Allotropes of carbon

dierently from its gem-grade counterpart. Industrial diamonds are valued mostly for their hardness and heat conductivity, making many of the gemological characteristics of diamond, including clarity and color, mostly irrelevant. This helps explain why 80% of mined diamonds
(equal to about 100 million carats or 20 tonnes annually)
are unsuitable for use as gemstones and known as bort,
are destined for industrial use. In addition to mined diamonds, synthetic diamonds found industrial applications
almost immediately after their invention in the 1950s;
another 400 million carats (80 tonnes) of synthetic diamonds are produced annually for industrial use which
is nearly four times the mass of natural diamonds mined
over the same period.
The dominant industrial use of diamond is in cutting,
drilling (drill bits), grinding (diamond edged cutters), and
polishing. Most uses of diamonds in these technologies do not require large diamonds; in fact, most diamonds that are gem-quality can nd an industrial use.
Eight allotropes of carbon: a) diamond, b) graphite, c) Diamonds are embedded in drill tips or saw blades, or
lonsdaleite, d) C60 buckminsterfullerene, e) C540 , Fullerite f) ground into a powder for use in grinding and polishing
C70 , g) amorphous carbon, and h) single-walled carbon nan- applications (due to its extraordinary hardness). Specialized applications include use in laboratories as containotube.
ment for high pressure experiments (see diamond anvil),
high-performance
bearings, and limited use in specialized
Carbon is capable of forming many allotropes due to its
windows.
valency. Well-known forms of carbon include diamond
and graphite. In recent decades many more allotropes With the continuing advances being made in the producand forms of carbon have been discovered and researched tion of synthetic diamond, future applications are beginincluding ball shapes such as buckminsterfullerene and ning to become feasible. Garnering much excitement is
sheets such as graphene. Larger scale structures of car- the possible use of diamond as a semiconductor suitable
bon include nanotubes, nanobuds and nanoribbons. Other to build microchips from, or the use of diamond as a heat
unusual forms of carbon exist at very high temperature or sink in electronics. Signicant research eorts in Japan,
extreme pressures.
Europe, and the United States are under way to capitalize on the potential oered by diamonds unique material
properties, combined with increased quality and quantity
of supply starting to become available from synthetic di1 Diamond
amond manufacturers.
Each carbon atom in a diamond is covalently bonded to
four other carbons in a tetrahedron. These tetrahedrons
together form a 3-dimensional network of six-membered
Diamond is a well known allotrope of carbon. The hard- carbon rings (similar to cyclohexane), in the chair conforness and high dispersion of light of diamond make it use- mation, allowing for zero bond angle strain. This stable
ful for both industrial applications and jewelry. Diamond network of covalent bonds and hexagonal rings, is the reais the hardest known natural mineral. This makes it an son that diamond is so strong.
excellent abrasive and makes it hold polish and luster extremely well. No known naturally occurring substance
can cut (or even scratch) a diamond, except another diamond.
Main article: Diamond

The market for industrial-grade diamonds operates much

1

Graphite

AMORPHOUS CARBON

planes, brittleness and inconsistent mechanical properties.

In its pure glassy (isotropic) synthetic forms, pyrolytic

graphite and carbon ber graphite are extremely strong,
heat-resistant (to 3000 C) materials, used in reentry
Graphite, named by Abraham Gottlob Werner in 1789, shields for missile nosecones, solid rocket engines, high
from the Greek (graphein, to draw/write, for temperature reactors, brake shoes and electric motor
its use in pencils) is one of the most common allotropes brushes.
of carbon. Unlike diamond, graphite is an electrical con- Intumescent or expandable graphites are used in re seals,
ductor. Thus, it can be used in, for instance, electrical arc tted around the perimeter of a re door. During a re
lamp electrodes. Likewise, under standard conditions, the graphite intumesces (expands and chars) to resist re
graphite is the most stable form of carbon. Therefore, it is penetration and prevent the spread of fumes. A typical
used in thermochemistry as the standard state for dening start expansion temperature (SET) is between 150 and
the heat of formation of carbon compounds.
300 C.
Main article: Graphite

