WO2023068969A1 - Élément de chauffage électrique, cellule haute pression - Google Patents

Élément de chauffage électrique, cellule haute pression Download PDF

Info

Publication number
WO2023068969A1
WO2023068969A1 PCT/RU2022/050326 RU2022050326W WO2023068969A1 WO 2023068969 A1 WO2023068969 A1 WO 2023068969A1 RU 2022050326 W RU2022050326 W RU 2022050326W WO 2023068969 A1 WO2023068969 A1 WO 2023068969A1
Authority
WO
WIPO (PCT)
Prior art keywords
heating element
conductive material
electric heating
electrically conductive
element according
Prior art date
Application number
PCT/RU2022/050326
Other languages
English (en)
Russian (ru)
Inventor
Александр Владимирович КОЛЯДИН
Теймураз Юрьевич ХИХИНАШВИЛИ
Original Assignee
Общество С Ограниченной Ответственностью "Научно-Производственный Комплекс "Алмаз" (Ооо "Нпк "Алмаз")
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from RU2021130416A external-priority patent/RU2771977C1/ru
Application filed by Общество С Ограниченной Ответственностью "Научно-Производственный Комплекс "Алмаз" (Ооо "Нпк "Алмаз") filed Critical Общество С Ограниченной Ответственностью "Научно-Производственный Комплекс "Алмаз" (Ооо "Нпк "Алмаз")
Publication of WO2023068969A1 publication Critical patent/WO2023068969A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material

