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The Graphitization of Diamond

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1962 Proc. Phys. Soc. 80 648 (http://iopscience.iop.org/0370-1328/80/3/310) View the table of contents for this issue, or go to the journal homepage for more

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PROC. P H Y S . SOC.,

1 9 6 2 , VOL. 80

The Graphitization of Diamond

BY V. R. HOWES J. J. Thomson Physical Laboratory, University
of Reading

Communicated by R. W. Ditchburn; M S . received 16th March 1962, in revised form 16th April 1962

Abstract. In experiments on diamond octahedra at temperatures of 1700 'c a d above in high vacua, graphite has been observed to develop both internally a d on the surfaces. The surface graphite that has been observed is different from
that associated with etching, and is independent of the gaseous environment. Its development increases with t h e and rapidly increases with temperature. The internal graphite always has associated with it an intense strain in the surrounding diamond. It has varied in appearance from isolated particles to orientated distributions of crystallographic microscopic inclusions. Some diamonds have remained completely free from internal changes. For the diamonds which have developed inclusions the changes have occurred suddenly and discontinuously, the internal graphite generally not extending with time or increasing temperature. It is thought that both phenomena are due to a physical phase transformation, and that defects, of some particular kind which are present inside many but not all diamonds, initiate the transformation which has given rise to the internal changes that have been observed.

5 1. I N T R O D U C T I O N
N the experiments to be described, natural diamonds have been carefully examined with an optical microscope before and after being heated to temperatures within the range 1400-2100 OC. A vacuum of 5 x 10-6 m H g or better has usually been m i an tained during the heat treatment. This allows the changes that occur to be studied without the obscuring and complicating effects of etching by the surrounding gases. The results are drawn from experiments on thirty-five diamonds, seventy-five furnace runs having been carried out on different diamonds for different times and temperatures, The diamonds were small octahedra; thus the only faces observed were (111) faces except where (110) faces developed with the heat treatment. The weight of each diamond was approximately carat. Friedel and Ribaud (1924) first reported the development of a black layer on the surface of diamond at temperatures between 1500 O c and 1800 O c , which was bright and hard and dissimilar to the graphite associated with the 'burning' of diamonds. They also reported the total transformation of diamond to graphite at a temperame of around 1900 OC. They found that a large and sudden change occurred i the b k n fringence pattern just before the bursting and graphitization of the stone. Seal (1958) studied the surfaces of octahedral diamonds after heating up to 1800 OC and observed raised triangular pyramids of graphite, but the vacuum in which the diamonds Were heated was only lO-4mmHg and no mention is made of the appearance after de. graphitization. Seal also reports evidence of graphitization occurring at points just below the diamond surface and bursting through to the surface. The present work shows that on all the diamonds heated above 1700 O C graphite was found on the surfaces. Its formation was independent of the surrounding gas pressure. The graphite started to form at points, and then spread and increasedfo build a layer similar to that described by Friedel and Ribaud. Many of the diamonds$
648

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but sipficantly not all, developed black inclusions upon heating. These ranged from ;solated particles to distributions of crystallographically orientated microscopic inclusions. The structure, time and temperature dependence, and other properties of both the inclusions and the surface graphite have been observed.

$ 2.

