CN116970854A - Laves phase precipitation strengthening tungsten filament and preparation and application thereof - Google Patents
Laves phase precipitation strengthening tungsten filament and preparation and application thereof Download PDFInfo
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- CN116970854A CN116970854A CN202310951102.0A CN202310951102A CN116970854A CN 116970854 A CN116970854 A CN 116970854A CN 202310951102 A CN202310951102 A CN 202310951102A CN 116970854 A CN116970854 A CN 116970854A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 239000010937 tungsten Substances 0.000 title claims abstract description 135
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 134
- 238000005728 strengthening Methods 0.000 title claims abstract description 74
- 229910001068 laves phase Inorganic materials 0.000 title claims abstract description 53
- 238000001556 precipitation Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 22
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 45
- 238000005242 forging Methods 0.000 claims description 41
- 230000009467 reduction Effects 0.000 claims description 25
- 229910052684 Cerium Inorganic materials 0.000 claims description 24
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 18
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 claims description 18
- 229910000568 zirconium hydride Inorganic materials 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005520 cutting process Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 9
- 239000011246 composite particle Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000000280 densification Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000000462 isostatic pressing Methods 0.000 claims description 6
- 238000003754 machining Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000007723 die pressing method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 235000012431 wafers Nutrition 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 229910003460 diamond Inorganic materials 0.000 description 16
- 239000010432 diamond Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 12
- 238000005491 wire drawing Methods 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005482 strain hardening Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000005516 engineering process 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
- 239000000203 mixture Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research 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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017464 nitrogen compound 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
- 230000008520 organization Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
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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
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- 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 the technical field of tungsten wires, and particularly relates to a laves phase precipitation strengthening tungsten wire which comprises a tungsten matrix, oxides dispersed in the tungsten matrix and a laves strengthening phase formed in situ; the laves strengthening phase comprises NiW 2 、WFe 2 And WZr (WZr) 2 The method comprises the steps of carrying out a first treatment on the surface of the The oxide is ZrO 2 And CeO 2 In the laves phase precipitation strengthening tungsten filament, the Ni content is 0.2-0.6wt%, the Fe content is 0.2-0.6wt%, the Zr content is 0.3-0.8wt%, the Ce content is 0.1-1.2wt%, and the balance is tungsten. The invention also relates to an in-situ synthesis method of the tungsten filament. The process of the invention can improve the performance of tungsten wires.
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 laves phase precipitation and a preparation method thereof.
Background
The diamond wire replaces the traditional mortar to cut the semiconductor silicon plate to drive the photovoltaic industry to rapidly develop, and the process characteristics of high efficiency and mild environment of the diamond wire cutting become the main stream development direction of photovoltaic consumable processing in the future. However, the excessive material loss caused by the large cutting wear marks of diamond wire cutting is still worth further optimization compared with mortar cutting. Obviously, the size of the core wire of the diamond wire is thinned to reduce the silicon loss of the raw material, however, the continuous thinning of the core wire is accompanied by low breaking force value of the wire. At this time, the continuous increase of the tensile strength of the core wire becomes a key for further thinning of the supporting diamond wire. The core wire of the current mainstream diamond wire adopts a steel wire, and although cold drawing work hardening, grain refinement and component optimization can further improve the tensile strength of the steel wire, the improvement of the overall performance brought by the steel wire is insufficient to meet the performance requirement of the industry on the superfine wire diameter core wire. Meanwhile, the technical bottleneck problem to be solved for improving the performance of the ultra-fine ultra-high strength steel wire is still far, and although the steel yield in China is far away and ahead of the world, the ultra-high strength steel wire and related product fields still have larger gaps, so that the ultra-fine ultra-high strength steel wire occupies a place in the ultra-fine diamond wire field, and the development of a core wire material with higher performance and larger prospect is needed to realize curve overtaking.
Research shows that the high-strength tungsten wire is completely expected to replace the steel wire in view of the characteristics of the material and the resource reserve of China so as to realize the aim of further refining the diamond wire. Compared with steel wires, tungsten wires have higher elastic modulus, theoretical tensile strength and better conductivity, and are expected to become ideal choices of new generation superfine diamond wire core wires. Currently, the main stream tungsten core wire in the market is usually doped with rare earth such as lanthanum, cerium, rhenium and the like, and the unusual tensile strength value is obtained through work hardening and grain refinement generated by multi-pass drawing, but the grain boundary strengthening and work hardening obtained through deformation grain refinement are not enough to completely obtain ideal mechanical properties. Although rare earth element doping has both performance strengthening and improving the machinability of the tungsten wire, the second phase strengthening contributed by the dispersion distribution of a small amount of rare earth oxide is insufficient to achieve the expected material strengthening effect, and the addition of excessive rare earth element brings remarkable second phase strengthening effect in favor of improving the material performance, but the hard and brittle rare earth oxide greatly shortens the machining process window of the tungsten wire, and the lower machining yield and the addition of excessive noble rare earth element greatly increase the preparation cost of the material. Insufficient material strengthening and performance improvement become main obstacles for limiting further refinement of the wire diameter of the tungsten wire. In addition, oxide dispersion strengthening in the drawing process is insufficient to provide sufficient work hardening capacity, necking is easy to generate in the tungsten wire drawing process, and wire breakage is caused, so that the yield of the tungsten wire is greatly limited.
