CN116970855A - Mu-phase intermetallic compound in-situ reinforced tungsten wire and preparation and application thereof - Google Patents
Mu-phase intermetallic compound in-situ reinforced tungsten wire and preparation and application thereof Download PDFInfo
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- CN116970855A CN116970855A CN202310951215.0A CN202310951215A CN116970855A CN 116970855 A CN116970855 A CN 116970855A CN 202310951215 A CN202310951215 A CN 202310951215A CN 116970855 A CN116970855 A CN 116970855A
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- tungsten
- intermetallic compound
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- tungsten wire
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 75
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000010937 tungsten Substances 0.000 claims abstract description 133
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 127
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 66
- 238000005242 forging Methods 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 238000005728 strengthening Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 19
- 238000005520 cutting process Methods 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 239000012456 homogeneous solution Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000462 isostatic pressing Methods 0.000 claims description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000003754 machining Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010419 fine particle Substances 0.000 abstract description 3
- WVBBLATZSOLERT-UHFFFAOYSA-N gold tungsten Chemical compound [W].[Au] WVBBLATZSOLERT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 44
- 229910003460 diamond Inorganic materials 0.000 description 19
- 239000010432 diamond Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005491 wire drawing Methods 0.000 description 9
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000000280 densification Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 229910001080 W alloy Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005482 strain hardening Methods 0.000 description 4
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten dioxide Inorganic materials O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- -1 and preferably Chemical compound 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- FAYUQEZUGGXARF-UHFFFAOYSA-N lanthanum tungsten Chemical compound [La].[W] FAYUQEZUGGXARF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 2
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- AWOORJZBKBDNCP-UHFFFAOYSA-N molybdenum;oxotungsten Chemical compound [Mo].[W]=O AWOORJZBKBDNCP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- 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
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
-
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
-
- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28D—WORKING STONE OR STONE-LIKE MATERIALS
- B28D5/00—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor
- B28D5/04—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor by tools other than rotary type, e.g. reciprocating tools
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
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- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to a combinationThe technical field of gold tungsten wires, in particular discloses a mu-phase intermetallic compound in-situ reinforced tungsten wire which comprises a fibrous tungsten matrix and La dispersed in situ 2 O 3 And a mu-phase intermetallic compound, the mu-phase intermetallic compound being Co-containing 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Is a complex intermetallic compound of (a); in the mu-phase intermetallic compound in-situ reinforced tungsten filament, the content of Co is 0.2-0.6wt%, the content of Fe is 0.2-0.5wt%, the content of La is 0.1-1.5wt%, the content of Mo is 1-5wt%, and the balance is W. The invention also comprises a preparation method of the tungsten filament. The tungsten filament disclosed by the invention can synergistically improve the performance of the tungsten filament based on the combined control of the composite mu phase and the element content, and can also show excellent comprehensive performance under the condition of fine particle size.
Description
Technical Field
The invention belongs to the technical field of tungsten filament materials, and particularly relates to an ultrafine high-strength tungsten filament reinforced by intermetallic compound mu phase precipitation and a preparation method thereof.
Background
The cutting of the hard and brittle silicon wafer in the photovoltaic industry is subjected to technical innovation from mortar cutting to diamond wire processing, so that the cutting quality and efficiency are greatly improved, and meanwhile, the problem of huge pollution caused by the traditional mortar cutting processing is solved. The development of diamond wire is a revolutionary advancement to the solar silicon material cutting industry. However, with the reduction of financial subsidy force in the photovoltaic industry, the extension to the consumable cutting aspect is quite obvious, and meanwhile, the cutting is more efficient and the silicon chip is low in loss, so that the method is a new target for developing the whole industry. The photovoltaic industry is still required to be continuously promoted to be new, and higher-end products are developed to meet the development requirement of the new energy industry.
The silicon wafer line mark of diamond wire cutting is larger than that of traditional mortar cutting, but with the development and application of ultra-fine diamond wires, the loss of the silicon wafer is greatly reduced. Currently, ultra-fine steel core wires are developed to be less than 50 mu m, and the loss of silicon wafers is further reduced along with the thinning of wire diameters, so that the wafer yield is greatly improved. But is limited by the limited breaking force and cutting force of the steel wire, and in addition, the low-cost guiding provides more severe single-blade yield and wire breakage rate, and even if ultra-high-strength carbon steel is adopted, the application working condition of the ultra-fine diamond wire is still difficult to meet. In view of the defects of steel wires in the application of ultra-fine wire diameter diamond wires, in addition, a certain technical bottleneck still exists in the field of ultra-fine ultra-high strength carbon steel wire preparation in China, and researchers turn to aim at ultra-fine tungsten wires with larger application potential. Firstly, the high tensile strength and the elastic modulus of the tungsten wire create possibility for further refinement of the diamond wire; and secondly, the tungsten wire has better electric conductivity than the steel wire, and the process scheme of electroplating the silicon carbide is feasible and has excellent corrosion resistance. In conclusion, tungsten wire becomes the ideal core wire choice for ultra-fine diamond wire.
Currently, tungsten wires are subjected to multi-pass drawing to obtain sufficient grain refinement to the nanometer level, so that excellent mechanical properties are obtained, for example, the tensile strength of lanthanum tungsten wires with the wire diameter of 0.03mm is higher than 5000MPa. Rare earth is widely used as a common doping element in tungsten wires, wherein rare earth lanthanum is dispersed and distributed in a tungsten matrix mainly in an oxidation state so as to inhibit coarsening of crystal grains in the process. The high breaking strength of the ultra-fine wire diameter lanthanum tungsten wire mainly comes from Hall-Petch strengthening brought by ultra-fine grains and multi-pass cold drawing to generate strong work hardening, meanwhile, lanthanum oxide in a matrix is uniformly distributed to bring a certain degree of contribution of dispersion strengthening, and the extra solid solution strengthening effect brought by excessive addition of rare earth elements is obviously insufficient to greatly improve the mechanical property of the tungsten wire, and meanwhile, the extremely high resource consumption and the cost increase are generated. While rare earth doped tungsten wires have prompted tungsten wires to achieve target sizes and good fracture force values, it is still imperative to develop higher fracture strength tungsten wires to increase the cutting loading of diamond wires in order to further increase cutting efficiency. Obviously, the residual performance of the tungsten wire is difficult to excite only by virtue of the grain boundary strengthening and the dispersion strengthening effect of the rare earth oxide, and further performance breakthrough is required to be further obtained by assisting other material strengthening means.
