RU2106437C1 - Method of synthesis of monocrystals of diamonds and reactor for its realization - Google Patents

Abstract

FIELD: synthesis of monocrystals of diamonds. SUBSTANCE: invention refers to synthesis of monocrystals of diamonds including those with semiconductor properties. Reactor for realization of method has vessel 1 manufactured in the form of shell 2 with cover 3 and bottom 4, unit 13 to load burden, unit 16 to drain reaction products, unit 20 to heat burden, unit 27 to feed carbon-carrying (hydrocarbon), nitrogen-carrying and doping materials, unit 50 (atomizer) to inject water steam, heat exchanger 6 for cooling, unit 41 to fix monocrystal of diamond and branch pipe 14 to release gaseous reaction products with pressure control valve 15. Burden of specified composition is loaded to 2/3 of volume of vessel space. Burden is locally heated to temperature above 1500 C, hydrocarbon and if necessary doping materials are injected and are cooled with the aid of heat exchanged 6 to temperature 750- 1050 C with formation of convective circulation flows of heterogeneous medium in which synthesized monocrystals of diamonds are fixed under pressure 0.12- 16.0 MPa on combs 43 in cooled zone. Nitrogen or air or nitrogen-carrying low-molecular compounds as well elements of III and V groups may be injected into formed heterogeneous medium through units 20 or 27. Water steam may be injected into burden in central zone of reactor in the amount of 0.15-150.0% of summary present rate of hydrocarbons which improves quality of monocrystals of diamonds. On completion of process of synthesis of monocrystals of diamonds combs 43 are turned through 90 deg, monocrystals of diamonds are lowered into drain zone, pressure in reactor is reduced to normal one and monocrystals of diamonds are brought out of reactor through unit 16. EFFECT: enhanced efficiency of method. 2 cl, 1 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 for producing artificial diamond [1], as well as a method [2], 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.

 The disadvantage of this method [2] is the lack of potential for producing single crystals of high carat diamond.

 A device for producing artificial diamond, comprising a housing with nodes for heating and supplying carbon-containing gas [3].

 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. [4] - a prototype.

