Carbon nanotube

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This animation of a rotating carbon nanotube shows its 3D structure.

Powder of carbon nanotubes

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes have been constructed with length-to-diameter ratio of up to 28,000,000:1,^[1] which is significantly larger than any other material. These cylindrical carbon molecules have novel properties that make them potentially useful in many applications in nanotechnology, electronics, optics and other fields of materials science, as well as potential uses in architectural fields. They exhibit extraordinary strength and unique electrical properties, and are efficient conductors of heat. Their final usage, however, may be limited by their potential toxicity.

Nanotubes are members of the fullerene structural family, which also includes the spherical buckyballs. The ends of a nanotube might be 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 1/50,000th of the width of a human hair), while they can be up to several millimeters in length (as of 2008). Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs).

The nature of the bonding of a nanotube is described by applied quantum chemistry, specifically, orbital hybridization. The chemical bonding of nanotubes is composed entirely of sp² bonds, similar to those of graphite. This bonding structure, which is stronger than the sp³ bonds found in diamonds, 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 the possibility of producing strong, unlimited-length wires through high-pressure nanotube linking.

[edit] Types of carbon nanotubes and related structures

[edit] Single-walled

Electron micrograph showing an individual nanotube

Most single-walled nanotubes (SWNT) have a diameter of close to 1 nanometer, with a tube length that can be many millions of times longer. 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".

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 nanotubes are the most likely candidate for miniaturizing electronics beyond the micro electromechanical scale currently used in electronics. The most basic building block of these systems is the electric wire, and SWNTs can be excellent conductors.^[2][3] One useful application of SWNTs is in the development of the first intramolecular field effect transistors (FET). Production of the first intramolecular logic gate using SWNT FETs has recently become possible as well.^[4] To create a logic gate you must have both a p-FET and an n-FET. Because SWNTs are p-FETs when exposed to oxygen and n-FETs otherwise, it is possible to protect half of an SWNT from oxygen exposure, while exposing the other half to oxygen. This results in a single SWNT that acts as a NOT logic gate with both p and n-type FETs within the same molecule.

Single-walled nanotubes are still very expensive to produce, around $1500 per gram as of 2000, 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.^[5] Several suppliers offer as-produced arc discharge SWNTs for ~$50–100 per gram as of 2007.^[6][7]

[edit] Multi-walled

SEM image of carbon nanotubes bundles.

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, e.g. a (0,8) single-walled nanotube (SWNT) within a larger (0,10) single-walled nanotube. In the Parchment model, a single sheet of graphite is rolled in around itself, resembling a scroll of parchment or a rolled newspaper. The interlayer distance in multi-walled nanotubes is close to the distance between graphene layers in graphite, approximately 3.3 Å (330 pm).

The special place of double-walled carbon nanotubes (DWNT) must be emphasized here because their morphology and properties are similar to SWNT but their resistance to chemicals is significantly improved. This is especially important when functionalization is required (this means grafting of chemical functions at the surface of the nanotubes) to add new properties to the CNT. In the case of SWNT, covalent functionalization will break some C=C double bonds, leaving "holes" in the structure on the nanotube and thus modifying both its mechanical and electrical properties. In the case of DWNT, only the outer wall is modified. DWNT synthesis on the gram-scale was first proposed in 2003^[8] by the CCVD technique, from the selective reduction of oxide solutions in methane and hydrogen.

[edit] Torus

A nanotorus is a theoretically described as 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.^[9] Properties such as magnetic moment, thermal stability etc. vary widely depending on radius of the torus and radius of the tube.^[9][10]

[edit] Nanobud

A stable nanobud structure

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 nanotube. This hybrid material has useful properties of both fullerenes and carbon nanotubes. In particular, they have been found to be exceptionally good field emitters. In composite materials, the attached fullerene molecules may function as molecular anchors preventing slipping of the nanotubes, thus improving the composite’s mechanical properties.

[edit] Properties

[edit] Strength

Carbon nanotubes are the strongest 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. In 2000, a multi-walled carbon nanotube was tested to have a tensile strength of 63 gigapascals (GPa). (This, for illustration, translates into the ability to endure weight of 6300 kg on a cable with cross-section of 1 mm².) Since carbon nanotubes have a low density for a solid of 1.3-1.4 g·cm⁻³,^[5] its specific strength of up to 48,000 kN·m·kg⁻¹ is the best of known materials, compared to high-carbon steel's 154 kN·m·kg⁻¹.

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

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, torsional or bending stress.

