Pergamon

OOOS-6223(96)00170-O
Carbon Vol. 34, No. 2, pp. 141-153,1996
Copyright 0 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
000%6223/96 $15.00 + 0.00
REVIEW ARTICLE
THE PRESSURE-TEMPERATURE PHASE AND
TRANSFORMATION DIAGRAM FOR CARBON; UPDATED
THROUGH 1994
F. P. BUNDY,~ W. A. BASSETT,~ M. S. WEATHERS,~ R. J. HEMLEY,~ H. K. MAO~ and
A. F. GONCHAROV~
Retired General Electric R & D Center; Home address, 4607 Swallow Court, Lebanon, OH 45036-9541,
U.S.A.
bDepartment of Geological Sciences, Snee Hall, Cornell University, Ithaca, NY 14853-1504, U.S.A.
Geophysical Laboratory and Center for High-Pressure Research, Carnegie Institution of Washington,
5251 Broad Branch Rd, NW, Washington DC, 20015-1305, U.S.A.
(Received 5 June 1995; accepted in revised form 12 September 1995)
Abstract-In recent years, important advances in our understanding of the pressure-temperature phase
and transformation diagram for carbon have occurred as a result of developments in both experimental
and theoretical techniques. Graphite, diamond, liquid and vapor remain the major thermodynamically
stable forms of carbon, However, due to the high activation energies for solid-state transformations and
the specific effects of reaction paths, other metastable forms and a wide spectrum of complex hybrid
forms may be generated, and possibly quenched-in, to survive metastably. This paper focuses primarily
on developments since the last review of the carbon phase diagram published in 1989, but also includes
references to the reliable older work. Some of the newer conclusions include the following: the Clapeyron
slope of the diamond melting line, dT,/dP, is positive; the liquid is metallic and there appears to be no
evidence for a transformation between electrically conducting and non-conducting forms; melted droplets
of carbon less than 0.2 pm in diameter quench to a giant fullerene structure even in the stability field of
diamond; graphite transforms to a transparent phase on compression at room temperature; this phase
reverts to graphite on decompression at this temperature from pressures as high as 100 GPa.
1. INTRODUCTION
The purpose of this article is to bring up to date
what is known about the thermodynamically stable
and metastable phases of elemental carbon and the
reaction dynamics among them over a very wide
range of pressure, temperature and reaction condi-
tions. Earlier reports of this type were published
[l&6] as new results, knowledge, and interpretations
of experimental results and theory developed. In
recent years new experiments and results, some of
which are unpublished, have been generated.
Therefore, it is deemed appropriate to present the
topic as an updated whole. The plan for this article
is to present the entire phase diagram as we currently
understand it and then discuss each part giving the
salient references and brief descriptions of the work
upon which it is based. For the new parts the
experimental background and results will be covered
in more detail.
The binding energy between atoms of carbon is
very large; for example, the cohesive energy of dia-
mond is 717 kJ/mol. This property is also demon-
strated by the extremely high melting temperatures
of its solid forms (- 5000 K). In addition, once carbon
atoms are locked into a given phase configuration,
typically a large amount of activation energy is
required to produce a different stable phase; in other
words, very high temperatures are often required to
initiate spontaneous transformations from one solid
phase to another. Recent work, however, has shown
that this is not always true: new pressure-induced
transformations have been documented at room tem-
perature, as discussed below.
In addition to the well known crystalline forms of
carbon, i.e. graphite and diamond, there are amor-
phous forms, such as glassy carbon and carbon
black, and possibly metastable solid forms referred
to as carbynes. The latter are believed to be solid
condensations of linear molecules of carbon but
remain controversial. Also, there are the more
recently discovered crystalline forms of pure carbon
molecules, the fullerenes such as ChO buckyballs and
C,, buckyfootballs. Because of the high cohesive and
activation energy, carbon polymorphs typically exist
metastably well into a T,P region where a different
solid phase is thermodynamically stable. For example,
diamond survives indefinitely at room conditions
where graphite is the thermodynamically stable form.
Conversely, except at very high temperatures, graph-
ite stubbornly persists at pressures far into the dia-
mond stability field. The same is true of fullerene and
amorphous carbons.
There are two preferred forms of electronic bonding
of carbon atoms in the solid state, viz.: (i) the sp
type in which a given atom is bonded to three
141
142 F. P. BUNDY et al.
equidistant nearest neighbors 120 apart in a plane,
as in graphite; and (ii) the sp3 type in which a given
carbon atom is bonded to four equidistant nearest
neighbors arranged in tetrahedral symmetry, as in
diamond. The amorphous or glassy carbon forms are
thought to be micro-zonal mixtures exhibiting these
two types of bonding.
2. THE PHASE AND REACTION DIAGRAM
The T,P phase and reaction diagram over a wide
range of pressures for pure carbon is presented in
Fig. 1. The topology of stability fields of the thermo-
dynamically stable phases is quite simple: (i) the
boundary between the graphite and diamond stable
regions which runs from 1.7 GPa/O K, to the
graphite/diamond/liquid triple point at about
12 GPa/5000 K; (ii) the melting line of graphite
extending from the graphite/liquid/vapor triple point
at 0.011 GPa/5000 K to the graphite/diamond/liquid
triple point at 12 GPa/5000 K; and (iii) the diamond
melting line that runs to higher P and T above the
triple point. The graphite/liquid/vapor triple point,
and the graphite/vapor and the liquid/vapor phase
boundaries, which occur at pressures too low for the
scale of Fig. 1, will be shown and discussed later.
Other features illustrated in the diagram include the
thermal reaction rate thresholds for the solid-solid
transformations; these will also be discussed later.
In discussing the various features of the diagram
shown in Fig. 1, it is important to clarify that there
are two principal crystallographic forms of both
graphite and diamond: hexagonal and rhombohe-
dral graphite; and hexagonal and cubic diamond.