Disclosure of Invention
The invention aims to solve the problem that the performance of a high-strength steel core wire is insufficient in the process of pursuing wire diameter refinement of a diamond wire, and meanwhile to further obtain tungsten wire reinforcement and solve the problem of wire breakage in drawing.
The second object of the present invention is to provide an ultra-fine high strength tungsten wire reinforced by precipitation of a second phase (Laves phase) and a method for producing the same, aiming to obtain an ultra-high strength tungsten core wire with a finer wire diameter.
The third object of the invention is to provide the application of the laves phase precipitation strengthening tungsten wire in the cutting of semiconductor silicon plates and the device thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
the laves phase precipitation strengthening tungsten filament comprises a tungsten matrix, oxides dispersed in the tungsten matrix and a laves strengthening phase generated in situ;
the laves strengthening phase comprises NiW 2 、WFe 2 And WZr (WZr) 2 ；
The oxide is ZrO 2 And CeO 2 ；
In the laves phase precipitation strengthening tungsten filament, the content of Ni is 0.2-0.6wt%, the content of Fe is 0.2-0.6wt%, the content of Zr is 0.3-0.8wt%, the content of Ce is 0.1-1.2wt%, and the balance is tungsten.
The invention provides an in-situ composite NiW 2 、WFe 2 And WZr (WZr) 2 The tungsten filament of the laves strengthening phase can realize synergy based on the joint control of the strengthening phase components and the proportion, and can synergistically improve the performance of the tungsten filament.
In the invention, the components of the laves strengthening phase, the in-situ dispersion strengthening structural mode and the combined control of the content are key to synergistically improve the performance of the tungsten filament.
Preferably, in the laves phase precipitation strengthening tungsten filament, the Ni content is 0.2-0.5 wt%, the Fe content is 0.2-0.4 wt%, the Zr content is 0.3-0.7 wt%, the Ce content is 0.2-1.0 wt%, and the balance is W;
preferably, the Ni content is 0.2-0.45 wt%, the Fe content is 0.2-0.35 wt%, the Zr content is 0.4-0.7 wt%, the Ce content is 0.4-1.0 wt%, and the balance is W;
further preferably, the Ni content is 0.3 to 0.4wt%, the Fe content is 0.25 to 0.3wt%, the Zr content is 0.6 to 0.7wt%, the Ce content is 0.7 to 0.9wt%, and the balance is W;
preferably, the size of the labes strengthening phase is <300nm;
preferably, the diameter of the laves phase precipitation strengthening tungsten filament is 30-40 mu m.
The invention also provides a preparation method of the laves phase precipitation strengthening tungsten filament, which comprises the following steps:
step (1): batching according to the element content of the laves phase precipitation strengthening tungsten filament, spraying and compositing a solution dissolved with required amounts of nickel source, iron source and cerium source on the surface of tungsten source powder, and then carrying out reduction treatment to obtain Ni-Fe-Ce coated W composite particles, wherein the temperature of the reduction stage is 800-900 ℃;
step (2): compounding and molding the Ni-Fe-Ce coated W composite particles and zirconium hydride with required amount to obtain a composite blank;
step (3): presintering the composite blank at 1200-1400 ℃ in advance, and finally sintering at 2000-2400 ℃ to obtain a sintered blank;
step (4): and (3) carrying out rotary swaging, annealing, tandem forging and drawing on the sintering material to obtain the laves phase precipitation strengthening tungsten filament.
How to form the labes phase in situ in the tungsten filament matrix is a key and difficult point of successfully preparing the tungsten filament of the present invention. Aiming at the preparation difficulty, the invention discovers that the nickel source, the iron source, the cerium source and the zirconium hydride in the proportion are innovatively adopted as raw materials, the nickel source, the iron source and the cerium source are innovatively carried out in advance by wet method and are reduced and coated on the surface of tungsten source powder, and then the nickel source, the iron source and the cerium source are compounded, molded and sintered with the zirconium hydride, and further cooperate with the combination of the reduction process and the sintering process, so that the synergy can be realized, and the nickel source, the iron source and the cerium source can be unexpectedly dispersed in situ in the tungsten matrix to form the synergy containing NiW 2 、WFe 2 And WZr (WZr) 2 Is helpful for improving the comprehensive performance of the prepared material.
In the invention, the type, proportion and combination control of the reduction pre-coating after liquid phase spraying and the subsequent sintering process of the raw materials are key to cooperatively inducing the formation of the cooperative laves strengthening phase and uniform dispersion distribution.
In the invention, in the step 1, the nickel source, the iron source and the cerium source with required contents are dissolved in advance to form a homogeneous solution, then the homogeneous solution is uniformly compounded on the surface of tungsten source powder based on known means such as a spraying, matching and stirring mode, then reduction is carried out, and the required amount of nickel and iron are reduced in situ and coated on the surface of the tungsten source powder, so that the subsequent process can be matched, and the formation of a laves strengthening phase is facilitated.