Disclosure of Invention
In order to solve the problem of insufficient performance of the traditional high-strength carbon steel-based diamond wire in the photovoltaic product processing process, the invention aims to provide a mu-phase intermetallic compound in-situ reinforced tungsten wire and aims to provide an ultrafine tungsten wire with excellent comprehensive strength.
The second object of the invention is to provide a method for preparing mu-phase intermetallic compound in-situ reinforced tungsten filament, which aims to successfully prepare the superfine tungsten filament.
The third object of the invention is to provide the application of the mu-phase intermetallic compound in-situ reinforced tungsten wire in the cutting of semiconductor silicon plates and the device thereof.
A mu-phase intermetallic compound in-situ reinforced tungsten wire comprises a fibrous tungsten matrix and La dispersed in-situ 2 O 3 And a mu-phase intermetallic compound, the mu-phase intermetallic compound being Co-containing 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Is a complex intermetallic compound of (a);
in the mu-phase intermetallic compound in-situ reinforced tungsten filament, the content of Co is 0.2-0.6wt%, the content of Fe is 0.2-0.5wt%, the content of La is 0.1-1.5wt%, the content of Mo is 1-5wt%, and the balance is W.
The invention provides a Co 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Is a complex mu-phase intermetallic compound and La 2 O 3 The tungsten alloy wire with combined dispersion strengthening is further based on the combined control of the composite mu phase and the element content, so that the performance of the tungsten wire can be synergistically improved, and the tungsten alloy wire can also show excellent comprehensive performance under the condition of fine particle size.
In the present invention, the composition contains Co 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Composite mu-phase, la 2 O 3 And the combined control of the element content are key to synergistically improving the comprehensive performance of the tungsten filament fiber.
In the mu-phase intermetallic compound in-situ reinforced tungsten filament, the content of Co is 0.2-0.5 wt%, the content of Fe is 0.2-0.4 wt%, the content of La is 0.3-1.2 wt%, the content of Mo is 1-4 wt%, and the balance is W;
preferably, in the mu-phase intermetallic compound in-situ strengthening tungsten wire, the content of Co is 0.2-0.45 wt%, the content of Fe is 0.2-0.35 wt%, the content of La is 0.5-1.1 wt%, the content of Mo is 2-4 wt%, and the balance is W;
preferably, in the mu-phase intermetallic compound in-situ strengthening tungsten wire, the content of Co is 0.3-0.4 wt%, the content of Fe is 0.2-0.3 wt%, the content of La is 0.7-0.9 wt%, the content of Mo is 2.5-3 wt%, and the balance is W; with the preferable content, a better synergistic effect can be obtained, and the comprehensive performance of the tungsten filament can be further improved.
Preferably, the wire diameter of the mu-phase intermetallic compound in-situ strengthening tungsten wire is 0.030-0.045 mm;
preferably, said La 2 O 3 Grains of mu-phase intermetallic compound<300nm。
The invention also provides a preparation method of the mu-phase intermetallic compound in-situ reinforced tungsten wire, which comprises the following steps:
step (1):
compounding according to the metal content of the mu-phase intermetallic compound in-situ reinforced tungsten wire, compounding a composite homogeneous solution dissolved with an iron source, a cobalt source and a lanthanum source on the surface of tungsten-molybdenum composite metal powder to obtain a precursor, and carrying out reduction treatment on the precursor to obtain Fe-Co-La coated W/Mo composite metal powder; wherein the temperature of the reduction stage is 800-900 ℃;
step (2): forming and pressing the Fe-Co-La coated W/Mo composite metal into a tungsten rod;
step (3): the tungsten rod is subjected to first-stage presintering at 1100-1300 ℃, and then is heated to 1900-2400 ℃ to be subjected to final densification stage sintering, so that a sintering material is obtained;
step (4): and (3) performing rotary forging cogging, annealing, rotary forging tandem forging and drawing treatment on the sintering material to obtain the mu-phase intermetallic compound in-situ reinforced tungsten wire, wherein the annealing temperature is 1600-1850 ℃.
How to form the mu-phase intermetallic compound and La in situ by dispersion in tungsten filament matrix 2 O 3 Is the key and the difficulty of successfully preparing the tungsten filament. Aiming at the preparation problem, the invention discovers that the invention innovatively takes the cobalt source, the iron source and the lanthanum source compounds as the precursor raw materials, and innovatively loads and reduces and coats the cobalt source, the iron source and the lanthanum source compounds on the surface of tungsten-molybdenum powder in advance to form Fe-Co-La coated W/Mo composite metal powder with a coating structure, and then the Fe-Co-La coated W/Mo composite metal powder is pressed, molded and sintered to further cooperate with the combination of the reduction process and the sintering process, thus realizing synergy and being capable of being unexpectedly and uniformly dispersed in situ in tungsten matrix to form the synergyCo-containing Co 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Is helpful for improving the comprehensive performance of the prepared material.
In the invention, the type, the proportion and the combination control of the reduction pre-coating after the liquid phase spraying and the subsequent sintering process of the raw materials are key to cooperatively inducing the formation and the uniform dispersion distribution of the cooperative composite mu phase.
In the invention, in the step 1, the compounds of cobalt source, iron source and lanthanum source with required content are dissolved in advance to form a homogeneous solution, and then are compounded on the surface of the tungsten-molybdenum composite powder based on known means such as a spraying mode, and then are reduced; thus being beneficial to in-situ formation of the uniformly dispersed composite mu-phase tungsten wire.
