A process for the synthesis of granular diamond

Abstract: Granular diamond suitable for use as an abrasive grain for polishing is synthesized from gaseous phase by a process for the synthesis of granular diamond, comprising subjecting a mixed gas containing an organic compound and hydrogen to a treatment to form plasma and depositing diamond on substrate grains dispersed and fluidized in the resulting plasma space, characterized in that the substrate grains are dispersed and fluidized by the mixed gas fed at a flow rate of at least the terminal velocity of the grains and an AC or DC electric field is applied to a zone whose grain concentration in the space is in the range of 1 to 20% by volume.

Description: This invention relates to a vapour phase method for the synthesis of diamond utilizing plasma and more particularly, it is concerned with a vapour phase method for the synthesis of granular diamond suitable for use as an abrasive or as grinding grains. A vapour phase synthesis method of the prior art using plasma will now be illustrated with reference to Fig. 2 of the accompanying drawings. Referring to Fig. 2, a quartz tube 1 is arranged in microwave producing apparatus 5 and in this quartz tube 1 is arranged a support base 8 on which a plate-shaped substrate 7 is placed. As indicated by the arrows, a mixed gas (raw material gas) of a volatile organic compound and hydrogen is subjected to microwave irradiation to form plasma and diamond is deposited on the above-described plate-shaped substrate 7 arranged in the plasma space. However, the diamond synthesized in this way is film-shaped and can not readily be applied to articles needing granular shapes, for example, grinding grains. As is well known in the art, the vapour growth of granular diamond is carried out by a method comprising dispersing and arranging substrate grains of diamond or silicon, instead of the plate-shaped substrate 7, on the support base 8 in Fig. 2 and growing granular diamond from the substrate grains. However, in this method, the number of substrate grains dispersed and arranged is very small and hence the number of granular diamond shapes obtained from one batch is so small that the production cost is increased and mass-production is hard. The reason why the number of the substrate grains to be arranged is small is that the only arrangement thereof is in two dimensions, that is, on only a certain plane. If the substrate grains could be arranged in three dimensions, that is, could be filled into a vessel, the number of substrate grains is markedly increased. When the substrate grains are merely filled therein, however, there are small voids among the substrate grains, so that a raw material gas does not form plasma even if irradiated by microwave. In order to render the raw material gas plasma-conditioned and thus to deposit diamond on the substrate grains, it is necessary to provide voids at least in a certain proportion amongst the substrate grains. Furthermore, it is apparent that even if plasma is formed, the thus formed diamond is not in granular form. The introduction of spaces or voids among the substrate grains has, for example, been carried out by a method comprising arranging a vibration plate at the lower end of a packed layer of substrate grains and vibrating the vibration plate to disperse and float the substrate grains, as disclosed in Japanese Patent Publication No. 57568/1987. According to this method, however, zones are formed where the grains exist in high concentration and where no grains exist and it is difficult to maintain a large amount of the grains well dispersed. As another method for the introduction of spaces or voids among the substrate grains, utilization of a gas-fluidized bed has been known as disclosed in EP-A-0286310, in which a mixed gas of hydrogen and a carbon-containing gas is exposed to a plasma generated by a high temperature and, for example, microwave energy and diamond is deposited on fluidised substrate grains formed of, for example, diamond, Si, SIC, or AlN. In addition, a process has been proposed for producing composite powdered grains, comprising feeding a mixed gas of CH₄ and H₂ under an excited state by a physical or chemical method and bringing it into contact with a powdered substrate in a CVD reaction apparatus. According to this process, however, it is also difficult to obtain a large amount of good quality composite powdered grains. We have now developed a gaseous phase method for the synthesis of diamond using plasma in which granular diamond suitable for use as an an abrasive grain for polishing is produced. Accordingly, the present invention provides a process for the synthesis of granular diamond, comprising subjecting a mixed gas containing an organic compound and hydrogen to a treatment to form plasma and depositing diamond on substrate grains dispersed and fluidized by the mixed gas in the resulting plasma space, characterized in that the mixed gas is fed at a flow rate of at least the terminal velocity of the grains and an electric field is applied to a zone whose grain concentration in the space is in the range of 1 to 20% by volume. The accompanying drawings are to illustrate in detail the principle and merits of the present invention. Fig. 1 is a schematic view of an apparatus for the practice of the process according to the present invention and Fig. 2 is a schematic view of an apparatus of the prior art. The method for effectively and simply introducing voids or spaces required for forming