WO2010124625A1 - 生产大颗粒金刚石的方法和设备 - Google Patents
生产大颗粒金刚石的方法和设备 Download PDFInfo
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- WO2010124625A1 WO2010124625A1 PCT/CN2010/072253 CN2010072253W WO2010124625A1 WO 2010124625 A1 WO2010124625 A1 WO 2010124625A1 CN 2010072253 W CN2010072253 W CN 2010072253W WO 2010124625 A1 WO2010124625 A1 WO 2010124625A1
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- diamond
- gas
- reaction zone
- temperature resistant
- carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/129—Radiofrequency
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/10—Heating of the reaction chamber or the substrate
- C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0869—Feeding or evacuating the reactor
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/12—Processes employing electromagnetic waves
- B01J2219/1203—Incoherent waves
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/12—Processes employing electromagnetic waves
- B01J2219/1203—Incoherent waves
- B01J2219/1206—Microwaves
Definitions
- This invention relates to diamond production techniques, and more particularly to a method and apparatus for producing large particle diamond. Background technique
- diamond As the hardest substance in nature, diamond has many important industrial uses, such as: fine abrasive materials, high-hard cutting tools, various drill bits, wire drawing dies, and many precision instrument parts. However, high quality, large particle natural diamonds are very rare and expensive, requiring the artificial synthesis of diamond.
- diamond can be artificially produced by a Chemical Vapor Deposition (CVD).
- a carbon-containing gas such as decane CH 4
- hydrogen 3 ⁇ 4
- RF Radio Frequency
- a direct current arc a microwave plasma
- a hot filament a combustion flame.
- RF Radio Frequency
- the main technical problem solved by the present invention is to provide a method for producing large-grain diamond, in which high-temperature resistant small-grain seeds are controlled to grow diamond under dynamic conditions, and large-diameter diamond can be obtained without cutting the diamond sheet. Achieve large-scale, low-cost production of large-grain diamonds.
- Another main technical problem to be solved by the present invention is to provide an apparatus for producing a method of producing large-grain diamond of the present invention to realize large-scale, low-cost production of large-grain diamond.
- the present invention provides a method of producing large-grain diamonds, the method comprising:
- the high temperature resistant small particle seed is controlled to remain dynamic in the reaction zone at a temperature suitable for diamond growth to produce large particle diamond.
- the carbon-containing gas may include any one or a combination of the following: methane, acetylene, and ethanol gas, and a gas containing carbon, hydrogen, oxygen, and nitrogen;
- the auxiliary gas includes any one or a combination of the following: hydrogen, Oxygen and an inert gas;
- the high temperature resistant small particle seed comprises any one or a combination of the following: diamond, carbon, graphite, silicon, ceramic, and small particles of high temperature resistant metal.
- the high temperature resistant small particle seed can be controlled to remain dynamic in the reaction zone by the following method:
- the high temperature resistant small particle seed remains dynamic in the reaction zone.
- controlling the high temperature resistant small particle seed to maintain dynamics in the reaction zone comprises: controlling the high temperature resistant small particle seed to remain dynamic in at least two of the reaction zones; or controlling the high temperature resistant small particle Seed dynamics are repeatedly passed through the reaction zone; or, the high temperature resistant small particle seed is controlled to remain dynamic within the reaction zone; in particular, the high temperature resistant small particle seed is controlled to rotate itself in the reaction zone.
- repeatedly controlling the dynamics of the high temperature resistant small particle seed through the reaction zone comprises: controlling the high temperature resistant small particle seed to repeatedly pass the reaction from top to bottom, bottom to top, or dynamically at any angle region.
- the high temperature resistant small particle seed can be controlled at the temperature suitable for diamond growth by direct and/or indirect cooling. Further, the method further comprises: continuously adding the high temperature resistant small particle seed, and collecting the generated large particle diamond.
- reaction region suitable for diamond growth comprises: a direct current arc formed by the carbon-containing gas and the auxiliary gas; or a high-temperature flame formed by combustion of the carbon-containing gas and the auxiliary gas; or An activation region formed by the hot gas by the carbon-containing gas and the auxiliary gas; or a microwave plasma region formed by the microwave activation by the carbon-containing gas and the auxiliary gas; or formed by the high frequency of the carbon-containing gas and the auxiliary gas RF plasma activated area.
- the method for producing large-grain diamond maintains dynamics in a reaction zone suitable for diamond growth by controlling high temperature resistant small particle seeds at a temperature suitable for diamond growth, so that the surfaces of the high temperature resistant small particle seeds are continuously extended.
- the diamond is grown, thereby producing large-grain diamond, which realizes large-scale, low-cost production of large-grain diamond.
- the present invention also provides an apparatus for a method of producing large particle diamond of the present invention, the apparatus comprising:
- At least one reaction zone generating device for forming a carbon-containing gas and an auxiliary gas into a reaction region suitable for diamond growth
- a dynamic generating device for controlling the high temperature resistant small particle seed to remain dynamic in the reaction region formed by the reaction region generating device to generate large particle diamond
- a temperature maintaining means for controlling the temperature resistant small particle seed remaining dynamic in the reaction zone at the temperature suitable for diamond growth.
- the dynamic generating device comprises: a spouted bed reactor, a fluidized bed reactor, a moving bed reactor or a rotary kiln reactor, or a pneumatic generating device, a vibrating device or a mechanical conveying device.
- the setting of the reaction zone generating device includes one of the following: locating the kinetic generating device in the reaction region, or forming the reaction region in the dynamic generating device.
- the dynamic generating device is a pneumatic generating device, a vibration device or a mechanical handling device, and the device further comprises a reactor cavity, wherein the dynamic generating device is located in the reactor cavity.
- the reaction region generating device includes: a device for forming a DC arc of a carbon-containing gas and an auxiliary gas; or a device for burning a carbon-containing gas and an auxiliary gas to form a high-temperature flame; or a device for forming an activation region through a hot wire by a carbon gas and an auxiliary gas; or a device for forming a microwave plasma region by microwave activation of a carbon-containing gas and an auxiliary gas; or for forming a carbon-containing gas and an auxiliary gas through a high frequency A device for the activation of a radio frequency plasma.
- the apparatus further includes: a gas mixing device connected to the gas inlet of the reaction zone generating device; and a cooling collecting device for cooling and collecting the generated large particle diamond.
- the apparatus for producing the large-grain diamond of the present invention can control the high-temperature resistant small-grain seed to maintain dynamics in a reaction zone suitable for diamond growth at a temperature suitable for diamond growth, so that the high temperature resistance is small
- the surfaces of the granule seeds are continuously epitaxially grown to form diamonds, thereby producing large-grain diamonds, thereby realizing large-scale, low-cost production of large-grain diamonds.
- FIG. 1 is a schematic view showing an embodiment of a method for producing large-grain diamond according to the present invention
- FIG. 2 is a schematic view showing a first embodiment of a process for producing large-grain diamond according to the present invention
- FIG. 3 is a schematic view showing a second embodiment of a process for producing large-grain diamond according to the present invention.
- FIG. 4 is a schematic view showing a third embodiment of a process for producing large-grain diamond according to the present invention.
- Figure 5 is a schematic view showing the fourth embodiment of the process for producing large-grain diamond according to the present invention.
- Fig. 6 is a schematic view showing the fifth embodiment of the process for producing large-grain diamond according to the present invention.
- Figure 7 is a Raman shift line of a conventional pyrolytic carbon particle.
- Figure 8 is a Raman shift spectrum of a large grain diamond produced in an embodiment of the present invention. detailed description
- Step 101 Form a carbon-containing gas and an auxiliary gas into at least one reaction region suitable for diamond growth.
- the carbon-containing gas may include any one or a combination of the following: decane, ethylene, acetylene, ethanol gas, and a gas containing carbon, hydrogen, oxygen, nitrogen, wherein the ethanol gas represents vaporized ethanol, containing carbon, hydrogen
- the gas of oxygen and nitrogen represents a gas formed by vaporization of an organic substance containing carbon, hydrogen, oxygen, and nitrogen;
- the auxiliary gas may include any one or a combination of the following: hydrogen, oxygen, and an inert gas.