Definitions

  • the proposed invention in general, relates to the field of production and/or processing of superhard materials, in particular diamonds, by the high pressure and high temperature method (High Pressure/High Temperature, HPNT).
  • HPNT High Pressure/High Temperature
  • the present invention relates to an electric heating element capable of being installed in a high pressure cell for producing and/or processing superhard material by HPHT, a high pressure cell and a method for producing and/or processing superhard material by HPHT.
  • HPHT method is traditionally used to produce various superhard materials such as diamond single crystals, diamond polycrystals, diamond powders, cubic boron nitride, etc., as well as to process diamonds to give them special properties.
  • one of the well-known methods for obtaining diamonds involves the treatment of carbon, for example, in the form of graphite, with high pressure and temperature in the presence of a metal solvent catalyst in a high pressure cell, as disclosed in US patents 4340576 and US 4617181.
  • a metal solvent catalyst in a high pressure cell, as disclosed in US patents 4340576 and US 4617181.
  • This processing is carried out at pressure and temperature, the values of which are in the diamond stability field on the carbon phase diagram.
  • HPHT equipment such as cube presses, belt presses, toroidal presses, pressless machines. "cut sphere” type and others.
  • HPV high-pressure cell
  • HPNT equipment With the help of HPNT equipment, the necessary pressure and temperature are created in the HPT, as a result of which the processing and/or production of superhard materials takes place.
  • the JVD body is made from various ceramic materials or a mixture of ceramic material with any other suitable materials.
  • JVDs with a body made of pyrophyllite (author's certificate SU 636515), zirconium dioxide (patent RU 152200), or a mixture of cesium chloride with ceramic material (author's certificate SU 1814218) are known.
  • the heater material is graphite or mixtures of graphite with other suitable materials.
  • the heater may be plate-shaped, cylindrical, or any other suitable shape.
  • the creation and maintenance of the given parameters of the temperature field with the necessary temperature gradients in the HPT is a complex and very important task, especially in the case of growing diamond single crystals by the method temperature gradient.
  • the conditions for crystal growth are determined by the magnitude of the temperature gradient between the carbon source and the growing crystals.
  • to create a temperature field with given temperature gradients not one, but several heaters are used (application US 2012/0312227, patent US 10252233).
  • One disadvantage of all such multi-heater systems is their complexity. The presence of several current-carrying circuits noticeably complicates the design of the NPV, and, as a result, leads both to the complication of the process control system and a decrease in its reliability and stability, and to an increase in the cost of production.
  • the shape of the temperature field depends on the materials of the reaction zone, their thermal conductivity, geometry, etc.
  • One of the ways to create the necessary temperature field in the reaction zone is to change the materials used, which make up the JVD. But this method is limited by a rather short list of materials that can work under the conditions of the HPHT method.
  • the problem solved by the proposed invention is the creation of an improved design of the high-pressure cell, which provides the possibility of a simpler and more reliable creation of the necessary temperature field and its control both for the production of superhard materials and for their processing.
  • an electrical heating element capable of being installed in a high pressure cell for producing and/or processing a superhard material using a high pressure high temperature (HPHT) process, characterized in that it is made of at least one electrically conductive material. and at least one non-conductive material, wherein the weight ratio of said at least one electrically conductive material to said at least one non-conductive material varies in the electrical heating element along at least one direction.
  • HPHT high pressure high temperature
  • the electrically conductive material may be selected, without limitation, from, for example, carbon (C) in any electrically conductive allotropic modification, lanthanum chromite (LaCrO3), platinum (Pt), tantalum (Ta), rhenium (Re), or mixtures thereof.
  • C carbon
  • LaCrO3 lanthanum chromite
  • Pt platinum
  • Ta tantalum
  • Re rhenium
  • the electrically conductive material may be carbon (C) in any electrically conductive allotropic modification.
  • the non-conductive material of the electrical heating element may be selected, without limitation, from, for example, carbon (C) in any non-conductive allotropic modification, zirconia (ZrCh), cesium chloride (CsCl), sodium chloride (NaCl), oxide magnesium (MgO), chromium oxide (CrO3) and mixtures thereof.
  • C carbon
  • ZrCh zirconia
  • CsCl cesium chloride
  • NaCl sodium chloride
  • MgO oxide magnesium
  • CrO3 chromium oxide
  • the non-conductive material may be zirconia (ZrCh).
  • the non-conductive material may be carbon (C) in any non-conductive allotropic modification.
  • the weight ratio of electrically conductive material to non-conductive material may decrease from the end portions of the electrical heating element towards the portion of the electrical heating element where the maximum temperature is to be generated.
  • the part of the electric heating element in which it is necessary to create the maximum temperature is its central part.
  • the weight ratio of electrically conductive material to non-conductive material may vary from 100 wt%, to 0 wt%, at the ends of the electric heating element to 50 wt%, to 50 wt%, in the central part of the electric heating element.
  • the weight ratio of electrically conductive material to non-conductive material may vary from 95 wt%, to 5 wt%, in the end portions of the electric heating element to 70 wt%, to 30 wt%, in the central portion of the electric heating element.
  • the mass ratio conductive material to non-conductive material can vary from 90 wt%, to 10 wt%, in the end parts of the electric heating element to 80 wt%, to 20 wt%, in the central part of the electric heating element.
  • the weight ratio of the amount of electrically conductive material to the amount of non-conductive material may vary continuously.
  • the weight ratio of the amount of electrically conductive material to the amount of non-conductive material may vary in steps.
  • the mass ratio of the amount of electrically conductive material to the amount of non-conductive material may change disproportionately or without any patterns at all (randomly).
  • the electrical heating element may be made of boron-doped diamond.
  • the boron content in the diamond crystal lattice in the central part of the electric heating element, is 0.5 wt. %, and at the edges of the electric heating element, the boron content in the diamond crystal lattice increases to 3 wt.
  • the change in composition is proportional to the distance from the center of the electric heating element.
  • the electrical heating element may be cylindrical, tubular, lamellar or otherwise.
  • a high pressure cell for producing and/or processing a superhard material using a high pressure high temperature (HPHT) process, characterized in that it contains the above electrical heating element.
  • HPHT high pressure high temperature
  • a process for producing and/or processing a superhard material using a high pressure high temperature (HPHT) process first, a high pressure cell containing an electrical a heating element. Then the high-pressure cell is placed in the high-pressure apparatus, the necessary pressure is created in the high-pressure cell, the high-pressure cell is heated by supplying power to the electric heating element to ensure the formation of a temperature gradient in the said cell, the power supply to the electric heating element is stopped, the pressure is released, and removing the high pressure cell from the high pressure apparatus. At the same time, the specified temperature gradient is formed using the electric heating element disclosed above.
  • the superhard material that is obtained and/or processed in the proposed method is a diamond single crystal, a diamond polycrystal, diamond powder, or cubic boron nitride.
  • the technical result provided by the proposed invention is to provide the possibility of creating the necessary temperature gradient in the HP and controlling the configuration of the thermal field inside the reaction zone without changing the composition and geometry of the cell elements using only one electric heating element.
  • the specified technical result is achieved by the fact that the electric heating element is made of electrically conductive and non-conductive materials not with a uniform composition throughout the heater, but from such a composition in which the mass ratio of one material to another changes over the heater.
  • the ratio of the electrically conductive material to the non-conductive material in different parts of the heater it is possible to create the necessary temperature field for the production and/or processing of materials in the JVD by the HPNT method.
  • figure 1 shows a schematic representation of the high pressure cell
  • figure 2 shows a schematic representation of an electric heating element in accordance with the proposed invention and the configuration of the thermal field created by it.
  • a high pressure cell for the production and/or processing of superhard materials by the HPHT method, a high pressure cell is provided.
  • An electric heating element 1 is placed in the high-pressure cell housing, made of ceramic or other suitable material.
  • An insulating sleeve (not shown) with an upper insulating washer 2 and a lower insulating washer 3 is placed inside the heating element, forming a reaction zone, inside which a source 4 is located.
  • carbon usually in the form of graphite or other diamond or non-diamond form of carbon, and a catalyst metal 5.
  • the catalyst metal 5 may be iron, cobalt, nickel or manganese, or mixtures of these metals, including with the addition of any other suitable elements.
  • a substrate 6 with a diamond seed 7 located on it is placed in the HPC. Above and below the HPC, an upper current lead 8 and a lower current lead 9 are provided for supplying electric power to the electric heating element 1.
  • a high pressure apparatus which may be any suitable apparatus suitable for the production of superhard materials, such as a cube press, a belt press, a toroidal press, a split sphere pressless apparatus, or other device that provides the ability to create high pressure.
  • a high pressure is created in the JVD, usually in excess of 4.5 GPa.
  • the pressure may be between 4.5 and 10 GPa.
  • the high-pressure cell is heated and, as a result, the reaction zone is heated by supplying electric current to the heating element to ensure the formation of a temperature gradient in the JVD.
  • the heating power is increased at a rate of 30 watts per minute.
  • the heating power is reached, for example, 6.5 kW, the operator stops the process of increasing the power.
  • a soak in one embodiment, for example about 300 hours, the operator stops the heating.
  • the JVD is removed from the high-pressure apparatus. Inside the cell is a diamond single crystal.
  • the creation and maintenance of the given parameters of the temperature field with the necessary temperature gradients in the HPT is a complex and very important task, especially in the case of growing diamond single crystals by the temperature gradient method.
  • the conditions for crystal growth are determined by the magnitude of the temperature gradient between the carbon source and the growing crystals.
  • the carbon of the source which is at a temperature of T1
  • dissolves in the catalyst metal then the carbon is transferred (diffuses) by convective flows to the zone where the diamond seed is located.
  • the seed is at a temperature T2 ⁇ T1. Carbon is deposited on the seed, crystal growth occurs. If the temperature difference between T1 and T2 is small, the growth rate will not be sufficient for cultivation. Conversely, if there is a large difference between T1 and T2, the growth rate will be too high and the crystal will grow with numerous defects.
  • the required temperature gradient between the carbon source and the growing crystal is provided using an electrical heating element made of at least one electrically conductive material and at least one non- electrically conductive material, while the mass ratio of the specified at least one electrically conductive material to the specified at least one non-conductive material is changed in the electrical heating element along at least one direction, as shown in FIG.
  • the electric heating element is in the form of a hollow cylinder (tubular shape).
  • the heating element may have, for example, lamellar or other suitable shape.
  • the heating element is made of a mixture of graphite and non-carbon material, such as cubic zirconia, and the mass ratio of graphite and non-carbon material varies from the ratio of 95% of the mass, graphite and 5% ZrCh in the cold end parts of the HP to 70% graphite and 30% ZrCh in the HP part , in which it is necessary to create the maximum temperature.
  • the mass ratio of the amount of graphite and non-carbon material change continuously, for example, linearly, in accordance with any dependence or without it.
  • the mass ratio of the amount of electrically conductive material to the amount of non-conductive material can also change in steps, or change continuously in some parts of the heating element, and in steps in others.
  • changing the composition of the mixture from which the heating element is made ensures the creation of a temperature field gradient.
  • the proposed heating element is a chain of resistors connected in series with different electrical conductivity, which ensures the creation of a temperature gradient.
  • electrically conductive material such as lanthanum chromite LaCrO3 or high melting point metals such as platinum Pt, tantalum Ta or rhenium Re or their alloys, or diamond doped with boron, or diamond doped with any other element, increasing its electrical conductivity.
  • lanthanum chromite LaCrO3 high melting point metals such as platinum Pt, tantalum Ta or rhenium Re or their alloys, or diamond doped with boron, or diamond doped with any other element, increasing its electrical conductivity.
  • any non-conductive allotropic modification for example, in the form of diamond, which does not contain alloying elements, can be used as non-conductive, increasing its electrical conductivity.
  • the high-pressure cell consists of a ceramic shell, a graphite heater made in the form of a cylinder, the heater is locked from above and below by current-carrying washers connected to the current leads.
  • the heater is made by pressing from a mixture of graphite and stabilized cubic zirconia.
  • the heater consists of 80% of the mass, graphite and 20% of the mass.
  • ZrO 2 At the edges of the heater, its composition is a mixture of 90 wt% graphite and 10 wt%. ZrO 2 .
  • a cylindrical source of carbon in the form of graphite.
  • a metal washer made of a mixture of Fe and Co.
  • a substrate made of ceramic material, with a seed pressed into it - a diamond crystal.
  • the JVD is placed in a cubic press, and with the help of a press, a pressure of more than 4.5 GPa is created in the cell.
  • the heating power is increased at a rate of 30 W per minute.
  • the heating power reaches 6.5 kW, the operator stops the process of increasing the power. After a 300-hour exposure, the operator turns off the heating. After the pressure is released, the JVD is taken out of the cubic press. Inside the cell is a single crystal of diamond weighing 25 carats.
  • composition of the heater smoothly changes from 70 wt%, graphite and 30 wt%.
  • ZrO 2 in the central part of the JVD up to 90% of the mass, graphite and 10% of the mass.
  • ZrO 2 along the edges, and the change in composition is carried out in proportion to the distance from the center of the JVD.
  • a single crystal of diamond weighing 55 carats is located inside the cell.
  • the heater is made of diamond doped with boron, while in the central part of the heater the boron content in the diamond lattice is 0.5 wt%, and at the edges of the heater the boron content increases to 3%. And mass., and the change in composition is carried out in proportion to the distance from the center of the cell.
  • the JVD is placed in a cubic press, and with the help of a press, a pressure of more than 15 GPa is created in the cell.
  • NPD nano-polycrystal diamond

