CN114918417B - Preparation method of spherical silicon-tungsten composite powder - Google Patents
Preparation method of spherical silicon-tungsten composite powder Download PDFInfo
- Publication number
- CN114918417B CN114918417B CN202210619330.3A CN202210619330A CN114918417B CN 114918417 B CN114918417 B CN 114918417B CN 202210619330 A CN202210619330 A CN 202210619330A CN 114918417 B CN114918417 B CN 114918417B
- Authority
- CN
- China
- Prior art keywords
- powder
- silicon
- tungsten
- composite powder
- tungsten composite
- 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 277
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000002131 composite material Substances 0.000 title claims abstract description 153
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 71
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 69
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 46
- 238000001238 wet grinding Methods 0.000 claims abstract description 37
- 238000001694 spray drying Methods 0.000 claims abstract description 30
- 238000007873 sieving Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 51
- 238000000498 ball milling Methods 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000012300 argon atmosphere Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 28
- 230000001681 protective effect Effects 0.000 claims description 25
- 239000012159 carrier gas Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000011362 coarse particle Substances 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 abstract description 20
- 239000010937 tungsten Substances 0.000 abstract description 20
- 229910052710 silicon Inorganic materials 0.000 abstract description 16
- 239000010703 silicon Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000013077 target material Substances 0.000 abstract description 3
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 11
- 238000000227 grinding Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000010952 cobalt-chrome Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/026—Spray drying of solutions or suspensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the field of powder metallurgy, and particularly relates to a preparation method of spherical silicon-tungsten composite powder. The invention provides a preparation method of spherical silicon-tungsten composite powder, which aims to solve the problems that the silicon-tungsten composite powder prepared by the method in the prior art is not uniform spherical and has poor fluidity. The preparation method of the invention takes tungsten powder and silicon powder as raw materials, and prepares the spherical silicon-tungsten composite powder after wet grinding, spray drying, plasma spheroidization and sieving. The method can be used for preparing the spherical silicon-tungsten composite powder with evenly distributed silicon and tungsten, high balling rate and good fluidity, thereby better meeting the requirements of silicon-tungsten target material market on higher quality and larger yield of the spherical silicon-tungsten composite powder. The silicon-tungsten composite powder prepared by the preparation method can be applied to preparing silicon-tungsten targets with evenly distributed silicon and tungsten, and further expands the application range of the silicon-tungsten composite powder.
Description
Technical Field
The invention belongs to the field of powder metallurgy, and particularly relates to a preparation method of spherical silicon-tungsten composite powder.
Background
The synchronous development of sputtering targets and sputtering technology has greatly satisfied the development demands of various novel electronic components since the 90 th century. For example, in the semiconductor integrated circuit manufacturing process, aluminum film wiring is replaced with a copper conductor thin film having a low resistivity: in the flat panel display industry, various display technologies (such as LCD, PDP, OLED and FED) have been developed simultaneously, and some have been used for the manufacture of computers and displays of computers; in the information storage industry, the storage capacity of magnetic memories is continuously increased, new magneto-optical recording materials are continuously pushed out, and these materials all put higher and higher demands on the quality of required sputtering targets, and the number of demands is also increased year by year.
The silicon tungsten target is widely applied to the fields of electronic grid materials, electronic films and the like because the sputtered film is a good conductor. The silicon tungsten composite powder is used as a main raw material of the silicon tungsten target, and the diversity of the performance of the silicon tungsten composite powder directly influences the performance of the subsequent target, so that the silicon tungsten composite powder with different performances is researched and developed, and the application market of the silicon tungsten composite powder and the silicon tungsten target can be widened. The performance of the silicon-tungsten composite powder influences the performance of the silicon-tungsten product to a great extent. The quality of the silicon-tungsten composite powder is guaranteed to ensure the excellent performance of the silicon-tungsten alloy, the silicon-tungsten composite powder industry faces great challenges, the increasingly high requirements of the market on the silicon-tungsten composite powder must be met, the production of the silicon-tungsten composite powder has not only the requirements on chemical purity, but also the requirements on physical performance and technological performance, and particularly the preparation technology of superfine tungsten silicon powder for meeting some special purposes is still to be solved. The silicon-tungsten composite powder is prepared by adopting silicon oxide and tungsten trioxide as raw materials through hydrogen reduction reaction, and the silicon-tungsten composite powder is one of the processes; the traditional hydrogen reduction process flow is to bake the raw materials to obtain tungsten trioxide and silicon oxide, and then reduce the tungsten silicon powder in two stages to obtain tungsten silicon powder, and the following problems exist in the preparation of the tungsten silicon powder by using the traditional process: 1. the reduction temperature is low, the reaction time is long, and the time is wasted; 2. the tubular reduction furnace is adopted, so that the equipment is complex and energy is not saved; 3. the product purity is low, and the continuous production is difficult.
