Carbon, 1.

General
HUBERT JA GER, SGL Carbon GmbH, Meitingen, Germany
WILHELM FROHS, SGL Carbon GmbH, Meitingen, Germany
GERD COLLIN, DECHEMA e.V., Frankfurt am Main, Germany
FERDINAND VON STURM, former SIGRI GmbH, Meitingen, Germany
OTTO VOHLER, former SIGRI GmbH, Meitingen, Germany
GABRIELE NUTSCH, former Technische Universitat Ilmenau, Germany

Carbon is the sixth element of the periodic table

with an atomic mass of 12.01115
0.000 05. It
consists of 98.89% of the isotope 12C, 1.11% of
the isotope 13C, and several unstable isotopes
with mass numbers between 9 and 16. The
isotope 14C, which is formed in the atmosphere
by the reaction 14N(n,p)14C, is used in archaeology for age determination and tracing of
chemical compounds [1]. The half-life of this
b emitter is about 5570 years.
Carbon is the thirteenth most abundant element. The earths crust, including the lithosphere, hydrosphere, and atmosphere, contains
about 3  1016 t of carbon, which corresponds
to 0.09 wt% or 0.15 atom%, most of which is
present as compounds, and only a small portion
in elementary form. The carbon contents of sea
water, the atmosphere, and the biosphere are
about 4  1013 t, 4  1011 t, and 3  1011 t,
respectively.
Carbon exists in several allotropic modifications (Fig. 1). The modifications differ from one
another in the arrangement of the carbon atoms
in their crystals (Figs. 2 and 3).
Diamond is the metastable phase of carbon
under standard conditions and can be transformed into graphite by heating above
2000 K [4] (see Fig. 4). The transformation of
graphite into diamond (diamond synthesis) is
only possible at high temperatures and high
pressures [5]. The atoms in the diamond lattice
are singly bonded. The four symmetrical sp3
s-bonds point to the corners of a regular tetrahedron (Fig. 3). Therefore, diamonds have a
rigid and isotropic structure and are usually
2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a05_095.pub2

cubic. Hexagonal diamond (londsdaleite) was

first found as a product of diamond synthesis,
but meanwhile it has also been discovered in
meteorites [6]. According to Figure 4 diamond
can be produced at low pressure by chemical
vapor deposition (CVD; see Section ! Carbon,
2. Diamond, Section 2.2).
Graphite is characterized by its layered
lattice structure due to association by p-bonds
perpendicular to the s-bonds layers. Hence,
graphite is highly anisotropic. However, only
a few natural graphites and hot-worked pyrographite samples are nearly perfect crystals.
Most synthetic graphites deviate more or less
from the perfect crystal structure. Graphite is the
thermodynamically most stable allotrope of
carbon at room temperature and pressure (see
Fig. 4). It is characterized by double bonds
between sp2 carbon atoms (see Fig. 3) and a
regular stacking sequence of the graphite layers.
At atmospheric pressure, graphite vaporizes
without melting at ca. 38954020 K. The heat
of sublimation depends on the vapor composition. It amounts to 711, 825, and 788 kJ/mol for
mono-,di-,andtriatomicmolecules,respectively.
At 4000 K, about 80% of carbonvapor consists of
C3 molecules.By using a laser-heating technique,
a graphiteliquidvapor equilibrium pressure of
10.7
0.2 MPa at a temperature of about
4000 K was found [7].
Non-graphitic carbon consists mainly of
the element carbon. The carbon atoms are
arranged in a two dimensional, planar
hexagonal network. The crystallographic order