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

 A known reactor for the synthesis of single crystals of diamond, containing a housing placed on it with nodes of heating and supply of carbon-containing gas [4] is a 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,%: SiO ₂ - 25-44; MgO - 15-30; Al ₂ O ₃ - 1.5-9; Fe ₂ O ₃ - 4-12; 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 and alloying elements of III or V groups of the periodic system of elements in an amount of 0.05-7 wt.% , 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 flow rate of 1 - 80% of the flow rate of unbound oxygen and, as a carbon-containing substance, a hydrocarbon combustible substance with a coefficient excess oxide of Tell equal to 0.85-1.05, and when the resulting heterogeneous medium temperature over 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, whereupon a heterogeneous the medium is introduced water vapor in an amount of 25 - 150 wt.% of the total current flow of hydrocarbons into the charge and carry out its zonal cooling to a temperature of 750-1050 ^o C with the formation of natural convective circulating flows of a heterogeneous medium, while synthesis diamond single crystals are fixed in the cooled zones of the circulation flows of a heterogeneous medium, the temperature of which ranges from 1400 ^o C to 750 ^o C at a pressure of 0.12 - 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 - 4-12; 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 0.5-5% of chloride compounds or metal halides of groups I, II of the periodic system of elements and alloying elements of III or V groups of the periodic system of elements in an amount of 0.05-7 wt.% , introduction to the charge of consumable components: 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 flow rate of 1 - 80% of the flow rate of unbound oxygen and hydrocarbon combustible substances, followed by their burning with an excess coefficient oxidizing agent, pa nym 0.85-1.05, heating the charge to a temperature above 150 ^o C, followed by introduction into the resulting heterogeneous medium as a carbonaceous material of low molecular weight hydrocarbon compounds and alloying elements with coefficient adjusting excess oxidant to 0,25-0,85, subsequent introduction in a heterogeneous environment of water vapor in an amount of 25 -. 150% by weight of the total current consumption of hydrocarbon introduced into the charge while the zonal cooling of the heterogeneous medium to 750-1050 ^o C temperature to form the natural convective TSIR ulyatsionnyh heterogeneous medium flows fixing synthesized diamond monocrystals in cooled areas circulation flows heterogeneous environment in which the temperature is from 1400 to 750 ^o C, maintaining the process at a pressure of 0.12 - 16 MPa, after the batch temperature above 750 ^o C during allows formed repeatedly repeating thermodynamic cycles (full convective circulations of flows of a heterogeneous medium) to sequentially carry out:
intensive generation of a cleavage component - SiR - silicon carbide SiC (in a high-temperature heterogeneous medium at T _HS > 1500 ^o C during the introduction of low molecular weight hydrocarbon compounds into it, bringing the oxidizer excess coefficient in it to 0.25--0.85 (hydrocarbon pyrolysis and polycondensation);
generation of splittable components (of the form A _k B _c Si _m O _n , where A is the mono- or divalent metals K, Na, Ca, Mg, Fe, Mn; B is the trivalent metals Al, Fe, Cr or O ₂ (oxygen); k, c, m, n are the coefficients of the ratio 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, 11, 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 splitting of high-modulus silicates (RV RVS) in a cooled heterogeneous medium (at T _GS 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 energy release and periodically repeating 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 get Roguin 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 the release of heat and closure of the thermodynamic cycle);
to obtain diamond single crystals with uniform characteristics, including a given habit, by creating stable energy and chemical parameters of the AGS surrounding each diamond single crystal, starting from the moment the mass of single crystals reaches more than 1-2 carats, and the synthesis of diamond single crystals at elevated pressures in the range 0.12-16.0 MPa after reaching a charge temperature of more than 750 ^o C leads to an increase in the rate of formation of cleavage components and the regeneration of high modulus silicates and ultimately more the intensive process of RV RVS and, accordingly, to the accelerated synthesis of MCA, and when a mixture of oxygen with nitrogen or air, or a mixture thereof with nitrogen-containing low molecular weight compounds, for example NH ₃ , HNO ₃ , KNO ₃ , CaCN ₂ and Ca _{2 is} introduced into the charge as an oxygen-containing oxidizing substance etc., with a nitrogen flow rate of 1 - 80% of the mass flow rate of free oxygen, it is possible to realize in a heterogeneous medium at a temperature of more than 1200 ^o C an intensive process of generating 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 of 750 - 1450 ^o C (in the cooled zone) initiate the RVS RV with pulsed release of energy, 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 to the formation of nitrogen-containing AGS states under optimal energy and catalytic conditions peripheral functional groups in the boundary layer of the diamond – AGS system with their subsequent “suturing” into diamond macromolecules in the process of dynamic compaction of the boundary layer under the influence of detonation microwaves arising from the flow of the RVS RV, repeated generation of Si ₃ N _4, continuing the initiation of the RV RVS with a gradual their attenuation as the BC and RC are generated at the end of each convective cycle (during the convective circulation of a heterogeneous medium), which together allows the synthesis of nitrogen-containing single crystals of alm aase with high physicomechanical properties (5–10% higher than that of nitrogen-free diamonds) due to the formation of a wide spectrum 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 AGS and which should be directed to useful consumers and energy converters, while introducing alloying elements of groups III or V of the periodic system of elements into the charge or introduced hydrocarbon substances the amount of 0.05-7 wt. % allows one to obtain diamond single crystals with semiconductor properties by ensuring uniform incorporation of alloying elements, first into peripheral functional groups, and then their “suturing” into the diamond crystal structure and their subsequent “pulling” with the rapid growth of the diamond crystal lattice with the formation of distortions and structural violations in the vicinity of the resulting 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 the diamond crystal is cooled, will lead to the formation of a vacancy and instertial and together allows programmatically synthesize n- and p-type diamond semiconductors, and the subsequent introduction of water vapor into the cooled heterogeneous medium in an amount 25 - 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 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 cuttings and located on the shell of the body, in the lid, neck and bottom holes are made, hermetically connected along the outer perimeter, respectively, by the charge loading unit, a pipe for removal of gaseous reaction products and a drain of reaction products located outside the case, in the cavity of the case, from the bottom, sequentially one above the other along its axis of symmetry and concentric to it, a heating unit is installed, including at least one block, consisting of nozzles for introducing oxidizer and fuel, equipped with a spark plug amenia and located in the near-bottom zone, a carbon-containing and dopant injection unit, containing at least one hydrocarbon and dopant injection nozzle and located in the area between the heating unit and 1/3 of the cavity cavity height, and water vapor injection nozzles located in the near-bottom zone the reactor and its middle part, with holes made in the bottom and the shell, and nozzles communicated through nozzles passing through the holes and hermetically fixed along the outer perimeter of the holes on the bottom and the shell the housing, respectively, with manifolds for the supply of oxidizing, hydrocarbon fuel, carbon-containing and dopant substances and water vapor, moreover, the reactor control units are made in the form of control valves installed at the inlet at all collectors and at the inlet pipe of the heat exchanger, while in the shell around the circumference of the shell the sides of the bottom and in its middle part are made radial holes in which and through which the fixation units of diamond single crystals are made in the form of rods with variable "comb-like" profile, with the possibility of their movement, respectively, along and 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 pear-shaped body of rotation with a neck in the region of the lid, equipping the reactor vessel with a cooling heat exchanger with inlet and outlet pipes, making holes in the cover, neck and bottom hermetically connected along the external perimeter with, respectively, a charge-loading unit for a lock-type charge, a pipe for removing gaseous reaction products, and a discharge unit for reaction products, installation 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, comprising at least one unit consisting of injectors of the oxidizer and fuel, equipped with a spark plug, and placing it in the bottom zone of 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 height of the cavity of the body and nozzles for introducing water vapor located in the bottom zone of the reactor and its medium days of the part, making holes in the bottom and shell of the body through which the nozzles are connected through nozzles hermetically secured around the outer perimeter of the holes to the collectors for the supply of oxidizing, hydrocarbon fuel, carbon-containing and alloying substances and water vapor located outside the body, mounted on the collectors and the inlet pipe of the cooling heat exchanger of the valve-regulators, performing the functions of the reactor control units, performing in the shell of the body, in its middle and bottom parts, radial holes, in which and through which the fixation 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 to the axis of the hole, provides: loading the charge, its heating, chemical reactions and CR of RVS in the formed active heterogeneous medium, synthesis of high carat MCA in the near-wall cooled zone of the reactor during convective circulation of AGS flows, the possibility of controlling eniya ICA parameters, their withdrawal from the cavity of the reactor by removing MCA latches AGS followed by draining through a drain node of ICA (s recommended subsequent foaming heterogeneous medium and recovering the mAb by known techniques). Moreover, 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 of polycondensation of hydrocarbons into carbon monoxide, with the simultaneous formation of conditions for creating an optimal redox environment, which allows to intensify the process a mazoobrazovaniya with improved quality of synthesized diamond monocrystals with a decrease in hydrocarbon flow 6-14%.