In the present invention, the nickel source may be any nickel raw material having solubility, for example, nickel nitrate.
In the present invention, the iron source may be any iron source having solubility, for example, iron nitrate;
in the present invention, the cerium source may be any cerium source having solubility, for example, iron nitrate.
Preferably, the solvent in the 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 v%;
preferably, the total concentration of solutes in the solution is 0.2-0.4g/ml;
preferably, the tungsten source powder is metal tungsten powder and/or blue tungsten powder; preferably blue tungsten powder. Research shows that blue tungsten powder is favorable for further cooperation with the process of the invention, and the comprehensive performance of the prepared material can be further improved.
In the invention, the granularity of tungsten source powder is less than 2 mu m;
preferably, the solution is sprayed on the surface of the tungsten source powder and is uniformly stirred and mixed, and the subsequent reduction treatment is carried out after the drying treatment.
In the invention, the atmosphere in the reduction stage is a hydrogen-containing atmosphere; it may be pure hydrogen, hydrogen-nitrogen compound gas, or hydrogen-argon compound gas.
In the invention, the temperature of the reduction stage is 840-860 ℃; 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 further be 2 to 3 hours.
In the invention, in the step (2), zirconium hydride is adopted as a zirconium source, and the zirconium hydride and Ni-Fe-Ce are coated with W composite particles, so that the preparation of the laves phase precipitation strengthening tungsten filament is facilitated. The successful addition of Laves phase formation components is realized by designing the addition of zirconium hydride powder, meanwhile, the thermally stable zirconium oxide is introduced into the tungsten filament by the oxidation of trace zirconium, a certain dispersion strengthening effect is obtained while the coarsening of crystal grains in the processing process is effectively inhibited, and the whole preparation technology has simple route and strong repeatability.
In the present invention, the compounding manner and the molding manner of the zirconium hydride, ni-Fe-Ce coated W composite particles may be conventional. For example, the Ni-Fe-Ce coated W composite particles and zirconium hydride are combined in a protective atmosphere. The molding mode is one of steel mould pressing and isostatic pressing; the pressing pressure is 200-300 MPa, and the pressure maintaining time is 3-5 min;
preferably, the compact density of the composite blank obtained by molding is 9.0 to 14.0g/cm 3 。
In the invention, the formed composite blank is sintered, and the combination of sintering technology is favorable for combining and cooperating with the preamble technology and parameters, thereby being more favorable for in-situ formation and uniform dispersion strengthening of the labes phase.
In the invention, the molded composite blank can be heated to the presintering temperature, the presintering is kept warm for deoxidization and impurity removal, and then the temperature is raised to the sintering temperature again for densification sintering. Wherein, in the process of heating to presintering, four heat preservation platforms are arranged at the temperature of 350-450 ℃, 550-650 ℃, 750-850 ℃ and 1200-1400 ℃, and the heat preservation time of each heat preservation platform is 10-30 min;
preferably, the presintering time is 45-80 min;
preferably, the final densification sintering time is 200 to 300 minutes.
In the invention, after sintering treatment, the sintered material can be subjected to rotary forging, annealing, tandem forging and drawing based on known principles and means to prepare the laves phase precipitation strengthening tungsten filament.
Preheating in a hydrogen atmosphere protection furnace for 20-40 min before rotary forging cogging, wherein the preheating temperature is 1400-1600 ℃, the processing deformation of rotary forging cogging passes is 1-1.5 mm, and the next rotary forging is carried out after the return furnace heat preservation is carried out for 3-5 min after each pass of processing;
performing rotary forging and tandem forging to obtain a thin tungsten rod with the diameter of 3.5-3.9 mm;
the atmosphere in the annealing stage is hydrogen-containing atmosphere;
the annealing temperature is 1600-1900 ℃;
the drawing steps are sequentially carried out by chain drawing and turntable drawing, wherein the diameter of a chain drawn tungsten wire is 2.4-2.8 mm;
and then carrying out rotary disk drawing on the tungsten wire after chain drawing, wherein the diameter of the tungsten wire after rotary disk drawing is 30-40 mu m.
The invention also provides an application of the laves phase precipitation strengthening tungsten wire, which is used for a cutting device of a semiconductor silicon wafer.
The invention also provides a cutting device of the semiconductor silicon plate, which comprises the laves phase precipitation strengthening tungsten wire prepared by the preparation method.
The invention has the beneficial effects that:
1. the invention provides a laves phase precipitation strengthening tungsten filament which has excellent tensile strength and high elastic modulus.
2. The invention innovatively adopts the nickel source, the iron source, the cerium source and the zirconium hydride in the proportion as raw materials, and innovatively loads the nickel source, the iron source and the cerium source in advance by a wet method and reduces and coats the nickel source, the iron source and the cerium source on the surface of tungsten source powder, and then composites, forms and sinters the tungsten source powder with the zirconium hydride, and further cooperates with the combination of the reduction process and the sintering process to realize synergy, and can be accidentally dispersed in situ in the tungsten matrix to form the synergistic NiW 2 、WFe 2 And WZr (WZr) 2 Is helpful for improving the comprehensive performance of the prepared material.
