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Carbon nanotube

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3D model of three types of single-walled carbon nanotubes.
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3D model of three types of single-walled carbon nanotubes.

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 micrometers in length. There are two main types of nanotubes: single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs).

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 http://www.ncnr.nist.gov/staff/taner/nanotube/interlink.pdf.

While it has long been known that carbon fibers can be produced with a carbon arc, and patents were issued for the process, it was not until 1991 that Sumio Iijima, a researcher with the NEC Laboratory in Tsukuba, Japan, observed that these fibers were hollow. This feature of nanotubes is of great interest to physicists because it permits experiments in one-dimensional quantum physics.

Types of carbon nanotube

Single-walled

The (n,m) nanotube naming scheme can be thought of as a vector (Ch) in an infinite graphene sheet that describes how to 'roll up' the graphene sheet to make the nanotube. T denotes the tube axis, and a1 and a2 are the unit vectors of graphene in real space.
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The (n,m) nanotube naming scheme can be thought of as a vector (Ch) in an infinite graphene sheet that describes how to 'roll up' the graphene sheet to make the nanotube. T denotes the tube axis, and a1 and a2 are the unit vectors of graphene in real space.

Most SWNTs have a diameter of close to 1nm, with a tube length that can be many thousands of times larger. SWNTs with length up to orders of centimeters have been produced (Zhu, et al., 2002). 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 integers 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".

SWNTs are a very important variety of carbon nanotube because they exhibit important electric properties that are not shared by the multi-walled carbon nanotube (MWNT) variants. SWNTs are the most likely candidate for miniaturizing electronics past the microelectromechanical scale that is currently the basis of modern electronics. The most basic building block of these systems is the electric wire, and SWNTs can be excellent conductors (Dekker, et al., 1999). One useful application of SWNTs is in the development of the first intramolecular field effect transistors (FETs). The production of the first intramolecular logic gate using SWNT FETs has recently become possible as well (Derycke, et al., 2001). To create a logic gate you must have both a p-FET and an n-FET. Because SWNTs are p-FETs when exposed to air and n-FETs when unexposed to oxygen, they were able to protect half of a SWNT from oxygen exposure, while exposing the other half to oxygen. The result was a single SWNT that acted as a NOT logic gate with both p and n-type FETs within the same molecule.

SWNTs are still very expensive to produce, and the development of more affordable synthesis techniques is vital to the future of carbon nanotechnology. If cheaper means of synthesis cannot be discovered, it would make it financially impossible to apply this technology to commercial-scale applications.

Multi-walled

Multiwalled nanotubes (MWNT) consist of multiple layers of graphite rolled in on themselves to form a tube shape. There are two models which can be used to describe the structures of multiwalled nanotubes. In the Russian Doll model, sheets of graphite are arranged in concentric cylinders, eg a (0,8) SWNT within a larger (0,10) SWNT. In the Parchment model, a single sheet of graphite is rolled in around itself , resembling a scroll of parchment or a rolled up newspaper.

Fullerite

Fullerite is a highly incompressible nanotube form. Polymerized single walled nanotubes (P-SWNT) are a class of fullerites and are comparable to diamond in terms of hardness (see also ultrahard fullerite).

Torus

A nanotorus is a carbon nanotube bent into a torus (donut shape). Nanotori have many unique properties, such as magnetic moments 1000 times larger than previously expected for certain specific radii. Many properties such as magnetic moment, thermal stability, etc. vary widely depending on radius of the torus and radius of the tube.

Properties

Strength

Carbon nanotubes are one of the strongest materials known to man, both in terms of tensile strength and elastic modulus. This strength results from the covalent sp2 bonds formed between the individual carbon atoms. In 2000, an MWNT was tested to have a tensile strength of 63 GPa http://sciencemag.org/cgi/content/abstract/287/5453/637. In comparison, high-carbon steel has a tensile strength of approximately 1.2 GPa. CNTs also have very high elastic modulus, on the order of 1 TPa http://ipn2.epfl.ch/CHBU/papers/ourpapers/Forro_NT99.pdf. Since carbon nanotubes have a low density for a solid of 1.3-1.4, its specific strength is the best of known materials.

Under excessive tensile strain, the tubes will undergo plastic deformation, which means the deformation is permanent. This deformation begins at strains of approximately 5% [Qian et al, 2002] and can increase the maximum strain the tube undergoes before fracture by releasing strain energy.

CNTs are not nearly as strong under compression. Because of their hollow structure, they tend to undergo buckling when placed under compressive, torsional or bending stress.

Dynamic properties

Multiwalled carbon 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 bearinghttp://dx.doi.org/10.1126/science.289.5479.505ehttp://dx.doi.org/10.1126/science.289.5479.602. This is one of the first true examples of molecular nanotechnology, the precise positioning of atoms to create useful machines. Already this property has been utilized to create the world's smallest rotational motorhttp://dx.doi.org/10.1038/nature01823 and a nanorheostathttp://dx.doi.org/10.1103/PhysRevLett.93.086801. Future applications such as a gigahertz mechanical oscillator are envisionedhttp://focus.aps.org/story/v9/st4.

