Graphitization of Diamond at Zero Pressure and at a High Pressure Author(s): G. Davies and T.

Evans Reviewed work(s): Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, Vol. 328, No. 1574 (Jun. 13, 1972), pp. 413-427 Published by: The Royal Society Stable URL: http://www.jstor.org/stable/78141 . Accessed: 25/01/2012 12:20
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Proc. B. Soc. Lond. A. 328, 413-427 (1972) Printed in Great Britain

Graphitizationof diamond at zero pressure and at a high pressure

BY G. DAVIES AND T. EVANS

Park, J. J. ThomsonPhysical Laboratory,Whiteknights The University,Reading, Berkshire,England (Communicated R. W Ditchburn,F.R.S. - Received3 January 1972) by
[Plates 2 and 3] Niatural diamonds have been heated in the temperature range of 1850 to 2000 0C at zero pressure and the rates at which diamond transforms to graphite measured. For {111} and {110} surfaces activation energies of 253+18 and 174+12 kcal mol1 (1159+75 and 728 + 50 kJ/mol) respectively have been obtained. Diamonds have also been heated in the temperature range of 1950 to 2200 0C under a pressure of 48 ? 3 kbar (4.8 + 0.3 GPa) and an activation volume of about 10 cm3 molhL obtained for both {111} and {1 10} surfaces. It is proposed that the rate controlling process in the graphitization of diamond is the detachment of a single atom from the diamond surface. This is contrary to previous proposals in which the detachment of groups of atoms have been considered to be the rate-controlling process. In the present work, it is suggested that the rate-controlling step for graphitization is the detachment of a triply bonded atom from a {111} surface and of a doubly bonded atom from a {110} surface. INTRODUCTION

Although at all temperatures diamond is thermodynamically the unstable form of carbon at zero pressure (Berman & Simon 1955) the conversion to graphite, in an inert environment, is not detectable experimentally until a temperature of about 1500?C is reached (Evans & James I964). At higher temperatures the rate of graphitization increases rapidly until at 21000C a diamond octahedron of mass 0.02 g is converted completely to graphite in less than 3 min (Howes I962). There is, however, very little information on the rates of graphitization at different temperatures and the effect of high pressures on these rates. Bridgman (1947) reported work in which diamonds were subjected to pressures between 15 and 30 kbar (1.5 and 3.0 GPa) and heated under pressure by means of a modified thermite reaction. There was a wide scatter in the amount of graphitization achieved at the same estimated temperature and pressure due presumably to the uncertainty in *thetemperatures achieved in the experiments. Eyring & Cagle (1952), assuming an intermediate activated state in the graphitization process, calculated from Bridgman's results the activation volume for the process to be 63 cm3 mol-1. Rodewald (I960) recalculated the activation volume using the most reliable results of Bridgman and obtained a value of 120 cm3 mol-1. The difference in the molar volumes of graphite and diamond is much less, namely 1.9 cm3 mol-1. From this work Rodewald argued that the most likely mechanism for the graphitization process is that groups of carbon atoms break off from the diamond surface to form [ 413 ] Vol. 328. A. 26

414

G. Davies and T. Evans

a disordered activated phase which then condenses rapidly into the stable graphite structure. Groups of carbon atoms were postulated rather than a single atom unit process because of the large estimated activation volume. Bovenkerk et al. (1959) reported an activation volume of about 160cm3 moland Bundy, Bovenkerk, Strong & Wenthorf (I96I) obtained an activation volume of about 170 cm3 mol-l in experimentson graphitizationof small pieces of diamond under high temperature and pressure conditions. They obtained, under zero pressure, a value for the activation energy of about 175 keal mol-1 (730kJ mol-1) which is the vaporization energy for diamond. No indication was given of the errors in the stated values for the activation energy and activation volume. Both Bovenkerk et al. and Bundy et al. also stated that because of the large activation volumes the unit graphitization process involves groups of atoms. In the present work diamonds have been heated to high temperatures at zero pressure and at a high pressure. From the measurement of rates of graphitization it is postulated that, in fact, the rate-controlling step in the graphitization of {111} surfaces of diamond is the detachment of a single carbon atom from the diamond surface with the breaking of three carbon-carbon bonds, requiring an activation energy of 11.0 + 0.8 eV. The rate-controlling step in the graphitization of {110} surfaces is the detachment of a surface atom with the breaking of two carbon-carbon bonds, requiring an activation energy of 7.4 + 0.5 eV. This interpretation is supported by the fact that very low activation volumes, compared with previous work, have been obtained. The measured activation volumes have been about 10 cm3 mol-' which is equivalent to an activation volume of 0.016nm3 for a single atom process. This low value for the measured activation volume is consistent with a single atom process being involved in graphitization.

