WO2016152780A1 - 多結晶タングステン及びタングステン合金焼結体並びにその製造方法 - Google Patents
多結晶タングステン及びタングステン合金焼結体並びにその製造方法 Download PDFInfo
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- WO2016152780A1 WO2016152780A1 PCT/JP2016/058713 JP2016058713W WO2016152780A1 WO 2016152780 A1 WO2016152780 A1 WO 2016152780A1 JP 2016058713 W JP2016058713 W JP 2016058713W WO 2016152780 A1 WO2016152780 A1 WO 2016152780A1
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- sintered body
- tungsten
- average
- polycrystalline tungsten
- polycrystalline
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- 229910052721 tungsten Inorganic materials 0.000 title claims description 74
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 71
- 239000010937 tungsten Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229910001080 W alloy Inorganic materials 0.000 title abstract description 68
- 238000000034 method Methods 0.000 title description 24
- 239000013078 crystal Substances 0.000 claims abstract description 94
- 239000002245 particle Substances 0.000 claims abstract description 85
- 239000000843 powder Substances 0.000 claims abstract description 63
- 239000011148 porous material Substances 0.000 claims abstract description 59
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims description 22
- 238000003825 pressing Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 2
- 230000005484 gravity Effects 0.000 description 17
- 229910001182 Mo alloy Inorganic materials 0.000 description 14
- 238000007796 conventional method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 11
- 238000003466 welding Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 238000004663 powder metallurgy Methods 0.000 description 6
- 238000007088 Archimedes method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000005242 forging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000009703 powder rolling Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F1/0003—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- 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
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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
- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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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
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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
- C22C1/045—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
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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Definitions
- the present invention relates to a polycrystalline tungsten sintered body having high density and high isotropy, a polycrystalline tungsten alloy sintered body, and a manufacturing method thereof.
- This application claims priority based on Japanese Patent Application No. 2015-60039 filed in Japan on March 23, 2015 and Japanese Patent Application No. 2016-051244 filed in Japan on March 15, 2016. Is hereby incorporated by reference.
- Polycrystalline tungsten and polycrystalline tungsten alloys are used in many fields, for example, non-consumable electrodes for welding, target materials, X-ray shielding materials, and corrosion resistant materials.
- polycrystalline tungsten and polycrystalline tungsten alloy are required to have high strength, hardness, and high specific gravity. Examples of conventional uses and production methods of polycrystalline tungsten and polycrystalline tungsten alloys include those shown in Patent Documents 1 to 4 below.
- Patent Document 1 as an electrode for fusing welding to which heating and pressurization are repeatedly applied, it is made of Cu or a Cu alloy in order to suppress degranulation wear and loss at the tip and to stably enhance durability.
- the electrode core material of the dual structure electrode in which an electrode core material based on W or Mo or an alloy based on them is attached to the tip of the electrode body, sintering and swaging, and annealing W or Mo having a fibrous structure that has been subjected to heat treatment has an average particle diameter of 50 ⁇ m or more in cross section, and extends in the axial direction so that an aspect ratio is 1.5 or more, or an alloy based on them. It has been proposed to be used as an electrode material for fusing welding.
- Patent Document 2 the purification effect of molybdenum, tungsten, or a high-purity refractory metal or alloy containing these as a main component is enhanced, and the functionality (superconducting properties, corrosion resistance, high-temperature heat resistance, etc.) and workability (forging) of the material are increased.
- Refractory metals made of tungsten, molybdenum or metals or alloys based on these, vanadium, chromium, manganese, iron, etc.
- One or more additive elements selected from the group consisting of transition metal elements and rare earth elements consisting of cobalt and nickel are pre-pressed into powders or small blocks of raw material, and the formed material is further heated at a high temperature and high pressure of 1000 ° C.
- the low-order compound or non-stoichiometric compound (additive element) with the impurity gas component is dissolved by electron beam melting.
- Volatile purification of various impurities contained in the dissolved material in the form of a phase transformation of a stoichiometric compound between an impurity metal and an impurity gas component or between metals under high pressure and high temperature conditions has been proposed to improve the effect of removing impurities.
- Patent Document 3 in order to enhance the durability of the electrode and improve the impact resistance and fracture resistance of the electrode, a resistance is achieved with any sintered alloy of tungsten and molybdenum in which a fibrous structure is formed by rolling.
- a resistance welding electrode in which a welding electrode material is configured and the end surface of the fibrous structure of the electrode material is a welding surface that clamps a workpiece.
- Patent Document 4 discloses molybdenum-tungsten as a sputtering target material with 30 to 70 wt% tungsten and the balance being molybdenum for the purpose of increasing the density and life of the sputtering target material used in flat displays.
- molybdenum-tungsten powder of a predetermined composition is pressed by a predetermined pressing pressure and sintered under a predetermined sintering condition. It has been proposed that a sintered body having a relative density of 93% to 94.5% can be made by combining the above, followed by rolling or forging at a heating temperature of 1400 to 1600 ° C. to increase the density.
- Japanese Unexamined Patent Publication No. 2008-73712 A) Japanese Patent Laid-Open No. 8-165528 (A) Japanese Unexamined Patent Publication No. 2000-158178 (A) Japanese Patent Laid-Open No. 9-3635 (A) Japanese Unexamined Patent Publication No. 2003-226964 (A)
- Patent Documents 1 to 4 as a method for producing polycrystalline tungsten and polycrystalline tungsten alloy, powder metallurgy (see Patent Documents 1, 3, 4, and 5) or dissolution method (see Patent Document 2) Is well known.
- the polycrystalline tungsten sintered body and the polycrystalline tungsten alloy sintered body manufactured by the powder metallurgy method have a low density (small specific gravity), and therefore, post-processing such as forging and rolling as a means for increasing the density. Is generally performed (see Patent Documents 3 and 4).
- post-processing such as rolling and forging is performed, anisotropy occurs in the crystal structure by the processing, and thus anisotropy occurs in the sintered body properties (for example, strength) after processing.
- anisotropic means a state in which a large number of crystal grains having a high aspect ratio are contained in the crystal structure of the crystal grains constituting the sintered body. This means that the aspect ratio exceeds 2.5.
- the inventors of the present application have studied various manufacturing methods for the purpose of obtaining polycrystalline tungsten and polycrystalline tungsten alloy having a high density and a fine grain structure and having no anisotropy.
- a polycrystalline tungsten powder, a polycrystalline tungsten alloy powder, or a compacted body thereof is sintered at an ultra-high pressure of 2.5 GPa or higher and a high temperature condition of 1200 ° C. or higher to obtain a high-density and fine-grained structure.
- a polycrystalline tungsten sintered body and a polycrystalline tungsten alloy sintered body having no anisotropy (or low anisotropy) can be obtained.
