US3031269A - Method of diamond growth and apparatus therefor - Google Patents

Method of diamond growth and apparatus therefor Download PDF

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Publication number
US3031269A
US3031269A US855787A US85578759A US3031269A US 3031269 A US3031269 A US 3031269A US 855787 A US855787 A US 855787A US 85578759 A US85578759 A US 85578759A US 3031269 A US3031269 A US 3031269A
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diamond
temperature
catalyst
reaction vessel
carbon
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US855787A
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Harold P Bovenkerk
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General Electric Co
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General Electric Co
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Priority to DENDAT1176623D priority Critical patent/DE1176623B/de
Priority to NL258431D priority patent/NL258431A/xx
Application filed by General Electric Co filed Critical General Electric Co
Priority to US855787A priority patent/US3031269A/en
Priority to GB38180/60A priority patent/GB971157A/en
Priority to BE597127A priority patent/BE597127A/fr
Priority to BE597128A priority patent/BE597128A/fr
Priority to CH1312460A priority patent/CH401927A/de
Priority to FR845070A priority patent/FR1274254A/fr
Priority to GB40633/60A priority patent/GB973503A/en
Priority to CH1326460A priority patent/CH440235A/de
Priority to SE11395/60A priority patent/SE305855B/xx
Priority to NL60258431A priority patent/NL148012B/xx
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/065—Presses for the formation of diamonds or boronitrides
    • B01J3/067—Presses using a plurality of pressing members working in different directions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/062—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies characterised by the composition of the materials to be processed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • B01J3/065—Presses for the formation of diamonds or boronitrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B01J2203/0605—Composition of the material to be processed
    • B01J2203/061—Graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B01J2203/0605—Composition of the material to be processed
    • B01J2203/0625—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B01J2203/065—Composition of the material produced
    • B01J2203/0655—Diamond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2203/00—Processes utilising sub- or super atmospheric pressure
    • B01J2203/06—High pressure synthesis
    • B01J2203/0675—Structural or physico-chemical features of the materials processed
    • B01J2203/068—Crystal growth
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S425/00—Plastic article or earthenware shaping or treating: apparatus
    • Y10S425/026—High pressure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1096—Apparatus for crystallization from liquid or supercritical state including pressurized crystallization means [e.g., hydrothermal]

Definitions

  • this invention in one form comprises ice placing reaction material which is a catalyst and a nondiamond form of carbon in a reaction vessel in such a manner that the reaction material is indirectly heated and thereafter raising the pressure and temperature in a specified manner to a predetermined range where large diamond crystals may be grown.
  • FIG. 1 is an illustration of the high temperature high pressure apparatus described as the belt
  • FIG. 2 is an enlargement and assembled view of the center portion of FIG. 1 illustrating a reaction vessel and gasket assembly
  • FIG. 3 illustrates a series of curves each defining a.
  • FIG. 4 is one form of a reaction vessel employing indirect heating
  • FIG. 1 is exemplary of one preferred form of apparatus together with appropriate proportion and scale.
  • Apparatus 10 includes a pair of punch assemblies 11 and 11 together with a lateral pressure resisting or belt member assembly 12. Since the punch assemblies 11 and 11 are similar in nature a description of one sufiices for the other.
  • Punch assembly 11 includes a central punch 13 of a hard material, such as tool steel, cemented tungsten. carbide etc. which is surrounded by a plurality of binding rings 14, 15 and 16.
  • Punch 13 has a generally narrowing tapered portion 17, the taper of which is a smooth diametrical increase from the pressure area or surface 13 axially along the length of the punch to a given larger area 19.
  • Tapered portion 17 includes an end portion 20 offrusto-conical configuration with, for example, an-
  • punch 13 is prestressed by being mounted concentrically within a plurality of metal annular, backing or binding rings 14, 15 and 16.
  • binding rings may be assembled by well known methods of press fitting or shrink fitting.
  • punch assembly 11 consists of a punch 13, two hardened alloy steel press fitting backing rings 14 and 15, and an outer soft steel guard ring 16. Interference and proper stressing is supplied in one form by providing a taper and interference on each of the mating surfaces.
  • binding rings are employed together with a Carboloy cemented carbide punch 13, fracture is maintained at a minimum.
  • the principal'function of the binding rings is to provide sufiicient radially inward compressive force on punch 13 to oppose the radially outward force developed within the punch and to prevent the punch from fracturing at high pressures.
  • Punch assemblies 11 and 11' are employed in conjunction with a lateral pressure resisting or die assembly 12, comprising a die 21 having a central opening or aperture 22 therein which is defined by a tapered or curved wall surface 23.
  • Wall surface 23 generally describes a narrowing tapered or convergent die chamber or opening into which punches 13 and 13' may move or progress to compress a specimen or material, for example, a reaction vessel as illustrated in FIG. 2. This combination of tapered punches and tapered die chamber contributes to the strength of both punches 13 and 13 and die 21.
  • die 21 is also made of a high strength material, such as Carboloy cemented carbide, for example, grade 44A, similar to that of punch 13. Prestressing of die 21 may be achieved in the same manner as prestressing of punch 13. Tapered wall 23 of chamber 22 is prestressed to its limitative hoop compression. Binding rings 24 and 25 are employed for purposes similar to rings 14 and 15 as described and are preferably of the materials, while ring 26 is preferably of low carbon steel similar to ring 16. Binding rings 24 and 25 and die 21 increase in height to provide approximately a 7 taper with the horizontal, a taper which provides an increase in cross section of material for imposed forces in the same manner as the taper of the frusto-conical portion of punch 13.
  • a high strength material such as Carboloy cemented carbide, for example, grade 44A
  • tapered wall 23 includes a pair of frusto-conical sections 27 and 27 meeting at a horizontal center line of die 21 and having an angle of about 11 to the vertical.
  • a gasket is employed between the opposed tapered surfaces of the die 23 and punch 13.
  • a gasket must have the property of gripping the surfaces of the punch and die and be capable of undergoing large plastic shear distortions without losing shear strength.
  • the shear strength of the material should be great enough to prevent gasket blow-out during all parts of the operation cycle, yet not resist movement of the punch excessively.
  • the force imposed upon the gasket structure is not uniform, but varies from a maximum adjacent the innermost edge of the frusto-conical portion'of the punch to a minimum at the outer extremity adjacent the 7 tapered portion 28.
  • a gasket serves several functions including; first, sealing in the contents of the chamber; second, allowing a rather large movement of the punch relative to the die; and third, providing electrical insulation between the die and the punches when resistance heating is employed.
  • a metal gasket for example mild steel, as the center element of a composite gasket sandwich structure to impart cohesiveness, tensile strength and ductility to the gasket structure as a whole.
