CN113181831B - Nonmetallic material powder and preparation method thereof - Google Patents
Nonmetallic material powder and preparation method thereof Download PDFInfo
- Publication number
- CN113181831B CN113181831B CN202110486263.8A CN202110486263A CN113181831B CN 113181831 B CN113181831 B CN 113181831B CN 202110486263 A CN202110486263 A CN 202110486263A CN 113181831 B CN113181831 B CN 113181831B
- Authority
- CN
- China
- Prior art keywords
- powder
- air flow
- nonmetallic
- heat source
- workpiece
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- 239000000843 powder Substances 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims description 25
- 238000007664 blowing Methods 0.000 claims abstract description 63
- 230000008018 melting Effects 0.000 claims abstract description 43
- 238000002844 melting Methods 0.000 claims abstract description 43
- 239000012768 molten material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000009833 condensation Methods 0.000 claims abstract description 15
- 230000005494 condensation Effects 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 239000007769 metal material Substances 0.000 claims abstract description 4
- 230000007246 mechanism Effects 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 27
- 238000004880 explosion Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000005192 partition Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011863 silicon-based powder Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
Abstract
The invention relates to non-metallic material powder and a preparation method thereof. The preparation method of the powder comprises the following steps: under the atmosphere of protective gas, the rotation of the nonmetallic workpiece is controlled, and the relative movement of the heat source and the nonmetallic workpiece is controlled, so that the heat source acts on the surface of the nonmetallic workpiece and forms a melting zone on the surface; introducing pulse air flow and blowing air flow into the melting area, enabling the pulse air flow and the blowing air flow to act on the melting area to enable the molten material to explode, and enabling the blowing air flow to blow out the exploded molten material; condensing the blown molten material to form a powder; the powder was collected in stages. Wherein the frequency of the pulse air flow is controlled, and the flow speed and the pressure of the blowing air flow are controlled to adjust the grain diameter of the molten material after explosion; the condensation rate is controlled to adjust the sphericity of the powder. The method can effectively improve the flexibility of nonmetal powder preparation and the accuracy of nonmetal powder particle size control.
Description
Technical Field
The invention relates to the field of powder material preparation, in particular to non-metal material powder and a preparation method thereof.
Background
In the forming process of the material, the powder is used as the raw material to prepare the corresponding product, and the method has more advantages, such as high process controllability, high preparation precision and the like. When preparing corresponding products from powders, the preparation of the powders is an important factor restricting the manufacture of the products. Taking silicon powder as an example, the methods which are commonly used at present are a mechanical ball milling method, a chemical vapor deposition method, a fluidized bed method, an evaporation condensation method and the like.
Specifically, the mechanical ball milling method mainly uses mechanical rolling force and shearing force generated by mechanical rotation and interaction among particles to grind materials with larger diameters into micrometer or even nanometer powder, and has the advantages of lower cost and simpler operation, but impurities can be introduced, the purity is low, the particles are irregularly shaped, and the particle size distribution cannot be effectively controlled. The chemical vapor deposition method and the fluidized bed method mainly pyrolyze silane to obtain corresponding silicon powder, and have the advantages of high purity, uniform particle size distribution and regular shape, but have the problems of complex process, high cost, high requirement on equipment and difficult preservation of raw materials. The evaporation condensation method gasifies the reaction raw material into gaseous atoms, molecules or partial ions into ions through a heat source, and the solid powder is obtained through rapid condensation.
In these methods, although some satisfactory powders can be obtained, the methods require continuous operation of the raw materials as a whole, have low flexibility, require complicated equipment and high energy consumption, require the whole treatment of the materials, and are difficult to perform fixed-point processing, resulting in an increase in the production cost of the powders.
Disclosure of Invention
Based on this, it is necessary to provide a nonmetallic material powder capable of effectively improving the processing flexibility of raw materials and improving the accuracy of particle diameter control, and a method for producing the same.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of nonmetal material powder comprises the following steps:
under the atmosphere of protective gas, controlling the nonmetallic workpiece to rotate, and controlling the heat source and the nonmetallic workpiece to move relatively, so that the heat source acts on the surface of the nonmetallic workpiece and forms a melting zone on the surface; introducing pulse air flow and blowing air flow into the melting area, wherein the pulse air flow and the blowing air flow act on the melting area to explode the molten material, and the blowing air flow blows out the exploded molten material; condensing the blown molten material to form a powder; classifying and collecting the powder;
wherein the frequency of the pulse air flow is controlled, and the flow speed and the pressure of the blowing air flow are controlled to adjust the grain size of the exploded molten material; the condensation rate is controlled to adjust the sphericity of the powder.
In one embodiment, the nonmetallic workpiece is in the shape of a block, a bar or a special-shaped shape.
In one embodiment, the heat source is a plasma heat source, an electron beam heat source, or a laser heat source.
In one embodiment, the air flow direction of the pulse air flow is perpendicular to the air flow direction of the blowing air flow, the air flow direction of the pulse air flow is perpendicular to the melting region, and the air flow direction of the blowing air flow is parallel to the melting region.