Carbon, 1. General

Figure 1. Allotropic modifications of carbon

in the third c-direction, like in the case of

graphite is not detectable by X-ray diffraction.
Non-graphitic carbons which have passed
through a liquid phase during thermal degradation can be converted by heat treatment (> 2500
K) into synthetic graphite. Others which remain
solid during thermal degradation cannot be
transferred into synthetic graphite by heat
treatment solely, they remain non-graphitic
carbons.
Chaoite, a member of the carbyne group,
was found in small quantities together with
graphite in the rocks of the N
ordlinger Ries in
Germany, which were transformed by meteoritic impact [8]. Small quantities of other members
of the carbyne group were found together with
graphite in carbon layers formed by vaporized
carbon, in laser-heated carbon, and also in meteorites. The transformation of sp-hybridized
carbon molecules (carbyne) into diamond by
shock wave experiments has been investigated
[9]. A common feature of the numerous
members of this group are triple bonds [1012].
Fullerenes are a new allotropic form of
carbon [13], the method for their bulk production was discovered in 1990 [14]. These allcarbon cage molecules constitute the fourth
allotropic form of carbon. They are composed
of more or less deformed sp2-bonded carbon
atoms. Fullerenes are formed in condensing
carbon vapor in which linear carbon chains
link together and form graphene sheets. These

free-floating sheets cannot tie up the dangling

bonds on their edges. Elimination of the dangling bonds by curling up serves the physical
tendency to reach the lowest energy level available. Thus, the fullerenes are a pure, finite form
of carbon. The three other forms, diamond,
graphite and non-graphite carbon, are infinite
network solids.
Giant fullerenes in the form of nanotubes and
buckyonions have further expanded the realm of
this new form of carbon. The fullerene-related
nanotubes are formed by a single-layer graphitic
network of hexagons (Fig. 2). The presence of
pentagonal or heptagonal carbon rings renders
their physical properties different from those of
graphite. There are no sp3 bonds, grain boundaries, or edges, and they contain no hydrogen
[2, 15].
Fullerene derivatives can be created by adding endo- or exohedral substituents. This opens
the possibility of obtaining a wide range of
building blocks for developing new materials
with unique properties.
History of Carbon. The milestones of carbon history are presented in Table 1.
Elemental carbon was formed firstly after
the big ban about 13  109 years ago. As the
prime matter has cooled down to about 600 K,
the light elements hydrogen and helium were
generated. These elements formed by gravitation spiral nebulas with stars, composed mainly
of hydrogen. This star breeding continues still
today, e.g., in the horse-head nebula near the belt

Carbon, 1. General

Figure 2. The four most important allotropic forms of solid elemental carbon and their main derivatives [2, 3]

stars of the Orion. Within the bright stars several

exothermic nuclear fusion processes proceed.
By these processes, lighter elements are transformed to heavier one, e.g., hydrogen to helium

and helium to carbon. Old stars can collapse and

explode as novae. Then the built-up heavier
elements such as carbon erupt into the interstellar cosmic space. They soil the spiral nebulas,

Carbon, 1. General

Figure 3. Bonding hybridization and corresponding crystal structure of the carbon allotropes [2]

from them new stars and solar systems emerge

(cosmic recycling). Our galaxy contains
about 10 wt% interstellar matter, consisting of
on average 86% hydrogen, 10% helium and 4%
dust. This dust is composed of water ice,

silicates, organic compounds and elemental

carbon. Hence, carbon is widespread within
the universe. The earths crust (including the
hydrosphere and atmosphere) contains about
3  1016 t carbon, i.e., nearly 0.1 wt%, but

Carbon, 1. General

Figure 4. Phase diagram of different carbon modifications

mostly chemically bound and only a small share

occurs in elemental form as graphite and diamond [19, 20].
Natural diamond crystallized under high
pressure in earths magma about 1.5 to
4  109 years ago. The crystals were thrown
through volcanic pipes together with the mineral melt of kimberlite near to the earths surface.
Since antiquity, about 4  109 carat (800 t)
were mined, cumulatively. The actual production amounts to about 120  106 carat (24 t)
annually, from which about 90% are used for
industrial purposes. New deposits of diamonds
are still being found [20].
Natural graphite occurs similar to coal in
seams whose age is estimated to at least  109
years. About the history of origin, biogenic and
inorganic hypotheses are propounded. Natural
graphite is used since the La Tene Age by the

