RU2118672C1 - Diamond monocrystal synthesis method and reactor - Google Patents

Abstract

FIELD: synthesis of diamond monocrystals from low-molecular carbonaceous compounds. SUBSTANCE: reactor has housing 1 formed as shell 2 with closure 3 and bottom 4, burden charging unit 13, reaction product discharge unit 16, burden heating unit 20, carbonaceous (hydrocarbon), nitrogen-bearing and alloying substance charging unit 27, water steam supplying unit 50 (nozzles), cooling heat-exchanger 6, diamond monocrystal retaining unit 41, gaseous reaction product discharge branch pipe 14 provided with pressure regulating valve 15. Method involves charging burden of predetermined composition into housing 1 through charging unit 13 so that it fills 2/3 of housing cavity; switching on burden heating unit 20 operating on oxygen-hydrocarbon or air-hydrocarbon components; providing local (successive) heating of burden to temperature exceeding 1,500 C, with oxidant excess coefficient being equal to 0.85-1.05; introducing hydrocarbon and, when required, alloying substances into formed ascending flow of heterogeneous medium through unit 27 so that excess coefficient reaches 0.25-0.85; providing zonal cooling of heterogeneous medium in layer adjacent to wall by means of heat-exchanger 6 to temperature of 750-1.050 C to form convective circulating flows of heterogeneous medium, in which synthesized diamond monocrystals 42 are fixed at pressure of 0.12-16 MPa in cooling medium on horizontal combs 43. Nitrogen or air or nitrogen-bearing low-molecular compounds or elements of 111 or V groups of periodic system may be introduced into heterogeneous medium. Water steam may be introduced into heterogeneous medium in an amount of 0.15-150% of total current flow rate of hydrocarbon added into burden. Upon termination of process, combs 43 are turned through 90 deg, diamond monocrystals are lowered to discharge zone, pressure in reactor is reduced to normal value and diamond monocrystals are discharged from reactor through discharge unit 16. EFFECT: increased efficiency by providing high carat diamond crystal synthesis. 7 cl, 4 dwg, 1 tbl

Description

 The invention relates to methods for the synthesis of diamond crystals (KA), and more specifically to methods for the synthesis of single crystals of diamond (MCA) from low molecular weight carbon-containing compounds at high temperatures under the conditions of essentially non-stationary processes in heterogeneous silicate systems.

 A known method of producing artificial diamond, which consists in the fact that a sample of graphite and metal is subjected to pressure and heating by passing an electric current pulse through the sample (USSR patent N 1820890, C 01 B 31/06, 1993).

 The disadvantage of this method is the lack of potential for producing single crystals of high carat diamond.

 A device for producing artificial diamond is known, comprising a housing with units for heating and supplying carbon-containing gas (ed. St. USSR N 327776, C 01 B 31/06, 1983).

 A disadvantage of the known device is the lack of the possibility of obtaining high-carat diamond single crystals in it.

A known method for the synthesis of single crystals of diamond, which consists in the fact that diamonds are synthesized in a mixture at high temperature and when a carbon-containing gas is supplied. The polycondensation process is carried out in a macroscopic open catalytic system with a constant supply of the initial carbon-containing compounds CH ₄ , CO, etc. or their mixtures with oxidative products CO ₂ , H ₂ O and others in alkaline melts (KOH, KOH + MgO) under stationary nonequilibrium conditions in the system, including due to the constant removal of oxidizing products CO ₂ , H ₂ O, etc. (A. P. Rudenko, I. I. Kulakova and V. L. Skvortsova "Chemical synthesis of diamond. Aspects of the general theory", Advances in chemistry , 62 (2), 1993, pp. 104-105 prototype).

 The disadvantage of this method is the impossibility of synthesizing single crystals of high carat diamond with desired, including semiconductor properties.

 A well-known reactor for the synthesis of diamond single crystals, containing a housing with nodes for heating and supplying carbon-containing gas (A.P. Rudenko, I.I. Kulakova and V.L. Skvortsova "Chemical synthesis of diamond. Aspects of the general theory". Advances in chemistry, 62 (2), 1993, pp. 104-105, prototype).

 A disadvantage of the known reactor is the impossibility of synthesizing high carat diamond single crystals with desired, including semiconductor, properties.

 The basis of the invention is the task of creating a method for the synthesis of diamond single crystals, in which it is possible to synthesize single crystals of high carat diamond, including those with semiconductor properties.

The task of creating a method for the synthesis of diamond single crystals is solved by the fact that in the method for the synthesis of diamond single crystals, which consists in the fact that diamonds are synthesized in a charge at a high temperature and when a carbon-containing substance is fed, according to the invention, a charge composed of components, the total composition of which is expressed in terms of oxides of its constituent elements, corresponds to: SiO ₂ - 25-44%; MgO - 15-30%; Al ₂ O ₃ - 1.5-9%; Fe ₂ O ₃ - 4-10%; FeO - 1.5-10%; K ₂ O - 1.5-7%; Cr ₂ O ₃ - 0.2-3%; Na ₂ O - 0.05-2%; CaO - 0.5-11%; MnO - 0.01-0.5%; TiO ₂ - 0.6-4%; CO ₂ - 0.05-11%; H ₂ O - 0.5-20%, as well as 0.5-5% of chloride compounds or metal halides of groups I, II of the periodic system of elements; consumable components are introduced into the charge: an oxidizing substance - oxygen or a mixture of oxygen and nitrogen, or air or their mixture with nitrogen-containing low molecular weight compounds with a nitrogen flow rate of 1 to 80% of the flow rate of unbound oxygen and, as a carbon-containing substance, a hydrocarbon combustible substance with an oxidizer excess ratio of 0.85-1.05, and when the temperature of the resulting heterogeneous wednesday its 1500 ^o C therein introduce additional carbonaceous substance - a substance with low molecular weight hydrocarbon by adjusting the equivalence ratio of oxidant to 0.25 - 0.85 and implementing the zonal cooling to 750-1050 ^o C temperature to form the natural convective flow patterns of the heterogeneous medium, while the synthesized diamond single crystals are fixed in the cooled zones of the circulation flows of a heterogeneous medium, the temperature in which is from 1400 ^o C to 750 ^o C at a pressure of 0.12 to 16 MPa.

The use of a mixture composed of components, the total composition of which, expressed through the oxides of its constituent elements, is: SiO ₂ - 25-44%; MgO - 15-30%; Al ₂ O ₃ - 1.5-6%; Fe ₂ O ₃ - 4-10%; FeO - 1.5-10%; K ₂ O - 1.5-6%; Na ₂ O - 0.05-2%; Cr ₂ O ₃ - 0.1-3%; CaO - 0.5-10%; Mn - 0.01-1.1%; TiO ₂ - 0.1-6%; CO ₂ - 0.05-11%; H ₂ O - 0.5-20%, as well as 0.5-5% of chloride compounds or metal halides of groups I, II of the periodic system of elements, the introduction of the charge components: oxidizing substance - oxygen or a mixture of oxygen with nitrogen, or air , or mixtures thereof with nitrogen-containing low molecular weight compounds with a nitrogen flow rate of from 1 to 80% of the flow rate of unbound oxygen and hydrocarbon combustible substances, followed by their combustion with an excess coefficient of oxidizing agent equal to 0.85-1.05, heating the mixture to a temperature of more than 1500 ^o C followed by introduction into the formed a heterogeneous medium as a carbon-containing substance of low molecular weight hydrocarbon substances and alloying elements, bringing the oxidizer excess coefficient to 0.25-0.85 while simultaneously zoning it to a temperature of 750-1050 ^o C with the formation of natural convective circulation flows of a heterogeneous medium, with fixation of the synthesized single crystals of diamond in the cooled zones of the circulation flows of a heterogeneous medium, the temperature in which is from 1400 to 750 ^o C with the process under pressure from 0.2 to 16 MPa, after reaching a charge temperature of more than 750 ^o C, during the formed, repeatedly repeated thermodynamic cycles (full convective circulations of flows of a heterogeneous medium), the following can be sequentially performed:
- intensive generation of a cleavage component - SiR - silicon carbide SiC (in a high-temperature heterogeneous medium at T _rc > 1500 ^o C during the introduction of low molecular weight hydrocarbon compounds into it, bringing the coefficient of excess oxidizer in it to 0.25-0.85 (hydrocarbon pyrolysis reaction and polycondensations);
- generation of splittable components (of the type A _k B _c Si _m O _n , where A is the mono- or divalent metals K, Ma, Ca, Mg, Fe, Mn; B is the trivalent metals Al, Fe, Cr or O ₂ (oxygen) ; k, c, m, n are the coefficient ratios of atoms in an elementary crystalline cell, which can take values: k = 1,2,3; c = 1,2,3; m = 1,2 or 3; n = 6, 7,8,9,10,12 or 16), formed during intensive cooling of a heterogeneous medium to a temperature of 750-1050 ^o C (with the removal of heat to useful consumers or energy converters);
- automatic chain reactions of the cleavage of high-modulus silicates (CV RVS) in a cooled heterogeneous medium (at T _rc - 750-1050 ^o C) during the interaction of IUD microcrystals of the form A _k B _c Si _m O _n with SiC microparticles embedded in them with the release of energy and periodically repeated microimpulses of pressure and temperature in a heterogeneous medium of the charge melt as a result of chain reactions of the splitting of high-modulus silicate systems, leading to the formation of the necessary energy and catalytic properties of the active erogennoy medium (AGS) and intense and steady process of synthesizing diamond single crystal;
- additional oxidation of the decomposition products of the IUD to complete oxides in the zone of introduction of the oxidizing substance — oxygen into the heterogeneous medium (with heat evolution and closure of the thermodynamic cycle).

Fixing the synthesized diamond single crystals in the resulting heterogeneous medium allows one to obtain diamond single crystals with uniform characteristics, including a given habit due to the creation of stable energy and chemical parameters of the AGS surrounding each diamond single crystal, starting from the moment of reaching the mass of single crystals of more than 1-2 carats, and maintaining synthesis of diamond single crystals at elevated pressures in the range of 0.1-16.0 MPa after reaching a charge temperature of more than 750 ^o C leads to an increase in the speed of images the formation of fissile components and the regeneration of high-modulus silicates and, ultimately, a more intensive process of RV RVS and, accordingly, accelerated synthesis of MCA, and when a mixture of oxygen with nitrogen or air, or their mixture with nitrogen-containing low-molecular compounds, is introduced into the charge as an oxygen-containing oxidizing substance, for example , NH ₃ , HNO ₃ , KNO ₃ , CaCN ₂ and others with a flow rate of 1 to 80% of the mass flow of free oxygen, allows you to implement an intensive gene process in a heterogeneous medium at a temperature of more than 1200 ^o C radios of nitrogen-containing cleaving (SiR) components (nitrides), for example, Si ₃ N ₄ (exothermic reaction), the interaction of which (along with SiC) with high-modulus silicates, in the temperature range from 750 to 1450 ^o C (in the cooled zone) initiate RVS RVS with pulsed energy release, the formation of nitrous oxide, which immediately decomposes in a spontaneous chain reaction with the formation of nitrogen-containing radicals and cyanides (for example, KCN, CaCN ₂ , etc.), the cyanide ions of which in their catalytic properties are similar to halide ions, which together leads in ptimalnyh energy and catalytic conditions state ACS to the formation of nitrogen-containing peripheral functional groups in the boundary layer of diamond - AGS with subsequent "Attaching" a macromolecule diamond during dynamic compaction of the boundary layer under the influence of the detonation of the microwaves arising during the flow of the CR PBC re-generation Si ₃ N ₄ , the continuation of the initiation of the RV RVS with their gradual attenuation as the aircraft and RK develop at the end of each convective cycle (during convective circulation of the hetero environment), which together allows one to synthesize nitrogen-containing diamond single crystals with high physical and mechanical properties (5-10% higher than that of nitrogen-free diamonds) due to the formation of a wide range of nitrogen defects in diamond microcrystals.

 Along the way, during the process of synthesis of MCA, a large amount of heat is released, which must be removed from the cooled zones of the gas station and which should be directed to useful consumers and energy converters.

 It is advisable to introduce alloying elements of the third or fifth group of the periodic system of elements into the mixture or introduced hydrocarbon substances in an amount of 0.05-7 wt.%.

The introduction of alloying elements of the third or fifth group of the periodic system of elements into the mixture or introduced hydrocarbon substances in an amount of 1-7 wt.% Allows to obtain diamond single crystals with semiconductor properties by ensuring uniform introduction of alloying elements at first into peripheral functional groups, and then their "suturing" into the crystal structure of diamond and their subsequent “pulling” during the rapid growth of the diamond crystal lattice with the formation of distortions and structural disturbances in it in the vicinity of the formed defects, which in turn can initiate:
a) the next introduction of an interstitial doping atom; b) the formation of a vacancy; c) energetically non-optimal or only partial involvement of valence bonds of atoms, which, when a diamond crystal is cooled, will lead to the formation of a vacancy and instertial and, together, allows programmatically synthesizing n- and p-type semiconductor diamond single crystals.

 It is advisable to introduce water vapor into the cooled heterogeneous medium in an amount of from 25 to 150 wt.% Of the total current consumption of hydrocarbons in the charge.

The introduction of water vapor into the cooled heterogeneous medium in an amount of 25 to 150 wt.% Of the total current flow rate of hydrocarbons introduced into the charge allows the remaining part of the “unreacted” carbon from SiO ₂ to be converted to carbon monoxide, with the formation of an optimal redox environment, to activate the process of formation of AGS and, as a result, synthesize MCAs with an improvement in their quality and a decrease in the consumption of hydrocarbons by 6-14%.

 Another objective of the invention is the creation of a reactor for the synthesis of diamond single crystals, including those with semiconductor properties and the associated production of thermal energy.

 The task of creating a reactor for the synthesis of diamond single crystals is solved by the fact that in the reactor for the synthesis of diamond single crystals containing a housing with heating, supplying carbon-containing substance units and a reactor control unit according to the invention, the reactor housing is made in the form of a shell with a lid and a bottom and is equipped with external heat-insulating coating, the shell of the shell is made in the form of a pear-shaped body of rotation with a neck in the region of the lid, the reactor is equipped with a cooling heat exchanger with inlet and outlet holes and holes located on the shell of the body, in the lid, neck and bottom, are hermetically connected along the external perimeter, respectively, with the charge loading unit, a pipe for removing gaseous reaction products, and a reaction product discharge unit located outside the case in the body cavity, with side of the bottom, successively one above the other along its axis of symmetry and concentric with it, a heating unit is installed, comprising at least one block consisting of injectors for introducing an oxidizer and fuel, equipped with a candle in ignition, and located in the bottom zone, the input unit of carbon-containing and dopant substances, containing at least one nozzle of the input of hydrocarbon and dopant substances and placed in the area between the heating unit and 1/3 of the height of the cavity of the body, with holes made in the bottom and shell, and the nozzles are communicated through nozzles passing through the holes and hermetically fixed along the outer perimeter of the holes on the bottom and the shell of the housing, respectively, with the manifolds for the supply of oxidative, hydrocarbon mountains moreover, carbon-containing and dopant substances, moreover, the reactor control units are made in the form of control valves installed at the inlet on all collectors and at the inlet pipe of the heat exchanger, while radial openings are made in the shell of the housing along its circumference from the bottom and in its middle part, in which and through which in the cavity of the casing the fixing units of diamond single crystals are installed, made in the form of rods with a variable "comb-like" profile, with the possibility of their movement, respectively, along and relative relative to the axis of the hole.

 The execution of the reactor vessel in the form of a shell with a lid and the bottom, the supply of its external heat-insulating coating, the execution of the shell in the form of a rotation body of a "pear" shape with a neck in the region of the cover, the equipment of the reactor vessel with a cooling heat exchanger with inlet and outlet pipes, execution in the cover, neck and the bottom of the holes, hermetically connected along the outer perimeter with, respectively, the loading unit of the charge of the gateway type, a pipe for the removal of gaseous reaction products and a discharge unit of the reaction products in the cavity of the housing from the bottom along the axis of symmetry of the housing one above the other of the heating unit, including at least one unit consisting of injectors of the oxidizer and fuel, equipped with a spark plug, and placing it in the bottom zone, the input unit of carbon-containing and alloying substances, containing at least one nozzle for introducing hydrocarbon and dopant substances and located in the area between the heating unit and 1/3 of the body cavity height, making holes in the bottom and shell of the case through which the nozzles by means of nozzles sealed around the outer perimeter of the holes, respectively, they are connected to the manifolds for supplying oxidizing, hydrocarbon fuel, carbon-containing and alloying substances located outside the casing, installation on the collectors and inlet pipe of the heat exchanger cooling valves-regulators that act as control units of the reactor, in the shell of the body, in its middle and bottom parts, of the radial holes in which and through which the fixation nodes are installed in the body cavity diamond single crystals, made in the form of rods with a variable comb-shaped profile, with the possibility of their movement, respectively, along and relative to the axis of the hole, provides: loading the charge, heating it, carrying out chemical reactions and CR of RVS in the formed active heterogeneous medium, synthesis of high-carat ICA in the near-wall cooled zone of the reactor in the process of convective circulation of AGS flows, the ability to control the MCA parameters, their output from the reactor cavity by removing the MCA clamps, followed by th ACS with MCA through the drain assembly (the recommended subsequent foaming heterogeneous medium and recovering the mAb by known techniques).

 It is advisable to place nozzles for introducing water vapor directly inside the vessel directly in the bottom zone of the reactor and its middle part concentrically relative to its axis.

 The placement of water vapor injection nozzles in the bottom zone of the reactor and its middle part concentric with respect to its axis makes it possible to uniformly introduce water vapor into the AGS in the areas before the AGS enters the heating zone and after the formation of SiR with programmed cooling of the AGS, transferring the remaining part of the graphite formed in the process polycondensation of hydrocarbons into carbon monoxide, with the simultaneous formation of conditions for creating an optimal redox environment, which allows you to intensify the process of diamond Azov with an improvement in the quality of synthesized single crystals of diamond, while reducing the flow of hydrocarbons by 6-14%.

 It is advisable to arrange the nozzles of the nodes for introducing water vapor, carbon-containing and alloying substances tangentially relative to the sectional plane of the housing perpendicular to its axis.

 The location of the nozzles of the steam inlet nodes tangentially relative to the sectional plane of the casing, perpendicular to its axis, makes it possible to uniformly introduce consumables into the AGS, contribute to the formation of vortex convective (circulating) flows of the AGS, their mixing and alignment of the temperature fields of the AGS in the wall zone (MCA growth zone ), which together provides the synthesis of MCA with uniform characteristics (according to the levels of MCA location in the reactor).

 It is advisable to provide the reactor with an additional tubular cooling heat exchanger, made in the form of a spiral and mounted on the inner surface of the shell of the shell.

 The installation of an additional tubular cooling heat exchanger, made in the form of a spiral, mounted on the inner surface of the casing, allows for more efficient cooling of the AGS in the wall zone, simplify the design of the reactor, use non-deficient construction materials, reduce heat loss, increase the working pressure in the reactor, and increase its working life .

 In FIG. 1 shows a structural diagram of a reactor for the synthesis of diamond single crystals; in FIG. 2 - the location of the nozzles for introducing water vapor into the reactor; in FIG. 3 is a structural diagram of a reactor with a tangential arrangement of nozzles for the injection of consumables; in FIG. 4 - location of an additional tubular spiral heat exchanger in the reactor.

 The reactor contains a housing 1 (see Fig. 1), consisting of a shell 2, a cover 3 and a bottom 4. The upper part of the shell in the vicinity of the cover is made in the form of a neck 5. A cooling heat exchanger 6, for example, a slotted type with a supply pipe, is integrated in the housing 1 7 and a discharge pipe 8. A heat-insulating coating is installed on the outside of the reactor vessel 9. Holes 10, 11, 12 are made in the cover, neck, and bottom, in which, respectively, the charge loading unit 13, pipe 14 for removing gaseous reaction products with set to n m valve 15 the pressure control assembly 16 discharge the reaction products (letka) comprising a control mechanism 17 of valve 18.

 In the cavity 19 of the housing 1 from the bottom 4, successively one above the other along its axis of symmetry and concentrically installed there is a heating unit 20, including at least one block 21 (or several blocks, see Fig. 2), consisting of nozzles 22 for entering the oxidizer and fuel 23 provided with a spark plug 24, and nozzles 25, 26, a carbon-containing and dopant substance injection unit 27, consisting of at least one nozzle 28 (or several nozzles, see FIG. 3), a nozzle 29 located between the heating unit 20 and 1/3 of the height of the cavity of the housing 1. In d 4 and a shell 2 are provided with openings 30 through which nozzles 25, 26 and 29 pass, communicating nozzles 22, 23 and 28 with manifolds 31, 32, 33 and 34 for supplying consumables, respectively, oxidizing, hydrocarbon, carbon-containing and alloying substances, while the nozzles 25, 26 and 29 are hermetically connected to the walls of the housing 1 along the outer perimeter of the holes 30. At the inlet to the collectors of consumables 31-34, reactor control units are installed in the form of control valves 35, 36, 37, 38, and control valves 39 and 15 mounted on the inlet ohm branch pipe of the cooling heat exchanger and branch pipe of the removal of gaseous reaction products. In the middle and bottom part of the shell 2 there are made radial holes 40, in which and through which the nodes 41 for fixing single crystals of diamond 42 made in the form of rods with comb-like protrusions 43 (with the possibility of axial and reciprocal movements along the axis of the hole), a mixture of oxygen with nitrogen or (heated) air, or a mixture of them with nitrogen-containing low molecular weight compounds, is fed through the nozzles 22 of the oxidizing agent or partially (low molecular weight) connection) through the nozzle 28 of the input ulgerodsoderzhashchih substances.

 The charge loading unit 13 can be made in the form of a small cone 44, which closes the feed funnel 45, and a large cone 46, which closes the outlet funnel 47, of the storage hopper 48. The small and large cones 44 and 46 are mounted with the possibility of separate axial movement, while the cavity of the storage the hopper 48 is in communication with the cavity of the housing 1 through the equalizing valve 49 (Fig. 1, 2, 4).

 The reactor can be equipped with nozzles 50, 51 for introducing water vapor concentrically placed with respect to its axis directly in the bottom part of the reactor and in its central zone above the inlet 27 of carbon-containing and alloying substances communicated by nozzles 52 with a flow control valve 53 (Fig. 2).

 The nozzles 28 of the input unit 27 of carbon-containing, alloying substances and water vapor can be installed tangentially relative to the sectional plane of the housing perpendicular to its axis (Fig. 3).

 The reactor can be equipped with an additional tubular heat exchanger 54, made in the form of a spiral and mounted on the inner surface of the shell 2 of the housing 1 (Fig. 4).

 The method of synthesis of single crystals of diamond is as follows.

In the housing 1, through the charge loading unit 13, a charge is loaded, the total composition of which, expressed through the oxides of its constituent elements, is: SiO ₂ - 25-44%; MgO - 15-30%; Al ₂ O ₃ - 1.5-6%; Fe ₂ O ₃ - 4-12%; FeO - 1.5-10%; K ₂ O - 1.5-6%; Na ₂ O - 0.05-2%; Cr ₂ O ₃ - 0.1-3%; CaO - 0.5-10%; Mn - 0.01-1.1%; TiO ₂ - 0.1-6%; CO ₂ - 0.05-11%; H ₂ O - 0.5-20%, as well as 0.1-5% of chloride compounds or metal halides of groups I-III of the periodic system of elements (with an acceptable content of background impurities of other elements in the amount of not more than 1.5 wt.%) .

 The loading of the reactor is carried out by batch feeding the charge into the feed funnel 45, after which the small cone 44 is lowered, the charge is poured into the storage hopper 48, the cone 44 is closed. The equalizing valve 49 opens, the large cone 46 is lowered, the charge is poured into the reactor cavity 19, the cone 46 rises. The loading process is repeated until the cavity 19 of the reactor is filled into 2/3 of the volume. Comb 43 of the MCA fixation unit 41 is installed in a horizontal position with simultaneous axial movement of it to a predetermined zone of the reactor. After this, the spark plug 24 is turned on, valves 35 and 36 open, the process of heating the charge begins with an excess coefficient of the oxidizing agent equal to 0.85-1.05. At the same time, the valve 39 for supplying the coolant (water vapor, water) to the cooling heat exchanger 6 opens.

At a charge temperature of more than 350 ^o C, the process of chlorination of free silica begins when it interacts with chlorinating agents contained in the charge, which is necessary to prepare the surface of SiO ₂ particles for carbonization in order to increase the efficiency of the process of SiC formation.

At the same time, the valve 37 of the node 27 for supplying a hydrocarbon substance, for example, CH ₄ , CH ₂ O ..., is turned on at a flow rate corresponding to providing an oxidizer excess coefficient of 0.25-0.85, due to the pyrolysis of which SiO ₂ particles are enveloped by soot carbon.

When the temperature of the mixture reaches approximately> 750 ^o C, the pressure control valve 15 is turned on and the set working pressure in the reactor is set (from 0.12 to ≈16 MPa).

The mixture, heated to a temperature of more than 1500 ^o C in the central zone of the reactor, section AB (see Fig. 1, 2), passes into the melt - a heterogeneous medium (HS), in which, when interacting with carbon-containing substances, the formation of SiC begins ( SiR is a cleavage component, region B-C) with the simultaneous formation of a reducing medium (due to the pyrolysis of hydrocarbons) in the HS.

During the resulting convective flows, the HS rises to the middle part of the reactor cavity, interacts with a relatively cold charge and introduced hydrocarbon gases and is somewhat cooled (to a temperature below 1450 ^o C), which leads to the onset of crystallization of high-modulus silicates (A) of the form A _k B _c Si _m O _n (with SiC particles already embedded in them (see the CD section [Fig. 1, 2]) and the formation of an active heterogeneous medium (AGS). With further cooling of the AGS during its convective movement along intensively cooled reactor walls (section DE ) BC crystallization continues and at the same time, as a result of the interaction of silicates of the type A _k B _with Si _m O _n , for example, KAlSi ₃ O ₈ (orthoclase), NaAlSi ₃ O ₈ (albite), Ca ₃ Cr ₂ (SiO ₄ ) ₃ (ouvarit) , Mg ₃ Al ₂ (SiO ₄ ) ₃ (pyrope), Ca ₃ Fe ₂ (SiO ₄ ) ₃ (andratite), Ca ₃ Al ₂ (SiO ₄ ) ₃ (grossular), K ₂ OSiO ₃ O ₆ , Na ₂ OSiO ₆ and others with a silicon-oxygen-free compound SiR (where in this case R is carbon), a well-known chain reaction of the cleavage of the above high-modulus silicates (CR RVS) develops [Kulikov A.I. "Power unit of a thermal power plant using a new energy source with renewable energy resources." Izv. AN Energy, N 4, 1992, pp. 104-110; Kulikov A.I. "Thermal unit on a new source of energy in industrial energy." Prom. energetics, N 4, 1992, pp. 10-14] with the release of energy and subsequent self-heating of the mixture, which leads to an increase in the liquid phase fraction of high-modulus silicates of the type A _k B _c Si _m O _n and the initiation of local detonation-type chain reactions with high energy release but low gassing (low propelling ability).

Theoretically, for the decomposition process to start, for example, Na ₂ OSi ₃ O ₆ under the influence of silicon-oxygen-free compounds, an external supply of the initial energy Q _{o is} necessary from the outside.

The result is the formation of silicate Na ₂ OSi ₃ O ₆ in the liquid phase, which is part of the critical mass (m _o ).

где
MS¹ - расщепляемый в 1 звене цепи силикат;
Q₁ - теплота в 1 звене цепи;
K¹ - константа химического взаимодействия в 1 звене цепи;
K $\genfrac{}{}{0ex}{}{\text{1}}{\text{1}}$ - константа фазового превращения в 1 звене цепи;
α - коэффициент реакции;
SiR - кремнийбескислородное соединение;
(тв), (ж) - индексы, характеризующие агрегатное состояние вещества.As a result of this transformation, according to the energy chain, a chain reaction begins to develop:

Where
MS ¹ - silicate split in 1 chain link;
Q ₁ - heat in 1 chain link;
K ¹ - constant chemical interaction in 1 chain link;
K $\genfrac{}{}{0ex}{}{\text{1}}{\text{1}}$ - phase transformation constant in 1 chain link;
α is the reaction coefficient;
SiR - silicon-oxygen-free compound;
(tv), (g) - indices characterizing the state of aggregation of a substance.

As a result, the initial mass of silicate in the solid phase changes to a critical mass of M ₁ , and subsequently, accordingly, to critical masses of M ₂ , M ₃ ... M _n .

This decay of the critical mass of silicate will be due to the supply of heat Q ₁ , Q ₂ . ..Q _n , which is liberated during the above reaction of the formation of silicate Na ₂ OSi ₃ O ₆ in the liquid phase with a silicon-oxygen-free compound.

A constant supply of heat Q _n and a decrease in the critical mass of silicates will lead to an increase in the formation of Na ₂ OSi ₃ O ₆ silicate in the liquid phase, and the consequence of this process is the emergence of new decomposition chains of this silicate under the influence of SiR according to the chain mechanism with the release of energy exponentially. In this case, the "chemistry" of the chain process in silicates plays the role of a kind of "stoker" in the splitting of the critical mass (when supplying portions of heat). At the same time, new portions of silicate are released in the liquid phase, and this, in turn, causes an avalanche-like chain reaction with energy release through the following chain reaction:
Upon the complete transition of the critical mass of silicate M _n to the liquid state M _k , abrupt release of reaction by-products and energy (explosion) occurs, as is seen with a low emission of gaseous reaction products and, accordingly, with low propelling ability, but high pressure behind the detonation wave front (in local areas with prepared conditions for the course of the RV RVS), which leads to the formation of diamond matter, and then the formation of conditions for the growth of MCA.

A feature of the physicochemical reactions of RVS is their auto-regulation in the temperature range 750-1500 ^o C with the simultaneous regeneration of energy components (subject to the thermodynamic balance and supply of the necessary gaseous components - O ₂ , N ₂ , CO ₂ , H ₂ , etc. and the presence of zones AGS cooling), which provides long “survivability” times of an active heterogeneous medium.

 In the general case, the directivity (type) of the RVS RV - (controlled reaction, detonation process, or combined type of reactions) is a function of the type and concentration of high-modulus silicates and SiR, the temperature regime in the reaction zone, and the catalytic properties of the system.

The most optimal type of CV RVS for the proposed process of diamond formation is the combined type of TsR RVS, occurring in diluted active heterogeneous media (SiO ₂ content <44%), in which the flow of TsR RVS is accompanied by the generation of local wave processes with high pressure and temperature zones behind the front of detonation waves accompanied by the decay of molecules, the processes of dissociation of carbon-containing molecules, with simultaneous compaction of the boundary layer (AGS - diamond) during the process of diamond polycondensation (graph ita).

 In the general case, during the growth process, a diamond crystal is a bulk macromolecule consisting of a carbon core and peripheral functional groups (PFGs) localizing the free valencies of carbon atoms on the surface of a diamond crystal.

V_ал > V_гр; V_о(ал) << V_о(гр),
т. е. в пограничном слое (независимо от фазы процесса) должны быть сформированы и автоматически поддерживаться оптимальные окислительно-восстановительные условия при обеспечении соответствующих (необходимых) каталитических свойств (прямого и обратного действия) активной гетерогенной среды (АГС) в ходе динамического синтеза алмаза при широкой вариации кинетических и макрокинетических условий протекания реакций - от близких к равновесию до предельно неравномерных с фазами протекания локальных микродетонационных процессов с генерацией ударных микроволн, обеспечивающих уплотнение атомов углерода и легирующих элементов при их вхождении в углеродное ядро (кристалл) и образование новых ПФГ, в то время как гетерогенная среда должна выполнять функции поставщика необходимых соединений и элементов (в том числе энергетических и легирующих) в пограничную зону АГС - АЛМАЗ и обеспечивать отвод излишков CO₂ и H₂O, что и реализуется в предлагаемом процессе синтеза МКА.In the proposed method for the synthesis of diamond, the entry of each new carbon atom (or block of atoms) into the diamond (or graphite) lattice and the formation of the corresponding chemical bonds is due to the kinetics of the polycondensation of the initial carbon-containing molecules with reaction groups in the boundary layer — genealogical precursors of diamond or graphite (preferably having a crystal structure correspondence with the arrangement of carbon atoms on the faces of diamond). The transition of atoms (carbon, etc.) from the boundary layer to the crystal should be accompanied by the process of their compaction under the following conditions:
- the rate of formation of diamond (V _{al is} higher than the rate of formation of graphite (V _g ), and most importantly, the rate of oxidation of graphite V _{(g) is} much higher than the rate of oxidation of diamond V _{o (diamond)}

V _al > V _gr ; V _{o (al)} << V _{o (gr)} ,
i.e., in the boundary layer (regardless of the phase of the process), optimal redox conditions should be formed and automatically maintained while ensuring the corresponding (necessary) catalytic properties (direct and reverse action) of the active heterogeneous medium (AGS) during the dynamic synthesis of diamond at a wide variation of the kinetic and macrokinetic conditions for the course of reactions - from close to equilibrium to extremely uneven with the phases of local microdetonation processes with generation shock microwaves providing compaction of carbon atoms and alloying elements when they enter the carbon core (crystal) and the formation of new PFGs, while a heterogeneous medium should serve as a supplier of the necessary compounds and elements (including energy and alloying) to the AGS boundary zone - DIAMOND and to ensure the removal of excess CO ₂ and H ₂ O, which is implemented in the proposed synthesis process of MCA.

So, in the melting zone of the charge (section AB, Fig. 1, 2) at a temperature of more than 1500-2200 ^o C a heterogeneous medium is formed (molten silicates + crist. Phase + gas).

 After the introduction of hydrocarbons into the HS (section B-C) as a result of their pyrolysis, the HE is saturated with free carbon and the intensive formation of SiC begins.

Теоретически процесс образования алмаза в АГС может протекать по широкой гамме реакций, например, по пути поликонденсации из углеводородов:
CH₂ ⇄ C_ал. + 2H₂
С₂H₂ ⇄ 2C_ал. + H₂,
с возможными сопутствующими термодинамическими процессами поликонденсации алмаза (графита)

а также реакций с участием твердофазных компонентов:

Одновременно происходит интенсивная генерация SiC, который образуется при взаимодействии SiO₂, SiO (продукт РВС) и подаваемых в активную зону углеводородных компонентов, например C, CH₄, CH₂O и др. в присутствии катализаторов, например хлористых соединений KCl, NaCl или галогенидов металлов I-II групп периодической системы элементов (ПСЭ).During the cooling of the HS (CD section) below a temperature of 1450 ^o C, the BC crystallization process begins with the formation of AGS, characterized by the onset of the RV RVS with the formation of the optimal redox environment for the formation of diamond matter:
C _gr + H ₂ O ⇄ CO + H ₂
C _gr + CO ₂ ⇄ 2CO

Theoretically, the process of diamond formation in AGS can proceed along a wide range of reactions, for example, along the path of polycondensation from hydrocarbons:
CH ₂ ⇄ C _al. + 2H ₂
C ₂ H ₂ ⇄ 2C _al. + H ₂ ,
with possible concomitant thermodynamic processes of polycondensation of diamond (graphite)

as well as reactions involving solid-phase components:

At the same time, intense generation of SiC occurs, which is formed by the interaction of SiO ₂ , SiO (the product of PBC) and hydrocarbon components fed into the active zone, for example C, CH ₄ , CH ₂ O, etc. in the presence of catalysts, for example, chloride compounds KCl, NaCl or halides metals of I-II groups of the periodic system of elements (PSE).

However, in the zones of intense flow of the CV of the RVS, AGS overheating is possible (at T _ags - 1200-1450 ^o C), which will lead to a decrease in the intensity of the CR and, accordingly, to a sharp decrease in the rate of diamond formation.

Одновременно увеличивается интенсивность ЦР РВС (участок D-E, фиг. 1), что обусловлено высокой концентрацией BC, расщепляющего компонента SiC и оптимальной температурой АГС T_агс.ср. - 800-1200^oC в пристеночном слое. В ходе циркуляции АГС растущие МКА, при достижении размеров, превосходящих размер проходного сечения гребенки 43, задерживаются в ней до окончания процесса синтеза МКА.To intensify the process of diamond formation, it is necessary to regenerate AGS with an excess content of the liquid phase in AGS with a high content of high-modulus silicates. For this, AGS, as the content of the liquid phase increases, it is necessary to continue to cool to a temperature below the onset temperature of crystallization of high-modulus silicates, but at the same time maintain high fluidity (mobility) of the AGS, i.e. to a temperature of 750-1050 ^o C. AGS cooling is achieved by the fact that the formed AGS upstream (section CD, Fig. 1), due to the presence of a temperature gradient and bubbling of the AGS by hydrocarbon gases, interacts with the charge in the upper part of the reactor, cools, and begins the process of regeneration (crystallization) of high-modulus silicates during their immersion along the cooled walls of the reactor vessel 1 (sections CD and DE), for example

At the same time, the intensity of the RV RVS (site DE, Fig. 1) increases, which is due to the high concentration of BC, the cleaving component of SiC and the optimum temperature of the AGS T _ags. - 800-1200 ^o C in the parietal layer. During AGS circulation, growing MCAs, upon reaching sizes exceeding the size of the passage section of comb 43, are retained in it until the end of the synthesis process of MCAs.

Next, the AGS stream again enters the heating zone (section AB), where its temperature rises from 750-900 ^o C to more than 1500 ^o C - at the stage of bringing the process to operating mode, and up to 1300-1600 ^o C - at the stage of steady-state working process In this case, BC cleavage products (SiO, SiO ₂ , CO, etc.) again interact with oxygen and hydrocarbon components introduced into the mixture (exothermic reactions predominate) and the process repeats again, forming stable circulation flows with working phases (energy-technological cycle):
Phase AB - heating the mixture to a temperature of more than 1500 ^o C with its transfer to a heterogeneous medium in order to prepare the conditions for the formation of fissile components (SiR) and the formation of convective circulating AGS flows. After the conclusion of the process to the operating mode, the temperature in the zone can be maintained in the range of 1300-1600 ^o C.

 Phase B-C — hydrocarbon pyrolysis, saturation of the HS with carbon, active generation of SiR, the beginning of the cooling of the HS with BC crystallization.

 Phase C-D - continued cooling of the HS, an increase in the concentration of SiR and BC microparticles, the beginning of the course of the RV RVS, the formation of AGS. When water vapor is introduced into the AGS, the formed carbon displaces hydrogen from the water, forming a reducing medium, and at the same time, the AGS is freed from carbon particles, which, during the further process of the formation of diamond matter, makes it possible to obtain diamond crystals of high purity.

Phase DE - recrystallization zone - intensive cooling of the AGS to a temperature of 750-1100 ^o C during the course of stable and intense CR of RVS with the creation of the most favorable conditions for the growth of large and high-quality diamond crystals in a dynamic growth-oxidation regime characteristic of the recrystallization zone. Moreover, diamond single crystals captured by dies 43 are constantly located in the zone with stable, but controlled AGS parameters, which makes it possible (unlike natural MCAs) to obtain MCAs with desired properties.

 At the same time, during the AGS cooling process, by means of a heat exchanger 6 and 54 (heat carrier - water vapor), heat is removed from the reactor to useful consumers and energy converters.

 Phase E-A is the return of the AGS flow to the high-temperature zone A-B with the additional oxidation of the products of the cleavage of BC with oxygen (air) ... and the closure of the energy technology cycle.

During the process, part of the final reaction products (olivines, etc.) having a density of g> 3.3-3.5 g / cm ³ - settles in the lower part of the reactor in the vicinity of the discharge unit, part settles on the walls with partial assimilation of H ₂ O and CO ₂ (contained in the AGS) parietal, relatively cold layer, for example:
4H ₂ O + 3Mg ₂ SiO ₄ = Mg ₆ [SiO ₄ O ₁₀ ] OH ₈
CO ₂ + M = MCO ₃
Where
M - Ca, Mn, Na, K, Mg,
with the subsequent formation of a carbonate-serpentine protective layer (3C), simultaneously performing the functions of thermal protection of the housing.

 Thus, the growth of MCA with the desired properties is carried out on fixators located in the near-wall chilled zone during a long process of circulation of (silicate) AGS under the conditions of controlled physical and chemical reactions of the RCS from carbon of hydrocarbon components introduced into the AGS, as well as in the near-wall layer in the middle and the lower part of the reactor when they are deposited in the carbonate-serpentine protective layer in the inclined or bottom part of the bottom of the reactor.

Upon completion of the synthesis of diamond single crystals (from 50 to 700 hours or more), the charge is stopped, the temperature of the heating units 20 is set T _AGS <1000 ^o C, the comb 43 is rotated into a vertical position, the MCA are lowered into the discharge zone, the pressure in the reactor rises to 0 , 12 MPa due to the supply of nitrogen or inert gas with the pressure control valve 15 closed, the drain assembly 16 is opened and the AGS is drained with the MCA located in them, for example, onto rotating cooled rollers installed with a gap of 30-40 mm while simultaneously foaming with an inert gas, followed by extraction of diamond crystals by known technologies.

A similar process is carried out when, as an oxidizing substance, a mixture of oxygen with nitrogen or (heated to> 300 ^o C) air, or their mixture with nitrogen-containing low molecular weight compounds, for example: NH ₃ , HNO ₃ , KNO ₃ , etc., is introduced into the charge (AGS) .d., with a content of nitrogen or nitrogen-containing compounds from 1 to 80% of the mass flow of unbound oxygen.

This leads to the formation of microparticles of silicon nitride Si ₃ N ₄ , which, along with SiC, is a cleavage component, in the interaction of nitrogen (N ₂ ) with SiO ₂ in the presence of hydrogen and metal halides of the I, II groups of PSE (during the course of the RC RVS). with silicates of the type A _k B _c Si _n O _n initiates the decomposition of the latter by a chain mechanism with the release of energy and the formation of nitrous oxide N ₂ O, which immediately decomposes by a spontaneous chain reaction (with a decay time of t _p = 0.002 s at T _AGS = 1100 ^o C)
5Na ₂ OSi ₃ O ₆ + 2Si ₃ N ₄ = 5Na ₂ SiO ₃ + 4N ₂ O + 16SiO
including, directly in the AGS boundary layer — diamond with the formation of nitrogen-containing peripheral functional groups and their “suturing” into diamond macromolecules in the process of dynamic compaction of the boundary layer under the influence of detonation waves from the RC of the RCS with the formation of the corresponding defects.

 At the same time, the growth rate of MCA increases and (while maintaining the heat productivity of the process), the consumption of hydrocarbons and oxygen to maintain a given temperature regime of the process decreases sharply.

Alloying elements of the third or fifth group of the periodic system of elements in the amount of 0.05-7 wt.%, For example, boron — B, lantonoids, yttrium — Y, etc., can be introduced into the mixture or introduced hydrocarbon substances, and the alloying elements can be introduced into the charge, including in the form of high-modulus silicates, for example (M _n , Y ₃ ) A ₁₂ (SiAl) ₃ O ₁₂ (spessartine) and others, which allows to obtain single crystals of diamond with semiconductor properties by ensuring uniform introduction of alloying elements first to peripheral functional ith groups, and then their “suturing” into the crystal structure of diamond with their subsequent “pulling in” with the rapid growth of the diamond crystal lattice with the formation of distortions and structural defects in it in the vicinity of the formed defects, which, in turn, can initiate:
a) the next introduction of an interstitial doping atom;
b) the formation of vacancies;
c) energetically non-optimal or only partial involvement of valence bonds of atoms, which, when the diamond crystals are cooled, will lead to the formation of vacancies and instertial and, together, allows synthesizing semiconductor n- and p-type diamond single crystals.

 The method is carried out as described above.

 When implementing the method, water vapor in the amount of 25 to 150 wt.% Of the total current flow of hydrocarbons into the charge can be introduced into the cooled heterogeneous medium through nozzles 50.

This leads to the formation of carbon monoxide, which is necessary for the diamond formation process, to purification of the HS from the solid phase of carbon and, as a result, the formation of “pure” MCAs, the formation of a reducing medium, and accelerated cooling of the HS in the interaction of free carbon contained in the HS with H ₂ O during its transition to the AGS, a decrease in the consumption of hydrocarbons by 6-14%.

 Otherwise, the method is carried out as described above.

Application examples of the method
1. In the housing 1 (with a capacity of 1.2 m ³ ) through the charge loading unit 13, a charge (2/3 of the volume of the reactor cavity) is loaded, composed of components: iron ore pellets, kaolinite, serpentine, dolomite, sand (SiO ₂ ), granite conglomerate, as well as alloying components - Ti, KCl, Fe, Cr, with a common chemical composition according to option 1 (see table). Combs 43 of fixation units MKA 40 are brought upright, valves 15 m 39 are open. After that, the spark plug 24 is turned on, the valves 35 and 36 for supplying the oxidizing agent (oxygen) and fuel (CH ₄ ) to the heating unit 20 are opened and, with an oxidizer excess coefficient of 0.85-1.05, the process of heating the charge in the central zone to a temperature of more than 1500 ^o C (in the range up to 3000 ^o C), i.e. before the charge is melted with its transfer to a heterogeneous medium. When the temperature of the charge in the central zone of 300 ^o C is reached, the valve 37 opens and hydrocarbons (CH ₄ ) are injected through the nozzle 28 into the charge, bringing the oxidizer excess coefficient to 0.6-0.7. After melting 80% of the charge (with the exception of 20% of the charge located in the upper part of the reactor, which is necessary to “suppress” foam formation), the reactor is put into operation; the average temperature of the "core" (section AB) is set at 1300-1400 ^o C at a local temperature in the area of the nozzle> 1600 ^o C = 800 ^o C, the temperature in the near-wall zone (section DE) is 750-1100 ^o C, in the near-wall (carbonate -serpentine protective) layer from 200 ^o C to 750 ^o C, the temperature of the reactor vessel 200-50 ^o C. The chemical analysis of the AGS is clarified and, if necessary, alloyed through the loading unit 13 or through the nozzle 28 from the collector 34 (gaseous or liquid alloying components). Combs 43 are deployed in a horizontal position and introduced into the formed convective flows of the AGS with a temperature of from 800 to 1100 ^o C.

 The pressure control valve is set to an operating pressure of 1 MPa.

The thermal power of the reactor is 60-200 kW (with 1 m ^{3 of} AGS, the hydrocarbon flow rate is from 3 g / s at the stage of putting the reactor into operation up to 0.2-0.5 g / s - at steady state operation.

 MCA growth is carried out on the combs during the long process of AGS circulation, as well as in the near-wall layer in the middle part of the reactor when the MCA is deposited in the carbonate-serpentine protective layer in the inclined or bottom part of the bottom 6.

The synthesis of the MCA is carried out for 250 hours, after which the pressure control valve 15 opens, the combs 43 are moved to the vertical position (but can also be removed during the operation of the reactor to control the process), the heating unit is put into operation with an oxidizer excess coefficient <0.85 at T = 800-1000 ^o C, the valve 18 of the AGS drainage unit opens together with the formed MCA (SPOTTED STONES - 3-7 carats). The separation of the MCA from the "slag" is carried out according to known technologies, while the slag can be reused with additional alloying (if necessary).

2. In the housing 1 is loaded with a mixture of composition according to option 2 (see table). The method is carried out in the same way as described in paragraph 1, except that the heated air is used as the oxidizing substance (T _asc. > 400 ^o C), and 30 wt. % ammonia (NH ₃ ) from the consumption of hydrocarbons (which simultaneously leads to the intensive formation of cyanides in the AGS whose cyanide ions act as halide ions, i.e., catalysts). The process is conducted at a pressure of 0.5 MPa. As a result, nitrogen-containing MCAs with semiconductor properties (1.5-8 carats) were obtained with a 50% less hydrocarbon consumption.

3. In the housing 1 is loaded a mixture with the composition according to option 3 (see table) with the introduction of an alloying component (B ₂ O ₃ - 3.3%). Further, the method is carried out similarly to that described in paragraph 1. As a result, MCAs with semiconductor properties are obtained.

4. A mixture with the composition according to option 4 is loaded into the housing 1. Next, the method is carried out in the same way as described in paragraph 2, except that water vapor in the amount of 100 wt.% From the total hydrocarbon consumption. As a result, MCAs with semiconductor properties (3-7 carats in size) were obtained with an MCA yield of 20% more than in paragraph 2 and a 7% less hydrocarbon consumption (CH ₄ ).

The use of a mixture composed of components, the total composition of which, expressed through the oxides of its constituent elements, is: SiO ₂ - 25-44%; MgO - 15-30%; Al ₂ O ₃ - 1.5-6%; Fe ₂ O ₃ - 4-10%; FeO - 1.5-10%; K ₂ O - 1.5-6%; Na ₂ O - 0.05-2%; Cr ₂ O ₃ - 0.1-3%; CaO - 0.5 - 10%; Mn - 0.01-1.1%; TiO ₂ - 0.1-6%; CO ₂ - 0.05-11%; H ₂ O - 0.5-20%, as well as 0.5-5% of chloride compounds or metal halides of groups I, II of the periodic system of elements, the introduction of the charge components: oxidizing substance - oxygen or a mixture of oxygen with nitrogen, or air , or mixtures thereof with nitrogen-containing low molecular weight compounds with a nitrogen flow rate of from 1 to 80% of the flow rate of unbound oxygen and hydrocarbon combustible substances, followed by their combustion with an excess coefficient of oxidizing agent equal to 0.85-1.05, heating the mixture to a temperature of more than 1500 ^o C followed by introduction into the formed a heterogeneous medium as a carbon-containing substance of low molecular weight hydrocarbon substances and alloying elements, bringing the oxidizer excess coefficient to 0.25-0.85 while simultaneously zoning it to a temperature of 750-1050 ^o C with the formation of natural convective circulation flows of a heterogeneous medium, fixing the synthesized single crystals diamond in the cooled zones of the circulation flows of a heterogeneous medium, the temperature in which is from 1400 to 750 ^o C with the process at a pressure of from 0.12 to 16 M PA, after reaching a charge temperature of more than 750 ^o C, allows to collectively create periodically repeating pressure and temperature micro pulses in a heterogeneous medium (charge melt + crystalline phase + gas) as a result of chain reactions of the splitting of high-modulus silicate systems, leading to the formation of the necessary energy and the catalytic properties of an active heterogeneous medium and an intensive and stable process for the synthesis of high carat diamond single crystals with specified parameters.

The introduction of alloying elements of the third or fifth group of the periodic system of elements into the mixture or introduced hydrocarbon substances in an amount of 1-7 wt.% Allows to obtain diamond single crystals with semiconductor properties by ensuring uniform introduction of alloying elements at first into peripheral functional groups, and then their "suturing" into the crystal structure of diamond and their subsequent “pulling” during the rapid growth of the diamond crystal lattice with the formation of distortions and structural disturbances in it in the vicinity of the formed defects, which in turn can initiate:
a) the next introduction of an interstitial doping atom;
b) the formation of a vacancy;
c) energetically non-optimal or only partial involvement of valence bonds of atoms, which, when a diamond crystal is cooled, will lead to the formation of a vacancy and instertial and, together, allows programmatically synthesizing n- and p-type semiconductor diamond single crystals.

Introduction to a cooled heterogeneous medium of water vapor in an amount of from 25 to 150 wt. % of the total current flow rate of hydrocarbons introduced into the charge allows us to transfer the remainder of the “unreacted” carbon from SiO ₂ to carbon monoxide, with the formation of an optimal redox environment, to activate the formation of AGS and, as a result, to obtain improved quality microcircuit at a lower consumption hydrocarbons by 6-14%.

 The execution of the reactor vessel 1 in the form of a shell 2 with a cover 3 and the bottom 4, the supply of its outer heat-insulating coating 9, the execution of the shell 2 in the form of a rotation body of a "pear" shape with a neck 5 in the vicinity of the lid, equipping the reactor vessel with a cooling heat exchanger 6 with inlet and outlet pipes 7 and 8, making holes 10, 11, 12 in the cap 3, the neck and bottom, hermetically connected along the outer perimeter with, respectively, the loading unit 13 of the charge-type charge, the pipe 14 for discharging gaseous reaction products and the discharge unit 16 reaction products, installation in the cavity of the housing from the bottom of the 4 along the axis of symmetry of the housing one above the other heating unit 20, comprising at least one block 21, consisting of injectors of the input of the oxidizer 22 and fuel 23, equipped with a spark plug 24, and placing it in the bottom zone, node 27 of the input of carbon-containing and dopant substances containing at least one nozzle 28 of the input of hydrocarbon and dopant substances and placed in the area between the heating unit and 1/3 of the height of the cavity of the housing, execution in the bottom and the shell of the housing openings 30 through which the nozzles 22, 23, 28 by means of nozzles 25, 26, 29 sealed around the outer perimeter of the holes 20 are in communication with the collectors 31, 32, 33, 34 for supplying oxidizing, hydrocarbon fuel, carbon-containing and alloying substances, respectively located outside the housing, installation on the collectors 31, 32, 33, 34 and the inlet 7 of the cooling heat exchanger 6 control valves 35, 36, 37, 38, 39, performing the functions of the reactor control units, performing in the shell of the housing 1, in its middle and bottom parts radial holes 40, in which and through which fixation nodes 41 of diamond single crystals 42 are installed in the cavity of the housing 1, made in the form of rods 43 with a variable comb-like profile, with the possibility of their movement, respectively, along and relative to the axis of the hole 40, provides: loading of the charge, it heating, the implementation of chemical reactions and RV RVS in the resulting active heterogeneous medium, the synthesis of large MCA MCA in the wall cooling zone of the reactor in the process of convective circulation of AGS flows, the ability to control steam ICA meters, their withdrawal from the cavity of the reactor by removing MCA latches followed drain AGS with MCA unit 42 through the drain 16 (the recommended subsequent foaming heterogeneous medium and recovering the mAb by known techniques).

 The placement of nozzles 50, 51 for introducing water vapor in the bottom zone of the reactor and its middle part concentrically with respect to its axis makes it possible to evenly introduce water vapor into the AGS in the areas before the AGS enters the heating zone and after the formation of SiR with programmed cooling of the AGS, transferring the remaining part of graphite, formed during the process of polycondensation of hydrocarbons into carbon monoxide with the simultaneous formation of conditions for creating an optimal redox environment, which allows to intensify the diamond process formations with improved quality of the synthesized single crystals of diamond, while reducing the flow of hydrocarbons by 6-14%.

 The location of the nozzles 50, 51 for introducing water vapor and the nozzles of the nodes for entering the consumables 28, 21 tangentially with respect to the sectional plane of the housing 1 perpendicular to its axis, makes it possible to uniformly introduce the consumables into the AGS, to facilitate the formation of convective (circulating) AGS flows, their mixing, and equalization of the temperature fields of the AGS in the near-wall zone (MCA growth zone), which together provides synthesis of MCAs with uniform characteristics (according to the levels of MCA location in the reactor).

 The installation of an additional tubular cooling heat exchanger 54, made in the form of a spiral mounted on the inner surface of the housing 1, allows for more efficient cooling of the AGS in the wall zone, simplify the design of the reactor, use non-deficient construction materials, reduce heat loss, increase the working pressure in the reactor, and increase the resource his works.

The process of generation of diamond products in AGS and the growth of diamond single crystals during the course of dynamic energy CR of RVS (in the proposed reactor) is in good agreement with the evolution of growth and the manifestations of various morphological types of diamonds in kimberlite and non-kimberlite diamond-bearing rocks during their formation in light of the dynamic nature of diamond growth in high-temperature three-phase active heterogeneous system. The initial phase of the course of the RVS RVS (end of the CD phase, recovery medium) corresponds to the highest energy state of this AGS and, accordingly, the highest impulse pressure accompanying the RVS RVS, which leads to intensive nucleation of diamond nuclei in the form of spheroids (which is associated with a higher formation energy) epitaxial molecular films with a regular single-crystal structure on the faces of single crystals of an active substrate, for example, SiC, having a two-dimensional crystal structure similarity, and others. macro rukturnyh forms diamond substance (depending on the monomers employed), the high concentration which results in a sharp (10 ³ -10 ⁷ fold) increase in the growth rate of diamond monocrystals, including at the subsequent growth phase (taking into account their partial dissolution).

 As the energy state of the AGS in the convective flow changes and the process shifts to the peripheral (parietal) zone (DE) with an increased oxidation potential, the pressure weakening behind the shock microwaves front and the rounded diamond surfaces begin to face with complex indexing surfaces, which corresponds to the energy parameters during crystallization diamond and is well confirmed by x-ray diffraction patterns of the internal structure of diamond with different morphologies - from complexly distorted tetrahexahedrons through cubes ides to dodecahedrons with subsequent conversion to octahedra (end of phase D-E). Often, in a number of crystals of an octahedral habit, one can observe the entire gamut of morphological transformation. In this case, depending on the rate of production of the determining energy component, the zone where the crystal is in the reactor volume (and, accordingly, the oxidation potential, the concentration of diamond nuclei and the ratio of their types), the percentage of the involved forms in the total crystal volume changes. Upon reaching the optimal parameters corresponding to the optimal conditions for the equilibrium state of the crystal, the diamond crystallizes in the form of an octahedron.

The implementation of the process of synthesis of diamond single crystals in an active heterogeneous medium under substantially nonequilibrium conditions with long-term functioning of an open catalytic system and a controlled (controlled) chemical composition of AGS under the conditions of controlled chain reactions of RVS will allow to grow high-quality diamond single crystals of various types, including nitrogen, nitrogen-free impurity, with semiconductor properties - n- and p-conductivity, etc., while reducing their cost (by about 10-20% or more) s and due to the high productivity of the process (more than 1000 carats with 1 m ^{3 of} charge per month with the mass of individual MCAs from 2.5 to ≈ 100-500 carats) and in the process of obtaining cheap thermal energy (from 60 to 2000 kW with m ³ AGS), whose cost will be more than 20 times lower than the existing level.

Claims (7)

1. The method of synthesis of diamond single crystals, which consists in the fact that diamonds are synthesized in a mixture at high temperature and when a carbon-containing substance is fed, characterized in that they use a mixture composed of components, the total composition of which, expressed through the oxides of its constituent elements, corresponds to: SiO ₂ - 25 - 44%, MgO - 15 - 30%, Al ₂ O ₃ - 1.5 - 9%, Fe ₂ O ₃ - 4 - 10%, FeO - 1.5 - 10%, K ₂ O - 1.5 - 7%, Cr ₂ O ₃ - 0.2 - 3%, Na ₂ O - 0.05 - 2%, CaO - 0.5 - 11%, MnO - 0.01 - 0.5%, TiO ₂ - 0.6 - 4%, CO ₂ - 0.05 - 11%, H ₂ O - 0.5 - 20%, as well as 0.5 - 5% of chloride compounds or metal halides of groups I, II of the Periodic system ale nt, consumable components are introduced into the charge: an oxidizing substance - oxygen or a mixture of oxygen with nitrogen or air, or a mixture thereof with nitrogen-containing low molecular weight compounds with a nitrogen or nitrogen-containing compounds content from 1.0 to 80% of the mass flow of free oxygen and as a carbon-containing substance - hydrocarbon combustible with oxidant excess ratio of 0.85 - 1.05 and at temperatures reaching resulting heterogeneous medium over 1500 ^o C therein additional carbonaceous material is introduced - Carbs orodnye low molecular weight substances with oxidant by adjusting the equivalence ratio up to 0.25 - 0.85 and implementing the zonal cooling to a temperature of 750 - 1050 ^o C to form a natural convective flow patterns of the heterogeneous medium, the synthesized diamond monocrystals were fixed in chilled zones of circulating flows heterogeneous medium , the temperature in which is from 1400 to 750 ^o C, and upon reaching the charge temperature of more than 750 ^o C the process of synthesis of diamond single crystals is carried out at a pressure of 0.12 - 16 MPa.  2. The method according to claim 1, characterized in that alloying elements of the third or fifth group of the Periodic system of elements are introduced into the charge or introduced hydrocarbon substances in an amount of 1 to 7 wt.%.  3. The method according to claims 1 and 2, characterized in that water vapor is introduced into the resulting heterogeneous medium in an amount of 25 to 150 wt.% Of the total current flow of hydrocarbons into the charge.  4. A reactor for the synthesis of diamond single crystals, containing a housing consisting of a shell, a bottom and a cover with heating, supplying carbon-containing substances and controlling the reactor units located on it, characterized in that the reactor shell is provided with an external heat-insulating coating, the shell of the shell is made in the form of a body of revolution with a neck in the region of the lid, the reactor is equipped with a cooling heat exchanger with inlet and outlet pipes located on the shell of the housing, holes are made in the lid, neck and bottom, hermetically connected along the external perimeter, respectively, with a charge loading unit, a pipe for removing gaseous reaction products, and a reaction product discharge unit located outside the body, in the body cavity, on the bottom side, sequentially one above the other along its axis of symmetry and a heating unit is installed concentrically to it, including at least one block consisting of oxidizer and fuel injection nozzles, equipped with a spark plug and located in the bottom zone, a carbon-containing and alloying substance inlet unit, containing at least one nozzle for introducing hydrocarbon and dopant substances and located on the section between the heating unit and 1/3 of the height of the cavity of the body, while holes are made in the bottom and the shell, and nozzles are communicated through nozzles passing through the holes and hermetically fixed along the outer perimeter of the holes on the bottom and the shell of the housing, respectively, with manifolds for the supply of oxidizing, hydrocarbon fuel, carbon-containing and alloying substances, and the control units of the reactor are made in the form of control valves of holes installed at the inlet on all collectors and at the inlet pipe of the heat exchanger, while radial holes are made in the shell of the housing along its circumference from the bottom and in its middle part, in which and through which the fixation units of diamond single crystals are made in in the form of rods with a variable comb-like profile with the possibility of their movement, respectively, along and relative to the axis of the hole.  5. The reactor according to claim 4, characterized in that it is equipped with additional nozzles for introducing water vapor, mounted inside the housing directly in the bottom zone of the reactor and its middle part concentrically relative to its axis.  6. The reactor according to claims 4 and 5, characterized in that the nozzles for introducing carbon-containing and alloying substances and water vapor are located tangentially relative to the sectional plane of the casing, perpendicular to its axis.  7. The reactor according to PP.4 to 6, characterized in that it is equipped with an additional tubular cooling heat exchanger, made in the form of a spiral, mounted on the inner surface of the shell of the housing.

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