In one embodiment, when the heat source and the nonmetallic workpiece move relatively, the heat source moves in the X-axis direction relative to the nonmetallic workpiece and/or the heat source moves in the Y-axis direction relative to the nonmetallic workpiece, and the nonmetallic workpiece moves in the Z-axis direction relative to the heat source.
In one embodiment, the heat source is controlled to move relative to the nonmetallic workpiece to form a molten zone of a preset size at a preset location on the surface of the nonmetallic workpiece.
In one embodiment, the size of the melt zone ranges from 1 μm to 50 μm.
In one embodiment, the frequency of the pulsed air flow and the flow rate and pressure of the blowing air flow are controlled to obtain powders of different particle sizes simultaneously.
In one embodiment, the powder is collected in stages within the air flow field created by the blowing air flow as the powder is collected in stages.
A non-metallic material powder obtainable by the method of preparation as described in any one of the preceding examples.
The preparation method of the nonmetallic material powder comprises the following steps: under the atmosphere of protective gas, the rotation of the nonmetallic workpiece is controlled, and the relative movement of the heat source and the nonmetallic workpiece is controlled, so that the heat source acts on the surface of the nonmetallic workpiece and forms a melting zone on the surface; introducing pulse air flow and blowing air flow into the melting area, enabling the pulse air flow and the blowing air flow to act on the melting area to enable the molten material to explode, and enabling the blowing air flow to blow out the exploded molten material; condensing the blown molten material to form a powder; the powder was collected in stages. Wherein the frequency of the pulse air flow is controlled, and the flow speed and the pressure of the blowing air flow are controlled to adjust the grain diameter of the molten material after explosion; the condensation rate is controlled to adjust the sphericity of the powder. When the preparation method is adopted to prepare the nonmetal material powder, the specified positions on the nonmetal workpiece can be processed by the action of the heat source, the pulse air flow and the blowing air flow and by the cooperation of the relative movement of the heat source and the nonmetal workpiece, so that the corresponding nonmetal powder is obtained, and the preparation flexibility of the nonmetal powder can be effectively improved. In addition, the particle size of the molten material after explosion is adjusted by controlling the frequency of the pulse air flow and controlling the flow speed and the pressure of the blowing air flow; the condensing rate is controlled to adjust the sphericity of the powder, so that the accuracy of controlling the particle size of the nonmetallic powder can be effectively improved.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a powder of a nonmetallic material according to an embodiment of the present invention;
FIG. 2 is an enlarged view of a portion of FIG. 1 at A;
FIG. 3 is a schematic view of the powder preparation device of FIG. 1 at another angle;
FIG. 4 is a schematic view of the powder preparation device of FIG. 1 at another angle;
FIG. 5 is a schematic structural diagram of the powder prepared in example 1;
FIG. 6 is a schematic diagram of the structure of the powder prepared in example 2.
The figure indicates:
100. a nonmetallic material powder preparation device; 101. a case; 102. a clamp; 103. a nozzle; 104. an air flow pulse member; 105. a heat source; 106. a circulation pump; 107. a clamp driving mechanism; 108. a multi-axis driving mechanism; 109. a filter; 110. a pressure release valve; 111. a condensing member; 112. a heat exchanger; 113. a shielding gas supply device; 114. a reversing valve; 115. a partition plate; 116. a door; 1161. a transparent window; 117. a controller; 200. a nonmetallic workpiece; 300. and (3) powder.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
In the description of the present invention, it should be understood that the terms "center," "upper," "lower," "bottom," "inner," "outer," and the like are used in the description of the present invention merely for convenience in describing the present invention and to simplify the description, and do not denote or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
It should be understood that the terms "first," "second," and the like are used herein to describe various information, but such information should not be limited to these terms, which are used merely to distinguish one type of information from another. For example, a "first" message may also be referred to as a "second" message, and similarly, a "second" message may also be referred to as a "first" message, without departing from the scope of the invention. Two elements will also be considered to be "connected" when they are of unitary construction.
It will be understood that when an element is referred to as being "fixed to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the invention provides a preparation method of nonmetal material powder. The preparation method comprises the following steps: under the atmosphere of protective gas, the rotation of the nonmetallic workpiece is controlled, and the relative movement of the heat source and the nonmetallic workpiece is controlled, so that the heat source acts on the surface of the nonmetallic workpiece and forms a melting zone on the surface; introducing pulse air flow and blowing air flow into the melting area, enabling the pulse air flow and the blowing air flow to act on the melting area to enable the molten material to explode, and enabling the blowing air flow to blow out the exploded molten material; condensing the blown molten material to form a powder; classifying and collecting the powder; wherein the frequency of the pulse air flow is controlled, and the flow speed and the pressure of the blowing air flow are controlled to adjust the grain diameter of the molten material after explosion; the condensation rate is controlled to adjust the sphericity of the powder.