At present, the preparation of the tungsten silicon composite powder generally has a mechanical mixing mode, and generally has a wet mixing and dry mixing mode, but for silicon powder and tungsten powder with smaller granularity, if dry mixing is adopted, on the one hand, the silicon powder and the tungsten powder are not easy to mix uniformly, on the other hand, dust is easy to fly, and researchers adopt a series of modes to solve the problems, for example, chinese patent with the authority of publication number CN 103695852B and entitled "manufacturing method of tungsten silicon target" discloses: the tungsten powder and the silicon powder are mixed in a wet mixing mode, tungsten balls are used as grinding medium balls, the proper mass ratio of the balls is (2:1) - (5:1), the added liquid is a mixed solution of ethanol and glycerol with the mass ratio of 1:1, in the method disclosed by the patent, although dust flying can be avoided, the liquid used for wet mixing is based on the ethanol, glycerol is used, the viscosity of the glycerol is high, the tungsten powder and the silicon powder are bonded together in the mixing and stirring process, and the composite powder is easy to agglomerate, so that the composite powder is uneven, the surface morphology of the prepared composite powder is irregular, and the performance is poor; as another example, application number 202111133848.8, a technical scheme disclosed in the chinese patent application entitled "a method for preparing a tungsten-silicon target blank" is to perform high-energy ball milling on mixed powder of tungsten powder and silicon powder to obtain primary alloy powder, so that the obtained powder has the defects of powder agglomeration, uneven morphology and the like, and meanwhile, the ball milling time is 50-60h, the time is too long, and the cost is high.
The tungsten silicon composite powder prepared by the prior method is not uniform spherical, so the problem of poor fluidity is common. And for the technicians in the industry, the spherical silicon-tungsten composite powder has the advantage of good fluidity, and can meet the higher requirements and special requirements of the industry on the fluidity of the silicon-tungsten composite powder. In the preparation of spherical metal powders, a great deal of research has been conducted by numerous researchers. For example, patent CN108213445a discloses a plasma preparation method of spherical cobalt chromium powder for laser selective melt forming, which comprises the following steps: 1) Selecting raw materials: respectively selecting 27-30wt% of chromium, 5-7wt% of molybdenum, less than or equal to 1wt% of silicon, less than or equal to 1wt% of manganese, less than or equal to 0.5wt% of nickel, less than or equal to 0.2wt% of tungsten, less than or equal to 0.7wt% of iron and the balance of cobalt according to the total mass of the raw materials of 100 wt%; 2) Smelting raw materials: uniformly mixing the selected raw materials and smelting to obtain an alloy ingot; 3) Annealing: annealing the alloy ingot in a vacuum environment; 4) Crushing: crushing the annealed alloy ingot into powder to prepare cobalt-chromium alloy powder; 5) Preparing spherical cobalt-chromium alloy powder by using plasma: establishing a stable plasma torch; argon carries cobalt-chromium alloy powder into a plasma torch, so that the cobalt-chromium alloy powder is melted into liquid drops, and the liquid drops are cooled and solidified to obtain spherical cobalt-chromium powder. Further, as disclosed in patent CN110605385a, a method for preparing a tungsten-based micro-nano composite powder and the tungsten-based micro-nano composite powder are disclosed, which comprises the following steps: s1: adding spherical tungsten powder and spherical nano powder into a solvent, fully stirring by using a stirrer, and then performing ultrasonic treatment by using ultrasonic waves to obtain paste; s2: stopping ultrasonic treatment, and stirring again by using a stirrer after the solvent in the paste is completely volatilized to obtain powder; s3: filtering the powder through a screen to obtain the tungsten-based micro-nano composite powder.
Although the above method has been well studied for preparing spherical metal powder, at present, researchers have not explored how to prepare spherical silicon-tungsten composite powder with uniform distribution of silicon and tungsten and good fluidity, and the above method is still complex and high in cost for preparing spherical metal powder, the spherical distribution is not uniform enough, and the fluidity of the product needs to be further improved. Therefore, along with the increasing demand of the market for spherical silicon-tungsten composite powder with evenly distributed silicon and tungsten and better fluidity, how to prepare spherical silicon-tungsten composite powder with evenly distributed silicon and tungsten and better fluidity is a technical problem to be solved.
Disclosure of Invention
In order to solve the problems that the silicon-tungsten composite powder prepared by the existing method is not uniform spherical and has poor fluidity, the invention provides the preparation method of the spherical silicon-tungsten composite powder, and the spherical silicon-tungsten composite powder with uniformly distributed silicon and tungsten, high balling rate and good fluidity can be prepared by adopting the method of the invention, so that the requirements of silicon-tungsten target material market on higher quality and higher yield of the spherical silicon-tungsten composite powder are better met.
In one aspect of the invention, the invention provides a method for preparing spherical silicon-tungsten composite powder, which comprises the following steps: the spherical silicon-tungsten composite powder is obtained by taking tungsten powder and silicon powder as raw materials and performing wet grinding, spray drying, plasma spheroidization and sieving.
In another aspect of the invention, the invention provides a preparation method of spherical silicon-tungsten composite powder, which comprises the following specific steps:
(1) In a ball mill, wet-milling tungsten powder and silicon powder in a wet-milling medium and a protective atmosphere until the tungsten powder and the silicon powder are uniformly mixed;
(2) Spray drying the wet-ground mixture in the step (1) to prepare a spheroid-like mixture;
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder.
Further, the wet milling medium in step (1) is selected to be alcohol.
Further, the protective atmosphere argon in the step (1) is adopted.
Further, the mass content of tungsten powder in the powder after uniform mixing in the step (1) is 60-80%.
Further, in the wet milling process in the step (1), the ball-material ratio is controlled to be 1:1-3:1, the solid-liquid ratio of materials in the ball mill is controlled to be 3:1-4:1, and the ball milling time is 6-10 h.
Further, the spray drying in the step (2) is performed at 80 to 90 ℃.
Further, during spray drying in the step (2), argon atmosphere is adopted, the spray rotating speed is controlled to be 20-40 Hz, and the feeding speed is controlled to be 80-120 Hz.
