Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, electronics, optics and other fields of materials science and technology. Owing to the material's exceptional strength and stiffness, nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1, significantly larger than for any other material.
In addition, owing to their extraordinary thermal conductivity, mechanical, and electrical properties, carbon nanotubes find applications as additives to various structural materials. For instance, nanotubes form a tiny portion of the material(s) in some (primarily carbon fiber) baseball bats, golf clubs, car parts or damascus steel.
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 involves entirely sp2-hybrid carbon atoms. These bonds, which are similar to those of graphite and stronger than those found in alkanes and diamond (which employ sp3-hybrid carbon atoms), provide nanotubes with their unique strength.
There is no consensus on some terms describing carbon nanotubes in scientific literature: both "-wall" and "-walled" are being used in combination with "single", "double", "triple" or "multi", and the letter C is often omitted in the abbreviation; for example, multi-walled carbon nanotube (MWNT).
where a = 0.246 nm.
SWNTs are an important variety of carbon nanotube because most of their properties change significantly with the (n,m) values, and this dependence is non-monotonic (see Kataura plot). In particular, their band gap can vary from zero to about 2 eV and their electrical conductivity can show metallic or semiconducting behavior. Single-walled nanotubes are likely candidates for miniaturizing electronics. The most basic building block of these systems is the electric wire, and SWNTs with diameters of an order of a nanometer can be excellent conductors. One useful application of SWNTs is in the development of the first intermolecular field-effect transistors (FET). The first intermolecular logic gate using SWCNT FETs was made in 2001. A logic gate requires 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 expose half of an SWNT to oxygen and protect the other half from it. The resulting SWNT acts as a not logic gate with both p and n-type FETs in the same molecule.
Prices for single-walled nanotubes declined from around $1500 per gram as of 2000 to retail prices of around $50 per gram of as-produced 40–60% by weight SWNTs as of March 2010. As of 2016 the retail price of as-produced 75% by weight SWNTs were $2 per gram, cheap enough for widespread use. SWNTs are forecast to make a large impact in electronics applications by 2020 according to The Global Market for Carbon Nanotubes report.
Multi-walled nanotubes (MWNTs) consist of multiple rolled layers (concentric tubes) of graphene. There are two models that 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 (0,17) 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 3.4 Å. The Russian Doll structure is observed more commonly. Its individual shells can be described as SWNTs, which can be metallic or semiconducting. Because of statistical probability and restrictions on the relative diameters of the individual tubes, one of the shells, and thus the whole MWNT, is usually a zero-gap metal.
Double-walled carbon nanotubes (DWNTs) form a special class of nanotubes because their morphology and properties are similar to those of SWNTs but they are more resistant to chemicals. This is especially important when it is necessary to graft chemical functions to the surface of the nanotubes (functionalization) to add properties to the CNT. Covalent functionalization of SWNTs 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 DWNTs, only the outer wall is modified. DWNT synthesis on the gram-scale was first proposed in 2003 by the CCVD technique, from the selective reduction of oxide solutions in methane and hydrogen.
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 nanomechanical devices. Retraction force that occurs to telescopic motion caused by the Lennard-Jones interaction between shells and its value is about 1.5 nN.
Junctions between 2 or more nanotubes have been widely discussed theoretically. Such junctions are quite frequently observed in samples prepared by arc discharge as well as by chemical vapor deposition. The electronic properties of such junctions were first considered theoretically by Lambin et al., who pointed out that a connection between metallic tube and a semiconducting one would represent a nanoscale heterojunction. Such a junction could therefore form a component of a nanotube-based electronic circuit. The image on the right shows a junction between two multiwalled nanotubes. Junctions between nanotubes and graphene have been considered theoretically, but not widely studied experimentally. Such junctions form the basis of pillared graphene, in which parallel graphene sheets are separated by short nanotubes. Pillared graphene represents a class of three-dimensional carbon nanotube architectures.