 Installation of a (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 the resource his works.

 Figure 1 shows a structural diagram of a reactor for the synthesis of diamond single crystals.

 The reactor contains a housing 1 (Fig. 1), consisting of a shell 2, a cover 3 and a bottom 4. The upper part of the shell in the region 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 7, is integrated in the housing 1 outlet pipe 8. On the outside of the reactor vessel a heat-insulating coating is installed 9. Holes 10, 11, 12 are made in the cover, neck and bottom, in which the charge loading unit 13, pipe 14 for removing gaseous reaction products with installed cells Pan 15, the pressure control unit 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 of the bottom 4 successively one above the other along its axis of symmetry and concentric to it, a heating unit 20 is installed, including at least one block 21 (or several blocks), consisting of nozzles 22 for entering the oxidizer and fuel 23, equipped with a candle ignition 24, and the nozzles 25, 26, the node 27 of the input of carbon-containing and dopant substances, consisting of at least one nozzle 28 (or several nozzles), a nozzle 29 located in the area between the heating unit 20 and 1/3 of the height of the cavity of the housing 1. In the bottom 4 and the shell 2 in holes 30 are made through which pipes 25, 26 and 29 pass, communicating nozzles 22, 23 and 28 with manifolds 31, 32, 33 and 34 supplying consumables of oxidizing, hydrocarbon, carbon-containing and alloying substances, respectively, with pipes 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, as well as control valves 39 and 15, installed on the inlet cooling exchanger and a branch pipe for 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 displacements 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 supplied through the nozzles 22 of the oxidizer or partially (low molecular weight) compounds) through nozzles 28 for introducing carbon-containing 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 by means of equalizing valve 49 (figure 1).