The basic chemical bonding is the same in both kinds
of graphite (i.e. sp) and the same in both kinds of
diamond (i.e. sp3). The slight crystallographic differ-
ences are the result of different sequences of layering
in the crystal. In each of the hexagonal types of
graphite and diamond the layering sequence is
ABABAB--; that is the third layer of atoms exactly
superposes the first layer. In rhombohedral graphite
and cubic diamond the layering sequence is
ABCABC-; that is the fourth layer exactly super-
poses the first layer. The two kinds of diamond and
hexagonal graphite will be referred to in the following
discussion of Fig. 1.
Region A in Fig. 1 is the T,P region utilized for
the high-pressure commercial synthesis of diamond
from graphite. Although the process starts with solid
graphite and ends with solid diamond, it is not a
truly solid-solid transition because in this process
carbon from the graphite source dissolves into the
ambient catalyst-solvent fluid metal layer and precipi-
I
J
I
G
I31 &ND
F
I
I E
\
\
.
LIQ.
GRAPHITE
I
i0 100
Temperature (K)
Fig. 1. P,T phase and transition diagram for carbon as understood from experimental observations through 1994. Solid
lines represent equilibrium phase boundaries. A: commercial synthesis of diamond from graphite by catalysis; B: P/7
threshold of very fast (less than 1 ms) solid-solid transformation of graphite to diamond; C: P/T threshold of very fast
transformation of diamond to graphite; D: single crystal hexagonal graphite transforms to retrievable hexagonal-type
diamond; E: upper ends of shock compression/quench cycles that convert hex-type graphite particles to hex-type diamond;
F: upper ends of shock compression/quench cycles that convert hex-type graphite to cubic-type diamond; B,F,G: threshold
of fast P/T cycles, however generated, that convert either type of graphite or hexagonal diamond into cubic-type diamond;
H,l,J: path along which a single crystal hex-type graphite compressed in the c-direction at room temperature loses some
graphite characteristics and acquires properties consistent with a diamond-like polytype, but reverses to graphite upon
release of pressure.
P,T phase and transformation diagram for carbon 143
tates out on the growing diamond sink. The activation
energy of solution is only about 125-165 kJ/mol, so
this process can proceed at relatively low temper-
atures and pressures at a rate useful for synthesis.
The B region on the dashed line B,F,G marks the
temperature/pressure threshold of very fast (< 1 ms)
and complete solid-solid transformation of graphite
to diamond. This transformation always yields cubic-
type diamond. Experimentally, it is done by pressuriz-
ing graphite above 12 GPa and heating the sample
with a pulse of electric current or laser radiation.
The shaded line, C, marks the temperature/pressure
threshold of very fast and complete transformation
of diamond to graphite. It is accomplished experimen-
tally by compressing diamond crystals embedded in
a graphite rod and then flash-heating the assembly
with a pulse of electric current to the threshold
temperature (or above). No graphitization of the
diamond specimen occurs unless the critical temper-
ature is reached, at which point graphitization is
complete.
Region D delineates the general area in which
single-crystal hexagonal graphite transforms grad-
ually to retrievable hexagonal-type diamond. This
transformation occurs when the graphite is subjected
to a deviatoric stress of at least 12 GPa with the
principal stress parallel to the c crystallographic axis
and annealing temperatures of 800-2000 K. Region
E marks the upper ends of shock compression/quench
cycles that convert hex-type graphite particles,
embedded in a metal matrix for thermal quenching,
to hex-type diamond. Note that there is an upper
limit on the temperature if hex-type diamond is to
be retrieved.
Region F designates the upper ends of shock
compression/quench cycles that convert hex-type
graphite (embedded in a thermal-quenching metal
matrix) to cubic-type diamond. The dashed line
B,F,G, marks the threshold of fast pressure/
temperature cycles that, however generated, convert
either type of graphite or hexagonal diamond into
cubic-type diamond. There have been a number of
relatively recent experimental results in this area
which will be described later in the article.
When single-crystal hex-type graphite is com-
pressed in the c-direction at room temperature along
the path H,I,J on the diagram, it maintains its com-
pressed graphite structure until, in the pressure region
H-I, it loses some of its graphite characteristics such
as reflectivity, conductivity and optical opacity. From
pressures of I (about 23 GPa) up to J and above, the
Raman spectrum is similar to that of amorphous
carbon. If such a specimen, under pressure, is heated
from region J to G, it very quickly organizes itself
into cubic-type diamond. The experimental evidence
indicates that the dashed line BFG, as noted above,
marks the activation energy threshold for the fast
transformation of compressed graphite, or hex-type
diamond, into the thermodynamically stable cubic-
type diamond. According to one theoretical study
[ 71 perfect single crystal graphite, compressed at zero
0.1
0
0 -
4000 5000 6000
Temperature (K)
Fig. 2. P,Tphase diagram for the lower pressure region. The
question marks following carbynes indicate that the exis-
tence of carbyne solid phases in this P,Tregion is controver-
sial (see text). The question marks in the liquid phase region
indicate that the newest more rigorous experimental results
do not support the earlier experimental interpretations that
a non-conducting liquid phase of carbon exists (see text).
K, could be compressed to a pressure of 80 GPa
before it would spontaneously transform to diamond.
These results are discussed in more detail in a later
section.
The low pressure part of the carbon T,P phase
diagram (O-O.3 GPa) is shown in Fig. 2. The major
features are the graphite (and carbyne?)/vapor line,
the liquid/vapor line and the graphite (carbyne?)
melting line. Evidence has been reported that the low
pressure liquid is electrically non-conducting whereas
the higher pressure liquid is conducting. Indeed, a
phase boundary between the two kinds of liquids has
been suggested, as illustrated in the figure. The
liquid/vapor line should end at a critical point which
has been estimated to be roughly in the vicinity of
0.2 GPa/6800 K. At high temperatures below melting
there is some evidence for transformations from
graphite to other solid phases which are proposed to
be carbyne (linear molecules) or chaoite-like [ S,9], -
but this remains controversial and unresolved [ 3, lo].