- said polycrystalline tungsten sintered compact and polycrystalline tungsten alloy sintered compact were excellent in intensity
- This invention is made
- the polycrystalline tungsten crystal according to (1) wherein the average crystal grain size is 0.8 ⁇ m to 33.4 ⁇ m.
- the tungsten alloy is one selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn.
- Raw material powder composed of tungsten particles having an average particle size of 50 ⁇ m or less, or tungsten particle powder having an average particle size of 50 ⁇ m or less and Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and an average particle size of 50 ⁇ m or less, and A raw material powder containing one or more kinds of alloy component particle powders selected from Mn or a powder compact thereof is charged into a pressure sintering apparatus, and the raw material powder or a compact compact is obtained.
- the W sintered body and the W alloy sintered body (hereinafter referred to as “the W sintered body of the present invention” and the “W alloy sintered body of the present invention”), which is an embodiment of the present invention, have a relative density of 99%.
- the pore ratio measured in an arbitrary cross section of the sintered body is 0.2 area% or less, the average crystal grain size is 50 ⁇ m or less, and the average aspect ratio of the crystal grains is 1 to 2.5.
- W sintered bodies and W alloy sintered bodies it has a high density, fine grain structure, and is homogeneous without anisotropy, so it is excellent in various application fields such as target materials and electrode materials. The characteristics can be demonstrated over a long period of time.
- tissue photograph of W sintered compact of this invention is shown.
- An example of a structure photograph of a W sintered body produced by a conventional method (combination of powder metallurgy and rolling) is shown.
- tissue photograph of the W sintered compact produced by the conventional method (dissolution method) is shown.
- tissue photograph of W alloy (W: 50 mass%, Mo: 50 mass%) sintered compact of this invention is shown.
- An example of the pore detection result measured (use software: Image J) about the W alloy (W: 50 mass%, Mo: 50 mass%) sintered compact of this invention of FIG. 4 is shown. In this pore detection result, the pore rate was below the detection limit.
- tissue photograph of W alloy (W: 50 mass%, Mo: 50 mass%) sintered compact produced by the conventional method is shown.
- An example of the pore detection result measured about W alloy (W: 50 mass%, Mo: 50 mass%) sintered compact produced by the conventional method (HIP method) of FIG. 6 (use software: Image J) is shown. In this pore detection result, the pore rate was 0.659% area.
- “relative density” in the present invention means the ratio of the density of the polycrystalline tungsten sintered body measured by the Archimedes method to the theoretical density of tungsten, and the density of the polycrystalline tungsten alloy sintered body. Is a ratio to the theoretical density of the alloy determined by the content ratio of tungsten and its alloy constituent elements.
- “pore ratio (area%)”, “average crystal grain size ( ⁇ m)” and “average aspect ratio of crystal grains (long side of crystal grains / short side of crystal grains)” in the sintered body are all The mean value of the numerical values measured from the observation of the structure using a scanning electron microscope (SEM) and an electron beam backscattering diffractometer (EBSD) for any cross section of the sintered body.
- the “average particle size” of the raw material powder is the particle size (cumulative median diameter: 50%) in the particle size distribution obtained by the laser diffraction / scattering method (microtrack method) for the powder before sintering. Mean median diameter, d50).
- the “polycrystalline tungsten alloy sintered body” in the present invention refers to a sintered body made of a tungsten alloy containing 25% by mass or more of tungsten.
- the present invention relates to a polycrystalline tungsten sintered body and a polycrystalline tungsten alloy sintered body and a method for producing the same.
- the polycrystalline tungsten sintered body is referred to as a “W sintered body”
- the crystalline tungsten alloy sintered body is abbreviated as “W alloy sintered body”
- tungsten is abbreviated as “W”.
- the W sintered body of the present invention is produced by sintering W particle powder having an average particle size of 50 ⁇ m or less.
- the high temperature sintering temperature is used.
- W particles used as a raw material powder because the impurity component contained in W tends to cause variations in the sinterability of the W sintered body and the structure, material, and characteristics of the W sintered body are likely to be inhomogeneous.
- the purity of is desirably 99.9% by mass or more.
- the W particle powder can be directly charged into a pressure sintering apparatus and sintered.
- the W particle powder is prepared in advance as a green compact, and this is subjected to pressure sintering. It can also be charged and sintered in a binding device.
- the average particle size of the W particles of the raw material powder exceeds 50 ⁇ m, a fine grain structure having an average crystal particle size of the sintered body of 50 ⁇ m or less cannot be obtained by grain growth during sintering.
- the average particle size of W particles is 50 ⁇ m or less, but a more preferable average particle size is 0.25 to 50 ⁇ m.
- FIG. 1 shows an example of a structure photograph of the W sintered body of the present invention. In the W sintered body shown in this structure photograph, the presence of pores was not confirmed (pore ratio ⁇ 0 area%), and the average It can be seen that the crystal grain size is 50 ⁇ m or less and the average aspect ratio of the crystal grains is a fine grain structure satisfying 1 to 2.5 and has an isotropic crystal structure.
- the W sintered body of the present invention shown in FIG. 1 was sintered at 1700 ° C. for 20 minutes with an applied pressure of 6.1 GPa, and the relative density measured by Archimedes method was 99.69%. It was a high density W sintered body of (specific gravity: 19.24), Vickers hardness HV: 460, and high hardness.
- the Vickers hardness HV can be measured by a method defined in JIS standard Z2244.
- the pore ratio was determined to be 0.2 area% or less, and when the pore ratio exceeded 0.2 area%, it could not be said to be a dense, high-density W sintered body having a large specific gravity. Or, for example, when a W sintered body having a pore ratio exceeding 0.2 area% is used as a welding electrode, only the pore portion is in an insulating state, and in particular, high voltage welding tends to be a starting point of fracture. is there. Further, when a W sintered body having a pore ratio exceeding 0.2 area% is used as a target material, a portion with pores causes abnormal discharge or shows a non-uniform reduction method.
- the preferred range of the pore ratio is from more than 0 area% to 0.2 area%. A more preferable range of the pore ratio is 0.02 area% to 0.19 area%. An even more preferable range of the pore ratio is 0.02 area% to 0.15 area%. An even more preferable range of the pore ratio is 0.02 area% to 0.12 area%.
- the average crystal grain size is set to 50 ⁇ m or less when the average grain size exceeds 50 ⁇ m. Because there is no.
- the preferred range of the average crystal grain size is 0.8 ⁇ m to 33.4 ⁇ m. A more preferable range of the average crystal grain size is 0.8 ⁇ m to 18.3 ⁇ m.