- a carbon-containing gas and an auxiliary gas are introduced from the gas inlet of the reaction zone generating means into the reaction zone generating means, and then activated by the reaction zone generating means to form a reaction zone suitable for diamond growth.
- the reaction zone generating means may have one or more to form one or more reaction zones, and the plurality of reaction zones may be vertically or horizontally connected in series.
- the reaction region generating device may include at least one of the following: (1) a device for forming a direct current arc for the carbon-containing gas and the auxiliary gas, wherein the peripheral portion of the direct current arc is a reaction region suitable for diamond growth,
- the cross section of the direct current arc may be circular, square or rectangular, and the cross-sectional area is stable; (2) a device for burning a carbon-containing gas and an auxiliary gas to form a high-temperature flame, the intermediate portion of the high-temperature flame being a reaction suitable for diamond growth a region; (3) means for forming a carbon-containing gas and an auxiliary gas through the hot wire to form an activation region, the activation region being a reaction region suitable for diamond growth; (4) for activating the carbon-containing gas and the auxiliary gas through microwaves a device for forming a microwave plasma region, wherein the microwave plasma region is a reaction region suitable for diamond growth, and the microwave plasma region may be a spherical region or an annular region; (5) for forming a
- Lux and Haubner divide the activation method into the following four categories: 1. High temperature activation (eg hot wire, laser, arc discharge) , arc plasma injection, combustion flame, etc.; 2, electrical or electromagnetic discharge activation (such as microwave, RF discharge, DC and AC Huiwen); 3, plasma injection method (such as RF, microwave, DC plasma spray, etc.); 4 , compound method (such as hot wire + T wave, hot wire + DC discharge, hot wire + bias).
- the purity of the carbon-containing gas and the auxiliary gas, the ratio of use of the carbon-containing gas and the auxiliary gas, the temperature of the plasma atmosphere, and the degree of vacuum in the environment in which the plasma atmosphere is located are suitable.
- the degree of vacuum in the environment in which the plasma atmosphere is located are suitable.
- the most common methods such as DC arc, high temperature flame, hot wire, microwave plasma or radio frequency plasma are used to activate the carbon-containing gas and the auxiliary gas.
- This embodiment does not limit the specific activation method, as long as it will be included.
- the carbon gas and the auxiliary gas are activated to generate a reaction region suitable for diamond growth.
- the method of forming a high temperature flame by acetylene oxygen combustion can be seen in: Y.
- Step 102 Control the high temperature resistant small particle seed to remain dynamic in the reaction zone at a temperature suitable for diamond growth to generate large particle diamond.
- the high temperature resistant small particle seed in the present invention may include any one or a combination of the following: diamond, carbon, graphite, silicon, ceramic, and high temperature resistant metal small particles, as long as it is resistant to high temperature (the high temperature is a temperature suitable for diamond growth, Small particles between 700 and 1000 ° C can be used as seeds for the production of large grain diamonds.
- the large-grained diamond in the present invention means particles having a particle diameter larger than that of the particles as seeds and whose surface composition is a diamond structure.
- the reaction zone is an activation space region suitable for diamond growth, and the high-temperature small particle seed with a particle size higher than 'j, is put into the reaction zone at the system control point, and is controlled by the dynamic generating device.
- the high temperature resistant small particle seed dynamically passes through the reaction zone, or controls the high temperature resistant small particle seed to remain dynamic inside the reaction zone, and can also control the high temperature resistant small particle seed to maintain its own rotation during the above movement; It is also possible to control the high temperature resistant small particle seed to remain dynamic in at least two reaction zones.
- the high temperature resistant small particle seed remains dynamic (especially self-rotating) in the reaction zone, carbon in the reaction zone adheres to the surface of the high temperature resistant small particle seed and grows on the surface of the particle, and has a diamond structure. Seeds of smaller particles can be grown into larger particles of diamond. Compared with the prior art method of growing diamond using a substrate, in the present invention, since the seed remains dynamic in the reaction region, all surfaces of the seed have an opportunity to grow diamond, thereby obtaining a large particle diamond with higher efficiency.
- the existing method can only grow diamond in one direction on the substrate, and the efficiency is low; and since the seed in the invention can rotate itself in the reaction region, the diamond grown on the surface of the seed is relatively symmetrical, and The seeds are completely wrapped, so when non-diamond is used as the seed, the large-grained diamond with a tight surface can be obtained, which is convenient for industrial applications.
- the dynamic generating device can also control the high temperature resistant small particle seed to repeatedly pass through the reaction area, so that the particles can be continuously grown to avoid a plurality of particles forming a whole piece.
- the dynamic generating device may be a spouted bed reactor, a fluidized bed reactor, a moving bed reactor or a rotary kiln reactor, and the high temperature resistant small particle seed is located in any of the above reactors, and correspondingly, in the reactor There is a reaction zone suitable for diamond growth or the reactor is entirely in a reaction zone suitable for diamond growth, and the reactor is driven by the high temperature resistant small particle seed to remain dynamic in the reaction zone.
- the dynamic generating device can also be a pneumatic generating device, a vibrating device or a mechanical handling device.
- the dynamic generating device is a pneumatic generating device, a vibrating device or a mechanical handling device
- the dynamic generating device is located in a reactor chamber, and a reaction region suitable for diamond growth generated by the reaction region generating device is located in the reactor chamber or located Outside the reactor chamber
- a dynamic generating device moves the high temperature resistant small particle seed in the reaction zone, that is, by using pneumatic, vibration, mechanical handling, inversion or throwing, the high temperature resistant small particle seed is dynamically passed through the reaction zone.
- controlling the high temperature resistant small particle seed to be in a moving state in the reaction zone, wherein the manner of dynamically repeating the reaction zone may be self Bottom-up or top-down, it can also be repeated horizontally or dynamically at any angle.
- the high temperature resistant small particle seed can be controlled at a temperature suitable for the growth of the diamond by direct and/or indirect cooling.
- a heat exchange device can be arranged on the reactor cavity, and the high temperature resistant small particle seed located inside the reactor cavity is ensured to be at a temperature suitable for diamond growth by heat exchange; and can also pass through the high temperature resistant small particle seed.
- the gas stream reduces the temperature of these particles to ensure that the particles are at a temperature suitable for diamond growth.
- large-grain diamond can be produced by a batch or continuous process, and when continuously producing large-grain diamond, high-temperature resistant small-particle seeds can be continuously added to the reactor, and continuously from the reactor.
- the large-grain diamond produced by Captain General is separated to achieve large-scale continuous production.
- the method for producing large-grain diamond maintains dynamics in a reaction zone suitable for diamond growth at a temperature suitable for diamond growth by controlling high-temperature resistant small-grain seeds, so that each surface of the high-temperature resistant small particle seed Continuously epitaxy, diamonds are grown, which produces large-grain diamonds, enabling large-scale continuous, low-cost production of large-grain diamonds.
- the present invention has at least the following advantages: 1.
- the particles are always dynamic in the reaction area, avoiding the formation of a graphite layer on the surface of the particles fixedly placed on the substrate; 2.
- the diamond particles directly produced are No need for subsequent cutting and processing operations, greatly reducing product cost and improving production efficiency; 3.
- the particles are dynamic in the reaction area, so that all surfaces have the opportunity to grow diamonds, thereby improving production efficiency; 4. Due to the present invention The particles in the movement can also rotate by themselves when moving in the reaction zone, so that the diamond grown on the surface of the particles is relatively symmetrical, and the particles can be completely wrapped, so when non-diamond is used as the seed, the large-grain diamond with tight surface wrapping can be obtained. Industrial applications.
- the apparatus includes: at least one reaction zone generating device, a dynamic generating device, and a temperature maintaining device.
- reaction zone generating device for forming a carbon-containing gas and an auxiliary gas to form a reaction suitable for diamond growth Should be the area.