Graphite conducts electricity, due to delocalization of the

pi bond electrons above and below the planes of the carbon atoms. These electrons are free to move, so are able
to conduct electricity. However, the electricity is only
conducted along the plane of the layers. In diamond, all
four outer electrons of each carbon atom are 'localised'
between the atoms in covalent bonding. The movement
of electrons is restricted and diamond does not conduct
an electric current. In graphite, each carbon atom uses
only 3 of its 4 outer energy level electrons in covalently
bonding to three other carbon atoms in a plane. Each carbon atom contributes one electron to a delocalised system
of electrons that is also a part of the chemical bonding.
The delocalised electrons are free to move throughout the
plane. For this reason, graphite conducts electricity along
the planes of carbon atoms, but does not conduct in a direction at right angles to the plane.
Graphite powder is used as a dry lubricant. Although it
might be thought that this industrially important property
is due entirely to the loose interlamellar coupling between
sheets in the structure, in fact in a vacuum environment
(such as in technologies for use in space), graphite was
found to be a very poor lubricant. This fact led to the discovery that graphites lubricity is due to adsorbed air and
water between the layers, unlike other layered dry lubricants such as molybdenum disulde. Recent studies suggest that an eect called superlubricity can also account
for this eect.
When a large number of crystallographic defects bind
these planes together, graphite loses its lubrication properties and becomes what is known as pyrolytic carbon,
a useful material in blood-contacting implants such as
prosthetic heart valves.

Density: graphites specic gravity is 2.3, which makes it

lighter than diamonds.
Chemical activity: it is slightly more reactive than diamond. This is because the reactants are able to penetrate
between the hexagonal layers of carbon atoms in graphite.
It is unaected by ordinary solvents, dilute acids, or fused
alkalis. However, chromic acid oxidises it to carbon dioxide.

2.1 Graphene
Main article: Graphene
A single layer of graphite is called graphene and has extraordinary electrical, thermal, and physical properties.
It can be produced by epitaxy on an insulating or conducting substrate or by mechanical exfoliation (repeated
peeling) from graphite. Its applications may include replacing silicon in high-performance electronic devices.

3 Amorphous carbon
Main article: Amorphous carbon
Amorphous carbon is the name used for carbon that
does not have any crystalline structure. As with all glassy
materials, some short-range order can be observed, but
there is no long-range pattern of atomic positions. While
entirely amorphous carbon can be produced, most amorphous carbon actually contains microscopic crystals of
graphite-like,[3] or even diamond-like carbon.[4]

Graphite is the most stable allotrope of carbon. Contrary

to popular belief, high-purity graphite does not readily
burn, even at elevated temperatures.[1] For this reason, it
is used in nuclear reactors and for high-temperature crucibles for melting metals.[2] At very high temperatures Coal and soot or carbon black are informally called amorand pressures (roughly 2000 C and 5 GPa), it can be phous carbon. However, they are products of pyrolysis
transformed into diamond.
(the process of decomposing a substance by the action
Natural and crystalline graphites are not often used in of heat), which does not produce true amorphous carbon
pure form as structural materials due to their shear- under normal conditions.

4
4.1

Nanocarbons
Buckminsterfullerenes

Main article: Fullerenes

The buckminsterfullerenes, or usually just fullerenes or
buckyballs for short, were discovered in 1985 by a team of
scientists from Rice University and the University of Sussex, three of whom were awarded the 1996 Nobel Prize in
Chemistry. They are named for the resemblance of their Computer models of stable nanobud structures
allotropic structure to the geodesic structures devised by
the scientist and architect Richard Buckminster Bucky
Fuller. Fullerenes are molecules of varying sizes com- fullerenes and carbon nanotubes. For instance, they have
posed entirely of carbon, which take the form of a hollow been found to be exceptionally good eld emitters.
sphere, ellipsoid, or tube.
As of the early twenty-rst century, the chemical and
physical properties of fullerenes are still under heavy
study, in both pure and applied research labs. In April
2003, fullerenes were under study for potential medicinal
use binding specic antibiotics to the structure to target resistant bacteria and even target certain cancer cells
such as melanoma.