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne un élément de chauffage électrique, une cellule haute pression et un procédé de production et/ou traitement d'un matériau super-dur selon un procédé à haute pression et haute température. La cellule haute pression comprend un élément de chauffage électrique fait d'au moins un matériau conducteur d'électricité et d'au moins un matériau non conducteur d'électricité; le rapport en poids entre ledit au moins un matériau conducteur d'électricité et ledit au moins un matériau non conducteur d'électricité varie dans l'élément de chauffage électrique le long d'au moins une direction.
PCT/RU2022/050326 2021-10-19 2022-10-12 Élément de chauffage électrique, cellule haute pression WO2023068969A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2021130416 2021-10-19
RU2021130416A RU2771977C1 (ru) 2021-10-19 Электрический нагревательный элемент, ячейка высокого давления и способ получения и/или обработки сверхтвердого материала методом высокого давления и высокой температуры

Publications (1)

Publication Number Publication Date
WO2023068969A1 true WO2023068969A1 (fr) 2023-04-27

Family

ID=86058490

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2022/050326 WO2023068969A1 (fr) 2021-10-19 2022-10-12 Élément de chauffage électrique, cellule haute pression

Country Status (1)

Country Link
WO (1) WO2023068969A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU647894A1 (ru) * 1976-02-13 1979-02-15 Институт геологии и геофизики СО АН СССР Резистивный нагреватель
JPH0780275A (ja) * 1993-09-13 1995-03-28 Matsumoto Yushi Seiyaku Co Ltd 高温高圧用静水圧性ヒーター
US6124573A (en) * 1999-12-28 2000-09-26 Hall; David R. Metallized graphite heater for a high-pressure high-temperature reaction vessel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU647894A1 (ru) * 1976-02-13 1979-02-15 Институт геологии и геофизики СО АН СССР Резистивный нагреватель
JPH0780275A (ja) * 1993-09-13 1995-03-28 Matsumoto Yushi Seiyaku Co Ltd 高温高圧用静水圧性ヒーター
US6124573A (en) * 1999-12-28 2000-09-26 Hall; David R. Metallized graphite heater for a high-pressure high-temperature reaction vessel

Similar Documents

Publication Publication Date Title
Bundy et al. Diamond‐graphite equilibrium line from growth and graphitization of diamond
US3297407A (en) Method of growing diamond on a diamond seed crystal
Gendre et al. A study of the densification mechanisms during spark plasma sintering of zirconium (oxy-) carbide powders
JP4275896B2 (ja) ダイヤモンド多結晶体およびその製造方法
US4104441A (en) Polycrystalline diamond member and method of preparing same
US4643741A (en) Thermostable polycrystalline diamond body, method and mold for producing same
EP2641868B1 (fr) Corps polycristallin en diamant conducteur très dur et procédé de production
US7126090B2 (en) Ceramic heaters, a method for producing the same and articles having metal members
RU2771977C1 (ru) Электрический нагревательный элемент, ячейка высокого давления и способ получения и/или обработки сверхтвердого материала методом высокого давления и высокой температуры
JPH07278813A (ja) 熱拡散体を含むダイヤモンド化学蒸着装置
WO2023068969A1 (fr) Élément de chauffage électrique, cellule haute pression
Chen et al. Bridgman growth, crystallographic characterization and electrical properties of relaxor-based ferroelectric single crystal PIMNT
Kong et al. Synthesis of β-WC 1− x in an atmospheric-pressure, thermal plasma jet reactor
Wang et al. Graphite/diamond transformation mechanism under the action of an iron-based catalyst
JPH03199379A (ja) 化学蒸着法を用いる微結晶固体粒子の蒸着方法
DE69826193T2 (de) Bordotierter isotopischer Diamant und Verfahren zu seiner Herstellung
US3310501A (en) Preparation of elongated needle-like diamond having electrically conductive properties
US4231796A (en) Internal zone growth method for producing metal oxide metal eutectic composites
De la Fuente et al. Crystal fibers of Bi Sr Ca Cu O materials grown by the laser floating zone method
DE102011014204B4 (de) Verfahren zur Synthese von Diamanten
Stergioudi et al. Production and structural characterization of tailored made open-cell alumina–vanadia foams
JPS5825044B2 (ja) 炭化物の超微粉末製造方法およびその装置
Sorb et al. Diamond: high-pressure synthesis
Hong et al. Diamond formation from a system of SiC and a metal
RU2752346C1 (ru) Способ получения сверхтвёрдых материалов

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22884152

Country of ref document: EP

Kind code of ref document: A1