Further, in the step (3), the flow rate of the powder feeding carrier gas is set to be 5-15L/min, the flow rate of the plasma gas is set to be 2-8L/min, and the flow rate of the protective gas is set to be 10-30L/min during the spheroidization of the plasma.
Further, in the step (3), the powder feeding rotating speed is controlled to be 2-10 r/min during the plasma spheroidization.
Further, the preparation method further comprises the step of sieving the silicon-tungsten composite powder after the spheroidization in the step (3) to remove coarse particles, thereby obtaining the spherical silicon-tungsten composite powder.
In another aspect of the invention, the invention provides spherical silicon-tungsten composite powder, which is prepared by adopting the method.
In another aspect of the invention, the invention also provides application of the spherical tungsten silicon composite powder in preparing tungsten silicon targets.
The invention has the beneficial effects that:
1. the tungsten powder and the silicon powder can be effectively mixed by wet grinding under the atmosphere of alcohol and argon; alcohol is used as a grinding medium and argon atmosphere is used as a shielding gas, so that the material oxygenation in the wet grinding process can be avoided, and the quality of subsequent products is influenced.
2. The mixture after wet grinding can be made into spheroidal shape by spray drying, so that the fluidity of the mixture is improved, and the subsequent plasma spheroidization powder feeding is facilitated; meanwhile, the alcohol can be removed, and adverse effects caused by the alcohol in the plasma spheroidizing process are avoided, so that the silicon-tungsten composite powder with good sphericity is prepared.
3. The silicon-tungsten composite powder prepared by the method has high balling rate, good fluidity and best flow rate of 7.5s.
Drawings
FIG. 1 is a process flow diagram of a method of making the present invention;
FIG. 2 is a graph of the microscopic morphology of the composite powder with high balling rate prepared in example 1;
FIG. 3 is a graph of the microscopic morphology of the composite powder with a general ball forming rate prepared in comparative example 1.
Detailed Description
The present invention will be further described in the following examples for the purpose of more clearly understanding the objects, technical solutions and advantageous effects of the present invention, but the scope of the present invention is not limited to the following examples, which are given by way of illustration only and are not intended to limit the scope of the present invention in any way. The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the related raw materials are all commercial conventional industrial raw materials unless specified; the processing and manufacturing methods are conventional methods unless otherwise specified. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
In order to solve the problems that the silicon-tungsten composite powder prepared by the existing method is not uniform spherical and has poor fluidity, the invention provides the preparation method of the spherical silicon-tungsten composite powder, and the spherical silicon-tungsten composite powder with uniformly distributed silicon and tungsten, high balling rate and good fluidity can be prepared by adopting the method of the invention, so that the requirements of silicon-tungsten target material market on higher quality and higher yield of the spherical silicon-tungsten composite powder are better met.
In one aspect of the invention, the invention provides a method for preparing spherical silicon-tungsten composite powder, which comprises the following steps: the spherical silicon-tungsten composite powder is obtained by taking tungsten powder and silicon powder as raw materials and performing wet grinding, spray drying, plasma spheroidization and sieving.
In another aspect of the invention, the invention provides a preparation method of spherical silicon-tungsten composite powder, which comprises the following specific steps:
(1) In a ball mill, wet-milling tungsten powder and silicon powder in a wet-milling medium and a protective atmosphere until the tungsten powder and the silicon powder are uniformly mixed;
(2) Spray drying the wet-ground mixture in the step (1) to prepare a spheroid-like mixture;
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder.
Further, in an embodiment of the present invention, the wet milling medium in step (1) is selected to be alcohol. Oxidation of the mixture during wet milling is a detrimental effect, and the wet milling medium is selected as alcohol in order to minimize the effect of oxidation. Further, in order to minimize the influence of oxidation, the present invention preferably uses absolute alcohol as a wet milling medium, and more preferably, the present invention selects the absolute alcohol to have a purity of 99% or more. However, the alcohol of the present invention is not particularly limited, and any commercially available alcohol materials known to those skilled in the art may be used.
Further, in an embodiment of the present invention, the protective atmosphere is argon in step (1). The oxidation of air in the wet milling process of the mixture is a detrimental effect, and in order to minimize the effect of the oxidation, the protective atmosphere is preferably argon. Further preferably, the protective atmosphere is high-purity argon, and further preferably, the purity of the high-purity argon is 99.999%; however, the argon gas is not particularly limited, and commercially available argon gas, which is well known to those skilled in the art, may be used.
Further, in the embodiment of the invention, the tungsten powder and the silicon powder can be effectively mixed by wet grinding under the atmosphere of alcohol and argon; alcohol is used as a grinding medium and argon atmosphere is used as a shielding gas, so that the material oxygenation in the wet grinding process can be avoided, and the quality of subsequent products is influenced.
Further, in the embodiment of the invention, the mass content of the tungsten powder in the powder after being uniformly mixed in the step (1) is 60% -80%. The inventor researches find that the spherical tungsten silicon composite powder is easier to prepare in the reasonable tungsten powder mass content range. The tungsten powder is difficult to mix uniformly when the mass content is too low, and the silicon and tungsten in the composite powder are unevenly distributed; the tungsten powder has the advantages of excessively high mass content, reduced balling rate and poor powder flowability. Therefore, the mass content of the tungsten powder in the range can ensure the best silicon and tungsten uniform distribution and good fluidity effect of the prepared spherical tungsten silicon composite powder.