A P P A R A T U S AND P R O C E D U R E

The furnace used was of the design described by Haworth (1958) and consisted essentially of a cylindrical tungsten element, surrounded by radiation shields, with water-cooled electrodes, inside a water-cooled vacuum chamber. The temperature was measured with an optical pyrometer which had been checked against standard melting points to allow for possible non-black-body conditions; measurements were made with estimated error of i30 OC. The diamond specimen, placed between two flat diamonds, 172s held in a tungsten clip which was balanced on top of a tungsten pedestal inside the element. Thus only diamond and tungsten were in the hot zone of the furnace. At high temperatures it was found that diamond was attacked by tungsten vapour, tungsten carbide being formed. The two diamond flats were used to protect the top and bottom faces of the octahedral specimen from this attack, so that these faces and the interior could be examined free from the interfering effect of the tungsten reaction. Careful microscopic examination was carried out to select diamonds with no unusual surface features, and no visible internal flaws or inclusions. For this examination, illumination at right angles to the direction of observation was used, together with an objective lens which had just sufficient working distance to be able to focus through from face to face of the diamonds available. A maximum limit to the magnification of 500 was obtainable, so that with careful scanning one could be sure of detecting inclusions of size 1 micron or bigger. Before being put into the furnace the diamonds were boiled in concentrated nitric acid, washed in distilled water, and refluxed in alcohol vapour; after the acid treatment the diamonds were handled only with glass tweezers. Because of the importance of obtaining as high a vacuum as possible, the vacuum furnace was pumped down overnight before each experiment, a liquid air trap was used during each experiment, and the heating up was carefully controlled to allow for outgassing. In this way a vacuum of 5 x 10-6 mmHg or better was maintained. However, for temperatures greater than 2000 O c the rapidity of graphitization made it necessary to keep the times very short, SO that some pressure rise was inevitable; the procedure then followed is described later. After an experiment the temperature could be reduced to below 1400 OC in less than 30 seconds. After the furnace runs a study was made of the surfaces of the diamond specimens. Then the stones were boiled in a strong degraphitizing agent consisting of 3 parts 60% perchloric acid, 1 part concentrated nitric acid and 4 parts concentrated sulphuric acid. Finally, a thorough examination of surface and interior was carried out.

$3.

T H E S U R F A C E PHENOMENA

3.1. The Exposed and the Protected Faces After experiments at 1700 O and above, x-ray examination has shown the presence c Ofa tungsten carbide layer on the specimen surfaces that had been exposed during the heating, and a graphite layer on the protected surfaces. The former layer had a rough etch appearance showing no regular structure. Every diamond that has been used in at temperatures of 1700 O and above has shown the formation of black c
6

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V. R.Howes

nuclei on the protected faces. These nuclei have extended and increased in number with time of heating, until by interweaving they have formed a continuous black layer of graphite. The observations described below have been made on the protected faces of the diamond specimens.

3.2. Time and Temperature Dependence After experiments at 1400 OC for periods of up to 20 hours duration and at 1600 oc lasting up to 5 hours, no nuclei could be detected on the surfaces examined using t6e highest optical microscope magnifications. At 1700 O c the black nuclei form slowly, not being detectable with less than 15 minutes heating. After 30 minutes they are Seen clearly as isolated propeller shapes-figures l(a) and (b) show the same area of surface after 15 and 45 minutes. Figure l(e) shows the whole of another diamond face approximately half its area still clear after 120 minutes. At higher temperatures the graphitization increases rapidly; figure l(c) shows the same area as figure l(b) &er a further 5 minutes at 1800 OC. After 5 minutes at 1900 OC the surface was completely covered, the interwoven appearance of the layer is seen in figure l(f) where some of the graphite has been removed.
3.3. The Nuclei These grow as propeller shapes as seen in figure 2(a), with the three blades being in the (112) directions parallel to the (111) plane of the diamond. The orientation with respect to the triangular face of the diamond octahedra can be seen in figure l(e). Side branches develop from the main branches, again in (112) directions, forming complex nuclei as in figure 2(b). Although nucleation of these isolated propellers does occur all over the surfaces, steps, such as the edges of growth sheets, trigons, and ring cracks, do form preferential sites. The nuclei which then develop have single or double blades extending away from the step edge in (112) directions. The nuclei also appear on (111) cleavage faces when cleaved diamonds are heated, single blades occurring densely at the cleavage steps in all three (112) directions according to the direction of the step, as seen figure 2(c). Some isolated nuclei were also observed. On the cleavage face of another diamond a t i boundary was observed, but after heating no nucleation had occurred wn at this boundary, although graphite blades were profusely clustered along the cleavage steps crossing it. In order to see if the graphite propeller nuclei were atmosphere dependent, the pressure was increased up to 5 pmHg during a furnace run of 15 minutes at 1700 'C. No increase in number or size of nuclei was observed but only the rough etch attack shown in figure l(d). This can be compared with figure l(a) for which the pressure did not rise above 0.01 pmHg. At 1800 O c with an air pressure of 5 pmHg, the intense etch attack on the diamond and the graphite by the air left only an extremely rough black surface. However, after the matt black graphite layer due to the etching readon had been removed by degraphitization, propeller-shaped markings could be seen On the surface beneath. Another experiment done without using the liquid air trap on the vacuum system, so that the oil vapour pressure inside the furnace was Sfighds increased, gave no visible change in the appearance of the diamond surfaces. When the diamond specimens were boiled in the degraphitization agent it was noted that the propeller-shaped nuclei were very little changed. Figures 2(a) and 2(b) are Of surfaces that have undergone this treatment and it can be seen that the graphiteba been removed only at the smallest propellers and at the very edges of the larger ones) an imprint in the diamond surface remaining.