In the present invention, the iron source is an iron compound which can be dissolved and is favorable for forming a homogeneous solution, such as ferric nitrate;
the lanthanum source is a lanthanum compound which can be dissolved and is favorable for forming a homogeneous solution, for example, lanthanum nitrate;
the cobalt source is a cobalt compound which can be dissolved and is favorable for forming a homogeneous solution, such as cobalt nitrate;
preferably, the solvent in the composite homogeneous solution is at least one solvent of alcohol and water, preferably an alcohol-water mixed solvent, and more preferably an alcohol-water solvent with the alcohol volume content of 30-80% by volume;
preferably, the total concentration of the solute in the composite homogeneous solution is 0.2-0.4 g/ml;
in the invention, the purity of the adopted raw materials can meet the use requirements of industry, for example, the purity is over 99 percent.
Preferably, the composite homogeneous solution is sprayed on the surface of tungsten and molybdenum composite metal powder, and the precursor is obtained through drying treatment.
In the invention, the compound with the required content is innovatively compounded on the surface of tungsten-molybdenum particles, and then reduction treatment is carried out to obtain the metal powder with the coating structure, thus being beneficial to obtaining the dispersion compound mu phase tungsten wire.
Preferably, the tungsten-molybdenum composite metal powder is a mixture of a tungsten source and a molybdenum source, and the tungsten source is elemental tungsten and/or blue tungsten; the molybdenum source is elemental molybdenum and/or molybdenum oxide; further preferably, the tungsten-molybdenum composite metal powder is a mixture of blue tungsten and molybdenum oxide. It has been found that the preferred starting materials can further synergistically improve the properties of the tungsten filament produced.
In the present invention, the atmosphere in the reduction stage is a hydrogen-containing atmosphere. In the present invention, the hydrogen-containing atmosphere may be hydrogen, a hydrogen-inert gas mixture, or the like. In the present invention, the hydrogen content of the hydrogen-containing atmosphere is 50% or more, and preferably pure hydrogen.
Preferably, the temperature of the reduction stage is 840 to 860 ℃; research shows that under the preferred conditions, better tungsten filament performance can be obtained.
Preferably, the treatment time in the reduction stage is 2 to 4 hours, and may be further 2 to 3 hours.
In the invention, the Fe-Co-La coated W/Mo composite metal powder can be used for forming tungsten bars with required sizes based on a known mode.
Preferably, the pressing forming mode is one of steel mould pressing and isostatic pressing;
preferably, the pressure in the compression molding stage is 200-300 MPa, and the pressure maintaining time is 3-5 min;
in the invention, the compact density of the tungsten rod is 9.0-14.0 g/cm 3 。
In the invention, the roasting conditions are controlled in a combined way, so that the dispersion distribution of the composite mu phase is induced, and the preparation performance is improved.
Preferably, the heat preservation time of the first stage sintering is 50-80 min;
preferably, the heat preservation time of the second-stage sintering is 200-300 min;
in the invention, the sintering material is subjected to conventional rotary forging cogging, annealing, rotary forging tandem forging and drawing treatment to obtain the tungsten wire with the required size.
For example, in the invention, the forging is preheated in a hydrogen atmosphere protection furnace for 20-40 min before the forging and cogging, the preheating temperature is 1400-1550 ℃, the working deformation of the forging and cogging pass is 1-1.5 mm, and the next forging is carried out after the forging and cogging pass is finished and the temperature is kept for 3-5 min;
preferably, annealing in a hydrogen atmosphere furnace after rotary forging cogging;
preferably, the annealing temperature is 1600-1800 ℃;
preferably, the annealed tungsten rod is subjected to rotary forging and tandem forging to obtain a thin tungsten rod with the diameter of 3.5-3.8 mm.
In the invention, the drawing steps are sequentially performed by chain drawing and turntable drawing, wherein the diameter of a chain drawn tungsten wire is 2.5-2.8 mm;
preferably, the diameter of the turntable pullout is 30-40 μm.
The invention also provides an application of the mu-phase intermetallic compound in-situ reinforced tungsten wire, which is used for a cutting appliance of a semiconductor silicon plate.
The invention also provides a cutting device of the semiconductor silicon plate, which comprises the mu-phase intermetallic compound in-situ reinforced tungsten wire.
The invention has the beneficial effects that:
1. the invention provides a Co 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 The composite mu-phase intermetallic compound dispersion strengthening tungsten alloy wire is further based on the combined control of the composite mu-phase and the element content, can realize synergy, can synergistically improve the performance of the tungsten wire, and can also show excellent comprehensive performance under the condition of fine particle size.
2. The invention innovatively takes cobalt source, iron source and lanthanum source compounds as precursor raw materials, and innovatively loads and reduces and coats the cobalt source, iron source and lanthanum source compounds on the surface of tungsten-molybdenum powder in advance in a wet method to form Fe-Co-La coated W/Mo composite metal powder with a coating structure, and then the Fe-Co-La coated W/Mo composite metal powder is pressed, molded and sintered to realize synergy by further combining the reduction process and the sintering process, so that Co can be uniformly dispersed in situ in tungsten matrix unexpectedly to form synergized Co 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Is helpful for improving the comprehensive performance of the prepared material. The tungsten filament prepared by the preparation method has more excellent strength and high elastic modulus, and meanwhile, the addition of large-content rare earth elements is avoided, so that the preparation cost is greatly reduced.
Detailed Description
The present invention will be further described with reference to specific examples on the premise of the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
The invention relates to an intermetallic compound reinforced superfine high-strength tungsten wire and a preparation method thereof, wherein the final wire diameter of the tungsten wire is 0.030-0.045 mm. The high-strength alloy tungsten wire comprises a tungsten matrix and La dispersed in the tungsten matrix 2 O 3 And in situ formed mu-phase intermetallic compounds, the mu-phase intermetallic compounds being predominantly Co 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 。
In the invention, the La 2 O 3 And mu-phase intermetallic compound are generated in situ, and La in the finished tungsten wire 2 O 3 And mu-phase intermetallic compound to nano level<300nm)。
Preferably, the method is used. The tungsten wire is prepared by adopting a powder metallurgy process and multi-pass drawing, and the raw material powder is commercial high-purity (> 99.9%) ultrafine (< 2 mu m) powder.