Recently, several studies have highlighted the prospect of using carbon nanotubes as building blocks to fabricate three-dimensional macroscopic (>100 nm in all three dimensions) all-carbon devices. Lalwani et al. have reported a novel radical initiated thermal crosslinking method to fabricate macroscopic, free-standing, porous, all-carbon scaffolds using single- and multi-walled carbon nanotubes as building blocks. These scaffolds possess macro-, micro-, and nano- structured pores and the porosity can be tailored for specific applications. These 3D all-carbon scaffolds/architectures may be used for the fabrication of the next generation of energy storage, supercapacitors, field emission transistors, high-performance catalysis, photovoltaics, and biomedical devices and implants.
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.
A carbon peapod is a novel hybrid carbon material which traps fullerene inside a carbon nanotube. It can possess interesting magnetic properties with heating and irradiation. It can also be applied as an oscillator during theoretical investigations and predictions.
In theory, a nanotorus is a 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.
Graphenated carbon nanotubes are a relatively new hybrid that combines graphitic foliates grown along the sidewalls of multiwalled or bamboo style CNTs. The foliate density can vary as a function of deposition conditions (e.g. temperature and time) with their structure ranging from few layers of graphene (< 10) to thicker, more graphite-like. The fundamental advantage of an integrated graphene-CNT structure is the high surface area three-dimensional framework of the CNTs coupled with the high edge density of graphene. Depositing a high density of graphene foliates along the length of aligned CNTs can significantly increase the total charge capacity per unit of nominal area as compared to other carbon nanostructures.
Cup-stacked carbon nanotubes (CSCNTs) differ from other quasi-1D carbon structures, which normally behave as quasi-metallic conductors of electrons. CSCNTs exhibit semiconducting behaviors due to the stacking microstructure of graphene layers.
The observation of the longest carbon nanotubes grown so far are over 1/2 m (550 mm long) was reported in 2013. These nanotubes were grown on silicon substrates using an improved chemical vapor deposition (CVD) method and represent electrically uniform arrays of single-walled carbon nanotubes.
The thinnest carbon nanotube is the armchair (2,2) CNT with a diameter of 0.3 nm. This nanotube was grown inside a multi-walled carbon nanotube. Assigning of carbon nanotube type was done by a 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 0.43 nm in diameter. Researchers suggested that it can be either (5,1) or (4,2) SWCNT, but the exact type of carbon nanotube remains questionable. (3,3), (4,3) and (5,1) carbon nanotubes (all about 0.4 nm in diameter) were unambiguously identified using aberration-corrected high-resolution transmission electron microscopy inside double-walled CNTs.
The highest density of CNTs was achieved in 2013, grown on a conductive titanium-coated copper surface that was coated with co-catalysts cobalt and molybdenum at lower than typical temperatures of 450 °C. The tubes averaged a height of 380 nm and a mass density of 1.6 g cm−3. The material showed ohmic conductivity (lowest resistance ∼22 kΩ).
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 (9,100,000 psi). (For illustration, this translates into the ability to endure tension of a weight equivalent to 6,422 kilograms-force (62,980 N; 14,160 lbf) on a cable with cross-section of 1 square millimetre (0.0016 sq in).) Further studies, such as one conducted in 2008, revealed that individual CNT shells have strengths of up to ≈100 gigapascals (15,000,000 psi), which is in agreement with quantum/atomistic models. Since carbon nanotubes have a low density for a solid of 1.3 to 1.4 g/cm3, 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.
Although the strength of individual CNT shells is extremely high, weak shear interactions between adjacent shells and tubes lead to significant reduction in the effective strength of multi-walled carbon nanotubes and carbon nanotube bundles down to only a few GPa. This limitation has been recently addressed by applying high-energy electron irradiation, which crosslinks inner shells and tubes, and effectively increases the strength of these materials to ≈60 GPa for multi-walled carbon nanotubes and ≈17 GPa for double-walled carbon nanotube bundles. 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.
On the other hand, there was evidence that in the radial direction they are rather soft. The first transmission electron microscope observation of radial elasticity suggested that even the van der Waals forces can deform two adjacent nanotubes. Later, nanoindentations with atomic force microscope were performed by several groups to quantitatively measure radial elasticity of multiwalled carbon nanotubes and tapping/contact mode atomic force microscopy was also performed on single-walled carbon nanotubes. Young's modulus of on the order of several GPa showed that CNTs are in fact very soft in the radial direction.