2.1. Diamond/graphite equilibrium line
The position of the diamond/graphite equilibrium
line has been quite accurately established by
thermodynamic calculations based upon the mea-
sured physical properties of graphite and diamond in
the temperature range from 300 to about 1200 K
[ 1 I-131 and by experiments on growing or graphit-
ization of diamond [ 14,151. The position of the
upper part of the line, where it approaches the
graphite/diamond/liquid triple point, is established
by the confluence of the lines B and C, Fig. 1, which
correspond to very fast transition of graphite to
diamond and the reverse, respectively [ 16-191.
144 F. P. BUNDY et u/.
2.2. Gruphite melting line and properties of liquid
carbon
The graphite melting line at low pressures is now
well established [20-261. However, there are differ-
ences of hundreds of degrees in the temperatures
reported in the region of the graphite/liquid/vapor
triple point. There are many difficulties involved in
obtaining reliable temperature measurements under
such high temperature conditions. With improve-
ments in pyrometric equipment and procedures over
the decades, the quality of the measurements has
become considerably better. The temperature
assigned to the triple point has been moved up from
about 4000 K in the 1940s to about 5000 K in recent
years. In Fig. 1 we show 5000 K as being the most
probable value for the temperature at the triple
point [ 271.
The graphite melting line has been investigated
experimentally by Bundy [ 161, Fateeva and
Vereshchagin [ 281 and Togaya er al. [ 191 using flash
electrical resistance heating of graphite specimens in
static high pressure apparatus. All studies found the
melting temperature to increase with pressure to a
maximum at 5-6GPa, then to decrease toward the
graphite/diamond/liquid triple point. The temper-
ature of the latter is about the same as that of the
graphite/liquid/vapor triple point. These studies dis-
agree, however, on the magnitude of the temperature
at the maximum. Fateeva and Vereshchagin [28]
reported that temperature at the maximum was
1200 K above the triple point, whereas Bundy [ 161
reported a temperature difference of 600 K and
Togaya et ~2. found 200 K. The study of Togaya et al.
[19] utilized the most sophisticated apparatus and
instrumentation, so it may be considered the most
reliable. In this work, the temperatures were based
on his measured values of enthalpy to melting, which
were then converted to temperatures by applying the
data of Scheindlin and Senchenko 1251 on enthalpy
versus temperature at conditions near the melting
point.
Experimental measurements of the heat of fusion
of graphite to liquid were reported by Bundy 1161,
Heremans et al. [26] and Baitin et cd. [27]. The data
of Bundy [16] and of Heremans et al. [26] both
indicate a value of about 105 kJ/mol and the observa-
tions of Baitin et ul. [27] show it to be greater than
80 kJ/mol. These investigations, together with those
of Gathers er LI/. 1231 and Togaya et ul. [ 191, indicate
that the enthalpy increase of graphite from room
temperature to melting. lies in the range of
92-t 15 kJ/mol. The value 115 kJ/mol is probably the
most reliable.
Observations on the electrical conductivity of
liquid carbon are varied and contradictory.
Experiments have been performed in which the speci-
men is confined by solid refractory walls and flash-
heated with a short pulse of electrical current through
the specimen itself [ 16,191. All such experiments at
higher pressures indicate that the resistivity of the
liquid phase is about 60-70s of that of the solid
graphite at the melting temperature. In Bundys [ 161
experiments at 4.8 GPa the resistivity of the liquid
carbon was observed to be about 350 @cm, whereas
the data of Togaya et (II. [ 191 at 5.6 GPa show about
460 @cm.
Experiments have also been performed in which a
rod or bar-shaped specimen is mounted in a chamber
with a high pressure atmosphere of an inert gas (such
as argon) to prevent vaporization and heated with
an electric current, usually in milliseconds or micro-
seconds [20,22,23,26]. These experiments yield
widely different values for the resistivity of the liquid
phase. Ludwig [ZO] and Jones [22] reported the
resistivity of the liquid formed from melting graphite
to be very high, practically an insulator. Gathers
et d. 1231 measured values of about 1000 @cm.
Heremans vt (II. [26] melted graphite fibers under
similar conditions and report values of 30-70 @2cm.
Vaporization and melting of graphite have also
been investigated by intensive surface-heating with
focused lasers. Both continuous wave and pulsed
experiments as short as 90 fs have been performed
[27.29%321. Among the objectives of these investiga-
tors were the determination of the optical, electrical
and thermal properties of liquid carbon. The results
tend to be contradictory, depending upon the energy
insertion time, the method of monitoring the sample
spot, etc. Experiments reported before 1988 are dis-
cussed by Bundy 143 and will not be treated further
here. Baitin et al. [27] found the emissivity of liquid
carbon at i=O.65 jtrn to be about 0.60; this is close
to values for liquid metals and is therefore consistent
with liquid carbon being metallic. Reitze et al. [32]
used 90 fs laser pulses which. due to inertial effects,
result in heating at constant volume. The sample
surface was probed with approximately 100 fs reso-
lution without interference from vaporized carbon.
According to the argument of Bundy [4] regarding
thermal pressure due to heating at nearly constant
volume (see Figs 3 and 4 in Ref. [4]), the pressure in
the zone of the sample melted by the laser would be
in the range of 5-10 GPa and the carbon melt would
be electrically conducting with a resistivity of about
400 &?cm. Optically derived d.c. resistivities from the
experiments of Reitze et ul. [32] are about 600 $2cm.
which is in quite good agreement with the static
pressure results of Bundy [ 161 and Togaya clt LI/.
[ 191. All of the results listed above, except for those
of Malvezzi et a/. [31], are consistent with liquid
carbon having semimetallic properties.
Consideration of all the reported experimental
observations brings up the question of whether there
is in fact an electrically insulating phase of liquid
carbon. In exploding wire types of experiments, a
wire or rod specimen is heated into the liquid state
very rapidly in a gas or vacuum environment. As
soon as the sample begins to melt, its physical shape
becomes unstable due to surface tension and electro-
magnetic forces, as demonstrated by stroboscopic
and streak camera photographic measurements. Even
in the most recent carbon melting experiments, in
which the best circuit control and diagnostic tech-
niques are used. it has not generally been possible to
P,T phase and transformation diagram for carbon 145
reach complete melting without disruptive instabilit-
ies occurring. In order not to lose the specimen by
disintegration, the power to the specimen may be cut
off at the instability point by crow bar shunt cir-
cuitry. There appears to be no firm evidence from
the most recent experiments that supports the exis-
tence of an electrically insulating form of liquid
carbon.