Table 1. Milestones of carbon history [1, 2, 46]

13  109 years ago
4  109 years ago
>1  109 years ago
30 000 years ago
8 000 B.C.
3 500 B.C.
1 500 B.C.
500 B.C.
1220
1456
1565
1709
1772
1810
1822
1844
1854
1866
1878
1886
1892
1893
1895
1900
1909
1925
1935
1942
1955
1956
1958
1965
1985
1990
1991

the element carbon is formed in the first stars of the universe

the first terrestrial diamonds grow in volcanic magma
the first terrestrial deposits of graphite emerge
carbon black and charcoal are used as color pigments for cave-painting
charcoal is used for the reduction of metal ores
Indian ink with carbon black is invented by the Hindu PANNINGRISHEE
charcoal powder is used as medicine in Egypt
Celts form ceramic flagons from clay and natural graphite
Bavarian peasants near Passau win natural graphite for crucibles and cart grease
JOHANNES GUTENBERG prints the Bible in Mainz with printers ink (carbon black)
pencils with natural graphite are manufactured by sheep farmers in Cumberland
coal coke is used in a blast furnace by ABRAHAM DARBY I at Coalbrookdale (England)
graphite and diamond are identified as elemental carbon by ANTOINE DE LAVOISIER
the first electric arc with charcoal is generated by HUMPHRY DAVY in London
carbon black is produced from natural gas by SAMUEL and GODFREY CABOT in the USA
the first useful arc lamp with carbon rods is constructed by LEON FOUCAULT in Paris
aluminum is manufactured with carbon electrodes by ROBERT BUNSEN in Heidelberg
WERNER SIEMENS constructs the dynamo with carbon brushes in Berlin
JOSEPH SWAN and THOMAS A. EDISON invent filament lamps with carbon fibers
aluminum is produced with carbon electrodes by CHARLES HALL and PAUL HE ROULT
Chlor-alkali electrolysis with Hg and carbon anodes, invented by HAMILTON Y. CASTNER
synthetic graphite by lengthwise graphitization, invented by HAMILTON Y. CASTNER
synthetic graphite by crosswise graphitization, invented by EDWARD G. ACHESON
R. VON OSTREJKO invents activated carbon by chemical and gas activation
the industrial production of activated carbon from charcoal starts at Ratibor (Silesia)
carbon black produced by the furnace black process, developed in the United States
carbon black from tar aromatics by the Degussa gas black process (HARRY KLOEPFER)
ENRICO FERMI constructs the first nuclear reactor with reactor graphite in Chicago
General Electric starts the industrial diamond synthesis by the high-pressure process
BORIS SPITSYN and BORIS DERJAGIN invent the low-pressure diamond synthesis
General Electric starts the production of glass-like carbon shapes
J. D. BROOKS and G. H. TAYLOR discover the carbo-mesophase in coal-tar pitch
H. W. KROTO, R. F. CURL and R. E. SMALLEY discover the fullerenes
W. KRA TSCHMER et al. invent the fullerene synthesis by the electric arc process
SUMIO IIJIMA discovers the carbon nanotubes in the NEC laboratory of Tsukuba