In the mu-phase intermetallic compound in-situ reinforced tungsten filament, the content of Co is 0.2-0.6wt%, the content of Fe is 0.2-0.5wt%, the content of La is 0.1-1.5wt%, the content of Mo is 1-5wt%, and the balance is W.
Preferably, in the mu-phase intermetallic compound in-situ strengthening tungsten wire, the content of Co is 0.2-0.45 wt%, the content of Fe is 0.2-0.35 wt%, the content of La is 0.5-1.1 wt%, the content of Mo is 2-4 wt%, and the balance is W;
preferably, in the mu-phase intermetallic compound in-situ strengthening tungsten wire, the content of Co is 0.3-0.4 wt%, the content of Fe is 0.2-0.3 wt%, the content of La is 0.7-0.9 wt%, the content of Mo is 2.5-3 wt%, and the balance is W;
in a preferred scheme, the diameter of the superfine tungsten filament is 30-45 mu m, the tensile strength is more than or equal to 6100MPa, the breaking elongation is 1.5-3%, and the elastic modulus is 360-450 GPa.
In a further preferable scheme, the diameter of the superfine tungsten filament is 30-45 mu m, the tensile strength is more than or equal to 6600MPa, the breaking elongation is 1.5-2.4%, and the elastic modulus is 390-450 GPa.
The invention relates to an intermetallic compound reinforced superfine high-strength tungsten wire and a preparation method thereof, comprising the following steps:
step 1: uniformly mixing the raw material tungsten and molybdenum powder according to a proportion to obtain mixed powder;
step 2: weighing ferric nitrate nonahydrate, cobalt nitrate hexahydrate and lanthanum nitrate according to a proportion, fully dissolving, uniformly spraying the mixture on the mixed powder obtained in the step 1 under the stirring condition,
step 3: and (3) carrying out primary hydrogen reduction on the uniformly doped powder obtained in the step (2) in a hydrogen reduction furnace at 800-900 ℃ to obtain alloy tungsten powder.
Step 4: pressing the alloy tungsten powder obtained in the step 3 to obtain a tungsten rod with a pressed compact density of 9.0-14.0 g/cm 3 。
Step 5: presintering the tungsten rod blank obtained in the step 4 in a hydrogen furnace at 1100-1300 ℃ for 50-80 min, presintering the bar stock, and then presintering the bar stock in an intermediate frequency induction furnace at 1900-2400 ℃ for 200-300 min.
Step 6: and (3) performing rotary forging cogging on the sintered tungsten alloy rod obtained in the step (5), and then annealing in a hydrogen atmosphere furnace, wherein the annealing temperature is 1100-1300 ℃.
Step 7: and (3) performing rotary swaging and tandem forging on the annealed tungsten rod obtained in the step (6) to obtain a thin tungsten rod with the diameter of 3.5-3.8 mm.
Step 8: and (3) uniformly coating graphite emulsion on the fine tungsten rod obtained in the step (7), and then carrying out chain drawing through a hard alloy die, wherein the diameter of the tungsten wire is 2.5-2.8 mm after 4 die drawing.
Step 9: and (3) further carrying out turntable drawing on the tungsten wire obtained in the step (8) through a diamond die, and carrying out multi-pass drawing on the tungsten wire until the diameter of the tungsten wire is 30-45 microns.
Preferably, the raw material powder of tungsten and molybdenum in the step 1 is preferably ultrafine%<2 μm) blue tungsten (WO 2.9 ) And molybdenum oxide (MoO) 2 ) The powder, blue tungsten and molybdenum oxide powder has better fluidity than tungsten and molybdenum powder, is easier to fully stir and mix uniformly, adopts oxide mixed powder to carry out solid-liquid doping with cobalt nitrate, iron and lanthanum solution, and is easier to realize doping homogenization. In addition, tungsten molybdenum oxide is easy to reduce in hydrogen atmosphere, and the process scheme is feasible.
Preferably, the solution for dissolving ferric nitrate nonahydrate, cobalt nitrate hexahydrate and lanthanum nitrate in the step 2 may be alcohol and water, and preferably, alcohol is used to dissolve the nitric acid compound in consideration of easy drying of alcohol during the solid-liquid stirring and mixing process.
Preferably, the superfine tungsten filament comprises the following components in percentage by mass: co:0.2 to 0.6 percent, fe:0.2 to 0.5 percent, la:0.1 to 1.5 percent, mo:1 to 5 percent, the impurity content is lower than 0.01 percent, and the balance is W.
As a further preferred option, molybdenum and tungsten are uniformly mixed by powder, and Co, fe and La are added in the form of cobalt nitrate hexahydrate, iron nitrate nonahydrate and lanthanum nitrate, respectively, nitric acid compounds of cobalt, iron and lanthanum are sufficiently dissolved with absolute ethanol, and then an alcoholic solution is solid-liquid doped with the mixed tungsten powder in a stirring state.
As a further preference, the sum of the mass percentages of Co and Fe in the tungsten filament is 0.4-0.8%, and the mass percentage of molybdenum is 2-4%. Co and Fe are added as transition metal elements formed by strong intermetallic compounds, and the purpose is to react with added molybdenum and matrix tungsten elements to generate intermetallic compound mu phase, so that too much intermetallic compounds are generated to be unfavorable for drawing processing, meanwhile, the melting point of the molybdenum is lower than that of the tungsten, and the excessive molybdenum content is harmful to the elastic modulus and the performance of the alloy tungsten wire.
As a further preferred mode, the mass percentage of lanthanum in the tungsten filament is 0.3-1.2%, rare earth element lanthanum is converted into lanthanum oxide to be dispersed and distributed in a matrix in the technical process, high-melting-point oxide effectively inhibits coarsening of crystal grains in the sintering and hot working processes and simultaneously contributes to a certain degree of dispersion strengthening effect, the addition amount of lanthanum is too small to effectively inhibit migration coarsening of high-temperature grain boundaries, and weak performance optimization caused by excessive addition is not as high as possible.