4.2

5 Glassy carbon

Carbon nanotubes

Main article: Carbon nanotube

Carbon nanotubes, also called buckytubes, are cylindrical carbon molecules with novel properties that make
them potentially useful in a wide variety of applications (e.g., nano-electronics, optics, materials applications, etc.). They exhibit extraordinary strength, unique
electrical properties, and are ecient 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 centimeters in length. There are two main types of
nanotubes: single-walled nanotubes (SWNTs) and multiwalled nanotubes (MWNTs).

4.3

Carbon nanobuds

Main article: Carbon nanobud

A large sample of glassy carbon.

Main article: Glassy carbon

Glassy carbon or vitreous carbon is a class of nongraphitizing carbon widely used as an electrode material
in electrochemistry, as well as for high-temperature crucibles and as a component of some prosthetic devices.
It was rst produced by Bernard Redfern in the mid1950s at the laboratories of The Carborundum Company,
Manchester, UK. He had set out to develop a polymer matrix to mirror a diamond structure and discovered a resole
(phenolic) resin that would, with special preparation, set
without a catalyst. Using this resin the rst glassy carbon
was produced.

The preparation of glassy carbon involves subjecting the

organic precursors to a series of heat treatments at temCarbon nanobuds are a newly discovered allotrope peratures up to 3000 C. Unlike many non-graphitizing
of carbon in which fullerene like buds are cova- carbons, they are impermeable to gases and are chemlently attached to the outer sidewalls of the carbon nan- ically extremely inert, especially those prepared at very
otubes. This hybrid material has useful properties of both high temperatures. It has been demonstrated that the

11 OTHER POSSIBLE FORMS

rates of oxidation of certain glassy carbons in oxygen,

carbon dioxide or water vapour are lower than those of
any other carbon. They are also highly resistant to attack
by acids. Thus, while normal graphite is reduced to a
powder by a mixture of concentrated sulfuric and nitric
acids at room temperature, glassy carbon is unaected by
such treatment, even after several months.

Atomic and diatomic carbon

Main articles: Atomic carbon and diatomic carbon

Under certain conditions, carbon can be found in its
atomic form. It is formed by passing large electric currents through carbon under very low pressures. It is extremely unstable, but it is an intermittent product used in
the creation of carbenes.[5]

Ti3 AlC2 , Mo2 C, etc. This synthesis is accomplished using chlorine treatment, hydrothermal synthesis, or hightemperature selective metal desorption under vacuum.
Depending on the synthesis method, carbide precursor,
and reaction parameters, multiple carbon allotropes can
be achieved, including endohedral particles composed
of predominantly amorphous carbon, carbon nanotubes,
epitaxial graphene, nanocrystalline diamond, onion-like
carbon, and graphitic ribbons, barrels, and horns. These
structures exhibit high porosity and specic surface areas,
with highly tunable pore diameters, making them promising materials for supercapacitor-based energy storage,
water ltration and capacitive desalinization, catalyst support, and cytokine removal.[8]