Further, in the embodiment of the present invention, in the wet milling process in the step (1), the ball-to-material ratio is controlled to be 1:1-3:1; ball-to-material ratio refers to the ratio of the weight of the ground balls to the weight of the material in the ball mill. The larger the ball-to-material ratio is, the larger the contact area between the ball and the material is, and the higher the grinding efficiency is. In a certain range, the ball-material ratio is improved, so that the grinding efficiency can be improved, the performance of the mixture is changed, and good product organization structure and performance can be obtained, but the ball-material ratio cannot be excessively large. The ball-to-material ratio is too large, so that the idle work of friction and impact between the grinding balls and between the grinding balls and the inner wall of the ball mill cylinder is increased, the efficiency is reduced, and the energy consumption and the abrasion of the grinding balls and the ball mill cylinder are increased. If the ball-to-material ratio is too small, the buffer effect of the increase of the material on the impact of the grinding ball is enhanced, meanwhile, the grinding ball is reduced, the impact and friction times of the grinding ball are correspondingly reduced, and the efficiency and the crushing effect are also not ideal. Therefore, the spherical material ratio in the range of the invention can ensure the best silicon and tungsten uniform distribution and better fluidity effect of the prepared spherical silicon-tungsten composite powder.
Further, in the embodiment of the invention, the solid-to-liquid ratio of the materials in the ball mill in the wet milling process in the step (1) is 3:1-4:1. The solid-to-liquid ratio refers to the ratio of the weight of the added mixture to the volume of the liquid medium. In general, the slurry has an optimum polishing efficiency when the solid-to-liquid ratio is proper. Therefore, the solid-liquid ratio in the range can ensure the best silicon and tungsten uniform distribution and good fluidity effect of the prepared spherical silicon-tungsten composite powder.
Further, in the embodiment of the present invention, the ball milling time is controlled to be 6 to 10 hours during the wet milling in the step (1). The ball milling time cannot be too short, otherwise, silicon and tungsten cannot be well distributed uniformly; however, the milling time is not too long, and the specific surface area and oxygen content of the mixture are increased synchronously with the extension of the wet milling time, and the milling time is preferably selected to be 6-10 h in order to minimize the influence of oxidation.
Further, in an embodiment of the present invention, the spray drying in step (2) is performed at 80 to 90 ℃. Spray drying is a process in which a high-speed rotating atomizer is used to disperse a feed liquid into fine droplets and rapidly evaporate the solvent in a hot drying medium to form a dry powder product. A complete spray drying apparatus system should include: the system comprises an air supply system, an exhaust system, a drying system, a separation system and a cleaning system. The method can directly dry the solution and emulsion into powder or granular products, and can omit the procedures of evaporation, crushing and the like. The drying temperature is an important factor affecting the physicochemical properties of the spray-dried powder. Higher drying temperatures provide more heat to the drying chamber, which increases the drying rate and reduces the moisture of the spray-dried product. However, the drying temperature is not too high, which results in an increased evaporation of water, which results in a faster formation of microspheres without sufficient time for shrinkage, resulting in larger particle sizes and thus affecting the quality of the final product.
Further, in the embodiment of the present invention, during the spray drying in the step (2), an argon atmosphere is used, the spraying rotation speed is controlled to be 20-40 Hz, and the feeding speed is controlled to be 80-120 Hz. In spray drying, the feed rate is one of the important influencing factors. The feed rate determines the residence time of the material in the drying chamber, separator and conveyor, and also affects the atomization of the material and the size of the droplets. The feed rate is essentially dependent on the speed of the atomizer, the higher the pump speed, the faster the feed rate. However, higher feed rates slow heat transfer, making it difficult to dry the droplets sufficiently and easily causing wall sticking.
Furthermore, in the embodiment of the invention, the wet-ground mixture can be prepared into a spheroid by spray drying, so that the fluidity of the mixture is improved, and the subsequent plasma spheroidization powder feeding is facilitated; meanwhile, the alcohol can be removed, and adverse effects caused by the alcohol in the plasma spheroidizing process are avoided, so that the silicon-tungsten composite powder with good sphericity is prepared. Therefore, the spray drying conditions in the range can ensure the best silicon and tungsten uniform distribution and good fluidity of the prepared spherical tungsten silicon composite powder.
Further, in the embodiment of the invention, the powder feeding carrier gas flow rate is set to be 5-15L/min, the plasma gas flow rate is 2-8L/min, and the protection gas flow rate is 10-30L/min during the plasma spheroidization in the step (3). The inventor researches and discovers that the spherical silicon-tungsten composite powder is easier to prepare and obtain within the reasonable condition range.
Further, in an embodiment of the present invention, the principle of the plasma spheroidization technique is: the high temperature environment of thermal plasma is utilized, the carrier gas is used for feeding the powder into the high temperature plasma, the powder particles are rapidly absorbed in heat and then are melted on the surface (or the whole), and the powder particles are condensed into spherical liquid drops under the action of surface tension, and the spherical liquid drops enter a cooling chamber and are quenched and solidified to fix the spherical liquid drops, so that the spherical powder is obtained. According to the excitation mode of plasma, the plasma spheroidization method can be divided into two main types, namely direct current plasma and radio frequency plasma. The direct current plasma spheroidizing technology has the advantages of high energy conversion rate, high product yield, low investment, easy realization of large-scale industrial production and the like; the RF plasma spheroidizing technology is to induce the Joule heating effect of current to heat airflow to very high temperature under the action of strong electromagnetic coupling to form self-sustaining plasma. The heating temperature range can reach 10000-30000K, the quenching speed can reach 105K/S, and the method is a good way for preparing spherical powder with uniform components, high sphericity and good fluidity. Further, in the embodiments of the present invention, the present invention preferably employs direct current plasma spheroidization.