EXPERIMENTAL

The conversion of diamond to graphite occurs at diamond surfaces because the density of graphite is less than that of diamond. Some internal graphitization does take place (Howes I962), but is confined to microcracks and inclusions. Previous work has shown that graphitization of octahedral surfaces is an autocatalytic process as it is initiated at discrete nuclei and progresses by spreading out from these nuclei. Thus the number of active sites available for graphitization increases with
DESCRIPTION OF PLATE

FIGuRE 1. Micrograph of a {111} surface after it had been roughened by oxidation at 850 'C. The surface consists of overlapping triangular etch pits in the positive orientation. (Magn. x 2250.) FIGuRE 6. Micrograph of a diamond after graphitization showing a triangular {111} surface and three {1 10} surfaces. The original diamond was an octahedron and further graphitization will produce a dodecahedron. (Magn. x 40.) FIGuRE7. Micrograph of a {1 10} surface after graphitization. The graphite has been removed from the surface. (Magn. x 2250.)

Davies & Evans

Proc. B. Soc. Lond. A, volume 328, plate 2

'~V'

FIGURES 1, 6 and 7. For legend see opposite page.

(Facing p. 414)

Davtes & Evans

Proc. R. Soc. Lond. A, volume 328, plate 3

FIGURE

10. Micrograph of a heavily graphitized {I 11) surface, after the graphite had been removed from the surface. The triangular pits are in the negative orientation. (Magn. x 533.)

FIGURE11. Micrograph of a diamond consisting of four { 1 0} surfaces and two {100} surfaces after graphitization. The blackened surfaces are {1 10} surfaces and the white surface is a {100} surface. (Magn. x 30.)

Graphitizationof diamond

415

time until the whole surface is saturated with active sites due to the overlapping of the regions of graphitization. Thereafter, the density of active sites remains constant with further graphitization. In order to simplify the interpretation of results, the diamonds in the present work were roughened by oxidation before being graphitized in an attempt to saturate the surfaces with active sites from the onset of graphitization. The diamonds available were regular natural octahedra of gem quality with no detectable microcracks or inclusions. The mass of each diamond was about 0.02 g. Several octahedra were placed in a tube which could be rotated so that all the diamond faces were exposed to a flow of purified argon gas which contained purified oxygen gas at a pressure of about 4 Torr ( 500 Pa), the gas mixture being at atmospheric pressure. The octahedra were tumbled at 850 0C in this gas flow for 15 min and then rapidly cooled. The surfaces were uniformly etched as shown in figure 1, plate 2, with a weight loss of about 2 %. The etch pattern consisted of overlapping triangular etch pits with <110> sides in the positive orientation, i.e. with the triangles of the etch pits in the same sense as the triangular {1 1 } surface (for definition of positive and negative pits see Frank, Puttick & Wilks 1958). Two types of experiments were done with these roughened octahedra: (1) Heating in the temperature range of 1850 to 20000C at zero pressure for various times and the graphitization rates measured in order to obtain an activation energy for the process. (2) Heating in the temperature range of 1950 to 22000C under high pressure and again the graphitization rates measured in order to determine the activation volume of the process. These two types of experiment will now be described. (1) Graphitizzationat zero pressure Diamond is attacked by oxygen, water vapour and other gases above about 600N0 and it is essential for the diamonds to be heated in an inert environment for reliable results to be obtained on graphitization rates. So as to protect a roughened diamond from active gases, it was completely surrounded by clean diamond powder contained in a graphite crucible which had previously been degassed at 2000 0C for 30 min at a pressure of 10-5Torr ( 1mPa). The crucible was supported in the centre of a cylindrical tungsten element on a small tungsten plate to which had been welded a tungsten/tungsten + 26 % rhenium thermocouple. Good thermal contact was ensured between the tungsten plate and the crucible by sticking them together with colloidal graphite. The dimensions of the crucible were extremely small compared with those of the hot zone in the heating element and the temperature gradient between the diamond specimen and the thermocouple junction was negligibly small. The heating apparatus was contained in a vacuum chamber. In a typical experiment the apparatus was evacuated for 48 h and a vacuum of better thaii 10-6Torr (0.1 mPa) obtained. The specimen which had previously been weighed was then heated to 1600 00 at a rate such that the pressure did not rise above 8 x 10-6 Torr (1 mPa). The temperature was maintained constant at 1600 0C