  • FIG. 1 provides an exploded view of the sandwich type frusto-conical gasket assembly 30 which surrounds tapered surface 17 of punch 13, and comprises a pair of thermally and electrically insulating, pressure resistant frusto-conical ceramic or stone gaskets 31 and 32 with a metallic frusto-conical gasket 33 between adjacent gaskets 31 and 32.
  • gasket 31 serve to electrically in- Sulate the punch from the die, but also gaskets 32 on punches 13 and 13 meet in abutting relationship in chamber 22 to provide a liner or insulator therefor.
  • specific configurations and compositions of gasket assembly 30 have been described above, it is obvious that any suitable gasket assembly meeting the requirements described may be employed.
  • reaction vessel 34 is approximately 0.350 inch in diameter and 0.450 inch in length positioned in chamber 22 between punches 13 and 13 and includes a cylinder 35 of electrically insulating material such as prophyllite or catlinite, talc, etc, positioned between a pair of spaced electrically conductive discs 36 and 36'.
  • a washer assembly 37 is positioned between each punch 13 and 13' and its associated disc 36 and comprises a heat insulating core '38 with a surrounding outer electrical conductive ning 39 in contact with punches 13 and 13, to complete the reaction vessel.
  • Rings 39 and 39 are preferably of a hard steel and together with cores 38 provide a cap assembly for reaction vessel 34 which thermally insulates the centers of the punch faces and provides a current path to the material in reaction vessel 34.
  • the punch and die assembly of FIGS. 1 and 2 is positioned between platens or pistons of any suitable press apparatus to provide motion of one or both punches.
  • Each punch assembly is provided with an electrical connection (FIG. 1) in the form of an annular conducting ring 40 or 40' with connectors 41 and 41, to supply electric current from a source of electrical power (not shown) through punch assemblies 11 and 11, to a high temperature high pressure reaction vessel 34.
  • a source of electrical power not shown
  • punch assemblies 11 and 11 to a high temperature high pressure reaction vessel 34.
  • - Pressure is applied to the vessel 34 by movement of one or both punches 13 and 13' towards each other in a press apparatus.
  • electric current is supplied from one electrical connector, such as upper connector 41 to upper conducting ring 40 to the punch assembly 11.
  • FIG. 2 current flows from punch 13 to ring 39 and disc 36. From this point, current either flows through a suitable heater provided in the reaction specimen or through the specimen itself. The current path continues from lower disc 36', ring 39' to punch 13'. Referring again to FIG. 1, the current path continues through punch assembly 11, conductor ring 40' and connector 41' to the electrical source (not shown).
  • Temperature in the reaction vessel is determined by fairly conventional means such as by placing a thermocouple junction in the reaction vessel and measuring the temperature of the junction in the usual manner. Electrical energy at a predetermined rate is then supplied the apparatus and the temperature produced by this power is measured by the thermocouple assembly. This same procedure is repeated a number of times with different power inputs to produce a calibration curve of power.
  • Example I The reaction vessel of FIG. 2 was assembled employing alternate small solid cylinders of commercially obtained graphite of spectroscopic purity and nickel, 99.6% nickel. The vessel was subjected to a pressure of about 90,000 atmospheres together with a temperature of about 1600 C. These conditions were maintained for about 3 minutes. After removal from the apparatus the reaction vessel was found to contain diamonds.
  • the present invention to be applied to the foregoing description of one exemplary method and apparatus, is temperature control.
  • This control should be as precise as possible under existing conditions. Pressure and temperature in the reaction vessel are constantly changing because of changing internal conditions. During and upon reaching the desired temperatures, some parts of the apparatus expand while others melt with a corresponding reduction or increase in volume. For example, stone loses volume due to a phase change and metal increases in volume when it melts, pressure causes contraction of the reaction vessel and contents because of such occurrences as filling of voids and general compressibility of the pants employed. It is, therefore, desirable that the changes relating to increase in Volume and the changes relating to decrease in volume balance each other and it is believed that this is somewhat true as indicated by pressure and temperature measurements over literally hundreds of operations.
  • a catalyst should be employed in the reaction for good diamond growth conditions.
  • These catalysts include generally those metals of the group VIII metals of the periodic table of elements and also manganese, tantalum and chromium.
  • Catalysts may be employed in various forms, such as for example, elemental metal form, alloys of such metals, and numerous other arrangements and configurations. Alloys permit lower pressure operation and their description and operating parameters are best described in copending application S.-N. 655,885, H. M. Strong, filed April 29, 1957, now abandoned and continuation-in part thereof of SN. 707,433, now U.S. Patent 2,947,609, and assigned to the same assignee as the present invention. The subject matter of that application is incorporated herewith. However, not all catalysts will provide diamond growth in the same range of pressures and temperatures, since it has been further discovered that there exists a defined range for each catalyst metal and/ or also for each alloy and for each alloy composition.
  • FIG. 3 there is illustrated a group of exemplary curves defining individual ranges of pressures and temperatures for diamond growth for given catalyst.
  • curves F, N, R, P and T represent iron, nickel, rhodium, palladium and platinum respectively.
  • Other catalysts and combinations provide similar curves. These indicated ranges have not been determined with absolute precision or defined with high exactness, but have been determined by numerous tests and experiments of hundreds of individual runs to define a region where diamonds are either formed or not formed with a particular catalyst. It should be noted that the right-hand portions of the curves generally define a theoretical line of separation of the diamond and non-diamond phases of carbon, or a graphite-to-diamond equilibrium line.
  • Such a line is generally referred to as the diamond-to-graphite equilibrium line on the phase diagram of carbon.
  • the position of this line has been determined by the pressure and temperature measuring methods set forth in this application in conjunction with hundreds of operations determining pressures and temperatures Where diamonds grow or do not grow. Temperature measurements, for example, were obtained with commercially available platinum-platinum rhodium (the rhodium being 10%, by Weight, of the total Weight of the platinum and rhodium), chromel-alumel, rhodium-platinum, etc. thermocouples.
  • the thermocouple junctures were positioned generally centrally within the reaction chamber with lead wires extending laterally opposite through carefully drilled holes in the reaction vessel and then through holes in the gasket assembly to the measuring apparatus. High pressure effects on these and other thermocouples were not found to be seriously affecting the reading obtained.
  • the bottom or lowermost portion of the curves are defined generally by the melting temperature of the particular catalyst in the presence of carbon at the given pressure.
  • the lefthand portion of the curves are generally straight and nearly vertical lines since the points therealong are determined by the melting temperature of the catalyst in the presence of carbon at the given pressures, an approximately linear function.