Further, in the embodiment of the present invention, the flow rate of the powder feeding carrier gas is one of important process parameters affecting the spheroidization effect, and generally, the spheroidization rate increases as the powder feeding rate decreases. This is because the smaller the powder feeding rate, the fewer powder particles passing through the high temperature region of the plasma torch per unit time, the more heat is absorbed by the individual particles, the more the powder particles are melted, and the spheroidization rate is improved. However, if the powder feeding rate is too low, the powder absorbs too much heat, so that the powder volatilizes and is aggravated, the powder yield is reduced, and the production efficiency is affected. And the carrier gas flow rate affects the spheroidization effect mainly by affecting the residence time of the powder particles in the plasma torch. In addition, when the carrier gas flow rate is increased, the temperature of the plasma torch is reduced, the high-temperature region is contracted, the heat absorption of powder particles in the spheroidization process is reduced, and the spheroidization rate is reduced. When the carrier gas flow is too small, the powder dispersibility is poor, the heat transfer is affected, meanwhile, bonding particles can appear, and the spheroidization rate is affected. The most commonly used gas for metal powder spheroidization is argon, and then hydrogen, and a certain amount of hydrogen is added into a plasma atmosphere to generally improve the spheroidization effect.
Further, in the embodiment of the invention, in order to ensure the best effect of uniformly distributing silicon and tungsten and having better fluidity of the prepared spherical silicon-tungsten composite powder, the powder feeding carrier gas flow rate is preferably set to be 5-15L/min, the plasma gas flow rate is 2-8L/min, the protection gas flow rate is 10-30L/min, and the powder feeding rotating speed is controlled to be 2-10 r/min during the plasma spheroidization in the step (3). If the powder feeding carrier gas amount is too large, the powder feeding amount is large, so that more powder cannot be effectively spheroidized, the spheroidization efficiency is reduced, and the fluidity is reduced; the powder feeding carrier gas amount is too small, so that the powder feeding amount is small, the balling rate is high, the fluidity is good, but the yield is low, and the production cost is high. If the flow rate of the plasma gas is too large, the energy consumption is increased, and more plasma gas acts idle work; if the plasma air flow is too small, the powder cannot be effectively spheroidized, the spheroidization efficiency is low, and the fluidity is poor. The waste of the protective gas is larger when the protective gas flow is too large, so that the performance of the product is not influenced; when the protective gas flow is too small, the protective gas is easy to oxidize, and the oxygen content of the spherical powder is increased. When the powder feeding rotating speed is too high, the feeding quantity is large, the spheroidization is easy to incomplete, and the fluidity is poor; the powder feeding rotating speed is too small, so that the yield is low and the production cost is high.
Further, in the embodiment of the invention, the preparation method further comprises sieving the silicon-tungsten composite powder obtained through the spheroidization in the step (3) to remove coarse particles, thereby obtaining the spherical silicon-tungsten composite powder.
Further, in the embodiment of the invention, the invention provides spherical silicon-tungsten composite powder, which is prepared by adopting the method. Furthermore, the silicon-tungsten composite powder prepared by the method has high balling rate, good fluidity and best flow rate of 7.5s.
Furthermore, in the embodiment of the invention, the invention also provides application of the spherical silicon-tungsten composite powder in preparing silicon-tungsten targets. The silicon tungsten composite powder can be used as a main raw material of a silicon tungsten target, and the silicon tungsten target is a good conductor because of a sputtering film of the silicon tungsten composite powder, and is widely applied to the fields of electronic grid materials, electronic films and the like.
Further, in the examples of the present invention, the powder flow rate of the present invention was measured according to the "standard hopper method (hall flowmeter) for measuring metal powder flowability" of GB/T1482-2010/ISO 4490:2001. The standard specifies a method for measuring the flowability of metal powders, including cemented carbide powders, using a standard funnel (hall flowmeter). The standard applies to powders that can freely flow through a defined pore size. This test measures the time required for 50g of metal powder to flow through a standard sized hopper hole. The standard funnel of this test is made of a non-magnetic corrosion resistant metallic material and has sufficient wall thickness and hardness to prevent deformation and excessive wear. The balance of this test has a sufficient range to weigh the sample to 0.05g. The measuring time of the stopwatch of the test should be accurate to 0.1s. In this test, the funnel outlet was closed with a finger, and the sample was placed in the funnel. Ensure that the powder fills the bottom of the funnel. When the funnel aperture is opened, the stopwatch is started and when the powder in the funnel is completely discharged, the stopwatch is terminated. The time was recorded to the nearest 0.1s. The arithmetic mean of the three test results was calculated and the time in seconds per 50g of sample was reported.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way. In addition, the percentages stated in the examples refer generally to percent by mass unless otherwise indicated.
Example 1
A preparation method of spherical silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The microscopic morphology of the prepared silicon-tungsten composite powder is shown in figure 2, the balling rate is high, the granularity of the obtained composite powder is 30 mu m, the powder flow rate is 7.5s, and the oxygen content is 510ppm.
Example 2
A preparation method of spherical silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 25Hz, and the feeding speed is 100Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 5L/min, the protective gas flow is set to be 20L/min, and the powder feeding rotating speed is set to be 6r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The prepared silicon-tungsten composite powder has high balling rate, the granularity of the obtained composite powder is 25 mu m, the powder flow rate is 9s, and the oxygen content is 470ppm.