The preferable scheme comprises the following added constituent elements in percentage by mass: co:0.2 to 0.5 percent, fe:0.2 to 0.4 percent, la:0.3 to 1.2 percent, mo:1 to 4 percent, the impurity content is lower than 0.01 percent, and the balance is W.
Further preferably, the added constituent elements are as follows by mass percent: co:0.2 to 0.45 percent, fe:0.2 to 0.35 percent, la:0.5 to 1.1 percent, mo: 2-4%, impurity content is lower than 0.01%, and the balance is W.
Still more preferably, the added constituent elements are as follows by mass percent: co:0.3 to 0.4 percent, fe:0.25 to 0.3 percent, la:0.7 to 0.9 percent, mo: 2.5-3%, impurity content is lower than 0.01%, and the balance is W.
Preferably, the hydrogen concentration in the hydrogen reduction in the step 3 is not lower than 99%, and the high-temperature reduction and heat preservation time of the hydrogen furnace is not lower than 2 hours.
Preferably, the pressing in the step 4 can be one of steel die pressing and isostatic pressing, and the isostatic pressing is preferably used for ensuring the density uniformity of the pressed compact, the pressing pressure is 200-300 MPa, and the holding time is 3-5 min.
Preferably, the sintered tungsten rod is preheated in a hydrogen atmosphere protection furnace for 30min before rotary forging and cogging, the preheating temperature is 1400-1550 ℃, the machining deformation of rotary forging and cogging passes is 1-1.5 mm, and the next rotary forging is carried out after the rotary forging and cogging passes are finished and the heat preservation is carried out for 3-5 min.
Preferably, the preheating temperature of the rotary forging tandem forging tungsten rod in the step 7 is 1350-1500 ℃, a heat preservation furnace is added between two-pass tandem forging devices to heat and preserve heat through the tungsten rod, and the temperature of the heat preservation furnace is 1300-1500 ℃.
Preferably, the lubricant graphite emulsion in step 8 is prepared by continuously stirring and mixing graphite powder and a thickener uniformly, and the non-drawn section of the tungsten rod is immersed in the pumped graphite emulsion slurry to ensure that the surface is fully coated.
Further preferably, the graphite powder used as the raw material of the graphite emulsion in the step 8 adopts D 50 =0.2 μm graphite nanoscale powder, fine graphite micropowder contributes to stronger lubrication effect, is favorable for reducing wire surface defects and reducing loss of a die.
Preferably, the tungsten filament in step 8 is preheated to 1050-1200 ℃ and then subjected to chain drawing, the wire drawing die is heated to 800-900 ℃ and then subjected to wire drawing, the wire drawing die preferably adopts a high-metal binding phase hard alloy die, the hard alloy is more resistant to high-temperature oxidation than a diamond die, and the chain drawing preferably adopts the hard alloy die, so that the service life of the die can be prolonged.
Preferably, the preheating temperature of the rotary disc drawing filament in the step 9 is 500-1100 ℃, the heating temperature of the wire drawing die is 400-800 ℃, the wire drawing die is subjected to multi-pass drawing to obtain a filament with the diameter of 30-45 mu m, and the wire drawing die preferably adopts a 7-8 DEG small-angle hard alloy die, so that the local large deformation in the wire drawing process is reduced, and the phenomenon of necking and wire breakage is avoided. The pass deformation gradually decreases with the thinning of the diameter, and the preheating temperature of the wire and the die temperature also gradually decrease with the thinning of the diameter.
Further preferably, the small-diameter tungsten filament with the diameter of 30-45 μm in the step 9 is obtained through 38 times of diamond die drawing.
In the technical scheme of the invention, the relative content sum of the transition metal element and tungsten and molybdenum is the basis for realizing precipitation of the mu phase of intermetallic compound, however, the content, the morphology and the distribution of the mu phase are adjusted by coordinating the whole process, and the processability of the drawn filament of the tungsten wire is ensured. The high-fluidity oxide powder and the nitrate alcohol solution of cobalt, iron and lanthanum are uniformly stirred and mixed, so that the uniformity of solid-liquid doping is ensured. Rare earth lanthanum is added in a small amount to form lanthanum oxide which is dispersed and distributed in the matrix so as to inhibit coarsening of crystal grains in the sintering and hot working processes; the multi-pass diamond die drawing ensures the quality of tungsten wires and obtains sufficient grain boundary strengthening and work hardening. The whole technological process coordinates and regulates proper phase distribution and tissue morphology to obtain superfine high-strength tungsten filament material with excellent performance.
Inventive example 1
Preparing an intermetallic compound reinforced superfine high-strength tungsten wire, and weighing raw material powder according to a design formula, wherein the tungsten wire comprises the following components in percentage by mass: co:0.4%, fe:0.3%, la:0.8%, mo:3 percent, the impurity content is lower than 0.01 percent, the balance is W, and the preparation method is as follows:
(1) Weighing powder of blue tungsten and molybdenum dioxide according to the component proportion, and uniformly mixing oxide powder in a V-shaped mixer for 24 hours. Weighing ferric nitrate nonahydrate, cobalt nitrate hexahydrate and lanthanum nitrate according to the component proportion, and fully stirring and dissolving the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate and the lanthanum nitrate in sufficient alcohol. Spraying the alcohol solution of the nitrated compound on the surface of the oxide mixed powder uniformly in a mixing stirrer, and stirring the solid-liquid mixture until the alcohol volatilized powder is not agglomerated any more.
(2) And (3) carrying out high-temperature reduction on the uniformly doped mixed powder in a hydrogen reduction furnace at 850 ℃ for 3 hours to obtain alloy tungsten powder, and carrying out isostatic pressing on the alloy tungsten powder under the pressure of 250MPa to obtain a tungsten rod, wherein the pressing pressure maintaining time is 4min.
(3) Presintered the pressed tungsten rod in a hydrogen furnace at 1200 ℃ for 50min, and then presintered tungsten rod is presintered (densification sintering, namely second-stage sintering, with the temperature marked as T1) in an intermediate frequency induction furnace at 2100 ℃ for 240min to obtain the sintered tungsten rod.