- the dynamic generating means is for controlling the high temperature resistant small particle seed to remain dynamic in the reaction zone formed by the reaction zone generating means to generate large particle diamond.
- the temperature holding device is used to control the high temperature resistant small particle seed that remains dynamic in the reaction zone at a temperature suitable for diamond growth.
- the dynamic generating device may comprise: a spouted bed reactor, a fluidized bed reactor, a moving bed reactor, a rotary kiln reactor, a pneumatic generating device, a vibrating device or a mechanical carrying device.
- the apparatus further includes a reactor chamber, and the dynamic generating device is located within the reactor chamber.
- the pneumatic generating device, the vibrating device or the mechanical carrying device can control the high temperature resistant small particle seed dynamically passing through the reaction area or controlling the high temperature resistant small particle seed in the reaction area by pneumatic, vibration, mechanical handling, inversion or throwing.
- the state of motion preferably, also controls the rotation of the particles themselves; wherein the manner of dynamically passing the reaction zone may be bottom-up or top-down, or may be horizontal or at any angle.
- the dynamic generating device comprises: a spouted bed reactor, a fluidized bed reactor, a moving bed reactor or a rotary kiln reactor
- the dynamic generating device itself is a reactor, which provides the diamond growth reaction required The reactor chamber
- the dynamic generating device comprises a pneumatic generating device, a vibrating device or a mechanical handling device
- the dynamic generating device is merely a transmitting or vibrating device, thereby requiring a reactor chamber.
- the arrangement of the reaction zone generating means includes one of the following cases: the dynamic generating device is placed in the reaction region, or the region is formed in the dynamic generating device.
- the reaction zone generating device may comprise any one of the following devices or any combination thereof: a device for forming a direct current arc of a carbon-containing gas and an auxiliary gas; a device for burning a carbon-containing gas and an auxiliary gas to form a high-temperature flame; a device for forming an activation region through a hot wire by a carbon gas and an auxiliary gas; a device for forming a microwave plasma region by activating the carbon-containing gas and the auxiliary gas through microwaves; and forming a radio frequency plasma activation region by passing the carbon-containing gas and the auxiliary gas through a high frequency s installation.
- reaction zone generating means may have one or more to form one or more reaction zones, and the plurality of reaction zones may be vertically or horizontally connected in series.
- apparatus may further include: a gas mixing device and a cooling collecting device.
- the gas mixing device is connected to the gas inlet of the reaction zone generating device for supplying the carbon-containing gas and the auxiliary gas to the reaction zone generating device.
- a cooling collection device is used to cool and collect the generated large particle diamond.
- the apparatus provided in this embodiment may further include a vacuum generating device for providing a vacuum environment to the reaction region.
- a vacuum generating device for providing a vacuum environment to the reaction region. A certain degree of vacuum is required for the diamond to grow in the microwave plasma region or the radio frequency plasma activated region, thereby requiring a vacuum generating device to provide a certain degree of vacuum to the reactor chamber.
- the apparatus provided in the embodiment can be used for batch or continuous production of large-grain diamond; when continuously producing large-grain diamond, the apparatus can further include a continuous feeding device to continuously add high-temperature resistant small particles in the reactor. The seeds, and the larger particles of diamond are continuously separated from the reactor by means of a collecting device to achieve large-scale continuous production.
- the apparatus provided by the embodiment of the invention can control the high temperature resistant small particle seed to maintain dynamicity in a reaction zone suitable for diamond growth at a temperature suitable for diamond growth, so that the surface of the high temperature resistant small particle seed continuously grows diamond.
- the large-grain diamond is thus produced, and large-scale, low-cost production of large-grain diamond is realized.
- the apparatus provided in this embodiment is used to produce large-grain diamond, and the advantages described in the method embodiments are also omitted.
- Fig. 2 is a schematic view showing a first embodiment of a process for producing large-grained diamond according to the present invention, which is a schematic view for producing large-grain diamond in a plurality of regions, as shown in Fig. 2:
- the apparatus for producing large-grain diamond includes a plurality of plasma generators 110, a reactor chamber 130, a delivery system 140, a vacuum pump 160, and a plasma system 110 and a plasma generator 110 to eject the plasma.
- the sub-flame is located inside the reactor cavity 130.
- a plurality of plasma flame activation regions 120 are respectively ejected from the plurality of plasma generators 110 (ie, corresponding to the reaction regions in the foregoing embodiments); the plurality of high temperature resistant small particle seeds can be formed into a circulating particle stream 150 by the delivery system 140; Vacuum pump 160 provides the desired degree of vacuum to the interior of reactor chamber 130.
- the carbon-containing gas and hydrogen gas are introduced into the plurality of plasma generators 110, and then a plurality of plasma flame activation regions 120 are ejected by the plurality of plasma generators 110; the vacuum pump 160 provides a vacuum degree suitable for diamond growth inside the reactor chamber 130.
- the delivery system 140 carries the high temperature resistant small particle seeds, and the small particle seeds are circulated through the plurality of plasma flame activation regions 120.
- the small particle seeds continuously react to absorb the diamond components and gradually grow into sizes as they pass through the plasma flame activation region 120. Larger diamond particles.
- a plurality of plasma generators are used so that the small particle seeds can pass through a plurality of plasma atmospheres in one cycle, thereby increasing the growth rate of the diamond.
- this embodiment does not limit the number of plasma generators, and may be one or more.
- Fig. 3 is a schematic view showing the second embodiment of the process for producing large-grained diamond according to the present invention, wherein the reactor in the process is a spouted bed reactor, as shown in Fig. 3:
- the apparatus for producing large particle diamond includes a spouted bed reactor 210 and a plasma generator 220.
- the spouted bed reactor 210 can be a dynamic generating device as described in the foregoing embodiments.
- the plasma generator 220 ejects the plasma flame 230 (i.e., corresponds to the reaction zone in the previous embodiment).
- the RF high frequency induction coil 240 may also be included in this embodiment.
- the diamond particles 250 placed in the spouted bed reactor 210 are tumbling up and down due to the spraying action of the plasma flame 230 formed by the plasma generator 220, and the diamond particles 250
- the plasma flame 230 is continuously fed in and out, and whenever the diamond particles 250 enter the plasma flame 230, they are deposited on the surface of the diamond and continue to grow, eventually growing into larger-sized diamond particles.
- FIG. 4 is a schematic view showing a third embodiment of the process for producing large-grain diamond according to the present invention, wherein the reactor in the process is a rotary reactor, as shown in FIG. 4:
- the apparatus for producing large-grain diamond includes a rotary reactor 310 and a plasma generator (not shown); wherein the rotary reactor 310 can be a dynamic generating device as described in the foregoing embodiments, and the rotary reaction
- the unit 310 includes: a reactor funnel 320 and a copy board 350.
- the plasma generator forms a plasma activation region 330 (corresponding to the reaction region in the foregoing embodiment) located in the cavity of the rotary reactor 310 (ie, corresponding to the reaction region in the foregoing embodiment); if necessary, a vacuum pump can be added to provide a certain vacuum in the reactor. degree.
- the rotary reactor 310 is rotated counterclockwise at a constant lower rotational speed by an external force, and the diamond particles 340 placed in the rotary reactor 310 are transported to the reactor funnel 320 under the transfer plate 350 provided on the inner wall of the reactor chamber.
- the upper portion then falls into the reactor funnel 320 under the action of gravity, and passes through the plasma activation region 330 to grow and absorb the diamond component when it passes through the plasma activation region 330. After falling through the plasma activation region 330, it is copied.
- the plate 350 is collected and transported into the next cycle, and the cycle is repeated to allow the smaller diamond particles to grow into larger-sized diamond particles.
- Fig. 5 is a schematic view showing the fourth embodiment of the process for producing large-grained diamond according to the present invention, wherein the reactor in the flow is a rotary reactor for continuously growing large-grain diamond by using an annular activation space region, as shown in Fig. 5:
- the apparatus for producing large-grain diamond includes a rotary reactor 410.