416

G. Davies and T. Evans

for a few minutes with continuous pumping until the pressure dropped below 5 x 106 Torr (0.6 mPa). This temperature was chosen because the graphitization rate is extremely low at 160000. The temperature was then increased quickly to the operating temperature between 1850 and 200000 and maintained at that temperature for the required time. During this period the pressure never rose above 2 x 10-5Torr (3 mPa). After the required time at the operating temperature the specimen was cooled rapidly to room temperature. Control experiments showed that the precautions against attack by active gases were effective. After removal from the furnace the diamond was covered with a coating of graphite which was removed by heating the specimen in a boiling acid mixture (40 % by volume of HC104, 10O HN03, 50 %H2S04). The diamond was then washed in distilled water and weighed to determine the amount of diamond which had been removed by graphitization. The amount of graphitization for various times was determined at temperatures of 1850, 1900, 1960 and 2000 00. For reasons which will be described in the results section regular octahedra were not suitable for some of the measurements of graphitization rates and diamonds in the shape of flat plates and termed macles were used. These had {1 11} large surfaces with a twin boundary passing through the centre and parallel to the large faces. These macles after roughening by oxidation were heated in the same way as has been described but, after cleaning, the amount of graphitization was determined by measuring the change in thickness of the plates.

(2) Graphitization underhighpressure

The high-pressure apparatus was of the tetrahedral type originally designed by Hall (I958) and later modified by Lloyd, Hutton & Johnson (1959). The pressure cell itself consisted of a pyrophyllite tetrahedron of side length 1.125 in (2.86 cm) through which a cylindrical hole of diameter 0.1875 in (0.476 cm) had been drilled from the centroid of one face to that of an adjacent face. A cylindrical carbon heater of wall thickness 0.015in (0.038 cm) and outside diameter 0.1870in (0.475 cm) was inserted into this hole as in figure 2. Carbon disks 0. 020 in (0.051 cm) in thickness were placed in countersunk holes at either end of the heater to establish good electrical contact to anvils which touched the faces. A roughened diamond octahedron weighing about 0.004 g was placed in the centre of the heater and firmly packed with dry hexagonal boron nitride powder. The remainder of the space in the heater cylinder was packed with pyrophyllite powder. The boron nitride was used as packing around the diamond to ensure ease of extraction of the diamond after an experiment and because boron nitride did not react chemically with the diamond during the high temperature - high-pressure treatment. A tungsten/iridium thermocouple was led into the cell so that the hot junction was near the diamond. The calibration of this thermocouple for temperature measurement at high pressure will be described in a later section. The temperature was raised by passing an a.c. current through the carbon heater and the power input measured as a function of the thermocouple reading. The pressure was imposed by anvils pressing on each of

Graphitizationof diamond

417

the faces of the pyrophyllite tetrahedron. The pressure calibration will be described in a later section. In a typical experiment a roughened diamond octahedron, which had previously been weighed, was placed in the pressure cell and the pressure raised to the required value by imposing a load of 190 tonf (1.9 MN) on the faces of the tetrahedron. The temperature was then increased to the required temperature and maintained there for the necessary time. At the completion of the treatment the temperature was reduced to room temperature and the pressure released. The graphite was removed from the diamond surfaces by heating in the boiling acid solution, cleaned and weighed. Roughened macles were also used and the amounts of graphitization determined as before by thickness changes.
carboncontactdisks pyrophyllite tetrahedron hexagonalboron nitridepacking plug solid pyrophyllite
\ it /