^EExperimental observation

^TTheoretical prediction

The above discussion referred to axial properties of the nanotube, whereas simple geometrical considerations suggest that carbon nanotubes should be much softer in the radial direction than along the tube axis. Indeed, TEM observation of radial elasticity suggested that even the van der Waals forces can deform two adjacent nanotubes^[18]. Nanoindentation experiments, performed by several groups on multiwalled carbon nanotubes, ^[19][20] indicated Young's modulus of the order of several GPa confirming that CNTs are indeed rather soft in the radial direction.

[edit] Kinetic

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. 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 motor^[21]. Future applications such as a gigahertz mechanical oscillator are also envisaged.

[edit] 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 n = m, the nanotube is metallic; if n − m is a multiple of 3, then the nanotube is semiconducting with a very small band gap, otherwise the nanotube is a moderate 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 carry an electrical current density of 4×10⁹ A/cm² which is more than 1,000 times greater than metals such as copper^[22].

[edit] 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. It is predicted that carbon nanotubes will be able to transmit up to 6000 watts per meter per Kelvin at room temperature; compare this to copper, a metal well-known for its good thermal conductivity, which transmits 385 watts per meter per K. The temperature stability of carbon nanotubes is estimated to be up to 2800^oC in vacuum and about 750^oC in air.^[23]

[edit] Defects

As with any material, the existence of a crystallographic defect 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%. Another form of carbon nanotube defect is the Stone Wales defect, which creates a pentagon and heptagon pair by rearrangement of the bonds. Because of the very small structure of CNTs, the tensile strength of the tube is dependent on its weakest segment in a similar manner to a chain, where the strength of the weakest link becomes the maximum strength of the chain.

Crystallographic defects also affect the tube's electrical properties. A common result is lowered conductivity through the defective region of the tube. A defect in armchair-type tubes (which can conduct electricity) can cause the surrounding region to become semiconducting, and single monoatomic vacancies induce magnetic properties^[24].

Crystallographic defects strongly affect the tube's thermal properties. 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. Phonon transport simulations indicate that substitutional defects such as nitrogen or boron will primarily lead to scattering of high-frequency optical phonons. However, larger-scale defects such as Stone Wales defects cause phonon scattering over a wide range of frequencies, leading to a greater reduction in thermal conductivity^[25].

[edit] One-dimensional transport

Due to their nanoscale dimensions, electron transport in carbon nanotubes will take place through quantum effects and will only propagate along the axis of the tube. Because of this special transport property, carbon nanotubes are frequently referred to as “one-dimensional” in scientific articles.

[edit] Toxicity

Determining the toxicity of carbon nanotubes has been one of the most pressing questions in nanotechnology. Unfortunately such research has only just begun and the data is still fragmentary and subject to criticism. Preliminary results highlight the difficulties in evaluating the toxicity of this heterogeneous material. Parameters such as structure, size distribution, surface area, surface chemistry, surface charge, and agglomeration state as well as purity of the samples, have considerable impact on the reactivity of carbon nanotubes. However, available data clearly show that, under some conditions, nanotubes can cross membrane barriers, which suggests that if raw materials reach the organs they can induce harmful effects such as inflammatory and fibrotic reactions.^[26]

A study led by Alexandra Porter from the University of Cambridge shows that CNTs can enter human cells and accumulate in the cytoplasm, causing cell death.^[27]

Results of rodent studies collectively show that regardless of the process by which CNTs were synthesized and the types and amounts of metals they contained, CNTs were capable of producing inflammation, epithelioid granulomas (microscopic nodules), fibrosis, and biochemical/toxicological changes in the lungs.^[28] Comparative toxicity studies in which mice were given equal weights of test materials showed that SWCNTs were more toxic than quartz, which is considered a serious occupational health hazard when chronically inhaled. As a control, ultrafine carbon black was shown to produce minimal lung responses.^[29]

The needle-like fiber shape of CNTs, similar to asbestos fibers, raises fears that widespread use of carbon nanotubes may lead to mesothelioma, cancer of the lining of the lungs often caused by exposure to asbestos. A recently-published pilot study^[30] supports this prediction. Scientists exposed the mesothelial lining of the body cavity of mice, as a surrogate for the mesothelial lining of the chest cavity, to long multiwalled carbon nanotubes and observed asbestos-like, length-dependent, pathogenic behavior which included inflammation and formation of lesions known as granulomas. Authors of the study conclude:

"This is of considerable importance, because research and business communities continue to invest heavily in carbon nanotubes for a wide range of products under the assumption that they are no more hazardous than graphite. Our results suggest the need for further research and great caution before introducing such products into the market if long-term harm is to be avoided."^[31]