(4) The sintered tungsten rod is preheated in a hydrogen atmosphere protection furnace for 30min, then is rotary-forged and cogged, the preheating temperature is 1500 ℃, the machining deformation of rotary-forging and cogging passes is 1-1.5 mm, and the next rotary forging is carried out after the rotary-forging and cogging passes are finished and the heat preservation is carried out for 4min. And performing rotary forging and cogging to obtain a tungsten rod with the diameter of 9mm, and then performing intermediate frequency induction annealing at 1800 ℃ for 1min. And preheating the annealed tungsten rod at 1450 ℃ for 15min, and performing rotary forging tandem forging to obtain the thin tungsten rod with the diameter of 3.6 mm.
(5) The thin tungsten rod obtained by rotary forging and tandem forging uniformly passes through flowing graphite emulsion slurry, is preheated by a 1150 ℃ furnace and then is subjected to chain drawing by a hard alloy die, the heating temperature of the hard alloy die is 900 ℃, and the diameter of a tungsten wire is 2.6mm after 4 die drawing. And then carrying out rotary disc drawing on the tungsten wire obtained by chain drawing, wherein the tungsten wire drawing is subjected to a stage of thick wire to thin wire, and the preheating temperature and the die temperature are gradually reduced along with the reduction of wire diameter, wherein the preheating temperature is 500-1100 ℃, the heating temperature of a wire drawing die is 400-800 ℃, and the tungsten wire is subjected to 38-pass drawing to obtain the thin black tungsten wire with the diameter of 36 mu m.
The tensile strength of the 36 mu m-diameter tungsten black wire prepared by the method is 6945MPa, the breaking elongation is 1.6%, and the elastic modulus of the tungsten wire is 415GPa.
Example 2
In example 2, as compared with example 1, blue tungsten and molybdenum dioxide were still used as mixed raw material powders, and the tungsten wire had the following mass percentage composition: co:0.2%, fe:0.2%, la:0.4%, mo:2%, impurity content lower than 0.01% and balance W. Example 2 the process was the same as in example except that the tungsten blank was densified at a sintering temperature of 2200 c and subjected to the same 38 passes of diamond die drawing to obtain a 36 μm diameter fine tungsten filament. Through detection, the prepared 36 mu m-diameter tungsten black wire has the tensile strength of 6183MPa, the breaking elongation of 2.6 percent and the elastic modulus of 426GPa. When the content of mu phase constituent elements of intermetallic compound and rare earth oxide elements are reduced, the tensile strength of the drawn tungsten wire is slightly reduced, and the fracture elongation of the tungsten wire is increased to a certain extent.
Example 3
Example 3 compared with example 1, the same tungsten wire mass percentage composition was adopted, and tungsten powder and molybdenum powder were directly adopted as raw material powder, and the same preparation process was performed to obtain a 36 μm diameter fine tungsten wire. Through detection, the tensile strength of the 36 mu m-diameter tungsten black wire prepared by the method is 6578MPa, the breaking elongation is 1.7%, and the elastic modulus of the tungsten wire is 413GPa. Tungsten powder and molybdenum powder with poor fluidity are used as mixed raw materials, and the uniformity of mixing materials is lower than that of tungsten oxide and molybdenum oxide powder with excellent fluidity when cobalt, iron and lanthanum sources are introduced, so that the tensile strength of tungsten wires prepared under the same components is lower than that of tungsten wires prepared by using a higher-quality mixture.
Example 4
Example 4 differs from example 1 only in that the reduction temperature in step 2 was changed to 900 ℃ and the reduction was carried out for 4 hours, and the other operations and parameters were the same as in example 1.
Through detection, the prepared 36 mu m-diameter tungsten black wire has the tensile strength of 6752MPa, the breaking elongation of 1.7 percent and the elastic modulus of 416GPa. The W/Mo coated Fe-Co-La composite metal powder obtained by adopting a higher reduction temperature and a longer reduction time has coarser powder granularity, the sintering activity of the reduction coarse powder is slightly poorer than that of the fine powder in the same sintering and processing technology, the prepared sintered blank has slightly lower density and coarser original grain size, and the tensile strength of the wire after the subsequent drawing processing is slightly lower than that of the tungsten wire prepared by adopting the raw material powder which is rapidly reduced in a shorter time.
Example 5
Example 5 compared to example 2, with the same raw material powder and tungsten wire composition ratio, only the densification sintering temperature of the tungsten blank was increased from 2200 to 2400 ℃, followed by the same 38-pass diamond die drawing to obtain a 36 μm diameter thin tungsten filament. Through detection, the tensile strength of the tungsten black wire with the diameter of 36 mu m prepared by the method is 6054MPa, the breaking elongation is 2.7%, and the elastic modulus of the tungsten wire is 423GPa. Example 5 raising the densification temperature of the tungsten blank resulted in coarser grains of the sintered tungsten blank, which was subsequently subjected to the same processing to prepare a tungsten wire, which had slightly lower tensile strength than example 2 due to coarser grain size of the as-green blank.
Comparative example 1
Compared with the embodiment 1, the difference is that the designed mass percentages of the elements in the tungsten filament are respectively as follows: co:0.1%, fe:0.1%, la:0.1%, mo:1% impurity content less than 0.01%, balance W, other operations and parameters were the same as in example 1.
The tensile strength of the 36 mu m-diameter tungsten black wire prepared by the method is 5587MPa, the breaking elongation is 3.2%, and the elastic modulus of the tungsten wire is 445GPa. From comparative example 1, when the addition amounts of the intermetallic compound forming element and the rare earth element are small, only work hardening and fine grain strengthening by the drawing process are relied on, and insufficient intermetallic compound precipitation strengthening and rare earth oxide dispersion strengthening are difficult to greatly improve the tensile strength of the tungsten filament, so that the intermetallic compound forming element and the rare earth element are required to be ensured to have a certain addition amount.