When the preparation method in the embodiment is adopted to prepare the nonmetal material powder, the specified position on the nonmetal workpiece can be processed by the action of the heat source, the pulse air flow and the blowing air flow and by the relative motion of the heat source and the nonmetal workpiece, so that the corresponding nonmetal powder is obtained, and the preparation flexibility of the nonmetal powder can be effectively improved. In addition, the particle size of the molten material after explosion is adjusted by controlling the frequency of the pulse air flow and controlling the flow speed and the pressure of the blowing air flow; the condensing rate is controlled to adjust the sphericity of the powder, so that the accuracy of controlling the particle size of the nonmetallic powder can be effectively improved.
It is understood that the nonmetallic workpieces are in the shape of blocks, bars, or profiled shapes. The block shape means a shape having a plurality of ridges such as prisms, pyramids, and the like. Specifically, triangular prisms, quadrangular prisms, pentagonal prisms, hexagonal prisms, triangular pyramids, rectangular pyramids, pentagonal pyramids, hexagonal pyramids, and the like. The bar shape means a cylindrical shape, a truncated cone shape, or the like. The irregularly shaped means a shape irregularly shaped, such as a shape without an axis of symmetry.
It is understood that the heat source is a plasma heat source, an electron beam heat source, or a laser heat source. In the preparation process, different heat sources 105 can be configured for the preparation device according to different customer needs, material properties and particle size requirements of the powder 300, so as to improve heating efficiency.
In a preferred embodiment, the direction of the pulsed air flow is perpendicular to the direction of the blowing air flow, the direction of the pulsed air flow is perpendicular to the melting zone, and the direction of the blowing air flow is parallel to the melting zone.
Specifically, when the heat source and the nonmetallic workpiece are relatively moved, the heat source moves in the X-axis direction relative to the nonmetallic workpiece and/or the heat source moves in the Y-axis direction relative to the nonmetallic workpiece, and the nonmetallic workpiece moves in the Z-axis direction relative to the heat source.
In one specific example, the relative movement of the heat source and the nonmetallic workpiece is controlled to form a molten zone of a preset size at a preset location of the surface of the nonmetallic workpiece.
Specifically, the size of the molten zone ranges from 1 μm to 50 μm. The size of the molten zone indicates the extent to which the nonmetallic workpiece melts. In some specific examples, the size of the melt zone ranges from 1 μm, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm.
In a specific example, the frequency of the pulsed air flow and the flow rate and pressure of the blowing air flow are controlled to obtain powders of different particle sizes simultaneously.
In a specific example, the powder is collected in stages in a gas flow field created by the gas flow of the blowing gas.
As a preferable range of the nonmetallic workpart spin speed, the nonmetallic workpart spin speed is 100rpm to 4000rpm. It is understood that the nonmetallic workplace spin speed may be, but is not limited to, 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, 1200rpm, 1500rpm, 1800rpm, 2000rpm, 2500rpm, 3000rpm, 3500rpm, or 4000rpm.
As a preferred range of the pulse gas flow frequency, the pulse gas flow frequency is 1-100kHz. It is understood that the frequency of the pulsed air flow may be, but is not limited to, 1kHz, 2kHz, 5kHz, 10kHz, 20kHz, 30kHz, 40kHz, 50kHz, 60kHz, 70kHz, 80kHz, 90kHz.
As a preferable range of the flow rate of the blowing air flow, the flow rate of the blowing air flow is 2 to 50L/min. For example, the flow rate of the blowing air flow may be, but is not limited to, 5L/min, 10L/min, 15L/min, 20L/min, 25L/min, 30L/min, 40L/min, or 45L/min.
As a preferable range of the pressure of the blowing air flow, the pressure of the blowing air flow is 2 to 20MPa. Alternatively, the pressure of the blowing gas stream may be, but is not limited to, 2MPa, 5MPa, 6MPa, 8MPa, 12MPa, 15MPa, 18MPa, or 20MPa.
As a preferred range of cooling rates for the condensing member, the cooling rate for the condensing member is 1000-10000K/s. For example, the cooling rate of the condensing member is 1000K/s, 2000K/s, 3000K/s, 4000K/s, 5000K/s, 6000K/s, 7000K/s, 8000K/s, 9000K/s.
In a further embodiment of the invention, a non-metallic powder is provided, which is obtained by the above preparation method.
In yet another embodiment, the invention provides a non-conductive powder prepared by any of the above methods.
In yet another embodiment, the invention provides an insulator powder prepared by any of the above methods of preparation.
In yet another embodiment, the present invention provides a semiconductor powder prepared by any one of the above preparation methods.
In yet another embodiment, the invention provides an alumina powder prepared by any of the above methods of preparation.
In yet another embodiment, the invention provides a silica powder prepared by any of the above methods.
In yet another embodiment, the present invention provides a silicon nitride powder prepared by any of the above methods.
In yet another embodiment, the invention provides a silicon carbide powder prepared by any of the above methods.
In yet another embodiment, the invention provides a silicon powder prepared by any of the above methods of preparation.