According to co-author Dr. Andrew Maynard:

"This study is exactly the kind of strategic, highly focused research needed to ensure the safe and responsible development of nanotechnology. It looks at a specific nanoscale material expected to have widespread commercial applications and asks specific questions about a specific health hazard. Even though scientists have been raising concerns about the safety of long, thin carbon nanotubes for over a decade, none of the research needs in the current U.S. federal nanotechnology environment, health and safety risk research strategy address this question."^[32]Video commentary

Although further research is required, results presented today clearly demonstrate that, under certain conditions, especially those involving chronic exposure, carbon nanotubes can pose a serious risk to human health.^{[26][27][29][31]}

[edit] 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). Most of these processes take place in vacuum or with process gases. CVD growth of CNTs can occur 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.

[edit] Arc discharge

Nanotubes were observed in 1991 in the carbon soot of graphite electrodes during an arc discharge, by using a current of 100 amps, that was intended to produce fullerenes.^[33] However the first macroscopic production of carbon nanotubes was made in 1992 by two researchers at NEC's Fundamental Research Laboratory.^[34] The method used was the same as in 1991. During this process, the carbon contained in the negative electrode sublimates because of the high discharge temperatures. Because nanotubes were initially discovered using this technique, it has been the most widely-used method of nanotube synthesis.

The yield for this method is up to 30 percent by weight and it produces both single- and multi-walled nanotubes with lengths of up to 50 micrometers.^[5]

[edit] 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.

This process was developed by Dr. Richard Smalley and co-workers at Rice University, who at the time of the discovery of carbon nanotubes, were blasting metals with a laser to produce various metal molecules. When they heard of the existence of nanotubes they replaced the metals with graphite to create multi-walled carbon nanotubes.^[35] Later that year the team used a composite of graphite and metal catalyst particles (the best yield was from a cobalt and nickel mixture) to synthesize single-walled carbon nanotubes.^[36]

The laser ablation method yields around 70% and produces primarily single-walled carbon nanotubes with a controllable diameter determined by the reaction temperature. However, it is more expensive than either arc discharge or chemical vapor deposition.^[5]

[edit] Chemical vapor deposition (CVD)

Nanotubes being grown by plasma enhanced chemical vapor deposition

The catalytic vapor phase deposition of carbon was first reported in 1959,^[37] but it was not until 1993^[38] that carbon nanotubes were formed by this process. In 2007, researchers at the University of Cincinnati (UC) developed a process to grow aligned carbon nanotube arrays of 18 mm length on a FirstNano ET3000 carbon nanotube growth system.^[39]

During CVD, a substrate is prepared with a layer of metal catalyst particles, most commonly nickel, cobalt^[40], iron, or a combination^[41]. The metal nanoparticles can also be produced by other ways, including reduction of oxides or oxides solid solutions. 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 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. This mechanism is still being studied. The catalyst particles can stay at the tips of the growing nanotube during the growth process, or remain at the nanotube base, depending on the adhesion between the catalyst particle and the substrate.

CVD is a common method for the commercial production of carbon nanotubes. For this purpose, the metal nanoparticles are mixed with a catalyst support such as MgO or Al₂O₃ to increase the surface area for higher yield of the catalytic reaction of the carbon feedstock with the metal particles. One issue in this synthesis route is the removal of the catalyst support via an acid treatment, which sometimes could destroy the original structure of the carbon nanotubes. However, alternative catalyst supports that are soluble in water have proven effective for nanotube growth.^[42]

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 field.^[43] By adjusting the geometry of the reactor it is possible to synthesize vertically aligned carbon nanotubes^[44] (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 often randomly oriented. Under certain reaction conditions, even in the absence of a plasma, closely spaced nanotubes will maintain a vertical growth direction resulting in a dense array of tubes resembling a carpet or forest.

Of the various means for nanotube synthesis, CVD shows the most promise for industrial-scale deposition, because of its price/unit ratio, and because 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. In 2007, a team from Meijo University demonstrated a high-efficiency CVD technique for growing carbon nanotubes from camphor.^[45] Researchers at Rice University, until recently led by the late Dr. Richard Smalley, have concentrated upon finding methods to produce large, pure amounts of particular types of nanotubes. Their approach grows long fibers from many small seeds cut from a single nanotube; all of the resulting fibers were found to be of the same diameter as the original nanotube and are expected to be of the same type as the original nanotube. Further characterization of the resulting nanotubes and improvements in yield and length of grown tubes are needed.