EA006011B1 - Process for synthesis of superhard materials - Google Patents

Abstract

The present invention relates generally to methods for the synthesis of superhard materials (SHM) including to diamond synthesis, cubic boron nitride, polycrystalline and composite materials based thereon, making powders and tools comprising such materials and usable, in particular, for making abrasive and cutting tools. The task of the present invention is to work out such a method of making superhard materials which can provide high output SHM at lowered temperatures and comparatively low pressure without using any catalysts. The method is characterized in that superdispersed powder of cubic structure material is used as crystalline-forming additions. Superdispersed diamond powder is used as a superdispersed powder of cubic structure material in one of alternatives. According to the invention SHM (diamond and/or BN) synthesis is carried out at extremely low temperatures (by 800-1000 degree C lower than at catalytic synthesis) and relatively low pressure. Yet the SHM output is increased to 96-100%with no foreign admixtures which permits to make tools of the required structure and features. High-cost materials and power are saved considerably.

Description

The invention relates to a technique for producing superhard materials (STM), namely, the synthesis of diamonds, cubic boron nitride, polycrystalline and composite materials based on them, the production of powders and tools containing such materials, and are used, in particular, for the manufacture of abrasive and cutting tool.

Prior art

Currently, superhard materials include diamond, cubic boron nitride, fullerenes, as well as their powders, polycrystalline and composite materials based on them.

In industry, various methods are used to produce artificial diamonds from graphite under conditions of high pressures and temperatures. Similar methods are also known to obtain cubic boron nitride from hexagonal boron nitride.

Known methods for producing artificial diamonds by exposure to high pressure and temperature on the mixture containing graphite, as the main component, in a mixture with a catalyst, for a specified time (see Vereshchagin LF- Selected works. Synthetic diamonds and hydroextrusion. M .: Science. 1982. - S. 43-47, 78-86). To increase the degree of conversion of graphite into diamond, doping additives are introduced into the catalyst, increasing the pressure and synthesis time. However, the introduction of alloying additives complicates the process, therefore, as a rule, one type of catalyst is used to create cost-effective processes. The change of synthesis time in a wide range is limited by the heat resistance of the material of the heat-insulating container and the durability of high-pressure apparatus made of hard alloy. A long synthesis time also increases energy consumption and, accordingly, the cost of STM. Increasing the pressure in order to increase the degree of transition of graphite to diamond for a chamber of one volume leads to a decrease in the number of its working cycles, which is not economically profitable. The use of high-pressure chambers of 7-10 GPa of a different design with the same pressing equipment is associated with a decrease in chamber volume, which leads to an increased consumption of cemented carbide used to manufacture high-pressure chambers.

Similar problems arise in the synthesis of other superhard materials, for example, cubic boron nitride, which in many cases is of greater interest because of its greater heat resistance than diamond with near-diamond hardness and technological compatibility with iron and its alloys.

A method of obtaining artificial diamonds, including pulsed impact on a sample of graphite and metal by pressure and heating by passing a pulse of electric current on a sample containing a metal from the group: copper, aluminum, nickel, iron with the inclusion of fine particles of graphite, the average size of which is 5-150 microns , in the following ratio of components, vol.%: graphite - 5-55, the metal of the specified group - 45-95 (see RF Patent No. 1820890, IPC C 01 B 31/06. published on 07.06.93).

The known method allows to simplify the technology of obtaining diamonds, however, for a known method is characterized by a low yield of diamonds, the need to use catalysts and, therefore, additional technological processes of their manufacture and chemical removal after synthesis. The synthesized particles have a wide variation in size. In addition, this method also remains extremely energy-intensive.

A method of producing diamonds is known, which includes exposing the carbon-containing material to high pressure when heated in the region of diamond stability. Alpha-carbin in amorphous form is used as a carbon-containing material. Alpha-carbin may contain carbon in the amount of 99.0-99.9 wt.%, And heating is carried out to a temperature of 1400-1700 ° C (see auth. St. USSR No. 1533221, IPC C 01B 31/06, published 23.02 .93).

The known method allows you to speed up the process and slightly increase the yield of diamonds, but the percentage of output is still not high enough. This method also remains energy-intensive.

A method of obtaining polycrystalline diamond, comprising heating the carbon-containing material, separated from the catalyst by a separating layer, under pressure, followed by exposure to the temperature and pressure of synthesis. The material is heated with a speed of 1500-2000 degrees / s with a change in pressure with a speed of 3-4 GPa. The shutter speed is carried out for 0.5-5.0 s, while the material with a hardness of 0.45-5.0 GN / m and a dispersion of 1-10 microns is used as a separating layer. Exposure in the synthesis is carried out at 1800-2100 K and a pressure of 7-8 GPa (see av. St. USSR № 1340030. IPC C 01B 31/06, published. 06/15/96).

The known method requires the use of quite high temperatures and pressures and does not provide for the production of large-sized diamonds. This method also uses synthesis catalysts and the sizes of the synthesized particles have a wide range of values.

A method of obtaining diamond, including the compression of carbon-containing material to a sufficient size and its heating, followed by exposure at a temperature and pressure of synthesis. Fullerene of various molecular weights (from C ₃₇ to C ₈₄ ) is used as a carbon-containing material. A pressure gradient above 1 GPa / mm can be created deep in the sample. The value of the main pressure

- 1 006011 leeni reaches 15-25 GPA. The pressure can be reduced by heating to a temperature below 1000 ° C (see international application \ ¥ O No. 93/02012, IPC C 01 B 31/00, published on 04.02.93).

The known method allows to obtain high quality diamonds, in particular polycrystalline, but its implementation requires the use of excessively high pressures and / or the creation of a pressure gradient, which significantly complicates the equipment used.

A method for producing diamonds from a starting powder material containing carbon as a main component is known, and includes exposing the material to a pressure of 250 GPa when applying a pressure gradient to the material and simultaneously heating the part of the material to which the maximum pressure is applied is irradiated by laser radiation. Fullerene C ₆₀ or carbon microtubes were taken as the main component of the powdered material (US Patent No. 5,360,477. IPC C 30B 29/00, published November 11, 1994).

The known method allows you to maintain a constant sample temperature for a long time, however, this greatly complicates the equipment used. Laser heating also requires significant energy consumption.

Another well-known method, quite close to the one proposed by essential features, includes the impact on fullerene powder placed between two layers of graphite with a total mass of about 10% by weight of fullerene, pressure of 6.7 GPa and heating to a temperature of 1200-1850 ° С with catalysts : nickel, cobalt and cobalt alloy (Voes. | w11n S. C. Voalseule S., Ebege S., Ba55a1A.– C ₆₀ EuPegeie a§ Saguio 8oigse £ og P1asooib 8uyel515, - 1оиги.Рюу5Сйеш, - 1993. .9.96. pp. 12924-12927).

The known method allows you to raise the output of diamonds to a value of the order of 90%, however, this has to be affected by a sufficiently high pressure (6.7 GPa), which leads to complication of the equipment used. In addition, the attached temperatures are quite high and cause large energy consumption and the high cost of the diamonds produced.

The closest known method for the synthesis of diamonds is known, in which fullerene powder distributed in graphite is used as a crystal-forming or catalytic additive. In this method, the synthesis occurs at relatively low pressures (4.5-5.5 GPa). The method is also characterized by a relatively high yield of diamond.

There is a method of sintering cubic boron nitride from the charge on the author ed.St. USSR № 4460599 S. Nuzhdina and others. According to this method, the mixture for the manufacture of a superhard composite material contains a mixture of ultrafine boron nitride powder, cubic boron nitride powder with a grain size of 3-100 μm and wurzite-like boron nitride at the following ratio, wt.%: Ultradispersive boron nitride powder 10-20, wurtzite-like nitride boron 3-4, cubic boron nitride with a grain size of 3-100 microns the rest. This mixture with catalytic additives and a binder is sintered at high temperature and pressure.

This method actually provides only sintering of particles using a binder, and not the synthesis of superhard material. In addition, the sintering temperature also remains high.

For the manufacture of high-quality carbide tools, various methods of sintering STM powders with grains of various sizes and cementing and plasticizing additives as a binder are commonly used. Materials for carbide tools get a three-dimensional combination of components, one of which is plastic (binder), and the other has high strength, hardness, resistance to abrasive wear and rigidity (filler). The required instrumental properties are provided by the highly dispersed structure of the ligament. There is a fundamental need to preserve the ultrathin structure in the synthesized material either in its entire mass or in the intergranular region, which serves as a cementing and plasticizing ligament.

A known method of manufacturing a diamond tool by sintering micron-sized diamond powders with ultrafine diamond powder. This forms a high-quality tool with a density of up to 85% of the density of the diamond. This method does not use graphite, and sintering of powders occurs at the grain boundaries. See Japanese Patent Application 1P 2030667, for authors ΚΟΝΏΟ KEMS1P et al., For the name 1 O1b & EAT8 SO,, published. 1990-02-01.

This method requires a large amount of the original diamond powder, and is also carried out at sufficiently high temperatures.

To obtain powders of superhard materials obtained as a result of thermobaric treatment, bake, crush, pickle to remove residual catalyst and other components. Then the powders are separated in size and shape. All these operations increase the cost of STM powders:

1. N.V. Novikov, D.V. Fedoseev, A.A. Shulzhenko, G.P. Bogatyreva Synthesis of Diamonds - Kiev, Naukova Dumka, 1987, pp. 37, 42-46, 133-144.

2. Superhard materials - Under the general editorship of the Academician of the Ukrainian Academy of Sciences I.N. Frantsevich, Kiev Naukova Dumka, 1980, pp. 195-210.

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DISCLOSURE OF INVENTION

The present invention was to develop such a method of producing superhard materials, which would provide a high yield of STM at low temperatures and relatively low pressure without the use of catalysts.