plasma among substrate grains filled in three dimensions, even in the case of relatively large grains, adopted in the present invention is the fluidized bed technique widely employed in the chemical industry. The fluidized bed technique generally means a method wherein a reaction between a gas and the grains is carried out by feeding the gas at a high flow rate from the bottom of a tube filled with the grains and thus dispersing and fluidized the grains to bring them into close contact with each other. One preferred embodiment of the present invention is illustrated in Fig. 1 in which the process for the synthesis of granular diamond is carried out using a system comprising a quartz tube 1 for fluidizing and subjecting to plasma formation a raw material gas G and substrate grains 6, provided with a dispersing plate 2 at the bottom thereof, a microwave generating means 5 for forming plasma P, a pipe for feeding the raw material gas G, a pipe for discharging a dispersion D, a cyclone 3 for separating the substrate grains 6 from the dispersion and a pipe for recycling the substrate grains 6. Referring to Fig 1, a raw material gas G is fed in the direction shown by arrows to a quartz tube 1 packed with substrate grains 6 from the bottom thereof and brought into contact with substrate grain 6 through a dispersing plate 2. When the flow rate of the raw material gas is higher than a certain value called "minimum fluidization velocity", the weight of the grain and the drag of the gas acting on the grain are balanced and the grains are maintained by the gas to expand the grain layer. That is, the void ratio or porosity is increased. This expanded zone is shown by A in Fig. 1 and the zone A is generally called "fluidized bed". Firstly, when microwave was applied to the zone A, there was no occurrence of plasma. This is due to that the void ratio of the zone A is only increased by 20 to 30% as compared with the packed layer and the grain concentration is still higher. On the other hand, in the tube 1, there is a grain-diluted or smoke-like zone above the zone A, as shown by B. When microwave was applied to the zone B, there occurred a plasma sufficient to grow diamond. However, the grain concentration in the zone B is too dilute to maintain high the growth efficiency even if diamond can be grown, and it is thus not considered that synthesis of diamond is carried out with an economical cost on commercial base. In order to raise this growth efficiency, it is necessary to increase the grain concentration in the zone B as far as possible within such a range as capable of generating plasma. In the general fluidized bed, however, control of the grain concentration in the zone B is difficult. According to the present invention, the above described problem is solved by feeding a gas at a sufficient flow rate to carry away the grains out of the tube, i.e., to give at least the terminal velocity thereto, thereby carrying away a part of the grains out of the tube, separating the thus entrained grains from the gas by means of a cyclone 3 and then recycling again the grains to the quartz tube 1. The terminal velocity is a constant value that the settling speed of a grain reaches finally when the single grain is added to a stationary fluid. Thus, when a fluid is flowed upward at a flow rate of more than the terminal velocity, the grain is entrained with the fluid and carried away from the system. This terminal velocity depends on the size, shape and density of a grain and the density and viscosity of a fluid, i.e., gas in this case. The terminal velocity used in the present specification is defined by the following relationship: wherein v t = terminal velocity, g = gravitational acceleration, ρ p = density of grain, ρ f = density of gas, d p = grain diameter, µ = gaseous viscosity. Since the general fluidized bed is operated in such a manner that grains are not carried away from a tube, control of the density of the zone B is impossible. On the other hand, the present invention is characterized by carrying out positively the carrying-away of the grains to control the concentration thereof, i.e. void ratio. The concentration of the zone B, depending upon the variety of a raw material gas and the pressure in the system, should be at most 20% by volume, preferably 5 to 15% by volume. The present invention should be carried out with caring about withdrawal of the grains in the tube and control of the flow rate of a raw material gas. That is, the grains gradually grow, the size of the every grain, one by one, and the bulk of all the grains naturally being increased, so it is required to withdraw the grains and control the gas flow rate correspondingly to the growth of the grains in order to maintain the grain concentration in the zone B under optimum state. As a means for generating plasma, an AC or DC electric field can be used, but it is preferred to use microwaves or high frequency of 30 kHz to 50 GHz capable of generating plasma without inserting an electrode in a reactor, for example, quartz tube. Preferably, microwaves of at least 300 MHz can be used and more preferably, a microwave of 2.45 GHz is used in view of industrial regulation. As a raw material gas, any of gaseous materials generally used for the vapor growth of diamond can be used independently of the variety and composition, but for the purpose of rapid growth of diamond, it is preferable to use mixed gases of hydrogen gas, inert gases and gaseous organic compounds, as described in Japanese Patent Laid-Open