  • Diamond growth at the points establishing a curve is effected by the heretofore described changing temperature and pressure conditions, so for example, referring to any point within any curve of FIG. 3 generally adjacent the lower end on the curves, it is understood that a slight change in pressure and temperature may cause change of conditions out of the diamond growth region into the graphite region resulting in either no diamonds grown or, depending on the degree of change, graphitization of previously grown diamond. Such change may or may not take place, and the frequency or degree or rapidity there of, or the exact point at the completion of the test where pressure and temperature have remained constant may not be accurately ascertained.
  • reaction vessel 34- is heated, in one form, by resistance heating. Accordingly, when pressure and temperature are raised to proceed into the diamond growing region defined by a particular catalyst curve, carbon transforms from the non-diamond form to diamond. However, in so doing, the resistivity of the sample changes drastically as more and more carbon transforms from the electrically conducting carbon form to electrically nonconducting diamond. It is, therefore, apparent that the final temperature or resistance heating may depend on such variables as the volume of carbon, the shape, the amount of diamond formed, formation rate, position of the crystals formed in the reaction vessel, changes of resistance with respect to temperature and other variables. In one respect, a further problem is encountered when employing larger reaction vessels.
  • This invention discloses an improved reaction vessel in which temperature can be more precisely controlled.
  • One principle upon which this invention is based is temperature control. Temperature control is achieved, then, in the first instance through choice of materials and/or the arrangement of these materials in a preferred configuration.
  • the reaction vessel illustrated in FIG. 2 has been described as being particularly susceptible to wide variations in temperature, proper choice of parts may minimize these variations.
  • the use of thicker or thinner end discs 36 as well as discs of greater or less electrical and thermal conductivity will provide different degrees of heating and will affect changes of the position of the hotter zone in the reaction vessel.
  • the use of copper discs with high electrical and heat conductivity increases the heating at the central portion of the vessel, while lesser conductive metals increase the heating at the end portions of the vessel.
  • the time interval from the application of power to the proper temperature rise is quite small, for example, 1 to seconds. Therefore, changes in temperature may be quickly adjusted for in order to maintain constant temperature.
  • the disadvantages of such a reaction vessel in practicing this invention in best form include, first, that with increasing size of vessel the time interval is proportionately longer, and control more difiicult, and larger vessels are physically necessary for larger crystal growth, second, that the vessel configuration under prolonged conditions of high temperature and high pressure develops leaks or the stone materials decompose with the products thereof affecting the reaction.
  • FIG. 4 there is illustrated a reaction vessel which comprises in one example a pyrophyllite cylinder 51 of about inch wall thickness and %1 inch outside diameter. Placed concentrically Within the cylinder 51 is heating tube 52 of graphite, for indirect heating, which lies adjacent to and contiguous with cylinder 51. A further cylinder 53 of alumina is placed within the graphite heater tube 52 to the adjacent thereto. Graphite 54 from which diamonds are grown in is then placed in a diamond metal catalyst tube 55 and thereafter positioned centrally within the alumina cylinder 53. For other applications, 54 may be other reactants and tube 55 other catalysts.
  • a plug of alumina 56 and 56 fits with the upper and lower portions of graphite heater tube 52 to support and insulate the graphite and catalyst in the same manner as does the sides of vessel 56. Only one plug may be necessary for resistance heating since a single plug will prevent an electric circuit through the graphite. Suitable end discs 57 and 57 are provided to convey current to heater tube 52.
  • Alumina cylinder 53 should be of the pre-fired variety so that it is relatively soft. Pre-firing is a firing temperature of about 1100 to l200 and generally not over this temperature because the alumina then becomes hard fired. Hard fired alumina is a deterrent to substantial hydrostatic pressure transmission at the higher pressures and temperatures.
  • Alumina cylinder 53 in one example, was of a commercial grade, 96 to 99+% aluminum oxide, with the remainder materials of a nature not affecting the diamond growing reaction, and about .0l0.050 inch in thickness. A general range of about .030-.100 inch thickness provides good results.
  • Graphite heater tube 52 is preferably spectroscopically pure, 99+ graphite with no impurities which will decompose or change electrical resistance at high pressures and temperatures.
  • This type of reaction vessel provides the important features of a vessel in that it will not leak under high pressure and high temperature conditions, maintains a practically constant (temperature over all of the graphite undergoing transformation both in the vertical and horizontal directions, maintains its particular geometry under the high pressures and high temperatures, and provides a heater tube, i.e., graphite, whose resistance does not change appreciably under high pressures and temperatures and, therefore, constant heating is obtained.
  • the desired geometric stability and the prevention of extensive catalyst intermixing are achieved by insulating the reactants from the heater tube with such materials as alumina, zirconia, magnesia, etc'.
  • the molten catalyst wets alumina cylinder 53 and causes it to remain intact, sealed, protected, etc., since the alumina becomes entirely covered with the catalyst. This also permits heating the reactants to any reasonable temperature up to at least the melting point of the insulation with no change in geometry with respect to time.
  • the use of a metal catalyst in tube form permits sbstantial compression of the reaction vessel together with marked decrease in axial dimension without cracking or leaking of either the cylinder 53 or the tube, which would result in the decomposition products or melt of the cylinder 51 affecting the diamond reaction.
  • Tube 55 being also of good thermal conductivity aids in avoiding a large axial temperature gradient.
  • a further advantage of this system is that when diamond starts to grow inwardly from the catalyst tube, the growth is in the direction of extremely low temperature gradient. This also provides better control of the diamond growing conditions and reduces the rate of growth. The result of using these stable growing conditions is the production of a larger diamond crystal. For example, using nickel as a catalyst, it has been possible to grow diamond crystals from 500 microns to over 1 millimeter in length (considerably larger than by any other system) with pressures in the region of 76 to 78 kiloatmospheres, a temperature of 1500 centigrade, and a growth rate period of about 30 minutes.
  • FIG. 5 there is illustrated a multiple concentric cylinder vessel 60.
  • Vessel 60 in one example, includes an outer cylinder 61 similar to cylinder 51 of FIG. 4.
  • a graphite heater tube 62 is positioned concentrically within cylinder 61 to provide resistance heating.
  • a cylinder of alumina 63 is positioned within graphite tube 62 to act as insulation and a catalyst stabilizer.
  • the core of the reaction vessel includes a central rod 64 of alumina about which is a tube of catalyst metal 65.
  • Catalyst metal tube 65 is surrounded by a cylinder of graphite 66 for diamond growth, and another cylinder 67 of catalyst metal.
