Allotropes of

carbon
With
illustration
Notes
 Eight allotropes of carbon:
(a) diamond, (b) graphite, (c) lonsdaleite, (d) C buckminsterfullerene,
60

(e) C fullerite (f) C fullerene, (g) amorphous carbon, (h) zig-zag single-walled carbon
540 70

nanotube. Missing: cyclocarbon, carbon nanobuds, schwarzites, glassy carbon,

and linear acetylenic carbon (carbyne)

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Carbon is capable of forming many allotropes (structurally different forms of the same
element) due to its valency. Well-known forms of carbon include diamond and graphite.
In recent decades, many more allotropes have been discovered and researched,
including ball shapes such as buckminsterfullerene and sheets such as graphene.
Larger-scale structures of carbon include nanotubes, nanobuds and nanoribbons. Other
unusual forms of carbon exist at very high temperatures or extreme pressures. Around
500 hypothetical 3-periodic allotropes of carbon are known at the present time,
according to the Samara Carbon Allotrope Database (SACADA).[1]
Atomic and diatomic carbon[edit]
Main articles: Atomic carbon and diatomic carbon
Under certain conditions, carbon can be found in its atomic form. It can be formed by
vaporizing graphite, by passing large electric currents to form a carbon arc under very
low pressure. It is extremely reactive, but it is an intermediate product used in the
creation of carbenes.[2]
Diatomic carbon can also be found under certain conditions. It is often detected
via spectroscopy in extraterrestrial bodies, including comets and certain stars.[3][4]
Diamond[edit]
Main article: Diamond
Diamond is a well-known allotrope of carbon. The hardness, extremely high refractive
index, and high dispersion of light make diamond useful for industrial applications and
for jewelry. Diamond is the hardest known natural mineral. This makes it an excellent
abrasive and makes it hold polish and luster extremely well. No known naturally
occurring substance can cut or scratch diamond, except another diamond. In diamond
form, carbon is one of the costliest elements.
The crystal structure of diamond is a face-centered cubic lattice having eight atoms per
unit cell to form a diamond cubic structure. Each carbon atom is covalently bonded to
four other carbons in a tetrahedral geometry. These tetrahedrons together form a 3-
dimensional network of six-membered carbon rings in the chair conformation, allowing
for zero bond angle strain. The bonding occurs through sp3 hybridized orbitals to give a
C-C bond length of 154 pm. This network of unstrained covalent bonds makes diamond
extremely strong. Diamond is thermodynamically less stable than graphite at pressures
below 1.7 GPa.[5][6][7]
The dominant industrial use of diamond is cutting, drilling (drill bits), grinding (diamond
edged cutters), and polishing. Most uses of diamonds in these technologies do not
require large diamonds, and most diamonds that are not gem-quality can find an
industrial use. Diamonds are embedded in drill tips and saw blades or ground into a
powder for use in grinding and polishing applications (due to its extraordinary
hardness). Specialized applications include use in laboratories as containment for high
pressure experiments (see diamond anvil), high-performance bearings, and
specialized windows of technical apparatuses.
The market for industrial-grade diamonds operates much differently 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.
With the continuing advances being made in the production of synthetic diamond, future
applications are beginning to become feasible. Garnering much excitement is the
possible use of diamond as a semiconductor suitable to build microchips from, or the
use of diamond as a heat sink in electronics. Significant research efforts
in Japan, Europe, and the United States are under way to capitalize on the potential
offered by diamond's unique material properties, combined with increased quality and
quantity of supply starting to become available from synthetic diamond manufacturers.
[citation needed]