Carbon, 1. General

Celts for sealing clay flagons to store and transport water and wine. At the latest since the
Middle Ages, natural graphite has been mined
in Bavaria near Passau for manufacturing crucibles and cart grease. Since the 16th century,
pencils have been made with natural graphite as
lead, firstly by sheep farmers in Cumberland
(England). Only in 1772, the French chemist
ANTOINE DE LAVOISIER detected by his combustion experiments with oxygen that graphite as
well as diamonds are modifications of pure
carbon and not special forms of lead and minerals, respectively. Proved reserves of natural
graphite will last several hundred years with a
current production of about 0.5  106 t per
year [20].
Charcoal is the oldest form of man-made
carbon. It was used by stone-age humans for
cave-painting and since about 8 000 B.C. for the
reduction of metal ores, firstly for the production of lead, later on for copper, bronze, and iron.
The oldest sites with deposits of terrestrial iron
and steel are in Egypt, India, and other parts of
Southeast Asia. In Europe the Illyrians were the
first who embarked on the Iron Age. Their
culture is known as the Hallstatt Age after a
site discovered at Hallstatt Lake (1000 to 850
B.C.). In the Modern Age, England was to be the
forerunner in iron-making. In 1709, ABRAHAM
DARBY I was the first to successfully replace the
scant and expensive charcoal with coal coke in a
blast furnace at the English Coalbrookdale Ironworks. Today, charcoal is produced, e.g., for
barbecues and for production of activated
carbon [21].
Carbon black as man-made form of carbon is
as old as charcoal. It was also used in the stoneage by the Homo sapiens as stable color pigment
for cave-painting. Since about 3 500 B.C. carbon
black was manufactured by incomplete burning
of vegetable oil, e.g., in China and India, and
was used for the production of Indian ink. The
invention of Indian ink for writing on papyrus
and parchment represented major technical and
cultural progress compared to the previous cuneiform writing on wood and stone. In the
Modern Age carbon black is manufactured as
black pigment for printers ink. In the 19th and
20th century several new industrial processes
have been developed for the production of various types of carbon black by incomplete combustion and pyrolysis of natural gas, coal-tar

aromatics, and petrochemical residual oils. The

production has grown to about 7  106 t per
year, predominantly because of the increasing
demand as active filler for car tires [22].
Activated carbon from charcoal for medical
usage has been described as early as 1550 B.C. in
an ancient Egyptian papyrus and later on by
HIPPOCRATES and GAIUS PLINIUS SECUNDUS the
Elder. The first industrially manufactured activated carbons have been produced from charcoal by gas activation with steam and carbon
dioxide since 1909 by the Chemische Werke
Carbon at Ratibor (Silesia) according to
patents of R. VON OSTREJKO under the trade name
Eponit. Eponit was used predominantly for
decolorizing of sugar solutions. In 1911 the
Dutch Norit NV began with commercial gas
activation of peat by steam. The chemical
activation of sawdust with zinc chloride was
sterreichischer Verein fur chepatented to the O
mische und metallurgische Produktion in 1913,
and the production began at Aussig (Bohemia,
now Usti nad Labem/CZ). During World War I
the production of activated carbon from charcoal for gas masks started at Leverkusen (Farbenfabriken Bayer), Brilon-Wald (Hiag/Degussa) and Hajnowka near Bialystok (now Poland).
In the United States also during World War I, the
activation of coconut charcoal for gas masks
was developed (Calgon Corp.). Also coal, lignite, and straw became raw materials for production of activated carbon. In the 1930s the
German company Lurgi developed formed
activated carbon under the trade name
Supersorbon, which could be reactivated. In
1965, the German Bergbau-Forschung began
with the development of activated coke from
coal for the adsorptive desulfurization and catalytic denitrification of flue gas. Main application fields became water purification, solvent
recovery, cleaning of exhaust gases, and gas
separation by molecular sieves. The total
production rate grew up to about 0.5  106 t
per year [19].
Synthetic graphite and other non-graphitic
carbon products have played an important role
in the Second Industrial Revolution, namely
the switch form water- and later steam-powered
mechanization to the electrification of technology. WERNER (VON) SIEMENS, who invented the
dynamo in 1866, is regarded as the founder of
modern electrical engineering, which utilizes