  • FIG. 6 there is illustrated, for the purposes of explanation, the diamond forming region as previously determined for an alloy of 80% nickel and 20% chrome (by weight) as a catalyst. It is a relatively simple manipulation to increase the pressure and temperature of the reaction vessel in accordance with this invention to the range enclosed by the curve OA and OB. Now that the reaction vessel is of such a nature that the temperature may be more precisely controlled FIGS. 4 and 5 particularly), the following results have been found. When raising the pressure and temperature to the general area indicated by O, A, C, D, and maintaining that temperature within controlled limits from a few seconds to an hour or longer, it has been found that the diamond crystals grow in the form of cubes, which are generally of a very poor grade, and black in color.
  • this region is hereinafter referred to as the cube region.
  • the upper limit of extension of line DEC is unknown as is the upper extension of line OA.
  • the method portion of this invention is to raise the temperature and pressure to a particular diamond forming area within a particular region defined by a given catalyst; where the area is closely adjacent a curve of the diamond forming region defined by an equilibrium line between graphite and dia mond, and to maintain the temperature constant with respect to time in that area to provide the desired crystal formaion.
  • the temperature should be held at point T1, a threshold temperature, for the following reasons. If an attempt were made to reach temperature T2 immediately even though the temperature time rise is extremely small, chances are excellent for overshooting the mark and ending about T3 which is in the non-diamond or graphite stable region, and variances of temperature back and forth between the diamond growing region and the non-diamond or graphite stable region affects the reaction to a considerable degree.
  • the period of time necessary to change the temperature from T1 to T2 may be so extensive that diamonds are formed in the reaction vessel in that pediod of time and in that range between temperature T1 and the shaded area so that diamonds start to form in the region of poor growth affecting the quality of the diamond then grown in the shaded area. Therefore, the method of raising the temperature to point T1 permits the reaction vessel temperature and pressure to become stabilized in the non-diamond growing region before diamond growth and thereafter only a small temperature rise is necessary to proceed immediately to T2 in the shaded area.
  • temperature T1 After temperature T1 is reached and stabilized, more power is added to the reaction vessel to raise the temperature in a matter of a few seconds to T2 in the shaded area and because of the rapidity of temperature rise from T1-T2 very few, if any, diamond crystals are grown prior to reaching the shaded area.
  • the temperature may thereafter be controlled in the shaded area for varying periods from a few minutes to several hours to grow larger diamond crystals.
  • Example I A reaction vessel (34 of FIG. 2 approximately inch diameter and inch in length) was assembled with a substantially pure nickel slug in the hollow core and a spectroscopically pure graphite slug at each end of the nickel slugs to fill the core. Pressure on the reaction vessel was raised to about 78,000 atmospheres. Temperature was stabilized to about 1350" C. and thereafter increased to about 1450 C. in from l-3 seconds. This temperature was maintained for about 10 minutes. Upon removal from the press, the reaction vessel was found to contain several diamond crystals from .2 to .4 mm. in the longer dimension.
  • Example 2 The procedure of Example 1 was followed but with a nickel chromium catalyst of nickel and 20% chromium (by weight) and the reaction vessel of FIG. 4 (about inch diameter and 1 inch in length). Threshold temperature was 1250 C., maximum pressure was 72,000 atmospheres, maximum temperature was 1320 C. Elapsed time was about 2 hours. Upon removal of the reaction vessel from the press, it was found to contain 3 diamond crystals from /2 to 2 mm. average diameter.
  • Example 3 The procedure and reaction vessel of Example 2 was again followed but with a nickel iron catalyst, 35% nickel, 65% iron (by weight). Maximum pressure was 66,000 atmospheres, threshold temperature was about 1150 C., maximum temperature about 1250" C., and elapsed time 3 hours. Upon removal of the reaction vessel from the press, it was found to contain several diamond crystals somewhat smaller than 2 mm. average.
  • Example 4 The procedure, reaction vessel, and catalyst of Example 3 was followed wherein temperature was quickly increased to pass through the diamond growing region to stabilize, out of said region, about 1400 C. The temperature was thereafter reduced to about 1250 C. and maintained for about 1 /2 hours. Upon removal of the reaction vessel, it was found to contain several diamond crystals of about 1.5 mm. in the longer dimension.
  • any carbonaceous material the graphite being merely exemplary for this application.
  • any carbon-containing material may be employed which when heated will carbonize and form graphite before the diamond reaction takes place. Diamonds have been produced when the initial material has been carbon, wood, pitch, adamantane, etc.
  • the invention is also applicable to the growth of various crystals where an equilibrium line of pressure and temperature exists, where temperature control is desirable and where it is not desirableto pass current through the reactant material.
  • this invention is applicable to crystal growth of silicon, germanium, etc., as Well as to the cubic form of boron nitride disclosed and claimed in copending application S.N. 707,434, Wentorf, filed January 6, 1958, now US. Patent 2,947,617, and assigned to the same assignee as the present invention.
  • a method of producing diamond crystals from a combination of a non-diamond carbon together with a catalyst which includes subjecting the said non-diamond form of carbon and the catalyst to high pressures and high temperatures above the graphite-to-diamond equilibrium line on the phase diagram of carbon to provide diamond growth from said non-diamond carbon
  • the improvement of growing larger diamonds comprising, raising the said pressure and temperature to that range of pressures and temperatures in the diamond growing region for the given catalyst, above the said graphite-todiamond equilibrium line on the phase diagram of carbon, at a point closely adjacent the said graphite to diamond equilibrium line and above the cube region wherein diamonds crystallize predominantly in cube form, maintaining the temperature constant over an extended period of time at said point, reducing the temperature and pressure, and recovering diamond so grown.
  • a method of producing diamond crystals from the combination of non-diamond carbon together with a catalyst which includes subjecting the said, combination to combined pressures and temperatures above the graph.- ite to diamond equilibrium line on the phase diagram of carbon to provide diamond growth from said non-diamond carbon
  • the improvement of producing larger crystals comprising, raising the pressure to above the said graphite to diamond equilibrium line and within the diamond forming region of the given catalyst at a temperature less than existing in said region, increasing the temperature to a point corresponding to said pressure and adjacent to but outside of the diamond forming region of the said given catalyst, maintaining this threshold temperature for stabilization purposes, thereafter increasing the temperature on said combination of catalyst and non-diamond carbon to a point closely adjacent and above the graphite to diamond line and above the cube region wherein diamond crystallizes predominantly in cube form, maintaining temperature constant over an extended period of time at said point, reducingsaid temperature and pressure, and recovering diamond so grown.