Example 3
A preparation method of spherical silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 4:1, after weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 3:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 4:1 in the ball milling process, and the ball milling time is 6 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is set to 90 ℃, the spray rotating speed is set to 30Hz, and the feeding speed is set to 120Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is 15L/min, the plasma gas flow is 8L/min, the protective gas flow is 30L/min, and the powder feeding rotating speed is 10r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The prepared silicon-tungsten composite powder has high balling rate, the granularity of the obtained composite powder is 18 mu m, the powder flow rate is 11s, and the oxygen content is 560ppm.
Example 4
A preparation method of spherical silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 3:2, after weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 1:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 3:1 in the ball milling process, and the ball milling time is 10 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is set to be 80 ℃, the spray rotating speed is set to be 20Hz, and the feeding speed is set to be 80Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 5L/min, the plasma gas flow is set to be 2L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The prepared silicon-tungsten composite powder has high balling rate, the granularity of the obtained composite powder is 20 mu m, the powder flow rate is 10s, and the oxygen content is 340ppm.
Example 5
A preparation method of spherical silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 3:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 4r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The prepared silicon-tungsten composite powder has high balling rate, the granularity of the obtained composite powder is 27 mu m, the powder flow rate is 8.2s, and the oxygen content is 390ppm.
Comparative example 1
The preparation method of the silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 3:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 20L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 12r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The microscopic morphology of the prepared silicon-tungsten composite powder is shown in figure 3, and the balling rate is common, the granularity of the obtained composite powder is 25 mu m, the powder flow rate is 19s, and the oxygen content is 600ppm.
Comparative example 2
The preparation method of the silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 9:1, after weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The balling rate of the prepared silicon-tungsten composite powder is common, the granularity of the obtained composite powder is 33 mu m, the powder flow rate is 18s, and the oxygen content is 320ppm.
Comparative example 3
The preparation method of the silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 1:1, after weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The balling rate of the prepared silicon-tungsten composite powder is general, the granularity of the obtained composite powder is 26 mu m, the powder flow rate is 15s, and the oxygen content is 450ppm.
Comparative example 4
The preparation method of the silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with water, then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and ensuring the solid-liquid ratio of materials in the ball mill to be 3:1 in the ball milling process, and the ball milling time to be 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The particle size of the prepared silicon-tungsten composite powder is 30 mu m, the powder flow rate is 7.4s, and the oxygen content is 4200ppm.
Comparative example 5
The preparation method of the silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an air atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The powder particle size of the prepared silicon-tungsten composite powder is 30 mu m, the powder flow rate is 7.7s, and the oxygen content is 2600ppm.
Comparative example 6
A preparation method of the shape silicon tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 5:1, and the solid-liquid ratio of materials in the ball mill is ensured to be 1:1 in the ball milling process, and the ball milling time is 3 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The ball forming rate of the prepared silicon-tungsten composite powder is general, the granularity of the obtained composite powder is 14 mu m, the powder flow rate is 23s, and the oxygen content is 700ppm.
Comparative example 7
A preparation method of the shape silicon tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is set to be 70 ℃, the spray rotating speed is set to be 15Hz, and the feeding speed is set to be 70Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The humidity of the spheroidic mixture prepared by spray drying is high, powder cannot be normally fed, and a spheroidization experiment cannot be performed.
Comparative example 8
A preparation method of the shape silicon tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7: and 3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, and then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and the solid-liquid ratio of materials in the ball mill is 3:1 in the ball milling process, and the ball milling time is 8 hours.
(2) And after ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is set to be 100 ℃, the spray rotating speed is set to be 40Hz, and the feeding speed is set to be 130Hz.
(3) And (3) performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the powder feeding carrier gas flow is set to be 10L/min, the plasma gas flow is set to be 3L/min, the protective gas flow is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process.
(4) And (3) sieving the spheroidized silicon-tungsten composite powder with a 80-mesh sieve to remove coarse particles, so as to ensure the uniformity of the powder, and preparing the silicon-tungsten composite powder.
The prepared silicon-tungsten composite powder has poor balling rate, the granularity of the obtained composite powder is 15 mu m, the powder flow rate is 30s, and the oxygen content is 650ppm.
The results of measuring the tungsten silicon composite powder obtained in the examples and comparative examples are shown in the following table 1:
TABLE 1
| Numbering device | Particle size (μm) | Powder flow rate(s) | Oxygen content (ppm) |
| Example 1 | 30 | 7.5 | 510 |
| Example 2 | 25 | 9 | 470 |
| Example 3 | 18 | 11 | 560 |
| Example 4 | 20 | 10 | 340 |
| Example 5 | 27 | 8.2 | 390 |
| Comparative example 1 | 25 | 19 | 600 |
| Comparative example 2 | 33 | 18 | 320 |
| Comparative example 3 | 26 | 15 | 450 |
| Comparative example 4 | 30 | 7.4 | 4200 |
| Comparative example 5 | 30 | 7.7 | 2600 |
| Comparative example 6 | 14 | 23 | 700 |
| Comparative example 7 | - | - | - |
| Comparative example 8 | 15 | 30 | 650 |
Therefore, the spherical silicon-tungsten composite powder prepared by the method has more uniform silicon and tungsten distribution, higher balling rate and better fluidity.