3. The invention prepares the low-cost high-performance ultrafine tungsten wire under the composite actions of fine crystal strengthening, laves phase precipitation strengthening and oxide dispersion strengthening, avoids the addition of a large amount of expensive rare earth elements in the traditional high-strength ultrafine tungsten wire preparation, and greatly reduces the preparation cost.
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 present invention relates to a superfine high-strength tungsten wire reinforced by precipitation of a second phase, wherein the final wire diameter of the tungsten wire can be adjusted according to the use situation, for example, when the tungsten wire is used for cutting a semiconductor silicon wafer plate, the tungsten wire and the semiconductor silicon wafer plate can be 0.03-0.04 mm in consideration of the suitability of the cutting process of the tungsten wire and the semiconductor silicon plate.
The high-strength alloy tungsten wire comprises a tungsten matrixAnd oxides and Laves phases generated in situ, wherein the oxides are ZrO generated by reaction 2 And rare earth oxide CeO 2 Whereas the Laves phase is mainly NiW 2 、WFe 2 And WZr (WZr) 2 。
Preferably, the rare earth oxide and the Laves phase are generated in situ, and after the tungsten wire is subjected to multi-pass drawing and crushing, the rare earth oxide and the Laves phase in the finished tungsten wire reach the nanometer level (< 300 nm).
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 laves phase precipitation strengthening tungsten filament, the content of Ni is 0.2-0.6wt%, the content of Fe is 0.2-0.6wt%, the content of Zr is 0.3-0.8wt%, the content of Ce is 0.1-1.2wt%, and the balance is tungsten.
In the laves phase precipitation strengthening tungsten filament, the Ni content is 0.2-0.5 wt%, the Fe content is 0.2-0.4 wt%, the Zr content is 0.3-0.7 wt%, the Ce content is 0.2-1.0 wt%, and the balance is W;
preferably, the Ni content is 0.2-0.45 wt%, the Fe content is 0.2-0.35 wt%, the Zr content is 0.4-0.7 wt%, the Ce content is 0.4-1.0 wt%, and the balance is W;
more preferably, the Ni content is 0.3 to 0.4wt%, the Fe content is 0.25 to 0.3wt%, the Zr content is 0.6 to 0.7wt%, the Ce content is 0.7 to 0.9wt%, and the balance is W.
In a preferred scheme, the diameter of the superfine tungsten filament is 30-40 mu m, the tensile strength is more than or equal to 6300MPa, the breaking elongation is 1.4-2.8%, and the elastic modulus is 350-430 GPa.
In a further preferable scheme, the diameter of the superfine tungsten filament is 30-40 mu m, the tensile strength is more than or equal to 6800MPa, the breaking elongation is 1.5-2.2%, and the elastic modulus is 380-430 GPa.
The invention relates to a typical intermetallic compound reinforced superfine high-strength tungsten wire and a preparation method thereof, comprising the following steps:
step 1: the nickel nitrate, the ferric nitrate nonahydrate and the cerium nitrate are weighed according to the proportion and then are fully dissolved, and then are evenly sprayed on the tungsten source powder under the stirring working condition.
Step 2: and (3) carrying out primary hydrogen reduction on the uniformly doped powder obtained in the step (1) in a hydrogen reduction furnace at 800-900 ℃ to obtain alloy tungsten powder.
Step 3: and (3) uniformly mixing the reduced alloy tungsten powder obtained in the step (2) with a small amount of added zirconium hydride powder under a protective atmosphere.
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 1200-1400 ℃ for 45-80 min, presintering the bar stock, and then presintering the bar stock in an intermediate frequency induction furnace at 2000-2400 ℃ 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 medium-frequency induction heating furnace in a hydrogen atmosphere, wherein the annealing temperature is 1600-1900 ℃.
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 3.5-3.9 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 2.4-2.8 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 30-40 microns.
Preferably, the tungsten raw material powder in the step 1 is preferably ultrafine #<2 μm) blue tungsten (WO 2.9 ) The fluidity of the powder is better than that of ultrafine tungsten powder, the powder is easier to be fully stirred and mixed with other metal components uniformly, oxide powder, nickel nitrate, iron and cerium alcohol solution are adopted for solid-liquid doping, and the doping homogenization is easy to be realized. In addition, tungsten, nickel and iron oxides and the oxides are easy to reduce in a hydrogen atmosphere, and the addition process scheme is feasible.
Zirconium and tungsten are uniformly mixed through powder, ni, fe and Ce are added in the form of nickel nitrate, ferric nitrate nonahydrate and cerium nitrate respectively, nitrate compounds of nickel, iron and cerium are fully dissolved by absolute ethyl alcohol, and then an alcohol solution and tungsten powder are subjected to solid-liquid doping under a stirring state.
By using superfine ZrH 2 Powder [ (B)<2 μm) instead of Zr powder addition, avoiding that Zr is completely oxidized before sintering.
The sum of the mass percentages of Ni and Fe in the tungsten filament is 0.4-0.8%, and the mass percentage of Zr added is 0.3-0.7%. Ni, fe and Zr are added as forming elements of Laves phases, and the purpose of the invention is to react with tungsten element of a matrix to precipitate out a second phase, so that too much Laves phases are generated, which is unfavorable for drawing processing.