- anisotropy occurs in the crystal structure, and a homogeneous material and characteristics cannot be obtained. That is, in the present specification, “there is no anisotropy” with respect to the crystal structure means that the average aspect ratio of the crystal grains in the target sintered body is in the range of 1 to 2.5. Conversely, “having anisotropy” means that the average aspect ratio is outside the range of 1 to 2.5.
- the preferred average aspect ratio range is 1 to 2.2.
- a more preferred average aspect ratio range is from 1 to 1.4.
- the W sintered body of the present invention has a pore ratio, an average crystal grain size, and an average aspect ratio of crystal grains measured in an arbitrary cross section of the sintered body, not a specific cross section, and are within the above range. It can be seen that the sintered body has an isotropic structure without anisotropy.
- FIG. 2 and FIG. 3 show structural photographs of a W sintered body produced by a conventional method.
- FIG. 2 is an example of a structure photograph on a surface along the rolling direction of a W sintered body (see Patent Documents 3 and 4) produced by combining powder metallurgy and rolling. After producing a W sintered body by powder metallurgy, it is possible to increase the density of the sintered body to some extent by performing processing such as rolling. In FIG. 2, the relative density is 99.48% (specific gravity: 19.2) and Vickers hardness HV: 500 is obtained. However, on the other hand, anisotropy occurs in the crystal structure of the sintered body due to processing (in FIG.
- FIG. 3 is an example of a structure photograph of a W sintered body produced by a melting method (see Patent Document 2).
- W sintered body obtained by the melting method shown in FIG. 3 sufficient density cannot be increased (relative density: 99.33% (specific gravity: 19.17)), and hardness (Vickers hardness HV). : 440) is not sufficient.
- anisotropy occurs because the crystal growth rate differs depending on the cooling temperature gradient, and a W-sintered body having a fine and uniform structure cannot be obtained.
- the W sintered body of the present invention can be manufactured, for example, by the following method.
- the W particle powder having a purity of 99.9% by mass or more and an average particle size of 0.25 to 50 ⁇ m was charged into a pressure sintering apparatus, and the powder was added to 2.55 GPa or more and 13 GPa.
- the pore ratio, average crystal grain size, crystal A W sintered body having an average aspect ratio of grains and a high density and fine grain structure and no anisotropy can be produced.
- the sintering pressure is less than 2.55 GPa, the densification does not occur. On the other hand, adding pressure exceeding 13 GPa is not economical from the viewpoint of equipment development cost and actual operation, so the sintering pressure is 2.55 GPa. The pressure was set to 13 GPa or less. Further, when the sintering temperature is less than 1200 ° C., the solid phase reaction does not proceed. On the other hand, when the sintering temperature exceeds the melting point, the same problems as in the production by the melting method (for example, coarsening of crystal grains, solidification process) Anisotropy of the crystal structure in the region), and it becomes impossible to obtain a W sintered body having a high density, a fine grain, and a uniform structure.
- the temperature range was set to 2000 ° C. or lower.
- the W particle powder Prior to sintering, the W particle powder is prepared in advance as a green compact, and the green compact is sintered at the above-described sintering pressure, sintering temperature, and sintering time.
- the W sintered body of the present invention can also be obtained.
- a fine W particle powder having a large specific surface area (for example, an average particle size of 0.25 to 4 ⁇ m) is used as the raw material powder, this is used as a green compact and, for example, 10 ⁇ 1 prior to sintering.
- a vacuum atmosphere of Pa or less, or in an atmosphere where the heat treatment container is replaced with nitrogen gas or argon gas, etc. the surface of the W particles is cleaned by performing a heat treatment at an ultimate temperature of 450 to 1200 ° C. for 30 to 180 minutes. Since the reaction easily proceeds, it is possible to increase the density of the sintered body in a short time even in a relatively low pressure condition and a low temperature region. Even if an impurity element such as oxygen is present in the W particle powder to some extent, it can be removed and cleaned by the heat treatment in the vacuum or in an inert gas atmosphere. Can be increased to 99.9% by mass or more.
- the average particle size of the W particle powder is desirably in the range of 0.25 to 50 ⁇ m as a whole, but it is necessary that the particle size distribution frequency has one peak (indicating a single-peak peak particle size distribution).
- W particle powder having a plurality of particle size distribution frequency peaks can also be used.
- the sintered body can be further densified and a W sintered body having a fine grain structure and no anisotropy can be obtained.
- sintering is performed under the above-described conditions, and a sufficient sintering time is given, so that W particles under high temperature and high pressure are plastically deformed and rearranged, so that high density W firing is achieved. A ligation can be obtained.
- this invention is 1 type chosen from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn as an alloy ingredient with W particle powder or
- a raw material powder in which two or more kinds of alloy component particle powders are blended a W alloy sintered body having a high density and a fine grain structure and no anisotropy can be obtained.
- the W alloy sintered body containing one or more components selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn as alloy components is, for example, although it is used as an electrode material for resistance welding, a target material, etc., in any case, a W alloy sintered body having a high density and a fine grain structure and having no anisotropy is required, as with the W sintered body. .
- a W alloy sintered body with a low W content it was possible to increase the density of the sintered body by a conventional method of producing a sintered body, such as HIP, but the W content increased.
- a conventional method could not obtain a W alloy sintered body having a high density and a fine grain structure and no anisotropy.
- the W content is 25% by mass or more
- the alloy component is one or two selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn.
- a W alloy sintered body having a high density and a fine grain structure and no anisotropy can be obtained as in the case of the W sintered body.
- the W alloy sintered body of the present invention can be produced by sintering under the same conditions as in the production of the W sintered body.
- one or more alloy component particle powders selected from among raw material powders of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Mn can be used to refine the structure of the sintered body. From these viewpoints, metal particle powder having an average particle diameter of 50 ⁇ m or less is used.
- One or more alloy component particle powders selected from W particle powder having an average particle size of 50 ⁇ m or less and Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn having an average particle size of 50 ⁇ m or less The raw material powder blended so that the W content in the sintered body is 25% by mass or the green compact produced from the raw material powder is charged into a pressure sintering apparatus to obtain 2.55 GPa. By sintering in a temperature range of 1200 ° C. or higher and a melting point or lower with a pressure of 13 GPa or less applied, a W alloy sintered body having a high density and a fine grain structure and having no anisotropy can be produced.
- a powder having a large specific surface area for example, an average particle size of 0.25 to 4 ⁇ m
- this is used as a green compact and, for example, 10 ⁇ 1 Pa before sintering.