- the combustion flame forms an annular activation region 420 (i.e., corresponding to the reaction region in the foregoing embodiment); the rotary reactor 41 0 may be the foregoing A dynamic generating device in each of the embodiments, the rotating reactor 410 is provided with a diamond particle flow control device 440, by which the diamond particles can be controlled to pass through the annular activation region 420 when moving up and down.
- the rotating reactor 410 continuously rotates up and down about the rotating shaft 450, and the diamond particles 430 placed in the control device 440 move back and forth under the action of gravity at both ends of the control device 440 and continuously pass through the annular activation region 420, passing through the annular activation region.
- the reaction absorbs the diamond component and gradually grows into larger-sized diamond particles.
- FIG. 6 is a schematic view showing the fifth embodiment of the process for producing large-grain diamond according to the present invention,
- the reactor is a rotating reactor for continuously growing large particle diamonds using a spherical active space region, as shown in Figure 6, the apparatus comprising:
- the apparatus for producing large-grain diamond includes a rotary reactor 510, a plasma generator (not shown), and a vacuum pump (not shown).
- the plasma generator forms a spherical plasma activated region 520, the region is a spherical shape having gas components and temperature conditions suitable for diamond growth;
- the rotating reactor 510 can be one of the foregoing embodiments.
- a dynamic generating device is provided with a diamond particle flow control device 540.
- the control device 540 can control the diamond particles to pass through the spherical plasma activation region 520 when moving up and down.
- the rotating reactor 510 continuously rotates up and down about the rotating shaft 550, and the diamond particles 530 placed in the control device 540 move back and forth between the two ends of the control device 540 under gravity and continuously pass through the plasma activation region 520, while passing through the plasma activation region 520.
- the reaction absorbs the diamond component and gradually grows into larger-sized diamond particles.
- a combustion flame of acetylene and pure oxygen (ratio 1:1, flow rate 6-7 s lpm) in a 40 ⁇ diameter tapered quartz
- the bottom of the tube is ejected to form a spouted bed.
- the pyrolytic carbon particles circulate up and down in the spouted bed; the quartz tube and the outside are not insulated, and the infrared thermometer shows that during steady state operation, the particle temperature is 800 °C - 900 °C, after the system is operated for two hours, The temperature was increased to 3.78 g.
- Figure 7 is a Raman shift line of a conventional pyrolytic carbon particle in which there are only two broad peaks corresponding to graphite for the pyrolytic carbon particles not participating in the reaction.
- 8 is a Raman shift spectrum of a large-grained diamond produced by an embodiment of the present invention. As shown in FIG. 8, in addition to the Raman shift peak of the above graphite, there is a relatively obvious diamond signal, which proves that the diamond component is long. Particle surface. The increase in total weight indicates that the particle size of the particles grows.
- the above process can be carried Continue until the desired diamond particles of the desired particle size are obtained.
- the pyrolytic carbon particles in the experimental example can be replaced with any other high-temperature resistant small particle seed provided in the invention, and the diamond particles having a large particle size are obtained according to the same method;
- the bed is replaced by any of the dynamic generating devices provided in the invention, and the combustion flame is exchanged for any other reaction region provided in the invention, and diamond particles having a large particle diameter can be obtained as well.