Graphite[edit]
Main article: Graphite
Graphite, named by Abraham Gottlob Werner in 1789, from the Greek γράφειν
(graphein, "to draw/write", for its use in pencils) is one of the most common allotropes of
carbon. Unlike diamond, graphite is an electrical conductor. Thus, it can be used in, for
instance, electrical arc lamp electrodes. Likewise, under standard conditions, graphite is
the most stable form of carbon. Therefore, it is used in thermochemistry as the standard
state for defining the heat of formation of carbon compounds.
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 'localized' 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 delocalized system of electrons
that is also a part of the chemical bonding. The delocalized electrons are free to move
throughout the plane. For this reason, graphite conducts electricity along the planes of
carbon atoms, but does not conduct electricity 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 graphite's lubricity is due to adsorbed air and water between the layers, unlike other
layered dry lubricants such as molybdenum disulfide. Recent studies suggest that an
effect called superlubricity can also account for this effect.
When a large number of crystallographic defects (physical) bind these planes together,
graphite loses its lubrication properties and becomes pyrolytic carbon, a useful material
in blood-contacting implants such as prosthetic heart valves.
Graphite is the most stable allotrope of carbon. Contrary to popular belief, high-purity
graphite does not readily burn, even at elevated temperatures.[8] For this reason, it is
used in nuclear reactors and for high-temperature crucibles for melting metals.[9] At very
high temperatures and pressures (roughly 2000 °C and 5 GPa), it can be transformed
into diamond.[citation needed]
Natural and crystalline graphites are not often used in pure form as structural materials
due to their shear-planes, brittleness and inconsistent mechanical properties.
In its pure glassy (isotropic) synthetic forms, pyrolytic graphite and carbon fiber graphite
are extremely strong, heat-resistant (to 3000 °C) materials, used in reentry shields for
missile nosecones, solid rocket engines, high temperature reactors, brake shoes
and electric motor brushes.
Intumescent or expandable graphites are used in fire seals, fitted around the perimeter
of a fire door. During a fire the graphite intumesces (expands and chars) to resist fire
penetration and prevent the spread of fumes. A typical start expansion
temperature (SET) is between 150 and 300 °C.
Graphite's specific gravity is 2.3, which makes it less dense than diamond.
Graphite 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 unaffected
by ordinary solvents, dilute acids, or fused alkalis. However, chromic acid oxidizes it to
carbon dioxide.
Graphene[edit]
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. With two layers
stacked, bilayer graphene results with different properties.
Lonsdaleite (hexagonal diamond)[edit]
Lonsdaleite is an allotrope sometimes called "hexagonal diamond", formed
from graphite present in meteorites upon their impact on the earth. The great heat and
pressure of the impact transforms the graphite into a denser form similar to diamond but
retaining graphite's hexagonal crystal lattice. "Hexagonal diamond" has also been
synthesized in the laboratory, by compressing and heating graphite either in a static
press or using explosives. It can also be produced by the thermal decomposition of a
polymer, poly(hydridocarbyne), at atmospheric pressure, under inert gas atmosphere
(e.g. argon, nitrogen), starting at temperature 110 °C (230 °F).[10][11][12]
Graphenylene[edit]
Graphenylene[13] is a single layer carbon material with biphenylene-like subunits as basis
in its hexagonal lattice structure. It is also known as biphenylene-carbon.
Carbophene[edit]
Carbophene is a 2 dimensional covalent organic framework.[14] 4-6 carbophene has been
synthesized from 1-3-5 trihydroxybenzene. It consists of 4-carbon and 6-carbon rings in
1:1 ratio. The angles between the three σ-bonds of the orbitals are approximately 120°,
90°, and 150°.[15]
AA'-graphite[edit]
AA'-graphite is an allotrope of carbon similar to graphite, but where the layers are
positioned differently to each other as compared to the order in graphite.
Diamane[edit]
Diamane is a 2D form of diamond. It can be made via high pressures, but without that
pressure, the material reverts to graphene. Another technique is to add hydrogen
atoms, but those bonds are weak. Using fluorine (xenon-difluoride) instead brings the
layers closer together, strengthening the bonds. This is called f-diamane.[16]
Amorphous carbon[edit]
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 contains microscopic
crystals of graphite-like,[17] or even diamond-like carbon.[18]
Coal and soot or carbon black are informally called amorphous carbon. However, they
are products of pyrolysis (the process of decomposing a substance by the action of
heat), which does not produce true amorphous carbon under normal conditions.
Nanocarbons[edit]
Buckminsterfullerenes[edit]
Main article: Fullerene
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 to the geodesic structures devised by Richard Buckminster
"Bucky" Fuller. Fullerenes are positively curved molecules of varying sizes composed
entirely of carbon, which take the form of a hollow sphere, ellipsoid, or tube (the C60
version has the same form as a traditional stitched soccer ball).
As of the early twenty-first 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 specific antibiotics to
the structure to target resistant bacteria and even target certain cancer cells such as
melanoma.
Carbon nanotubes[edit]
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 efficient conductors of heat. Non-carbon
nanotubes have also been synthesized. Carbon nanotubes are a members 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 multi-walled nanotubes (MWNTs).
Carbon nanobuds[edit]