Publication No. 22640/1988, for example, a mixed gas of H₂, Ar and CH₄ in a proportion by volume of 50;25:1, since these gases are expensive and in the present invention, large amounts of the gases are used, it is preferred to provide the system of the present invention with a circulation installation for using again the gas discharged from the cyclone as a part of the raw material gas. As a substrate grain, there can be used any of materials which can be coated with diamond. When using diamond as the substrate grain, it is natural to obtain a crystal with most excellent crystalline property and highest strength, but depending on the purpose of use, SiC, AlN, Si, etc. can be used. As illustrated above, according to the present invention, a larger amount of granular diamond can be obtained by one batch as compared with the prior art, thus resulting in marked reduction of the production cost. Furthermore, a continuous operation without stopping the installation can be rendered possible by providing additional apparatus for supplementing and discharging the grains in suitable manner. Therefore, synthesis of diamond abrasive grains from gaseous phase can be carried out on a commercial scale. The following examples are given in order to illustrate the present invention in greater detail without limiting the same. Example 1 An apparatus as shown in Fig. 1 was used in which a quartz tube 1 having an inner diameter of 40 mm was packed with diamond powder having a mean grain diameter of 50 µm in a height of 40 mm. A mixed gas of H₂, Ar and CH₄ in a proportion by volume of 50:25:1 was fed to the lower part of the diamond packed layer at a flow rate of 4 SLM (standard liter per minute) at the initial period, the flow rate being increased with the growth of the grains, during which the pressure in the system was maintained at 6666 Pa (50 Torr) by a vacuum pump 4 connected with a cyclone 3, and the grains up to a height of 100 mm from a dispersing plate 2 were in a considerably thickened state with a grain concentration of 35% by volume, above which the upper grains were smoke-like and led to the cyclone 3. Under this state, a microwave of a frequency of 2.45 GHz was applied to a zone with a height of 150 to 200 mm from the dispersing plate 2 and with an average grain concentration of 10% by volume at an output of 800 W for 50 hours, thus recovering all the diamond grains grown to a mean grain diameter of 75 µm. With the progress of the reaction, the grain diameter was gradually increased to gradually lower the grain concentration in space, as apparent from the foregoing formula (1), so the grain concentration in space in the range of a height between 150 mm and 200 mm was controlled to 10% by volume by gradually increasing the flow rate. Example 2 An apparatus as shown in Fig. 1 was used in which a quartz tube having the diameter as that of Example 1 was packed with SiC grains having a mean grain diameter of 100 µm in a height of 60 mm. A mixed gas of H₂, Ar and C₂H₅OH in a proportion by volume of 50:25:2 was fed to the quartz tube from the bottom thereof at a flow rate of 8 SLM, during which the pressure in the system was maintained at 5333 Pa (40 Torr). A microwave of 1 kW and 2.45 GHz was applied in an analogous manner to Example 1 to a zone with a height of 200 to 250 mm from the dispersing plate 2 and having a grain concentration of 5% by volume, which was continued for 100 hours while withdrawing the grains in the system every 10 hours so that the total weight of the grains in the system be not so changed. Consequently, all the SiC grains were fully coated with diamond to give a grain diameter of about 200 µm.

Claims: A process for the synthesis of granular diamond, comprising subjecting a mixed gas containing an organic compound and hydrogen to a treatment to form plasma and depositing diamond on substrate grains dispersed and fluidized by the mixed gas in the resulting plasma space, characterized in that the mixed gas is fed at a flow rate of at least the terminal velocity of the grains and an electric field is applied to a zone whose grain concentration in the space is in the range of 1 to 20% by volume. A process as claimed in claim 1, wherein the electric field is an AC or DC electric field. A process as claimed in claim 1 or claim 2, wherein the mixed gas contains hydrogen gas, an inert gas and an organic compound. A process as claimed in claim 3, wherein the mixed gas contains H₂, Ar and CH₄. A process as claimed in any one of the preceding claims wherein the substrate grains are selected from the group consisting of diamond, SiC, AlN and Si powders. A process as claimed in any one of the preceding claims wherein the deposition of diamond is carried out in an apparatus comprising a quartz tube provided with a dispersing plate at the bottom thereof, a microwave generating means, a pipe for feeding a raw material gas, a pipe for discharging a dispersion, a cyclone for separating substrate grains from the dispersion and a pipe for recycling the substrate grain.

Inventors: AJIRI YOSHIFUMI, DEGAWA JUNJI C O ITAMI WORKS O, FUJIMORI NAOJI C O ITAMI WORKS, FURUSAWA TAKEHIKO, IMAI TAKAHIRO C O ITAMI WORKS, AJIRI, YOSHIFUMI, DEGAWA, JUNJI C/O ITAMI WORKS OF, FUJIMORI, NAOJI C/O ITAMI WORKS OF SUMITOMO, FURUSAWA, TAKEHIKO, IMAI, TAKAHIRO C/O ITAMI WORKS OF SUMITOMO
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO ELECTRIC INDUSTRIES, LTD.
Application year: 1989
Main classification: C23C16
IPC codes: C23C16, C30B29, B01J8, C30B25, C01B31