pyrophyllite pow~~~~~~poder
thermocouple

diamond

specimen

/
/

~~~~~~~~~~~insulator

coating ~~~~~~~~~~~plastic

carbonheatertube tungstenwire iridiumwire

FIGURE 2. Schematic diagram of the pressure cell with the diamond and the

tungstenliridium thermocouple in position.

The main difficulty about high temperature-high-pressure work is to determine the actual temperatures and pressures to which the specimen is subjected in an experiment and so it is necessary to describe the way in which these two parameters were determined. (a) Temperature measurement in the high-pressure apparatus The e.m.f. generated by thermocouples is affected by pressure and most work on the pressure dependence of the e.m.f. has been carried out on chromel/alumel and platinum/platinum + 10 % rhodium thermocouples. As the temperatures of interest

418

G. Davies and T. Evans

in the graphitization of diamond under pressure are above 1900 'C, the chromel/ alumel thermocouple was not suitable as it failed at about 13500C under the pressure used in the present experiments due to melting at the position where the thermocouple passed through the heater. Also the platinum/platinum+ 10 % rhodium thermocouple failed at about 17500C under the same conditions due to melting at the heater. Thus a tungsten/iridium thermocouple which can reach a temperature of about 2300 0C under pressure was chosen. The pressure correction for this thermocouple has not been determined and so a pair of thermocouples,

platinum

<

platinum+ 10% rhodium iridium

tungsten

FIGuInE3. Schematic diagram of the platinum, tungsten, iridium, platinum 10% rhodium

wires connectedto a commonhot junction in position in the pressurecell.

with a common hot junction, were made as shown in figure 3 to determine the pressure correction for the tungsten/iridium thermocouple. Each face of the pressure cell was subjected to a load of 190 tonf (1.9 MN) (this is the load used in all the experiments described in this paper) and the cell gradually heated. The outputs from the Pt/Pt 10 % Rh thermocouple and from the W/Ir thermocouple were measured by a pair of carefully calibrated digital voltmeters. Readings were taken at 200C intervals until the Pt/Pt + 100 Rh thermocouple failed, usually at a temperature of just above 17000. After the appropriate pressure corrections had been made to the Pt/Pt +10 %O output, the pressure calibration for the W/Ir thermocouple Rh was determined and extrapolated from 1700 to above 20000C. Several separate calibration experiments gave the same results within experimental error. The pressure correction used for the Pt/Pt + 10 % Rh thermocouple was that given by Getting & Kennedy (I970). Thereafter in the experiments with the diamond in position in the pressure cell a W/Ir thermocouple was used for the deterinination of temperature.

Graphittzationof diamond
of (b) Calibration pressure

419

The pressure calibration of the pressure cell at room temperature was done in the usual manner by measuring the imposed load at which a bismuth wire, which has been inserted into the pressure cell changed resistivity when the wire underwent a phase change from bismuth I -- II at 25.4 kbar (2.54 GPa). Thallium wire was substituted for the bismuth wire and the load for the transition from thallium II -+ III at 36.7 kbar (3.67 GPa) was measured. All experiments, as has already been mentioned, were done at an imposed initial load of 190 tonf (1.9 MN) which was equivalent to a pressure af 36 kbar (3.6 GPa) at room temperature in the centre of the pressure cell. It has been shown by Hulse & Graf (I965) that pyrophyllite undergoes a series of changes in structure and strength as the temperature is increased beyond 400 00. As the pyrophyllite at the heating tube was above 200000 near its centre and the outside of the tetrahedron was only at a few hundred degrees the mechanical properties of the pyrophyllite changed widely as the temperature was raised and the pressure calibration at room temperature was not applicable at higher pressures for the same imposed load. Following the work of Strong & Tuft (I969) we produced a thermocouple junction of platinum, iron and platinum +10 %O rhodium wires and inserted it into the centre of the pressure cell. The thermoelectric voltage between the Pt + 10 % Rh wire and the Fe wire was measured by connecting them to the Y-axis terminals of an XY recorder and that between the Pt and Pt 10 %Rh wires by connecting them to the X terminals. The initial load of 190 tons was imposed and the temperature slowly increased. When the iron at the hot junction underwent the transition from acto y iron a peak was produced on the X-Y trace, the X position of which gave the temperature of the transition. The temperature observed was not corrected for pressure effects as the data used to obtain the pressure were determined by using the same type of