Referring to fig. 1 to 4, still another embodiment of the present invention provides a non-metal powder preparing apparatus 100, which is used to prepare non-metal powder. The powder preparation apparatus 100 includes a housing 101, a jig 102, a nozzle 103, an airflow pulse member 104, a heat source 105, a circulation pump 106, a jig driving mechanism 107, and a multi-axis driving mechanism 108. The clamp 102 is connected to the case 101 for clamping the nonmetallic workpiece 200, and the clamp driving mechanism 107 is connected to the clamp 102 for driving the clamp 102 to rotate so as to realize rotation of the nonmetallic workpiece 200. The multi-axis drive mechanism 108 is coupled to the heat source 105 for driving the heat source 105 in a plurality of different directions, the heat source 105 being capable of moving proximate to the nonmetallic workpiece 200 and forming a molten zone at the surface of the nonmetallic workpiece 200. The gas pulse 104 is connected to the tank 101 for forming a pulse gas flow and blowing the pulse gas flow to the melting zone, and the circulation pump 106 is connected to the gas pulse 104 for transferring the gas to the gas pulse 104. A nozzle 103 is connected to the tank 101 for introducing a blowing air flow in the melting zone and blowing out the molten material.
The relative movement of the heat source 105 and the nonmetallic workpiece 200 is controlled by a multi-axis drive mechanism 108. The frequency at which the air flow pulse 104 forms the pulse air flow is controlled, and the flow rate and pressure of the air-blowing air flow introduced from the nozzle are controlled to adjust the particle size of the molten material after explosion.
When the preparation device in this embodiment is used to prepare the powder 300, the nonmetallic workpiece 200 is mounted on the fixture 102, the fixture 102 is driven to rotate by the fixture driving mechanism 107 to realize the rotation of the nonmetallic workpiece 200, the position of the heat source 105 is adjusted by the multi-axis driving mechanism 108, so that the heat source 105 acts on the nonmetallic workpiece 200 and forms a melting area on the surface of the nonmetallic workpiece 200, the air flow pulse piece 104 forms pulse air flow and blows the pulse air flow to the melting area, and meanwhile, the nozzle 103 introduces air flow in the melting area to blow out the molten material. Under the action of the pulsed air flow and the air flow introduced from the nozzle 103, the molten material in the molten zone is dispersed to form droplets and blown out. The droplets are blown out and then condensed to form powder 300. Meanwhile, under the action of the clamp 102, the nonmetallic workpiece 200 is in a self-rotation state, so that liquid drops can be thrown out through centrifugal action, the dispersion degree of the liquid drops is improved, the interaction among the liquid drops is reduced, and the sphericity of the powder 300 is improved. In this process, the particle size of the powder 300 can be effectively controlled by controlling the rotation speed of the jig 102, the power of the heat source 105, the frequency of the airflow pulse member 104, the flow rate of the fluid medium, and the like. In addition, when the powder 300 preparation device is used, the relative movement of the heat source 105 and the nonmetal workpiece 200 can be realized by adjusting the position of the heat source 105, so that the processing travel range of the heat source 105 on the nonmetal workpiece 200 can be ensured, the preparation flexibility can be improved, and the powder preparation efficiency can be improved.
Further, when the preparation device of the invention is used for preparing the powder 300, the required powder 300 can be obtained through the cooperation of the clamp 102, the heat source 105, the airflow pulse piece 104 and the nozzle 103, the strict reaction condition is not needed, the operation method is simple, and the method is suitable for industrial production. In addition, through the arrangement of the circulating pump 106, a circulating flow field can be formed in the box body 101, so that the gas can be recycled, the gas emission is effectively avoided, the gas consumption is reduced, and the preparation cost of the powder 300 is reduced. In addition, other impurities are not introduced in the process of preparing the powder 300 due to the recycling of the gas, so that the purity of the powder 300 can be effectively improved.
In a preferred example, the number of nozzles 103 is plural, and the plurality of nozzles 103 are uniformly distributed on the outer periphery of the jig 102 for blowing out the molten material at different positions while the nonmetallic workpiece 200 rotates. Further preferably, a plurality of nozzles 103 are located on the same circumference. In this embodiment, the number of the nozzles 103 is 4, and the 4 nozzles 103 are located on the same circumference, so that in the rotation process of the non-metal workpiece 200, molten materials at different positions on the non-metal workpiece 200 can be timely blown out through the 4 nozzles 103, and the problem that the powder preparation is affected by condensation and solidification of the molten materials on the non-metal workpiece is avoided. It is understood that the number of nozzles 103 may be, but is not limited to, 1, 2, 3, 4, 5, etc.
It is understood that the nonmetallic workpiece 200 is a solid-of-revolution or non-solid-of-revolution structure. The rotation of the nonmetallic workpiece 200 is more stable at this time, so that the heat source 105 and the gas stabilize, and the molten material is more easily blown out. Preferably, the nonmetallic workpiece 200 is a cylindrical solid of revolution structure.
It will also be appreciated that in this embodiment the gas flows in the gas conduit, i.e. the transport of the gas is effected through the gas conduit. The gas pipeline is a conventional gas pipeline.