The mass percentage of cerium in the tungsten filament is 0.2-1.0%, rare earth element cerium is converted into cerium oxide to be dispersed and distributed in a matrix in the process, and meanwhile, partial zirconium is oxidized to produce zirconium dioxide in a trace amount in the process, which also plays a role in inhibiting grain coarsening and dispersion strengthening in the sintering and hot working processes. The addition amount of cerium is too small to achieve the effects of inhibiting coarsening of crystal grains and strengthening dispersion, and the composite effect caused by zirconium can reduce excessive addition of cerium so as to reduce cost.
The added components in percentage by mass are: ni:0.2 to 0.5 percent, fe:0.2 to 0.4 percent of Zr:0.3 to 0.7 percent, ce: 0.2-1.0%, impurity content lower than 0.01% and balance W.
The added components in percentage by mass are: ni:0.2 to 0.45 percent, fe:0.2 to 0.35 percent of Zr:0.4 to 0.7 percent, ce:0.4 to 1.0 percent, the impurity content is lower than 0.01 percent, and the balance is W.
The added components in percentage by mass are: ni:0.3 to 0.4 weight percent of Fe:0.25 to 0.3 weight percent of Zr:0.6 to 0.7 weight percent, ce:0.7 to 0.9 weight percent, and the balance of W.
Preferably, the hydrogen concentration in the hydrogen reduction in the step 2 is not less than 99%, and the high-temperature reduction and heat preservation time of the hydrogen furnace is not less than 2 hours.
Preferably, the reduced tungsten alloy powder and the superfine zirconium hydride powder (< 2 μm) in the step 3 are mixed for more than 12 hours by adopting a V-shaped mixer, and are subjected to pre-vacuumizing and then are subjected to argon atmosphere protection mixing.
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 pre-sintering of the pressed tungsten rod in the step 5 is carried out by arranging three heat preservation platforms at 400 ℃, 600 ℃ and 800 ℃ for 20 minutes, so as to ensure that zirconium hydride powder is mildly and thoroughly dehydrogenated into zirconium powder in the low-temperature heat preservation stage.
Preferably, the sintered tungsten rod is preheated in a hydrogen atmosphere protection furnace for 30min before rotary forging and cogging in the step 6, the preheating temperature is 1400-1600 ℃, 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, the preheating temperature of the rotary forging tandem forging tungsten rod in the step 7 is 1350-1550 ℃, the tungsten rod fed by a heat preservation furnace is added between two times of tandem forging equipment for heating and heat preservation, and the temperature of the heat preservation furnace is 1300-1500 ℃.
Preferably, the lubricant graphite emulsion in step 8 adopts D 50 The nano graphite powder with the thickness less than or equal to 0.2 mu m and the thickener are continuously stirred and mixed uniformly, and uniformly penetrate and infiltrate into the pumped graphite emulsion slurry before the tungsten rod is drawn, so as to ensure that the surface of the tungsten wire is fully coated with the graphite emulsion. The lubrication effect of wire drawing can be enhanced by adopting finer graphite powder, so that the generation of defects on the surface of the wire in the wire drawing process and the loss of a wire drawing die are further reduced.
Preferably, the tungsten filament in step 8 is preheated to 1100-1200 ℃ and then subjected to chain drawing, the wire drawing die is heated to 800-900 ℃ and then subjected to drawing, the wire drawing die preferably adopts a hard alloy die, the hard alloy die 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 30-40 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 30-40 μm in the step 9 is obtained through 40 times of diamond die drawing.
In the technical scheme of the invention, the control of the relative content of transition metal elements and tungsten is the basis for realizing precipitation of Laves phase, but the preparation process technology is required to be matched in a coordinated manner to obtain the target organization and distribution, and the process from tungsten powder to final superfine micron-sized tungsten wire is ensured to be feasible. The transition element is uniformly mixed by uniformly mixing high-fluidity blue tungsten powder with nickel nitrate, iron and cerium solution; the zirconium hydride powder is added to ensure that the easily oxidized element is successfully alloyed into the matrix; the rare earth cerium forms a dispersion-distributed oxide in the technical process, and a small amount of oxidized zirconium can also serve as a grain coarsening inhibitor and a dispersion-strengthening second phase in a matrix; the multipass drawing deformation achieves sufficient work hardening and grain refinement strengthening. Under the combined action of multiple strengthening mechanisms, the high-performance superfine tungsten filament is ensured to be obtained.
Example 1
Preparing a laves phase precipitation strengthening ultrafine high-strength tungsten filament, and weighing raw material powder according to a design formula, wherein the tungsten filament comprises the following components in percentage by mass: ni:0.4%, fe:0.3%, zr:0.7%, ce:0.8%, impurity content lower than 0.01%, and balance W, and its preparation method is as follows:
(1) Weighing nickel nitrate, ferric nitrate nonahydrate and cerium nitrate according to the component proportion, and fully stirring and dissolving the nickel nitrate, the ferric nitrate nonahydrate and the cerium nitrate in sufficient alcohol. Uniformly spraying the nitrate alcohol solution on the surface of the blue tungsten powder in a mixing stirrer, and stirring the solid-liquid mixture until the alcohol volatilized powder is not agglomerated any more.