thermocouple and were presented in uncorrected form. The effect of pressure on the ac-p- y transition temperature in iron is given by Kaufman, (lougherty & Weiss (I963). For the initial load of 190 tonf (1.9 MN), at a temperature of 661 + 700 a pressure of 45+ 2kbar (4.5 + 0.2 GPa) was obtained. Thus a substantial pressure rise from 36 kbar (3.6 GPa) at room temperature occurred on heating to about 660 0C. It was next necessary to measure the pressure at temperatures above 1000 0C to determine if this increase in pressure with temperature was maintained. The melting-points of gold and nickel under pressure were obtained by using a bridge circuit which was capable of detecting small abrupt changes in resistance when the metal melted. For gold, a thermocouple was made by fusing a platinum wire of 0.5 mm diameter, to one end of a piece of gold wire, 1 mm in length and 0.25 mm in diameter. The other end of the gold wire was connected to a platinum+10%O rhodium wire of 0.5mm diameter. This junction was placed in the centre of the pressure cell as shown in figure 4 and a 1.2 kHz signal applied to

420

G. Davies and T. Evans

the thermocouple. The a.c. voltage, which was proportional to the resistance, was rectified and amplified and the d.c. output monitored by the Y-axis deflexion oil an X-Y recorder. The thermoelectric voltage, which was unaffected by the a.c. signal, of the thermocouple was monitored by the X-axis deflexion. An initial load of 190 tonf (1.9 MN) was applied and the temperature raised at a conistant rate. When the gold melted a small step parallel to the Y-axis was produced on the recorder trace and the melting temperature was then obtained from the X-axis positionl of the step. The data used for the melting-points of gold as with pressure were those of Mitra, Decker & Vanfleet (I967) which were in substantial agreement with those of Cohen, Klement & Kennedy (I966). The gold wire melted at 1325 ? 100C which showed that the pressure in the cenitre of the cell was 47 + 2 kbar (4.7 + 0.2 GPa) at that temperature. The same procedure was carried out with nickel wire substituted for gold wire. The data concerning the melting-points of nickel under pressure were those of Strong & Bundy (I959) after correction of their pressure scale. This was the least accurate temperature-pressure point obtained and gave a pressure of 47+6 kbar (4.7 + 0.6 GPa) at 1615 + 15 00. Thus it is evident that beyond 6600C the increase in pressure with temperature was small and that it was reasonable to assume a pressure of 48 + 3 kbar (4.8 + 0.3 GPa) at 2000 0C.

gold

platinum- FIGRE

--platinum +

10% rhodium

4. Schematic diagram of platinum and platinum 10% rhodiumwires connected to either end of a gold wire and positionedin the pressurecell.

RESULTS Graphitization at zero pressure In the first series of experiments a roughened regular octahedron was placed in the furnace and heated to the required temperature for a certain time. The diamond

Graphitizationof diamond
12000?C

421

60
640

/
It

11960

iX

1900.

" 1850'C*

~40-

l5~~~p'

~20!

CO

11

_,

/ 1.,.1^

40

120 80 time/min

160

200

FiGuRE 5. Graphs of the percentage loss due to graphitization against time at various temperatures. Each graph shows the weight loss with time for one diamond.

was then removed, and after the graphite had been dissolved from its surfaces, weighed and then returned to the furnace for another interval of heating at the, same temperature. This process was then repeated. Diamonds were heated in this.
way at 1850, 1900, 1960 and 20000C and the results are shown in figure 5 which gives. graphs of the percentage mass loss against time at these temperatures. At first, sight it might appear from the shapes of the graphs that the initial roughening of the octahedra had not saturated the surfaces with active sites as the curves have thesame shapes as would be expected from an autocatalytic reaction. For instance, with the 19000C graph, the shape of the gra-ph from the origin to A could be explained by a progressive increase in the number of active surface sites with time until at A the surface became saturated. Then from A to B there would be a linear region when the density of active sites did not change and the slight curve down-wards after B could be due to the small size of specimen remaining. In fact, this. interpretation for the shapes of the graphs is not correct. An examination of the specimens with an optical microscope showed that between the origin and A with the 190000C graph, {1I 0} surfaces moved rapidly inwards from the edges of the original octahedron and as A was approached the surface area became increasingly composed of {1 10} surfaces and less of {1 11} surfaces. At A the original {1 11} surfaces had disappeared and the specimen was in the shape of a dodecahedron. Figure 6, plate 2, shows a micrograph of a specimen after graphitization in the region between the origin and A and showing a triangular {1 1 1} surface with the larger {I1 0} surfaces at the sides. The linear region from A to B was determined by the rate of graphitiza-. tion of a dodecahedron with {1 10} surfaces. The {1 10} surfaces were roughened due to the graphitization as shown in figure 7, plate 2. Beyond B the graph does reduce its slope, presumably owing to the reduction in surface area as the diamond became