Unlike graphene, which is a two-dimensional semimetal, carbon nanotubes are either metallic or semiconducting along the tubular axis. For a given (n,m) nanotube, if n = m, the nanotube is metallic; if n − m is a multiple of 3 and n ≠ m and nm ≠ 0, then the nanotube is quasi-metallic with a very small band gap, otherwise the nanotube is a moderate semiconductor.  Thus all armchair (n = m) nanotubes are metallic, and nanotubes (6,4), (9,1), etc. are semiconducting. Carbon nanotubes are not semimetallic because the degenerate point (that point where the π [bonding] band meets the π* [anti-bonding] band, at which the energy goes to zero) is slightly shifted away from the K point in the Brillouin zone due to the curvature of the tube surface, causing hybridization between the σ* and π* anti-bonding bands, modifying the band dispersion.
The rule regarding metallic versus semiconductor behavior has exceptions, because curvature effects in small diameter tubes can strongly influence electrical properties. Thus, a (5,0) SWCNT that should be semiconducting in fact is metallic according to the calculations. Likewise, zigzag and chiral SWCNTs with small diameters that should be metallic have a finite gap (armchair nanotubes remain metallic). In theory, metallic nanotubes can carry an electric current density of 4 × 109 A/cm2, which is more than 1,000 times greater than those of metals such as copper, where for copper interconnects current densities are limited by electromigration. Carbon nanotubes are thus being explored as interconnects, conductivity enhancing components in composite materials and many groups are attempting to commercialize highly conducting electrical wire assembled from individual carbon nanotubes. There are significant challenges to be overcome, however, such as undesired current saturation under voltage, the much more resistive nanotube-to-nanotube junctions and impurities, all of which lower the electrical conductivity of the macroscopic nanotube wires by orders of magnitude, as compared to the conductivity of the individual nanotubes.
Because of its nanoscale cross-section, electrons propagate only along the tube's axis. As a result, carbon nanotubes are frequently referred to as one-dimensional conductors. The maximum electrical conductance of a single-walled carbon nanotube is 2G0, where G0 = 2e2/h is the conductance of a single ballistic quantum channel.
Due to the role of the π-electron system in determining the electronic properties of graphene, doping in carbon nanotubes differs from that of bulk crystalline semiconductors from the same group of the periodic table (e.g. silicon). Graphitic substitution of carbon atoms in the nanotube wall by boron or nitrogen dopants leads to p-type and n-type behavior, respectively, as would be expected in silicon. However, some non-substitutional (intercalated or adsorbed) dopants introduced into a carbon nanotube, such as alkali metals as well as electron-rich metallocenes, result in n-type conduction because they donate electrons to the π-electron system of the nanotube. By contrast, π-electron acceptors such as FeCl3 or electron-deficient metallocenes function as p-type dopants since they draw π-electrons away from the top of the valence band.
Carbon nanotubes have useful absorption, photoluminescence (fluorescence), and Raman spectroscopy properties. Spectroscopic methods offer the possibility of quick and non-destructive characterization of relatively large amounts of carbon nanotubes. There is a strong demand for such characterization from the industrial point of view: numerous parameters of the nanotube synthesis can be changed, intentionally or unintentionally, to alter the nanotube quality. As shown below, optical absorption, photoluminescence and Raman spectroscopies allow quick and reliable characterization of this "nanotube quality" in terms of non-tubular carbon content, structure (chirality) of the produced nanotubes, and structural defects. Those features determine nearly any other properties such as optical, mechanical, and electrical properties.
Carbon nanotubes are unique "one-dimensional systems" which can be envisioned as rolled single sheets of graphite (or more precisely graphene). This rolling can be done at different angles and curvatures resulting in different nanotube properties. The diameter typically varies in the range 0.4–40 nm (i.e. "only" ~100 times), but the length can vary ~10,000 times, reaching 55.5 cm. The nanotube aspect ratio, or the length-to-diameter ratio, can be as high as 132,000,000:1, which is unequalled by any other material. Consequently, all the properties of the carbon nanotubes relative to those of typical semiconductors are extremely anisotropic (directionally dependent) and tunable.