  • a method of producing diamond crystals from a combination of a non-diamond. carbon together with a catalyst which includes subjecting said combination to pressures and temperatures above the graphite to diamond equilibrium line on the phase diagram of carbon to provide diamond growth from said non-diamond carbon
  • the improvement of producing large crystals comprising, raising the pressure to about opposite a point in the diamond forming region of the given catalyst and outside of said diamond forming region, increasing the temperature on said combination for the temperature curve to pass from outside the said diamond forming region through the said diamond forming region for the given catalyst and thereafter into the non-diamond form of graphite region, maintaining the pressure and temperature conditions for stabilization in the non-diamond form of graphite region, thereafter reducingthe temperature until a point is reached in the diamond forming region for the given catalyst at a point closely adjacent and above the graphite to diamond line and slightly above the cube region, maintaining the temperature constant at this point over an extended period of time, reducing said temperature and pressure, and recovering diamond so grown.
  • a method of producing large diamond crystals from the combination of a non-diamond carbon together with a catalyst taken from the metals consisting of those metals of group Vill of the periodic table of elements, chromium, manganese and tantalum, and alloys of these metals which comprises subjecting said non-diamond carbon and catalyst to a pressure generally corresponding to a temperature in the diamond forming region of said catalyst, employing an indirectly heated reaction vessel to ,eat said catalyst and non-diamond carbon to a temperature generally corresponding to said pressure and lying within the diamond forming region of the given catalyst above the cube region where diamond crystallizes predominantly in cube form and closely adjacent the graphite to diamond dividing line, maintaining the temperature constant for an extended period of time at said point, reducing said temperature and pressure, and recovering diamond so grown.
  • said indirectly heated reaction vessel comprises in combination, a thermally insulating and electrically nonconductive vessel having an opening therein, a relatively thin electrically conductive heater tube positioned Within said opening and contiguous with said vessel, a hollow electrically conductive and thermally insulating cylinder positioned concentrically within and contiguous with said heater tube, a diamond catalyst metal cylinder whose length is less than that of said tube positioned concentrically within said tube and contiguous therewith, a non-diamond form of carbon within said catalyst cylinder, an electrically nonconductive and thermal insulating stone plug positioned within said heater tube adjacent one end of said heater tube and non-diamond form of carbon to provide a substantially solid reaction vessel, an electrically conductive disc on each end of said heater tube and vessel and in contact therewith, so that an electrical current applied to said end discs flows through said heater tube to indirectly heat the combination of the catalyst and a non-diamond form of carbon.
  • said indirectly heated reaction vessel comprises in combination, a first hollow stone electrically nonconductive and thermally insulating cylinder, an electrically conductive graphite heater tube positioned concentrically within and contiguous with said hollow cylinder, a hollow electrically nonconducting and thermally insulating second stone cylinder positioned concentrically within said heater tube and contiguous therewith, a catalyst metal tube of less axial dimension than said first cylinder positioned within and concentrically with said second cylinder and contiguous therewith, a non-diamond form of carbon within said catalyst tube, a stone plug positioned Within said reaction vessel on each end thereof to provide a solid cylindrical configuration, an electrically conductive metal disc positioned on each end of said reaction vessel so that current applied to said end discs flows through said graphite heater tube to indirectly heat the combination of carbon and catalyst metal in said reaction vessel.
  • said indirectly heated reaction vessel comprises in combination, a hollow electrically nonconducting and thermally insulating stone vessel, a thin graphite heater tube positioned within and contiguous with said vessel, a hollow cylindrical electrically nonconductive and thermally insulating stone cylinder positioned with said heater tube and contiguous therewith, a metal catalyst cylinder positioned within said second stone cylinder and contiguous therewith, said catalyst cylinder being axially shorter than the said first cylinder, an annulus of a non-diamond form of carbon positioned Within said catalyst metal tube and contiguous therewith, a second cylinder of catalyst metal positioned within said non-diamond carbon annulus and contiguous therewith, a central core of stone material positioned within said latter catalyst cylinder, a plug of stone material positioned within said heater tube in one end of said reaction vessel to provide a substantially solid vessel, a pair of electrically conductive metal discs positioned on each end of said vessel and in contact with said heater tube so that current applied to said
  • An indirectly heated reaction vessel comprising in combination, a hollow electrically nonconductive and thermally insulating vessel, a thin electrically conductive heater tube positioned within and contiguous with said vessel, a hollow electrically nonconductive and thermally insulating cylinder positioned concentrically within and contiguous with said heater tube, a metallic cylinder whose length is less than that of said tube positioned concentrically within said tube and contiguous therewith and adapted to contain a reactant material, an electrically nonconductive and thermal insulating plug positioned within one end of said reaction vessel to provide a substantially solid reaction vessel, an electrically conductive disc on each end of said heater tube and in contact therewith so that an electrical current applied to said end discs flows through said heater tube to indirectly heat the combination of the catalyst and reactant.
  • An indirectly heated reaction vessel comprising in combination, a hollow electrically nonconductive and thermally insulating cylinder, a thin electrically conductive heater tube positioned concentrically within and contiguous with said cylinder, a hollow electrically nonconductive and thermally insulating cylinder positioned concentrically within and contiguous with said heater tube, a' diamond catalyst metal cylinder whose length is less than that of said tube positioned concentrically within said tube and contiguous therewith, a non-diamond form of carbon within said catalyst cylinder, an electrically nonconductive and thermal insulating plug positioned within one end of said reaction vessel to provide a substantially solid cylindrical vessel, an electrically conductive disc on each end of said cylinder and in contact therewith so that an electrical current applied to said end discs flows through said heater tube to indirectly heat the combination of the catalyst and a non-diamond form of carbon.
  • An indirectly heated reaction vessel comprising in combination, a first hollow electrically nonconductive and thermally insulating stone cylinder, a graphite heater tube positioned concentrically within and contiguous with said hollow cylinder, a second hollow electrically nonconducting and thermally insulating stone cylinder positioned concentrically within said heater tube and contiguous therewith, a catalyst metal tube of less axial dimension than first cylinder positioned within and concentrically with said second cylinder and contiguous therewith, a non-diamond form of carbon within said catalyst tube, a stone plug positioned within said reaction vessel on one end thereof to provide a solid cylindrical configuration, an electrically conductive metal disc positioned on each end of said reaction vessel such that current applied to said end discs flows through said graphite heater tube to indirectly heat the combination of carbon and catalyst metal in said reaction vessel.