Specifically, still another embodiment of the present invention provides a non-conductor powder manufacturing apparatus 100, the non-conductor powder manufacturing apparatus 100 including a housing 101, a jig 102, a nozzle 103, an air flow pulse 104, a heat source 105, a circulation pump 106, a jig driving mechanism 107, and a multi-axis driving mechanism 108. The clamp 102 is connected to the case 101 for clamping the nonmetallic workpiece 200, and the clamp driving mechanism 107 is connected to the clamp 102 for driving the clamp 102 to rotate so as to realize rotation of the nonmetallic workpiece 200. The multi-axis drive mechanism 108 is coupled to the heat source 105 for driving the heat source 105 in a plurality of different directions, the heat source 105 being capable of moving proximate to the nonmetallic workpiece 200 and forming a molten zone at the surface of the nonmetallic workpiece 200. The gas pulse 104 is connected to the tank 101 for forming a pulse gas flow and blowing the pulse gas flow to the melting zone, and the circulation pump 106 is connected to the gas pulse 104 for transferring the gas to the gas pulse 104. A nozzle 103 is connected to the tank 101 for introducing a flow of air in the melting zone and blowing out the molten material.
As a preferred embodiment, when the airflow pulse member 104 is selected, the airflow pulse member generating the pulse waveform as a sine waveform is selected.
It will be appreciated that the multi-axis drive mechanism 108 is coupled to the heat source 105 for driving movement of the heat source 105 in a plurality of different directions, and in particular, the multi-axis drive mechanism 108 is coupled to the heat source 105 for driving movement of the heat source 105 in the X-axis, Y-axis, and Z-axis.
In a specific example, the air flow pulse 104 has an air outlet direction perpendicular to the air outlet direction of the nozzle 103. By setting the direction of the gas outlet of the nozzle 103 to be perpendicular to the direction of the gas outlet of the gas flow pulse member 104, the gas ejected from the nozzle 103 and the pulse gas flow formed by the gas flow pulse member 104 can be made to interact better. Further, the air outlet direction of the nozzle 103 is parallel to the rotation axis of the non-metal workpiece 200, and the air outlet direction of the air flow pulse member 104 is perpendicular to the rotation axis of the non-metal workpiece 200, so that the pulse air flow can act on the melting region of the non-metal workpiece 200 more fully to form a more uniform melting material, which is beneficial to improving the uniformity of the powder 300.
It is understood that one end of the circulation pump 106 is connected to the nozzle 103, and the other end is connected to the tank 101. Thus, the gas in the tank 101 can be circulated to the nozzle 103 by the circulation pump 106 to realize recycling. The process can not produce harmful substances such as waste gas, waste liquid, solid waste and the like, and is favorable for promoting the green development of powder preparation.
Preferably, the powder preparation device 100 further comprises a filter 109, the filter 109 being provided inside the tank 101 and being located at a position where the circulation pump 106 communicates with the penetration of the tank 101. By providing the filter 109, the powder 300 can be effectively separated from the gas, and adverse effects on the circulation line caused by the circulation line of the powder 300 can be effectively avoided. In this embodiment, the number of filter elements 109 is 2, and 2 filter elements 109 are respectively located at the inlet position and the outlet position of the circulating air flow in the box 101, so as to prevent the powder 300 from performing a circulation pipeline.
In a preferred embodiment, the powder preparation device 100 further comprises a pressure release valve 110, wherein the pressure release valve 110 is disposed outside the tank 101 and is located at a position where the circulation pump 106 is in communication with the penetration of the tank 101 for releasing pressure of the tank 101. In the preparation process of the powder 300, the inside of the box body 101 may form a large-pressure environment, the pressure of the box body 101 is relieved through the pressure relief valve 110, when the pressure inside the box body 101 is overlarge, the pressure inside the box body 101 can be timely reduced, the preparation of the powder 300 can be smoothly carried out, the stability of the box body 101 can be improved, and adverse effects of the high pressure on the device are avoided.
In another preferred embodiment, the powder preparing device 100 further comprises a condensing member 111, the condensing member 111 being provided inside the tank 101 for condensing the molten material. When the temperature of the molten material is high after the molten material is blown out by the gas, the cooling efficiency of the molten material can be improved and the powder forming efficiency of the powder 300 can be improved by providing the condensation member 111. It will be appreciated that when the powder 300 is attached to the condensation member 111, the powder 300 may be scraped off. Further, a storage plate, a storage cloth, or the like may be attached to the condensation material 111, and after the powder 300 is attached to the storage plate or the storage cloth, the powder 300 may be taken out by removing the storage plate or the storage cloth.
Further, the powder manufacturing apparatus 100 further includes a heat exchanger 112, and the heat exchanger 112 is connected to the condensation member 111 for reducing the temperature of the condensation member 111. The temperature of the condensing part 111 can be reduced by the arrangement of the heat exchanger 112, and the condensing efficiency can be improved. Meanwhile, the temperature in the box body 101 can be adjusted through the arrangement of the heat exchanger 112, so that the temperature condition suitable for preparing powder is kept in the box body 101, the temperature in the box body 101 is convenient to adjust, the preparation efficiency of the powder 300 can be further improved, and the quality of the powder 300 is improved.
