APPARATUS AND METHODS FOR THE MANUFACTURE OF SYNTHETIC DIAMONDS AND CUBIC BORON NITRIDE

Abstract

An apparatus for the manufacture of cubic Boron Nitride includes a pressure vessel having a chamber therein, and a body located in the chamber. The pressure vessel and the body are formed of materials having different coefficients of expansion. The coefficient of expansion of the body is greater than the coefficient of expansion of the pressure vessel. The pressure vessel is formed from a material having a melting point in excess of 1327° C. and capable of withstanding a pressure of at least 4.4Gpa at a temperature of at least 1327° C. The chamber is configured to receive the body, and a Boron Nitride source, the apparatus further comprising a furnace configured to heat at least the body to a temperature at least of 1327° C. The coefficient of expansion of the body is selected such that upon heating thereof to at least 1327° C. the pressure exerted on the Boron Nitride source is at least 4.4Gpa.

Claims

1. An apparatus for the manufacture of cubic Boron Nitride comprising: a pressure vessel having a chamber therein; and a body located in the chamber, wherein the pressure vessel and the body are formed of materials having different coefficients of expansion, the coefficient of expansion of the body being greater than the coefficient of expansion of the pressure vessel; wherein the chamber is configured to receive the body, and a Boron Nitride source; wherein the pressure vessel is formed from a material having a melting point in excess of 1327° C. and capable of reacting and withstanding forces generated by a pressure of at least 4.4 GPa located at the source of Boron Nitride in the apparatus, said pressure generated by differential thermal expansion of the body within the chamber when the pressure vessel is at temperatures in excess of 1327° C.; wherein the pressure vessel includes at least one housing member configured to resist said forces generated by differential thermal expansion of the body upon heating thereof; wherein the at least one housing member is formed from a material selected from the group consisting of: W; tungsten carbide; doped tungsten carbides; 3% Co doped tungsten carbide; boron carbide; carbon reinforced composites; carbon-fiber reinforced composites, carbon-fiber reinforced carbon composites, carbon reinforced graphite, carbon fiber reinforced graphite, and carbon-carbon; wherein the apparatus further comprises a furnace and the pressure vessel is situated in the furnace, said furnace configured to heat the pressure vessel, the body, and the Boron Nitride source to a temperature of at least 1327° C.; and wherein the coefficients of expansion of the body and the pressure vessel are selected such that upon heating thereof by said furnace to at least 1327° C. the pressure exerted on the Boron Nitride source is at least 4.4 GPa.

2. The apparatus according to claim 1, wherein: the body has at least two body surfaces, expansion of at least one of the body surfaces is constrained by engagement of the at least one of the body surfaces with a surface of the chamber, another of the body surfaces is not engaged with a surface of the chamber, and the Boron Nitride source is situated between a surface of the chamber and the another of the body surfaces that is not engaged by the surface of the chamber; or the body has at least one body surface, and the Boron Nitride source is situated around the body between the at least one body surface and the surface of the chamber.

3. The apparatus according to claim 1, wherein the body includes a piston.

4. The apparatus according to claim 3, wherein the chamber is in the form of a cylinder and the piston is arranged in the cylinder.

5. The apparatus according to claim 1, comprising a catalyst located in the chamber.

6. The apparatus according to claim 5, wherein the catalyst is comprised in the body.

7. The apparatus according to claim 6, wherein the catalyst comprises an alkali boro-nitride salt or an alkali earth boro-nitride salt.

8. The apparatus according to claim 1, wherein the Boron Nitride source is a part of the body.

9. The apparatus according to claim 1, wherein the Boron Nitride source is hexagonal Boron Nitride.

10. The apparatus according to claim 1, wherein: the pressure vessel includes a plurality of inserts each of which forms at least one surface of the chamber, and at least two housing members and fastening elements which fasten together the housing members; the inserts sit inside the housing members; and the inserts, the housing members and the fastening elements resist pressure generated by expansion of the body upon heating thereof.

11. The apparatus according to claim 10, wherein the inserts together form a sphere and the housing members each comprise a hemispherical shell shaped and dimensioned to receive the assembled inserts.