The above embodiments are only illustrative of and explain the present invention and should not be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Claims (1)
1. A preparation method of spherical silicon-tungsten composite powder comprises the following steps:
(1) According to the mass ratio of 7:3, weighing tungsten powder and silicon powder, adding the tungsten powder and the silicon powder into a ball mill filled with alcohol, then performing wet milling under an argon atmosphere, wherein the ball-material ratio is 2:1, and ensuring the solid-liquid ratio of materials in the ball mill to be 3:1 in the ball milling process, wherein the ball milling time is 8 hours;
(2) After ball milling, carrying out spray drying on the wet-milled mixture in an argon atmosphere to obtain a spheroidic mixture, wherein the drying temperature is 85 ℃, the spray rotating speed is 20Hz, and the feeding speed is 90Hz;
(3) Performing plasma spheroidization on the spheroidized mixture obtained in the step (2) to obtain spheroidized silicon-tungsten composite powder, wherein the flow rate of powder feeding carrier gas is set to be 10L/min, the flow rate of plasma gas is set to be 3L/min, the flow rate of protective gas is set to be 10L/min, and the powder feeding rotating speed is set to be 2r/min in the spheroidization process;
(4) Sieving the spheroidized silicon-tungsten composite powder with an 80-mesh sieve to remove coarse particles, and ensuring the uniformity of the powder to prepare the silicon-tungsten composite powder;
the particle size of the prepared silicon-tungsten composite powder is 30 mu m, the powder flow rate is 7.5s, and the oxygen content is 510ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210619330.3A CN114918417B (en) | 2022-06-02 | 2022-06-02 | Preparation method of spherical silicon-tungsten composite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210619330.3A CN114918417B (en) | 2022-06-02 | 2022-06-02 | Preparation method of spherical silicon-tungsten composite powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114918417A CN114918417A (en) | 2022-08-19 |
| CN114918417B true CN114918417B (en) | 2024-04-05 |
Family
ID=82812781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210619330.3A Active CN114918417B (en) | 2022-06-02 | 2022-06-02 | Preparation method of spherical silicon-tungsten composite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114918417B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294156A (en) * | 1999-10-20 | 2001-05-09 | 中国科学院金属研究所 | Microspherial Ni-base powder as coating material |
| CN101176920A (en) * | 2007-11-22 | 2008-05-14 | 上海交通大学 | Method for preparing active metal titanium and boron carbide complex spherical hot spraying powder |
| CN101817546A (en) * | 2010-03-23 | 2010-09-01 | 大连理工大学 | Method for synthesizing spherical alkali-earth metal oxide homogenous phase mixed powder |
| CN103695852A (en) * | 2012-09-27 | 2014-04-02 | 宁波江丰电子材料有限公司 | Manufacturing method of tungsten silicon target material |
| CN108274016A (en) * | 2018-03-14 | 2018-07-13 | 浙江工业大学 | A kind of method that spray-wall interaction reduction method directly prepares samarium ferroalloy powder |
| CN108907210A (en) * | 2018-07-27 | 2018-11-30 | 中南大学 | A method of increasing material manufacturing is prepared with solid globular metallic powder |
| CN108941596A (en) * | 2018-09-03 | 2018-12-07 | 湖南伊澍智能制造有限公司 | A kind of 3D printing special alloy powder and preparation method thereof |
| CN110014163A (en) * | 2019-04-19 | 2019-07-16 | 广东省材料与加工研究所 | Tungsten alloy powder and its preparation method and application |
| CN110405218A (en) * | 2018-04-26 | 2019-11-05 | 广东正德材料表面科技有限公司 | A kind of high sphericity nanostructure powder of stainless steel and preparation method thereof |
| CN111575573A (en) * | 2020-06-16 | 2020-08-25 | 中山火炬职业技术学院 | High sphericity Cr-base alloy-TiB2Micro-nano powder and preparation method thereof |
| CN111940723A (en) * | 2020-08-30 | 2020-11-17 | 中南大学 | Nano ceramic metal composite powder for 3D printing and application |
| CN112692294A (en) * | 2020-12-22 | 2021-04-23 | 厦门钨业股份有限公司 | High-specific gravity tungsten alloy powder and preparation method thereof |
| CN112974799A (en) * | 2021-02-05 | 2021-06-18 | 中国人民解放军陆军装甲兵学院 | Composite powder for preparing self-repairing coating, preparation method of composite powder, titanium-based wear-resistant self-repairing coating and preparation method of titanium-based wear-resistant self-repairing coating |
| CN113020605A (en) * | 2020-12-17 | 2021-06-25 | 南京航空航天大学 | Special in-situ toughening high-performance spherical tungsten powder for laser 3D printing and preparation method thereof |
| CN113862623A (en) * | 2021-09-27 | 2021-12-31 | 宁波江丰电子材料股份有限公司 | Preparation method of tungsten-silicon target blank |
| CN114289722A (en) * | 2021-12-08 | 2022-04-08 | 北京科技大学 | Preparation method of fine-grained spherical tungsten powder |
-
2022
- 2022-06-02 CN CN202210619330.3A patent/CN114918417B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294156A (en) * | 1999-10-20 | 2001-05-09 | 中国科学院金属研究所 | Microspherial Ni-base powder as coating material |
| CN101176920A (en) * | 2007-11-22 | 2008-05-14 | 上海交通大学 | Method for preparing active metal titanium and boron carbide complex spherical hot spraying powder |