(2) The evenly doped mixed powder is reduced for 3 hours at high temperature in a hydrogen reduction furnace at 850 ℃ to obtain alloy tungsten powder, and the fully cooled alloy tungsten powder and the zirconium hydride powder added according to the component ratio are evenly mixed for 24 hours under the protection of argon gas in a V-shaped mixer. And (3) isostatic pressing the uniformly mixed alloy tungsten powder into a tungsten rod under the pressure of 200MPa, wherein the pressing pressure maintaining time is 5min.
(3) Presintering the pressed tungsten rod in a hydrogen furnace at 1300 ℃ for 50min, setting three heat preservation platforms at 400 ℃, 600 ℃ and 800 ℃ before the highest temperature, respectively preserving heat for 20min, and then presintering the presintered tungsten rod in an intermediate frequency induction furnace at 2100 ℃ for 240min (densification sintering, wherein the temperature is marked as T1) 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 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 4 min. 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 2.8mm 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 40 times of drawing to thin tungsten wires with the diameter of 34 mu m.
The tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 7124MPa, the breaking elongation is 1.5%, and the elastic modulus of the tungsten wire is 408GPa.
Example 2
Example 2 differs from example 1 only in that the content of Ni, fe, zr, ce in the raw material is controlled, wherein the tungsten filament comprises the following components in percentage by mass: ni:0.2%, fe:0.2%, zr:0.4%, ce:0.4%, impurity content lower than 0.01% and balance W, the preparation process of example 2 is the same as that of example 1, only the densification sintering temperature of the tungsten blank is 2200 ℃ (T1), and the tungsten blank is subjected to the same 40 times of diamond die drawing to obtain the thin tungsten filament with the diameter of 34 mu m. Through detection, the tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 6336MPa, the breaking elongation is 2.7%, and the elastic modulus of the tungsten wire is 427GPa.
Example 3
Example 3 compared with example 1, the same tungsten wire mass percentage composition was adopted, and tungsten powder was directly adopted as the raw material powder, and the same preparation process was carried out to obtain a fine tungsten wire with a diameter of 34 μm. Through detection, the tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 6814MPa, the breaking elongation is 1.8%, and the elastic modulus of the tungsten wire is 412GPa. Tungsten powder with poor fluidity is used as a mixed raw material, and when nickel, iron and cerium sources are introduced, tungsten oxide raw materials with poor mixing uniformity and excellent fluidity are used, and tungsten wires prepared under the same components have poor tensile strength and tungsten wires prepared by more uniform mixed materials.
Example 4
Compared with example 1, example 4 adopts the identical tungsten filament mass percentage composition, and 2300 ℃ (T1) is selected for heat preservation for 240min during final densification sintering, and then the thin tungsten filament with the diameter of 34 mu m is obtained through the same preparation process. Through detection, the tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 6774MPa, the breaking elongation is 1.9%, and the elastic modulus of the tungsten wire is 415GPa. Example 4 raising the densification temperature of the tungsten blank resulted in coarser grains of the sintered tungsten blank, which were subsequently prepared into tungsten filaments using the same process, and the coarser grain size in the primary blank resulted in a final filament tensile strength slightly lower than that of example 1.
Example 5
The difference compared to example 2 is that in step 2, the reduction temperature is 900℃and the reduction time is 4 hours, and other operations and parameters are the same as in example 2.
Through detection, the tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 6156MPa, the breaking elongation is 2.8%, and the elastic modulus of the tungsten wire is 423GPa. The W-coated Ni-Fe-Ce composite metal powder obtained by adopting a higher reduction temperature and a longer reduction time has coarser powder granularity, and when the same sintering and processing technology is adopted later, the sintering activity of coarse powder is lower than that of fine powder, the prepared sintered blank has slightly lower density and coarser grain size, and the wire subjected to subsequent drawing processing has slightly lower tensile strength than that of tungsten wire prepared from raw material powder which is rapidly reduced in a shorter time.
Comparative example 1
Compared with the embodiment 1, the difference is that the raw materials in the tungsten wire are designed according to the mass percentage: ni:0.1%, fe:0.1%, zr:0.2%, ce:0.1%, impurity content less than 0.01%, balance W, other operations and parameters were the same as in example 1.
The tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 5673MPa, the breaking elongation is 2.8%, and the elastic modulus of the tungsten wire is 429GPa. From comparative example 1, when the addition amounts of intermetallic compound and rare earth oxide forming elements are small, it is difficult to greatly improve the tensile strength of tungsten filament by only work hardening, fine grain strengthening and weak intermetallic compound precipitation strengthening and oxide dispersion strengthening in the drawing process, so that the addition amounts of Laves phase forming elements and rare earth elements are required to be ensured.
Comparative example 2
The difference from example 1 is that in step 1, ni, fe, zr are not added, that is, the designed mass percentage composition of the raw materials in the tungsten filament is: ni:0%, fe:0%, zr:0%, ce:0.5%, impurity content lower than 0.01%, and balance W.