Carbon, 1. General

various forms of graphitic carbon: firstly carbon

brushes for dynamos and rods for electric arc
lamps, later on carbon anodes and cathodes for
electrolytic recovery of aluminum, graphite
electrodes for arc furnaces for the production
of electro-steel, graphite plates and rods for
chlor-alkali electrolysis and other electrolytic
processes, molded carbon bodies and carbon
bricks for furnace linings, battery carbon,
nuclear reactor graphite, and fine-grained graphite materials for various special applications.
Thus, the production rate grew continually to
around 20  106 t per year [16, 18, 19].
Carbon fibers from cellulose precursors were
manufactured in 1878 for electrical filament
lamps by the American inventor THOMAS ALVA
EDISON and his British competitor JOSEPH
WILSON SWAN. In the 1950s, W. F. ABBOTT developed a process for carbonizing rayon into a
fibrous carbon material for insulation, filtration
and adsorption. In 1959, Union Carbide Corp.
started the production of those fibers, and other
companies in the USA followed. Main application became the reinforcement of phenolic resins for rockets and missile components. Since
1950, synthetic polyacrylonitrile fibers (PAN)
were oxidized and heat-treated to black fibers,
whose came into usage for flameproof textiles in
1960 (Black Orlon/Dupont). The oxidizingblackening treatment was 1959 complemented
by carbonization in Japan (A. SHINDO). In the
1960s, flexible and high-strength carbon fibers
of various qualities were developed from PAN
and further processed to multifilament spun
yarns, woven fabrics, and felts in particular for
reinforcement of plastics and carbon itself. In
1963, the Japanese SUGIO OTANI observed that
some pitches are spinnable to pitch fibers, which
can be converted by carbonization to carbon
fibers. These pitch-based carbon fibers are produced since 1970 in Japan by Kureha Chemical
Industries. In 1985, the American Ashland
Comp. started production of several carbon fiber
types from petroleum pitch. In 1976, J. C. LEWIS,
L. SINGER and coworkers developed high-modulus carbon fibers by spinning, carbonizing and
graphitizing of mesophase pitch. Earlier in
1965, the liquid-crystalline mesophase was discovered in coal-tar pitch by the Australian geologists J. D. BROOKS and G. H. TAYLOR. Production and usage of different types of carbon fibers
predominantly from PAN and for reinforcing of

materials grew up to about 40 000 t per

year [23].
Diamond synthesis under high pressure, firstly invented in 1895 by the French chemist and
later Nobel-prize winner (1906) HENRI MOISSAN,
was commercially realized in 1955 by the General Electric Co., using the belt reactor, which
was developed by the American physicist PERCY
W. BRIDGMAN (Nobel-prize winner for physics in
1946). These synthetic diamonds are used similar to natural diamonds predominantly for cutting, grinding and drilling tools. Their production rate grew up to 200 t per year, actually. The
synthesis of diamond thin films by chemical
vapor deposition (CVD) under low pressure was
invented in 1956 by the Russian chemists BORIS
SPITSYN and BORIS DERJAGIN and commercially
realized in the 1980/90th by several Japanese,
American and European companies. Because of
their excellent physical and chemical properties
as hardness, transparency, chemical inertness,
thermal conductivity and electrical resistance,
these films play a growing role in materials
sciences and technology [17, 19, 24].
Fullerenes and Carbon Nanotubes. The
buckyball molecule C60 and other fullerenes
were discovered in 1985 by the British chemist
HARRY W. KROTO and his American colleagues
ROBERT F. CURL and RICHARD E. SMALLEY, who
won the Nobel prize for chemistry in 1996. The
C60 and C70 fullerenes were firstly synthesized
1990 in an electric-arc reactor by the German
physicist WOLFGANG KRA TSCHMER and his coworkers at the Max-Planck-Institut fur Kernphysik in Heidelberg.
Using a similar electric-arc reactor, the
Japanese SUMIO IIJIMA, working for the NEC
Corp. at Tsukuba, discovered 1991 the carbon
nanotubes. Up to now, the production of these
new forms of carbon has not started on a larger
scale, but a multitude of promising research
results and good proposals for application give
hope of an interesting industrial future [17, 24].

References
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Carbon, 1. General

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