The Graphitization of Diamond

65 1

Figure 1. (a), ( b ) , (c) x 141, part of an octahedral diamond face after 15 minutes at 1700 O c , after another 30 minutes at 1700 Oc, after another 5 minutes at 1800 "c respectively; (d) 141, another face exposed to air at 5 pmHg pressure for 15 minutes x at 1700 " c ; ( e ) x 60, the whole of another face after 120 minutes at 1700 Oc; (f) x 372, a face after 5 minutes at 1900 O c when the surface graphite has been partially cleaned off.

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Figure 2. ( a ) , (h) x 10.50, surface graphite nuclei; (c) x4.50, nuclei forming at cleavage steps on a cleavage face o f diamond.

3.4. The Layer T h e graphite layer that was formed on the (111) faces of the diamond octahedra was smooth and compact, and was extremely difficult to remove with the degraphitization agent used; even prolonged boiling in the agent removed only small patches. At these patches the thickness of the layer was measured, by the fine focusing control on the microscope, to be of the order of 1 micrometre. An attempt was made to polish the layer off the surface using a fine alumina polishing powder, and figure l(f)shows the appearance afterwards. T h e exposed diamond surface had a grooved pattern corresponding exactly to the structure of the graphite layer. T h e graphite layer was studied by reflection electron diffraction, which revealed that the graphite had a grain size of the order of 100 A. 'fhere was definite evidence of a preferred orientation such that the c axis and the a axis of the graphite were in the plane of \the surface, i.e. were orthogonal to the diamond (111 ) direction. But there was also evidence of randomly orientated graphite being present as well.

5 4. T H E

INTERNAL PHENOMENA

4.1. Results for Thirty-Jive Diamonds In the initial examination of all diamonds available, the proportion of rejections amongst gem quality diamonds was high. For example, in one batch of forty-fivegem

The Graphitization of Diamond

653

quality octahedra only nineteen had no visible inclusions. Many of the inclusions seen

in the rest were far too small to be detected by eye or with a hand lens.
Of the thirty-five diamonds free from visible inclusions that were used in the experiments, sixteen contained black inclusions after heating at temperatures above 1500 OC. Ofthe rest, thirteen diamonds remained quite clear, no inclusions being visible with b e most careful examination, and for six diamonds observation of the interior was not possible because of the surface graphitization that had occurred. In further experiments at 1800 O c and 1900 OC for the diamonds which had remained clear at 1700 O c , none showed inclusions after the higher temperature treatment. For those in which inclusions had been found after heating at 1700 OC, none showed additional new inclusions at the higher temperatures, and in only two special cases had the original inclusions extended. For seven of the sixteen diamonds affected internally by the heat treatment, the inclusions had shapes and orientations crystallographically related to the diamond. The other nine diamonds had inclusions that were irregular and non-crystallographic.