422

G. Davies and T. Evans

smaller. It appears reasonable that the linear regions of all the graphs can be taken as a measure of the rate of graphitization of the { 103} surfaces at the temperatures used in the experiments. The rate of graphitization dx/dt can be expressed as

dx/dt = A eASIR e-AEITR

where A is a parameter containing a frequency factor and the number of active surface sites available for graphitization. AE is the activation energy at zero pressure for the graphitization process and AS is the entropy change. This equation can be expressed as dx/dt = C e-AEIRT, where C is a constant if the density of active surface sites is constant which appears likely in the linear parts of the curves in figure 5 owing to the uniform roughness of the {1 103 surfaces in these parts. The activation energy AE can be determined from the slope of an Arrhenius plot of ln (dx/dt) against 1/T. Figure 8 is a graph of a quantity which is proportional to the mass loss per unit area per unit time on a logarithmic scale against IIT of the linear { 103 parts of the graphs in figure 5. The slope gives an activation energy AE of 175 + 12 kcal mol-b (732 + 49 kJ molb) for the graphitization of {1 103} surfaces of diamond. The linearity of the graph in figure 8 shows that it is reasonable to interpret the graphitization results in terms of an activation energy for the process. 80 40\ 20_ 10_
6 4 -I 2I _ 4.4 1 4.5
X _I _

4.6

4.7-

A--

104KIT
FIGuRE 8. Arrhenius plot of a quantity 1 which is proportional to the rates of graphitization

of the linear parts of the graphs in figure 5 against temperature-' for {110} surfaces. The ordinate has a logarithmic scale.

Although the original intention of the experiments was to measure the activation energy for graphitization of the original {1 11} octahedral surfaces, it was inot possible to do this because the {1 10} surfaces rapidly determined the graphitization rates. The region between the origin and A in figure 5 was determined by the differing rates of both the {110} surfaces and the {111} surfaces with the former surfaces getting larger and the latter getting smaller from the origin to A. All that can be

Graphitizationof diamond

423

said from this region is that the graphitization rate for {1 10} surfaces was faster than that for the {1 11} surfaces. Thus roughened flat plates, namely macles, with {111} large surfaces were substituted for the regular octahedra to determine the activation energy for {111} surfaces. The amount of graphitization was measured by the change in thickness of the plates. During graphitization {1 10} surfaces moved in from the edges of the plates but there were regions near the centre of the macles where sufficient thickness measurements could be made before the specimen was completely graphitized by the movement inwards of the {110} surfaces. Figure 9 is an Arrhenius plot of the rate of graphitization on a logarithmic scale against 1/T.
0 2.o

_ 1.0
0.5_ 0.2 -

e 0.1
4.4 4.5

-I'+\

4.6

104K/T
FIGuRE 9. Arrhenius plot of the rate of graphitization on a logarithmic scale against temper-

ature-' for [1111 surfaces. The graphitization rates were measured by changes in thickness of diamond macles.

The slope gives an activation energy at zero pressure of 253 + 18 kcal mol-1 (106 + 75 kJ mol-1) for the graphitization of {1 1 1} surfaces of diamond. The surface of a heavily graphitized surface is shown in figure 10, plate 3. There is evidence for triangular pits with <110> edge directions being formed with a negative orientation, i.e. the triangles outlining the pits were in the opposite sense to the triangular {1 11} surface and the corners of the pits were pointing to the edges of the triangular {1 1 1} surface. During the conversion of an octahedron into a dodecahedron there was no evidence for the formation of {100} surfaces due to the flattening of the corners of the original octahedron. Thus it may be inferred that the rate of graphitization on {100} surfaces would be much lower than that of the {110} surfaces. This was confirmed by heating to 1870 0Cfor 5 min a diamond which was in the shape of a brick and had four {1 10} and two {100} surfaces. Figure 11, plate 3, shows a micrograph of the specimen after the heat treatment. The {1 10} surfaces were covered with a black coating of graphite, but the {100} surfaces showed isolated small regions of graphitization and it was obvious that the rate of graphitization of {100} surfaces was very much slower than for the {110} surfaces.