Electrical

Because of the symmetry and unique electronic structure of graphene, the structure of a nanotube strongly affects its electrical properties. For a given (n,m) nanotube, if 2n + m=3q (where q is an integer), then the nanotube is metallic, otherwise the nanotube is a semiconductor. Thus all armchair (n=m) nanotubes are metallic, and nanotubes (5,0), (6,4), (9,1), etc. are semiconducting. In theory, metallic nanotubes can have an electrical current density more than 1,000 times greater than metals such as silver and copper.
See also: Fermi point

Thermal

All nanotubes are expected to be very good thermal conductors along the tube, exhibiting a property known as "ballistic conduction," but good insulators laterally to the tube axis.

Defects

As with any material, the existence of defects affects the material properties. Defects can occur in the form of atomic vacancies. High levels of such defects can lower the tensile strength by up to 85%.http://lib.tkk.fi/Diss/2004/isbn9512273799/article5.pdf Another well-known form of defect that occurs in carbon nanotubes is known as the Stone Wales defect, which creates a pentagon and heptagon pair by rearrangement of the bonds. Because of the almost one-dimensional structure of CNTs, the tensile strength of the tube is dependent on the weakest segment of it in a similar manner to a chain, where a defect in a single link diminishes the strength of the entire chain.

The tubes electrical properties are also affected by the presence of defects. A common result is the lowered conductivity through the defective region of the tube. Some defect formation in armchair-type tubes (which are metallic) can cause the region surrounding that defect to become semiconducting. Furthermore single monoatomic vacancies induce magnetic properties.

The tube's thermal properties are heavily affected by defects. Such defects lead to phonon scattering, which in turn increases the relaxation rate of the phonons. This reduces the mean free path, and reduces the thermal conductivity of nanotube structures.

Synthesis

Techniques have been developed to produce nanotubes in sizeable quantities, including arc discharge, laser ablation, high pressure carbon monoxide (HiPco), and chemical vapor deposition (CVD). All of these processes take place in vacuum, with process gases. Large quantities of nanotubes can be synthesized by these methods; however, the cost is still too high to facilitate mass production.

Arc discharge

Nanotubes were observed in 1991 in the carbon soot of graphite electrodes during an arc discharge that was intended to produce fullerenes. During this process, the carbon contained in the negative electrode sublimates because of the high temperatures caused by the discharge. Because nanotubes were initially discovered using this technique, it has been perhaps the most widely used method of nanotube synthesis.

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. The 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.

Chemical vapor deposition (CVD)

Nanotubes being grown by plasma enhanced chemical vapor deposition
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Nanotubes being grown by plasma enhanced chemical vapor deposition

The catalytic vapor phase deposition of carbon was first reported in 1959P. L. Walker Jr. et al., J. Phys. Chem. 63, 133 (1959)., but it was not until 1993M. José-Yacamán et al., Appl. Phys. Lett. 62, 657 (1993). that carbon nanotubes could be formed by this process.

During CVD, a substrate is prepared with a layer of metal catalyst particles, 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. This can be controlled by patterned (or masked) deposition of the metal, annealing, or by plasma etching of a metal layer. The substrate is heated to approximately 700°C. To initiate the growth of nanotubes, two gases are bled into the reactor: a process gas (such as ammonia, nitrogen, hydrogen, etc.) and a carbon-containing gas (such as acetylene, ethylene, ethanol, etc.). Nanotubes grow at the sites of the metal catalyst; the carbon-containing gas is broken apart at the surface of the catalyst particle, and the carbon is transported to the edges of the particle, where it forms the nanotubes. The catalyst particles generally stay at the tips of the growing nanotube during the growth process, although in some cases they remain at the nanotube base, depending on the adhesion between the catalyst particle and the substrate.

If a plasma is generated by the application of a strong electric field during the growth process (plasma enhanced chemical vapor deposition), then the nanotube growth will follow the direction of the electric fieldZ. F. Ren et al., Science 282, 1105 (1998).. By properly adjusting the geometry of the reactor it is possible to synthesize vertically aligned carbon nanotubes (i.e., perpendicular to the substrate), a morphology that has been of interest to researchers interested in the electron emission from nanotubes. Without the plasma, the resulting nanotubes are randomly oriented, resembling a bowl of spaghetti.

Of the various means for nanotube synthesis, CVD shows the most promise for industrial scale deposition in terms of its price/unit ratio. There are additional advantages to the CVD synthesis of nanotubes. Unlike the above methods, CVD is capable of growing nanotubes directly on a desired substrate, whereas the nanotubes must be collected in the other growth techniques. The growth sites are controllable by careful deposition of the catalyst. Additionally, no other growth methods have been developed to produce vertically aligned nanotubes.