4.2. The Non-crystallographic Inclusions The non-crystallographic black inclusions that have been produced were generally less than 100 microns across, irregular and sometimes jagged. They varied in number per stone from one to ten or more, and in three stones at least occurred only just below an octahedral diamond surface. Intense localized strain patterns were detected at these particles, as seen for three of them in one diamond in figure 3(a),where the micrograph was taken with the polarizer and an analyser in crossed positions in the microscope. The small particles did not change in appearance or increase in number when further heated at 1700 OC. Similarly, when the diamonds containing such inclusions were heated at 1800 OC and 1900 Oc, the inclusions were not observably changed or increased in number. Also the strain patterns remained unchanged. Large irregular inclusions were found in two diamonds after they had been treated for 15 minutes at 1700 OC. Figure 3(b) shows six inclusions in the interior of one of these diamonds. Figure 3(c) shows the associated extreme state of strain which, in contrast to that for the small particles, extends throughout the crystal. It was also found for this particular diamond that some of the inclusions extended with further heating at 1700 OC, and with heating at higher temperatures. 4.3. The Crystallographic Inclusions After being heated above 1500 O c , three diamonds ex?iiibited needle-like inclusions crystallographically orientated with respect to the octahedral diamond, and four diamonds had inclusions in the form of platelets. The black needles, from 5 to 50 microns in length, were in all six (110) directions lying in (111) layers approximately 10 microns below the octahedral faces. Some of these needles can be seen in figure 4(a); the three (110) directions parallel to the surface are clearly seen. The other three (110) directions project as (112) directions on a (111) plane, and these needles appear short and blurred since each one cannot all be in focus at once. For one of these diamonds, needle inclusions were found approximately 10 microns below all eight faces. Distributions varied from a few needles only to a complete uniform layer, and from complete irregularity, as seen in figure 3 0 , to orientated triangular distributions, one of which is seen in figure 3(d). There was no apparent relation between the distributions on opposite or adjacent faces, and no inclusions at all were visible in the interior of the stone deeper than 20 microns below the faces. Each needle had an intense localized strain associated wt it, so that the ih layers of inclusions gave complicated strain patterns like that seen in figure 3(e) for the

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V . R. Howes

Figure 3. (a) x78, strain pattern associated with particle inclusions; (h) x27, and (c) x 30 inclusions inside a diamond and the general associated strain pattern; (4, (e) x 33, needle-like inclusions just below a surface, and the associated strain Pattern; (f) x 33, an irregular distribution of needle-like inclusions.

The Graphitization of Diamond

655

Figure 4. (a) x 249, the needle-like inclusions; (h) x 420, a layer of small platelet inclusions just below a surface; (c) x 108, two trails of platelet inclusions occurring through a diamond; (d) x 150,a central distribution of platelet inclusions found in C one diamond; (e) x7.8, a diamond after 5 minutes at 1900 ' before degraphitization; (f) x7.2, a diamond after 12 hours at 1700 O c after degraphitization.

65 6

V. R. Howes

distribution seen in figure 3(4. Away from the needles the diamond was nearly strain. free. Another diamond showed a layer of discontinuous inclusions about 10 microns below one (111) face after being heated for 15 minutes at 1700 OC. But in this case there was nothing visible beneath the other seven faces, and the inclusions Were veq small platelets, 2 to 5 microns across, as seen in figure 4(b). The largest of the platelets can be seen to be hexagonal and they have sides in (110) directions. Another diamond showed similar platelet inclusions just below the surface but only occurring i small n groups or singly. Platelets were found in two other diamonds after heating at 1700 OC, In one, several trails of small platelets extending a considerable distance through the stone could be seen, two of which are shown in figure 4(c) ; in the other an extensive formation of platelets was found centred in the middle of the diamond. Figure 4(d) shows this distribution which was approximately 6mm across comparing with the 1+mm length of edge of the triangular face of the octahedral diamond; the individual platelets were of the order of 10 microns across. Both the platelets and the boundary of the distribution as observed were hexagonal with sides parallel to the (110) directions of the diamond. Microscopic observations at different levels in the diamond, and the fact that the distribution appeared the same through all eight faces, have led to the conclusion that it consists of four hexagonal-shaped layers lying on the four (111) planes passing through the centre of the formation, each layer comprising many small hexagonal platelets. Figure 5 illustrates the composition diagrammatically. The linear

CO 1o

2/
!