9 Lonsdaleite
mond)

(hexagonal

dia-

Diatomic carbon can also be found under certain condiMain article: Lonsdaleite
tions. It is often detected via spectroscopy in extraterres[6][7]
trial bodies, including comets and certain stars.
Lonsdaleite is a hexagonal allotrope of the carbon allotrope diamond, believed to form from graphite present
in meteorites upon their impact to Earth. The great
7 Carbon nanofoam
heat and stress of the impact transforms the graphite
into diamond, but retains graphites hexagonal crystal
Main article: Carbon nanofoam
lattice. Hexagonal diamond has also been synthesized
in the laboratory, by compressing and heating graphite
Carbon nanofoam is the fth known allotrope of carbon either in a static press or using explosives. It can also
discovered in 1997 by Andrei V. Rode and co-workers at be produced by the thermal decomposition of a polymer,
the Australian National University in Canberra. It con- poly(hydridocarbyne), at atmospheric pressure, under insists of a low-density cluster-assembly of carbon atoms ert gas atmosphere (e.g. argon, nitrogen), starting at temperature 110 C (230 F).[9][10][11]
strung together in a loose three-dimensional web.
Each cluster is about 6 nanometers wide and consists
of about 4000 carbon atoms linked in graphite-like
sheets that are given negative curvature by the inclu- 10 Linear acetylenic carbon (LAC)
sion of heptagons among the regular hexagonal pattern.
This is the opposite of what happens in the case of Main article: Linear acetylenic carbon
buckminsterfullerenes, in which carbon sheets are given
positive curvature by the inclusion of pentagons.
A one-dimensional carbon polymer with the structure The large-scale structure of carbon nanofoam is similar (C:::C) .
to that of an aerogel, but with 1% of the density of previously produced carbon aerogels only a few times the
density of air at sea level. Unlike carbon aerogels, carbon 11 Other possible forms
nanofoam is a poor electrical conductor.

Carbide-derived carbon

Main article: Carbide-derived carbon

Carbide-derived carbon (CDC) is a family of carbon materials with dierent surface geometries and carbon ordering that are produced via selective removal of metals from metal carbide precursors, such as TiC, SiC,

Chaoite is a mineral believed to have been formed

in meteorite impacts. It has been described as
slightly harder than graphite with a reection colour
of grey to white. However, the existence of carbyne
phases is disputed see the entry on chaoite for details.
Metallic carbon: Theoretical studies have shown
that there are regions in the phase diagram, at extremely high pressures, where carbon has metallic
character.[12]

5
There is an evidence that white dwarf stars have
a core of crystallized carbon and oxygen nuclei.
The largest of these found in the universe so far,
BPM 37093, is located 50 light-years (4.71014
km) away in the constellation Centaurus. A news
release from the Harvard-Smithsonian Center for
Astrophysics described the 2,500-mile (4,000 km)wide stellar core as a diamond,[28] and it was named
as Lucy, after the Beatles song Lucy in the Sky
With Diamonds";[29] however, it is more likely an
exotic form of carbon.
Prismane C8 is a theoretically-predicted metastable
carbon allotrope comprising an atomic cluster of
eight carbon atoms, with the shape of an elongated
triangular bipyramida six-atom triangular prism
with two more atoms above and below its bases.[30]

Crystal structure of C8 cubic carbon

bcc-carbon: At ultrahigh pressures of above 1000

GPa, diamond is predicted to transform into the socalled C8 structure, a body-centered cubic structure
with 8 atoms in the unit cell. This cubic carbon
phase might have importance in astrophysics. Its
structure is known in one of the metastable phases
of silicon and is similar to cubane.[13] Superdense
and superhard material resembling this phase has
been synthesized and published in 1979 [14] and
2008.[15][16] The structure of this phase was proThe K4 crystal
posed in 2012 as carbon sodalite.[17]
bct-carbon: Body-centered tetragonal carbon proposed by theorists in 2010[18][19]
M-carbon: Monoclinic C-centered carbon was rst
thought to have been created in 1963 by compressing graphite at room temperature. Its structure was
theorized in 2006,[20] then in 2009 it was related[21]
to those experimental observations. Many structural
candidates, including bct-carbon, were proposed to
be equally compatible with experimental data available at the time, until in 2012 it was theoretically
proven that this structure is kinetically likeliest to
form from graphite.[22][23] High-resolution data appeared shortly after, demonstrating that among all
structure candidates only M-carbon is compatible
with experiment.[24][25]
Q-carbon: Ferromagnetic carbon discovered in
2015.[26]