- the particle surface is cleaned by performing a heat treatment at an ultimate temperature of 450 to 1200 ° C. for 30 to 180 minutes in the following vacuum atmosphere or in an atmosphere in which the heat treatment container is replaced with nitrogen gas, argon gas or the like, Even in a low pressure condition and a low temperature region, it is possible to increase the density of the sintered body in a short time, and there is a case where an impurity element such as oxygen exists to some extent in the particle powder.
- the pore ratio, average crystal grain size, and average aspect ratio of the crystal grains of the W alloy sintered body of the present invention is the same as that of the W sintered body, and in the W alloy sintered body of the present invention, However, the pore ratio, average crystal grain size, and average aspect ratio of crystal grains measured in an arbitrary cross section of the sintered body are not within a specific cross section, and are all anisotropic in the sintered body structure. It can be seen that it has an isotropic and non-isotropic organization.
- FIG. 4 an example of the structure
- the W alloy sintered body shown in FIG. 4 is a W—Mo alloy sintered body composed of W: 50 mass% and Mo: 50 mass%, and is applied with a pressure of 5.8 GPa at 500 ° C. ⁇ 20 It was produced by partial sintering.
- the W-Mo alloy sintered body of FIG. 4 is a high-density W-Mo alloy sintered body having a relative density of 99.32% (specific gravity: 13.27) measured by Archimedes method, and has a Vickers hardness of HV. Was 330 and had high hardness.
- the theoretical density of the W—Mo alloy sintered body comprising W: 50 mass% and Mo: 50 mass% is 13.36 (theoretical density of W: 19.3, the theoretical density of Mo: 10.2). .
- FIG. 5 shows the measurement of W-Mo alloy sintered body (hereinafter referred to as “the W-Mo alloy sintered body of the present invention”) which is another embodiment of the present invention shown in FIG. 4 (Software used: Image J).
- the pore detection result is shown. According to FIG. 5, it was confirmed that the pore ratio of the W—Mo alloy sintered body of the present invention was below the detection limit and substantially no pore was present.
- a W-Mo alloy sintered body having the same composition as that of the W-Mo alloy sintered body of the present invention and comprising W: 50% by mass and Mo: 50% by mass was prepared by a conventional method (HIP method).
- the manufacturing condition in the HIP method is a pressure of 34.32 MPa, 1400 ° C. ⁇ 3 hours.
- FIG. 6 shows an example of a structure photograph of a W—Mo alloy sintered body produced by the conventional method (HIP method).
- the relative density and Vickers hardness HV of the W-Mo alloy sintered body produced by the conventional method (HIP method) were measured, the relative density was 96.33% (specific gravity: 12.87), and the Vickers hardness HV.
- the relative density and hardness were inferior to the W-Mo alloy sintered body of the present invention.
- FIG. 7 shows an example of a pore detection result measured (software used: Image J) for a W—Mo alloy sintered body produced by the conventional method (HIP method) shown in FIG. According to FIG. 7, the pore ratio is 0.659 area%, and it is clear that the density increase is not sufficient.
- a W particle powder having an average particle size shown in Table 1 is prepared as a raw material, and this is pressure-sintered under the sintering conditions shown in Table 1 as well. 1 to 8 were produced.
- a W particle powder having a plurality of particle size distribution frequency peaks (multimodal frequency particle size distribution) shown in Table 1 was used as a raw material powder.
- the W sintered body 6-8 of the present invention after preparing the green compact from the W particles, prior to sintering, at ultimate temperature 580 ⁇ 620 ° C. in a vacuum atmosphere of 10 -1 Pa A vacuum heat treatment was applied for 30 to 40 minutes.
- the relative density (specific gravity) of these sintered bodies was measured by the Archimedes method.
- one sintered body section X is set in an arbitrary direction, a section Y and a section Z perpendicular to the set section X are set, and the sections X, Y,
- the pore ratio in Z, the average crystal grain size, and the average aspect ratio of the crystal grains were determined by structural observation using a scanning electron microscope (SEM) and an electron beam backscattering diffractometer (EBSD). Vickers hardness HV was measured.
- the pore ratio is a magnification at which about 15 to 30 W particles can be observed on the vertical and horizontal axes of the SEM image (for example, when the W particle diameter is 2 to 4 ⁇ m, the magnification is 3000 times,
- the image was binarized using Image J at a particle diameter of 10 to 20 ⁇ m (500 times), and the pores and non-pore portions were measured, and the average was obtained from three fields of view.
- the average crystal grain size and the average aspect ratio were calculated by the three-field average of the particle information obtained using EBSD at the same observation magnification as described above.
- Vickers hardness HV was computed as a 5-point average of the value measured with the load of 1 kg.
- Comparative Example W sintered bodies 1 to 5 having a pore ratio, an average crystal grain size, an average aspect ratio of crystal grains, and a Vickers hardness HV were produced.
- the relative density (specific gravity), the pore ratio, the average crystal grain size, the average aspect ratio of crystal grains, and the Vickers hardness HV were determined in the same manner as in Example 1. These results are shown in Table 4.
- conventional example W sintered bodies 1 and 2 were manufactured by a conventional manufacturing method using W particle powder having an average particle diameter shown in Table 3. Further, for the conventional W sintered bodies 1 and 2, the relative density (specific gravity), the pore ratio, the average crystal grain size, the average aspect ratio of the crystal grains, and the Vickers hardness HV were determined. These results are shown in Table 4.
- the conventional example W sintered body 1 is a W sintered body obtained by rolling as described in Patent Documents 3 and 4, and the conventional example W sintered body 2 is a patent. This is a W sintered body produced by a melting method as described in Document 2.
- FIG. 2 shows an example of the structure of the conventional example W sintered body 1 along the rolling direction, and FIG.
- Example W sintered body 3 shows an example of the structure of the conventional example W sintered body 2.
- the pore ratio, average crystal grain size, average aspect ratio and Vickers hardness HV of Comparative Example W sintered bodies 1 to 5 and Conventional Example W sintered bodies 1 and 2 are the same as those of the invention W sintered bodies 1 to 8 described above. It was obtained by the same method as in the case of.
- W particle powder having an average particle size shown in Table 5 and Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn having the average particle size also shown in Table 5
- two or more kinds of alloy component particle powders are prepared and blended so as to have the composition shown in Table 5 to produce a mixed raw material powder, and this mixed raw material powder is pressed under the sintering conditions shown in Table 5.
- Invention W alloy sintered bodies 11 to 20 shown in Table 6 were produced. Note that for the W alloy sintered bodies 18 to 20 of the present invention, after forming a green compact from a mixed raw material powder of W particle powder and alloy component particle powder, prior to sintering, a vacuum atmosphere of 10 ⁇ 1 Pa.
- FIG. 4 shows an example of the structure of the W alloy sintered body 15 of the present invention
- FIG. 5 shows pores measured (software used: Image J) for the W alloy sintered body of the present invention shown in FIG. An example of a detection result is shown.