It will be appreciated that the powder preparation device 100 further comprises a shielding gas supply 113, the shielding gas supply 113 being connected to the tank 101 for supplying shielding gas to the tank 101. The protective gas is provided for the box body 101 through the protective gas providing device 113, so that the preparation of the powder 300 is carried out under the protective gas atmosphere, external impurities are prevented from entering the box body 101, and the purity of the powder 300 is improved.
Preferably, the shielding gas supply apparatus 113 is located outside the case 101, and the shielding gas supply apparatus 113 is penetratingly connected to the case 101 for supplying shielding gas to the inside of the case 101. The protective gas is provided for the inside of the box body 101 through the protective gas providing device 113 so as to form a protective gas atmosphere in the box body 101, so that the purity of the powder 300 can be further improved, and the problems of oxidation, corrosion and the like of the powder 300 in the preparation process are avoided. The shielding gas supplied from the shielding gas supply device 113 may be an inert gas such as nitrogen gas or a rare gas.
Still further, the powder preparing apparatus 100 further includes a direction changing valve 114, the direction changing valve 114 being connected to the outside of the case 101 for adjusting the direction of the air flow, and the air flow pulsing member 104, the circulation pump 106, and the shielding gas supplying means 113 are connected to the direction changing valve 114, respectively. This can facilitate control of the flow direction of the gas and improve the preparation efficiency of the powder 300.
In one specific example, the powder preparation device 100 further includes a partition 115, the partition 115 protruding from the bottom of the tank 101 and/or the partition 115 protruding from the top of the tank 101 for separating the powders 300 of different particle sizes. It will be appreciated that the powder 300 has a range of particle sizes, and under the action of the airflow field, the powder 300 with a larger particle size has a shorter flight time, and the powder 300 with a smaller particle size has a longer flight time, so that the powder 300 can be primarily screened by the partition 115, and the workload of subsequent screening is reduced. In this embodiment, the number of the baffles 115 is 2, and 2 baffles 115 are respectively disposed at the top and bottom of the tank 101 for primarily screening the powder 300.
Referring again to fig. 4, it will be appreciated that the powder manufacturing apparatus 100 further includes a box door 116, and that the box door 116 cooperates with the housing 101 to form a sealed processing space in which the nonmetallic workpieces 200 are processed to manufacture the corresponding powders 300. Further, a transparent window 1161 is provided on the door 116 for observing the preparation inside the cabinet 101. Still further, the powder preparing device 100 further comprises a controller 117, wherein the controller 117 is used for controlling the rotation speed of the fixture 102, the power of the heat source 105, the frequency of the airflow pulse member 104, the parameters of the circulation pump 106, etc. to achieve intelligent preparation of the powder 300.
Referring to fig. 1 and 2 again, when the powder 300 is prepared, the non-metal workpiece 200 rotates under the driving of the fixture 102, the heat source 105 heats the non-metal workpiece 200 to form a melting zone, and the air flow pulse member 104 forms a pulse air flow, and the pulse air flow acts on the melting zone and blows out the molten material in cooperation with the action of the nozzle 103. In powder preparation, the heat source 105 can move in three directions of an X axis, a Y axis and a Z axis, so that the processing travel range of the heat source 105 on the nonmetallic workpiece 200 can be ensured, and the powder preparation efficiency is improved.
The following are specific examples.
Example 1
In the embodiment, the nonmetallic workpiece is a silicon rod of a revolving body, the diameter is 100mm, and the length is 300mm. Silicon powder was prepared using the apparatus shown in fig. 1. The heat source is a laser heat source. The shielding gas is argon.
And (5) after the workpiece is cleaned and dried, the workpiece is mounted on a clamp, and the box door is closed. A protective gas atmosphere is formed inside the case. The spin speed of the workpiece was adjusted to 2000rpm. And adjusting the relative position between the heat source and the workpiece, and applying the heat source to the surface of the nonmetallic workpiece to form a melting zone on the surface, wherein the size of the melting zone is 10-30 mu m.
The air flow direction of the pulse air flow is perpendicular to the air flow direction of the blowing air flow, the air flow direction of the pulse air flow is perpendicular to the melting area, and the air flow direction of the blowing air flow is parallel to the melting area. The frequency of the pulsed air flow was 20kHz. The flow rate of the blowing air stream was 5L/min. The pressure of the blowing air stream was 6MPa. The cooling rate of the condensate was 1000K/s. The collected powder structure is shown in fig. 5. As can be seen from fig. 5, the powder obtained in this example has a smaller particle size, higher uniformity, and higher sphericity.
Example 2
In the embodiment, the nonmetallic workpiece is a silicon rod of a revolving body, the diameter is 100mm, and the length is 300mm. Silicon powder was prepared using the apparatus shown in fig. 1. The heat source is a laser heat source. The shielding gas is argon.