12. The apparatus according to claim 11, wherein the chamber is spherical or comprises a volume enclosed by a plurality of planar or curved surfaces.

13. The apparatus according to claim 10, wherein the housing members each include a flange, and the flanges are aligned and fastened together with fastening means.

14. The apparatus according to claim 13, wherein: the fastening means comprises bolts which pass through aligned holes in the flanges; or the fastening means comprises a clamping ring including two clamping ring elements which are attached together and surround the flanges.

15. The apparatus according to claim 13, wherein: the fastening means comprises a clamping ring including two clamping ring elements which are attached together and surround the flanges; and the clamping ring elements each include a recess and wherein the flanges sit in the recesses.

16. The apparatus according to claim 1, wherein the material from which the body is formed includes at least one material selected from the group consisting of: W, Nb, Mo, Ta, V, Ru, MoSi.sub.2, Rh, and TZM.

17. The apparatus according to claim 1, wherein the material from which the chamber is formed includes at least one material selected from the group consisting of: W, Nb, Mo, Ta, Ru, MoSi.sub.2, Rh, a cermet, 3% Co doped tungsten carbide, Boron Nitride and diamond.

18. The apparatus according to claim 13, wherein a material from which the fastening means are formed includes at least one material selected from the group consisting of: W, Ta, Nb, carbon reinforced composites, carbon fiber reinforced composites, carbon fiber reinforced carbon composites, carbon reinforced graphite, carbon fiber reinforced graphite and carbon-carbon.

19. The apparatus according to claim 1, further comprising at least one gasket, each of the at least one gasket being situated between adjacent components of the apparatus.

20. The apparatus according to claim 10, further comprising at least one gasket, at least one of the at least one gasket being situated between adjacent inserts.

21. The apparatus according to claim 13, further comprising at least one gasket, at least one of the at least one gasket being situated between adjacent flanges.

22. The apparatus according to claim 19, wherein a material from which the at least one gasket is formed includes at least one material selected from the group consisting of: carbon, carbon reinforced composites, carbon fiber reinforced composites, carbon-carbon (including carbon reinforced carbon, carbon reinforced graphite, carbon fiber reinforced graphite, or carbon fiber reinforced carbon), soapstone, pyrophyllite, other materials capable of withstanding the temperatures experienced by the apparatus and functioning as a gasket, and any of the aforementioned in sheet form.

23. The apparatus according to claim 1, comprising at least one cubic Boron Nitride seed in the chamber.

24. The apparatus according to claim 23, wherein the at least one cubic Boron Nitride seed is comprised in the body.

25. The apparatus according to claim 1, wherein the furnace is adapted to create a temperature gradient across the chamber rising from one side of the chamber to the other.

26. The apparatus according to claim 6, wherein: the furnace is adapted to create a temperature gradient across the chamber rising from one side of the chamber to the other; and the temperature gradient rises from the surface of the chamber farthest from the body where the catalyst is situated to the surface of the body.

27. The apparatus according to claim 1, wherein the furnace is capable of heating the pressure vessel, the body and the Boron Nitride source to a temperature in the range of 1327° C. to 4000° C.

28. An apparatus according to claim 27, wherein the furnace is provided with a temperature sensor and a controller, the temperature sensor providing a furnace temperature feedback to the controller.

29. A method of manufacturing synthetic cubic Boron Nitride, comprising the steps of: providing an apparatus according to claim 1; raising a temperature of the pressure vessel to a selected temperature within the range of 1327° C. and 4000° C. for a period of between 20 minutes and 1 week, and controlling the temperature during the period; and generating a pressure of at least 4.4 GPa within the chamber for the period.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0095] In the Drawings, which illustrate the conditions for synthetic diamond formation, prior art HPHT apparatus and preferred embodiments of the present disclosure, and which are by way of example:

[0096] FIG. 1 is a schematic simplified representation of a first apparatus of the present disclosure;

[0097] FIG. 2 is a simplified schematic representation of a variation of the first apparatus of the present disclosure;