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Description
生产大颗粒金刚石的方法和设备 技术领域
本发明涉及金刚石生产技术, 尤其涉及一种生产大颗粒金刚石的方法和 设备。 背景技术
金刚石作为自然界中最坚硬的物质, 具有许多重要的工业用途, 例如: 精细研磨材料、 高硬切割工具、 各类钻头、 拉丝模, 以及很多精密仪器的部 件。 但是高质量、 大颗粒的天然金刚石非常稀少且价格昂贵, 由此需要人工 合成金刚石。
现有技术中, 可以采用气相法 ( Chemical Vapor Deposition, CVD ) 来人 工生产金刚石。在该方法中,先将含碳元素的气体(如曱烷 CH4 )与氢气(¾ ) 以一定比例混合后通过高频 RF ( Radio Frequency )等离子、 直流电弧、 微波 等离子、 热灯丝或燃烧焰等进行激活, 在预先放置有小颗粒单晶金刚石粒子 的耐高温材料衬底上反应, 使该较小颗粒单晶金刚石逐渐长大, 生成与金刚 石原子空间排列结构相同的薄膜涂层或较厚的多晶膜, 然后脱离衬底成为自 支撑多晶金刚石片。
但是在现有技术中至少存在如下问题: 在一生产过程结束后, 需要对生 成的金刚石片进行切割加工, 由此增加了生产成本、 降低了生产效率。 发明内容
本发明解决的主要技术问题为提供一种生产大颗粒金刚石的方法, 在反应 过程中控制耐高温小颗粒种子在动态下生长出金刚石, 不需对金刚石片进行切 割即可得到大颗粒金刚石, 从而实现大规模、 低成本的生产大颗粒金刚石。
本发明解决的另一主要技术问题为提供用于本发明的生产大颗粒金刚石 的方法的设备, 以实现大规模、 低成本的生产大颗粒金刚石。
为了解决上述技术问题, 本发明提供一种生产大颗粒金刚石的方法, 该 方法包括:
将含碳气体和辅助气体形成适于金刚石生长的反应区域;
在适于金刚石生长的温度下, 控制耐高温小颗粒种子在所述反应区域中 保持动态, 以生成大颗粒金刚石。
具体的, 所述含碳气体可以包括以下任一种或其组合: 甲烷、 乙炔和、 乙醇气和含碳、 氢、 氧、 氮的气体; 辅助气体包括以下任一种或其组合: 氢 气、 氧气和惰性气体; 所述耐高温小颗粒种子包括以下任一种或其组合: 金 刚石、 碳、 石墨、 硅、 陶瓷和耐高温金属小颗粒。
进一步的, 可以采用以下方法控制所述耐高温小颗粒种子在所述反应区 域中保持动态:
使用喷动床、 流化床、 移动床或回转炉, 控制所述耐高温小颗粒种子在 所述反应区域中保持动态; 或者, 使用气动、 震动、 机械搬运、 倒置或抛运 的方式, 控制所述耐高温小颗粒种子在所述反应区域中保持动态。
进一步的,所述控制耐高温小颗粒种子在所述反应区域中保持动态包括: 控制所述耐高温小颗粒种子在至少两个所述反应区域中保持动态; 或者, 控 制所述耐高温小颗粒种子动态的反复通过所述反应区域; 或者, 控制所述耐 高温小颗粒种子在所述反应区域内部保持动态; 特别是, 控制所述耐高温小 颗粒种子在所述反应区域中自身转动。
其中, 控制所述耐高温小颗粒种子动态的反复通过所述反应区域包括: 控制所述耐高温小颗粒种子自上而下、 自下而上、 或以任一角度动态的反复 通过所述反应区域。
具体的, 可以通过直接和 /或间接冷却的方法, 控制所述耐高温小颗粒种 子处于所述适于金刚石生长的温度。
进一步的, 该方法还包括: 连续加入所述耐高温小颗粒种子, 并收集生 成的所述大颗粒金刚石。
进一步的, 所述适于金刚石生长的反应区域包括: 由所述含碳气体和辅 助气体形成的直流电弧; 或者, 由所述含碳气体和辅助气体燃烧形成的高温 火焰; 或者, 由所述含碳气体和辅助气体通过热丝形成的激活区域; 或者, 由所述含碳气体和辅助气体通过微波激活形成的微波等离子区域; 或者, 由 所述含碳气体和辅助气体通过高频形成的射频等离子激活区域。
本发明提供的生产大颗粒金刚石的方法, 通过控制耐高温小颗粒种子在 适于金刚石生长的温度下、 在适于金刚石生长的反应区域中保持动态, 使得 耐高温小颗粒种子的各表面不断外延, 生长出金刚石, 由此生成了大颗粒金 刚石, 实现了大规模、 低成本的生产大颗粒金刚石。
为了解决上述技术问题, 本发明还提供一种用于本发明的生产大颗粒金 刚石的方法的设备, 该设备包括:
至少一个反应区域产生装置, 用于将含碳气体和辅助气体形成适于金刚 石生长的反应区域;
动态发生装置, 用于控制耐高温小颗粒种子在所述反应区域产生装置形 成的所述反应区域中保持动态, 以生成大颗粒金刚石;
温度保持装置, 用于控制在所述反应区域中保持动态的所述耐高温小颗 粒种子处于所述适于金刚石生长的温度。
进一步的, 所述动态发生装置包括: 喷动床反应器、 流化床反应器、 移 动床反应器或回转炉反应器, 或者气动发生装置、 震动装置或机械搬运装置。
进一步的, 所述反应区域产生装置的设置包括以下情况之一: 使所迷动 态发生装置位于所述反应区域内, 或者, 使所述反应区域形成于所述动态发 生装置内。
可选的, 所述动态发生装置为气动发生装置、 震动装置或机械搬运装置, 且所述设备还包括反应器腔体, 所述动态发生装置位于所述反应器腔体内。
进一步的, 所述反应区域产生装置包括: 用于将含碳气体和辅助气体形 成直流电弧的装置; 或者, 用于将含碳气体和辅助气体燃烧形成高温火焰的 装置; 或者, 用于将含碳气体和辅助气体通过热丝形成激活区域的装置; 或 者, 用于将含碳气体和辅助气体通过微波激活形成微波等离子区域的装置; 或者,用于将含碳气体和辅助气体通过高频形成射频等离子激活区域的装置。
进一步的, 所述设备还包括: 气体混合装置, 与所述反应区域产生装置 的气体入口连接; 冷却收集装置, 用于冷却和收集生成的所述大颗粒金刚石。
本发明提供的用于本发明的生产大颗粒金刚石的方法的设备, 可以控制 耐高温小颗粒种子在适于金刚石生长的温度下、 在适于金刚石生长的反应区 域中保持动态, 使得耐高温小颗粒种子的各表面不断外延, 生长出金刚石, 由此生成了大颗粒金刚石, 实现了大规模、 低成本的生产大颗粒金刚石。 附图说明
图 1为本发明生产大颗粒金刚石的方法实施例的示意图;
图 2为本发明生产大颗粒金刚石的流程实施例一的示意图;
图 3为本发明生产大颗粒金刚石的流程实施例二的示意图;
图 4为本发明生产大颗粒金刚石的流程实施例三的示意图;
图 5为本发明生产大颗粒金刚石的流程实施例四的示意图;
图 6为本发明生产大颗粒金刚石的流程实施例五的示意图。
图 7是现有的热解碳颗粒的 Raman位移谱线。
图 8是本发明实施例生产的大颗粒金刚石的 Raman位移谱线。 具体实施方式
下面结合附图和具体实施例进一步说明本发明实施例的技术方案。
图 1为本发明生产大颗粒金刚石的方法实施例的示意图, 如图 1所示, 该方法包括:
步驟 101、 将含碳气体和辅助气体形成至少一个适于金刚石生长的反应 区域。
其中, 含碳气体可以包括以下任一种或其组合: 曱烷、 乙烯、 乙炔、 乙 醇气和含碳、 氢、 氧、 氮的气体, 其中, 乙醇气表示气化的乙醇, 含碳、 氢、 氧、 氮的气体表示一含有碳、 氢、 氧、 氮元素的有机物气化后形成的气体; 辅助气体可以包括以下任一种或其组合: 氢气、 氧气和惰性气体。
将含碳气体和辅助气体从反应区域产生装置的气体入口通入该反应区域 产生装置中,然后由反应区域产生装置激活形成适合金刚石生长的反应区域。 反应区域产生装置可以有一个或多个, 以形成一个或多个反应区域, 多个反 应区域可以是垂直或水平串联的。
其中, 反应区域产生装置可以至少包括以下任一种: ( 1 )用于将含碳气 体和辅助气体形成直流电弧的装置, 该直流电弧的外围区间为适于金刚石生 长的反应区^ Ϊ, 该直流电弧的截面可以是圓形、 方形或矩形, 并且该截面区 域稳定; (2 )用于将含碳气体和辅助气体燃烧形成高温火焰的装置, 该高温 火焰中间区域为适于金刚石生长的反应区域; ( 3 )用于将含碳气体和辅助气 体通过热丝形成激活区域的装置,该激活区域为适于金刚石生长的反应区域; ( 4 ) 用于将含碳气体和辅助气体通过微波激活形成微波等离子区域的装置, 该微波等离子区域为适于金刚石生长的反应区域, 该微波等离子区域可以为 球状区或环状区; ( 5 )用于将含碳气体和辅助气体通过高频形成射频等离子 激活区域的装置, 该射频等离子激活区域为适于金刚石生长的反应区域。
其中 , 将含碳气体和辅助气体进行激活生成反应区域的方法有多种。 Lux 和 Haubner ( Lux, B. Haubner R., J. Ref. Hard Metals, 1989, 8(3): 158 )将激活的 方法分成以下四类: 1、 高温激活(例如热丝、 激光、 弧光放电、 弧光等离子 喷射、 燃烧火焰等) ; 2、 电或电磁放电激活(例如微波、 射频放电、 直流和 交流辉 文电); 3、 等离子喷射法(例如射频、 微波、 直流等离子喷射等); 4、 复合法 (例如热丝 + T波、 热丝 +直流放电, 热丝 +偏压) 。
需要说明的是, 本发明各实施例中, 含碳气体和辅助气体的纯度、 含碳 气体和辅助气体的使用比例、 等离子氛围的温度、 以及等离子氛围所处环境 中的真空度, 都是适于生产金刚石的。
本实施例以直流电弧、 高温火焰、 热丝、 微波等离子或射频等离子等最 常用的方法来对含碳气体和辅助气体进行激活为例, 本实施例并不限定具体 激活的方法, 只要将含碳气体和辅助气体进行激活生成适于金刚石生长的反 应区域即可。 其中, 通过乙炔氧气燃烧形成高温火焰的方法可以参见: Y.