424

G. Davies and T. Evans

Graphitization underhighpressure

It has been shown that the graphitization rates of roughened diamonds at zero pressure can be described by dxldt = C e-AEIRR. When graphitization is examined under high pressure the rate can be expressed as
dx/dt
-

C e(E+PAV)/R

where P is the imposed pressure and A V is the activation volume. In the present experiments specimens were heated at a pressure P and the temperature E4at which a particular rate of graphitization occurred was measured. If the same rate of graphitization occurred at zero pressure at a lower temperature T1 then

Ce-AE/RTI
Thus

C e-(+PAEV)IRT2.

AV = AE(T2-T1)/PT1.

The first specimen examined was a dodecahedron of mass 0.003 g which was produced by graphitization at zero pressure of a roughened octahedron. The size of the specimen for the high-pressure work was much smaller (about one-tenth) than those used in the heating experiments at zero pressure because more reliable and reproducible results could be obtained with the specimens being as small as possible owing to the steep thermal gradients in the centre of the high-pressure cell. With the pressure at 48 + 3 kbar (4.8 + 0.3 GPa) the rate of graphitization was 1 % of the initial weight of the specimen per minute at 2020 + 10 'C. At zero pressure this rate of graphitization was achieved at 1872 00, namely (T2- T1) was 148 + 10 0C. When these results are substituted into the last equation an activation volume A V for graphitization of {1 10} surfaces of 10.2 + 3.0 cm3 mol-' was obtained. This experiment was repeated several times and the same activation volume obtained within experimental error for different values of T2 and therefore also for T1. In the next experiments a flat roughened octahedron of weight about 0.004g, was used in one experiment at a pressure of 48 + 3 kbar (4.8 + 0.3 GPa). A rate of graphitization of 2.5 + 0.5 x 10-4mm/min was measured by the thickness change at 2020 + 100C. The same rate at zero pressure was at 19300C which gives a temperature difference of 90 '0. Thus an activation volume A V of 9.2 + 2.0 cm3 molwas obtained for graphitization on {111} surfaces. This specimen was in contact with hexagonal boron nitride during the high temperature-high pressure treatment and to confirm that no chemical attack by the boron nitride was occurring, a roughened flat octahedron again about 0.004 g in mass was coated with colloidal graphite to protect its surface from possible chemical attack by the boron nitride. A rate of graphitization of 39 x 10-4 mM/min was measured at 2160 + 200C at a pressure of 48+ 3 kbar (4.8 + 0.3 GPa) and the same rate at zero pressure occurred at a temperature of 2046 0C. This gave an activation volume AV of 11.0 + 3 cm3 mol- for graphitization of a {1 1 1} surface. Thus, within experimental

Graphitizationof diamond

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error, the two activation volumes for the {I 11} surfaces were the same despite the change in surfaces environment. Also within experimental error the activation volumes for both the {111} surfaces and the {110} surfaces were the same. The experiments were not sufficiently accurate to measure any difference, if present, in the activation volumes of the two types of surface and it is probably prohibitively difficult to get a sufficiently high precision in such high-pressure experiments.

DISCuSSION The low estimated activation volume for the graphitization of {111} and {110} surfaces, namely about 10 cm3 mol-1, indicates that the unit process involved is the detachment of a single atom from the diamond surface into an intermediate activated state. If a single atom process is involved, the value of 10 cm3 molk- would be equivalent to an atomic activation volume of 0.01666 nm3 which is the volume of a cube of side length 0.255 nm (ao for the unit cell of diamond is 0.3567 nm). Although there is no information on the size to be expected of a carbon atom in an activated state the measured activation volume seems to give a reasonable value for a single atom process. Certainly there is no need to postulate groups of atoms being involved in the unit process to explain this low activation volume. The concept of a process involving single atoms is also supported by the measured activation energy of 253 + 18 kcal mol- (106 + 75 kJ mol-1) for the {111} surface. If a single atom process is involved, this energy is equivalent to an energy of 11 + 0.8eeV being necessary to detach a single atom from the {1 1 1} surface. As the vaporization energy for diamond is 175 kcal mol-h (732 kJ mol-), which is equivalent to breaking two carbon-carbon bonds per surface atom, then the rate controlling step for the graphitization of a {1 11} surface is the detachment of a