4J
Figure 5. Four hexagonal distributions of equal density on the four (111) planes through a point as seen in a (111) direction.

inclusions, which also can be seen in figures 4(b) and 4(d), have thickness a d their lengths lie in (110) directions. Measurements of the ratio of the width to the length of some of the larger ones show that they are very probably projected views of hexagonal platelets lying on the other three (111)planes. Thus the layers are of hexagonal platelets lying in all four possible (111) planes randomly. It was found that both types of crystallographic inclusions were in no way altered either further heating at 1700 OC, or heating at higher temperatures of 1800 OC or 1900 c-

The Graphitization of Diamond

657

4.4. Attempted Correlations In trying to find an indication of the cause of the internal changes that have been described, several phenomena related to diamond were compared with the production of hternal inclusions upon heating, but no correlations were found: (i) Some type I diamonds gave inclusions, some did not. (5) The inclusions had no association with the surface graphite nuclei. (iii) Some diamonds having intense strain patterns before treatment developed inclusions, some did not. (iv) A diamond showing an intense fluorescent centre when exposed to ultra-violet fight remained free from internal graphite after heating at 1900 the centre not bekg visibly changed. (v) A twinned diamond gave no internal graphite after heating. (vi) After an irradiation with approximately 1017 fast neutrons[cm2 another diamond became transparent again after heating at 1700 O c but showed no inclusions.
OC,

35.

MACROSCOPIC CHANGES

5.1. Change in Shape Graphite formed at the (110) edges of the diamond octahedra much more rapidly than on the (111) faces. The edges became encrusted and rough in contrast to the smooth black faces, as can be seen in figure 4(e) which shows a diamond that had been heated for 5 minutes at 1900 The encrusted graphite at the edges was dissolved quite easily in the degraphitizing agent, revealing rough flat areas beneath. Another diamond, which had been heated at 1 7 0 0 " ~ 12 hours and then degraphitized, for showed that these areas were in fact dodecahedral faces. Figure 4f3 shows this stone with a remnant (111) face surrounded by three (110) faces which have become predominant. These (110) faces were rough and black, with nothing like the interwoven propeller structure seen on the (111) faces. Most, but not all, of the eight (111) faces still remained, but there were no cubic faces visible. Although the encrusted graphite on the edges readily dissolved in the degraphitizing agent, the (110) faces exposed remained quite as black as the (111) faces. That this was due to a thin layer only was proved by the clear diamond visible underneath where fragments had fractured off at the edges. A diamond that was superficially graphitized, but still with no internal inclusions after 10 minutes at 1900 OC, was transformed completely to graphite after 30 minutes at 1900
OC. OC.

5.2. Expmiments above 2000 OC Two diamonds, selected from those that had previously shown no visible internal changes when heated to 1700 O c , were heated above 2000 (2010 OC and 2120 "c) for as short a time as experimentally possible (up from 1700 OC and down again in three minutes). Both were very heavily graphitized superficially. After boiling in the degraphitization solution the diamonds were found, although in fragments, showing that complete graphitization had not occurred. Of the faces of the fragments some were cleavage, some original (111), and some (110). The original (111) faces and the (110) faces had the usual appearance of graphitization with a trace of additional rough etch. The cleavage (111) faces were often almost clear with a few graphite spikes and in Some cases again a trace of rough etch. It would seem that the diamonds had fractured at the end of the experiments, probably owing to the rapid cooling, SO that little graphitGation occurred on the cleavage faces before the temperature dropped below 1700 OC.
OC

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V. R. Homes

It is also a possibility that they did not completely break up until the boiling in the degraphihtion solution. At the maximum temperature the pressure in the furnace had risen to .$ pmHg, so that the rough etch effect was almost certainly due to some gas etching occurring before the pressure dropped again as the temperature was reduced,
$6. DISCUSSION 6.1. Surface Graphitization The surface graphite that forms on the octahedral diamond faces during the high temperature high vacuum experiments described is different in many ways from that formed during gas etching of octahedral diamond surfaces. The latter has been des. cribed by Evans and Sauter (1961), where it was concluded that the formation was due to the deposition of carbon on the diamond surface as a result of surface chemical reactions in the presence of the etchant gases. During etching, the graphite layer obtained is continuous over the surface and varies from thin grey to thick black according to the gas pressure and temperature. No distinct nuclei are visible, and the black layer has a matt and porous appearance. It is easily removed by the usual degraphitization agents. The graphite layer was found to be crystallographicallyorientated with respect to the diamond, the c axis of the graphite being perpendicular to the (111) diamond faces. Thus the two types of graphite layer differ in formation, in macroscopic and microscopic appearance, in adherence to the surface, and in crystallographic orientation, In the experiments described, the formation of the surface graphite was found to be independent of the surrounding atmosphere. The difficulty of removing the graphite, together with the observation of the imprint of its structure in the diamond beneath, indicates that the graphite was produced in the surface rather than superficially on it. At normal pressures diamond is the thermodynamically unstable form of carbon. The above evidence indicates that the surface graphite formed at 1700 OC and above in high vacuum is due to a physical phase change occurring at the surface, transforming the carbon from the diamond to the graphite structure. This surface graphitization has been shown experimentally to occur more rapidly at the (110) edges than on the (111) faces of the octahedrons of diamond, leading to the development of a dodecahedron from an original natural octahedron. A possible explanation of this is as follows: when the temperature is increased so that diamond nears the point at which it will become unstable and transform to graphite, atoms less strongly attached will break free from the diamond structure before those more strongly attached. Thus random fluctuations will be important if they preferentially weaken the bonding of surrounding atoms. If one atom from a (111) face randomly becomes free from the diamond lattice (three bonds being broken) it leaves triply bonded atom around it, which would then be susceptible only to similar random action. But if one atom from a (110) edge randomly becomes free (three bonds being broken) then the atoms on either side are only doubly bonded, so that they become more susceptible to transformation than other atoms. Each atom becoming free leaves the next along the edge only doubly bonded. Thus for a temperature range where normal triply bonded atoms are just stable apart from random fluctuations, but doubly bonded atoms are unstable, the freeing of one atom at an edge leads to the transformation of the whole row of edge atoms. This would lead to the &st sign of graphitization occurring at the (110) edges of an octahedral diamond, and to the continued preferential transformation at these edges. It is to be noted that the graphite nuclei which occur on the octahedral faces have been observed to form preferentially at steps on the surfaces, which do contain (110)

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659

&s. The electron-digraction results for the graphite layer show that both randomly ,ientated graphite and specifically orientated graphite are present; that for the latter he hexagonal rings of the graphite structure lie perpendicular to the diamond (111) surface;and that the a axis of the graphite is in the surface. Since the a spacing of the graphite (2.47 A) is very close to the atomic spacing in the (110) direction for diamond (2.52~), is a possibility that this forms the basis of the transformation. Figure 6 it

I2

Figure 6. Two puckered hexagons within the diamond lattice.