And (5) after the workpiece is cleaned and dried, the workpiece is mounted on a clamp, and the box door is closed. A protective gas atmosphere is formed inside the case. The spin speed of the workpiece was adjusted to 2000rpm. And adjusting the relative position between the heat source and the workpiece, and applying the heat source to the surface of the nonmetallic workpiece to form a melting zone on the surface, wherein the size of the melting zone is 10-30 mu m.
The air flow direction of the pulse air flow is perpendicular to the air flow direction of the blowing air flow, the air flow direction of the pulse air flow is perpendicular to the melting area, and the air flow direction of the blowing air flow is parallel to the melting area. The frequency of the pulsed air flow was 10kHz. The flow rate of the blowing air stream was 5L/min. The pressure of the blowing air stream was 5MPa. The cooling rate of the condensate was 1000K/s. The collected powder structure is shown in fig. 6. As can be seen from fig. 6, the powder obtained in this example has a smaller particle size, higher uniformity, and higher sphericity.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the nonmetallic material powder is characterized by comprising the following steps of:
under the atmosphere of protective gas, controlling the nonmetallic workpiece to rotate, and controlling the heat source and the nonmetallic workpiece to move relatively, so that the heat source acts on the surface of the nonmetallic workpiece and forms a melting zone on the surface; introducing pulse air flow and blowing air flow into the melting area, wherein the pulse air flow and the blowing air flow act on the melting area to explode the molten material, and the blowing air flow blows out the exploded molten material; condensing the blown molten material to form a powder; classifying and collecting the powder, wherein the powder is classified and collected in an air flow field formed by the blowing air flow;
the heat source is a plasma heat source, the airflow direction of the pulse airflow is vertical to the airflow direction of the blowing airflow, the airflow direction of the pulse airflow is vertical to the melting area, and the airflow direction of the blowing airflow is parallel to the melting area; controlling the frequency of the pulsed air flow and the flow rate and pressure of the blowing air flow to adjust the particle size of the exploded molten material; the condensation rate is controlled to adjust the sphericity of the powder.
2. The method for producing a nonmetallic material powder as defined in claim 1, wherein the nonmetallic workpiece has a block shape, a rod shape, or a special-shaped shape.
3. The method for producing a powder of a nonmetallic material according to claim 1, wherein the nonmetallic workpiece rotates at a speed of 100rpm to 4000rpm; and/or the flow speed of the blowing air flow is 2-50L/min; and/or the pressure of the blowing air flow is 2-20 MPa; and/or the frequency of the pulse airflow is 1-100 kHz; and/or the condensation rate is 1000-10000K/s.
4. The method for producing a powder of a nonmetallic material according to claim 1, characterized in that the powder is produced using a powder production apparatus; the powder preparation device comprises a box body, a clamp, a nozzle, an airflow pulse piece, a heat source, a circulating pump, a clamp driving mechanism and a multi-shaft driving mechanism;
the clamp is connected to the box body and used for clamping the nonmetallic workpiece, and the clamp driving mechanism is connected with the clamp and used for driving the clamp to rotate so as to realize rotation of the nonmetallic workpiece; the multi-shaft driving mechanism is connected with the heat source and used for driving the heat source to move in a plurality of different directions, and the heat source can move to be close to the nonmetallic workpiece and form the melting zone on the surface of the nonmetallic workpiece; the air flow pulse piece is connected with the box body and used for forming the pulse air flow and blowing the pulse air flow to the melting area; the circulating pump is connected with the airflow pulse piece and used for transferring the gas to the airflow pulse piece; the nozzle is connected to the tank for introducing the blowing gas stream at the melting zone and blowing the molten material out.
5. The method of producing a nonmetallic material powder as defined in claim 4, wherein the number of the nozzles is plural, and the plural nozzles are uniformly distributed on the outer periphery of the jig for blowing out the molten material at different positions when the nonmetallic workpiece rotates.
6. The method of producing a powder of a nonmetallic material according to any one of claims 1 to 5, wherein the heat source moves in an X-axis direction relative to the nonmetallic workpiece and/or the heat source moves in a Y-axis direction relative to the nonmetallic workpiece, and the nonmetallic workpiece moves in a Z-axis direction relative to the heat source, when the heat source and the nonmetallic workpiece move relatively.
7. The method of producing a powder of a nonmetallic material according to any one of claims 1 to 5, wherein the relative movement of the heat source and the nonmetallic workpiece is controlled to form a molten zone of a predetermined size at a predetermined position on the surface of the nonmetallic workpiece.
8. The method of claim 7, wherein the size of the molten zone is in the range of 1 μm to 50 μm.
9. The method for producing a powder of a nonmetallic material according to any one of claims 1 to 5, characterized in that the frequency of the pulsed air flow and the flow rate and pressure of the blowing air flow are controlled to obtain powders of different particle diameters at the same time.