Recent first-principles calculations by Galli et al.
[33] indicate that liquid carbon at low pressure and
5000 K should have mainly two-fold and three-fold
coordination. Similar calculations for liquid carbon
at 9000 K and pressures above 100 GPa [ 341 predict
the coordination to be mainly four-fold. A simple
theoretical approach to modelling liquid carbon has
been to consider it as a pseudo-binary mixture of
graphite-like and diamond-like states in which the
composition changes smoothly with pressure [ 351.
This approach leads to a melting curve maximum, as
is found experimentally for graphite. On the other
hand, the first-principles molecular-dynamics calcula-
tions performed along high-density isochores indicate
that the melting curve of diamond should have a
positive slope, i.e. (dP/dT, >O) to above 100 GPa
[34]. In the section on melting of diamond, it will
be shown that there is some experimental evidence
that liquid carbon at pressures above the
graphite/diamond/liquid triple point does contain
graphite-like and diamond-like linkages [ 36,371.
2.3. The diamond melting line
Prior to the mid-1980s it was thought that the
behavior of cubic-type diamond would be analogous
to that of the diamond-structure forms of the heavier
Group IV elements Si and Ge. Experiments demon-
strated that diamond-structure Si and Ge melt to
form metallic liquids of higher density than the solid,
which requires dT,/dP to be negative. It was also
known experimentally that at higher pressures, dia-
mond-structure Si and Ge undergo transitions at
room temperature to denser, metallic phases [6,38].
By analogy, the earlier T,P phase diagrams for carbon
showed the melting line of diamond with a negative
slope, extending to a diamond/metallic solid/liquid
triple point at higher pressure and lower temperature.
The melting line of the (supposed) metallic solid was
believed to have a positive slope, as found in Si and
Ge [ 1,2].
This was the case in the first experimental observa-
tions of melting of diamond at pressures above the
graphite/diamond/liquid triple point reported by
Bundy [ 16,171. The data indicated that at the triple
point, the slope of the diamond melting line,
dT,JdP, is about zero. However, by analogy with Si
and Ge the melting line was thought to curve back
to give a negative slope at higher pressures.
Shaner, er al. [39] shock compressed pyrolytic
graphite and measured the sound velocity in carbon
at shock pressures from 80 to 140GPa and corre-
sponding shock temperatures of 1500 to 5500 K,
respectively. The sound derived velocities are close
to the elastic longitudinal wave in solid diamond,
which is much higher than that for a bulk wave in a
carbon melt. They concluded that the diamond
carbon had not melted even though the shock states
reached far into the supposed region of liquid carbon
and that the diamond melting line must therefore
have a positive slope. At this same time diamond-
anvil cell experiments indicated the stability of cubic
diamond to extend to at least 275 GPa [40]. These
experimental results are consistent with theoretical
calculations of the phase stability of diamond relative
to the possible metallic forms [41-431 which indi-
cated that the cubic diamond form of carbon would
remain stable relative to all the likely metallic forms
up to pressures in the range of 1300-2300 GPa and
that the diamond melting line must have a positive
slope. This difference in behavior between carbon
and Si and Ge is attributed to the absence of
p-electron states in the 1s atomic core which allows
the p-character sp3 bonding electrons in diamond to
be held close to the nucleus [41].
Gold et al. [44] melted diamond at high pressure
in a diamond anvil cell. Later, Weathers and Bassett
[36] reported detailed results of diamond-anvil cell
experiments of melting small particles of diamond or
graphite in a NaCl matrix at pressures of 5530 GPa
by a pulsed Nd:YAG laser. They found that liquid
carbon is immiscible with molten NaCl and that the
carbon specimens quenched to spherical particles
ranging in size from - 1 pm down to less than a few
nanometers (Fig. 3). For the samples melted at
30 GPa the larger spherules (> 0.2 pm) were polycrys-
talline diamond with either a granular or radial
texture. The smaller spherules (< 0.2 pm) yielded
electron diffraction patterns with four diffuse rings
that correspond to the 002, 100, 004 and 110 d-
spacings of graphite - a pattern that is typical of
disordered graphite randomly oriented around the
c-axis. Dark-field electron microscope images pro-
duced by aperturing the 002 diffraction ring showed
that in the tiny spherules the c-axis had a radial
orientation. Also, it was found that the 002 and 004
(c-axis) spacings in quenched unloaded samples were
smaller in those samples that had been pulse heated
at higher pressures, while the 110 and 100 (a,b-axis)
spacings were insensitive to the pressure at the time
of pulse heating. This effect was interpreted to indicate
a graphitic structure with some sp3 diamond bond
stitching to hold the layers closer together on the
average and also that the diamond melt contains a
significant amount of sp2 as well as sp3 coordination
at pressures of 30 GPa. In 1993, after the fullerene
structures of carbon became well known and estab-
lished, Bassett and Weathers [ 371 re-interpreted their
1987 [ 361 results for the smaller (< 0.2 mm) spherules
of carbon as having the onion-like structure that has
come to be known as the giant fullerene structure
[37] similar to those reported by Ugarte [45]. They
observed evidence that the layers of graphite in their
giant fullerene structures were a graphite/diamond
hybrid, with a fraction of the bonding stitching the
thin onion-skin-like layers together. Since Bassett and
146 F. P. BUNDY et al.
Fig. 3. Bright field transmission electron microscope image showing the internal structure of quenched droplets of melted
diamond. These droplets were produced when diamond embedded in NaCl was melted at 30 GPa using a Q-switched YAG
laser. Spherules less than 0.2 pm in diameter consist of concentric layers of disordered graphite (giant fullerene) while
spherules larger than 0.2 pm in diameter consist of polycrystalline diamond. Bar scale =O. 1 pm.
Weathers had observed that the larger quenched
carbon spherules (> 0.2 mm) solidified as polycrystal-
line diamond, it was interesting to note that the
spherules of borderline size commonly had a polycrys-
talline diamond core surrounded by an onion-struc-
tured fullerene-like mantle. This indicates that under
special circumstances the hybrid fullerene structure
can be energetically stable relative to diamond even
at conditions well within the diamond stability field.
Togaya [ 181 reported experiments in which speci-
mens of boron-doped semiconducting diamond were
melted at ambient pressures of 6-18 GPa by flash-
heating them with controlled current from a capaci-
tor. Although the behavior of the resistance was
complicated somewhat by changes associated with
the doping element, and at the lower pressures by
the transformation to solid graphite, there were clear
indications that the T, of diamond increases with
pressure. This result is consistent with Togayas obser-
vation, and that of Bundy [ 171, that at confining cell
pressures of 14-18 GPa (well into the diamond-stable
region) the central pocket of liquid carbon, enclosed
by a rigid shell of solid diamond always freezes to a
mix of diamond and graphite. The explanation is that
the strong container of solid diamond with its low
coefficient of thermal expansion serves as a nearly
constant volume space for the freezing process. The
first liquid freezes as diamond having a smaller
specific volume than the liquid. The chamber being
constrained to constant volume loses ambient pres-
sure until the equilibrium pressure for graphite is
reached after which the remaining liquid freezes as
graphite. According to the Clapeyron equation, a
solid of smaller volume than the melt requires
dT,/dP to be positive since the entropy of the melt
is always larger than that of the solid.
The positive slope of diamond melting is further
supported by the early observation of Bundy [ 161
that the threshold T,P line for the fast transforma-
tion of diamond to graphite at pressures below the
graphite/diamond/liquid triple point (i.e. metastable
melting of diamond) has a positive slope (C in Fig. 1).
Additional experimental evidence that the slope,
dT,/dP, of the diamond melting line is positive was
obtained from an unpublished experimental study by
Bassett and Weathers. A mixture of Pt grains and
NaCl loaded in a diamond-anvil cell was brought up
to pressure and the individual Pt grains were heated
with a focused Nd-YAG laser. The temperature of
each grain was determined using spectroradiometric
techniques. After unloading, the Pt/NaCl specimen
was removed with the position of each Pt grain
indexed; the diamond anvil faces were then searched
for craters that would indicate melting of the diamond
face. The melt craters were observed and found to
correlate with adjacent Pt grains that were heated to
high temperatures.
In this manner, the P-T plot shown in Fig. 4 was
generated. The boundary line marks the minimum
temperature at which melt craters were observed.
This line is quite well defined and has a positive
slope. Note, however, that there is a large discrepancy
between the temperatures measured here and those
found for melting at the triple point graphite-dia-
mond-melt in quite different types of experiments;
this is shown by the dashed lines which are based on
the data presented in Fig. 1. Although the measure-
ment of absolute temperatures by this spectroradio-
P,T phase and transformation diagram for carbon 147
Temperature, K
Fig. 4. Plot of relative temperatures of melting of carbon as a function of pressure. Solid circles represent P,Tconditions
at which a melt crater was formed in the diamond anvil surface when a millisecond laser pulse heated a platinum grain
embedded in NaCl a few micometers from the anvil surface. Temperatures were based on black-body spectra of incandescent
light and pressures were measured by the ruby method. The dashed line corresponds to the melt lines shown for graphite
and diamond in Fig. 1 (see text regarding the displacement).
metric method is subject to many technical difficulties,
the relative temperature measurements are probably
quite reliable. The significant point in this case is that
all the data points shown in Fig. 4 were taken with
the same physical and optical set-up and so the slope
of the indicated melting line for diamond should be
meaningful, especially the indication that the sign of
the slope is positive.
Theoretical studies of the phase stability of carbon
at extremely high T,P by Young and Grover [46]
indicate the melting line of diamond and the
solid/solid phase boundary between diamond and the
(supposed) BC8 metallic phase are as shown in Fig. 5.
The maximum pressures and temperatures in the
interiors of the outer planets Uranus and Neptune
are in the range of 600 GPa/7000 K; under these
conditions, calculations by Ross [47] indicate that
the elemental carbon there would be in the diamond
phase. Available data indicate that free carbon in the
Earths mantle (to 135 GPa, 250%3500 K) would
also be solid diamond phase as well.
1500
G
&
w 1000
2
9
8
PI
500
0
DIAMOND
J
LIQUID
I
-I
0 5000 10,000
Temperature (K)
I I
Fig. 5. P,Tphase diagram for carbon up to extremely high
pressures based on theoretical calculations [46].
148 F. P. BUNDY et al.
2.4. The graphite-diamond direct conversion line
The dashed line, B-F-G, in Fig. 1 marks the thresh-
old of very fast (i.e. ms-ii) transition of highly
compressed graphite, or its low temperature deriva-
tives, to cubic-type diamond. The lower pressure
portion of the line near the graphite/diamond/liquid
triple point was first explored by Bundy [ 171 by
millisecond resistance heating of specimens in a high
compression belt apparatus. Recently, this threshold
was investigated by Bassett and Weathers [unpub-
lished] up to 35 GPa using the laser-heated diamond-
cell technique like that described above. In these
experiments. a shutter was installed to chop the
continuous infrared laser beam (i= 1.06 mm) into
pulses of approximately 200 ms. The spectrum was
recorded as a function of time and fit to black-body
curves by a least squares method. The wavelength of
the fluorescence emission from a chip of ruby [48,49]
in the sample was used to measure the pressure before
heating. Measurement of the temperature and pres-
sure of the graphite-diamond transition is particu-
larly well suited for investigation by this technique.
When graphite is converted to diamond, the sample
becomes transparent (Fig. 6) and the absorption of
the infrared light ceases. Thus, the temperature rises
to the transition temperature and remains there while
the conversion is taking place.
Samples for this study were prepared by placing
graphite fibers c 1 kern in diameter in a sodium chlo-
ride matrix and compressing the mixture in a stainless
steel gasket between diamond anvils ranging from
0.3 to 0.5 mm in diameter. The fibers were provided
by Dr Gary Tibbitts of General Motors. Temperature
measurements on the graphite-diamond conversion
can be made quite accurately and repeatably with
the technique for two reasons: (1) the graphite
behaves as an excellent black body; and (2) the
temperature at the conversion ceases to rise when the
carbon is converted to the transparent diamond form
and no longer absorbs the infrared radiation from
the laser.
The direct conversion graphite-diamond boundary
extends from the graphite/diamond/melt triple point
along a nearly straight line to 2500 K/l5 GPa with
a negative slope. It then makes a sharp turn and
follows a nearly straight line with a gentle negative
slope to the highest attainable pressure point at
2000 K/35 GPa (Fig. 7). This line is in fairly good
agreement with that determined by Bundy [ 171.
The large number of new data points collected in
the vicinity of 20 GPa/2500 K indicate a rather
abrupt change in slope. Figure 7 shows this abrupt
change in slope along with the metastable room
temperature transition (discussed below) reported by
Hanfland rr al. [SO], Goncharov [ 5 I] and Yagi rt trl.
[ 521. A metastable phase boundary may extend from
this room temperature metastable transition to the
point of abrupt slope change in our curve. resulting
in a metastable triple point there. The me&table
transition at room temperature is discussed in more
detail below.
The construction of a hypothetical phase line across
H,D,B (Fig. 1) as a metastable extension of the graph-
ite melting curve would imply structural similarity, if
not thermodynamic continuity, between the liquid
and the diamond-like phase produced in the low-
temperature compression experiments. In other
words, such topology would suggest that the material
is glassy. The transition could then be analogous to
the pressure-induced amorphization of ice-1 [ 533 also
observed for other materials in which the melting
curve has a negative slope combined with a frustrated
10pm
Fig. 6. Optical micrograph showing conversion by laser heating of graphite fibers to diamond (circled) at pressures greater
than 12.5 GPa. The preservation of the morphology of the fibers indicates that the graphite (opaque) does not melt. but
undergoes direct conversion to diamond (transparent).
P,T phase and transformation diagram for carbon 149
PHASES OF CARBON
I
CJ diamond I
I
I
e:
transparent
a
w
metastable & 1
:
20
graphite
b.0 0
0
I
a
\
01. I I. I. I, t. I
0 1000 2000 3000 4000 5000 6000
Temperature (K)
Fig. 7. P,Tplot of direct graphite-diamond conversion. The
dashed line separates P,T points of graphite fibers that
remained graphite (solid circles) from those at higher P,T
conditions that were converted to diamond by millisecond
laser heating pulses [Bassett and Weathers, unpublished].
solid-solid transition as in SiO, [54]. This inter-
pretation remains conjectural as the structural state
and thermodynamic properties of the carbon material
at high P-T(e.g. above the proposed metastable triple
point) has not been fully characterized. Alternatively,
the high temperature transition near 15 GPa (Fig. 7)
may be unrelated to the metastable extension of the
graphite melting curve, as indicated in Fig. 1.
Recent calculations of Zhang et al. [55] on the
reaction rate of the direct transition of graphite to
diamond as a function of P and Tyield a fast reaction
line on a P,Tchart that is remarkably similar to the
BFG threshold of Fig. 1 and Fig. 7. This similarity
implies that the shape of the BFG threshold may be
determined mainly by the reaction kinetics.
We also point out that this behavior of carbon is
analogous to that of the iso-electronic case of boron
nitride which was investigated by Corrigan and
Bundy [ 561. These studies of boron nitride indicated
a reaction rate controlled threshold line between
wurtzite BN (like hexagonal diamond) and zinc-
blende BN (like cubic-type diamond) which is very
similar to that of BFG for carbon in Fig. 1 and Fig. 7.
2.5. Cool compression ofgraphite (h,i,j, Fig. 1)
Aust and Drickamer [57] reported the first meas-
urements of the electrical resistivity behavior of single
crystal graphite compressed at room temperature
well into the lo-20 GPa pressure region. Compressed
in the c-direction and monitored in the a,b direction,
the graphite that they observed slowly underwent a
decrease of resistivity with increase of pressure to
- 12 GPa, whereupon the resistivity rapidly
increased. In some of the better specimens the resistiv-
ity rise was more than a factor of 10, suggesting a
change of phase to a non-conducting form.
Bundy and Kasper [ 581 reported results of similar
experiments with additional arrangements for heating
the specimen while under pressure to moderate tem-
peratures up to about 1500 K. For the room temper-
ature experiments the same fast rise of resistivity as
reported by Aust and Drickamer [57] started at
about 12 GPa, but upon return to room pressure the
resistivity returned to its initial value and the reco-
vered specimen proved to be graphite. By contrast,
when the graphite specimen was compressed into the
higher resistivity state and then heated to around
1200 K the resistivity increased significantly and when
it was cooled and decompressed the resistivity
increased even more. The recovered specimen was no
longer shiny like graphite, but a dull gun-metal gray.
It would scratch sapphire the way diamond does and
its X-ray diffraction pattern showed it to be mostly
hexagonal diamond. In general, the static pressure
experiments indicated that in order to retrieve hexag-
onal diamond, it was necessary to subject the speci-
men to P,Tconditions in area D of Fig. 1.
When diamond anvil cells became available to
generate pressures of up to many 10s of giga-Pascals,
the behavior of very small specimens of graphite and
graphitic carbons could be monitored by optical,
Raman, and X-ray diffraction techniques in situ at
high pressure, in contrast to the previous experiments
which were limited to electrical conductivity measure-
ments using opaque tungsten carbide anvils. Of these
types of measurements, X-ray diffraction and Raman
are able to add significant structural and crystal
chemical information to our knowledge of the carbon
phases. The observed behavior of a given specimen
during compression depends upon its initial degree
of crystallinity, the direction and homogeneity of the
pressure field, the rapidity of compression and the
type of measurement performed. These effects are
illustrated by the experimental results of a number
of different workers, some of which follow.