The Laves graph or K 4 crystal is a theoreticallypredicted three-dimensional crystalline metastable

carbon structure in which each carbon atom is
bonded to three others, at 120 angles (like
graphite), but where the bond planes of adjacent lie
at an angle of 70.5, rather than coinciding[31][32]
Penta-graphene
Haeckelites Ordered arrangements of pentagons,
hexagons, and heptagons which can either be at or
tubular.
Phagraphene Graphene allotrope with distorted
Dirac cones.

12 Variability of carbon

The system of carbon allotropes spans an astounding

T-carbon: Every carbon atom in diamond is re- range of extremes, considering that they are all merely
placed with a carbon tetrahedron (hence 'T-carbon'). structural formations of the same element.
This was proposed by theorists in 2011.[27]
Between diamond and graphite:

14

REFERENCES

14 References
[1] Glowing nuclear reactor graphite 2. YouTube (2007-1107). Retrieved on 2015-10-22.
[2] Crucibles, Artisan Foundry Shop. Artisanfoundry.co.uk.
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[3] Randall L. Vander Wal (1996). Soot Precursor Material: Spatial Location via Simultaneous LIF-LII Imaging
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198469.
[4] IUPAC Compendium of Chemical Terminology 2nd
Edition (1997) diamond-like carbon lms.
Diamond and graphite are two allotropes of carbon: pure forms
of the same element that dier in structure.

Diamond crystallizes in the cubic system but

graphite crystallizes in the hexagonal system.
Diamond is clear and transparent, but graphite is
black and opaque.
Diamond is the hardest mineral known (10 on the
Mohs scale), but graphite is one of the softest (12
on Mohs scale).
Diamond is the ultimate abrasive, but graphite is soft
and is a very good lubricant.
Diamond is an excellent electrical insulator, but
graphite is a conductor of electricity.
Diamond is an excellent thermal conductor, but
some forms of graphite are used for thermal insulation (for example heat shields and rebreaks).
At standard temperature and pressure, graphite is
the thermodynamically stable form. Thus diamonds
do not exist forever. The conversion from diamond
to graphite, however, has a very high activation energy and is therefore extremely slow.
Despite the hardness of diamonds, the chemical bonds
that hold the carbon atoms in diamonds together are actually weaker than those that hold together graphite. The
dierence is that in diamond, the bonds form an inexible three-dimensional lattice. In graphite, the atoms are
tightly bonded into sheets, but the sheets can slide easily
over each other, making graphite soft.[33]

13

See also

Superdense carbon allotropes

[5] Reactions of Atomic Carbon with Acid Chlorides. None.

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[7] Green Comet Approaches Earth.
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[9] Bianconi P, et al. (2004). Diamond and Diamondlike Carbon from a Preceramic Polymer. Journal of
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[11] Nur, Yusuf; Cengiz, Halime M.; Pitcher, Michael
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[12] Correa, Aa; Bonev, Sa; Galli, G (Jan 2006).
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[28] This Valentines Day, Give The Woman Who Has Everything The Galaxys Largest Diamond. Center for Astrophysics. Retrieved 2009-05-05.

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15 External links
Falcao, Eduardo H. L.; Wudl, Fred (2007). Carbon
allotropes: beyond graphite and diamond. Journal of Chemical Technology & Biotechnology. 82
(6): 524531. doi:10.1002/jctb.1693. ISSN 02682575.
http://www.dendritics.com/scales/c-allotropes.asp
http://cst-www.nrl.navy.mil/lattice/struk/carbon.
html
diamond 3D animation

16

16
16.1

TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Text and image sources, contributors, and licenses