  • An indirectly heated reaction vessel comprising in combination, a first hollow electrically and thermally nonconducting stone cylinder, a thin graphite heater tube positioned concentrically within and contiguous with said cylinder, a second hollow cylindrical electrically nonconductive and thermally insulating stone cylinder positioned within said heater and contiguous therewith, a metal catalyst cylinder positioned within said second stone cylinder and contiguous therewith, said catalyst cylinder being axially shorter than the said first cylinder, an annulus of a non-diamond form of carbon positioned within said catalyst metal tube and contiguous therewith, a second cylinder of catalyst metal positioned within said nondiarnond carbon annulus and contiguous therewith, a central core of stone material positioned within said latter catalyst cylinder, a plug of stone material positioned within said heater tube at one end of said reaction vessel to provide a substantially solid cylinder, a pair of electrically conductive metal discs positioned on each end of said cylinder and in contact with said heater tube so that current applied to said end disc
  • a method of growing large diamond crystals comprising in combination, subjecting graphite and an alloy metal catalyst taken from the group consisting of those metals of group VIII of the periodic table of elements, manganese, tantalum and chromium, to a temperature and pressure lying above the graphite to diamond dividing line on the phase diagram of carbon in the diamond forming region for the particular catalyst employed and above the cube region where diamond crystallizes predominantly in cube form, and closely adjacent the said dividing line, maintaining the temperature constant and within 50 C. of said line for a period of time in the range of at least about 2 minutes to several hours and thereafter reducing the temperature and pressure and recovering diamond formed.
  • an alloy metal catalyst taken from the group consisting of those metals of group VIII of the periodic table of elements, manganese, tantalum and chromium
  • a method of growing large diamond crystals comprising in combination, subjecting graphite and a metal catalyst which includes nickel to a temperature and pressure lying above the graphite-to-diamond dividing line on the phase diagram of carbon and out of the diamond forming region for said catalyst, reducing the temperature to a point lying within the diamond forming region for said catalyst above the graphite to diamond equilibrium line and within about 50 C. of said line, maintaining the temperature constant for a period of time from about 2 minutes to several hours and thereafter reducing the temperature and pressure and recovering diamond grown.
  • a method of producing diamond crystals from the combination of a non-diamond carbon together with a catalyst which includes subjecting the said combination to combined pressures and temperatures above the graphite to diamond equilibrium line on the phase diagram of carbon to provide diamond growth from said non-diamond carbon, the improvement of producing larger diamond crystals comprising, raising the pressure-temperature conditions to a point where said conditions are outside.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US855787A 1959-11-27 1959-11-27 Method of diamond growth and apparatus therefor Expired - Lifetime US3031269A (en)

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Application Number Priority Date Filing Date Title
DENDAT1176623D DE1176623B (de) 1959-11-27 Verfahren zur Herstellung von Diamantkristallen
NL258431D NL258431A (en)) 1959-11-27
US855787A US3031269A (en) 1959-11-27 1959-11-27 Method of diamond growth and apparatus therefor
GB38180/60A GB971157A (en) 1959-11-27 1960-11-07 Reaction vessel for high pressure high temperature apparatus
BE597128A BE597128A (fr) 1959-11-27 1960-11-16 Récipient de réaction pour appareil à haute pression et à haute température.
BE597127A BE597127A (fr) 1959-11-27 1960-11-16 Procédé d'obtention de diamants.
CH1312460A CH401927A (de) 1959-11-27 1960-11-23 Reaktionsgefäss für eine Vorrichtung zum Erzeugen von hohen Drücken und Temperaturen
FR845070A FR1274254A (fr) 1959-11-27 1960-11-25 Perfectionnements apportés aux procédés de synthèse du diamant
GB40633/60A GB973503A (en) 1959-11-27 1960-11-25 Method of making diamonds
CH1326460A CH440235A (de) 1959-11-27 1960-11-25 Verfahren zur Herstellung von Diamantkristallen
SE11395/60A SE305855B (en)) 1959-11-27 1960-11-25
NL60258431A NL148012B (nl) 1959-11-27 1960-11-26 Werkwijze voor het vormen van diamant, alsmede volgens deze werkwijze verkregen diamant.

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BE (2) BE597128A (en))
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GB (2) GB971157A (en))
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Cited By (42)

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US3297407A (en) * 1962-12-10 1967-01-10 Gen Electric Method of growing diamond on a diamond seed crystal
US3310501A (en) * 1962-12-31 1967-03-21 Gen Electric Preparation of elongated needle-like diamond having electrically conductive properties
US3332747A (en) * 1965-03-24 1967-07-25 Gen Electric Plural wedge-shaped graphite mold with heating electrodes
US3407445A (en) * 1966-03-02 1968-10-29 Gen Electric High pressure reaction vessel for the preparation of diamond
US3423177A (en) * 1966-12-27 1969-01-21 Gen Electric Process for growing diamond on a diamond seed crystal
US3488153A (en) * 1966-12-01 1970-01-06 Gen Electric Non-catalytically produced cubic and hexagonal diamond
US3652220A (en) * 1966-02-11 1972-03-28 Scandimant Ab Method of manufacturing synthetic diamonds
US4049783A (en) * 1970-01-04 1977-09-20 Leonid Fedorovich Vereschagin Method of producing polycrystalline diamonds
US4113846A (en) * 1974-09-11 1978-09-12 Sigurdssons Mek. Verkstad Method of pressure treatments of materials
US4128625A (en) * 1976-10-18 1978-12-05 Hiroshi Ishizuka Process for synthesizing diamonds
US4225300A (en) * 1979-08-27 1980-09-30 High Pressure Technology, Inc. Reliable high pressure apparatus
US4740147A (en) * 1984-11-29 1988-04-26 Kabushiki Kaisha Kobe Seiko Sho Ultra-high pressure solid pressing machine
US5080752A (en) * 1991-07-08 1992-01-14 The United States Of America As Represented By The Secretary Of The Navy Consolidation of diamond packed powders