[0098] FIG. 3 is a simplified schematic representation of a second apparatus of the present disclosure;

[0099] FIG. 4 is a simplified schematic representation of a third apparatus of the present disclosure;

[0100] FIG. 5 is a simplified schematic representation of a fourth apparatus of the present disclosure;

[0101] FIG. 6 is a simplified schematic representation of a fifth apparatus of the present disclosure;

[0102] FIG. 7 is a simplified schematic representation of a sixth apparatus of the present disclosure;

[0103] FIG. 8 is a schematic representation of a seventh apparatus of the present disclosure;

[0104] FIG. 9 is a cross-section through the apparatus illustrated in FIG. 8;

[0105] FIG. 10 is a set of four elevations of housing components of an eighth apparatus of the present disclosure: FIG. 10A is a perspective view of a housing component of an eighth apparatus of the present invention; FIG. 10B is a plan view of the housing component illustrated in FIG. 10A; FIG. 10C is a cross-sectional elevation on axis A-A in FIG. 10B; and FIG. 10D is an exploded view of the part of the housing component encircled in FIG. 10C;

[0106] FIG. 11 is a set of three elevations of anvil cell components of the eighth apparatus of the present disclosure: FIG. 11A is a perspective view of an anvil cell component of the eighth apparatus of the present invention; FIG. 11B is a side view of the cell component illustrated in FIG. 11A; and FIG. 11C is an end view of the cell component illustrated in FIG. 11A;

[0107] FIG. 12A is a perspective view of a first of a pair of clamping components of the eighth apparatus of the present disclosure; FIG. 12B is a perspective view of a second of a pair of clamping components of the eighth apparatus of the present disclosure; FIG. 12C is a front view of the clamping components illustrated in FIGS. 12A and 12B; and FIG. 12D is a cross-sectional elevation of the clamping components on the axis A-A in FIG. 12C;

[0108] FIG. 13A is a side view of a fastener of the eighth apparatus of the present disclosure; FIG. 13B is an exploded view of the encircled part of the fastener shown in FIG. 13A; and FIG. 13C is an end view of the fastener illustrated in FIG. 13A;

[0109] FIG. 14a is a schematic representation of a ninth apparatus of the present disclosure;

[0110] FIG. 14b is a schematic representation of the apparatus illustrated in FIG. 14a in assembled form;

[0111] FIG. 15 is a schematic illustration of the heating arrangement of the present disclosure;

[0112] FIG. 16 illustrates an arrangement comprising a stack of seed diamonds;

[0113] FIG. 17 is a schematic representation of a BARS apparatus of the prior art;

[0114] FIG. 18a is a chart illustrating the conditions under which synthetic diamonds may be formed;

[0115] FIG. 18b is a chart illustrating the conditions under which cubic Boron Nitride may be formed;

[0116] FIGS. 19 and 20 are schematic representations of an alternative embodiment of the present disclosure.

DETAILED DESCRIPTION

[0117] FIG. 1 illustrates an apparatus according to the present disclosure in simplified form. The apparatus 1 comprises a container 2 having a cylinder 4 formed therein. A piston 3 is located in the cylinder 4, the piston resting against one end of the cylinder 3 and occupying most of the cylinder volume. A small part of the end of the cylinder 4 receives a catalyst and a carbon source 6, that is a supply of carbon. The carbon source 6 could be graphite for example. The remainder of the volume of cylinder 4 is occupied by a catalyst 5.

[0118] To form synthetic diamonds, the whole apparatus is heated to a temperature at which diamonds will form. The piston 4 and container 2 are made from different materials which have different coefficients of expansion when heated. The materials are selected so that when heated to the afore-mentioned temperature the piston expands proportionately more than the cylinder and sufficient to exert the required pressure of at least 4.4 GPa (typically 5 GPa or greater) on the carbon source 6 and catalyst 5 contained within the cylinder 3.

[0119] By maintaining the temperature of the apparatus 1 the pressure exerted on the carbon source 6 and catalyst 5 is maintained.

[0120] FIG. 16 illustrates a stack of catalysts 5, carbon sources 6 and seed diamonds 5a-5d.