- Comparative W alloy sintered bodies 11 to 15 having (specific gravity), pore ratio, average crystal grain size, average aspect ratio of crystal grains, and Vickers hardness HV were produced.
- the relative density (specific gravity), the pore ratio, the average crystal grain size, the average aspect ratio of crystal grains, and the Vickers hardness HV were determined in the same manner as in Example 1. .
- W-particle powders and metal particle powders having an average particle size shown in Table 7 were used to produce conventional W alloy sintered bodies 11 and 12 by a conventional manufacturing method, and relative density (specific gravity).
- the pore ratio, the average crystal grain size, the average aspect ratio of the crystal grains, and the Vickers hardness HV were determined. These results are shown in Table 8.
- the conventional W alloy sintered body 11 is a W alloy sintered body obtained by rolling
- the conventional W alloy sintered body 12 is a W alloy sintered body produced by a melting method. Is the body.
- FIG. 6 shows an example of the structure of the conventional W alloy sintered body 11
- FIG. 7 shows the pores measured for the conventional W alloy sintered body shown in FIG. 6 (software used: Image J). An example of a detection result is shown.
- the present invention W sintered body and W alloy sintered body are both high in relative density of 99% or more, and
- the sintered body has a fine grain structure with a pore ratio of 0.2 area% or less, an average crystal grain size of 50 ⁇ m or less, and an average aspect ratio of crystal grains of 1 to 2.5, and is anisotropic. It is a sintered body without any.
- the comparative example W sintered body, the conventional example W sintered body, the comparative example W alloy sintered body, and the conventional example W alloy sintered body have a relative density, a pore ratio, an average crystal grain size, or a crystal grain size. It is obvious that at least one of the average aspect ratios is out of the range defined in the present invention, and it cannot be said that the sintered body has a high density and no anisotropy.
- the W sintered body and W alloy sintered body of the present invention have a high density and no anisotropy, they can be suitably used for applications such as sputtering target materials and welding electrode materials. .
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Abstract
Description
本願は、2015年3月23日に日本に出願された特願2015-60039号及び2016年3月15日に日本に出願された特願2016-051244号に基づき優先権を主張し、その内容をここに援用する。
従来から知られている多結晶タングステン及び多結晶タングステン合金の用途、製法としては、例えば、以下の特許文献1~4に示すものがあげられる。
ところで、粉末冶金法で製造された多結晶タングステン焼結体及び多結晶タングステン合金焼結体は、密度が低い(比重が小さい)ため、高密度化を図る手段として、鍛造・圧延等の後加工が一般的に行われている(特許文献3、4参照)。しかし、圧延・鍛造等の後加工を行った場合には、その加工によって結晶組織に異方性が生じるため、加工後の焼結体特性(例えば、強度)には異方性が発生する。
一方、密度の低いままの状態で使用すると、例えば、特許文献5に記載されているスパッタリング用タングステンターゲット材として使用すると、スパッタリング成膜時のパーティクル欠陥が増大する等ターゲット材の品質上、大きな課題を有している。
ここで「異方性」とは、焼結体を構成する結晶粒の結晶組織中に、アスペクト比の高い結晶粒が多く含まれている状態を意味し、より具体的には結晶粒の平均アスペクト比が2.5を超える場合を意味する。
多結晶タングステン焼結体及び多結晶タングステン合金焼結体の焼結体特性として異方性が発生すると、その多結晶タングステン焼結体及び多結晶タングステン合金焼結体により製造された部材の使用時に、結晶粒の向きに依存した偏った挙動(例えば、一方向に偏った損耗)を局所的に示す。
そして、結晶粒の向きに依存した偏った挙動は、多結晶タングステン焼結体及び多結晶タングステン合金焼結体により製造された部材の中長期における耐久性、信頼性等を低下させる原因となる。例えば、抵抗溶接用電極材(特許文献3参照)として繰り返し使用すると、圧延方向に沿って、粒界でのクラックが発生しやすく、結果として、比較的短い寿命を示す。圧延加工されたタングステンは繊維組織をもつが、残留応力の蓄積により、組織に沿ったクラックを誘発しやすい。