US5176788A (en) * 1991-07-08 1993-01-05 The United States Of America As Represented By The Secretary Of The Navy Method of joining diamond structures
WO2002016676A1 (en) * 2000-08-21 2002-02-28 Diamond Materials, Inc. High pressure and high temperature apparatus
US6402787B1 (en) 2000-01-30 2002-06-11 Bill J. Pope Prosthetic hip joint having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US6494918B1 (en) 2000-01-30 2002-12-17 Diamicron, Inc. Component for a prosthetic joint having a diamond load bearing and articulation surface
US20030019106A1 (en) * 2001-04-22 2003-01-30 Diamicron, Inc. Methods for making bearings, races and components thereof having diamond and other superhard surfaces
US6514289B1 (en) 2000-01-30 2003-02-04 Diamicron, Inc. Diamond articulation surface for use in a prosthetic joint
US20030057786A1 (en) * 2000-12-22 2003-03-27 Masashi Tado Extra high voltage generator
US6596225B1 (en) 2000-01-31 2003-07-22 Diamicron, Inc. Methods for manufacturing a diamond prosthetic joint component
US20030191533A1 (en) * 2000-01-30 2003-10-09 Diamicron, Inc. Articulating diamond-surfaced spinal implants
US6655845B1 (en) 2001-04-22 2003-12-02 Diamicron, Inc. Bearings, races and components thereof having diamond and other superhard surfaces
US6676704B1 (en) 1994-08-12 2004-01-13 Diamicron, Inc. Prosthetic joint component having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US6709463B1 (en) 2000-01-30 2004-03-23 Diamicron, Inc. Prosthetic joint component having at least one solid polycrystalline diamond component
US6793681B1 (en) 1994-08-12 2004-09-21 Diamicron, Inc. Prosthetic hip joint having a polycrystalline diamond articulation surface and a plurality of substrate layers
US20040199260A1 (en) * 2000-01-30 2004-10-07 Pope Bill J. Prosthetic joint component having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US20050087915A1 (en) * 1999-12-08 2005-04-28 Diamicron, Inc. Carbides as a substrate material in prosthetic joints
US20050110187A1 (en) * 1999-12-08 2005-05-26 Diamicron, Inc. Use of Ti and Nb cemented in TiC in prosthetic joints
US20050133277A1 (en) * 2003-08-28 2005-06-23 Diamicron, Inc. Superhard mill cutters and related methods
US20050153010A1 (en) * 2004-01-13 2005-07-14 Chien-Min Sung High pressure split die and associated methods
US20050158200A1 (en) * 1994-08-12 2005-07-21 Diamicron, Inc. Use of CoCrMo to augment biocompatibility in polycrystalline diamond compacts
US20050203630A1 (en) * 2000-01-30 2005-09-15 Pope Bill J. Prosthetic knee joint having at least one diamond articulation surface
US20060032431A1 (en) * 2004-01-13 2006-02-16 Chien-Min Sung High pressure crystal growth apparatuses and associated methods
US20060263233A1 (en) * 1999-12-08 2006-11-23 Diamicron, Inc. Use of a metal and Sn as a solvent material for the bulk crystallization and sintering of diamond to produce biocompatbile biomedical devices
US7396501B2 (en) 1994-08-12 2008-07-08 Diamicron, Inc. Use of gradient layers and stress modifiers to fabricate composite constructs
US20090263643A1 (en) * 2005-04-07 2009-10-22 Gardinier Clayton F Use of sn and pore size control to improve biocompatibility in polycrystalline diamond compacts
US20100025898A1 (en) * 2000-01-30 2010-02-04 Pope Bill J USE OF Ti AND Nb CEMENTED TiC IN PROSTHETIC JOINTS
US20100068122A1 (en) * 2008-08-25 2010-03-18 Chien-Min Sung Gem Growth Cubic Press and Associated Methods
US20100198353A1 (en) * 2000-01-30 2010-08-05 Pope Bill J USE OF Ti and Nb CEMENTED IN TiC IN PROSTHETIC JOINTS
EP1889656A4 (en) * 2005-02-21 2010-12-29 Inst De Monocristales S L Capsules and Elements for Making Synthetic Diamonds
US20110146348A1 (en) * 2009-06-26 2011-06-23 Harding David P Thick sintered polycrystalline diamond and sintered jewelry

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Publication number Priority date Publication date Assignee Title
US2941861A (en) * 1955-03-31 1960-06-21 Gen Electric Method of making garnet

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2941861A (en) * 1955-03-31 1960-06-21 Gen Electric Method of making garnet

Cited By (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297407A (en) * 1962-12-10 1967-01-10 Gen Electric Method of growing diamond on a diamond seed crystal
US3310501A (en) * 1962-12-31 1967-03-21 Gen Electric Preparation of elongated needle-like diamond having electrically conductive properties
US3332747A (en) * 1965-03-24 1967-07-25 Gen Electric Plural wedge-shaped graphite mold with heating electrodes
US3652220A (en) * 1966-02-11 1972-03-28 Scandimant Ab Method of manufacturing synthetic diamonds
US3407445A (en) * 1966-03-02 1968-10-29 Gen Electric High pressure reaction vessel for the preparation of diamond
US3488153A (en) * 1966-12-01 1970-01-06 Gen Electric Non-catalytically produced cubic and hexagonal diamond
US3423177A (en) * 1966-12-27 1969-01-21 Gen Electric Process for growing diamond on a diamond seed crystal
US4049783A (en) * 1970-01-04 1977-09-20 Leonid Fedorovich Vereschagin Method of producing polycrystalline diamonds
US4113846A (en) * 1974-09-11 1978-09-12 Sigurdssons Mek. Verkstad Method of pressure treatments of materials
US4128625A (en) * 1976-10-18 1978-12-05 Hiroshi Ishizuka Process for synthesizing diamonds
US4225300A (en) * 1979-08-27 1980-09-30 High Pressure Technology, Inc. Reliable high pressure apparatus
US4740147A (en) * 1984-11-29 1988-04-26 Kabushiki Kaisha Kobe Seiko Sho Ultra-high pressure solid pressing machine
US5080752A (en) * 1991-07-08 1992-01-14 The United States Of America As Represented By The Secretary Of The Navy Consolidation of diamond packed powders
US5176788A (en) * 1991-07-08 1993-01-05 The United States Of America As Represented By The Secretary Of The Navy Method of joining diamond structures
US7396501B2 (en) 1994-08-12 2008-07-08 Diamicron, Inc. Use of gradient layers and stress modifiers to fabricate composite constructs
US7396505B2 (en) 1994-08-12 2008-07-08 Diamicron, Inc. Use of CoCrMo to augment biocompatibility in polycrystalline diamond compacts
US7077867B1 (en) 1994-08-12 2006-07-18 Diamicron, Inc. Prosthetic knee joint having at least one diamond articulation surface
US20050158200A1 (en) * 1994-08-12 2005-07-21 Diamicron, Inc. Use of CoCrMo to augment biocompatibility in polycrystalline diamond compacts
US6676704B1 (en) 1994-08-12 2004-01-13 Diamicron, Inc. Prosthetic joint component having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US6800095B1 (en) 1994-08-12 2004-10-05 Diamicron, Inc. Diamond-surfaced femoral head for use in a prosthetic joint
US6793681B1 (en) 1994-08-12 2004-09-21 Diamicron, Inc. Prosthetic hip joint having a polycrystalline diamond articulation surface and a plurality of substrate layers
US7678325B2 (en) 1999-12-08 2010-03-16 Diamicron, Inc. Use of a metal and Sn as a solvent material for the bulk crystallization and sintering of diamond to produce biocompatbile biomedical devices
US20050087915A1 (en) * 1999-12-08 2005-04-28 Diamicron, Inc. Carbides as a substrate material in prosthetic joints
US20060263233A1 (en) * 1999-12-08 2006-11-23 Diamicron, Inc. Use of a metal and Sn as a solvent material for the bulk crystallization and sintering of diamond to produce biocompatbile biomedical devices
US7556763B2 (en) 1999-12-08 2009-07-07 Diamicron, Inc. Method of making components for prosthetic joints
US7569176B2 (en) 1999-12-08 2009-08-04 Diamicron, Inc. Method for making a sintered superhard prosthetic joint component
US20050110187A1 (en) * 1999-12-08 2005-05-26 Diamicron, Inc. Use of Ti and Nb cemented in TiC in prosthetic joints
US20040199260A1 (en) * 2000-01-30 2004-10-07 Pope Bill J. Prosthetic joint component having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US20100025898A1 (en) * 2000-01-30 2010-02-04 Pope Bill J USE OF Ti AND Nb CEMENTED TiC IN PROSTHETIC JOINTS
US20080215158A1 (en) * 2000-01-30 2008-09-04 Diamicron, Inc. Prosthetic hip joint having polycrystalline diamond articulation surfaces and at least one solid polycrystalline diamond compact
US6517583B1 (en) 2000-01-30 2003-02-11 Diamicron, Inc. Prosthetic hip joint having a polycrystalline diamond compact articulation surface and a counter bearing surface
US20080195220A1 (en) * 2000-01-30 2008-08-14 Diamicron, Inc. Prosthetic hip joint having polycrystalline diamond articulation surfaces and at least one solid polycrystalline diamond compact
US20100198353A1 (en) * 2000-01-30 2010-08-05 Pope Bill J USE OF Ti and Nb CEMENTED IN TiC IN PROSTHETIC JOINTS
US6514289B1 (en) 2000-01-30 2003-02-04 Diamicron, Inc. Diamond articulation surface for use in a prosthetic joint
US8603181B2 (en) 2000-01-30 2013-12-10 Dimicron, Inc Use of Ti and Nb cemented in TiC in prosthetic joints
US20050203630A1 (en) * 2000-01-30 2005-09-15 Pope Bill J. Prosthetic knee joint having at least one diamond articulation surface
US20030191533A1 (en) * 2000-01-30 2003-10-09 Diamicron, Inc. Articulating diamond-surfaced spinal implants
US6709463B1 (en) 2000-01-30 2004-03-23 Diamicron, Inc. Prosthetic joint component having at least one solid polycrystalline diamond component
US6494918B1 (en) 2000-01-30 2002-12-17 Diamicron, Inc. Component for a prosthetic joint having a diamond load bearing and articulation surface
US6402787B1 (en) 2000-01-30 2002-06-11 Bill J. Pope Prosthetic hip joint having at least one sintered polycrystalline diamond compact articulation surface and substrate surface topographical features in said polycrystalline diamond compact
US8016889B2 (en) 2000-01-30 2011-09-13 Diamicron, Inc Articulating diamond-surfaced spinal implants
US7494507B2 (en) 2000-01-30 2009-02-24 Diamicron, Inc. Articulating diamond-surfaced spinal implants
US20080154380A1 (en) * 2000-01-30 2008-06-26 Dixon Richard H Articulating diamond-surfaced spinal implants
US6596225B1 (en) 2000-01-31 2003-07-22 Diamicron, Inc. Methods for manufacturing a diamond prosthetic joint component
WO2002016676A1 (en) * 2000-08-21 2002-02-28 Diamond Materials, Inc. High pressure and high temperature apparatus
US20030057786A1 (en) * 2000-12-22 2003-03-27 Masashi Tado Extra high voltage generator
US6852163B2 (en) * 2000-12-22 2005-02-08 Sumitomo Heavy Industries Extra high voltage generator
US20090046967A1 (en) * 2001-04-22 2009-02-19 Pope Bill J Bearings, races and components thereof having diamond and other superhard surfaces
US6655845B1 (en) 2001-04-22 2003-12-02 Diamicron, Inc. Bearings, races and components thereof having diamond and other superhard surfaces
US7665898B2 (en) 2001-04-22 2010-02-23 Diamicron, Inc. Bearings, races and components thereof having diamond and other superhard surfaces
US20030019106A1 (en) * 2001-04-22 2003-01-30 Diamicron, Inc. Methods for making bearings, races and components thereof having diamond and other superhard surfaces
US20050133277A1 (en) * 2003-08-28 2005-06-23 Diamicron, Inc. Superhard mill cutters and related methods
US7540075B2 (en) 2004-01-13 2009-06-02 Chien-Min Sung Method of applying high pressures to a high pressure assembly
US7128547B2 (en) 2004-01-13 2006-10-31 Chien-Min Sung High pressure split die and associated methods
US20060032429A1 (en) * 2004-01-13 2006-02-16 Chien-Min Sung High pressure split die and associated methods
US7371280B2 (en) 2004-01-13 2008-05-13 Chien-Min Sung High pressure crystal growth apparatuses and associated methods
US20060032431A1 (en) * 2004-01-13 2006-02-16 Chien-Min Sung High pressure crystal growth apparatuses and associated methods
US20050153010A1 (en) * 2004-01-13 2005-07-14 Chien-Min Sung High pressure split die and associated methods
EP1889656A4 (en) * 2005-02-21 2010-12-29 Inst De Monocristales S L Capsules and Elements for Making Synthetic Diamonds
US20090263643A1 (en) * 2005-04-07 2009-10-22 Gardinier Clayton F Use of sn and pore size control to improve biocompatibility in polycrystalline diamond compacts
US8449991B2 (en) 2005-04-07 2013-05-28 Dimicron, Inc. Use of SN and pore size control to improve biocompatibility in polycrystalline diamond compacts
US9463092B2 (en) 2005-04-07 2016-10-11 Dimicron, Inc. Use of Sn and pore size control to improve biocompatibility in polycrystalline diamond compacts
US20100068122A1 (en) * 2008-08-25 2010-03-18 Chien-Min Sung Gem Growth Cubic Press and Associated Methods
US20110146348A1 (en) * 2009-06-26 2011-06-23 Harding David P Thick sintered polycrystalline diamond and sintered jewelry
US8663359B2 (en) 2009-06-26 2014-03-04 Dimicron, Inc. Thick sintered polycrystalline diamond and sintered jewelry
US9820539B2 (en) 2009-06-26 2017-11-21 Dimicron, Inc. Thick sintered polycrystalline diamond and sintered jewelry

Also Published As

Publication number Publication date
BE597128A (fr) 1961-03-15
SE305855B (en)) 1968-11-11
CH440235A (de) 1967-07-31
BE597127A (fr) 1961-03-15
DE1176623B (de) 1964-08-27
CH401927A (de) 1965-11-15
FR1274254A (fr) 1961-10-20
NL148012B (nl) 1975-12-15
GB973503A (en) 1964-10-28
NL258431A (en))
GB971157A (en) 1964-09-30

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