JPS58501430A - Production of carbide particles - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Production of carbide particles Technical field The present invention relates to the production of cemented carbide particles consisting essentially of carbon as a main component.

Background technology Various forms of carbon, including graphite, diamond and other hard carbon Many attempts were made to change the form until 1955, but none were properly put into practical use. Nothing was done. An appropriate diamond synthesis method consisting of 19551200° ~ At a temperature of 2400℃ and a pressure of 55,000 to 100,000 atmospheres or more transition metals (chromium, manganese, iron, cobalt, nickel, ruthenium, um, ) ξradium, osmium, iridium, platinum) or tantalum present Yoshi carbon changes into the form of diamond. Higher temperatures require higher pressure .

In addition to simpler carbon-to-diamond conversion methods, very complex methods have also been investigated.

Physical Review Letters Graphite When an ultra-high pressure explosive shock wave is applied to It has been shown that there is a possibility of obtaining mondo. In fact, carbon from the explosion shock wave The diamond was actually recovered.

Gases such as methane, ethane and pro-ξ decompose in contact with powdered diamond. Epitaxy methods that promote diamond growth have also been reported. But epi When performing the taxi method, the temperature near 1300° and the temperature between 10-3 and 10-4 atm. It turned out that a certain amount of pressure was required.

Conventional methods used to produce synthetic diamonds and other carbide carbon materials are at best impractical. It is clear that even when applied, it is cumbersome and expensive. Maintains temperature and pressure extremes This requires enormous amounts of energy and complicated equipment, which is why man-made diamonds There is no appeal for widespread commercialization of semiconductor manufacturing.

Disclosure of invention Manufacture cemented carbide particles while overcoming the drawbacks of conventional manufacturing methods This is one object of the present invention.

Manufacture cemented carbide particles without the need to use the extreme temperatures and pressures required by conventional techniques It is another object of the present invention to create a.

It is a further aspect of the invention to produce cemented carbide particles from graphite or anatomical carbon. This is another purpose.

The present invention is to produce cemented carbide particles using a carbon production reaction method driven by high thermodynamics. This is yet another purpose of Ming.

Metallic carbon such as aluminum carbide (14c’5) or beryllium carbide (Be2C) Cemented carbide particles are produced when the compound reacts with a halogen compound or a single halogen compound. It is a known fact that Substances that parasitically react with carbon or oxygen 2 and oxidizing power to reduce or eliminate the presence of reactants such as oxygenated adducts with attention is being paid. This reaction is highly exothermic at moderate temperatures and is extremely hard and active. However, there was a trend toward creating co-M-coupled lattice structures. This reaction takes place at a relatively low temperature ( The experiments were carried out at temperatures of several hundred degrees Celsius) and low pressure (several atmospheres or less). diamond graph The effective (natural) energy per Durham atom is more than 100 times the pyrite conversion energy. We have created a system that performs the reaction of the present invention in ghee and that does not have solvent power for carbon. It was also an object of the present invention to use Under proper conditions, they can be separated individually Metal carbides waiting for carbon atoms are extremely reactive. In the actual reaction that took place, the reaction The conversion energy is extremely effective, with 100% of the graphite-carbon conversion energy It is known that the energy per carbon atom is more than twice as high.

BEST MODE FOR CARRYING OUT THE INVENTION The aluminum carbide or beryllium carbide used in the present invention contains relatively few impurities, In particular, it must be carbon-free. The presence of free carbon in metal carbides If so, nucleation of gelaphite may occur and greatly inhibit the generation of cemented carbide particles. There is. Therefore, it is slightly larger than that indicated by the molecular formula Al4C3 or Be2C. aluminum or aluminum carbide with a stoichiometric ratio of aluminum to carbon A starting material of rhodium or rhodium carbide is chosen. In the practice of this invention, carbonization The physical form of the aluminum or beryllium carbide is not an absolutely critical condition. deer However, with the miniaturized particles in the range of 50 to 500 particles, various reactions can be carried out more quickly. arise.

