SEMINAR REPORT ON

CARBON NANOTUBES

SUBMITTED TO

MECHANICAL ENGINEERING DEPARTMENT MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY

SUBMITTED BY ISHANT GUPTA B. Tech. MECHANICAL ENGINEERING, 4th YEAR

ABSTRACT
Carbon nanotubes (CNTs) are a recently discovered allotrope of carbon. They take the form of cylindrical carbon molecules and have novel properties that make them potentially useful in a wide variety of applications in nanotechnology, electronics, optics, and other fields of materials science. They exhibit extraordinary strength and unique electrical properties, and are efficient conductors of heat. Inorganic nanotubes have also been synthesized. A nanotube is a member of the fullerene structural family, which also includes buckyballs. Whereas buckyballs are spherical in shape, a nanotube is cylindrical, with at least one end typically capped with a hemisphere of the buckyball structure. Their name is derived from their size, since the diameter of a nanotube is on the order of a few nanometers (approximately 50,000 times smaller than the width of a human hair), while they can be up to several millimeters in length. There are two main types of nanotubes: single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). Manufacturing a nanotube is dependent on applied quantum chemistry, specifically, orbital hybridization. Nanotubes are composed entirely of sp2 bonds similar to those of graphite. This bonding structure, stronger than the sp3 bonds found in diamond, provides the molecules with their unique strength. Nanotubes naturally align themselves into "ropes" held together by Van der Waals forces. Under high pressure, nanotubes can merge together, trading some sp2 bonds for sp3 bonds, giving great possibility for producing strong, unlimited-length wires through high-pressure nanotube linking.

CONTENTS
Introduction History Classification of Carbon Nanotubes Single-Walled Carbon Nanotubes (SWCNTs) Multi-Walled Carbon Nanotubes (MWCNTs) Other Carbon Nanotube Structures Synthesis Of Carbon Nanotubes Arc Discharge Method Laser Ablation Chemical Vapor Deposition (CVD) Milestones in CNT Evolution Properties of CNTs Advantages Disadvantages Applications Challenges Conclusion References

INTRODUCTION
Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1, significantly larger than for any other material. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, electronics, optics and other fields of materials science and technology. In particular, owing to their extraordinary thermal conductivity and mechanical and electrical properties, carbon nanotubes find applications as additives to various structural materials. Nanotubes are members of the fullerene structural family. Their name is derived from their long, hollow structure with the walls formed by one-atom-thick sheets of carbon, called graphene. These sheets are rolled at specific and discrete (chiral) angles and the combination of the rolling angle and radius decides the nanotube properties, for example, whether the individual nanotube shell is a metal or semiconductor. Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs). Individual nanotubes naturally align themselves into "ropes" held together by van der Waals forces, more specifically, pi-stacking. Applied quantum chemistry, specifically, orbital hybridization best describes chemical bonding in nanotubes. The chemical bonding of nanotubes is composed entirely of sp2 bonds, similar to those of graphite. These bonds, which are stronger than the sp3 bonds found in alkanes and diamond, provide nanotubes with their unique strength.

2. HISTORY
The current huge interest in carbon nanotubes is a direct consequence of the synthesis of buckminsterfullerene, C60, and other fullerenes, in 1985. The discovery that carbon could form stable, ordered structures other than graphite and diamond stimulated researchers worldwide to search for other new forms of carbon. The search was given new impetus when it was shown in 1990 that C60 could be produced in a simple arcevaporation apparatus readily available in all laboratories. It was using such an evaporator that the Japanese scientist Sumio Iijima discovered fullerene-related carbon nanotubes in 1991. The tubes contained at least two layers, often many more, and ranged in outer diameter from about 3 nm to 30 nm. They were invariably closed at both ends.

A transmission electron micrograph of some multiwall nanotubes is shown in the figure (left). In 1993, a new class of carbon nanotube was discovered, with just a single layer. These single-walled nanotubes are generally narrower than the multiwall tubes, with diameters typically in the range 1-2 nm, and tend to be curved rather than straight. The image on the right shows some typical single-walled tubes. It was soon established that these new fibres had a range of exceptional properties, and this sparked off an explosion of research into carbon nanotubes. It is important to note, however, that nanometre scale tubes of carbon, produced catalytically, had been known for many years before Iijimas discovery. The main reason why these early tubes did not excite wide interest is that they were structurally rather imperfect, so did not have particularly interesting properties. Recent research has focused on improving the quality of catalytically-produced nanotubes.

3. CLASSIFICATION OF CARBON NANOTUBES

Carbon nanotubes are mainly classified into two: Single-walled Nanotubes (SWNTS); Multi-walled Nanotubes (MWNTS).

3.1 Single-Walled Nanotubes (SWNTs)

A single-walled carbon nanotube (SWNT) may be thought of as a single atomic layer thick sheet of graphite (called graphene) rolled into a seamless cylinder. Most single-walled nanotubes (SWNT) have a diameter of close to 1 nanometre, with a tube length that can be many millions of times longer. Single-walled nanotubes are an important variety of carbon nanotube because they exhibit electric properties that are not shared by the multi-walled carbon nanotube (MWNT) variants.

Single walled CNTs

3.1.1 Rolling Of Graphene Sheet into CNTs

The structure of a SWNT can be conceptualized by wrapping a one-atom-thick layer of graphite called graphene into a seamless cylinder. The way the graphene sheet is wrapped is represented by a pair of indices (n, m) called the chiral vector. The integer n and m denote the number of unit vectors along two directions in the honeycomb crystal lattice of graphene. If m = 0, the nanotubes are called "zigzag". If n = m, the nanotubes are called "armchair". Otherwise, they are called "chiral".

Rolling angle of Graphene Sheet

Armchair & Zig-zag CNT

3.2 Multi-Walled Nanotubes (MWNTs)

Multi-walled nanotubes (MWNT) consist of multiple rolled layers (concentric tubes) of graphite. There are two models which can be used to describe the structures of multi- walled nanotubes. In the Russian Doll model, sheets of graphite are arranged in concentric cylinders. In the Parchment model, a single sheet of graphite is rolled in around itself, resembling a scroll of parchment or a rolled newspaper (The Russian Doll structure is observed more commonly). The telescopic motion ability of inner shells and their unique mechanical properties will permit the use of multi-walled nanotubes as main movable arms in coming Nano mechanical devices.

Multi-walled CNTs

3.3 Other Carbon Nanotube Structures

Torus: Carbon nanotube bent into a torus (doughnut shape). Nanotori are predicted to have many unique properties, such as magnetic moments 1000 times larger than previously expected for certain specific radii. Properties such as magnetic moment, thermal stability, etc. vary widely depending on radius of the torus and radius of the tube. Nanobud: Carbon Nanobuds are a newly created material combining two previously discovered allotropes of carbon: carbon nanotubes and fullerenes. In this new material, fullerene-like "buds" are covalently bonded to the outer sidewalls of the underlying carbon. They are good field emitters. In composite materials, the attached fullerene molecules may function as molecular anchors preventing slipping of the nanotubes, thus improving the composites mechanical properties.

Torus

A Normal Nanobud

 Graphenated Carbon Nanotubes (G-CNTs): Graphenated CNTs are a relatively new hybrid that combines graphitic foliates grown along the sidewalls of multi walled or bamboo style CNTs use in super capacitor applications. Peapod Carbon Nanotubes: A Carbon peapod] is a novel hybrid carbon material which traps fullerene inside a carbon nanotube. Cup-Stacked Carbon Nanotubes: CSCNTs exhibit semiconducting behaviours due to the stacking microstructure of graphene layers. Nitrogen Doped Carbon Nanotubes: N-doping provides defects in the walls of CNT's allowing for Li ions to diffuse into inter-wall space. It also increases capacity by providing more favorable bind of N-doped sites. N-CNT's are also much more reactive to metal oxide nanoparticle deposition which can further enhance storage capacity, especially in anode materials for Li-ion batteries. However Boron doped nanotubes has been shown to make batteries with triple capacity.

Graphenated Carbon Nanotubes

4. SYNTHESIS OF CARBON NANOTUBES

Techniques have been developed to produce nanotubes in sizeable quantities, including arc discharge, laser ablation, high pressure carbon monoxide disproportionation reaction (HiPco), and chemical vapor deposition (CVD). Most of these processes take place in vacuum or with process gases. CVD growth of CNTs can take place in vacuum or at atmospheric pressure. Large quantities of nanotubes can be synthesized by these methods; advances in catalysis and continuous growth processes are making CNTs more commercially viable. SWNTs and MWNTs are usually made by carbon-arc discharge, laser ablation of carbon, or chemical vapour deposition (typically on catalytic particle). Nanotube diameters range from 0.4 to 3 nm for SWNTs and from 1.4 to at least 100 nm for MWNTs. Nanotube properties can thus be tuned by changing the diameter. Unfortunately, SWNTs are presently produced only on a small scale and are extremely expensive. All currently known methods of synthesis of SWNTs result in major concentrations of impurities. These impurities are typically removed by acid treatment, which introduces other impurities, can degrade nanotube length and perfection, and adds to nanotube cost. MWNTs produced catalytically by gas-phase pyrolysis, like the Hyperion nanotubes, have high defect densities compared to those produced by the more expensive carbon-arc process.

4.1 ARC DISCHARGE METHOD

CNT production requires 3 elements Carbon feed Metal catalyst Heat The nanotubes were initially discovered using this technique; it has been the most widely-used method of nanotube synthesis. Two Graphite electrodes placed in an inert Helium atmosphere. When DC current is passed anode is consumed and material forms on cathode. For SWNT mixed metal catalyst is inserted into anode. Pure iron catalyst + Hydrogen-inert gas mixture gives 20 to 30cm long tube.

4.2 LASER ABLATION

In the laser ablation process, a pulsed laser vaporizes a graphite target in a high- temperature reactor while an inert gas is bled into the chamber. Nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon condenses. A water-cooled surface may be included in the system to collect the nanotubes. The laser ablation method yields around 70% and produces primarily single-walled carbon nanotubes with a controllable diameter determined by the reaction temperature. It is more expensive than either arc discharge or chemical vapor deposition.

4.3 CHEMICAL VAPOR DEPOSITION (CVD)

During CVD, a substrate is prepared with a layer of metal catalyst articles, most commonly nickel, cobalt, iron, or a combination. The diameters of the nanotubes that are to be grown are related to the size of the metal particles. The substrate is heated to approximately 700c. To initiate the growth of nanotubes, two gases are bled into the reactor: a process gas (such as ammonia, nitrogen or hydrogen) and a carbon-containing gas (such as acetylene, ethylene, ethanol or methane). Nanotubes grow at the sites of the metal catalyst. The carbon-containing gas is broken apart at the surface of the catalyst particle, and the carbon is transported to the edges of the particle, where it forms the nanotubes.

COMPARISON OF DIFFERENT SYNTHESIS METHODS OF CNTs

ARC DISCHARGE METHOD Connect two graphite Rods to a power supply, place them millimeters apart, and throw switch. At 100 amps, carbon vaporizes in hot plasma. CHEMICAL VAPOUR DEPOSITION Place substrate in oven, Heat to 600 C, and slowly add a carbon-bearing gas such as methane. As gas decomposes it frees up carbon atoms, which recombine in the form of NTs Easiest to scale to industrial Production, long length LASER ABLATION (VAPORIZATION) Blast graphite with intense laser pulses, use the laser pulses rather than electricity to generate carbon gas from which the NTs form; try various conditions until hit on one that produces prodigious amounts of SWNTs Primarily SWNTs, with a large diameter range that can be controlled by varying the reaction temperature By far the most costly, because requires expensive lasers

Can produce SWNT & MWNTs with few structural defects Tubes tend to be short with random sizes and directions

NTs are usually MWNTs and often riddled with defects

5.MILESTONES IN CARBON NANOTUBE EVOLUTION

The observation of the longest carbon nanotubes (18.5 cm long) was reported in 2009. These nanotubes were grown on Si substrates using an improved chemical vapor deposition (CVD) method and represent electrically uniform arrays of single-walled carbon nanotubes. The shortest carbon nanotube is the organic compound cycloparaphenylene, which was synthesized in early 2009.The thinnest carbon nanotube is armchair (2,2) CNT with a diameter of 3 . This nanotube was grown inside a multi-walled carbon nanotube. Assigning of carbon nanotube type was done by combination of high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy and density functional theory (DFT) calculations. The thinnest freestanding single-walled carbon nanotube is about 4.3 in diameter. Researchers suggested that it can be either (5, 1) or (4, 2) SWCNT, but exact type of carbon nanotube remains questionable. (3, 3), (4, 3) and (5, 1) carbon nanotubes (all about 4 in diameter) were unambiguously identified using more precise aberrationcorrected high-resolution transmission electron microscopy. However, they were found inside of doublewalled carbon nanotubes.

6. PROPERTIES OF CARBON NANOTUBES

Strength: Carbon nanotubes are the strongest, flexible and stiffest materials yet discovered in terms of tensile strength and elastic modulus respectively. This strength results from the covalent sp2 bonds formed between the individual carbon atoms (which is stronger than the sp3 bonds found in Diamond & Alkenes). CNTs are not nearly as strong under compression. Because of their hollow structure and high aspect ratio, they tend to undergo buckling when placed under compressive, torsion or bending stress. Hardness: The hardness (152 Gpa) and bulk modulus (462546) of carbon nanotubes are greater than diamond, which is considered the hardest material (that of diamond is 150GPa & 420GPa). Kinetic Property: Multi-walled nanotubes, multiple concentric nanotubes precisely nested within one another; exhibit a striking telescoping property whereby an inner nanotube core may slide, almost without friction, within its outer nanotube shell thus creating an atomically perfect linear or rotational bearing, the precise positioning of atoms to create useful machines.

 Electrical Properties: Because of the symmetry and unique electronic structure of graphene, the structure of a nanotube strongly affects its electrical properties. Very high current carrying capacity. Thermal Conductivity : All nanotubes are expected to be very good thermal conductors along the tube.( Measurements show that a SWNT has a room-temperature thermal conductivity more than copper). Optical properties: EM Wave absorption-Current military push for radar absorbing materials (RAM) to better the stealth characteristics of aircraft and other military vehicles. (There has been some research on filling MWNTs with metals, such as Fe, Ni, Co, etc., to increase the absorption effectiveness of MWNTs in the microwave regime). Thermal properties: All nanotubes are expected to be very good thermal conductors along the tube, but good insulators laterally to the tube axis. (Measurements show that a SWNT has a room-temperature thermal conductivity along its axis of about 3500 Wm K whereas copper, a metal well known for its good thermal conductivity, transmits 385 Wm1K1).
-1 1

COMPARISON OF MECHANICAL PROPERTIES

Toxicity: Under some conditions, nanotubes can cross membrane barriers, which suggest that if raw materials reach the organs they can induce harmful effects such as inflammatory and fibrotic reactions. Crystallographic defect: As with any material, the existence of a crystallographic defect affects the material properties. Defects can occur in the form of atomic vacancies.

7. ADVANTAGES
Extremely small and lightweight. Resources required to produce them are plentiful, and many can be made with only a small amount of material. Are resistant to temperature changes, meaning they function almost just as well in extreme cold as they do in extreme heat. Improves conductive, mechanical, and flame barrier properties of plastics and composites. Enables clean, bulk micromachining and assembly of components. Improves conductive, mechanical, and flame barrier properties of plastics and composites.

8. DISADVANTAGES
Despite all the research, scientists still don't understand exactly how they work. Extremely small, so are difficult to work with. Currently, the process is relatively expensive to produce the nanotubes. Would be expensive to implement this new technology in and replace the older technology in all the places that we could. At the rate our technology has been becoming obsolete; it may be a gamble to bet on this technology.

10. APPLICATIONS Micro-electronics / semiconductors Conducting Composites Controlled Drug Delivery/release Artificial muscles Super capacitors Batteries Field emission flat panel displays Field Effect transistors and Single electron transistors Nano electronics Doping Nano balance Nano tweezers Data storage Magnetic nanotube Nano gear Space Elevator Nanotube actuator Molecular Quantum wires Hydrogen Storage Noble radioactive gas storage Solar storage Waste recycling Electromagnetic shielding Dialysis Filters Thermal protection Nanotube reinforced composites Reinforcement of armor and other materials Reinforcement of polymer

Avionics Collision-protection materials Fly wheels

11. CHALLENGE S The greatness of a single-walled nanotube is that it is a macro-molecule and a crystal at the same time. The dimensions correspond to extensions of fullerene molecules and the structure can be reduced to a unit-cell picture, as in the case of perfect crystals. A new predictable (in terms of atomic structure property relations) carbon fiber was born. The last decade of research has shown that indeed the physical properties of nanotubes are remarkable, as elaborated in the various chapters of this book. A carbon nanotube is an extremely versatile material: it is one of the strongest materials, yet highly elastic, highly conducting, small in size, but stable, and quite robust in most chemically harsh environments. It is hard to think of another material that can compete with nanotubes in versatility. There are also general challenges that face the development of nanotubes into functional devices and structures. First of all, the growth mechanism of nanotubes, similar to that of fullerenes, has remained a mystery .With this handicap; it is not really possible yet to grow these structures in a controlled way. Especially for electronic applications, which rely on the electronic structure of nanotubes, this inability to select the size

and helicity of nanotubes during growth remains a drawback. More so, many predictions of device applicability are based on joining Nano-tubes via the incorporation of topological defects in their lattices. There is no controllable way, as of yet, of making connections between nanotubes. Some recent reports, however, suggest the possibility of constructing these interconnected Structures by electron irradiation and by template mediated growth and manipulation. For bulk applications, such as fillers in composites, where the atomic structure (helicity) has a much smaller impact on the resulting properties, the quantities of nanotubes that can be manufactured still falls far short of what industry would need. There are no available techniques that can produce nanotubes of reasonable purity and quality in kilogram quantities. The industry would need tonnage quantities of nanotubes for such applications. Another challenge is in the manipulation of nanotubes. Nano-technology is in its infancy and the revolution that is unfolding in this .eld relies strongly on the ability to manipulate structures at the atomic scale. This will remain a major challenge in this field, among several others.

12.CONCLUS ION Nanotubes appear destined to open up a host of new practical applications and help improve our understanding of basic physics at the nonmetric scale. Nanotechnology is predicted to spark a series of industrial revolutions in the next two decades that will transform our lives to a far greater extent than silicon microelectronics did in the 20th century. Carbon nanotubes could play a pivotal role in this upcoming revolution if their remarkable structural, electrical and mechanical properties can be exploited. The remarkable properties of carbon nanotubes may allow them to play a crucial role in the relentless drive towards miniaturization scale. Lack of commercially feasible synthesis and purification methods is the main reason that carbon nanotubes are still not widely used nowadays. At the moment, nanotubes are too expensive and cannot be produced selectively. Some of the already known and upcoming techniques look promising for economically feasible production of purified carbon nanotubes. Some future applications of carbon nanotubes look very promising. All we need are better production technique for large amounts of purified nanotubes that have to be found in the near future. Nanotube promises to open up a way to new applications that might be cheaper, lower in weight and have a better efficiency.

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