Goncharov et al. [ 593, using a diamond anvil cell,
found that single crystal graphite transforms to an
optically transparent state at about 35 GPa. Although
this result suggested the formation of sp3 bonding,
the Raman spectra showed no hint of the diamond
Raman band and the spectral absorption edge was
too broad for that of diamond. Further work by
Goncharov [Sl] showed that the transition in single-
crystal graphite under hydrostatic conditions (He
medium) occurs at about 23 GPa, as indicated by an
abrupt change of the Raman spectrum and the open-
ing of the band gap. Specimens with less regular
stacking between hexagonal layers required higher
pressures (to 45 GPa) to achieve the same transition.
150 F. P. BUNDY et al.
Goncharov [Sl] also found that the transition pres-
sure for single-crystal graphite can be lowered to
about 14 GPa under uniaxial stress directed along
the c-axis of the crystal. These Raman and optical
observations were corroborated by Hanfland et ul.
[60] and Utsumi et ul. [61].
Hanfland et u[. [SO] used X-ray diffraction and
Raman spectroscopy to explore the behavior of
graphite in diamond cells at pressures in the range
of 14 GPa where the previously reported increase in
electrical resistance and decrease of reflectivity occurs.
From the behavior of the widths and shifts of the
critical Raman bands and the X-ray diffraction pat-
terns, these authors concluded that the phase trans-
ition started at about 14 GPa. Yagi et ul. [ 521 used
a cubic anvil apparatus with sintered diamond piston
tips and X-rays from a synchrotron source to study
the compression of graphite. They reported that for
room temperature compression the behavior is sensi-
tive to the crystal texture of the specimen, but that
in general, graphite begins to transform at about
18 GPa.
Kertesz and Hoffmann [62] and Fahy et ul. [ 71
performed theoretical calculations of the structure
and energy of graphite during cool compression as it
approached the density of diamond. These studies
indicated that a very high activation energy is associ-
ated with transforming the strained graphite to the
diamond. In particular, the study by Fahy et al. [7]
indicated that a pressure of over 80 GPa (T=O K)
would be required to force a spontaneous transition.
From these experiments and calculations, it may
be concluded that when single-crystal graphite is
compressed along the c-axis at room temperature
(H,I,J of Fig. 1 ), the material remains a good electrical
conductor in the a,b plane directions until about
12-14 GPa. At higher pressures decreasing electrical
conductivity and optical reflectivity and increasing
optical transmittance are observed. The fact that the
material remains transparent to visible light suggests
that it remains electrically non-conducting.
Mechanically, the material is extremely strong and
was observed to fracture the faces of the single-crystal
diamond anvils that push against it [Hemley and
Mao, unpublished]. Heating this material causes the
sample to transform into coherent hexagonal dia-
mond crystallites as shown by the experiments of
Bundy and Kasper [SS] and by Utsumi and Yagi
C631.
The changes in structure and other physical proper-
ties accompanying cool compression of graphitic
carbon are still not fully understood. It is likely that
sp3 bonding begins to develop at about 12-14 GPa,
thereby removing conduction electrons from the
system and decreasing the electrical conductivity and
optical reflectivity and increasing the optical transmit-
tance. The fact that decompression from this state
yields graphite implies either a martensitic trans-
formation or a small activation energy for the back
transformation. The latter is supported by very recent
observations of pressure quenching the transparent
form at low temperatures [Badding, private com-
munication]. It is also likely that small domains of
the high-pressure phase are formed initially on room-
temperature compression. Heat-annealing the mate-
rial may then cause the small domains to coalesce
and grow into coherent hexagonal diamond crystal-
lites that are large enough and stable enough to
survive decompression 158,631. Another explanation
is that the transparent high-pressure, room-temper-
ature phase is a new allotrope of carbon and perhaps
has the properties described here for reasons other
than sp3 bonding. Clearly further work is needed in
order to resolve this question.
2.6. Shock compression of graphites (e,f; Fig. 1)
Both temperature and pressure rise during shock
compression. The rise of temperature with pressure
takes place with the compressional work done on the
specimen, the PdVwork. The greater the compress-
ibility and porosity of the specimen material the
greater the temperature rise for a given increase in
pressure. On Fig. 1, the T,P paths for shock compres-
sion of graphite would pass from room T,P toward
D,E,F. The T,P path is not reversible and unless fast
thermal quenching is provided, the temperature drops
much less rapidly than the pressure during the decom-
pression. In the commercial production of diamond
powder from graphite powder, the body to be shock
compressed consists of small particles of graphite
dispersed in a matrix of metal, such as iron or copper,
which is a good thermal conductor and less compress-
ible than graphite. During shock compression, the
graphite particles heat up more than the surrounding
metal matrix, transform to diamond, and are ther-
mally quenched during the decompression by the
adjacent cooler metal. The type and size of diamond
particles that can be produced by this method are
established and limited by the shortness of the reac-
tion time and thermal/geometry requirements
[64468].
Shock compression experiments of this type on
hexagonal graphite particles yield mostly hexagonal
diamond if the top of the cycle goes to the E region
(Fig. 1) and mostly cubic-type diamond if the top of
the cycle goes past the BFG line. To be retrieved as
diamond the specimen particles have to be at high
temperature long enough to allow coalescing of the
diamond domains into crystallites large enough that,
with thermal quenching, they can survive decompres-
sion without graphitizing. Only small particles of
diamond can be produced by this method because of
the very short time at high T,P and the necessity
for the individual carbon particles to be small in
order to satisfy the fast thermal quench requirements.
3. DIAMOND SYNTHESIS UNDER METASTABLE
CONDITIONS
As early as 1910 Tammann [69] proposed a T,P
phase diagram for carbon which included a large T,P
area at lower pressures and temperatures in which
there would be pseudo-equilibrium between dia-
mond and graphite. During this time, it also was
P,T phase and transformation diagram for carbon 151
recognized that the free energy of carbon vapor was
far higher than in either the graphite or diamond
solid forms. The quantitative determination by
Rossini and Jessup [ 111 of the free energies of
graphite and diamond showed that their difference
at one atmosphere, 0 K, is only about 2.5 kJ/mol.