The problem is solved by the fact that in the method of producing STM, including artificial diamonds, including the effect of pressure and heating on the mixture with graphite or / and hexagonal boron nitride, a crystal-forming additive is introduced, followed by exposure at a temperature sufficient for synthesis.

It was unexpectedly discovered that if ultrafine particles of a material of cubic structure are introduced into a mixture containing graphite or another non-solid crystalline phase of a two-phase material, the synthesis temperature can be significantly reduced, and the STM yield will be significantly increased.

Experiments have shown that the introduction of ultrafine particles is a necessary condition for increasing the yield of STM.

The observed effect appears to be due to the fact that nanometer particles behave as a catalyst during the formation of STM, possibly acting as centers of crystallization of STM particles at low temperatures.

The method of synthesis of superhard materials, according to the claimed invention includes the preparation of the mixture, including materials of non-solid crystalline phase, the introduction of crystal-forming additives, the implementation of thermobaric treatment of the mixture at a pressure and temperature higher than certain values during a certain time interval.

The method is characterized by the fact that ultrafine powder of a material of cubic structure is used as crystal-forming additives.

In one embodiment, ultrafine diamond powder is used as the ultrafine powder of the material of the cubic structure.

In another embodiment, ultrafine boron nitride powder is used as an ultrafine powder of superhard material of a cubic structure.

Another embodiment of the method is characterized by the fact that ultrafine powder of the material of the fourth group is used as an ultrafine powder of superhard material of cubic structure.

The method can also be characterized by the fact that ultrafine powder of compounds А ³ В ^{5 is} used as an ultrafine powder of superhard material of cubic structure.

The method is also characterized by the fact that the particle size of the ultrafine additive is 2100 nm.

Most preferably, the dispersion of the additive is 4-40 nm.

According to the invention, the method is also characterized in that thermobaric treatment is carried out at temperatures above 300 ° C, but below the temperature of the reverse transition to the non-solid crystalline phase.

If hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with the ratio of the components of hexagonal boron nitride and ultrafine additive from 0.99-99.00 to 99.00-0.99 wt.%, The thermobaric treatment is preferably carried out at a temperature higher than at 500 ° C.

In another embodiment, as the starting component of the non-solid crystalline phase, graphite is used with a ratio of components of graphite and ultrafine additive from 0.99-99.00 to 99.00-0.99 wt.%, And thermobaric treatment is preferably carried out at a temperature above 700 ° WITH.

Further, a mixture of graphite and hexagonal boron nitride can be used as the initial component of the non-solid crystalline phase with a ratio of components from 0.99-99: 99-0.99 wt.%, In this case, the thermo-pressure treatment is preferably carried out at a temperature above 750 ° C.

The duration of thermobaric treatment according to the invention is 20-300 s.

Preferably thermobaric treatment is carried out for 40-80 s.

A method of manufacturing superhard instruments according to the invention includes the preparation of a batch comprising materials of non-solid and / or superhard crystalline phases, the introduction of crystal-forming additives, preliminary molding of the tool, the implementation of thermo-pressure treatment of the mixture at pressure and temperature above critical values during a certain time interval.

This method is characterized by the fact that ultrafine powder is used as crystal-forming additives.

The size of the particles of ultrafine additives are 2-100 nm.

Preferably the dispersion of the additive is 4-40 nm.

Further, the method is characterized by the fact that as an ultrafine powder using ultrafine powder material of a cubic structure.

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In one embodiment, ultrafine diamond powder is used as an ultrafine powder of a material of a cubic structure.

In another embodiment, ultrafine boron nitride powder is used as an ultrafine powder of superhard material of a cubic structure.

In another embodiment, as the ultrafine powder of superhard material of a cubic structure using ultrafine powder of the material of the fourth group.

Also, as an ultrafine powder of superhard material of a cubic structure, an ultrafine powder of compounds А ³ В ⁵ can be used.

A method of manufacturing tools is characterized by the fact that thermobaric treatment is carried out at a temperature above 300 ° C, but below the temperature of the reverse transition to the non-solid crystalline phase.

If hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with the ratio of the components of hexagonal boron nitride and ultrafine additive from 0.99-99.00 to 99.00-0.99 wt.%, The thermobaric treatment is preferably carried out at a temperature higher than at 500 ° C.

If graphite is used as the initial component of the non-solid crystalline phase with the ratio of the components of graphite and ultrafine additive from 0.99-99.00 to 99.00-0.99% by weight, the thermobaric treatment is preferably carried out at a temperature above 700 ° C.

In addition, a mixture of graphite and hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with a ratio of components from 0.99-99: 99-0.99 wt.%, And the thermobaric treatment is preferably carried out at a temperature above 700 ° C.

Further methods for the manufacture of tools are characterized by the fact that thermobaric treatment is carried out for 20-300 s.

Preferably thermobaric treatment is carried out for 40-80 s.

Another object of the invention is a method of manufacturing superhard powders of a given size, includes the preparation of a mixture including materials of a non-solid crystalline phase, the introduction of crystal-forming additives, pre-molding of a compact, the implementation of thermo-pressure treatment of the mixture at pressure and temperature, above critical values for a certain time interval and subsequent processing compact for the selection of powder required dispersion. This method is characterized by the fact that ultrafine powder is used as crystal-forming additives, and the treatment of the compact after thermobaric treatment is carried out by etching with alkali for materials containing boron nitride and / or by annealing in an oxygen environment for materials containing graphite.

The size of the particles of ultrafine additives are 2-100 nm.

Preferably the dispersion of the additive is 4-40 nm.

Further, the method is characterized by the fact that as an ultrafine powder using ultrafine powder material of a cubic structure.

In one embodiment, ultrafine diamond powder is used as an ultrafine powder of a material of a cubic structure.

In another embodiment, ultrafine boron nitride powder is used as an ultrafine powder of superhard material of a cubic structure.

In another embodiment, as the ultrafine powder of superhard material of a cubic structure using ultrafine powder of the material of the fourth group.

Also, as an ultrafine powder of superhard material of a cubic structure, an ultrafine powder of compounds А ³ В ⁵ can be used.

A method of manufacturing powders is characterized by the fact that thermobaric treatment is carried out at a temperature above the value of 300 ° C, but below the temperature of the reverse transition to the non-solid crystalline phase.

If hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with the ratio of the components of hexagonal boron nitride and ultrafine additive from 0.99-99.00 to 99.00-0.99 wt.%, The thermobaric treatment is preferably carried out at a temperature higher than at 500 ° C.

If graphite is used as the initial component of the non-solid crystalline phase with the ratio of the components of graphite and ultrafine additive from 0.99-99.00 to 99.00-0.99% by weight, the thermobaric treatment is preferably carried out at a temperature above 700 ° C.

In addition to the initial component of the non-solid crystalline phase, a mixture of graphite and hexagonal boron nitride is used with a ratio of components from 0.99-99: 99-0.99 wt.%, And the thermobaric treatment is preferably carried out at a temperature above 700 ° C.

Further methods for the manufacture of tools are characterized by the fact that thermobaric treatment is carried out for 20 s-300 s.

Preferably thermobaric treatment is carried out for 40-80 s.

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Examples of specific implementation

The inventive method of producing superhard materials is as follows. Prepare a mixture of graphite and / or hexagonal boron nitride with the addition of mixing crystal-forming additives in the mixer. The resulting mixture is briquetted under pressure and placed either in the cavity of a thermal insulating container for graphite, or in a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride, and then in the cavity of a thermal insulating container for hexagonal nitride, closed on both sides with lids made by pressing a mixture of graphite and hexagonal boron nitride. The container thus equipped is placed in a high-pressure apparatus and compressed to a pressure corresponding to the region of stable diamond formation, and then heated by passing an electric current through the charge or heating element to a temperature corresponding to this pressure, then kept at this temperature and pressure for given time. After holding, the electric current is switched off, the pressure is released and the product of STM synthesis is removed.

Brief Description of the Drawings

The effect obtained is most clearly seen from the spectrograms shown in FIG. 1, 2, 3, which show some results on the experimental determination of the dependence of the fraction of transition of hexagonal boron nitride to cubic boron nitride. Visibility is pronounced for boron nitride, because X-ray lines of different phases of boron nitride are well distinguished.

FIG. Figure 1 shows the X-ray diffraction characteristics measured during irradiation with CuCa ₁ (λ = 1.5405 A).

The composition of the mixture: 10 wt.% UDA, 90 wt.% HDD. Р = 5.0 GPa, T = 570 ° С, 1 = 100 s.

FIG. 2 shows the X-ray patterns of the samples synthesized at P = 6.0 GPa, T = 570 ° C at different time of thermobaric exposure. The composition of the initial mixture: 10 wt.% UDA; 90 wt.% HDD.

FIG. 3 shows the fragments of the radiograph of the sample, the composition of the initial mixture: 20 wt.% UDA; 80 wt.% Of HDD synthesized at P = 7.0 GPa, T = 650 ° C, 1 = 40 s. Radiographs show the complete α-β conversion in boron nitride.

FIG. 4 shows photographs of the chips of samples obtained in the synthesis of cubic boron nitride depending on the time of synthesis.

FIG. 5 shows the conventional schemes of superhard materials obtained with different content in the mixture UDA (extreme and average value), superhard component - filler (diamond) (extreme and average value) and binder (graphite) and dependencies:

a) the output of the superhard component (diamond) from the temperature (vertical) and

b) the size of the STM crystals from processing time (horizontally).

FIG. 6 shows the conditional schemes of superhard materials obtained with different content in the mixture UDA (extreme and average value), superhard component - filler (c-ΒΝ) (extreme and average value) and binder (11-ΒΝ) and dependencies:

a) the output of the superhard component (c-ΒΝ) from temperature (vertical) and

b) the size of the STM crystals from processing time (horizontally).

FIG. 7 shows the conditional schemes of composite superhard materials obtained with different contents in the UDA blend (extreme and average value), superhard component — filler (diamond and c-ΒΝ) (extreme and average value) and binder (graphite and 11-) and dependencies :

a) the output of the superhard component (diamond and c-ΒΝ) from the temperature (vertical) and

b) the size of the STM crystals from processing time (horizontally).

STM consists of diamond and c-ΒΝ in a ratio that is determined by the composition of the charge and the conditions of synthesis.

FIG. 8 shows comparative diagrams of technological processes for the synthesis of polycrystalline STM by the known and the claimed methods.

FIG. 9 shows comparative diagrams of technological processes for producing STM powders according to the known and the claimed methods.

Embodiments of the invention

Below are examples of the specific implementation of the method of producing artificial STM.

The inventive method of producing superhard materials is as follows.

Prepare a batch of the starting material (graphite, hexagonal boron nitride (HDD), or graphite mixed with hexagonal boron nitride) supplemented with ultrafine powders (e.g., Ultrafine diamond (UDD), ultrafine powder of cubic boron nitride (UDPNB), ultrafine powders of materials Group 4 , for example, silicon (UDPK), ultrafine powders of А ³ В ⁵ materials, for example, aluminum nitride (UDPNA) and mixing them in a mixer.

The resulting mixture is briquetted under pressure and placed into cylindrical heating elements from a mixture of graphite and hexagonal boron nitride in the cavity of a heat-insulating container, closing on both sides with lids made by pressing a mixture of graphite and hexagonal boron nitride.

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The container thus equipped is placed in a high-pressure apparatus and compressed to a pressure corresponding to the region of stable formation of a corresponding superhard material, and then heated by passing an electric current through a heating element or mixture to a temperature corresponding to this pressure, then maintained at these temperatures and pressures for a given time.

After aging, the electrical current is turned off, the pressure is removed, and the compact product is extracted; the superhard compact material containing the ultrafine powder of the charge, the superhard component (diamond, CBN, a mixture of diamond and CBN) and a binder (graphite, hexagonal boron nitride or a mixture of graphite with hexagonal boron nitride).

As a result, depending on the practical purpose, materials are obtained with different ratios between the superhard components (the fine component — UDD, UDPNB, UDPK, UDPNA, and the STM component with given particle sizes — diamond, CBN or their mixture) and the binder — graphite, GNB or their mixture.

The degree of transition of the non-solid phase of the material into the superhard phase is determined by the method of X-ray diffraction analysis. Determine the composition of the resulting product - a compact superhard material.

The resulting effect is clearly seen from the examples below.

1.1.Materials based on diamond.

A mixture of graphite starting material is prepared with additions by mixing ultrafine powders (for example, ultrafine diamond, ultrafine powder of cubic boron nitride, ultrafine powders of materials of group 4, ultrafine powders of materials A ³ B ⁵ ) in a mixer.

Then the mixture is briquetted, subjecting it to pressure P = 0.5 GPa and placed in a cylindrical container of a tepoelectrically insulating container, closing on both sides with pressed caps of a mixture of graphite and limestone.

The container thus equipped is placed in a high-pressure apparatus and compressed to a pressure corresponding to the region of stable diamond formation, and then heated by passing an electric current through the charge to a temperature corresponding to this pressure, then maintained at these temperatures and pressures for a predetermined time.

After holding, the electric current is switched off, the pressure is removed, and the superhard material containing UDA, diamond and graphite is removed from the synthesis product.

As a result, depending on the practical purpose, materials are obtained with different ratios between the superhard components (the fine component — UFD and diamond with given particle sizes) and the binder — graphite.

1.1.1. The use of ultrafine diamond (UDA).

Below are examples (Table 1) of the specific implementation of the method of producing artificial superhard materials containing UDA and diamond. As an ultrafine powder, ultrafine diamond powder is used.

Table 1. Examples of a specific implementation of the method of producing synthetic superhard materials containing UDA and diamond

Example number The composition of the initial mixture, the masses. % R, GPA t, ^p with graphite oud 1. Composition ishod I 99.5 0.5 6.0 800 2 99.0 1.0 6.0 800 95.0 5.0 6.0 800 four 80.0 20.0 6.0 800 five 50.0 50.0 6.0 800 6 5.0 95.0 6.0 800 7 1.0 99.0 6.0 800 2.3 dependence on eight 80.0 20.0 6.0 300 9 80.0 20.0 6.0 300 ten 80.0 20.0 6.0 850 eleven 80.0 20.0 6.0 1600 12 80.0 20.0 6.0 2000 13 80.0 20.0 6.0 2100 3.Time dependence 14 80.0 20.0 6.0 800 15 80.0 20.0 6.0 800 sixteen 80.0 20.0 6.0 800 17 80.0 20.0 6.0 800 18 80.0 20.0 6.0 800

(, sec. The composition of the synthesis product, mass. % The degree of conversion,% diamond graphite Uda bottom charge 40 0.8 98.7 0.5 0.8 40 7.0 92.0 1.0 7.0 40 28.5 66.5 5.0 30.0 40 52.0 28.0 20.0 65.0 40 32.5 17.5 50 65.0 40 4.0 1.0 95.0 80.0 40 0.9 0.1 99.0 85 t temperature thirty 0.6 79.4 20.0 0.8 thirty 3.2 76,8 20.0 4.0 thirty 56.0 24.0 20.0 70.0 thirty 72.0 8.0 20.0 90.0 thirty 2.4 77.6 20.0 3.0 thirty 0.0 80.0 20.0 0.0 thermobaric treatment five 0.6 79.4 20.0 0.7 ten 3.2 76,8 20.0 4.0 40 60.0 20.0 20.0 75.0 60 64.0 16,0 20.0 80.0 300 68.0 12.0 20.0 85.0

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1.2. Tools from superhard material based on diamond.

Example 19. Prepare a mixture of graphite with the addition of UDA in the ratio of 80.0 wt.% Graphite, 20.0 wt.% Coop.

The mixing of the components is carried out in a mixer, achieving the distribution of ultrafine diamond powder in the volume of graphite. Carry out the preliminary molding of the tool of the desired shape and size, fill the molding space with an inert high pressure, but easily removed after thermobaric treatment with a substance, for example # 1С1. Then, the workpiece is briquetted, subjecting it to pressure P = 0.5 GPa and placed in a cylindrical container of a heat-insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 6.5 GPa, heated by passing an electric current through the mixture to a temperature of 800 ° C, and the heat is turned off for 40 seconds, the pressure is removed and the product is removed. . After dissolution of the forming No. 1С1 in water, the necessary blank for the tool is obtained. The X-ray diffraction analysis method determines the fraction of the transition of graphite to diamond in the tool material, which averages 90.0% by weight of graphite. The composition of the material obtained for the tool is 20.0 wt.% UDA, 72.0 wt.% Diamond, 8.0 wt.% Graphite.

1.3. Getting diamond powders of a given grain.

Example 20. Prepare a mixture of graphite with the addition of UDA in the ratio of 90.0 wt.% Graphite, 10.0 wt.% Coop.

The mixing of the components is carried out in a mixer, achieving the distribution of ultrafine diamond powder in the volume of graphite. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 6.5 GPa, heated by passing an electric current through the mixture to a temperature of 800 ° C, and the heat is turned off for 40 seconds, the pressure is removed and the product is removed. . Determine the proportion of transition of graphite to diamond in the material of the tool, which averaged 95% by weight of graphite. The composition of the material obtained is 10 wt.% UDA, 85.5 wt.% Diamond, 4.5 wt.% Graphite. The method of calcination in an oxygen environment removes graphite. The yield of the product STM - 95.5 wt.%., Diamond - 86.5 wt.%. The size of the diamond particles is 1.3 ± 0.1 μm.

Example 21. Perform the same operations and at the same pressures and temperatures of exposure, as in example 20, but the heat treatment is carried out for 120 s. The composition of the material obtained is 10 wt.% UDA, 87.0 wt.% Diamond, 3.0 wt.% Graphite. The method of calcination in an oxygen environment removes graphite. The yield of the product STM - 97.0 wt.%., Diamond - 87.0 wt.%. The size of the diamond particles is 3.1 ± 0.1 μm.

Example 22. Perform the same operations and at the same pressures and holding temperatures as in example 20, but the heat treatment is carried out for 20 s. The composition of the material obtained is 10 wt.% UDA, 75.0 wt.% Diamond, 15.0 wt.% Graphite. The method of calcination in an oxygen environment removes graphite. The yield of the product STM - 85.0 wt.%, Diamond - 75.0 wt.%. The size of the diamond particles is 0.3 ± 0.05 microns.

2. Materials based on cubic boron nitride.

The mixture is prepared from a raw material of hexagonal boron nitride with additions by mixing ultrafine powders (for example, ultrafine diamond, ultrafine powder of cubic boron nitride, ultrafine powders of materials of group 4, ultrafine powders of materials A ³ B ⁵ ) in a mixer. The resulting mixture is briquetted under pressure P = 0.5 GPa and placed into cylindrical heating elements from a mixture of graphite and hexagonal boron nitride in the cavity of a heat-insulating container, closing on both sides with covers made by pressing a mixture of graphite and hexagonal boron nitride. The container thus equipped is placed in a high-pressure apparatus and compressed to a pressure corresponding to the region of stable formation of cubic boron nitride, and then heated by passing an electric current through the heating element to a temperature corresponding to this pressure, then kept at this temperature and pressure for given time. After aging, the electric current is turned off, the pressure is removed, and the synthesis product is removed — a superhard material containing UDD, CNS and binder-hexagonal boron nitride. As a result, depending on the practical purpose, materials are obtained with different ratios between the superhard components (the fine component — UDA and KNB with the given particle sizes) and the binding hexagonal boron nitride.

Below are examples of the specific implementation of the method of producing synthetic superhard materials containing UDA and cubic boron nitride.

2.1.1. The use of ultrafine diamond (UDA).

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Table 2. Examples of a specific implementation of the method of producing synthetic superhard materials containing UDA and cubic boron nitride

Example number The composition of the initial mixture, the masses. % R. GPa t ° one, seconds The composition of the synthesis product, mass. % The degree of transformation. % HDD Uda CBN HDD Uda 1. Composition of the initial charge 23 99.5 0.5 6.0 600 40 0.9 98.6 0.5 1.0 24 99.0 go 6.0 600 40 9.9 89.1 1.0 10.0 25 95.0 5.0 6.0 600 40 38.0 57.0 5.0 40.0 26 80.0 20.0 6.0 600 40 64.0 16,0 20.0 80.0 27 50.0 50.0 6.0 600 40 40 ten 50 80.0 28 5.0 95.0 6.0 600 40 4.9 0.1 95.0 98.0 29 1.0 99.0 6.0 600 40 1.0 0.0 99.0 99.5 2.3 temperature dependence thirty 80.0 20.0 6.0 200 thirty 0.8 79.2 20.0 1.0 31 80.0 20.0 6.0 300 thirty 4.0 76.0 20.0 5.0 32 80.0 20.0 6.0 700 thirty 64.0 16,0 20.0 80.0 33 80.0 20.0 6.0 1600 thirty 78.4 1.6 20.0 98.0 34 80.0 20.0 6.0 2000 thirty 4.0 76.0 20.0 5.0 35 80.0 20.0 6.0 2100 thirty 0.8 79.2 20.0 1.0 Z.Tepending time thermobaric processing 36 80.0 20.0 6.0 650 five 0.8 79.2 20.0 1.0 37 80.0 20.0 6.0 650 ten 4.0 76.0 20.0 5.0 38 80.0 20.0 6.0 650 40 72.0 8.0 20.0 90.0 39 80.0 20.0 6.0 650 60 72.0 8.0 20.0 90.0 40 80.0 20.0 6.0 650 300 76.0 4.0 20.0 95.0

2.2. Tools from superhard material based on cubic boron nitride.

Example 41. Prepare a mixture of hexagonal boron nitride with the addition of UDA in the ratio of 80.0 wt.% Hexagonal boron nitride, 20.0 wt.% UDA.

The components are mixed in the mixer, achieving the distribution of ultrafine diamond powder in the volume of hexagonal boron nitride.

Carry out the preliminary molding of the tool of the desired shape and size, press-molding the forming spaces with an inert high pressure, but easily removed after thermobaric treatment with a substance, for example, NaCl. Then, the workpiece is briquetted, subjecting it to pressure P = 0.5 GPa and placed in a cylindrical container of a heat-insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 6.0 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 700 ° C and maintained at these parameters for 40 seconds of shutdowns turn off the heat, relieve the pressure and remove the product of synthesis. After dissolving the forming NaC1 in water, the necessary blank for the tool is obtained. The X-ray diffraction analysis method determines the fraction of the transfer of HDD to CBN in the tool material, which averaged 95.0% by weight of hexagonal boron nitride. The composition of the material obtained for the instrument is 20.0 wt.% UDA, 76.0 wt.% CBF, 4.0 wt.% Hexagonal boron nitride.

2.3. Obtaining powders of cubic boron nitride of a given grain.

Example 42. Prepare a mixture of hexagonal boron nitride with the addition of UDA in the ratio of 90.0 wt.% Hexagonal boron nitride, 10.0 wt.% UDA.

The components are mixed in the mixer, achieving the distribution of ultrafine diamond powder in the volume of hexagonal boron nitride. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 6.5 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 650 ° C and maintained at these parameters for 40 s. extracts, turn off the heat, relieve pressure and remove the product of synthesis. Determine the proportion of transition hexagonal boron nitride in the CNS, which averaged 97% by weight of hexagonal boron nitride. The composition of the material obtained is 10 wt.% UDA, 88.0 wt.% CBF, 2.0 wt.% Hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The product yield STM - 98.0 wt.%., CNB - 88.0 wt. % The particle size of cubic boron nitride is 1.4 ± 0.1 μm.

Example 43. The same operations are performed at the same pressures and holding temperatures as in Example 42, but the heat treatment is carried out for 120 s. The composition of the material obtained is 10 wt.% UDA, 88.0 wt.% Cubic boron nitride, 2.0 wt.% Hexagonal boron nitride. Etching method in

- 8 006011 hot alkali removes hexagonal boron nitride .. Product yield STM - 98.0 wt.%, Cubic boron nitride - 88.0 wt.%. The particle size of cubic boron nitride is 3.3 ± 0.1 μm.

Example 44. Perform the same operations and at the same pressures and holding temperatures as in example 42, but the heat treatment is carried out for 20 s. The composition of the material obtained is 10 wt.% UDA, 77.0 wt.% Cubic boron nitride, 13.0 wt.% Hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The yield of the product STM is 87.0 wt.%, Cubic boron nitride - 77.0 wt.%. The particle size of cubic boron nitride is 0.5 ± 0.05 microns.

3.1. Materials based on diamond and cubic boron nitride.

The mixture is prepared from the raw material of graphite and hexagonal boron nitride with the addition of blending ultrafine powders (for example, ultrafine diamond, ultrafine powder of cubic boron nitride, ultrafine powders of materials A ³ B ⁵ ) in a mixer.

Then the mixture is briquetted, subjecting it to pressure P = 0.5 GPa, and placed in a cylindrical container of a heat-insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone.

The container thus equipped is placed in a high-pressure apparatus and compressed to a pressure corresponding to the region of stable formation of diamond and cubic boron nitride, and then heated by passing an electric current through a cylindrical heating element made of a mixture of graphite and hexagonal boron nitride to a temperature corresponding to this pressure is then maintained at this temperature and pressure for a predetermined time.

After holding, the electric current is switched off, the pressure is removed, and the superhard material containing UDA, diamond and cubic boron nitride and the binder graphite and hexagonal boron nitride are removed from the synthesis product.

As a result, depending on the practical purpose, materials are obtained with different ratios between the superhard components (the fine component — UFD and diamond and cubic boron nitride with given particle sizes) and the binder — a mixture of graphite and hexagonal boron nitride.

3.1.1. The use of ultrafine diamond (UDA).

Below are examples (Table 3) of the specific implementation of the method for producing artificial superhard materials containing UDD, diamond and cubic boron nitride. As an ultrafine powder, ultrafine diamond powder is used.

Table 3. Examples of a specific implementation of the method of obtaining synthetic superhard materials containing UDA, diamond and cubic boron nitride

Example number The composition of the initial mixture, the masses. % R, GPA t, “with ΐ, seconds The composition of the synthesis product, mass. % The degree of conversion,% graphitalmaz / GNBKNB Graphite / HDD Uda diamond / CBN graphite / HDD Uda 1. Composition of the initial charge 45 99.0 / 0.5 0.5 6.5 800 40 0.8 / 0.0 98.2 / 0.5 0.5 0.8 / 0.0 46 99.0 / 0.5 0.5 6.5 650 40 0.0 / 0.1 99.0 / 0.4 0.5 0.0 / 20.0 47 98.0 / 1.0 1.0 6.5 800 40 7.0 / 0.0 92.0 / 1.0 1.0 7.0 / 0.0 48 98.0 / 1.0 1.0 6.5 650 40 0.0 / 0.8 98.0 / 0.2 1.0 0.0 / 80.0 49 90.0 / 5.0 5.0 6.5 800 40 27.0 / 0.3 63.0 / 4.7 5.0 30.0 / 5.0 50 90.0 / 5.0 5.0 6.5 650 40 4.5 / 4.3 85.5 / 0.7 5.0 5.0 / 85.0 51 40.0 / 40.0 20.0 6.5 800 40 28.0 / 4.0 20.0 / 36.0 20.0 70.0 / 10.0 52 40.0 / 40.0 20.0 6.5 650 40 0.4 / 36.0 39.6 / 4.0 20.0 1.0 / 90.0 53 25.0 / 25.0 50.0 6.0 800 40 20.0 / 12.5 5.0 / 12.5 50 80.0 / 50.0 54 25.0 / 25.0 50.0 6.0 650 40 7.5 / 22.5 17.5 / 2.5 50 30.0.0 / 90.0 55 5.0 / 90.0 5.0 6.5 650 40 0.3 / 76.5 4.7 / 13.5 5.0 5.0 / 85.0 56 5.0 / 90.0 5.0 6.5 800 40 1.5 / 18.0 4.5 / 72.0 5.0 30.0 / 20.0 57 1.0 / 98.0 1.0 6.5 650 40 0.0 / 63.7 0.0 / 34.3 1.0 0.0 / 65.0 58 1.0 / 98.0 1.0 6.5 800 40 0.4 / 13.7 0.6 / 84.3 1.0 40.0 / 15.0 59 0.5 / 99.0 0.5 6.5 650 40 0.0 / 4.5 0.0 / 94.5 0.5 0.0 / 5.0 60 0.5 / 99.0 0.5 6.5 800 40 0.3 / 0.5 0.2 / 98.5 0.5 0.6 / 0.5

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61 5.0 / 5.0 90.0 6.0 800 40 3.7 / 2.0 1.3 / 3.0 90.0 75.0 / 40.0 62 5.0 / 5.0 90.0 6.0 650 40 0.05 / 3.5 4.8 / 1.5 90.0 1.0 / 70.0 63 2.5 / 2.5 95.0 6.0 800 40 2.0 / 0.9 0.5 / 1.6 90.0 80.0 / 35.0 64 2.5 / 2.5 95.0 6.0 650 40 0.02 / 1.0 2.45 / 1.5 90.0 1.0 / 40.0 65 0.5 / 0.5 99.0 6.0 800 40 0.0 / 0.0 0.5 / 0.5 90.0 0.1 / 0.1 66 0.5 / 0.5 99.0 6.0 650 40 0.0 / 0.0 0.5 / 0.5 90.0 0.1 / 0.1 2. Temperature dependence 67 40.0 / 40.0 20.0 6.0 300 40 0.2 / 0.4 39.8 / 39.6 20.0 0.05 / 0.1 68 40.0 / 40.0 20.0 6.0 650 40 0.4 / 36.0 39.6 / 4.0 20.0 1.0 / 90.0 69 40.0 / 40.0 20.0 6.0 700 40 3.2 / 36.0 36.8 / 4.0 20.0 8.0 / 90.0 70 40.0 / 40.0 20.0 6.0 750 40 20.0 / 28.0 20.0 / 12.0 20.0 50.0 / 70.0 71 40.0 / 40.0 20.0 6.0 800 40 28.0 / 4.0 2.0 / 36.0 20.0 70.0 / 10.0 72 40.0 / 40.0 20.0 6.0 850 40 30.0 / 0.4 10.0,39.6 20.0 75.0 / 1.0 73 40.0 / 40.0 20.0 6.0 1600 40 36.0 / 36.0 4.0 / 4.0 20.0 90.0 / 90.0 74 40.0 / 40.0 20.0 6.0 2000 40 1.2 / 2.0 38.8 / 38.0 20.0 3.0 / 5.0 75 40.0 / 40.0 20.0 6.0 2100 40 0.04 / 0.12 39.9 / 39.9 20.0 0.02 / 0.03 3. Thermobaric treatment time dependence 76 40.0 / 40.0 20.0 6.0 650 five 0.0 / 0.4 40.0 / 39.6 20.0 0.0 / 1.0 77 40.0 / 40.0 20.0 6.0 650 ten 0.0 / 2.0 40.0 / 38.0 20.0 0.01 / 5.0 78 40.0 / 40.0 20.0 6.0 650 20 0.02 / 16.0 39.9 / 24.0 20.0 0.05 / 40.0 79 40.0 / 40.0 20.0 6.0 650 thirty 0.2 / 28.0 39.8 / 12.0 20.0 0.5 / 70.0 80 40.0 / 40.0 20.0 6.0 650 40 0.4 / 36.0 39.6 / 4.0 20.0 1.0 / 90.0 81 40.0 / 40.0 20.0 6.0 650 60 1.2 / 36.0 38.8 / 4.0 20.0 3.0 / 90.0 82 40.0 / 40.0 20.0 6.0 650 300 2.4 / 38.0 37.6 / 2.0 20.0 6.0 / 95.0 83 40.0 / 40.0 20.0 6.0 800 five 0.3 / 0.2 39.7 / 39.8 20.0 0.7 / 0.5 84 40.0 / 40.0 20.0 6.0 800 ten 1.6 / 1.2 38.4 / 38.8 20.0 4.0 / 3.0 85 40.0 / 40.0 20.0 6.0 800 20 8.0 / 2.4 32.0 / 37.6 20.0 20.0 / 6.0 86 40.0 / 40.0 20.0 6.0 800 thirty 20.0 / 3.2 20.0 / 36.8 20.0 50.0 / 8.0 87 40.0 / 40.0 20.0 6.0 800 40 28.0 / 4.0 2.0 / 36.0 20.0 70.0 / 10.0 88 40.0 / 40.0 20.0 6.0 800 60 32.0 / 5.2 8.0 / 34.8 20.0 80.0 / 13.0 89 40.0 / 40.0 20.0 6.0 800 300 34.0 / 8.0 6.0 / 32.0 20.0 85.0 / 20.0

3.2. Tools made of superhard material based on diamond and cubic boron nitride.

Example 90. Prepare a mixture of 45.0 wt.% Graphite and 45.0 wt.% Hexagonal boron nitride with the addition of UDA in the ratio: 90.0 wt.% Graphite and hexagonal boron nitride, 10.0 wt.% UDA.

The components are mixed in the mixer, achieving a uniform distribution of graphite and hexagonal boron nitride. The mixing of the components is then carried out in a mixer, achieving the distribution of ultrafine diamond powder in the volume of graphite and hexagonal boron nitride. The tool is preformed to the required shape and size, and the forming spaces are pressed with inert high pressure but easily removed after thermobaric treatment with a substance, for example Iac1. Then, the workpiece is briquetted by exposing it to pressure P = 0.5 GPa and placed into cylindrical heating elements from a mixture of graphite and hexagonal boron nitride, which are then placed in a cylindrical container of a thermal insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 7.0 GPa, heated by passing electric current through the heating elements to a temperature of 730 ° C and maintained at these parameters for 40 s, shut off the heat, relieve the pressure and remove the products synthesis. After dissolving the formative IAS1 in water, the necessary blank for the instrument is obtained. The x-ray diffraction analysis method determines the fraction of transition of graphite and hexagonal boron nitride to diamond and cubic boron nitride in the tool material, which averaged 90.0% of the mass of graphite and hexagonal boron nitride. The composition of the material obtained for the tool is 10.0 wt.% UDA, 81.0 wt.% Diamond and cubic boron nitride (39.0 wt.% Diamond and 42 wt.% CBF), 9.0 wt.% Graphite and hexagonal boron nitride (respectively 6.0 wt.% graphite and 3.0 wt.% hexagonal boron nitride).

3.3. Obtaining powders of diamond and cubic boron nitride of a given grain.

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Example 91. Prepare a mixture of graphite and hexagonal boron nitride (45.0 wt.% Graphite and 45.0 wt.% Hexagonal boron nitride) with the addition of UDA in the ratio of 90.0 wt.% A mixture of graphite and hexagonal boron nitride, 10, 0 wt.% UDA.

The components are mixed in a mixer, achieving the distribution of ultrafine diamond powder in the volume of a mixture of graphite and hexagonal boron nitride. The equipped container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 6.5 GPa, heated by passing electric heating current through heating elements made of a mixture of graphite and hexagonal boron nitride to a temperature of 730 ° C and kept at these parameters for 40 seconds. heat, relieve pressure and extract the products of synthesis. The fraction of transition of graphite and hexagonal boron nitride to diamond and cubic boron nitride in the tool material is determined, which averaged 90.0% of the mass of graphite and hexagonal boron nitride. The composition of the material obtained is 10 wt.% UDA, 82.0 wt.% Diamond and cubic boron nitride (39.0 wt.% Diamond and 43.0 wt.% Cubic boron nitride) and 8.0 wt.% Graphite and hexagonal Boron nitride (6.0 wt.% of graphite and 2.0 wt.% of hexagonal boron nitride, respectively). Calcination and hexagonal boron nitride are removed by calcining oxygen in a hot alkali process. The yield of the product STM powder - 82.0 wt.%, Diamond and cubic boron nitride and 10 wt.% UDA. The size of the diamond particles and cubic boron nitride is 1.2 ± 0.1 μm.

Example 92. Perform the same operations and at the same pressures and holding temperatures as in Example 47, but the heat treatment is carried out for 120 s. The composition of the material obtained is 10 wt.% UDA, 87.0 wt.% Diamond and cubic boron nitride, 3.0 wt.% Graphite and hexagonal boron nitride. The method of calcination in the environment of oxygen and processing in hot alkali remove graphite and hexagonal boron nitride. The yield of the product STM - 97.0 wt.%, Diamond and cubic boron nitride - 87.0 wt.%. The size of the diamond particles and cubic boron nitride is -2.4 ± 0.1 μm.

Example 93. The same operations are performed under the same pressures and holding temperatures as in Example 47, but the heat treatment is carried out for 25 seconds. The composition of the material obtained is 10 wt.% UDA, 60.0 wt.% Diamond and cubic boron nitride, 30.0 wt.% Graphite and hexagonal boron nitride. The method of calcination in the environment of oxygen and processing in hot alkali remove graphite and hexagonal boron nitride. The product yield STM - 70.0 wt.%, Diamond and cubic boron nitride - 60.0 wt.%. The size of diamond particles and cubic boron nitride is 0.6 ± 0.05 microns.

4. The use of ultrafine powders of other materials: ultrafine powder of cubic boron nitride (UDIB), ultrafine powders of materials of the 4th group, for example, silicon (UPDK), ultrafine powders of A ³ B ⁵ materials, for example, aluminum nitride (UDPNA).

4.1. The use of ultrafine powder of boron nitride (UDIB).

4.1.1 Materials.

Table 4. Examples of a specific implementation of the method of producing synthetic superhard materials containing UDIBS and cubic boron nitride _____________________

Example number The composition of the initial mixture, the masses. % R, GPa T ° HDD UDPNB 1. Composition ishod 94 99.5 0.5 6.0 550 95 99.0 1.0 6.0 550 96 95.0 5.0 6.0 550 97 80.0 20.0 6.0 550 98 50.0 50.0 6.0 550 99 5.0 95.0 6.0 550 100 1.0 99.0 6.0 550 2. Dependence about 101 80.0 20.0 6.0 250 102 80.0 20.0 6.0 350 103 80.0 20.0 6.0 550 104 80.0 20.0 6.0 1600 105 80.0 20.0 6.0 2000 106 80.0 20.0 6.0 2100 3.Time dependence 107 80.0 20.0 6.0 550 108 80.0 20.0 6.0 550 109 80.0 20.0 6.0 550 110 80.0 20.0 6.0 550 111 80.0 20.0 6.0 550

1 sec The composition of the synthesis product, mass. % Degree of transformation % CBN GIB UDPNB ) BOTTOM CHARGE 40 1.2 98.3 0.5 1.2 40 11.9 87.1 1.0 12.0 40 40.1 54.9 5.0 43.0 40 68.0 12.0 20.0 85.0 40 43.5 6.5 50 87.0 40 4.7 0.3 95.0 95.0 40 1.0 0.0 99.0 98.0 > t temperature thirty 0.4 79.6 20.0 0.5 thirty 4.2 75.8 20.0 5.3 thirty 70.0 10.0 20.0 88.0 thirty 76.0 4.0 20.0 95.0 thirty 3.2 76,8 20.0 4.0 thirty 0.4 79.6 20.0 0.5 thermobaric treatment five 0.8 79.2 20.0 Г ι, ο ten 5.6 74.4 20.0 7.0 40 68.0 12.0 20.0 85.0 60 73.6 6.4 20.0 92.0 300 76.0 4.0 20.0 95.0

- 11 006011

4.1.2. Tools from superhard material based on cubic boron nitride.

Example 112. Prepare a mixture of hexagonal boron nitride with the addition of UDPNB in the ratio of 80.0 wt.% Hexagonal boron nitride, 20.0 wt.% UDPNB.

The mixing of the components is carried out in a mixer, achieving the distribution of UDPNB in the volume of hexagonal boron nitride. Carry out the preliminary molding of the tool of the desired shape and size, press-molding the forming spaces with an inert high pressure, but easily UDPNB with a substance removed after thermobaric treatment, for example, NaCl. Then, the workpiece is briquetted, subjecting it to pressure P = 0.5 GPa and placed in a cylindrical container of a heat-insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 6.0 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 550 ° C and maintained at these parameters for 50 seconds of shutdowns turn off the heat, relieve the pressure and remove the product of synthesis. After dissolution of the forming No. 1С1 in water, the necessary blank for the tool is obtained. The X-ray diffraction analysis method determines the fraction of the transfer of HDD to CBN in the tool material, which averaged 88.0% of the mass of hexagonal boron nitride. The composition of the material obtained for the tool is 20.0 wt.% UDPNB, 69.0 wt.% CNB, 11.0 wt.% Hexagonal boron nitride.

4.1.3. Obtaining powders of cubic boron nitride of a given grain.

Example 113. Prepare a mixture of hexagonal boron nitride with the addition of UDPNB in the ratio of 90.0 wt.% Hexagonal boron nitride, 10.0 wt.% UDPNB.

The mixing of the components is carried out in a mixer, achieving the distribution of UDPNB in the volume of hexagonal boron nitride. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 7.0 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 650 ° C and maintained at these parameters for 40 seconds, turn off the heat, relieve the pressure and remove the product of synthesis. The fraction of transition of hexagonal boron nitride to CBN is determined, which averaged 90.0% of the mass of hexagonal boron nitride. The composition of the obtained material is 10 wt.% UDPNB, 81.0 wt.% CNF, 9.0 wt.% Hexagonal boron nitride. Hexagonal boron nitride is removed by the etching method in hot alkali UDPNB. The product yield STM - 91,0 wt.%, KNB - 81,0 wt.%. The particle size of cubic boron nitride is 1.5 ± 0.1 μm.

Example 114. Perform the same operations and at the same pressures and holding temperatures as in example 20, but the heat treatment is carried out for 250 s. The composition of the obtained material is 10 wt.% UDPNB, 85.0 wt.% Cubic boron nitride, 5.0 wt.% Hexagonal boron nitride. Hexagonal boron nitride is removed by the etching method in hot alkali UDPNB. The product yield STM - 95.0 wt.%. cubic boron nitride - 85.0 wt.%. The particle size of cubic boron nitride is 5.5 ± 0.1 µm.

Example 115. The same operations are performed at the same pressures and holding temperatures as in example 20, but the heat treatment is carried out for 30 seconds. The composition of the material obtained is 10 wt.% UDPNB, 60.0 wt.% Cubic boron nitride, 30.0 wt.% Hexagonal boron nitride. Hexagonal boron nitride is removed by the etching method in hot alkali UDPNB. The product yield STM - 70.0 wt. %, cubic boron nitride - 60.0 wt.%. The particle size of cubic boron nitride is 0.7 ± 0.05 microns.

4.2. The use of ultrafine silicon powder (PDPC).

4.2.1. Materials

Table 5. Examples of a specific implementation of the method of producing synthetic superhard materials containing UPDK and cubic boron nitride

Example number The composition of the initial mixture, the masses. % R, GPA t ° and seconds The composition of the synthesis product, mass. % The degree of conversion,% HDD PDK CBN HDD PDK 1. Composition of the initial charge 116 99.5 0.5 7.0 900 50 0.0 99.5 0.5 0.0 117 99.0 1.0 7.0 900 50 5.0 94.0 1.0 5.0 118 95.0 5.0 7.0 900 50 19.0 76.0 5.0 20.0 119 80.0 20.0 7.0 900 50 32.0 48.0 20.0 40.0

- 12 006011

120 50.0 50.0 7.0 900 50 20.0 30.0 50 40.0 121 5.0 95.0 7.0 900 50 2.3 2.7 95.0 45.0 122 1.0 99.0 7.0 900 50 0.4 0.6 99.0 46.0 2.3 temperature dependence 123 80.0 20.0 7.0 700 50 0.0 80.0 20.0 0.0 124 80.0 20.0 7.0 800 50 1.6 78.4 20.0 2.0 125 80.0 20.0 7.0 900 50 32.0 48.0 20.0 40.0 126 80.0 20.0 7.0 1500 50 36.0 44.0 20.0 45.0 127 80.0 20.0 7.0 1900 50 1.6 78.4 20.0 2.0 128 80.0 20.0 7.0 2000 50 0.0 80.0 20.0 0.0 Z.Tepending time thermobaric processing 129 80.0 20.0 7.0 900 ten 0.0 80.0 20.0 0.0 130 80.0 20.0 7.0 900 thirty 4.0 76.0 20.0 5.0 131 80.0 20.0 7.0 900 50 36.0 44.0 20.0 45.0 132 80.0 20.0 7.0 900 80 37.0 43.0 20.0 47.0 133 80.0 20.0 7.0 900 300 40.0 40.0 20.0 50.0

4.2.2. Tools from superhard material based on cubic boron nitride.

Example 134

Prepare the mixture of hexagonal boron nitride with the addition of UDPPC in the ratio of 80.0 wt.% Hexagonal boron nitride, 20.0 wt.% UDPPC.

The mixing of the components is carried out in a mixer, achieving the distribution of the PDPC in the volume of hexagonal boron nitride. Carry out the preliminary molding of the tool of the desired shape and size, press-molding the forming spaces with an inert under high pressure, but easily removed after thermobaric treatment with a substance, for example # 1С1. Then, the workpiece is briquetted, subjecting it to pressure P = 0.5 GPa and placed in a cylindrical container of a heat-insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 7.0 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 900 ° C and maintained at these parameters for 50 seconds of shutdowns turn off the heat, relieve the pressure and remove the product of synthesis. After dissolving the forming NaC1 in water, the necessary blank for the tool is obtained. The X-ray diffraction analysis method determines the fraction of the transfer of HDD to CBN in the tool material, which averaged 45.0% by weight of hexagonal boron nitride. The composition of the material obtained for the tool is 20.0 wt.% UDPK, 36.0 wt.% CNB, 44.0 wt.% Hexagonal boron nitride.

4.2.3. Obtaining powders of cubic boron nitride of a given grain.

Example 135. Prepare a mixture of hexagonal boron nitride with the addition of UDPPC in the ratio of 90.0 wt.% Hexagonal boron nitride, 10.0 wt.% UDPPC.

The mixing of the components is carried out in a mixer, achieving the distribution of the PDPC in the volume of hexagonal boron nitride. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 7.0 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 900 ° C and maintained at these parameters for 50 seconds of shutdowns turn off the heat, relieve the pressure and remove the product of synthesis. Determine the proportion of transition hexagonal boron nitride in the CNS, which averaged 45.0% by weight of hexagonal boron nitride. The composition of the material obtained is 10% by weight of UDPC, 40.5% by weight of CNB, 49.5% by weight of hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The product yield STM - 50.5 wt.%, CNS - 40.5 wt.%. The particle size of cubic boron nitride is 0.7 ± 0.1 μm.

Example 136. The same operations are carried out at the same pressures and holding temperatures as in Example 20. But the heat treatment is carried out for 200 s. The composition of the material obtained is 10% by weight of UDPK, 43.0% by weight of cubic boron nitride, 47.0% by weight of hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The product yield STM-53.0 wt.%. cubic boron nitride - 43.0 wt. % The particle size of cubic boron nitride is 1.6 ± 0.1 μm.

Example 137. Perform the same operations and at the same pressures and holding temperatures as in example 20, but the heat treatment is carried out for 40 s. The composition of the material obtained is 10% by weight of UDPK, 40.0% by weight of cubic boron nitride, 50.0% by weight of hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The product yield STM - 50.0 wt.%, Cubic boron nitride - 40.0 wt.%. The particle size of cubic boron nitride is 0.3 ± 0.05 microns.

4.3. The use of ultrafine powder material A ³ B ⁵ -nitride of aluminum (UDPNA).

4.3.1. Materials

- 13 006011

Table 6. Examples of specific implementation of the method of obtaining synthetic superhard materials containing UDPNA and cubic boron nitride

Example number The composition of the initial mixture, the masses. % R, GPA T. with 1 sec The composition of the synthesis product, mass. % The degree of transformation. % HDD UPDNA CBN HDD UPDNA 1. Composition of the initial charge 138 99.5 0.5 7.0 1100 50 0.0 99.5 0.5 0.0 139 99.0 1.0 7.0 noo 50 4.0 95.0 1.0 4.0 140 95.0 5.0 7.0 1100 50 13.3 8E7 5.0 14.0 141 80.0 20.0 7.0 1100 50 21.0 59.0 20.0 26.0 142 50.0 50.0 7.0 1100 50 14.0 36.0 50 28.0 143 5.0 95.0 7.0 1100 50 1.6 3.4 95.0 32.0 144 1.0 99.0 7.0 1100 50 0.3 0.7 99.0 35.0 2.3 temperature dependence 145 80.0 20.0 7.0 900 50 0.0 80.0 20.0 0.0 146 80.0 20.0 7.0 1000 50 0.8 79.2 20.0 1.0 147 80.0 20.0 7.0 noo 50 21.0 59.0 20.0 26.0 148 80.0 20.0 7.0 1600 50 26.4 53.6 20.0 33.0 149 80.0 20.0 7.0 1900 50 1.6 78.4 20.0 2.0 150 80.0 20.0 7.0 2000 50 0.0 80.0 20.0 0.0 Time dependence thermobaric processing 151 80.0 20.0 7.0 1100 ten 0.0 80.0 20.0 0.0 152 80.0 20.0 7.0 1100 thirty 1.6 78.4 20.0 2.0 153 80.0 20.0 7.0 1100 50 24.0 56.0 20.0 30.0 154 80.0 20.0 7.0 1100 80 24.0 56.0 20.0 30.0 155 80.0 20.0 7.0 noo 300 25.6 54.4 20.0 32.0

4.3.2. Tools from superhard material based on cubic boron nitride.

Example 156. Prepare a mixture of hexagonal boron nitride with the addition of UDINA in the ratio of 80.0 wt.% Hexagonal boron nitride, 20.0 wt.% UDPNA.

The mixing of the components is carried out in a mixer, achieving the distribution of UDIN in the volume of hexagonal boron nitride. The tool is preformed to the required shape and size, and the forming spaces are pressed with inert high pressure but easily removed after thermobaric treatment with a substance, for example Iac1. Then, the workpiece is briquetted, subjecting it to pressure P = 0.5 GPa and placed in a cylindrical container of a heat-insulating container, closing on both sides with pressed caps from a mixture of graphite and limestone. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 7.0 GPa. heated by passing through a cylindrical heating element made from a mixture of graphite with hexagonal boron nitride, an electric current to a temperature of 1100 ° C and maintained at these parameters for 50 seconds, shut off the heat, relieve pressure and remove the product of synthesis. After dissolving the forming No. С1 in water, the necessary blank for the tool is obtained. The X-ray diffraction analysis method determines the fraction of the transfer of HDD to CBN in the tool material, which averaged 32.0% by weight of hexagonal boron nitride. The composition of the material obtained for the tool - 20.0 wt.% UDPNA. 25.6 wt.% CNB, 54.4 wt.% Hexagonal boron nitride.

4.3.3. Obtaining powders of cubic boron nitride of a given grain.

Example 157. Prepare a mixture of hexagonal boron nitride with the addition of UDPNA in the ratio of 90.0 wt.% Hexagonal boron nitride, 10.0 wt.% UDPNA.

The mixing of the components is carried out in a mixer, achieving the distribution of UDPNA in the volume of hexagonal boron nitride. The filled container is placed in a toroid-type high-pressure apparatus, compressed to a pressure of 7.0 GPa, heated by passing a cylindrical heating element made of a mixture of graphite with hexagonal boron nitride through an electric current to a temperature of 1100 ° C and maintained at these parameters for 50 seconds of shutdowns turn off the heat, relieve the pressure and remove the product of synthesis. Determine the proportion of transition hexagonal boron nitride in the CNS, which averaged 32.0% by weight of hexagonal boron nitride. The composition of the material obtained -10 wt.% UDPNA, 28.8 wt.% CBF, 61.2 wt. % hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The product yield STM-38,8 wt. %, CBN - 28.8 wt.%. The particle size of cubic boron nitride is 0.7 ± 0.05 microns.

Example 158. Perform the same operations and at the same pressures and holding temperatures as in example 20, but the heat treatment is carried out for 300 s. The composition of the material obtained is 10% by weight of UDPNA, 32.0% by weight of cubic boron nitride, 58.0% by weight of hexagonal boron nitride. By method

- 14 006011 etching in hot alkali removes hexagonal boron nitride. The product yield STM - 42.0 wt.%, Cubic boron nitride - 32.0 wt.%. The particle size of cubic boron nitride is 1.6 ± 0.1 μm.

Example 159. Perform the same operations and at the same pressures and holding temperatures as in example 20, but the heat treatment is carried out for 40 s. The composition of the material obtained is 10 wt.% UDPNA, 20.0 wt.% Cubic boron nitride, 70.0 wt.% Hexagonal boron nitride. Hexagonal boron nitride is removed by hot-alkali etching. The product yield STM-30.0 wt.%, Cubic boron nitride - 20.0 wt.%. The particle size of cubic boron nitride is 0.2 ± 0.02 µm.

Thus, outside the declared interval of the diamond content in the charge, the proportion of the transition of graphite to diamond is significantly reduced (to the level of the charge without diamond content).

5. Comparison with known methods for the catalytic synthesis of STM.

For comparison with the claimed method, the synthesis of STM was carried out by the method of conventional catalytic synthesis on the same equipment and under the same modes as in the examples given, but without introducing UDA, UDNB, UPC, UDNA, and conventional catalysts into the charge.

5.1. Using Νί-Mi-eutectic for diamond synthesis under the conditions of the above examples.

Table 7

Example number The composition of the initial mixture, the masses. % R, GPA t ° 1 sec The composition of the synthesis product, mass% The degree of conversion,% graphite Νί-Μη eutectic diamond graphite Νί-Μη eutectic 1. The composition of the original batch 160 99.5 0.5 6.0 800 40 0 99.5 0.5 0 161 99.0 1.0 6.0 800 40 0 99.0 1.0 0 162 95.0 5.0 6.0 800 40 0 95.0 5.0 0 163 80.0 20.0 6.0 800 40 0 80.0 20.0 0 164 50.0 50.0 6.0 800 40 0 50.0 50 0 165 5.0 95.0 6.0 800 40 0 5.0 95.0 0 166 1.0 99.0 6.0 800 40 0 1.0 99.0 0 2. Dependence from those peratur 167 80.0 20.0 6.0 300 thirty 0 80.0 20.0 0 168 80.0 20.0 6.0 300 thirty 0 80.0 20.0 0 169 80.0 20.0 6.0 850 thirty 0 80.0 20.0 0 170 80.0 20.0 6.0 1600 thirty 9.6 70.4 20.0 12.0 171 80.0 20.0 6.0 2000 thirty 0.8 77.6 20.0 1.0 172 80.0 20.0 6.0 2100 thirty 0.0 80.0 20.0 0.0 ___________________________________________________________________________________1_______________________________________________________ 1__________________________________________________________1___________________________________________1_______________________________________________________________1__________________________________________________________________1_______________________________________________________________________________1 3. Thermobaric treatment time dependence 173 80.0 20.0 6.0 800 five 0 80.0 20.0 0 174 80.0 20.0 6.0 800 ten 0 80.0 20.0 0 175 80.0 20.0 6.0 800 40 0 80.0 20.0 0 176 80.0 20.0 6.0 800 60 0 80.0 20.0 0 177 80.0 20.0 6.0 800 300 68.0 12.0 20.0 85.0

5.1. The use of the catalyst MdV ₂ for the synthesis of CNS in the conditions of the above examples

Table 8

No The composition of the initial mixture, the masses. % R, t, one, The composition of the synthesis product, mass. % Degree of transformation an example HDD MgB ₂ GPa ° s seconds CBN HDD McV 2 Shenia,%

The composition of the initial charge

178 99.5 0.5 6.0 600 40 0 99.5 0.5 0 179 99.0 1.0 6.0 600 40 0 99.0 1.0 0 180 95.0 5.0 6.0 600 40 0 95.0 5.0 0 181 80.0 20.0 6.0 600 40 0 80.0 20.0 0 182 50.0 50.0 6.0 600 40 0 50.0 50 0 183 5.0 95.0 6.0 600 40 0 5.0 95.0 0 184 1.0 99.0 6.0 600 40 0 1.0 99.0 0 2.3 temperature dependent

- 15 006011

185 80.0 20.0 6.0 200 thirty 0 80.0 20.0 0 186 80.0 20.0 6.0 300 thirty 0 80.0 20.0 0 187 80.0 20.0 6.0 700 thirty 0 80.0 20.0 0 188 80.0 20.0 6.0 1600 thirty 16,0 64.0 20.0 20.0 189 80.0 20.0 6.0 2000 thirty 0 80.0 20.0 0 190 80.0 20.0 6.0 2100 thirty 0 80.0 20.0 0 3. Thermobaric treatment time dependence

191 80.0 20.0 6.0 650 five 0 80.0 20.0 0 192 80.0 20.0 6.0 650 ten 0 80.0 20.0 0 193 80.0 20.0 6.0 650 40 0 80.0 20.0 0 194 80.0 20.0 6.0 650 60 0 80.0 20.0 0 195 80.0 20.0 6.0 650 300 0 80.0 20.0 0

As can be seen from the above and experiments, the present invention leads to a number of significant advantages compared with existing technologies:

1. The synthesis of STM (diamond and / or c-ΒΝ) is carried out at extremely low temperatures (8001000 ° C lower than during catalytic synthesis) and relatively low pressures.

2. The durability of high-pressure apparatus made of expensive hard alloy increases by orders of magnitude.

3. It is possible to use steel HP machines instead of hard metal devices.

4. Excludes the use of catalysts and, therefore, several technological, environmentally harmful, expensive production stages.

5. Production of materials containing STM is carried out in one technological cycle, with simultaneous synthesis and sintering of the material, as a result of which compact polycrystalline or composite products are obtained.

6. Upon receipt of polycrystalline or composite compact materials from the synthesized STM powder, technological processes for the preparation of a mixture of STM with a binder and its sintering are excluded (Fig. 8).

7. Grinding or chemical separation of compact polycrystalline or composite products leads to the production of STM powders (Fig. 9).

8. Ultra-dispersed particles of the material of the cubic structure are not only catalysts for the synthesis of STM, but also become components of the composite superhard material as a cementing and plasticizing ligament (Fig. 4 (photos)).

9. By varying the temperature and synthesis time at a given pressure, the degree of conversion of the non-solid phase to the solid phase can be controlled, thereby controlling the ratio between the binder and the filler to obtain materials of a particular practical purpose (Fig. 5).

10. It has been established that the particle sizes of the synthesized STM with given other synthesis parameters strongly depend on time. This allows you to control the size of the synthesized particles STM in a wide range of values (Fig. 4).

11. Production of synthesized STM particles at specified technological parameters (pressure, temperature, time) with a very narrow variation in particle size values, which excludes rather labor-intensive technological processes of separating particles by size and the classification of powders after synthesis (Fig. 4).

12. As a result, depending on the practical purpose, materials are obtained with a different ratio between the superhard components (the fine component and the component STM with the given dimensions) and the binder (Fig. 6-8).

13. Significantly increases the yield of the finished product (up to 96-100% versus 20-35% for CBF; up to 93-100% versus 10-35% for diamond; up to 90-100% for the diamond-cubic boron nitride composite material) (Fig. 3).

14. The cost of production due to savings on materials, energy consumption and the exclusion of a number of labor-intensive and expensive technological processes both in the synthesis of STM materials and in the production of powders, polycrystalline and composite materials are several times lower.

Claims (39)

CLAIM 1. The method of synthesis of superhard materials, including the preparation of a mixture including materials of a non-solid crystalline phase, the introduction of crystal-forming additives, thermobaric treatment of the mixture at a pressure and temperature above certain values for a certain period of time, characterized in that as crystal-forming additives 2. The method according to claim 1, characterized in that the particle size of the ultrafine additive is 2100 nm. 3. The method according to claim 2, characterized in that the particle size of the additive is 4-40 nm. 4. The method according to any one of claims 1 to 3, characterized in that the thermobaric treatment is carried out at a temperature above 300 ° C, but below the temperature of the return to the non-solid crystalline phase. 5. The method according to claim 1, characterized in that ultrafine diamond powder is used as an ultrafine powder of a cubic structure material. 6. The method according to claim 1, characterized in that the ultrafine powder of boron nitride is used as an ultrafine powder of a superhard material of a cubic structure. 7. The method according to claim 1, characterized in that as the ultrafine powder of a superhard material of a cubic structure, an ultrafine powder of a material of the fourth group is used 8. The method according to claim 1, characterized in that the ultrafine powder of compounds A ³ B ^{5 is} used as an ultrafine powder of a superhard material of a cubic structure. 9. The method according to any one of claims 1 to 8, characterized in that hexagonal boron nitride is used as the initial component of the non-solid crystalline phase, with a ratio of the components of hexagonal boron nitride and ultrafine additive from 0.99-99.00 to 99.00-0 , 99 wt.%, And thermobaric treatment is preferably carried out at a temperature above a value of 500 ° C. 10. The method according to any one of claims 1 to 8, characterized in that graphite is used as the initial component of the non-solid crystalline phase when the ratio of the components of the graphite and the ultrafine additive is from 0.99-99.00 to 99.00-0.99 weight. %, and thermobaric treatment is preferably carried out at a temperature above 700 ° C. 11. The method according to any one of claims 1 to 10, characterized in that the mixture of graphite and hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with a component ratio of 0.99-99: 99-0.99 wt.%, And thermobaric the treatment is preferably carried out at a temperature above 700 ° C. 12. The method according to any one of claims 1 to 11, characterized in that the thermobaric treatment is carried out for 20-300 s. 13. The method according to p. 12, characterized in that the thermobaric treatment is carried out for preferably 40-80 s. 14. A method of manufacturing superhard tools, including the preparation of a mixture comprising materials of superhard and / or non-solid crystalline phases, the introduction of crystal-forming additives, preliminary molding of the tool, thermobaric treatment of the mixture at a pressure and temperature above critical values for a certain period of time, characterized in that as crystal-forming additives, an ultrafine powder of a cubic structure material with a particle size of less than 0.1 microns is used in the size range from 1 to 100 nm. 15. The method according to 14, characterized in that the particle size of the ultrafine additive is 2-100 nm. 16. The method according to 14, characterized in that the dispersion of the additive is preferably 4-40 nm. - 16 006011 use an ultrafine powder of a cubic structure material with particle sizes less than 0.1 microns in a size range from 1 to 100 nm. - 17 006011 17. The method according to any one of paragraphs.14 and 15, characterized in that the thermobaric treatment is carried out at a temperature above a value of 300 ° C, but below the temperature of the reverse transition to a non-solid crystalline phase (graphitization). 18. The method according to 17, characterized in that the ultrafine powder of the material of the cubic structure using ultrafine diamond powder. 19. The method according to 17, characterized in that the ultrafine powder of boron nitride is used as an ultrafine powder of a superhard material of a cubic structure. 20. The method according to 17, characterized in that as the ultrafine powder of superhard material of a cubic structure using ultrafine powder of the material of the fourth group. 21. The method according to 17, characterized in that as the ultrafine powder of superhard material of a cubic structure, an ultrafine powder of compounds A ³ B ^{5 is used} . 22. The method according to any one of claims 13-19, characterized in that hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with a ratio of components of hexagonal boron nitride and ultrafine additive from 0.99-99.00 to 99.00-0 , 99 wt.%, And thermobaric treatment is preferably carried out at a temperature above a value of 500 ° C. 23. The method according to any one of paragraphs.13-19, characterized in that as the initial component of the non-solid crystalline phase, graphite is used with a ratio of the components of graphite and ultrafine additive from 0.99-99.00 to 99.00-0.99 weight. %, and thermobaric treatment is preferably carried out at a temperature above 700 ° C. 24. The method according to any one of paragraphs.13-21, characterized in that as the initial component of the non-solid crystalline phase, a mixture of graphite and hexagonal boron nitride is used with a component ratio of 0.99-99: 99-0.99 wt.%, And thermobaric the treatment is preferably carried out at a temperature above 700 ° C. 25. The method according to any one of paragraphs.13-22, characterized in that the thermobaric treatment is carried out for 20-300 s. 26. The method according to item 23, wherein the thermobaric treatment is carried out for preferably 40-80 C. 27. A method of manufacturing superhard powders of a given size, including the preparation of a mixture including materials of a non-solid crystalline phase, the introduction of crystal-forming additives, preliminary molding of the compact, thermobaric processing of the mixture at a pressure and temperature above critical values for a certain period of time, and subsequent processing of the compact to separate the powder the required dispersion, characterized in that as the crystal-forming additives use ultrafine th powder material of cubic structure with particle sizes less than 0.1 μm in the size range from 1 to 100 nm, and the processing of the compact after thermobaric treatment is carried out by etching with alkali. 28. The method according to item 27, wherein the particle size of the ultrafine additive is 2-100 nm. 29. The method according to p, characterized in that the dispersion of the additive is preferably 4-40 nm. 30. The method according to any one of paragraphs.27-29, characterized in that the thermobaric treatment is carried out at a temperature above a value of 300 ° C, but below the temperature of the reverse transition to a non-solid crystalline phase. 31. The method according to p. 28, characterized in that as the ultrafine powder of the material of the cubic structure using ultrafine powder of diamond. 32. The method according to p. 28, characterized in that the ultrafine powder of boron nitride is used as an ultrafine powder of a superhard material of a cubic structure. 33. The method according to p. 28, characterized in that as the ultrafine powder of superhard material of a cubic structure using ultrafine powder of the material of the fourth group. 34. The method according to p. 28, characterized in that as an ultrafine powder of superhard material of a cubic structure, an ultrafine powder of compounds A ³ B ^{5 is used} . 35. The method according to any one of paragraphs.27-34, characterized in that hexagonal boron nitride is used as the initial component of the non-solid crystalline phase with a ratio of hexagonal boron nitride and ultrafine additive components from 0.99-99.00 to 99.00-0 , 99 wt.%, And thermobaric treatment is preferably carried out at a temperature above a value of 500 ° C. 36. The method according to any one of paragraphs.27-34, characterized in that graphite is used as the initial component of the non-solid crystalline phase, with the ratio of the components of the graphite and the ultrafine additive from 0.99-99.00 to 99.00-0.99 weight. %, and thermobaric treatment is preferably carried out at a temperature above 700 ° C. 37. The method according to any one of claims 27-34, characterized in that a mixture of graphite and hexagonal boron nitride is used as the initial component of the non-solid crystalline phase at a component ratio of 0.99-99: 99-0.99 wt.%, And thermobaric the treatment is preferably carried out at a temperature above 700 ° C. 38. The method according to any one of paragraphs.27-37, characterized in that the thermobaric treatment is carried out for 20-300 C. 39. The method according to § 38, wherein the thermobaric treatment is carried out for preferably 40-80 s.