部材の使用用途によっては、高密度であり、異方性のない(又は異方性の低い)微細組織からなる多結晶タングステ及び多結晶タングステン合金が必要とされる場合がある。以上から、高密度、かつ、微粒組織であって、異方性のない多結晶タングステン及び多結晶タングステン合金が求められている。
そして、上記の多結晶タングステン焼結体及び多結晶タングステン合金焼結体は、強度、硬さにすぐれるとともに、均質な材質・特性を備えることを見出した。
(1)多結晶タングステン焼結体において、前記焼結体の相対密度は99%以上であり、前記焼結体の任意の断面で測定したポア率が0.2面積%以下、平均結晶粒径が50μm以下、結晶粒の平均アスペクト比が1~2.5である高密度かつ微粒組織で異方性のない多結晶タングステン焼結体。
(2)前記ポア率が0.02面積%~0.19面積%である前記(1)に記載の多結晶タングステン結晶体。
(3)前記ポア率が0.02面積%~0.15面積%である前記(1)に記載の多結晶タングステン結晶体。
(4)前記平均結晶粒径が0.8μm~33.4μmである前記(1)に記載の多結晶タングステン結晶体。
(5)前記平均結晶粒径が0.8μm~18.3μmである前記(1)に記載の多結晶タングステン結晶体。
(6)前記平均アスペクト比が1.0~2.2である前記(1)に記載の多結晶タングステン結晶体。
(7)前記平均アスペクト比が1.0~1.4である前記(1)に記載の多結晶タングステン結晶体。
(8)タングステンを25質量%以上含有する多結晶タングステン合金焼結体において、該タングステン合金は、Ti、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の合金成分を含有するタングステン合金であって、前記焼結体の相対密度は99%以上であり、前記焼結体の任意の断面で測定したポア率が0.2面積%以下、平均結晶粒径が50μm以下、結晶粒の平均アスペクト比が1~2.5である高密度かつ微粒組織で異方性のない多結晶タングステン基合金焼結体。
(9)前記ポア率が0.02面積%~0.19面積%である前記(8)に記載の多結晶タングステン基合金焼結体。
(10)前記ポア率が0.02面積%~0.15面積%である前記(8)に記載の多結晶タングステン基合金焼結体。
(11)前記平均結晶粒径が0.8μm~33.4μmである前記(8)に記載の多結晶タングステン基合金焼結体。
(12)前記平均結晶粒径が0.8μm~18.3μmである前記(8)に記載の多結晶タングステン基合金焼結体。
(13)前記平均アスペクト比が1.0~2.2である前記(8)に記載の多結晶タングステン基合金焼結体。
(14)前記平均アスペクト比が1.0~1.4である前記(8)に記載の多結晶タングステン基合金焼結体。
(15)平均粒径50μm以下のタングステン粒子からなる原料粉末、あるいは、平均粒径50μm以下のタングステン粒子粉末と平均粒径50μm以下のTi、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の合金成分粒子粉末を配合した原料粉末あるいはその圧粉成形体を、加圧焼結装置に装入し、該原料粉末あるいはその圧粉成形体に2.55GPa以上13GPa以下の加圧力を付加した状態で、1200℃以上融点以下の温度範囲で焼結することを特徴とする高密度かつ微粒組織で異方性のない多結晶タングステン焼結体あるいは多結晶タングステン合金焼結体の製造方法。
また、焼結体における「ポア率(面積%)」、「平均結晶粒径(μm)」および「結晶粒の平均アスペクト比(結晶粒の長辺/結晶粒の短辺)」は、いずれも、焼結体の任意の断面について、走査型電子顕微鏡(SEM)および電子線後方散乱回折装置(EBSD)を用いて行われた組織観察から測定された数値の平均値を意味する。
上記EBSDによる組織観察では、焼結体の任意の断面の210μm×140μm(縦横寸法)を観察視野とし、この観察視野中に含まれる全ての結晶粒子を、平均値を得るための観察対象とする。この場合、観察視野境界部に存在し、結晶の一部分のみが観察視野中に含まれるものについては、観察対象から除外する。
また、原料粉末の「平均粒径」とは、焼結前の粉末についてレーザー回折・散乱法(マイクロトラック法)によって求められた粒度分布における積算値50%での粒径(累積中位径:メディアン径、d50)を意味する。
また、本願発明でいう「多結晶タングステン合金焼結体」とは、タングステンを25質量%以上含有するタングステン合金からなる焼結体をいう。
なお、本願発明は、多結晶タングステン焼結体及び多結晶タングステン合金焼結体とその製造方法に関するものであるが、以下では、多結晶タングステン焼結体を「W焼結体」、また、多結晶タングステン合金焼結体を「W合金焼結体」と略記し、また、タングステンは「W」と略記する。
また、焼結を行うに際し、W粒子粉末を加圧焼結装置に直接装入して焼結することができるが、W粒子粉末を、予め圧粉成形体として作製し、これを加圧焼結装置に装入して焼結することもできる。
原料粉末のW粒子の平均粒径が50μmを超える場合には、焼結時の粒成長によって、焼結体の平均結晶粒径が50μm以下である微粒組織を得ることができないから、原料粉末のW粒子の平均粒径は50μm以下とするが、より好ましい平均粒径は、0.25~50μmである。
なお、相対密度が99%未満であると、焼結体の緻密化が十分であるとはいえないため、ポア率を0.2面積%以下に低減することができないので、W焼結体の相対密度を99%以上とする。
図1に、本願発明のW焼結体の組織写真の一例を示すが、この組織写真に示されるW焼結体においては、ポアの存在は確認されず(ポア率≒0面積%)、平均結晶粒径が50μm以下、結晶粒の平均アスペクト比が1~2.5を満足する微粒組織であって且つ等方的な結晶組織を備えていることが分かる。図1に示す本願発明W焼結体は、6.1GPaの加圧力を付加した状態で、1700℃で20分間焼結されたものであって、アルキメデス法により測定した相対密度:99.69%(比重:19.24)の高密度W焼結体であり、かつ、ビッカース硬さHV:460であり高硬度を有していた。
ビッカース硬さHVは、JIS規格Z2244で定められている方法で測定することができる。
特に必須な構成ではないが、好ましいポア率の範囲は0面積%超から0.2面積%である。より好ましいポア率の範囲は0.02面積%から0.19面積%である。さらにより好ましいポア率の範囲は0.02面積%から0.15面積%である。さらにより好ましいポア率の範囲は0.02面積%から0.12面積%である。
また、本願発明焼結体で、平均結晶粒径を50μm以下としたのは、平均粒径が50μmを超えた場合には粗大結晶粒組織となり、強度、硬さにすぐれた微粒組織が得られないからである。
特に必須な構成ではないが、好ましい平均結晶粒径の範囲は0.8μmから33.4μmである。より好ましい平均結晶粒径の範囲は0.8μmから18.3μmである。さらにより好ましい平均結晶粒径の範囲は2.6μmから14.0μmである。
また、本願発明焼結体で、結晶粒の平均アスペクト比(=結晶粒の長辺/結晶粒の短辺)を1~2.5と定めたのは、平均アスペクト比がこの範囲を外れると、結晶組織に異方性が生じ、均質な材質・特性が得られなくなるからである。すなわち、本明細書中で結晶組織について「異方性が無い」とは、対象となる焼結体で結晶粒の平均アスペクト比が1~2.5の範囲内にあることを意味する。逆に「異方性がある」とは、上記平均アスペクト比が1~2.5の範囲外にあることを意味する。