Computer models of stable nanobud structures

Main article: Carbon nanobud
Carbon nanobuds are a newly discovered allotrope of carbon in which fullerene like
"buds" are covalently attached to the outer sidewalls of the carbon nanotubes. This
hybrid material has useful properties of both fullerenes and carbon nanotubes. For
instance, they have been found to be exceptionally good field emitters.
Schwarzites[edit]
Schwarzites are negatively curved carbon surfaces originally proposed by
decorating triply periodic minimal surfaces with carbon atoms. The geometric
topology of the structure is determined by the presence of ring defects, such as
heptagons and octagons, to graphene's hexagonal lattice.[19] (Negative curvature bends
surfaces outwards like a saddle rather than bending inwards like a sphere.)
Recent work has proposed zeolite-templated carbons (ZTCs) may be schwarzites. The
name, ZTC, derives from their origin inside the pores of zeolites, crystalline silicon
dioxide minerals. A vapor of carbon-containing molecules is injected into the zeolite,
where the carbon gathers on the pores' walls, creating the negative curve. Dissolving
the zeolite leaves the carbon. A team generated structures by decorating the pores of a
zeolite with carbon through a Monte Carlo method. Some of the resulting models
resemble schwarzite-like structures.[20]
Glassy carbon[edit]
Main article: Glassy carbon

A large sample of glassy carbon.

Glassy carbon or vitreous carbon is a class of non-graphitizing 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 first produced by Bernard Redfern in the mid-1950s 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 first glassy carbon was
produced.
The preparation of glassy carbon involves subjecting the organic precursors to a series
of heat treatments at temperatures up to 3000 °C. Unlike many non-graphitizing
carbons, they are impermeable to gases and are chemically extremely inert, especially
those prepared at very high temperatures. It has been demonstrated that the rates of
oxidation of certain glassy carbons in oxygen, carbon dioxide or water vapor 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 unaffected by such treatment, even
after several months.
Carbon nanofoam[edit]
Main article: Carbon nanofoam
Carbon nanofoam is the fifth known allotrope of carbon, discovered in 1997 by Andrei
V. Rode and co-workers at the Australian National University in Canberra. It consists of
a low-density cluster-assembly of carbon atoms 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 inclusion of heptagons among the regular hexagonal pattern. This is the opposite of
what happens in the case of buckminsterfullerenes, in which carbon sheets are given
positive curvature by the inclusion of pentagons.
The large-scale structure of carbon nanofoam is similar 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 nanofoam is a poor electrical
conductor.
Carbide-derived carbon[edit]
Main article: Carbide-derived carbon
Carbide-derived carbon (CDC) is a family of carbon materials with different surface
geometries and carbon ordering that are produced via selective removal of metals from
metal carbide precursors, such as TiC, SiC, Ti3AlC2, Mo2C, etc. This synthesis is
accomplished using chlorine treatment, hydrothermal synthesis, or high-temperature
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 specific
surface areas, with highly tunable pore diameters, making them promising materials for
supercapacitor-based energy storage, water filtration and capacitive desalinization,
catalyst support, and cytokine removal.[21]
Other metastable carbon phases, some diamondlike, have been produced from
reactions of SiC or CH3SiCl3 with CF4.[22]
Linear acetylenic carbon[edit]
Main article: Linear acetylenic carbon
A one-dimensional carbon polymer with the structure —(C≡C)n—. Its structure is
relatively like that of Amorphous carbon.
Cyclocarbons[edit]
Main article: Cyclocarbon
Cyclo[18]carbon (C18) was synthesized in 2019.[23]
Other possible allotropes[edit]
Many other allotropes have been hypothesized but have yet to be synthesized.
 Crystal structure of the proposed C cubic form
8

of carbonbcc-carbon: At ultrahigh pressures of above 1000 GPa, diamond is

predicted to transform into a body-centered cubic structure. This phase has
importance in astrophysics and deep interiors of planets
like Uranus and Neptune. Various structures have been proposed.
Superdense and superhard material resembling this phase was synthesized
and published in 1979 and reported to have the Im3 space group with eight
atoms per primitive unit cell (16 atoms per conventional unit cell).[24] Claims
were made that the so-called C8 structure had been synthesized, having
eight-carbon cubes similar to cubane in the Im3m space group, with eight
atoms per primitive unit cell, or 16 atoms per conventional unit cell (also
called supercubane, see illustration to the right). But a paper in 1988 claimed
that a better theory was that the structure was the same as that of an
allotrope of silicon called Si-III or γ-silicon, the so-called BC8 structure with
space group Ia3 and 8 atoms per primitive unit cell (16 atoms per
conventional unit cell).[25][26] In 2008 it was reported that the cubane-like
structure had been identified.[27][28] A paper in 2012 considered four proposed
structures, the supercubane structure, the BC8 structure, a structure with
clusters of four carbon atoms in tetrahedra in space group I43m having four
atoms per primitive unit cell (eight per conventional unit cell), and a structure
the authors called "carbon sodalite". They found in favor of this carbon
sodalite structure, with a calculated density of 2.927 g/cm3, shown in the
upper left of the illustration under the abstract.[29] This structure has just six
atoms per primitive unit cell (twelve per conventional unit cell). The carbon
atoms are in the same locations as the silicon and aluminum atoms of the
mineral sodalite. The space group, I43m, is the same as the fully expanded
form of sodalite would have if sodalite had just silicon or just aluminum.[30]