 The reactor (may be) is 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.

 The reactor (may be) is 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.

 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 ^o C 25-44; MgO ^o C 15-30; Al ₂ O ₃ ^o C 1.5-6; Fe ₂ O ₃ ^o C 4-12; FeO ^o C 1.5-10; K ₂ O ^o C 1.5-6; Na ₂ O ^o C 0.05-2; Cr ₂ O ₃ ^o C 0.1-3; CaO ^o C 0.5-10; Mn ^o C 0.01-1.1; TiO ₂ ^o C 0.1-6; CO ₂ 0.05 ^° C 11; H ₂ O ^o C 0.5-20, as well as 0.1 ^o C5% of chloride compounds or metal halides of the I-III groups of the periodic system of elements and alloying elements of the III or V groups of the periodic system of elements in an amount of 0.05-7 wt. % (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 that, the spark plug 24 is turned on, valves 35 and 36 are opened, the process of heating the charge begins with an excess coefficient of the oxidizing agent equal to 0.85 ^{° C.} 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 carburization 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 with 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 about 750 ^o C, the pressure control valve 15 is turned on and the set working pressure in the reactor is set (0.12 - 16 MPa).

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

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 (already embedded therein SiC particles (CD 1 portion) and the formation of an active heterogeneous medium (AGS). Upon further cooling in the AGS process of convective motion along the walls of the reactor rapidly cooled (portion DE) continued aetsya crystallization sun while the interaction silicates form _{A k, B c, Si m} O n, e.g. KAlSi ₃ O ₈ (orthoclase), NaAlSi ₃ O ₈ (albite), Ca ₃ Cr ₂ (SiO _{4) 3} (uvarovite) , 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 OSi ₃ O ₆ , Na ₂ OSi ₃ O 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 (CV 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 fraction of the discount phase of high-modulus silicates of the type A _k B _c Si _m O _n and the initiation of local chain reactions of the detonation type with high energy release but low gassing (low propelling ability).

Theoretically, for the decay process to begin, for example, Na ₂ OSi ₃ O ₆ under the influence of silicon-oxygen-free compounds, an external supply of the initial energy Q _{0 is} necessary from the outside.

As a result, the formation of silicate Na ₂ OSi ₃ O ₆ in the liquid phase, which is part of the critical mass (m ₀ ), will occur.

где
MS¹ - расщепляемый в 1-м звене цепи силикат;
Q₁ - теплота в 1-м звене цепи;
K¹ - константа химического взаимодействия в 1-м звене цепи;
K $\genfrac{}{}{0ex}{}{\text{1}}{\text{1}}$ - константа фазового превращения в 1-м 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 cleaved in the 1st chain link;
Q ₁ - heat in the 1st chain link;
K ¹ is the constant of chemical interaction in the 1st chain link;
K $\genfrac{}{}{0ex}{}{\text{1}}{\text{1}}$ is the constant of phase transformation in the 1st 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 M ₁ , and subsequently to critical masses M ₂ , M ₃ ... M _n , respectively. This decay of critical masses of silicate will be due to the supply of heat Q ₁ , Q ₂ ... Q _n , which is released during the above-described reaction of the formation of silicate Na ₂ OSi ₃ O ₆ in a discount 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 chain reaction shown in Fig. 2.

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 with a low emission of gaseous reaction products and, accordingly, with low propelling ability but high pressure behind the detonation wave front (in local zones with prepared the conditions for the flow of the RV RVS), which leads to the formation of a diamond substance, 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 reaction) is a function of the type and concentration of high-modulus silicates and 81K., 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.

CO + H₂
v_ал > 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 неравновесных с фазами протекания вокальных 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 diamond faces. The process of transition of atoms (carbon, etc.) from the boundary layer to the crystal wives must be accompanied by a process of compaction subject to the following conditions:
the rate of formation of diamond (v _al ) is higher than the rate of formation of graphite (v _gr ), and most importantly, the rate of oxidation of graphite v _{(g) is} much higher than the rate of oxidation of diamond v _{о (diamond)}
C _al (C _gr ) + H ₂ O (CO ₂ , O ₂ )

CO + H ₂
v _al > 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 nonequilibrium with phases of the course of vocal micro-detonation 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) at a temperature of more than 1500-2200 ^o C a heterogeneous medium is formed (molten silicates + crystalline 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.