Comparative example 2 the same process as in example 1 was carried out except that the tungsten blank was densified at a sintering temperature of 2300 c and subjected to the same 40 passes of diamond die drawing to obtain a 34 μm diameter fine tungsten filament.
Through detection, the prepared 34 mu m-diameter tungsten black wire has the tensile strength of 5215MPa, the breaking elongation of 3.1 percent and the elastic modulus of 433GPa. Dispersion strengthening and drawn grain refinement and work hardening by only a small amount of rare earth oxide are insufficient to ensure high performance of the ultra-fine tungsten wire.
Comparative example 3
The difference from example 1 is that in step 1, fe, zr, ce are not added, that is, the mass percentage composition of the raw material design of the tungsten filament is: ni:0.4%, fe:0%, zr:0%, ce:0%, impurity content lower than 0.01%, and balance W.
Through detection, the tensile strength of the 34 mu m-diameter tungsten black wire prepared by the method is 5732MPa, the breaking elongation is 2.2%, and the elastic modulus of the tungsten wire is 418GPa. The preparation of ultra-high strength ultra-fine tungsten wires requires the synergistic addition of intermetallic forming elements and rare earth elements to obtain the composite reinforcement of in situ forming Laves phases and rare earth oxides.
Comparative example 4
Compared with the embodiment 1, the difference is that in the step 1, raw material powder is weighed according to a design formula, wherein the tungsten filament comprises the following components in percentage by mass: ni:0.9%, fe:0.8%, zr:0.9%, ce:1.2%, impurity content lower than 0.01%, and balance W, and its preparation method is as follows:
(1) Weighing nickel nitrate, ferric nitrate nonahydrate and cerium nitrate according to the component proportion, and fully stirring and dissolving the nickel nitrate, the ferric nitrate nonahydrate and the cerium nitrate in sufficient alcohol. Uniformly spraying the nitrate alcohol solution on the surface of the blue tungsten powder in a mixing stirrer, and stirring the solid-liquid mixture until the alcohol volatilized powder is not agglomerated any more.
(2) The evenly doped mixed powder is reduced for 3 hours at high temperature in a hydrogen reduction furnace at 850 ℃ to obtain alloy tungsten powder, and the fully cooled alloy tungsten powder and the zirconium hydride powder added according to the component ratio are evenly mixed for 24 hours under the protection of argon gas in a V-shaped mixer. And (3) isostatic pressing the uniformly mixed alloy tungsten powder into a tungsten rod under the pressure of 200MPa, wherein the pressing pressure maintaining time is 5min.
(3) Presintering the pressed tungsten rod in a hydrogen furnace at 1300 ℃ for 50min, setting three heat preservation platforms at 400 ℃, 600 ℃ and 800 ℃ before the highest temperature, respectively preserving heat for 20min, and then presintering the presintered tungsten rod 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 forging cracking is generated in the follow-up serial forging after the rotary-forging and cogging. The excessive addition of transition metal forming elements causes the formation quantity of brittle Laves phases to be too large, so that the thermoplasticity of the tungsten rod is poor, and the superfine tungsten wire cannot be prepared through subsequent serial-forging and drawing refinement.
Comparative example 5
Compared with the example 1, the method is only different in that in the step 1, the same tungsten wire mass percentage group as the example 1 is adopted, and blue tungsten powder is adopted as the mixed raw materialThe powder, ni and Fe are directly added by using micron-sized metal powder, the cerium source is added in the process of mixing the nano oxide, and the Zr source is ZrH 2 Mixing and adding the powder.
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 Laves phase with coarse size, so that the component formula cannot penetrate through the whole process of the superfine tungsten wire.
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 ultrafine tungsten filament prepared by the present invention has the characteristics of high breaking strength and high elastic modulus. The intermetallic compound is compounded to form the elemental metallic elements of nickel, iron and zirconium by the powder metallurgy technology, the Laves phase is precipitated in situ in the sintering preparation process, so that a remarkable precipitation strengthening effect can be brought to the tungsten wire, meanwhile, the superfine tungsten wire with excellent performance is obtained under the combined action of a multi-strengthening mechanism by assisting in drawing grain refinement strengthening and cerium dioxide and zirconium dioxide to inhibit grain coarsening and dispersion strengthening effects. 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)
- The laves phase precipitation strengthening tungsten filament is characterized by comprising a tungsten matrix, oxides dispersed in the tungsten matrix and a laves strengthening phase formed in situ;the laves strengthening phase comprises NiW 2 、WFe 2 And WZr (WZr) 2 ；The oxide is ZrO 2 And CeO 2 ；In the laves phase precipitation strengthening tungsten filament, the content of Ni is 0.2-0.6wt%, the content of Fe is 0.2-0.6wt%, the content of Zr is 0.3-0.8wt%, the content of Ce is 0.1-1.2wt%, and the balance is tungsten.
- 2. The laves phase precipitation strengthening tungsten filament according to claim 1, wherein the laves phase precipitation strengthening tungsten filament has a Ni content of 0.2 to 0.5wt%, a Fe content of 0.2 to 0.4wt%, a Zr content of 0.3 to 0.7wt%, a Ce content of 0.2 to 1.0wt%, and a balance W;preferably, the Ni content is 0.2-0.45 wt%, the Fe content is 0.2-0.35 wt%, the Zr content is 0.4-0.7 wt%, the Ce content is 0.4-1.0 wt%, and the balance is W;further preferably, the Ni content is 0.3 to 0.4wt%, the Fe content is 0.25 to 0.3wt%, the Zr content is 0.6 to 0.7wt%, the Ce content is 0.7 to 0.9wt%, and the balance is W;preferably, the size of the labes strengthening phase is <300nm;preferably, the diameter of the laves phase precipitation strengthening tungsten filament is 30-40 mu m.
- 3. A method of preparing a laves phase precipitation strengthening tungsten filament according to claim 1 or 2, comprising the steps of:step (1): batching according to the element content of the laves phase precipitation strengthening tungsten filament, spraying and compositing a solution dissolved with required amounts of nickel source, iron source and cerium source on the surface of tungsten source powder, and then carrying out reduction treatment to obtain Ni-Fe-Ce coated W composite particles, wherein the temperature of the reduction stage is 800-900 ℃;step (2): compounding and molding the Ni-Fe-Ce coated W composite particles and zirconium hydride with required amount to obtain a composite blank;step (3): presintering the composite blank at 1200-1400 ℃ in advance, and sintering at 2000-2400 ℃ to obtain a sintered blank;step (4): and (3) carrying out rotary swaging, annealing, tandem forging and drawing on the sintering material to obtain the laves phase precipitation strengthening tungsten filament.
- 4. The method for preparing a laves phase precipitation strengthening tungsten wire according to claim 3, wherein the nickel source is nickel nitrate;preferably, the iron source is ferric nitrate;preferably, the cerium source is cerium nitrate;preferably, the solvent in the 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 v%;preferably, the total concentration of solute in the solution is 0.2-0.4g/ml;preferably, the tungsten source powder is metal tungsten powder and/or blue tungsten powder;preferably, the solution is sprayed on the surface of the tungsten source powder and is uniformly stirred and mixed, and the subsequent reduction treatment is carried out after the drying treatment.
- 5. A method for preparing a laves phase precipitation strengthening tungsten wire according to 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. The method for preparing a laves phase precipitation strengthening tungsten filament according to claim 3, wherein in the step (2), the Ni-Fe-Ce coated W composite particles and zirconium hydride are combined in a protective atmosphere;preferably, the molding mode is one of steel die pressing and isostatic pressing; the pressing pressure is 200-300 MPa, and the pressure maintaining time is 3-5 min;preferably, the compact density of the composite blank obtained by molding is 9.0 to 14.0g/cm 3 。
- 7. The method for preparing a laves phase precipitation strengthening tungsten filament according to claim 3, wherein,in the process of heating to presintering, four heat preservation platforms are arranged at the temperature of 350-450 ℃, 550-650 ℃, 750-850 ℃ and 1200-1400 ℃, and the heat preservation time of each heat preservation platform is 10-30 min;preferably, the presintering time is 45-80 min;preferably, the final densification sintering time is 200 to 300 minutes.
- 8. The method for preparing the laves phase precipitation strengthening tungsten wire according to claim 3, wherein the method is characterized in that the method is carried out in a hydrogen atmosphere protection furnace for preheating for 20-40 min before rotary forging cogging, the preheating temperature is 1400-1600 ℃, the machining deformation of rotary forging 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 cogging passes are finished;preferably, the rotary forging is performed to obtain a thin tungsten rod with the diameter of 3.5-3.9 mm;preferably, the atmosphere of the annealing stage is a hydrogen-containing atmosphere;preferably, the annealing temperature is 1600-1900 ℃;preferably, the drawing steps are sequentially performed by chain drawing and rotary disc drawing, wherein the diameter of a chain drawn tungsten wire is 2.4-2.8 mm;preferably, the diameter of the turntable pullout is 30-40 μm.
- 9. Use of a laves phase precipitation-strengthened tungsten wire according to claim 1 or 2 or a laves phase precipitation-strengthened tungsten wire produced by the production method according to any one of claims 3 to 8, characterized by being used in a cutting tool for semiconductor silicon wafers.
- 10. A semiconductor silicon sheet cutting tool comprising the laves phase precipitation-strengthening tungsten wire according to claim 1 or 2 or the laves phase precipitation-strengthening tungsten wire produced by the production method according to any one of claims 3 to 8.
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| CN117600477A (en) * | 2024-01-24 | 2024-02-27 | 崇义章源钨业股份有限公司 | Tungsten filament containing lanthanum, rhenium and yttrium and preparation method thereof |
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| CN117600477A (en) * | 2024-01-24 | 2024-02-27 | 崇义章源钨业股份有限公司 | Tungsten filament containing lanthanum, rhenium and yttrium and preparation method thereof |
| CN117600477B (en) * | 2024-01-24 | 2024-03-22 | 崇义章源钨业股份有限公司 | Tungsten filament containing lanthanum, rhenium and yttrium and preparation method thereof |
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