[0121] The embodiment of the apparatus illustrated in FIG. 2 is similar to that shown in FIG. 1. The difference lies in presence of a body of iron 7 in the cylinder 3 instead of the catalyst of the embodiment illustrated in FIG. 1.

[0122] In the embodiments illustrated in FIGS. 1 and 2, the pressure exerted on the catalyst or iron and carbon source depends on the temperature to which the apparatus 1 is raised, the materials selected for the piston 4 and cylinder 3 and the length of the piston (a longer piston will expand more than a shorter piston for the same temperature rise where the pistons are otherwise the same).

[0123] The embodiment illustrated in FIG. 3 has a different configuration of cylinder 3′, 3″ and piston 4′, 4″. The piston 4′ has a projecting portion 4″ at one end. The cylinder 3′ includes a correspondingly shaped portion 3″ for receiving the projecting portion 4″ of the piston 4′. The catalyst 5 and carbon source 6 are situated in the portion 3″ of the cylinder 3′. The force generated upon expansion of the piston 3′, 3″ is therefore exerted over a smaller area than is the case with the embodiments illustrated in FIGS. 1 and 2 and hence a greater pressure is generated in comparison with the embodiments of FIGS. 1 and 2 for the same temperature rise, assuming that the apparatus 1 and 1′ are otherwise the same.

[0124] FIG. 4 illustrates an apparatus 10 comprising a container 12 having a cylinder 13 formed therein. A catalyst 15 and carbon source 16 are situated in the cylinder 13. In this embodiment the catalyst has a different coefficient of expansion to the container 12. The catalyst 15 fulfils the role of the piston in the earlier embodiments, expanding more than the container 12 when the two are heated.

[0125] FIGS. 5 to 7 illustrate embodiments having apparatus that corresponds to the apparatus shown in FIGS. 1, 3 and 4 respectively. The difference between the embodiments of FIGS. 5 to 7 when compared to the embodiments of FIGS. 1, 3 and 4 lies in the way in which the apparatus is heated and the use of a seed diamond. The seed diamond is placed at the end of the catalyst furthest away from the carbon source. The embodiments shown in FIGS. 5 to 7 are subject to a temperature gradient. The end of the cylinder were the seed diamond is located is 30 C cooler than the other end of the apparatus.

[0126] The characteristics needed for the material from which the container 2 is made are: stiffness (a stiff material is required); strength (a strong material is required); and a very high melting point.

[0127] The characteristics needed for the material from which the piston 4 is made are: a large difference in thermal expansion rate compared to the encapsulation material (the piston needs to expand more than the cylinder for a given temperature change); strength (a strong material is required); and a high melting point.

[0128] Candidate materials for both the container 2 and piston 4 may be selected from the Material Melting Point C Coefficient of Thermal

TABLE-US-00001 TABLE 1 Melting Coefficient of Thermal Material Point C. Expansion K.sup.-1 @ 20 C. W 3400 4.5 × 10.sup.-6 Nb 2469 7.3 × 10.sup.-6 Mo 2620 5.2 × 10.sup.-6 Ta 2980 6.5 × 10.sup.-6 V 1910 8.4 × 10.sup.-6 Ru 2482 6.4 × 10.sup.-6 MoSi.sub.2 2030 7.42 × 10.sup.-6  Rh 1964 8.2 × 10.sup.-6 Fe 1200  12 × 10.sup.-6 TZM 2623 5.3 × 10.sup.-6

[0129] One suitable combination of materials would be W for the container and Rh for the piston. As can be understood from the table, the piston will expand significantly more than the container for the same temperature rise.

[0130] FIG. 8 illustrates an alternative embodiment of the present disclosure. The apparatus 30 comprises two outer housings 31 each of which comprises a hemispheric shell 32 and a flange 33, the flanges comprising a series of holes for receiving fasteners to secure the two outer housings together. The hemispherical shells 32 each include a hemispherical recess 35, which together form a spherical chamber when the two outer housings 31 are fastened together. A set of eight inserts 36 form a sphere when brought together. The sphere fits inside the spherical chamber of the housings 31. Each of the inserts 36 includes a recess 37. When these inserts are brought together a central spherical chamber is formed in which the piston, catalyst, carbon source and seed diamond are placed. Of course, as in the apparatus illustrated in FIGS. 1 to 7 it is not essential to have a seed diamond, nor is a piston essential.