C_ал. + H₂O
Теоретически процесс образования алмаза в АГС может протекать по широкой гамме реакций, например по пути поликонденсации из углеводородов:
CH₂ ⇄ C_ал + 2H₂
C₂H₂ ⇄ 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 process of crystallization of the sun begins with the formation of the AGS, which is characterized by the beginning of the flow of the RV RVS while 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
CO + H ₂

C _al. + H ₂ O
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 may overheat (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.

,
Al₂O₃ + 6SiO₂ + Na₂O _→ 2NaAlSi₃O₈(альбит)
CaO + MgO + 2SiO₂ _→ CaMgSi₂O₆

,
Одновременно увеличивается интенсивность ЦР РВС (участок D-E фиг.1), что обусловлено высокой концентрацией ВС, 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. To do this, as the content of the liquid phase increases, it is necessary to continue cooling 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. Cooling of the AGS is achieved by the fact that the generated AGS upflow (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 the regeneration process begins (crystal ization) vysokomodulnyh silicates during their immersion along the cooled walls of the casing 1 of the reactor (portions CD and DE), for example:

,
Al ₂ O ₃ + 6SiO ₂ + Na ₂ O _ → 2NaAlSi ₃ O ₈ (albite)
CaO + MgO + 2SiO ₂ _ → CaMgSi ₂ O ₆

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

Then, 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 the process, while the products of the splitting of the arsenic (SiO, SiO ₂ , CO, etc.) again interact with the 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 heterostructure with carbon, active generation of SiR, the beginning of the cooling of the heterostructure with crystallization of the arsenic.

 The C-D phase is the continuation of the cooling of the HS, the 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 carbon formed 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, heat is removed from the reactor to useful consumers and energy converters through the heat exchanger 6 and 54 (heat carrier - water vapor).

 Phase E-A - return of the AGS flow to the high-temperature zone A-B with additional oxidation of the products of the breakdown of the aircraft 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 [Si 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 (ZS), simultaneously performing the functions of thermal protection of the body.

 Thus, the growth of MCA with the desired properties is carried out on the fixators located in the parietal cooled zone during a long process of circulation of (silicate) AGS under the conditions of controlled physical and chemical reactions of the RCS from the carbon of hydrocarbon components introduced into the AGS, as well as in the wall layer in the middle and 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 (50 - 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 an inert gas with the pressure control valve 15 closed, the drain assembly 16 opens 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 foaming it inert gas followed by the 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 , NHO ₃ , KNO ₃ , etc., is introduced into the mixture (AGS) .d., with the content of nitrogen or nitrogen-containing compounds 1 - 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 during 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 RV RVS). which 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.

Introduction to the composition of the mixture or the introduced hydrocarbon substances of alloying elements of the III or V groups of PSE in an amount of 0.05-7 wt.%, For example, nitrogen - N ₂ , boron - B, lantonoids, yttrium - Y, etc. (moreover, alloying elements can be introduced into the charge, including in the form of high-modulus silicates, for example (Mn, Y) ₃ A ₁₂ (SiAl) ₃ O ₁₂ (spessartine), etc.), it is possible to obtain diamond single crystals with semiconductor properties by ensuring uniform introduction of alloying elements first in peripheral functional groups, and then their "stitching" into the crystalline the structure of diamond and their subsequent “tightening” with the rapid growth of the diamond crystal lattice with the formation of distortions in it - and structural violations 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 introduction of water vapor into a cooled heterogeneous medium through nozzles 50, 51 in an amount of 25-150 wt.% Of the total current flow of hydrocarbons into the charge leads to the formation of carbon monoxide necessary for diamond formation during the interaction of free carbon contained in the HS with H ₂ O 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, accelerated cooling of the HS during its transition to the AGS, and reduction of hydrocarbon consumption by 6-14%.