This reaction takes place in a high temperature melting system. This melting system consists of two or more... It consists of a molten liquid of metal, which is the first metal in the periodic table. n, l [[Is it a family consisting of a family? ) rogane is selected from the group consisting of chlorine, bromine, iodine and fluorine. . Oxidizing anions such as sulfides, nitrides and carbides and hydroxides The presence of hydrogen-containing anions within the melt system should be avoided.

This melt system serves several valuable functions in the practice of this invention. First of all, this system is diamond mondo - at a temperature well below that at which graphite inversion occurs at a measurable rate. The reaction medium is fed at a temperature of 100°C. Next, we will consider this system as a heat sink (heat absorber). work. For example, lithium chloride (Li(J) and aluminum chloride (Al(J3) ) is fluid at temperatures as low as 150°C. ideally This melting system is aluminum halide (AIX5: X is c4Br or (represents chemical compound, and some F is also present), and alkali... logonide or consisting of a complex with one or more metal chlorides such as alkaline earth halides. can be done. T-4cl: AA’C13 weight molar ratio is greater than 1 When lithium chloride and aluminum chloride are used in combination in are Lj+, AlCl4- and CI! − is. When the ratio is high, LlCl or LlCl in the solid phase There is also a possibility that L15AIC16 exists. LiCl: II (J3 heavy 1 mo If the L ratio is less than 1:1, for example about 1:2, then the dominant melting element L 1+.

AIICIJ4- and Al12C:17-. 07 in whole or in part Alternatively, Br may be used. The amount that consists of either the initial or final melting system Fluorine, iodide or iodine exists in free form or aluminum-containing anionic form. Sometimes. Also, such a melt system can melt aluminum in the presence of oxygen or water. Al2O3 and hydroxide formed naturally on the surface of aluminum or aluminum carbide Shows high solvent properties and permeability to aluminum complexes. Al2O3 or The OH group film containing aluminum alloy atoms is extremely tough, and in carrying out the present invention, it is difficult to It becomes an obstacle. That is, the melting system that functions in the present invention consists of aluminum oxide, aluminum Solvent properties for aluminum-oxygen complexes and hydrogen-containing aluminum-oxygen complexes must have. This melting system also has the ability to wet the metal carbide surface. Must also not destroy halocarbon reactants or metal carbides Must have the ability. This system is also substantially anhydrous and substantially hydroxyl. It must not contain any radicals.

The invention can be practiced at pressures ranging from about 0.1 to 100 atmospheres. upper limit and If you can wait until the reaction reaches equilibrium, the diamond is stable. This reaction takes place at pressures as low as about 20,000 atmospheres, which is the form of carbon. It should occur. However, at pressures higher than 100 atmospheres, it takes Although it requires somewhat complicated equipment, there are few advantages for the reaction. Optimal temperature is melting may vary depending on the actual compound used to make the product and as the primary reactant. Dew. As a general rule, the temperature should be at least high enough to keep the molten system in the liquid phase. As such, a temperature of about 100-700°C is used to carry out the reaction.

Some specific examples of the present invention are shown below.

Example 1 In fact, allow sufficient time to ensure that all hydrogen and hydrogen chloride are evacuated from the system. A molten system is formed by preparing a solution of the rogen compound (heated mixture). let

In this example, 24.5ji of anhydrous Li07 was added to about 130-1 in a 500- Heated at 40°C for 2 days. Next, add about 67 liters of anhydrous AIIJ3 to an argon bran. Add this mixture under a blanket and raise the temperature to about 250°C. was stirred for 35 minutes. At this point, very slight I Hoe was observed.

After the molten system was formed, the metal carbide was added. In this example, A14052.99 is It was added and left for a while. Then add the reactant containing nitrogen in stages until an excess is reached. It can be added with. In this example, CCl41- each was applied at 10 minute intervals for a total of 10 m, followed by additional 2 additions every 10 minutes. OCj? 4 The temperature was kept at about 265° C. throughout the addition, after which the suspension was allowed to cool.

AA’4C5+ 3CO14→6C+4iC! 73 Formed by the reaction of the above formula The molten suspension was mixed into hydrogen chloride H (J10d) and water H2O200-. I washed it.

The suspension was boiled for 50 minutes. Instead, H2SO4 or 0H3So3H suspension in an aqueous solution of a non-oxidizing acid such as or an anhydrous system such as nitrobenzene. It could also be mixed in. The suspension was then filtered and the solid was dissolved in 1:10 H (Jlo Wash in Oml, then wash 3 times with 100% water, and then wash with Improv beer. It was completed with 2 washes with 40ml of alcohol and 4 washes with 25ml of acetone. . When the product was dried, cemented carbon particles were present.

Example 2 To the same melt system prepared in Example 1, in addition to Al4O3, approximately 22 more KBr was added. did. C! (Same as Example 1, using J4 as the dihalogen reactant) Added. The final cemented carbide product was washed and dried as in Example 1.

The melt system was the same as Example 1, but the reactants included Al4C3 and CBr4.

Specifically, after adding Al4C3 to the high temperature molten liquid, CBr41j1 is added. Then, 40.5 d of CCl was added every 5 minutes for a total of 10 m. This super The hard carbon product was washed as in Example 1.

Example 4 The melt system was prepared similarly to Example 1, with aluminum carbide Al4C as the first reactant. 3 was selected. CBr419 was added to the remaining reactant and 1.79 was added every 5 minutes. A total of 13.6 ta 02C16 were included. These carbide carbon particles were prepared as in Example 1. The sea urchin was washed and dried to yield the final product according to the following reaction.

2C2C16+Al4C3 → 4iC73+ 70 cases 5 A14052.59 and NaC11 as nucleating agent were added to the melt system prepared as in Example 1. Fee 2■ added to 8■ were added.

After mixing the latter additive in the melt system for about 10 minutes, CBr41j1 and C2C 1679 and the reaction mixture was refluxed at 240°C for about 65 minutes. (giggle) Add c2cit6 three times over the next 10 minutes, and then The suspension was refluxed for 20 minutes. Finally, C2CΔ63F was added for 20 minutes. and heated the suspension again for 30 minutes. Next, wash the carbide carbon particles in the same manner as in Example 1. and dry.

Example 6 A molten system was prepared as in Example 1 and added with A14C32,9 and Na as a nucleating agent. 209 containing 510% Fe in 0l was added. This reaction mixture was heated to approx. After stirring for 15 minutes at 240°C, add CBr42j' every 5 minutes for a total of 249 Added. Compound formula: %formula% The superhard carbon particles produced as the reaction progressed were filtered, washed, and dried in the same manner as in Example 1. .

Example 7 10 l of powdered KEr, 2 l of LlCl and about 67 g of AlC713. Upon mixing, a molten system was formed. This mixture was heated to about 240°C and under argon. The mixture was stirred for 1 hour. Adding HgCd22029 as a possible catalyst to this melt system , additional A14"32.92 was added. Leave for 5 minutes to add about 1- Added to hot melt. The solution was refluxed and after 10 minutes, 0Br41 was added. Ta. C2c141- were then added to the system at 10 minute intervals for a total of 94 doses. child The reactions were heated for 45 minutes, filtered, washed and dried as in Example 1. The reaction is The following formula: %formula% The process proceeded to produce cemented carbide particles.

Example 8 The melt system of Example 1 was prepared and added with A14032.9 and NaJ as a nucleating agent. and 20 μm of a mixture of 10% FeS were added. The second reactant Br28~ 0.4 m/each was added at 5 minute intervals. The reaction product was filtered and washed in the same manner as in Example 1. and when dried, the following formula %formula% produced a product.

Example 9 To the molten system prepared according to Example 1 was added 5 chloride. AA’4C for this! 3A1 403 at 250°C, and add this and 40.5d of CCl for a total of 2 times at 5 minute intervals. It was added to the system 0 times and reacted. The reaction produced carbide particles, which were then subjected to the procedure of Example 1. It was thoroughly filtered, washed and dried.

NaF 59 was added to the melt system prepared according to Example 1.

Approximately 2.889 pulverized Al4C3 is added to this melt system, and OCA'4 Each Id was added a total of 12 times at 10 minute intervals.

The reaction product was filtered, washed and dried according to Example 1 to obtain the cemented carbide material of the present invention. occured.

Example 11 A melt system consisting of L=c1429 and AlCl3134F was prepared as in Example 1. , to which A14032.769 of size 270 mesh was added. Approximately 236 A total of 23 Freon 11 (CC13F) 1- each at 5 minute intervals at a starting temperature of °C. Added twice. The reaction product was filtered, washed and dried as in Example 1 and A carbide carbon material was produced.

Example 12 The melt system of Example 1 was prepared and to which approximately 2.88 ji of 270 mesh of Al4C3 was added. Addition was made at 42°C. Next, chlorine gas is added to this high-temperature melting system at a rate of 0.05 ft5/hour ( 0,0014? Foaming is carried out at a rate of 1/2 hour (M5/hour). Then salt Raise the elementary gas to a rate of 0.1 ft'/hour (0,0028 m57 hours) and then apply the next 2N /2 hours, and the total amount of chlorine gas added was calculated as IQ and #. Similar to Example 1, this reaction The product was filtered, washed and dried to yield cemented carbon particles according to the present invention.

Example 13 Put Na0J 29.2F into a flask and heat under vacuum at 18CN for 2 hours. and left under full vacuum overnight. AlIC1 under argon blanket 3679 was added to complete the melt system. Add A14032.88F to this melt system. Then, as a second reactant, 41ffi/CCl was added at 10 minute intervals for a total of 13 times. Added. keeping the temperature above 300°C and filtering the reaction product according to Example 1; Washing and drying yielded the cemented carbide particles of the present invention.

Pour KCl37.3F into a flask and heat to 180℃ for 2 hours under complete vacuum. Ta. This Kcal was left under a complete vacuum overnight, and then the Al The melt was completed by adding Cl367'9. Next, add approximately 2.88 mm of Al4C3. CC/! was added 16 times in total at 10 minute intervals, 1 CC each! 4 and Made it react. As in Example 13, the reaction product produced by keeping the temperature higher than 600°C The material was filtered, washed and dried as in Example 1. This reaction is caused by the cemented carbide particles according to the present invention. gave birth to a child.

Example 15 IJ4C32,88j' was added to the melt system prepared according to Example 1, and CC4 2F2 was introduced at a rate of 0.1 ft'/hour (0,0028 m5/hour) and reacted. Ta. CCl2F2 was introduced into the system for 2 hours while maintaining the temperature between 260 and 245°C. and foamed. After these additions, the reaction product was filtered and washed according to Example 1. and dried to yield cemented carbide particles according to the invention.

Example 16 A melt system was prepared according to Example 1. At a temperature of about 247℃, A14C! 32.889 Add this to Q, i ft5/I temple (0,0028m34=) at 4 o'clock The mixture was reacted with CCl2F introduced into the high-temperature melting system. Keep the temperature at about 238℃ and filter Filtration, washing and drying yielded a reaction product with the properties of cemented carbon particles.

Example 17 A melt system according to Example 1 was prepared. Add to this about 2.92 Al4C3 and Na (10 % of FeS was added and heated for an additional 15 minutes. CHB A second reactant consisting of r3 was added in 0.5d increments at 5 minute intervals for a total of ZOd. this The reaction product is filtered, washed and dried, giving the following formula: % formula % produced cemented carbide particles.

Example 18 AA'4C! in the melt prepared according to Example 1! 5 t 59 and Na (mixed with J FeS20'mf was added. 0.5 d of the second reactant consisting of OH2 One addition was made at 5 minute intervals for a total of 54 additions under reflux. Then the product Wash and dry, then use the following formula: %formula% produced cemented carbide particles.

As can be seen from the above examples, from the group consisting of Al4C3 and Be2C selected metal carbide and canxAY(4-n)~A.

C! 2Hn’ XA’ Y (6-n”)-A’ + c2Hn’xA’y (4 - a product obtained by reacting n components selected from the group consisting of A' and X2; Thus, cemented carbide particles can be produced. However, X and Y are chlorine, bromine, iodine different halogens selected from the group consisting of elemental and fluorine, where A is an integer from 0 to 4 , A' is an integer of 0 to 6, and A' is an integer of 0 to 4, n is an integer of 0 to 4, n' is an integer from 0 to B; n' is an integer from 0 to 4; A, A', A', n, n' or n' are each selected arbitrary number of identical integers, and n+A=4 , n'+A'=6 and n'+A''-4.Actual reaction performed In this case, the reaction energy is extremely advantageous, and the graphite-carbon conversion energy is It was found that the size is more than 100 times that of a carbon atom.