Hirose etal, Appl. Phs.Lett. 1988, 52 (6): 437-438,和 S. Yugo etal, ppl. Phys. Lett. 1991, 58(10): 1036; 通过高压电极形成直流电弧的方法可以参见: Ohtake et al., "Diamond Film Preparation by Arc Discharge Plasma Jet Chemical Vapor
Deposition in the Methane Atmosphere", J. Electrochem. Soc. Vol.137, No.2
Feb.1990; 通过微波激活形成微波等离子区域可以参见: Wuyi Wang,
"Gem-quality Synthetic Diamonds Grown by a Chemical Vapor Deposition (CVD) Method", Gems & Gemology, Winter 2003 pp:268; 通过高频感应可以形成射频 激活区 i或的方法可以参见: S. K. Baldwin, et al "Growth Rate Studies of CVD Diamond in an RF Plasma Torch", Plasma Chem. And Plasma Processing, vol.14, No. 4, 1994。 上述公开的内容合并于此, 具体方法在此不再赘述。
步驟 102、 在适于金刚石生长的温度下, 控制耐高温小颗粒种子在反应 区域中保持动态, 以生成大颗粒金刚石。
本发明中的耐高温小颗粒种子可以包括以下任一种或其组合: 金刚石、 碳、 石墨、 硅、 陶瓷和耐高温金属小颗粒, 只要是耐高温 (该高温是适于金 刚石生长的温度, 在 700-1000°C之间) 的小颗粒, 都可以作为生产大颗粒金 刚石的种子。本发明中的大颗粒金刚石是指粒径大于作为种子的颗粒的粒径、 表面成份是金刚石结构的颗粒。
该反应区域是一适合金刚石生长的激活空间区域,将颗粒度较' j、的耐高 温小颗粒种子, 在系统控制点投入反应区域中, 并通过动态发生装置控制该
耐高温小颗粒种子动态的反复通过该反应区域, 或是控制耐高温小颗粒种子 在该反应区域内部保持动态, 并且还可以控制耐高温小颗粒种子在上述运动 过程中还保持自身转动; 此外, 还可以控制耐高温小颗粒种子在至少两个反 应区域中保持动态。
当耐高温小颗粒种子在反应区域中保持动态 (尤其是自身转动) 时, 反 应区域中的碳会附着在该耐高温小颗粒种子的表面, 并在颗粒表面生长, 且 呈金刚石结构, 由此使得较小颗粒的种子能生长成较大颗粒的金刚石。 相比 于现有的使用衬底生长金刚石的方法, 本发明中由于种子在反应区域中保持 动态, 使得该种子的所有表面都有机会生长上金刚石, 由此可以效率较高的 得到大颗粒金刚石, 而现有的方法只能在衬底上沿一个方向生长金刚石, 效 率较低; 并且由于本发明中的种子在反应区域中运动时还可以自身转动, 使 得种子表面生长的金刚石比较匀称, 能够将种子完全包裹, 所以当使用非金 刚石作为种子时, 仍可以得到表面包裹严密的大颗粒金刚石, 方便工业应用。 此外, 动态发生装置还可以控制耐高温小颗粒种子反复的通过该反应区域, 使得颗粒可以不断的长大而避免多个颗粒结成一个整块。
该动态发生装置可以为喷动床反应器、 流化床反应器、 移动床反应器或回 转炉反应器, 耐高温小颗粒种子位于上述任一反应器中, 相应的, 在该反应器 内存在有适于金刚石生长的反应区域或者该反应器整个处于适于金刚石生长 的反应区域中, 由该反应器带动耐高温小颗粒种子在该反应区域中保持动态。
该动态发生装置还可以为气动发生装置、 震动装置或机械搬运装置。 当该 动态发生装置为气动发生装置、 震动装置或机械搬运装置时, 该动态发生装置 位于一反应器腔体内,反应区域产生装置产生的适于金刚石生长的反应区域位 于该反应器腔体内或位于该反应器腔体外,动态发生装置使耐高温小颗粒种子 在该反应区域中运动, 即通过使用气动、震动、机械搬运、倒置或抛运的方式, 控制耐高温小颗粒种子动态通过该反应区域或者控制耐高温小颗粒种子在该 反应区域中处于运动状态, 其中, 动态的反复通过该反应区域的方式可以是自
下而上或自上而下, 也可以是水平或以任一角度动态的反复通过。
可以通过直接和 /或间接冷却的方法, 控制耐高温小颗粒种子处于适于金 刚石生长的温度。 例如: 可以在反应器腔体上设置热交换装置, 通过热交换 保证位于反应器腔体内部的耐高温小颗粒种子处于适于金刚石生长的温度; 还可以在传输耐高温小颗粒种子时, 通过气流降低这些颗粒的温度, 以保证 这些颗粒处于适于金刚石生长的温度。
根据本发明的具体实施方案, 可以通过间歇式或连续化过程生产大颗粒 金刚石 , 当连续化生产大颗粒金刚石时, 可以在反应器中连续的加入耐高温 小颗粒种子, 并不断的从反应器中将生成的大颗粒金刚石分离出来, 以实现 大规模连续化生产。
本发明实施例提供的生产大颗粒金刚石的方法, 通过控制耐高温小颗粒 种子在适于金刚石生长的温度下、在适于金刚石生长的反应区域中保持动态, 使得耐高温小颗粒种子的各表面不断外延, 生长出金刚石, 由此生成了大颗 粒金刚石, 实现了大规模连续化、 低成本的生产大颗粒金刚石。 并且相比于 现有技术, 本发明至少具有以下优点: 1、 颗粒一直在反应区域内处于动态, 避免了在衬底上固定放置的颗粒表面形成石墨层; 2、 直接生产出的就是金刚 石颗粒, 无需进行后续切割加工作业, 大大降低了产品成本, 提高生产效率; 3、 颗粒在反应区域中处于动态, 使得所有表面都有机会生长上金刚石, 由 此提高了生产效率; 4、 由于本发明中的颗粒在反应区域中运动时还可以自 身转动, 使得颗粒表面生长的金刚石比较匀称, 能够将颗粒完全包裹, 所以 当使用非金刚石作为种子时, 仍可以得到表面包裹严密的大颗粒金刚石, 方 便工业应用。
设备包括: 至少一个反应区域产生装置、 动态发生装置和温度保持装置。
反应区域产生装置用于将含碳气体和辅助气体形成适于金刚石生长的反
应区域。 动态发生装置用于控制耐高温小颗粒种子在反应区域产生装置形成 的反应区域中保持动态, 以生成大颗粒金刚石。 温度保持装置用于控制在反 应区域中保持动态的耐高温小颗粒种子处于适于金刚石生长的温度。
其中, 动态发生装置可以包括: 喷动床反应器、 流化床反应器、 移动床 反应器、 回转炉反应器、 气动发生装置、 震动装置或机械搬运装置。
当动态发生装置包括气动发生装置、 震动装置或机械搬运装置时, 该设 备还包括一反应器腔体, 且动态发生装置位于该反应器腔体内。 该气动发生 装置、 震动装置或机械搬运装置可以通过气动、 震动、 机械搬运、 倒置或抛 运的方式, 控制耐高温小颗粒种子动态通过反应区域或者控制耐高温小颗粒 种子在该反应区域中处于运动状态, 优选的, 还控制颗粒自身转动; 其中, 动态通过该反应区域的方式可以是自下而上或自上而下, 也可以是水平或以 任一定角度通过。
需要说明的是, 当动态发生装置包括: 喷动床反应器、 流化床反应器、 移动床反应器或回转炉反应器时, 动态发生装置本身就是一反应器, 提供了 金刚石生长反应所需的反应器腔体; 而当动态发生装置包括气动发生装置、 震动装置或机械搬运装置时, 动态发生装置仅仅是一传送或震动装置, 由此 需要一反应器腔体。
并且, 反应区域产生装置的设置包括以下情况之一: 使动态发生装置位 于反应区域内, 或者, 应区域形成于动态发生装置内。
反应区域产生装置可以包括以下任一装置或其任意组合: 用于将含碳气 体和辅助气体形成直流电弧的装置; 用于将含碳气体和辅助气体燃烧形成高 温火焰的装置; 用于将含碳气体和辅助气体通过热丝形成激活区域的装置; 用于将含碳气体和辅助气体通过微波激活形成微波等离子区域的装置; 用于 将含碳气体和辅助气体通过高频形成射频等离子激活区域的装置。
并且, 反应区域产生装置可以有一个或多个, 以形成一个或多个反应区 域, 多个反应区域可以是垂直或水平串联的。
进一步的, 该设备还可以包括: 气体混合装置和冷却收集装置。
气体混合装置与反应区域产生装置的气体入口连接, 用于将含碳气体和 辅助气体输送给反应区域产生装置。
冷却收集装置用于冷却和收集生成的大颗粒金刚石。
进一步的, 当适于生长金刚石的反应区域为微波等离子区域, 或者为射 频等离子激活区域时, 本实施例提供的设备还可以包括真空发生装置, 该真 空发生装置用于给反应区域提供真空环境。 金刚石在微波等离子区域或者射 频等离子激活区域中生长时需要一定的真空度, 由此需要真空发生装置来为 反应器腔体内提供一定的真空度。
使用本实施例提供的设备可以进行间歇式或连续化生产大颗粒金刚石; 当连续化生产大颗粒金刚石时, 该设备中可以还包括连续加料装置, 以在反 应器中不断的加入耐高温小颗粒种子, 并通过收集装置不断的从反应器中将 较大颗粒的金刚石分离出来, 以实现大规模连续化生产。