This difference is insignificant compared to
-712 kJ/mol of the vapor. Hence, with respect to
free energy, the condensation of carbon vapor to
graphite or diamond would be of nearly equal prob-
ability. By proper control of the reaction path and
the nucleation conditions it should be possible to
condense carbon vapor as diamond under low pres-
sure, metastable conditions.
The long history of attempts to accomplish this
include von Bolten [70], Ruff [71], Spitsyn and
Derjaguin [72], Oriani and Rocco [73], Eversole
[74], Angus et al. [75], Matsumoto et al. [76],
Kamo et al. [77] and Spitsyn et al. [78]. The method
was generally unsuccessful because of poor control
of graphite nucleation until the early 1980s when it
was found that carbon vapor deposition from a
plasma, which contained atomic hydrogen as well as
carbon vapor and hydrocarbon molecules, nearly
eliminated the competition of graphite nuclei [77].
This allowed only the diamond to exist and grow.
Under proper conditions it has become possible to
deposit films, and sheets, of polycrystalline diamond
which have commercial utility. Recent studies have
revealed that organic molecules in the vapor play an
important role by configuring the carbon to precipi-
tate as diamond [79].
4. FULLERENE CARBONS
Rohlfing et al. [SO] reported some curious results
from experiments with a cluster molecular beam
apparatus. They used a laser to produce puffs of
vapor from a carbon rod which was entrained and
cooled by expansion through a supersonic nozzle to
form small nanometer-size clusters of carbon atoms.
The relative abundance of clusters of different size
was examined on line by mass spectroscopy. In
addition to the usual 2-20-atom clusters studied
previously by numerous workers and different tech-
niques, carbon clusters in the 40-300-atom mass
range were observed. Interestingly, only even-num-
bered atom clusters formed.
In the following year, 1985, a similar apparatus
was set up by Kroto et al. [Sl] to synthesize and
study the chemical reactivity of the small 2-30-atom
clusters; in particular, to determine whether these
clusters had the same form as the long carbon linear
chains known to be abundant in interstellar space.
The study of the small clusters was successful, but
the most significant finding was that the C,, cluster
was outstandingly stable, as well as C,, and other
species. Thinking that the great stability might be
related to some kind of closed shell structure the idea
soon developed that C,, might be a truncated icosa-
hedral cage made up of hexagons and 12 pentagons
(like the markings on a soccer ball) with a carbon
atom at each intersection [ 811. Geometrically, it was
soon realized, 12 pentagonal defects convert a planar
hexagonal array of any size into a quasi-icosahedral
cage [ 823 as in C6,,, C240 and C,,,. C,, was visualized
as having 12 pentagons and 25 hexagons by Curl
and Smalley [83]. Kratchmer is credited with the
discovery that CeO and C,, are soluble in benzene.
That, together with Huffmans productive soot-
making apparatus [84,85] made it possible to pro-
duce macro amounts of C& and C,,, crystallize it
and determine the crystal structure. The lattice spac-
ings in the crystal were consistent with the presumed
size of the closed-cage molecules. The electronic and
vibrational spectra of the molecules had already been
probed by Curl and Smalley [S6] and, in these,
theory and observation agreed, indicating that the
closed cage structure of the molecules was correct.
The discovery and development of methods of
synthesizing and separating out bulk quantities of
fullerenes have opened up new fields in chemistry
and physics. No attempt is made to review these
large and rapid developments in this article. Earlier
in this article it was pointed out that Bassett and
Weathers now interpret the graphite-like spherules of
their quenched nanometer-sized carbon droplets as
being onion-layered giant fullerenes which formed in
the stability field of diamond. We note there have
been a number of studies of high-pressure trans-
formations of fullerenes. Some of the more interesting
ones are as follows: Duclos et al. [87] on the effects
of pressure and stress on C& fullerite to 20 GPa;
Samara et al. [ 881 on the pressure dependence of the
orientational ordering in solid C6,,; Regueiro et al.
[S9] on crushing of C,, to diamond at room temper-
ature; Chandrabhas et al. [90] on reversible pressure-
induced amorphization in solid (&; di Brozolo et al.
[91] on fullerenes in an impact crater on the LDEF
space craft; Nunez-Regueiro et al. [92] on polymer-
ized fullerite structures; Wolk et al. [93] on pressure-
induced structural metastability in crystalline C,,. A
curious reaction difference is indicated for Cc0 versus
CT0 in that CT0 compresses at room temperature to
amorphous form, much like graphite and decom-
presses reversibly back to the C,, crystalline structure,
whereas the amorphous &,-derived material
decompresses to a more dense diamond-like form.
Such behavior illustrates once again how, for carbon,
the initial state and the reaction paths are important
factors in what the end product will be.
5. THEORETICAL STUDIES
In addition to the new results coming from
improved experimental methods, the large number of
increasingly accurate theoretical studies are providing
important new insights into the stability and physical
properties of known and predicted carbon poly-
morphs [94- 1041.
152 F. P. BUNDY et (11.
6. CONCLUSIONS
Carbon, the lightest of the Group IV elements, is
certainly one of the most versatile, interesting and
useful of the chemical elements in respect of the
materials properties of its various phases and forms.
Although many new things have been learned during
the past few decades about its physical forms and
properties over a wide range of pressures and temper-
atures there is still much to be established accurately
and discrepancies to be resolved - possibly new
forms and properties to be discovered that may be
both technically useful and fundamentally important.
A deeper understanding of this important system will
surely emerge with the continued development of
experimental methods to probe higher pressures and
temperatures, with increasing accuracy, precision and
sensitivity, and with improving theoretical methods.
Acknowledgemmts~We thank John Badding for useful
comments and discussion. Work performed at the
Geophysical Laboratory and Cornell University was sup-
ported by the National Science Foundation.
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