Natural and incidental synthesis

Fullerenes and carbon nanotubes are not necessarily products of high-tech laboratories; they are commonly formed in such mundane places as candle flames. However, these naturally occurring varieties, because of the highly uncontrolled environment in which they are produced, are highly irregular in size and quality, lacking the high degree of uniformity necessary to meet the needs of both research and industry.

Applications

The joining of two carbon nanotubes with different electrical properties to form a diode has been proposed.
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The joining of two carbon nanotubes with different electrical properties to form a diode has been proposed.

The strength and flexibility of carbon nanotubes makes them of potential use in controlling other nanoscale structures, which suggests they will have an important role in nanotechnology engineering. The highest tensile strength an individual MWNT has been tested to be is 63 GPa http://sciencemag.org/cgi/content/abstract/287/5453/637. Bulk nanotube materials may never achieve a tensile strength similar to that of individual tubes, but such composites may nevertheless yield strengths sufficient for many applications. Carbon nanotubes have already been used as composite fibers in polymers and concrete to improve the mechanical, thermal and electrical properties of the bulk product.

Structural

Electromagnetic

Chemical

Mechanical

Carbon nanotubes in electrical circuits

Carbon nanotubes have many properties—from their unique dimensions to an unusual current conduction mechanism—that make them ideal components of electrical circuits. Currently, there is no reliable way to arrange carbon nanotubes into a circuit.

The major hurdles that must be jumped for carbon nanotubes to find prominent places in circuits relate to fabrication difficulties. The production of electrical circuits with carbon nanotubes are very different from the traditional IC fabrication process. The IC fabrication process is somewhat like sculpture - films are deposited onto a wafer and pattern-etched away. Because carbon nanotubes are fundamentally different from films, carbon nanotube circuits can so far not be mass produced.

Researchers sometimes resort to manipulating nanotubes one-by-one with the tip of an atomic force microscope in a painstaking, time-consuming process. Perhaps the best hope is that carbon nanotubes can be grown through a chemical vapor deposition process from patterned catalyst material on a wafer, which serve as growth sites and allow designers to position one end of the nanotube. During the deposition process, an electric field can be applied to direct the growth of the nanotubes, which tend to grow along the field lines from negative to positive polarity. Another way for the self assembly of the carbon nanotube transistors consist in using chemical or biological techniques to place the nanotubes from solution to determinate place on a substrate.

Even if nanotubes could be precisely positioned, there remains the problem that, to this date, engineers have been unable to control the types of nanotubes—metallic, semiconducting, single-walled, multi-walled—produced. A chemical engineering solution is needed if nanotubes are to become feasible for commercial circuits.

Carbon nanotube fiber & film

One application for nanotubes that is currently being researched is high tensile strength fibers. Two methods are currently being tested for the manufacture of such fibers. A French team has developed a liquid spun system that involves pulling a fiber of nanotubes from a bath which yields a product that is approximately 60% nanotubes[[Citing sourcescitation needed]]. The other method, which is simpler but produces weaker fibers uses traditional melt-drawn polymer fiber techniques with nanotubes mixed in the polymer. After drawing, the fibers can have the polymer component burned out of them leaving only the nanotube or they can be left as they are.

Ray Baughman's group from the NanoTech Institute at University of Texas at Dallas produced the current toughest material known in mid-2003 by spinning fibers of single wall carbon nanotubes with polyvinyl alcohol. Beating the previous contender, spider silk, by a factor of four, the fibers require 600 J/g to break[[Citing sourcescitation needed]]. In comparison, the bullet-resistant fiber Kevlar is 27-33J/g. In mid-2005 Baughman and co-workers from Australia's Commonwealth Scientific and Industrial Research Organization developed a method for producing transparent carbon nanotube sheets 1/1000th the thickness of a human hair capable of supporting 50,000 times their own mass. In August 2005, Ray Baughman's team managed to develop a fast method to manufacture up to seven meters per minute of nanotube tape http://www.worldchanging.com/archives/003330.html. Once washed with ethanol, the ribbon is only 50 nanometers thick; a square kilometer of the material would only weigh 30 kilograms.

In 2004 Alan Windle's group of scientists at the Cambridge-MIT Institute developed a way to make carbon nanotube fiber continuously at the speed of several centimetres per second just as nanotubes are produced. One thread of carbon nanotubes was more than 100 metres long. The resulting fibers are electrically conductive and as strong as ordinary textile threads http://news.bbc.co.uk/2/hi/science/nature/3872931.stm http://www.newscientist.com/news/news.jsp?id=ns99994769.

History of the nanotube

1985 1991 1993 1998 2001 2002 2003
As of 2003, nanotubes cost from 20 euro per gram to 1000 euro per gram, depending on purity, composition (single-wall, double-wall, multi-wall) and other characteristics.
2004
2005
Industry reports indicate nanotube production will increase by 10 to 100 times in the next 5 years for different types and purity of nanotubes.
2006
Prices halve in one year to €1.67 per gram in quantities of 1 kg as MWNT, >50 nm diameter, 50 micrometers long. http://www.cheaptubesinc.com/

References

External links and sources

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