[0131] The hemispherical shells 32 are formed from a metal such as tungsten or a cermet such as 3% tantalum carbide-doped tungsten carbide. Doping with tantalum carbide gives the material high tensile strength at high temperatures. Other materials could be used for these components such as Boron carbide, or high strength carbon-fiber reinforced carbon composites, often referred to as carbon-carbon composites.

[0132] The inserts 36 are formed of a cermet, which must have sufficient compressive strength to withstand forces at least of 4.4 GPa (typically 5 GPa or greater). One suitable material is a 3% Co doped tungsten carbide. Another suitable material is diamond itself.

[0133] The core 38 includes at least the catalyst and carbon source in the form of graphite. The core may also include a piston and where desired seed diamonds. The piston or the catalyst, which may serve the function of the piston in that the material of the catalyst may expand upon heating sufficiently to generate the required pressure for diamond formation, may be formed from one of the materials listed in Table 1.

[0134] FIG. 10 (including FIGS. 10A-10D), FIG. 11 (including FIGS. 11A-11C), FIGS. 12A-12D, and FIGS. 13A-13C collectively illustrate a variant of the embodiment illustrated in FIGS. 8 and 9. The apparatus comprises outer housings 31′, each including a hemispherical shell 32′ surrounded by a flange 33′.

[0135] An anvil cell is provided by six inserts 36′. Each insert 36′ has an end face 37′. When the six inserts are assembled within the housings 31′ a central cube shaped chamber is formed. A cube shaped core including the carbon source, catalyst, piston and seed diamonds (if seed diamonds are required) are placed in the cube shaped chamber.

[0136] The housings 31′ are held together by a clamping ring formed by clamp ring halves 40 and bolts 50. Each clamp ring half includes a recess 41 that is shaped and dimensioned to receive the flange 33′. The clamp ring halves are held together by bolts 50 passing through aligned holes 43. The flange 33′ has an angled face 39. The face 39 lies at an angle of 5 degrees to the horizontal in FIG. 10. The clamp ring halves have a correspondingly angled face 44. These angled faces ensure that as the clamp ring is tightened the housings 31′ are pressed together.

[0137] The housings 31′ and inserts 36′ are formed of the same materials as discussed above in relation to FIGS. 8 and 9.

[0138] FIGS. 14a and 14b illustrate a working embodiment of the concept apparatus illustrated in FIGS. 1 to 7. The apparatus 50 provides a container 2 with three co-operating segments 51 which are enclosed within a series of hoops 54 and end caps 55. These cooperating segments generate a multi-dimensional pressure as differential thermal expansion causes them to constrict the central chamber. The apex of each of the segments 51 is removed to form a concave recess 52. When the three segments 51 are brought together, as shown in FIG. 14b, the recesses 52 from a cylinder extending between the end caps 55. The cylinder may have a diameter of between 0.5 mm and 2.0 mm, although diameters below 0.5 mm and above 2.0 mm may also function. The segments 51 also include slots 53. The slots 53 of adjacent segments 51 align when the segments 51 are assembled to form holes through which locking bars 57 extend. The end caps 55 include slots 56 which are aligned with corresponding holes formed by slots 53. The locking bars 57 have lock elements 58 at each end thereof. When the segments 51, hoops 54, end caps 55 are assembled the lock elements 58 may be positioned to lock all the components together, as shown in FIG. 14b, or to permit the disassembly of the components. The components of the apparatus 50 may be disassembled by first turning the lock elements 58, and hence the locking bars 57 through 90 degrees from the position shown in FIG. 14b. The locking elements are then aligned with the slots 56 of the end caps 55 which may be removed.

[0139] The cylinder formed by recesses 52 is filled with the carbon source, seed diamonds if seed diamonds re to be used, a catalyst and a piston, if the catalyst is not to function as component that expands when heated to generate the desired pressure.