shows two ways of forming flat graphite-type hexagonal rings from the Puckered hexagonal rings of the diamond structure. Suppose atoms A B C D E F form one puckered ring in the surface (111) plane of a diamond octahedron, and at0ms G H I occur below C and E to complete another puckered hexagon C D E G 1H If the bonds . marked 1 are broken, then the hexagon A B C D E F becomes free to flatten, giving a graphite-type hexagon ring parallel to the diamond (111)plane. For graphite forming on this principle, the c axis would be perpendicular to the (111) diamond plane (this is the orientation of the graphite found on diamond octahedral faces after etching with Oxygen). If the bonds marked 2 are broken, then hexagon C D E G I H can flatten , merely by the swinging up of atom D and the swinging down of atom 1 atoms c , E, G and H having to move only very slightly. Graphite forming on this basis would have the c axis and the a a i s (direction c 3) in the (111) d i m " plane-which the orientation of the surface graphite formed in the experiments that have been described. In this model the a direction of the graphite hexagon is the (110) direction of the diamond structure, and a threefold symmetry would be expected i the development n of graphite across the (111) diamond surface involving the three (110) directions. However, if it is considered that the formation of a flat graphite-type hexagon ring Weakens the bonds from the atoms involved to other atoms around them, the type of Propagation that might be expected is illustrated in figure 7 . Here the atoms are shown UI a puckered (111) plane of diamond, the filled-in circles representing the lower atoms 6th the fourth bond going down, the open circles representing the upper atoms with the fourth bond coming up. Suppose a flat hexagon first starts to form on atoms B a d c, and the two beneath them (atom A breaking bond 1 and swinging into the new Position as shown). Then if it is considered that this weakens bonds marked 2, it is more likely that atoms D and E will swing into positions as shown to form further flat hexagonal rings, rather than into positions between B and F, and c and G respectively. At the same time, atoms H and 1are 1;kely t o swing into their new positions as shown.

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V. R. Howes

The propagation of graphite-type hexagon rings will then be in the directions marked by the large mows, which are (112) directions in the (111) diamond plane. This mechanism, although giving a development with orientation agreeing with that found experimentally, does not immediately give normal graphite, since the large value of the c spacing of normal graphite (6.8 A) has not been taken into account. But by selective development of some of the initial hexagon sheets, and a small relative shift of &emate sheets, the normal graphite structure could be obtained. The extra carbon atoms

Figure 7. The puckered (111) plane of diamond showing a possible development of perpendicular flat hexagon rings.

between the graphite sheets could form, after migration, the randomly orientated graphite also detected-it is to be noted that the graphite grain size is very small (1001). The model described is no more than an attempt to understand the adhesion and orientation of the graphite found on the diamond surfaces, particularly the orientation in (112) directions rather than (110) directions. The surface graphitization that occurs has been seen to increase with time and with higher temperatures, so that eventually the diamonds would be completely transformed to graphite. For the size of diamond used in the experiments described there will be a time t, for each temperature T, when all the diamond has been graphitized by the surface reaction. Thus, for T = 1700 O c , t > 12 hours T = 1900 OC, t > 10 minutes but < 30 minutes T = 2100 OC, t > 10 seconds but < 3 minutes.

It can be seen that considering just the surface graphitization alone, diamond is very rapidly transformed to graphite at temperatures around 2000 OC.
6.2. Internal Graphitization For the intemal inclusions that have been observed after heating diamonds to 1500 O C and above, the black material has not been directly analysed since it occurs inside the diamond octahedra and usually in discontinuous arrays of small particles.