特に必須な構成ではないが、好ましい平均アスペクト比の範囲は1から2.2である。より好ましい平均アスペクト比の範囲は1から1.4である。
本願発明のW焼結体は、特定の断面ではなく、焼結体の任意の断面で測定したポア率、平均結晶粒径および結晶粒の平均アスペクト比がいずれも前記の範囲内であることから、焼結体組織に異方性が無く、等方性のある組織を備えることが分かる。
図2は、粉末冶金法と圧延とを組み合わせて作製したW焼結体(特許文献3、4参照)の圧延方向に沿った面における組織写真の一例である。
粉末冶金法でW焼結体を作製した後、圧延等の加工を施すことによって、焼結体のある程度の高密度化は可能であり、図2では、相対密度:99.48%(比重:19.2)、また、ビッカース硬さHV:500が得られている。
しかし、その反面、加工によって焼結体の結晶組織に異方性が生じるため(図2中、縦縞状あるいは繊維状の結晶組織が観察され、圧延方向に沿った面における平均アスペクト比は6.5以上となっている。)、微粒で且つ均一な組織の焼結体は得られず、その結果、このW焼結体に等方的な特性を望むことはできない。
図3に示す溶解法により得たW焼結体では、十分な高密度化が図られず(相対密度:99.33%(比重:19.17))、また、硬さ(ビッカース硬さHV:440)も十分ではない。さらに、溶解後の凝固過程において、冷却温度勾配により、結晶の成長速度が異なるため異方性が生じ、微粒で且つ均一な組織のW焼結体は得られない。
前記のとおり、純度は99.9質量%以上で、かつ、平均粒径0.25~50μmに整粒したW粒子粉末を加圧焼結装置に装入し、該粉末に2.55GPa以上13GPa以下の加圧力を付加した状態で、1200℃以上融点以下(例えば、1200~2000℃)の温度範囲で10分以上焼結することによって、本願発明で規定するポア率、平均結晶粒径、結晶粒の平均アスペクト比を有する高密度かつ微粒組織で異方性のないW焼結体を製造することができる。
焼結圧力が2.55GPa未満では、高密度化が生じず、一方、13GPaを超える圧力を付加することは装置開発コスト・実操業の観点から経済性が低いので、焼結圧力は2.55GPa以上13GPa以下とした。
また、焼結温度が1200℃未満では、固相反応が進行せず、一方、焼結温度が融点を超えると、溶解法による製造と同様な問題点(例えば、結晶粒の粗大化、凝固過程における結晶組織の異方性)が生じ、高密度で微粒且つ均一な組織のW焼結体を得られなくなることから、焼結温度は、1200℃以上融点以下の温度範囲、好ましくは、1200℃以上2000℃以下の温度範囲と定めた。
なお、W粒子粉末は、焼結に先立って、予め圧粉成形体として作製しておき、この圧粉成形体を前記の焼結圧力、焼結温度、焼結時間で焼結することによって、本願発明のW焼結体を得ることもできる。
なお、仮に、W粒子粉末中に、酸素等の不純物元素がある程度存在する場合であっても、前記の真空、もしくは不活性ガス雰囲気中の熱処理によって除去・清浄化することができ、W粒子粉末の純度を99.9質量%以上に高めることができる。
いずれにしても、上記のような条件で焼結し、十分な焼結時間を与えることで、高温・高圧下のW粒子を塑性変形させ、また、再配列させることで、高密度のW焼結体を得ることができる。
ここで、前記Ti、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の各成分を合金成分として含有するW合金焼結体は、例えば、抵抗溶接用電極材料、ターゲット材料等として用いられているが、いずれの場合も、前記W焼結体と同様、高密度かつ微粒組織で異方性のないW合金焼結体が求められている。
W含有量が少ないW合金焼結体においては、従来の焼結体の製法、例えばHIP等により、焼結体の高密度化を図ることは可能であったが、W含有量が増加し、例えば、W含有量が25質量%以上であるW合金焼結体については、従来方法では、高密度かつ微粒組織で異方性のないW合金焼結体を得ることができなかった。
しかし、本願発明によれば、W含有量が25質量%以上であり、その合金成分としてTi、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上が含有されるW合金焼結体においても、前記W焼結体と同様、高密度かつ微粒組織で異方性のないW合金焼結体を得ることができる。
ただし、原料粉末であるTi、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の合金成分粒子粉末は、焼結体の組織を微細化するとの観点から、いずれも平均粒径50μm以下の金属粒子粉末を使用する。
平均粒径50μm以下のW粒子粉末と、平均粒径50μm以下のTi、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の合金成分粒子粉末を、焼結体におけるW含有量が25質量%以上となるように配合した原料粉末を、あるいは、原料粉末から作製した圧粉成形体を、加圧焼結装置に装入し、2.55GPa以上13GPa以下の加圧力を付加した状態で、1200℃以上融点以下の温度範囲で焼結することにより、高密度かつ微粒組織で異方性のないW合金焼結体を製造することができる。
また、原料粉末として、比表面積が大きい粉末(例えば、平均粒径0.25~4μm)を使用する場合には、これを圧粉成形体とし、焼結に先立って、例えば、10-1Pa以下の真空雰囲気中、もしくは熱処理容器を窒素ガスやアルゴンガス等で置換した雰囲気中で、到達温度450~1200℃で30~180分の熱処理を行って、粒子表面を清浄化すると、相対的に低圧条件、低温度領域であっても、短時間で焼結体の高密度化を図ることが可能であり、また、仮に、粒子粉末中に、酸素等の不純物元素がある程度存在する場合であっても、前記の真空、もしくは不活性ガス雰囲気中の熱処理によって除去・清浄化することができる。
本願発明のW合金焼結体のポア率、平均結晶粒径および結晶粒の平均アスペクト比を定めた理由は、前記W焼結体の場合と同様であり、本願発明のW合金焼結体においても、特定の断面ではなく、焼結体の任意の断面で測定したポア率、平均結晶粒径および結晶粒の平均アスペクト比がいずれも規定の範囲内であって、焼結体組織に異方性が無く、等方性のある組織を備えていることが分かる。
図4に示されるW合金焼結体は、W:50質量%、Mo:50質量%からなるW-Mo合金焼結体であり、5.8GPaの加圧力を付加した状態で500℃×20分焼結したことによって作製されたものである。
図4のW-Mo合金焼結体について、アルキメデス法により測定した相対密度は99.32%(比重:13.27)の高密度W-Mo合金焼結体であり、かつ、ビッカース硬さHVは330であり高硬度を有していた。
なお、W:50質量%、Mo:50質量%からなるW-Mo合金焼結体の理論密度は13.36(Wの理論密度:19.3、Moの理論密度:10.2)である。
図5によれば、本願発明のW-Mo合金焼結体についてのポア率は、検出限界以下であって、ポアが実質的に存在しないことが確認された。
なお、HIP法における製造条件は、34.32MPaの加圧力、1400℃×3時間である。
図6に、上記従来法(HIP法)で作製したW-Mo合金焼結体の組織写真の一例を示す。
上記従来法(HIP法)で作製されたW-Mo合金焼結体の相対密度とビッカース硬さHVを測定したところ、相対密度は96.33%(比重:12.87)、ビッカース硬さHVは255であり、相対密度、硬さともに本願発明のW-Mo合金焼結体に比して劣っていた。