Whereas mechanical, electrical and electrochemical (supercapacitor) properties of the carbon nanotubes are well established and have immediate applications, the practical use of optical properties is yet unclear. The aforementioned tunability of properties is potentially useful in optics and photonics. In particular, light-emitting diodes (LEDs) and photo-detectors based on a single nanotube have been produced in the lab. Their unique feature is not the efficiency, which is yet relatively low, but the narrow selectivity in the wavelength of emission and detection of light and the possibility of its fine tuning through the nanotube structure. In addition, bolometer and optoelectronic memory devices have been realised on ensembles of single-walled carbon nanotubes.
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 monatomic vacancies induce magnetic properties.
All nanotubes are expected to be very good thermal conductors along the tube, exhibiting a property known as "ballistic conduction", but good insulators lateral to the tube axis. Measurements show that an individual SWNT has a room-temperature thermal conductivity along its axis of about 3500 W·m−1·K−1; compare this to copper, a metal well known for its good thermal conductivity, which transmits 385 W·m−1·K−1. An individual SWNT has a room-temperature thermal conductivity across its axis (in the radial direction) of about 1.52 W·m−1·K−1, which is about as thermally conductive as soil. Macroscopic assemblies of nanotubes such as films or fibres have reached up to 1500 W·m−1·K−1 so far. The temperature stability of carbon nanotubes is estimated to be up to 2800 °C in vacuum and about 750 °C in air.
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.
Techniques have been developed to produce nanotubes in sizable quantities, including arc discharge, laser ablation, chemical vapor deposition (CVD) and high-pressure carbon monoxide disproportionation (HiPCO). Among these arc discharge, laser ablation, chemical vapor deposition (CVD) are batch by batch process and HiPCO is gas phase continuous process. Most of these processes take place in a vacuum or with process gases. The CVD growth method is popular, as it yields high quantity and has a degree of control over diameter, length and morphology. Using particulate catalysts, large quantities of nanotubes can be synthesized by these methods; But achieving the repeatability becomes a major problem with CVD growth. The HiPCO process advances in catalysis and continuous growth are making CNTs more commercially viable. In India, the company called NoPo Nanotechnologies is producing high purity single walled carbon nanotubes by NoPo HiPCO Process. It is also commercially available at lower cost. HiPCO process helps in producing high purity single walled carbon nanotubes in higher quantity. NoPo HiPCO reactor operates at higher temperature ~1000 °C under high pressure ~20-100 bar. It uses carbon monoxide as the carbon source and Nickel/ iron penta carbonyl as catalyst. These catalyst acts as the nucleation site for the nanotubes to grow.
Vertically aligned carbon nanotube arrays are also grown by thermal chemical vapor deposition. A substrate (quartz, silicon, stainless steel, etc.) is coated with a catalytic metal (Fe, Co, Ni) layer. Typically that layer is iron, and is deposited via sputtering to a thickness of 1–5 nm. A 10–50 nm underlayer of alumina is often also put down on the substrate first. This imparts controllable wetting and good interfacial properties. When the substrate is heated to the growth temperature (~700 °C), the continuous iron film breaks up into small islands… each island then nucleates a carbon nanotube. The sputtered thickness controls the island size, and this in turn determines the nanotube diameter. Thinner iron layers drive down the diameter of the islands, and they drive down the diameter of the nanotubes grown. The amount of time that the metal island can sit at the growth temperature is limited, as they are mobile, and can merge into larger (but fewer) islands. Annealing at the growth temperature reduces the site density (number of CNT/mm2) while increasing the catalyst diameter.
The as-prepared carbon nanotubes always have impurities such as other forms of carbon (amorphous carbon, fullerene, etc.) and non-carbonaceous impurities (metal pes used for catalyst). These impurities need to be removed to make use of the carbon nanotubes in applications.
For single-wall carbon nanotubes, ISO/TS 10868 describes a measurement method for the diameter, purity, and fraction of metallic nanotubes through optical absorption spectroscopy, while ISO/TS 10797 and ISO/TS 10798 establish methods to characterize the morphology and elemental composition of single-wall carbon nanotubes, using transmission electron microscopy and scanning electron microscopy respectively, coupled with energy dispersive X-ray spectrometry analysis.
