensors Battery and Energy Storage

CNTs REINFORCED POLYMER COMPOSITES By the addition of CNTs onto the polymer, we can improve the strength, elasticity, toughness and durability of the CNT reinforced polymer composites and also improve the mechanical, thermal, electrical and optical properties of the composite materials. CNTs reinforced polymer composites can be prepared by direct mixing, in-situ chemical polymerization (or) electrochemical polymerization processes.
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GENERAL APPLICATIONS OF CNTs

Depending on the size and length of the carbon nanotubes, its applications vary a lot. When the diameter is large, they can be used in energy devices such as Li- ion batteries, electric double layer capacitors, Fuel cells etc. On the other hand, if the CNTs has larger in length can be used in composites as a filler material to reinforcing the composite.

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Applications
The incorporation of CNTs in polymer matrices are suitable for variety of applications such as 1. Electrically conductive composites 2. Mechanically reinforced composites 3. Electrochemical capacitors 4. Solar cells 5. Light emitting diodes 6. Sensors and actuators 7. Fuel cells 8. Electromagnetic absorbers etc.
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Thank you

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