Comparative example 2
The only difference compared to example 1 is the absence of Co, iron and molybdenum, i.e. the designed mass percentages of the elements in the tungsten filament are: co:0%, fe:0%, la:0.4%, mo:0%, impurity content lower than 0.01%, and balance W. Comparative example 2 the same process as in example was carried out with only a tungsten blank densification sintering temperature of 2300 c and subjected to the same 38 passes of diamond die drawing to obtain a 36 μm diameter thin tungsten filament.
Through detection, the prepared 36 mu m-diameter tungsten black wire has the tensile strength of 5321MPa, the breaking elongation of 2.9% and the elastic modulus of 442GPa. Grain refinement and work hardening by only small amounts of rare earth oxide dispersion strengthening and drawing are not sufficient to maintain ultra-fine tungsten wire properties at very high levels.
Comparative example 3
The only difference compared with example 1 is that the designed mass percentages of the elements in the tungsten filament are: co:1.2%, fe:1.2%, la:0.4%, mo:4%, the impurity content is lower than 0.01%, the balance is W, and the preparation method is as follows:
(1) Weighing powder of blue tungsten and molybdenum dioxide according to the component proportion, and uniformly mixing oxide powder in a V-shaped mixer for 24 hours. Weighing ferric nitrate nonahydrate, cobalt nitrate hexahydrate and lanthanum nitrate according to the component proportion, and fully stirring and dissolving the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate and the lanthanum nitrate in sufficient alcohol. Spraying the alcohol solution of the nitrated compound on the surface of the oxide mixed powder uniformly in a mixing stirrer, and stirring the solid-liquid mixture until the alcohol volatilized powder is not agglomerated any more.
(2) And (3) carrying out high-temperature reduction on the uniformly doped mixed powder in a hydrogen reduction furnace at 850 ℃ for 3 hours to obtain alloy tungsten powder, and carrying out isostatic pressing on the alloy tungsten powder under the pressure of 250MPa to obtain a tungsten rod, wherein the pressing pressure maintaining time is 4min.
(3) Presintered the pressed tungsten rod in a hydrogen furnace at 1200 ℃ for 50min, and then presintered tungsten rod is presintered in an intermediate frequency induction furnace at 1800 ℃ for 240min to obtain a sintered tungsten rod.
(4) The sintered tungsten rod is preheated in a hydrogen atmosphere protection furnace for 30min, then is rotary-forged and cogged, the preheating temperature is 1450 ℃, the machining deformation of rotary-forging and cogging passes is 1-1.5 mm, and forging cracking is generated in the follow-up serial forging after the rotary-forging and cogging. The excessive addition of intermetallic forming elements promotes sintering shrinkage of the tungsten rod at lower temperature, but the excessive formation amount of brittle intermetallic compounds leads to poor thermoplasticity of the tungsten rod, and the superfine tungsten wire cannot be prepared through the complete process flow of rotary forging, tandem forging and drawing.
Comparative example 4
In comparison with example 1, only in the step 1, blue tungsten and molybdenum dioxide are used as mixed raw material powder, and Co and Fe are directly added by using micron-sized metal powder, and lanthanum source is added in the process of mixing in the form of nano oxide, and other operations and parameters are the same as in example 1.
By adopting the same preparation process as in example 1, the sintered bar has serious forging cracking in the rotary forging and cogging process, the subsequent tandem forging and drawing processing cannot be carried out, intermetallic compound forming elements are added in a powder form and are in situ compounded with a tungsten matrix to generate a brittle intermetallic compound phase with coarse size, so that the component formula cannot penetrate through the whole flow process of the superfine tungsten wire.
Comparative example 5
The only difference compared with example 1 is the lack of cobalt, la and Mo in the raw material, i.e. the designed mass percentage composition of tungsten filament is: co:0%, fe:0.3%, la:0%, mo:0%, impurity content lower than 0.01%, and balance W. Comparative example 5 the same process as comparative example 2 was carried out except that the densification sintering temperature of the tungsten ingot was 2200 c, and the same 38 passes of diamond die drawing was carried out to obtain a 36 μm diameter fine tungsten filament. Through detection, the tensile strength of the 36 mu m-diameter tungsten black wire prepared by the method is 5563MPa, the breaking elongation is 2.7%, and the elastic modulus of the tungsten wire is 427GPa. The preparation of ultra-high strength ultra-fine tungsten wires requires the synergistic addition of intermetallic forming elements and rare earth elements in order to obtain the composite reinforcement of in situ forming intermetallic compounds and rare earth oxides.
Comparative example 6
The only difference compared to example 1 is that in step 4 the annealing temperature is 1500 c and the other operations and parameters are the same as in example 1.
The bar still has larger residual stress, and forging fracture and drawing fracture occur in the subsequent tandem forging and drawing processing, so that the ultra-thin tungsten wire cannot be processed. Therefore, the preparation of the superfine tungsten filament is not necessary except the strict component control, and the whole process control of the matched components is also indispensable.
Table 1 comparison of mechanical properties of high speed steels prepared in examples and comparative examples
As is apparent from the comparison of the properties of examples and comparative examples, the tungsten filament reinforced by the mu phase precipitation of intermetallic compound prepared by the present invention has high breaking strength and elastic modulus, and the preparation process requires strict control of the intermetallic compound content and the grain coarsening inhibitor content to ensure excellent properties and workability of the tungsten filament, and simultaneously is supplemented with strict process control, and the components and process control complement each other to be key for preparing ultra-fine tungsten filament except for high strength. Compared with the preparation of superfine tungsten wire by adding rare earth, the tungsten wire prepared by the invention has excellent performance, does not need to add expensive rare earth elements in a large content, has simple process and lower cost, and can better meet the application requirements of diamond wire core wires.
Claims (10)
1. A mu-phase intermetallic compound in-situ reinforced tungsten wire is characterized by comprising a fibrous tungsten matrix and La dispersed in-situ 2 O 3 And a mu-phase intermetallic compound, the mu-phase intermetallic compound being Co-containing 7 Mo 6 、Co 7 W 6 、Fe 7 Mo 6 And Fe (Fe) 7 W 6 Is a complex intermetallic compound of (a);
in the mu-phase intermetallic compound in-situ reinforced tungsten filament, the content of Co is 0.2-0.6wt%, the content of Fe is 0.2-0.5wt%, the content of La is 0.1-1.5wt%, the content of Mo is 1-5wt%, and the balance is W.