使用本实施例提供的设备生产大颗粒金刚石的方法, 参见本发明方法实 施例的描述, 在此不再赘述。
本发明实施例提供的设备, 可以控制耐高温小颗粒种子在适于金刚石 生长的温度下、 在适于金刚石生长的反应区域中保持动态, 使得耐高温 小颗粒种子的各表面不断生长出金刚石, 由此生成了大颗粒金刚石, 实 现了大规模、 低成本的生产大颗粒金刚石。 并且使用本实施例提供的设备来 生产大颗粒金刚石, 还具有方法实施例中所述的优点, 在此不再赘述。
下面再结合附图对本发明实施例进行进一步描述。
图 2为本发明生产大颗粒金刚石的流程实施例一的示意图, 该流程为多 区域生产大颗粒金刚石的示意图, 如图 2所示:
该生产大颗粒金刚石的设备包括多个等离子发生器 110、反应器腔体 130、 输送系统 140、 真空泵 160; 输送系统 140和等离子发生器 110喷射出的等离
子焰位于反应器腔体 130内部。 由多个等离子发生器 110分别喷射出多个等 离子焰激活区 120 (即相当于前述实施例中的反应区域) ; 由输送系统 140 可以使多个耐高温小颗粒种子形成循环的颗粒流 150; 真空泵 160为反应器 腔体 130内部提供需要的真空度。
含碳气体和氢气通入多个等离子发生器 110中, 然后由多个等离子发生 器 110喷射出多个等离子焰激活区 120; 真空泵 160为反应器腔体 130内部 提供适于金刚石生长的真空度;输送系统 140对耐高温小颗粒种子进行搬运, 使这些小颗粒种子循环通过多个等离子焰激活区 120, 小颗粒种子在通过等 离子焰激活区 120时, 不断反应吸收金刚石成份而逐渐生长成尺寸较大的金 刚石颗粒。
该实施例中使用多个等离子发生器, 使得小颗粒种子在一次循环中就可 通过多个等离子氛围, 提高了金刚石的生长速度。 当然本实施例并不限定等 离子发生器的个数, 可以为一个或多个。
图 3为本发明生产大颗粒金刚石的流程实施例二的示意图, 该流程中的 反应器为喷动床反应器, 如图 3所示:
该生产大颗粒金刚石的设备包括喷动床反应器 210、 等离子发生器 220。 其中喷动床反应器 210可以为前述各实施例中所说的一种动态发生装置。 等 离子发生器 220喷射出等离子焰 230 (即相当于前述实施例中的反应区域) 。 在电感耦合情况下, 本实施例中还可以包括 RF高频感应线圈 240。
放置于喷动床反应器 210中的金刚石颗粒 250 (本实施例中的耐高温小 颗粒种子为金刚石颗粒) , 由于等离子发生器 220形成的等离子焰 230的喷 动作用而上下翻腾, 金刚石颗粒 250不断的进出等离子焰 230 , 每当金刚石 颗粒 250进入等离子焰 230时, 即在金刚石表面沉积并不断长大, 最终生长 成尺寸较大的金刚石颗粒。
图 4为本发明生产大颗粒金刚石的流程实施例三的示意图, 该流程中的 反应器为迴转反应器, 如图 4所示:
该生产大颗粒金刚石的设备包括迴转反应器 310、 等离子发生器(图中 未示出) ; 其中迴转反应器 310可以为前述各实施例中所说的一种动态发生 装置, 迴转反应器 310包括: 反应器漏斗 320和抄板 350。 等离子发生器形 成位于迴转反应器 310腔体内的一垂直于纸面方向的等离子激活区域 330(即 相当于前述实施例中的反应区域) ; 必要时可加真空泵为反应器内提供一定 的真空度。
迴转反应器 310在外力作用下逆时针方向以恒定的较低转速自转, 放置 在迴转反应器 310中的金刚石颗粒 340在反应器腔体内壁设置的抄板 350搬 运下到达反应器漏斗 320的上方,然后在重力作用下掉入反应器漏斗 320中, 并通过等离子激活区域 330, 在通过等离子激活区域 330时发生反应吸收金 刚石成份而生长, 在经过等离子激活区域 330下落后, 又被抄板 350收集搬 运进入下一次循环, 如此反复循环进行可使较小的金刚石颗粒生长成尺寸较 大的金刚石颗粒。
图 5为本发明生产大颗粒金刚石的流程实施例四的示意图, 该流程中的 反应器为利用环状激活空间区域连续生长大颗粒金刚石的转动反应器, 如图 5所示:
该生产大颗粒金刚石的设备包括转动反应器 410, 在转动反应器 410中, 燃烧火焰形成一环状激活区域 420 (即相当于前述实施例中的反应区域) ; 转动反应器 41 0可以为前述各实施例中所说的一种动态发生装置, 该转动反 应器 410内设有金刚石颗粒流动控制设备 440, 通过该控制设备 440可以控 制金刚石颗粒能够在上下运动时正好通过环状激活区域 420。
转动反应器 410不断绕转动轴 450上下转动, 放置在控制设备 440中的 金刚石颗粒 430在重力作用下在控制设备 440内部两端来回运动并不断通过 环状激活区域 420 , 在通过环状激活区域 420时发生反应吸收金刚石成份而 逐渐生长成尺寸较大的金刚石颗粒。
图 6为本发明生产大颗粒金刚石的流程实施例五的示意图, 该流程中的
反应器为利用球状状激活空间区域连续生长大颗粒金刚石的转动反应器, 如 图 6所示, 该设备包括:
该生产大颗粒金刚石的设备包括转动反应器 510、 等离子发生器 (图中 未示出) 、 真空泵(图中未示出) 。 其中, 等离子发生器形成一球状等离子 激活区域 520, 该区域为一球状, 该区域内有适于金刚石生长需要的气体成 份和温度条件; 转动反应器 510可以为前述各实施例中所说的一种动态发生 装置, 该转动反应器 510内设有金刚石颗粒流动控制设备 540 , 通过该控制 设备 540可以控制金刚石颗粒能够在上下运动时正好通过球状的等离子激活 区域 520。
转动反应器 510不断绕转动轴 550上下转动, 放置在控制设备 540中的 金刚石颗粒 530在重力作用下在控制设备 540内部两端来回运动并不断通过 等离子激活区域 520, 在通过等离子激活区域 520时发生反应吸收金刚石成 份而逐渐生长成尺寸较大的金刚石颗粒。 实检例
采用直径 0. 5- 2隱的热解碳颗粒( 50克), 由乙炔与纯氧(比例为 1 : 1 , 流量为 6- 7s lpm ) 的燃烧焰在一直径为 40 匪的锥形石英管底部喷出形成喷 动床。 热解碳颗粒在该喷动床中上下循环; 石英管和外部未作保温处理, 红 外测温仪显示在稳态运行时,颗粒温度为 800 °C— 900 °C , 系统运行两小时后 , 改为 Ar冷却到室温, 发现总重量增加了 3. 78克。
图 7是现有的热解碳颗粒的 Raman位移谱线, 该图中对于未参加反应的 热解碳颗粒只有两个对应于石墨的宽峰。 图 8是本发明实施例生产的大颗粒 金刚石的 Raman位移谱线, 如图 8所示, 该图中除了具有上述石墨的 Raman 位移峰之外, 有较明显的金刚石信号, 证明有金刚石成份长在颗粒表面。 总 重量的增加, 表明了颗粒的粒径长大。
按照上述连续运行(连续向喷动床中加入碳颗粒) , 可以使上述过程持
续进行直至得到需要的粒径长大的金刚石颗粒。
其中, 可以将本实验例中的热解碳颗粒换为本发明中提供的其他任一耐 高温小颗粒种子, 按照同样方法操作, 也得到了粒径长大的金刚石颗粒; 也 可以将喷动床换成本发明中提供的任一动态发生装置, 将燃烧焰换成本发明 中提供的其他任一反应区域, 同样可以得到粒径长大的金刚石颗粒。
通过上述各流程实施例生产大颗粒金刚石, 具有本发明前述方法实施例 和设备实施例中所述的优点, 在此不再赘述。
最后应说明的是: 以上实施例仅用以说明本发明的技术方案, 而非对其 限制; 尽管参照前述实施例对本发明进行了详细的说明, 本领域的普通技术 人员应当理解: 其依然可以对前述各实施例所记载的技术方案进行修改, 或 者对其中部分技术特征进行等同替换; 而这些修改或者替换, 并不使相应技 术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims
1、 一种生产大颗粒金刚石的方法, 其特征在于, 包括以下步驟: 将含碳气体和辅助气体形成至少一个适于金刚石生长的反应区域; 在适于金刚石生长的温度下, 控制耐高温小颗粒种子在所述反应区域中 保持动态, 以生成大颗粒金刚石。
2、 根据权利要求 1所述的生产大颗粒金刚石的方法, 其特征在于, 釆用 以下方法控制所述耐高温小颗粒种子在所述反应区域中保持动态:
使用喷动床、 流化床、 移动床或回转炉, 控制所述耐高温小颗粒种子在 所述反应区域中保持动态; 或者
使用气动、 震动、 机械搬运、 倒置或抛运的方式, 控制所述耐高温小颗 粒种子在所述反应区域中保持动态。
3、 根据权利要求 1所述的生产大颗粒金刚石的方法, 其特征在于, 所述 控制耐高温小颗粒种子在所述反应区域中保持动态包括:
控制所述耐高温小颗粒种子在至少两个所述反应区域中保持动态; 或者 控制所述耐高温小颗粒种子动态的反复通过所述反应区域; 或者 控制所述耐高温小颗粒种子在所述反应区域内部保持动态; 或者 控制所述耐高温小颗粒种子在所述反应区域中自身转动。
4、 根据权利要求 3所述的生产大颗粒金刚石的方法, 其特征在于, 所述 控制所述耐高温小颗粒种子动态的反复通过所述反应区域包括:
控制所述耐高温小颗粒种子自上而下、 自下而上、 或以任一角度动态的 反复通过所述反应区域。
5、 根据权利要求 1所述的生产大颗粒金刚石的方法, 其特征在于, 釆用 以下方法控制所述耐高温小颗粒种子处于所述适于金刚石生长的温度:
通过直接和 /或间接冷却, 控制所述耐高温小颗粒种子处于所述适于金刚 石生长的温度。
6、 根据权利要求 1所述的生产大颗粒金刚石的方法, 其特征在于, 还包 括: 连续加入所述耐高温小颗粒种子, 并收集生成的所述大颗粒金刚石。
7、根据权利要求 1-6任一所述的生产大颗粒金刚石的方法,其特征在于, 所述适于金刚石生长的反应区域包括:
由所述含碳气体和辅助气体形成的直流电弧; 或者
由所述含碳气体和辅助气体燃烧形成的高温火焰; 或者
由所述含碳气体和辅助气体通过热丝形成的激活区域; 或者
由所述含碳气体和辅助气体通过微波激活形成的微波等离子区域; 或者 由所述含碳气体和辅助气体通过高频形成的射频等离子激活区域。
8、根据权利要求 1-6任一所述的生产大颗粒金刚石的方法,其特征在于, 所述含碳气体包括以下任一种或其组合: 甲烷、 乙炔、 乙醇气和含碳、 氢、 氧、 氮的气体;
辅助气体包括以下任一种或其组合: 氢气、 氧气和惰性气体。
9、根据权利要求 1-6任一所述的生产大颗粒金刚石的方法,其特征在于, 所述耐高温小颗粒种子包括以下任一种或其组合: 金刚石、 碳、 石墨、 硅、 陶瓷和耐高温金属 'J、颗粒。
10、 一种用于权利要求 1-9任一项所述生产大颗粒金刚石的方法的设备, 其特征在于, 包括:
至少一个反应区域产生装置, 用于将含碳气体和辅助气体形成适于金刚 石生长的反应区 i或;
动态发生装置, 用于控制耐高温小颗粒种子在所述反应区域产生装置形 成的所述反应区域中保持动态, 以生成大颗粒金刚石;
温度保持装置, 用于控制在所述反应区域中保持动态的所述耐高温小颗 粒种子处于所述适于金刚石生长的温度。
11、根据权利要求 10所述的设备,其特征在于,所述动态发生装置包括: 喷动床反应器、 流化床反应器、 移动床反应器或回转炉反应器, 或者气动发
生装置、 震动装置或机械搬运装置。
12、 根据权利要求 10或 11所述的设备, 其特征在于, 所述反应区域产 生装置的设置包括以下情况之一:
使所述动态发生装置位于所述反应区域内, 或者
使所述反应区域形成于所述动态发生装置内。
13、 根据权利要求 10或 11所述的设备, 其特征在于, 所述动态发生装 置为气动发生装置、 震动装置或机械搬运装置, 且所述设备还包括反应器腔 体, 所述动态发生装置位于所述反应器腔体内。
14、 根据权利要求 10所述的设备, 其特征在于, 所述反应区域产生装置 包括以下任一装置或其组合:
用于将含碳气体和辅助气体形成直流电弧的装置; 或者
用于将含碳气体和辅助气体燃烧形成高温火焰的装置; 或者
用于将含碳气体和辅助气体通过热丝形成激活区域的装置; 或者 用于将含碳气体和辅助气体通过微波激活形成微波等离子区域的装置; 或者
用于将含碳气体和辅助气体通过高频形成射频等离子激活区域的装置。
15、 根据权利要求 10所述的设备, 其特征在于, 还包括:
气体混合装置, 与所述反应区域产生装置的气体入口连接;
冷却收集装置, 用于冷却和收集生成的所述大颗粒金刚石。
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US13/265,496 US9067797B2 (en) | 2009-04-28 | 2010-04-27 | Methods and systems to produce large particle diamonds |
EP10769314.5A EP2431327A4 (en) | 2009-04-28 | 2010-04-27 | METHOD AND APPARATUS FOR MANUFACTURING DIAMOND IN THE FORM OF LARGE PARTICLES |
CN2010800045712A CN102272046A (zh) | 2009-04-28 | 2010-04-27 | 生产大颗粒金刚石的方法和设备 |
US14/718,883 US20150353363A1 (en) | 2009-04-28 | 2015-05-21 | Method and System to Produce Large Size Diamonds |
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US14/718,883 Continuation US20150353363A1 (en) | 2009-04-28 | 2015-05-21 | Method and System to Produce Large Size Diamonds |
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Cited By (3)
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EP2788534A4 (en) * | 2011-12-09 | 2015-07-15 | Baker Hughes Inc | METHOD FOR PRODUCING CARBON-CONTAINING PARTICLES AND ARTICLES THEREOF |
US9481073B2 (en) | 2011-09-16 | 2016-11-01 | Baker Hughes Incorporated | Methods of forming polycrystalline diamond with liquid hydrocarbons and hydrates thereof |
US9499883B2 (en) | 2010-04-14 | 2016-11-22 | Baker Hughes Incorporated | Methods of fabricating polycrystalline diamond, and cutting elements and earth-boring tools comprising polycrystalline diamond |
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JP6415133B2 (ja) * | 2014-06-25 | 2018-10-31 | 国立大学法人 大分大学 | 導電性ダイヤモンド電極の製造方法 |
CN110616459A (zh) * | 2019-10-31 | 2019-12-27 | 北京大学东莞光电研究院 | 一种大颗粒金刚石的制备装置及其制备方法 |
CN114653936B (zh) * | 2022-05-05 | 2023-03-10 | 中国科学院过程工程研究所 | 一种双层包覆的金刚石工具烧结方法 |
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US9499883B2 (en) | 2010-04-14 | 2016-11-22 | Baker Hughes Incorporated | Methods of fabricating polycrystalline diamond, and cutting elements and earth-boring tools comprising polycrystalline diamond |
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EP2431327A1 (en) | 2012-03-21 |
CN104760955B (zh) | 2017-03-08 |
US9067797B2 (en) | 2015-06-30 |
EP2431327A4 (en) | 2014-04-30 |
CN104760955A (zh) | 2015-07-08 |
CN102272046A (zh) | 2011-12-07 |
US20150353363A1 (en) | 2015-12-10 |
US20120195819A1 (en) | 2012-08-02 |
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