10. A non-metallic material powder obtained by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110486263.8A CN113181831B (en) | 2021-04-30 | 2021-04-30 | Nonmetallic material powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110486263.8A CN113181831B (en) | 2021-04-30 | 2021-04-30 | Nonmetallic material powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113181831A CN113181831A (en) | 2021-07-30 |
| CN113181831B true CN113181831B (en) | 2024-01-30 |
Family
ID=76983409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110486263.8A Active CN113181831B (en) | 2021-04-30 | 2021-04-30 | Nonmetallic material powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113181831B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149506A (en) * | 1995-11-06 | 1997-05-14 | 中国科学院物理研究所 | Flame method for preparing micron crystal ball material |
| KR20040067608A (en) * | 2003-01-24 | 2004-07-30 | (주)나노닉스 | Metal powder and the manufacturing method |
| CN108025364A (en) * | 2015-06-05 | 2018-05-11 | 派洛珍尼西斯加拿大公司 | For with the plasma apparatus of high production capacity production high-quality spherical powder |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4689074A (en) * | 1985-07-03 | 1987-08-25 | Iit Research Institute | Method and apparatus for forming ultrafine metal powders |
| CN103433499B (en) * | 2013-08-27 | 2015-08-12 | 湖南航天工业总公司 | A kind of ultrasonic atomizatio preparation facilities of globular metallic powder and preparation method |
| CA3039695C (en) * | 2014-03-11 | 2019-10-29 | Tekna Plasma Systems Inc. | Process and apparatus for producing powder particles by atomization of a feed material in the form of an elongated member |
| CN106001589B (en) * | 2016-07-19 | 2017-12-05 | 株洲科能新材料有限责任公司 | A kind of method that brittle metal microballoon is prepared based on metallic microspheres shaped device |
| CN108637267A (en) * | 2018-05-14 | 2018-10-12 | 王海军 | A kind of device and method preparing spherical metal powder using metal wire material |
| CN109108301A (en) * | 2018-11-09 | 2019-01-01 | 中国工程物理研究院机械制造工艺研究所 | Based on laser molten metal atomising material milling method |
| CN110076347B (en) * | 2019-06-06 | 2020-09-01 | 南京工业大学 | Combined powder preparation method and device based on plasma smelting and disc rotary atomization |
-
2021
- 2021-04-30 CN CN202110486263.8A patent/CN113181831B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149506A (en) * | 1995-11-06 | 1997-05-14 | 中国科学院物理研究所 | Flame method for preparing micron crystal ball material |
| KR20040067608A (en) * | 2003-01-24 | 2004-07-30 | (주)나노닉스 | Metal powder and the manufacturing method |
| CN108025364A (en) * | 2015-06-05 | 2018-05-11 | 派洛珍尼西斯加拿大公司 | For with the plasma apparatus of high production capacity production high-quality spherical powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113181831A (en) | 2021-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100530530C (en) | Plasma processing apparatus and plasma processing method | |
| JP5346323B2 (en) | Method, system and classifier for dividing silicon piece mixture into at least two size distributions | |
| JP6495323B2 (en) | Glass batch processing method and apparatus using dual source cyclone plasma reactor | |
| KR101994140B1 (en) | Glaze composition for high hardness glaze layer and manufacturing method of ceramic floor tile having excellent scratch resistance using the composition | |
| CN107470639B (en) | A kind of preparation method of narrow size distribution globular tungsten powder | |
| RU2406592C2 (en) | Method and device to produce nanopowders using transformer plasmatron | |
| CN113181831B (en) | Nonmetallic material powder and preparation method thereof | |
| US7823810B2 (en) | Method and device for the production and/or conditioning of powdered material | |
| TWI723114B (en) | Method for producing nonstoichiometric titanium oxide fine particle | |
| KR101555328B1 (en) | Structure of multiple classification cyclone for manufacturing nano powder | |
| CN113042743A (en) | Powder preparation device | |
| TW202031590A (en) | Apparatus of producing fine particles and method of producing fine particles | |
| CN218946351U (en) | Powder preparation device | |
| KR20200056073A (en) | Manufacturing apparatus and manufacturing method of nanopowder using DC arc plasma and apparatus for manufacturing the same | |
| KR101724359B1 (en) | Method of manufacturing of silicon nanopowder and Apparatus of manufacturing of silicon nanopowder | |
| JP6941299B2 (en) | Surface treatment equipment and surface treatment method | |
| CN1559662A (en) | Production technology for synthesizing multikind nanometer powder by plasma | |
| TWI471266B (en) | Method for manufacturing carbide fine particles | |
| CN108190848A (en) | A kind of multistage fragmentation, the method for particle screen selecting prepare compound powder | |
| JPH06299209A (en) | Formation of powder granule of magnetic material | |
| CN1334159A (en) | Atomizing pulverization technology and apparatus by high-power high-frequency electromagnetic oscillasion | |
| Zhuo et al. | Possibilities of the Electron-Beam Machine «LUCH» for Dimensional Microprocessing of Glass and Ceramic Materials | |
| CN104962882B (en) | A kind of magnetic controlled plasma micro porous coating device | |
| KR20200105015A (en) | Apparatus for a oxide powder | |
| KR20190129420A (en) | Apparatus of manufacturing foamed metal by thermal spray |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |