Editing Carbon nanotube (section)

== History ==
{{See also|Timeline of carbon nanotubes|Fullerene#History}}
The true identity of the discoverers of carbon nanotubes is a subject of some controversy.<ref name="carbon1">{{cite thesis|title=Carbon Nanotubes as Platforms for Biosensors with Electrochemical and Electronic Transduction| vauthors = Pacios Pujadó M |publisher=Springer Heidelberg|year=2012|pages=xx, 208|doi=10.1007/978-3-642-31421-6|isbn=978-3-642-31421-6|series=Springer Theses|hdl=10803/84001|s2cid=199491391 |url=http://ddd.uab.cat/record/101063|hdl-access=free}}</ref> A 2006 editorial written by Marc Monthioux and Vladimir Kuznetsov in the journal ''Carbon'' described the origin of the carbon nanotube.<ref name="carbon">{{cite journal |vauthors = Monthioux M, Kuznetsov VL |title=Who should be given the credit for the discovery of carbon nanotubes? |journal=Carbon |date=August 2006 |volume=44 |issue=9 |pages=1621–1623 |doi=10.1016/j.carbon.2006.03.019 |bibcode=2006Carbo..44.1621M |url=https://nanotube.msu.edu/HSS/2006/1/2006-1.pdf |archive-url=https://ghostarchive.org/archive/20221009/https://nanotube.msu.edu/HSS/2006/1/2006-1.pdf |archive-date=2022-10-09 |url-status=live }}</ref> 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 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.<ref name="carbon1" />

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''.<ref name="CVD" /> 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:<ref name="carbon" /> {{blockquote|text=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 [[Centre national de la recherche scientifique|CNRS]] observed hollow tubes of rolled up graphite sheets synthesised by a chemical vapour-growth technique.<ref name="endo1" /> The first specimens observed would later come to be known as single-walled carbon nanotubes (SWNTs).<ref name="carbon2">{{cite report|title=WTEC Panel Report on 'International Assessment of Research and Development of Carbon Nanotube Manufacturing and Applications' Final Report| vauthors = Eklund PC |publisher=World Technology Evaluation Center (WTEC)|year=2007|url=http://www.wtec.org/cnm/CNM_final_report.pdf|access-date=5 August 2015|archive-url=https://web.archive.org/web/20170311174000/http://www.wtec.org/cnm/CNM_final_report.pdf|archive-date=11 March 2017}}</ref> 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.<ref>{{cite journal | vauthors = Oberlin A, Endo M, Koyama T |title=Filamentous growth of carbon through benzene decomposition |journal=Journal of Crystal Growth |date=March 1976 |volume=32 |issue=3 |pages=335–349 |doi=10.1016/0022-0248(76)90115-9 |bibcode=1976JCrGr..32..335O |url=http://www.kroto.info/wp-content/uploads/2015/10/1.M.ENdoJCrystalGrowth1976.pdf |archive-url=https://ghostarchive.org/archive/20221009/http://www.kroto.info/wp-content/uploads/2015/10/1.M.ENdoJCrystalGrowth1976.pdf |archive-date=2022-10-09 |url-status=live }}</ref> This appears to be the observation of multi-walled carbon nanotubes at the center of the fiber.<ref name="carbon2" /> The mass-produced MWCNTs today are strongly related to the VPGCF developed by Endo.<ref name="carbon2" /> In fact, they call it the "Endo process", out of respect for his early work and patents.<ref name="carbon2" /><ref>{{cite patent | inventor = Koyama T, Endo MT | gdate = 1983 | title = Method for Manufacturing Carbon Fibers by a Vapor Phase Process | country = JP | number = 1982-58,966 }}</ref> 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.<ref>{{cite journal | vauthors = Abrahamson J, Wiles PG, Rhoades BL |title=Structure of carbon fibres found on carbon arc anodes |journal=Carbon |date=January 1999 |volume=37 |issue=11 |pages=1873–1874 |doi=10.1016/S0008-6223(99)00199-2 |bibcode=1999Carbo..37.1873A }}</ref>

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 [[X-ray scattering techniques|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).<ref>{{cite journal | author = Missing | title = Missing | journal = Izvestiya Akademii Nauk SSSR Metally | trans-journal = Proceedings of the Academy of Sciences of the USSR. Metals | language = ru | date = 1982 | volume = 3 | pages = 12–17 }} {{full citation needed|date=October 2021}}</ref>

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&nbsp;nanometers..., length 10<sup>2</sup> times the diameter, and an outer region of multiple essentially continuous layers of ordered carbon atoms and a distinct inner core...."<ref>{{Ref patent|country=US|number=4663230|title=Carbon fibrils, method for producing same and compositions containing same|gdate=1987-05-05|fdate=1984-12-06| inventor = Tennent HG }}</ref>

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;<ref name=Iijima1 /> and Mintmire, Dunlap, and White's independent prediction that if single-walled carbon nanotubes could be made, they would exhibit remarkable conducting properties.<ref name=mintmire1 /> Nanotube research accelerated greatly following the independent discoveries<ref name=Iijima2 /><ref name=Bethune /> 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.<ref name=Thess /> 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]],<ref name="Kratschmer-C60">{{cite journal| vauthors = Krätschmer W, Lamb LD, Fostiropoulos KH, Huffman DR |year=1990|title=Solid C60: a new form of carbon|journal=Nature|volume=347|pages=354–358|doi=10.1038/347354a0 |issue=6291|bibcode = 1990Natur.347..354K|s2cid=4359360}}</ref>{{failed verification|date=October 2024}} 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.<ref name="carbon1" /><ref name="carbon2" />

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.<ref>{{cite journal | vauthors = Kokarneswaran M, Selvaraj P, Ashokan T, Perumal S, Sellappan P, Murugan KD, Ramalingam S, Mohan N, Chandrasekaran V | title = Discovery of carbon nanotubes in sixth century BC potteries from Keeladi, India | journal = Scientific Reports | volume = 10 | issue = 1 | page = 19786 | date = November 2020 | pmid = 33188244 | pmc = 7666134 | doi = 10.1038/s41598-020-76720-z | bibcode = 2020NatSR..1019786K }}</ref>