NIST SRM 2483 is a soot of single-wall carbon nanotubes used as a reference material for elemental analysis, and was characterized using thermogravimetric analysis, prompt gamma activation analysis, induced neutron activation analysis, inductively coupled plasma mass spectroscopy, resonant Raman scattering, UV-visible-near infrared fluorescence spectroscopy and absorption spectroscopy, scanning electron microscopy, and transmission electron microscopy. The Canadian National Research Council also offers a certified reference material SWCNT-1 for elemental analysis using neutron activation analysis and inductively coupled plasma mass spectroscopy. NIST RM 8281 is a mixture of three lengths of single-wall carbon nanotube.
For multiwall carbon nanotubes, ISO/TR 10929 identifies the basic properties and the content of impurities, while ISO/TS 11888 describes morphology using scanning electron microscopy, transmission electron microscopy, viscometry, and light scattering analysis. ISO/TS 10798 is also valid for multiwall carbon nanotubes.
Carbon nanotubes can be functionalized to attain desired properties that can be used in a wide variety of applications. The two main methods of carbon nanotube functionalization are covalent and non-covalent modifications. Because of their hydrophobic nature, carbon nanotubes tend to agglomerate hindering their dispersion in solvents or viscous polymer melts. The resulting nanotube bundles or aggregates reduce the mechanical performance of the final composite. The surface of the carbon nanotubes can be modified to reduce the hydrophobicity and improve interfacial adhesion to a bulk polymer through chemical attachment.
Current use and application of nanotubes has mostly been limited to the use of bulk nanotubes, which is a mass of rather unorganized fragments of nanotubes. 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. Bulk carbon nanotubes have already been used as composite fibers in polymers to improve the mechanical, thermal and electrical properties of the bulk product.
Other current applications include:
Current research for modern applications include:
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 of an individual multi-walled carbon nanotube has been tested to be 63 GPa. Carbon nanotubes were found in Damascus steel from the 17th century, possibly helping to account for the legendary strength of the swords made of it. Recently, several studies have highlighted the prospect of using carbon nanotubes as building blocks to fabricate three-dimensional macroscopic (>1mm in all three dimensions) all-carbon devices. Lalwani et al. have reported a novel radical initiated thermal crosslinking method to fabricated macroscopic, free-standing, porous, all-carbon scaffolds using single- and multi-walled carbon nanotubes as building blocks. These scaffolds possess macro-, micro-, and nano- structured pores and the porosity can be tailored for specific applications. These 3D all-carbon scaffolds/architectures may be used for the fabrication of the next generation of energy storage, supercapacitors, field emission transistors, high-performance catalysis, photovoltaics, and biomedical devices and implants.
Large quantities of pure CNTs can be made into a fiber (a.k.a. filament) by wet spinning. The fiber is either directly spun from the synthesis pot or spun from pre-made dissolved CNTs. Individual fibers can be turned into a yarn. Apart from its strength and flexibility, the main advantage is making an electrically conducting yarn. The electronic properties of individual CNT fibers (i.e. bundle of individual CNT) is governed by the two-dimensional structure of CNTs.. At 300 K, CNT fibers have a resistivity one order of magnitude higher than the best electrical conductors.
CNT-based yarns are suitable for applications in energy and electrochemical water treatment when coated with an ion-exchange membrane. Also, CNT-based yarns could replace copper as a winding material. Pyrhönen et al. (2015) have built a motor using CNT winding.
The National Institute for Occupational Safety and Health (NIOSH) is the leading United States federal agency conducting research and providing guidance on the occupational safety and health implications and applications of nanotechnology. Early scientific studies have indicated that some of these nanoscale particles may pose a greater health risk than the larger bulk form of these materials. In 2013, NIOSH published a Current Intelligence Bulletin detailing the potential hazards and recommended exposure limit for carbon nanotubes and fibers.
As of October 2016, single wall carbon nanotubes have been registered through the European Union's Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) regulations, based on evaluation of the potentially hazardous properties of SWCNT. Based on this registration, SWCNT commercialization is allowed in the EU up to 10 metric tons. Currently, the type of SWCNT registered through REACH is limited to the specific type of single wall carbon nanotubes manufactured by OCSiAl, which submitted the application.