[0140] The components of the whole apparatus are secured tightly together by the action of heat and the differential expansion of the materials from which the components of the apparatus are manufactured. In particular, the locking bars 57 and locking elements 58 are formed from carbon-carbon. This material expands significantly less than the metals or cermets from which the other components of the apparatus are manufactured. Hence, as the whole apparatus heats up, the components 51, 54, 55 expand much more than the locking bars 57 and locking elements 58 causing all the components to be pressed tightly together. As the apparatus 50 is heated the piston and or catalyst within the cylinder formed by recesses 52 expand more than the segments 53, causing the pressure within the cylinder to rise to the required level.

[0141] Referring also to FIGS. 19 and 20, which illustrate co-operating segments 51′ similar to the co-operating segments 51 illustrated in FIGS. 14a and 14b, the co-operating segments 51′ may be used in place of the segments 51 with the other components described with reference to FIGS. 14a and 14b. Adjacent segments 51′ have gaskets 59 inserted therebetween. Further gaskets 59′ are provided for the end faces of the assembled segments 51′, the gaskets 59′ sitting between the end caps 55 and the said end faces of the assembled segments 51′. Typically, the gaskets 59, 59; are formed of carbon, such as carbon sheets, carbon-carbon sheets, soapstone, pyrophyllite, or other materials capable of withstanding the temperatures experienced by the apparatus and capable of functioning as a gasket. Gaskets may also be provided between adjacent hoops 54.

[0142] FIG. 15 illustrates the apparatus 1 (which could equally be the apparatus illustrated in FIGS. 8 to 14b) mounted in a furnace 60. The furnace 60 is provided with a controller 61 and a thermocouple 62, which monitors the temperature within the furnace. The controller 61 uses the signal from the thermocouple to adjust the furnace so as to maintain the furnace temperature at or close to a desired set temperature.

[0143] The apparatus and method of the present disclosure allow synthetic diamonds to be formed by harnessing expansion of one material relative to another upon heating in order to generate the pressures required for synthetic diamond formation. This will allow much smaller apparatus to be manufactured. For example, the apparatus illustrated in FIG. 8 to 14 may weigh 20 Kg or less.

[0144] The apparatus of the present disclosure provides a much simplified means of applying pressure to a source of carbon in order to produce synthetic diamonds. The need for external pressure application devices is eliminated. All that needs to be controlled is temperatures, and the heating means provides for this to be done accurately.

[0145] The apparatus described above may be used to manufacture cubic Boron Nitride. When using the apparatus described herein to manufacture cubic Boron Nitride, instead of placing a carbon source within the chamber, a Boron Nitride source is placed within the chamber. The source is typically hexagonal Boron Nitride (hBN). This material is soft and has a similar structure to graphite. The seed diamonds used in the manufacture of synthetic diamonds are replaced by cubic Boron Nitride seeds.

[0146] Typically, a catalyst is also placed in the chamber. The catalyst may be alkali or alkali earth boro-nitride salts, such as Li.sub.3BN.sub.2, CA.sub.3BN.sub.3, Mg.sub.3N.sub.2 derived from salt like ionic nitrides.

[0147] In some embodiments, the catalyst may be one of metallic solves; (Fe, Co, Ni)—(Mo, Cr, V)—Al alloys, metallic Mg and Ca; or ionic boro-nitride solvents with the formula MxByNz formed in-situ by reaction with hexagonal Boron Nitride.

[0148] The reaction conditions for the formation of cubic Boron Nitride are illustrated in FIG. 18b.

[0149] A typical reaction for manufacturing cubic Boron Nitride in the apparatus of the invention would be: Li.sub.3BN.sub.2+hexagonal Boron Nitride in large excess+cubic Boron Nitride seeds at about 5 GPa and about 1500 degrees Celsius.fwdarw.Li.sub.3BN.sub.2+cubic Boron Nitride.

[0150] Li.sub.3BN.sub.2 may be formed by reacting Li.sub.3BN with hexagonal Boron Nitride.