Extremely high temperatures and pressures used to produce synthetic diamonds and other hard carbon particles Conditions such as force are completely unnecessary in the practice of the present invention.

If the metal is selected from the group consisting of metals of Groups 1, ■, and ■ of the periodic table, two or more compounds selected from the group consisting of chlorine, bromine, iodine and fluorine; This reaction is carried out in a high-temperature melting system consisting of a molten liquid of the metal halogenide above. Ta. The present invention also considers the use of a nucleating agent with a lattice constant close to that of diamond. . For example, using fine particles of FeS, cu or diamond itself. Can also be done. The present invention also contemplates the use of catalysts such as No. 2.

Each of the carbide carbon products produced by the cited examples above has a hardness and a corresponding abrasiveness. tested for. 1 is talcum, 7 is crystal, 9 is corundum, and 10 is die. The commonly used Moh scale from 1 to 10 (Moh65) Cale) is a grade based on pure hitting ability, and has no relative or quantitative meaning. stomach. Diamond is at least 100 times harder than corundum in abrasive tests. Show degree. Place a small amount of powdered abrasive on a glass plate, moisten the powder, and apply another Press it against a glass plate and rub it for a few seconds, wash the glass plate and then reflect the result. When viewed under a light microscope, significant qualitative and quantitative differences appear between the abrasives.

Fine-grained or powdered corantum or carborundum produces at most short grooves. Only.

These abrasive materials break down relatively quickly, and the glass plate quickly becomes frosted. It has the appearance of The fine diamond grains and carbon powder of the present invention behave completely differently. , giving rise to long, very characteristic meteor-like grooves. Hard carbon generation in the above cited example Testing each material at least shows a tendency to produce these characteristic meteor-like grooves. It was shown to the extent that

Claims (1)

[Claims] 1. Al4C3 and Be2C! A metal carbide selected from the group consisting of CHn XAY(4-n)-A+02Hn' XA' Y(6-n') A'+02 a component selected from the group consisting of 'n'XA'Y(4-nII)-A' and x2; Ultrahard particles consisting essentially of atomic iodine, including the products reacted with , X and Y are selected from the group consisting of chlorine, bromine, iodine, and fluorine. is an integer from 0 to 4, A' is an integer from 0 to B, and A' is 0. is an integer from 0 to 4, n is an integer from 0 to 4, n' is an integer from 0 to O, and gaba is an integer from 0 to 4. An integer of A, A', A'. n, n' or n' are each a selected specific number of the same integer, and n''A =4, n'+A'=6 and n'+A'-4. 2. The cemented carbide particles of claim 1, wherein the reaction is carried out in a high temperature molten system. . 3. The high-temperature melting system consists of a melt of two or more metal rogens, and the metal is the first in the periodic table. n, selected from the group consisting of Group III metals; 17. Claim 2, wherein the substance is selected from the group consisting of chlorine, bromine, iodine and fluorine. of carbide particles. 4. The high-temperature melting system substantially contains oxidizing anions and hydrogen-containing anions. Cemented carbide particles according to claim 1.2 dimension or claim 3. 5. The cemented carbide particles according to claim 1, wherein the metal carbide is Al4C3. 6. Claim No. 6, wherein said melt system exhibits significant solvent capacity for Al2O3. 2. Carbide particles. Z: the high-temperature melting system is substantially anhydrous and substantially free of hydroxyl groups; The cemented carbide particles according to claim 2. 8. The cemented carbide particles according to claim 1, wherein the reactant contains a crystal nucleating material. . 9. The crystalline nucleating material is a member of the group consisting of Fee, Cu, and diamond. The cemented carbide particles according to claim 8. 10, one of the metal halides contains iX3, and X is C1°Br, The cemented carbide particles of claim 3 selected from the group consisting of: 11. The metal halide is an alkali halogen compound and an alkaline earth halo 11. The cemented carbide particles of claim 10, which are selected from the group consisting of gen compounds. 12. The high temperature melting material is AlCl3 and LiCA! containing the molten liquid of Carbide particles in the desired range item 11.