The true identity of the discoverers of carbon nanotubes is a subject of some controversy. A 2006 editorial written by Marc Monthioux and Vladimir Kuznetsov in the journal Carbon described the interesting and often-misstated origin of the carbon nanotube. A large percentage of academic and popular literature attributes the discovery of hollow, nanometer-size tubes composed of graphitic carbon to Sumio Iijima of NEC in 1991. He published a paper describing his discovery which initiated a flurry of excitement and could be credited by inspiring the many scientists now studying applications of carbon nanotubes. Though Iijima has been given much of the credit for discovering carbon nanotubes, it turns out that the timeline of carbon nanotubes goes back much further than 1991.
In 1952, L. V. Radushkevich and V. M. Lukyanovich published clear images of 50 nanometer diameter tubes made of carbon in the Soviet Journal of Physical Chemistry. This discovery was largely unnoticed, as the article was published in Russian, and Western scientists' access to Soviet press was limited during the Cold War. Monthioux and Kuznetsov mentioned in their Carbon editorial:
The fact is, Radushkevich and Lukyanovich [..] should be credited for the discovery that carbon filaments could be hollow and have a nanometer- size diameter, that is to say for the discovery of carbon nanotubes.
In 1976, Morinobu Endo of CNRS observed hollow tubes of rolled up graphite sheets synthesised by a chemical vapour-growth technique. The first specimens observed would later come to be known as single-walled carbon nanotubes (SWNTs). Endo, in his early review of vapor-phase-grown carbon fibers (VPCF), also reminded us that he had observed a hollow tube, linearly extended with parallel carbon layer faces near the fiber core. This appears to be the observation of multi-walled carbon nanotubes at the center of the fiber. The mass-produced MWCNTs today are strongly related to the VPGCF developed by Endo. In fact, they call it the “Endo-process”, out of respect for his early work and patents.
In 1979, John Abrahamson presented evidence of carbon nanotubes at the 14th Biennial Conference of Carbon at Pennsylvania State University. The conference paper described carbon nanotubes as carbon fibers that were produced on carbon anodes during arc discharge. A characterization of these fibers was given as well as hypotheses for their growth in a nitrogen atmosphere at low pressures.
In 1981, a group of Soviet scientists published the results of chemical and structural characterization of carbon nanoparticles produced by a thermocatalytical disproportionation of carbon monoxide. Using TEM images and XRD patterns, the authors suggested that their “carbon multi-layer tubular crystals” were formed by rolling graphene layers into cylinders. They speculated that by rolling graphene layers into a cylinder, many different arrangements of graphene hexagonal nets are possible. They suggested two possibilities of such arrangements: circular arrangement (armchair nanotube) and a spiral, helical arrangement (chiral tube).
In 1987, Howard G. Tennent of Hyperion Catalysis was issued a U.S. patent for the production of "cylindrical discrete carbon fibrils" with a "constant diameter between about 3.5 and about 70 nanometers..., length 102 times the diameter, and an outer region of multiple essentially continuous layers of ordered carbon atoms and a distinct inner core...."
Iijima's discovery of multi-walled carbon nanotubes in the insoluble material of arc-burned graphite rods in 1991 and Mintmire, Dunlap, and White's independent prediction that if single-walled carbon nanotubes could be made, then they would exhibit remarkable conducting properties helped create the initial buzz that is now associated with carbon nanotubes. Nanotube research accelerated greatly following the independent discoveries by Bethune at IBM and Iijima at NEC of single-walled carbon nanotubes and methods to specifically produce them by adding transition-metal catalysts to the carbon in an arc discharge. The arc discharge technique was well-known to produce the famed Buckminster fullerene on a preparative scale, and these results appeared to extend the run of accidental discoveries relating to fullerenes. The discovery of nanotubes remains a contentious issue. Many believe that Iijima's report in 1991 is of particular importance because it brought carbon nanotubes into the awareness of the scientific community as a whole.
This article incorporates public domain text from National Institute of Environmental Health Sciences (NIEHS) as quoted.
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