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 the fixation nodes MCA 40 are brought upright, valves 15 and 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 - 200 - 750 ^o C, temperature of the reactor vessel - 200 - 750 ^o C. The chemical analysis of the AHS 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 800 - 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 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 be removed during operation of the reactor to control the process), the heating unit is put into operation with an oxidizer excess coefficient <0.85 at a temperature of 800-1000 ^o C, opens the valve 18 of the AGS drainage unit together with the formed MCA (Spotted Stones - 3-7 carats). The separation of 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 heated air is used as the oxidizing substance (T _asc. > 400 ^o C), and 30 wt.% Ammonia (NH ₃ ) is introduced through the nozzle 28 from the collector 34 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 case 1 is loaded with a mixture with the composition according to option 3 (see table) with the introduction of the 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, MCA Top Stones Est (size 3-7 carats) 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 - 4-12; 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 0.5-5% of chloride compounds or metal halides of groups I, II of the periodic system of elements and alloying elements of groups III or V of PSE in an amount of 0.05-7 wt.%, Introduction in the charge of consumable components: 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 flow rate of 1 - 80% of the flow rate of unbound oxygen and hydrocarbon combustible substances, followed by their combustion with an excess coefficient of the oxidizing agent, equal to 0.85-1.05, heating the mixture to eratury over 1500 ^o C, followed by introduction into the resulting heterogeneous medium as a carbonaceous material of low molecular weight hydrocarbon compounds and alloying elements with coefficient adjusting excess oxidant to 0,25-0,85, introduction of a heterogeneous environment of water vapor in an amount of 25 -. 150% by weight of the total current flow of hydrocarbons into the charge while its zonal cooling to 750-1050 ^o C temperature to form the natural convective flow patterns of the heterogeneous medium, fixing synthesize x diamond single crystals on cooled zones circulating flows heterogeneous environment in which the temperature is from 1400 to 750 ^o C to conduct the process at a pressure of 16 MPa 0,12- after reaching the batch over 750 ^o C temperature allows to create a plurality of repetitive pressure and micropulses temperature in a heterogeneous environment (charge melt + crist. 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 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. Moreover, the introduction of alloying elements III or V of the PSE group into the charge or introduced hydrocarbon substances in an amount of 0.05-7 wt.% Allows to obtain diamond single crystals with semiconductor properties by ensuring uniform introduction of alloying elements first in the peripheral functional groups, and then them stitching "into the crystal structure of diamond and their subsequent" tightening "with the rapid growth of the diamond crystal lattice with the formation of distortions and structural disturbances in it in the vicinity of the formed I have 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.

While the introduction of water vapor into the cooled heterogeneous medium in an amount of 25-150 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 intensify the formation of AGS and, as a result, to obtain MCAs of improved quality with a lower consumption of 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 external heat-insulating coating 9, the execution of the shell 2 in the form of a pear-shaped body of rotation with a neck 5 in the region of the lid, equipping the reactor vessel with a cooling heat exchanger 6 with inlet and outlet pipes 7 and 8, making in the cover 3, the neck and bottom of the holes 10, 11, 12, hermetically connected along the outer perimeter with, respectively, the loading unit 13 of the charge-type mixture, a pipe 14 for discharging gaseous reaction products, and a discharge unit 16 of reaction lines, installation in the cavity of the housing from the bottom of the housing 4 along the axis of symmetry of the housing one above the other of the heating unit 20, including at least one unit 21, consisting of injection nozzles of oxidizer 22 and fuel 23, equipped with a spark plug 24 and placing it in the bottom zone site 27 input carbon-containing and dopant substances containing at least one nozzle 28 input 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, the execution in the bottom and the shell of the housing rstium 30, through which the nozzles 22, 23, 28 by means of nozzles 25, 26, 29, hermetically fixed along the outer perimeter of the holes 30, respectively communicate with the collectors 31, 32, 33, 34 of the supply of oxidizing, hydrocarbon fuel, carbon-containing and alloying substances located outside the casing, installation on collectors 31, 32, 33, 34 and inlet pipe 7 of a cooling heat exchanger 6 control valves 35, 36, 37, 38, 39, acting as control units for the reactor, performing in the shell of the casing 1, in its middle and bottom parts radial rstiy 40, in which and through which in the cavity of the housing 1 are installed the fixing units 41 of single crystals of diamond 42, 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 the charge, heating it, the implementation of chemical reactions and RV RVS in the resulting active heterogeneous medium, the synthesis of large MCA in the wall cooling zone of the reactor in the process of convective circulation of AGS flows, the ability to control the parameter E mAb, their withdrawal from the reactor cavity by extracting clamps mAb followed by draining AGS with mAb 42 via the drain assembly 16 (with 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 implementation of the tubular cooling heat exchanger 54 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, to simplify the design of the reactor, use non-deficient structural materials, reduce heat loss, increase the working pressure in the reactor, and increase its operating life.