surface carbon atom by the breaking of three carbon-carbon bonds. There is a difficulty here as it is known that when an unroughened octahedron with {1 1 1} surfaces is graphitized, the graphitization spreads out from discrete nuclei and does not occur over the whole surface from the start of graphitization. However, on a geometrical model of a {1 11} surface of diamond, all the surface atoms are bonded by three carbon-carbon bonds with one 'dangling bond' per atom perpendicular to the surface. Thus it might be expected that if the measured activation energy is 11 + 0.8 eV graphitization should occur everywhere on the surface and not from discrete nuclei. Work by Lander & Morrison (i963) on low-energy electron diffraction from clean germanium and silicon {1 11} and {100} surfaces suggests an answer to this difficulty. They interpreted their measurements by stating that on both these types of surface the dangling bonds join by bridging, thus displacing the surface atoms from their normal lattice positions. If the same type of bridging of dangling bonds occurs on flat diamond surfaces an activation energy of greater than 11 eV would be required to detach an atom from a flat {1 11} surface and graphitization would proceed mainly from nuclei. It was stated in the results section that heavy graphitization of {1 11} surfaces produced triangular pits in the negative orientation with sides parallel to <110> directions. As Frank et at.

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pointed out a negative monomolecular step in a <110> direction has triply bonded atoms at the edge of the step and to breach the step, thus forming two kinks, an atom needs to be detached with the breaking of three carbon-carbon bands. Then the rest of the row of atoms at the edge of the step can be removed one by one from the kink sites by breaking two bonds per atom. It is suggested that the rate-controlling step in the graphitization of {111} surfaces is the breaching of a <110> negative step by the detachment of an atom from the edge of the straight step with the breaking of three carbon-carbon bonds. This would result in the formation of the negatively oriented triangular pits which have been observed. This is one of several possible mechanisms which would give a measured activation energy of 11 + 0.8 eV for the {111} surface. For graphitization of {1 10} surfaces the measured activation energy of 174 + 12 keal molh (728 + 49 kJ mol-1) (the vaporization energy for diamond is 175 kcal mol-1 (732 kJ mol-1)) gives an atomic activation energy of 7.4 + 0.5 eV. Thus the rate-controlling step is the detachment of a single atom from the surface with the breaking of two bonds. Examination of an atomic model of a (110) surface with the surface atoms in their normal lattice positions shows that each surface atom is bonded by three carbon-carbon bonds. Since the dangling bonds are unfavourably oriented for bridging and because of lack of low-energy electron diffraction information it is not clear if bridginig of dangling bonds takes place. If, however, it does not, the surface consists of zigzag parallel rows of surface atoms along the [110] direction, with each atom triply bonded. On a roughened (110) surface these rows would be frequently breached and rows can be removed atom by atom with the breaking of two bonds per atom. It is thus suggested that the measured activation energy is due to the removal of doubly bonded atoms from the ends of the rows. The low rate of graphitization of the {100} surface compared with that of the {1 10} surface follows from the bridging of dangling bands on the {100} surface as shown by Lander & Morrison for germanium and silicon. The dangling bonds on the {100} surface are favourably oriented and spaced for bridging to take place and thus a high energy (probably greater than 1 1 eV) is required to detach an atom from a flat {100}. In conclusion, the results of this paper favour the view that graphitization of diamond involves the detachment of single atoms from the diamond surface to an intermediate activated state and the rate-controlling step for the {11 1} surface is the breaking of three carbon-carbon bonds and for the {1 10} surface the breaking of two carbon-carbon bonds. Evans & James (I964) have suggested that the next step would be the growth of graphite grains from amorphous carbon produced by the primary graphitization process which has been considered in this paper. The authors are extremely grateful to the Science Research Council for providing the money to set up and run the high-pressure apparatus. The authors are also very grateful to Dr G. Kallman of the Diamond Research Laboratory, Johannesburg, for letting them know before publication about the technique of the 'gold wire' thermocouple which he developed.

Graphitizationqf diamond
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