2. The mu-phase intermetallic compound in-situ strengthening tungsten wire according to claim 1, wherein the content of Co in the mu-phase intermetallic compound in-situ strengthening tungsten wire is 0.2-0.5 wt%, the content of Fe is 0.2-0.4 wt%, the content of La is 0.3-1.2 wt%, the content of Mo is 1-4 wt%, and the balance is W;
preferably, in the mu-phase intermetallic compound in-situ strengthening tungsten wire, the content of Co is 0.2-0.45 wt%, the content of Fe is 0.2-0.35 wt%, the content of La is 0.5-1.1 wt%, the content of Mo is 2-4 wt%, and the balance is W;
preferably, in the mu-phase intermetallic compound in-situ strengthening tungsten wire, the content of Co is 0.3-0.4 wt%, the content of Fe is 0.2-0.3 wt%, the content of La is 0.7-0.9 wt%, the content of Mo is 2.5-3 wt%, and the balance is W;
preferably, the wire diameter of the mu-phase intermetallic compound in-situ strengthening tungsten wire is 0.030-0.045 mm;
preferably, said La 2 O 3 Grains of mu-phase intermetallic compound<300nm。
3. A method of preparing a mu-phase intermetallic compound in-situ strengthening tungsten wire as claimed in claim 1 or 2, comprising the steps of:
step (1):
compounding according to the metal content of the mu-phase intermetallic compound in-situ reinforced tungsten wire, compounding a composite homogeneous solution dissolved with an iron source, a cobalt source and a lanthanum source on the surface of tungsten-molybdenum composite metal powder to obtain a precursor, and carrying out reduction treatment on the precursor to obtain Fe-Co-La coated W/Mo composite metal powder; wherein the temperature of the reduction stage is 800-900 ℃;
step (2): forming and pressing Fe-Co-La coated W/Mo composite metal powder into a tungsten rod;
step (3): carrying out first-stage sintering on the tungsten rod at 1100-1300 ℃, and then heating to 1900-2400 ℃ to carry out second-stage sintering to obtain a sintered material;
step (4): and (3) performing rotary forging cogging, annealing, rotary forging tandem forging and drawing treatment on the sintering material to obtain the mu-phase intermetallic compound in-situ reinforced tungsten wire, wherein the annealing temperature is 1600-1850 ℃.
4. The method for preparing a mu-phase intermetallic compound in-situ reinforced tungsten wire according to claim 3, wherein the iron source is ferric nitrate;
preferably, the lanthanum source is lanthanum nitrate;
preferably, the cobalt source is cobalt nitrate;
preferably, the solvent in the composite homogeneous solution is at least one solvent of alcohol and water, preferably an alcohol-water mixed solvent, and more preferably an alcohol-water solvent with the alcohol volume content of 30-80% by volume;
preferably, the total concentration of the solute in the composite homogeneous solution is 0.2-0.4 g/ml;
preferably, the composite homogeneous solution is sprayed on the surface of tungsten and molybdenum composite metal powder, and the precursor is obtained through drying treatment;
preferably, the tungsten-molybdenum composite metal powder is a mixture of a tungsten source and a molybdenum source, and the tungsten source is elemental tungsten and/or blue tungsten; the molybdenum source is elemental molybdenum and/or molybdenum oxide.
5. A method for preparing a mu-phase intermetallic compound in-situ reinforced tungsten wire as claimed in claim 3 wherein the atmosphere in the reduction stage is a hydrogen-containing atmosphere;
preferably, the temperature of the reduction stage is 840 to 860 ℃;
preferably, the treatment time of the reduction stage is 2 to 4 hours.
6. A method for preparing a mu-phase intermetallic compound in-situ reinforced tungsten wire as claimed in claim 3 wherein the compact density of the tungsten rod is 9.0-14.0 g/cm 3 ；
Preferably, the pressing forming mode is one of steel mould pressing and isostatic pressing;
preferably, the pressure in the compression molding stage is 200-300 MPa, and the pressure maintaining time is 3-5 min;
preferably, the heat preservation time of the first stage sintering is 50-80 min;
preferably, the heat preservation time of the second stage sintering is 200-300 min.
7. The method for preparing the mu-phase intermetallic compound in-situ reinforced tungsten wire according to claim 3, wherein the method is characterized in that the method is preheated in a hydrogen atmosphere protection furnace for 20-40 min before rotary forging and cogging, the preheating temperature is 1400-1550 ℃, the machining deformation of rotary forging and cogging passes is 1-1.5 mm, and the next rotary forging is carried out after the rotary forging passes are finished and the temperature is kept for 3-5 min after the rotary forging passes are finished;
preferably, annealing in a medium-frequency induction heating furnace under the hydrogen atmosphere after rotary forging cogging;
preferably, the annealed tungsten rod is subjected to rotary forging and tandem forging to obtain a thin tungsten rod with the diameter of 3.5-3.8 mm.
8. The method for preparing a mu-phase intermetallic compound in-situ reinforced tungsten wire according to claim 7, wherein the drawing steps are sequentially performed by chain drawing and rotary disc drawing, wherein the diameter of the chain drawn tungsten wire is 2.5-2.8 mm;
preferably, the diameter of the turntable pullout is 30-40 μm.
9. Use of a mu-phase intermetallic compound in-situ strengthening tungsten wire according to claim 1 or 2 or prepared by a method according to any one of claims 3 to 8, for a cutting tool for semiconductor silicon sheets.
10. A cutting tool for a semiconductor silicon sheet, characterized in that it comprises a mu-phase intermetallic compound in-situ reinforced tungsten wire according to claim 1 or 2 or a mu-phase intermetallic compound in-situ reinforced tungsten wire produced by the production method according to any one of claims 3 to 8.
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