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, reducing 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, which have a two-dimensional crystal structure similarity and other macroscopes kturnyh 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 (near-wall) zone (D-E) with an increased oxidation potential, the pressure decreases behind the shock microwaves and the rounded diamond surfaces begin to face with complex indexing, which corresponds to the energy parameters during crystallization of diamond and is well confirmed by x-ray diffraction patterns of the internal structure of diamond with different morphologies - from complexly distorted tetrahexahedra through a cube ides a dodecahedron, with subsequent conversion to octahedrons (the 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 generation of the determining energy component of the zone where the crystal is located 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 RCS will allow to grow high-quality diamond single crystals of various types, including nitrogen, nitrogen-free, impurity , with semiconductor properties of n- and p-conductivity, etc., while reducing their cost (by about 10-20% or more) per Thu high productivity of the process (more than 1,000 carats with 1 m ³ of charge per month with a mass of individual ICA 2.5 to ≈ 100-500 carats) and with a tail receiving cheap heat energy (60 - 200 kW to 1 m ³ AGS), the cost which will be more than 20 times lower than the current level.

Claims (2)

1. The method of synthesis of single crystals of diamond, which consists in the fact that diamonds are synthesized in a charge at a high temperature and when a carbon-containing substance is fed, characterized in that they use a charge 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 - 9.0
Fe ₂ O ₃ - 4 - 12
FeO - 1.5 - 10.0
K ₂ O - 1.5 - 7.0
Cr ₂ O ₃ - 0.2 - 3.0
Na ₂ O - 0.05 - 2.0
CaO - 0.5 - 11.0
MnO - 0.01 - 0.5
TiO ₂ - 0.6 - 4.0
CO ₂ - 0.05 - 11.0
H ₂ O - 0.5 - 20.0
as well as 0.5 - 5% of chloride compounds or metal halides of groups I, II of the Periodic system of elements and alloying elements of groups III or V of the Periodic system of elements in an amount of 0.05 - 7 wt.%, consumable components are introduced into the charge: oxidizing substance - oxygen or a mixture of oxygen and nitrogen, or air, or a mixture thereof with nitrogen-containing low molecular weight compounds containing nitrogen or nitrogen-containing compounds, 1.0 to 80% of the mass flow of free oxygen and, as a carbon-containing substance, a hydrocarbon fuel your with an excess coefficient of the oxidizing agent equal to 0.85 - 1.05, and when the temperature of the resulting heterogeneous medium reaches more than 1500 ^o C, additional carbon-containing substances - hydrocarbon low molecular weight substances are introduced into it, bringing the coefficient of excess of the oxidizing agent to 0.25 - 0.85, whereupon the heterogeneous medium is introduced into the water vapor in an amount of 25 -. 150% by weight of the total hydrocarbon flow of current in the charge and a heterogeneous carried zonal cooling medium to a temperature of 750-1050 ^o C to form a natural convective circulation tional flow heterogeneous medium, wherein the synthesized diamond single crystals are fixed in cooled areas circulation streams of a heterogeneous environment in which the temperature is between 1400 ^o C to 750 ^o C, and upon reaching the batch temperature above 750 ^o C synthesis process of diamond monocrystals is carried out at a pressure of 0 12 - 16.0 MPa.  2. The 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 with, respectively, 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 spark plugs 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, and nozzles for introducing water vapor installed directly in the bottom zone of the reactor and its middle part, 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 fuel, carbon-containing and alloying substances, and 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 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 in the cavity of the casing are fixed nodes for fixing single crystals of diamond, made in the form of rods with a variable "comb-like" profile, with the possibility of their movement respectively along and relative about the axis of the hole.

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