Text

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Josve05a, Chemprof16, StringTheory11, Rcsprinter123, Donner60, Hedichirohamanaka, Whoop whoop pull up, ClueBot NG, JohnSRoberts99, SammyD173, Bibcode Bot, CitationCleanerBot, Gweenbwob, Rsamahamed, YFdyh-bot, Garamond Lethe, MadGuy7023,
ArtKa, Dexbot, Lugia2453, BeaumontTaz, Graphium, Jamesx12345, Kapoorritwik2, Jawshewah, Mferoz2612, DrBungle, Noyster, UY
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16.2

Images

File:C60-rods.png Source: https://upload.wikimedia.org/wikipedia/commons/0/09/C60-rods.png License: CC-BY-SA-3.0 Contributors:

? Original artist: ?
File:Cubic_Carbon_Nanocrystal.PNG Source: https://upload.wikimedia.org/wikipedia/commons/6/62/Cubic_Carbon_Nanocrystal.
PNG License: Public domain Contributors: Own work Original artist: SixFingeredMan
File:Diamond_and_graphite2.jpg Source: https://upload.wikimedia.org/wikipedia/commons/d/d9/Diamond_and_graphite2.jpg License: CC-BY-SA-3.0 Contributors: Diamond_and_graphite.jpg
File:Graphite-tn19a.jpg Original artist: Diamond_and_graphite.jpg: User:Itub
File:Eight_Allotropes_of_Carbon.png Source: https://upload.wikimedia.org/wikipedia/commons/f/f8/Eight_Allotropes_of_Carbon.
png License: CC-BY-SA-3.0 Contributors: Created by Michael Strck (mstroeck) Original artist: Created by Michael Strck (mstroeck)
File:Free-to-read_lock_75.svg Source: https://upload.wikimedia.org/wikipedia/commons/8/80/Free-to-read_lock_75.svg License: CC0
Contributors:
Adapted
from
<a
href='//en.wikipedia.org/wiki/File:Open_Access_logo_PLoS_white_green.svg'
class='image'
title='Open_Access_logo_PLoS_white_green.svg'><img
alt='Open_Access_logo_PLoS_white_green.svg'
src='//upload.wikimedia.
org/wikipedia/commons/thumb/9/90/Open_Access_logo_PLoS_white_green.svg/9px-Open_Access_logo_PLoS_white_green.svg.png'
width='9' height='14' srcset='//upload.wikimedia.org/wikipedia/commons/thumb/9/90/Open_Access_logo_PLoS_white_green.svg/
14px-Open_Access_logo_PLoS_white_green.svg.png 1.5x, //upload.wikimedia.org/wikipedia/commons/thumb/9/90/Open_Access_
logo_PLoS_white_green.svg/18px-Open_Access_logo_PLoS_white_green.svg.png 2x' data-le-width='640' data-le-height='1000'
/></a>
Original artist:
This version:Trappist_the_monk (talk) (Uploads)
File:Fullerene_Nanogears_-_GPN-2000-001535.jpg Source:
https://upload.wikimedia.org/wikipedia/commons/b/b6/Fullerene_
Nanogears_-_GPN-2000-001535.jpg License: Public domain Contributors: Great Images in NASA: Home - info - pic Original artist:
NASA
File:Glassy_carbon_and_a_1cm3_graphite_cube_HP68-79.jpg Source:
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href='//commons.wikimedia.org/wiki/User_talk:Alchemist-hp' title='User talk:Alchemist-hp'>talk</a>) (www.pse-mendelejew.de)
File:K_4_crystal.JPG Source: https://upload.wikimedia.org/wikipedia/commons/e/e6/K_4_crystal.JPG License: CC BY-SA 4.0 Contributors: Own work Original artist: Workbit
File:NanobudComputations70%.jpg Source: https://upload.wikimedia.org/wikipedia/commons/6/62/NanobudComputations70%25.
jpg License: CC BY-SA 3.0 Contributors: Own work Original artist: Arkady Krasheninnikov

16.3

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