| CN101817546A (en) * | 2010-03-23 | 2010-09-01 | 大连理工大学 | Method for synthesizing spherical alkali-earth metal oxide homogenous phase mixed powder |
| CN103695852A (en) * | 2012-09-27 | 2014-04-02 | 宁波江丰电子材料有限公司 | Manufacturing method of tungsten silicon target material |
| CN108274016A (en) * | 2018-03-14 | 2018-07-13 | 浙江工业大学 | A kind of method that spray-wall interaction reduction method directly prepares samarium ferroalloy powder |
| CN110405218A (en) * | 2018-04-26 | 2019-11-05 | 广东正德材料表面科技有限公司 | A kind of high sphericity nanostructure powder of stainless steel and preparation method thereof |
| CN108907210A (en) * | 2018-07-27 | 2018-11-30 | 中南大学 | A method of increasing material manufacturing is prepared with solid globular metallic powder |
| CN108941596A (en) * | 2018-09-03 | 2018-12-07 | 湖南伊澍智能制造有限公司 | A kind of 3D printing special alloy powder and preparation method thereof |
| CN110014163A (en) * | 2019-04-19 | 2019-07-16 | 广东省材料与加工研究所 | Tungsten alloy powder and its preparation method and application |
| CN111575573A (en) * | 2020-06-16 | 2020-08-25 | 中山火炬职业技术学院 | High sphericity Cr-base alloy-TiB2Micro-nano powder and preparation method thereof |
| CN111940723A (en) * | 2020-08-30 | 2020-11-17 | 中南大学 | Nano ceramic metal composite powder for 3D printing and application |
| CN113020605A (en) * | 2020-12-17 | 2021-06-25 | 南京航空航天大学 | Special in-situ toughening high-performance spherical tungsten powder for laser 3D printing and preparation method thereof |
| CN112692294A (en) * | 2020-12-22 | 2021-04-23 | 厦门钨业股份有限公司 | High-specific gravity tungsten alloy powder and preparation method thereof |
| CN112974799A (en) * | 2021-02-05 | 2021-06-18 | 中国人民解放军陆军装甲兵学院 | Composite powder for preparing self-repairing coating, preparation method of composite powder, titanium-based wear-resistant self-repairing coating and preparation method of titanium-based wear-resistant self-repairing coating |
| CN113862623A (en) * | 2021-09-27 | 2021-12-31 | 宁波江丰电子材料股份有限公司 | Preparation method of tungsten-silicon target blank |
| CN114289722A (en) * | 2021-12-08 | 2022-04-08 | 北京科技大学 | Preparation method of fine-grained spherical tungsten powder |
Non-Patent Citations (3)
| Title |
|---|
| 《等离子喷涂成形技术的研究现状和应用进展》;徐玄等;《中国钨业》;第第30卷卷(第第3期期);全文 * |
| 张莹莹 ; 周武平 ; 王铁军 ; 王学兵 ; 杨怀超 ; 梁俊才 ; .球形钨粉的制备技术研究进展.粉末冶金工业.2018,(第03期),全文. * |
| 球形钨粉的制备技术研究进展;张莹莹;周武平;王铁军;王学兵;杨怀超;梁俊才;;粉末冶金工业(第03期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114918417A (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102554242B (en) | Method for manufacturing micro-fine spherical titanium powder | |
| WO2019024421A1 (en) | Method for preparing target material and target material | |
| CN105397100B (en) | A kind of preparation method of refining metallic powder and the equipment for realizing this method | |
| CN110625112B (en) | Titanium or titanium alloy spherical powder with rare earth oxide distributed on surface and preparation method thereof | |
| CN109112346A (en) | A kind of preparation method of increasing material manufacturing copper alloy powder | |
| CN110405218B (en) | High-sphericity nano-structure stainless steel powder and preparation method thereof | |
| CN1513629A (en) | Manufacturing method for scale shaped metal powder | |
| CN101966587A (en) | Method for preparing high-performance heat conducting tube copper powder | |
| CN1676249A (en) | Method and apparatus for preparing sheet-type metal pwoder by atomized drop deformation | |
| CN105057680A (en) | Preparation method of mechanical alloying copper-tungsten alloy powder | |
| CN108500280B (en) | Device and method for preparing copper-indium-gallium alloy powder | |
| CN109518027A (en) | A kind of preparation method and application of fine grain Mg-Al-Ti-C intermediate alloy | |
| CN113579237B (en) | Preparation method for reducing apparent density of copper-tin alloy powder | |
| CN114918417B (en) | Preparation method of spherical silicon-tungsten composite powder | |
| CN108274011B (en) | Preparation method of metal powder with bimodal distribution suitable for 3D printing | |
| CN112620642A (en) | Centrifugal atomization device and method for preparing high-temperature high-surface-tension metal powder | |
| CN102161099B (en) | Method and device for producing nanocrystalline high-purity spherical magnesium alloy powder | |
| CN115846672A (en) | Preparation method of high-strength high-conductivity copper-based composite material for lead frame | |
| CN113020605B (en) | Special in-situ toughening high-performance spherical tungsten powder for laser 3D printing and preparation method thereof | |
| CN115196970A (en) | Preparation method of high-fluidity AlON spherical powder | |
| CN111804925B (en) | Method and device for preparing GRCop-42 spherical powder based on VIGA process | |
| CN206351253U (en) | A kind of rapid solidification prepares the device of refining metallic powder | |
| CN109019668B (en) | Method for preparing superfine active zinc oxide powder by hot ball milling oxidation | |
| CN102031434A (en) | Magnesium-based hydrogen storage alloy material and preparation method thereof | |
| CN114074186A (en) | Preparation method of spherical atomized magnesium-silicon-based multi-element alloy powder and obtained alloy powder |
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 |