 bct-carbon: Body-centered tetragonal carbon was proposed by theorists in

2010.[31][32]
 Chaoite is a mineral believed to have been formed in meteorite impacts. It
has been described as slightly harder than graphite with a reflection color of
grey to white. However, the existence of carbyne phases is disputed – see
the article on chaoite for details.
 D-carbon: D-carbon was proposed by theorists in 2018.[33] D-carbon is an
orthorhombic sp3 carbon allotrope (6 atoms per cell). Total-energy
calculations demonstrate that D-carbon is energetically more favorable than
the previously proposed T6 structure (with 6 atoms per cell) as well as many
others.
 Haeckelites: Ordered arrangements of pentagons, hexagons, and heptagons
which can either be flat or tubular.

The K crystal
4

 The Laves graph or K4 crystal is a theoretically predicted 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 layers lie at an angle of 70.5°, rather than coinciding.[34][35]
 M-carbon: Monoclinic C-centered carbon is thought to have been first
created in 1963 by compressing graphite at room temperature. Its structure
was theorized in 2006,[36] then in 2009 it was related to those experimental
observations.[37] Many structural candidates, including bct-carbon, were
proposed to be equally compatible with experimental data available at the
time, until in 2012 it was shown theoretically that this structure is kinetically
the most likely to form from graphite.[38][39] High-resolution data appeared
shortly after, demonstrating that among all structure candidates only M-
carbon is compatible with experiment.[40][41]
 Metallic carbon: Theoretical studies have shown that there are regions in
the phase diagram, at extremely high pressures, where carbon has metallic
character.[42] Laser shock experiments and theory indicate that above
600 GPa liquid carbon is metallic.[43]
 Novamene: A combination of both hexagonal diamond and sp2 hexagons as
in graphene.[44]
 Phagraphene: Graphene-like allotrope with distorted Dirac cones.
 Prismane C8 is a theoretically predicted metastable
carbon allotrope comprising an atomic cluster of eight carbon atoms, with the
shape of an elongated triangular bipyramid—a six-atom triangular prism with
two more atoms above and below its bases.[45]
 Protomene: A hexagonal crystal structure with a fully relaxed primitive cell
involving 48 atoms. Out of these, 12 atoms have the potential to switch
hybridization between sp2 and sp3, forming dimers.[46]
 Q-carbon: Ferromagnetic carbon was discovered in 2015.[47]
  T-carbon: Every carbon atom in diamond is replaced with a carbon
tetrahedron (hence 'T-carbon'). This was proposed by theorists in 1985.[48]
 There is 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 (4.7×1014 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,[49] and it was named as Lucy, after the Beatles' song "Lucy in
the Sky With Diamonds";[50] however, it is more likely an exotic form of
carbon. Penta-graphene is a predicted carbon allotrope that utilizes the Cairo
pentagonal tiling.
 U carbon is predicted to consist of corrugated layers tiled with six- or 12-
atom rings, linked by covalent bonds. Notably, it can be harder than steel, as
conductive as stainless steel, highly reflective and ferromagnetic, behaving
as a permanent magnet at temperatures up to 125 °C.[51]

 Zayedene: A combination of linear sp carbon chains and sp3 bulk carbon.

The structure of these crystalline carbon allotropes consists of sp chains
inserted in cylindrical cavities periodically arranged in hexagonal diamond
(lonsdaleite).[52][53]
Variability of carbon[edit]

Diamond and graphite are two allotropes of carbon: pure

forms of the same element that differ in structure.
The system of carbon allotropes spans an astounding range of extremes, considering
that they are all merely structural formations of the same element.
Between diamond and graphite:

 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 (1–2 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 an excellent
conductor.
  Diamond is an excellent thermal conductor, but some forms of graphite are
used for thermal insulation (for example heat shields and firebreaks).
 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
difference is that in diamond, the bonds form an inflexible three-dimensional lattice. In
graphite, the atoms are tightly bonded into sheets, but the sheets can slide easily over
each other, making graphite soft.[54]
See also[edit]
 Superdense carbon allotropes
References[edit]
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