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However, in three cases where the inclusions have been non-crystallographic and in mo cases for crystallographic inclusions (one for platelets and one for needles), the of black material occurring were much greater than the order of total impurity content, excluding nitrogen, that has been reported by Kaiser and Bond (1959). Since the black material appears similar in all the diamonds showing inclusions, and certainly h the same form for those diamonds where it occurs crystallographically, it would a Seem very likely that all the material that has been observed has been carbon occurring as graphite. The nucleation of the internal graphite may very well be associated with impurities in the diamonds. Some diamonds remain free from internal graphite, while for the others which do develop inclusions during heating, the graphite occurs discontinuously. These facts lead to the conclusion that the internal graphitization must be initiated at defects of some kind inside the stones. The sue of these defects must be something less than 1 micron, and different forms of defects may explain the various forms of the inclusions-lumps, particles, needles, platelets. For example, the source defect for a platelet must be effectively two-dimensional since nothing but single platelets have been observed (if the defects were points or three-dimensional, then 4 (111) planes could equally well be involved in the graphitization and multiple platelets should be observed ; if the defects were one-dimensional then 2 (111) planes could be involved and double platelets should be seen). I t is to be noted that no examples have been found of diamonds that have developed both types of crystallographic inclusions. It is possible that the defects, associated with graphitization, simply supply the extra space required for the initial transformation from the diamond to the graphite structure. Alternatively, a reaction may occur at the defects at the high temperatures obtained, which allows the required energy for transforming the carbon from the metastable to the stable state. The fact that the graphitization at the surface is still very slow at 1700 OC, while the internal graphite develops very rapidly, suggests the second possibility. Also the negative results following the irradiation experiments indicate that the first possibility is unlikely. The graphite formed distorts the surrounding diamond causing the intense localized strain that has been detected for all observed particles, platelets or needles of graphite. The impression is that a stimulated phase change occurs from the defect, and graphite rapidly develops until the pressure built up in the distorted diamond rises to a value for which diamond is again non-transformable. Bridgman (1947) has shown that such an inhibition of graphitization of diamond can occur below the theoretical thermodynamic equilibrium pressure. Thus the process is not reversible, and what graphite is formed will remain when the temperature is reduced. It has been shown experimentally that after further heating at a higher temperature no extension of the internal graphite distributions was observed, but it has been impossible to prove whether initial heating at 1900 O c instead of 1700 O c would have given larger inclusions. The frequent occurrence of the internal graphite in (111) plane layers parallel to the octahedral faces indicates a possible association with the growth process, the defects associated with graphitization being trapped between growth layers. The presence of the layers just beneath the diamond faces and not deeper has alternative explanations; first, that the defects associated with graphitization are trapped only in the last stages ofthe growth. The second explanation is that, in a general distribution, developing graphite can distend the diamond more easily near a free surface, SO growing to a visible size before the critical pressure is built up in the surrounding diamond. However, it Seems unlikely that the central symmetrical formation of platelets that was found Once could be directly connected with the growth of the crystd, or that an exactly

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V. R. Howes

similar pattern of defects associated with graphitization existed before the diamond was heated. A more likely explanation is that a central inclusion or fault, within a general distribution of defects, produced a strain effect on all the (111) planes through the inclusion when the diamond was heated, this effect accelerating graphitization at the defects on these planes. The development of a graphite platelet from a defect can be explained by the flattening out of the kinked hexagon rings in the (111) planes of the diamond lattice, If this were to happen uniformly, spreading from a central ring, then a flat hexagon sheet would be formed with (110) edges, thus having the same orientation as &e platelets. However, no mechanism can be offered at the moment for the development of the needle inclusions. The fact that diamond was still found after an experiment at 2100 OC is notable in &at up to this temperature at least spontaneous transformation from diamond to graphite does not occur. The increasingly rapid progressive surface graphitization that has been seen to occur at temperatures above 1900 OC indicates that in practice this process is likely to transform a diamond before the necessary temperature is attained for the spontaneous transformation. The bursting and disintegration of diamonds that have been reported by Friedel and Ribaud (1924) at temperatures around 1900 OC might well have been brought about by microscopic inclusions already present, or by internal graphite inclusions formed as the diamonds were heated. Their observations of a sudden change in birefringence followed by the bursting of the stone, could be caused by the strain associated with the inclusions at the high temperatures involved. It was to avoid these possibilities, experienced in preliminary experiments, that very careful initial examination of the diamonds ms carried out, and that before going to higher temperatures the diamonds were always first heated at 1700 OC in order to check whether or not internal graphite formed.

ACKNOWLEDGMENTS

The author would like to thank Dr. T. Evans for useful discussion of the work; also Dr. R. C. Newman of Associated Electrical Industries, Aldermaston Court, for carrying out the reflection electron diffraction examinations and for helpful discussions of the results obtained, and Dr. K. Robinson for carrying out the x-ray examination. Thanks are due to Professor R. W. Ditchburn for his encouragement of the work, which has been financed by a grant from the Industrial Distributors (1946) Ltd. Dr. J. F. H. Custers, Director of the Diamond Research Laboratory, Johannesburg, kindly supplied the diamonds used in the experiments.

REFERENCES

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