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Carbon nanotube

Allotropes of carbon with a cylindrical nanostructure

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Through Allotropes of carbon, Electrical resistivity and conductivity and Semiconductor

  • Single-walled carbon nanotubes (SWCNTs) have diameters around 0.5–2.0 nanometres, about a 100,000th the width of a human hair. They can be idealised as cutouts from a two-dimensional graphene sheet rolled up to form a hollow cylinder.
  • Multi-walled carbon nanotubes (MWCNTs) consist of nested single-wall carbon nanotubes in a nested, tube-in-tube structure. Double- and triple-walled carbon nanotubes are special cases of MWCNT.

Carbon nanotubes can exhibit remarkable properties, such as exceptional tensile strength and thermal conductivity because of their nanostructure and strength of the bonds between carbon atoms. Some SWCNT structures exhibit high electrical conductivity while others are semiconductors. In addition, carbon nanotubes can be chemically modified. These properties are expected to be valuable in many areas of technology, such as electronics, optics, composite materials (replacing or complementing carbon fibres), nanotechnology (including nanomedicine), and other applications of materials science.

The predicted properties for SWCNTs were tantalising, but a path to synthesising them was lacking until 1993, when Iijima and Ichihashi at NEC, and Bethune and colleagues at IBM independently discovered that co-vaporising carbon and transition metals such as iron and cobalt could specifically catalyse SWCNT formation. These discoveries triggered research that succeeded in greatly increasing the efficiency of the catalytic production technique, and led to an explosion of work to characterise and find applications for SWCNTs.

History

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 origin of the carbon nanotube. A large percentage of academic and popular literature attributes the discovery of hollow, nanometre-size tubes composed of graphitic carbon to Sumio Iijima of NEC in 1991. His paper initiated a flurry of excitement and could be credited with inspiring the study of many 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-nanometre diameter tubes made of carbon in the Journal of Physical Chemistry of Russia. 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 nanometre-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. Mass-produced MWCNTs 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 thermocatalytic 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 via this rolling, many different arrangements of graphene hexagonal nets are possible. They suggested two such possible arrangements: a 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...."

Helping to create the initial excitement associated with carbon nanotubes were Iijima's 1991 discovery of multi-walled carbon nanotubes in the insoluble material of arc-burned graphite rods; and Mintmire, Dunlap, and White's independent prediction that if single-walled carbon nanotubes could be made, they would exhibit remarkable conducting properties. Nanotube research accelerated greatly following the independent discoveries by Iijima and Ichihashi at NEC and Bethune et al. at IBM of methods to specifically produce single-walled carbon nanotubes by adding transition-metal catalysts to the carbon in an arc discharge. Thess et al. refined this catalytic method by vaporizing the carbon/transition-metal combination in a high-temperature furnace, which greatly improved the yield and purity of the SWNTs and made them widely available for characterization and application experiments. The arc discharge technique, well known to produce the famed Buckminsterfullerene, thus played a role in the discoveries of both multi- and single-wall nanotubes, extending the run of serendipitous 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.

In 2020, during an archaeological excavation of Keezhadi in Tamil Nadu, India, ~2600-year-old pottery was discovered whose coatings appear to contain carbon nanotubes. The robust mechanical properties of the nanotubes are partially why the coatings have lasted for so many years, say the scientists.

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