図7によれば、ポア率は0.659面積%であって、高密度化が十分でないことは明らかである。
なお、本願発明W焼結体6~8の作製に当たっては、原料粉末として、表1に示す複数の粒径分布度数ピーク(多峰性の頻度粒度分布)を備えたW粒子粉末を用いた。
また、本願発明のW焼結体6~8については、W粒子粉末から圧粉成形体を作製した後、焼結に先立って、10-1Paの真空雰囲気中で到達温度580~620℃で30~40minの真空熱処理を施した。
ついで、これらの焼結体について、アルキメデス法により相対密度(比重)を測定した。次いで、これらの焼結体に対して、任意の方向に一つの焼結体断面Xを設定し、この設定した断面Xに対して直交する断面Y、断面Zを設定し、断面X、Y、Zにおけるポア率、平均結晶粒径、結晶粒の平均アスペクト比を走査型電子顕微鏡(SEM)および電子線後方散乱回折装置(EBSD)を用いた組織観察によって求め、さらに、断面X、Y、Zにおけるビッカース硬さHVを測定した。
なお、ポア率は、SEM画像の縦軸と横軸で、15~30個程度のW粒子を観察できるような倍率(例えば、W粒子径が2~4μmの場合には3000倍、また、W粒子径が10~20μmの場合には500倍)において、Image Jを用いて二値化し、ポアとポアでない部分を測定し、3視野平均により求めた。
平均結晶粒径、平均アスペクト比は、上記と同様な観察倍率において、EBSDを用いて得た粒子情報の3視野平均により算出した。
また、ビッカース硬さHVは、荷重1kgで測定した値の5点平均として算出した。
これらの結果を、表2に示す。
図1に、本願発明のW焼結体5の組織の一例を示す。
この比較例W焼結体1~5について、実施例1と同様な方法で、相対密度(比重)、ポア率、平均結晶粒径、結晶粒の平均アスペクト比、ビッカース硬さHVを求めた。
これらの結果を、表4に示す。
また、従来例W焼結体1、2について、相対密度(比重)、ポア率、平均結晶粒径、結晶粒の平均アスペクト比、ビッカース硬さHVを求めた。
これらの結果を、表4に示す。
なお、従来例W焼結体1は、特許文献3、4に記載されるような圧延加工を行うことによって得られたW焼結体であり、また、従来例W焼結体2は、特許文献2に記載されるような溶解法で作製したW焼結体である。
図2に、従来例W焼結体1の圧延方向に沿った面における組織の一例を示し、また、図3に、従来例W焼結体2の組織の一例を示す。
なお、比較例W焼結体1~5と従来例W焼結体1、2のポア率、平均結晶粒径、平均アスペクト比およびビッカース硬さHVは、前記本願発明W焼結体1~8の場合と同様な方法で求めた。
なお、本願発明W合金焼結体18~20ついては、W粒子粉末と合金成分粒子粉末との混合原料粉末から圧粉成形体を作製した後、焼結に先立って、10-1Paの真空雰囲気中で到達温度580~620℃で30~40minの真空熱処理を施した。
そして、実施例1と同様な方法で、本願発明W合金焼結体11~20の相対密度(比重)、ポア率、平均結晶粒径、結晶粒の平均アスペクト比およびビッカース硬さHVを求めた。
これらの結果を、表6に示す。
また、図4に、本願発明W合金焼結体15の組織の一例を示し、図5には、図4に示した本願発明のW合金焼結体について測定(使用ソフト:Image J)したポア検出結果の一例を示す。
この比較例W合金焼結体11~15について、実施例1と同様な方法で、相対密度(比重)、ポア率、平均結晶粒径、結晶粒の平均アスペクト比、ビッカース硬さHVを求めた。これらの結果を、表8に示す。
これらの結果を、表8に示す。
なお、従来例W合金焼結体11は、圧延加工を行うことによって得られたW合金焼結体であり、また、従来例W合金焼結体12は、溶解法で作製したW合金焼結体である。
また、図6に、従来例W合金焼結体11の組織の一例を示し、図7には、図6に示した従来例のW合金焼結体について測定(使用ソフト:Image J)したポア検出結果の一例を示す。
これに対して、比較例W焼結体、従来例W焼結体、比較例W合金焼結体、従来例W合金焼結体は、相対密度、ポア率、平均結晶粒径あるいは結晶粒の平均アスペクト比のうちの少なくともいずれかが本願発明で定めた範囲を外れるものであって、高密度で且つ異方性のない焼結体であるとはいえないことは明らかである。
Claims (15)
- 多結晶タングステン焼結体において、前記焼結体の相対密度は99%以上であり、前記焼結体の任意の断面で測定したポア率が0.2面積%以下、平均結晶粒径が50μm以下、結晶粒の平均アスペクト比が1~2.5である高密度かつ微粒組織で異方性のない多結晶タングステン焼結体。
- 前記ポア率が0.02面積%~0.19面積%である請求項1に記載の多結晶タングステン結晶体。
- 前記ポア率が0.02面積%~0.15面積%である請求項1に記載の多結晶タングステン結晶体。
- 前記平均結晶粒径が0.8μm~33.4μmである請求項1に記載の多結晶タングステン結晶体。
- 前記平均結晶粒径が0.8μm~18.3μmである請求項1に記載の多結晶タングステン結晶体。
- 前記平均アスペクト比が1.0~2.2である請求項1に記載の多結晶タングステン結晶体。
- 前記平均アスペクト比が1.0~1.4である請求項1に記載の多結晶タングステン結晶体。
- タングステンを25質量%以上含有する多結晶タングステン基合金焼結体において、該タングステン基合金は、Ti、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の合金成分を含有するタングステン基合金であって、前記焼結体の相対密度は99%以上であり、前記焼結体の任意の断面で測定したポア率が0.2面積%以下、平均結晶粒径が50μm以下、結晶粒の平均アスペクト比が1~2.5である高密度かつ微粒組織で異方性のない多結晶タングステン基合金焼結体。
- 前記ポア率が0.02面積%~0.19面積%である請求項8に記載の多結晶タングステン基合金焼結体。
- 前記ポア率が0.02面積%~0.15面積%である請求項8に記載の多結晶タングステン基合金焼結体。
- 前記平均結晶粒径が0.8μm~33.4μmである請求項8に記載の多結晶タングステン基合金焼結体。
- 前記平均結晶粒径が0.8μm~18.3μmである請求項8に記載の多結晶タングステン基合金焼結体。
- 前記平均アスペクト比が1.0~2.2である請求項8に記載の多結晶タングステン基合金焼結体。
- 前記平均アスペクト比が1.0~1.4である請求項8に記載の多結晶タングステン基合金焼結体。
- 平均粒径50μm以下のタングステン粒子からなる原料粉末、あるいは、平均粒径50μm以下のタングステン粒子粉末と平均粒径50μm以下のTi、Zr、Hf、V、Nb、Ta、Cr、MoおよびMnのうちから選ばれる1種または2種以上の合金成分粒子粉末を配合した原料粉末あるいはその圧粉成形体を、加圧焼結装置に装入し、該原料粉末あるいはその圧粉成形体に2.55GPa以上13GPa以下の加圧力を付加した状態で、1200℃以上融点以下の温度範囲で焼結することを特徴とする高密度かつ微粒組織で異方性のない多結晶タングステン焼結体あるいは多結晶タングステン基合金焼結体の製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112760538A (zh) * | 2020-12-22 | 2021-05-07 | 宁波江丰电子材料股份有限公司 | 一种钒钨合金靶坯的制备方法 |
CN113523273A (zh) * | 2021-06-17 | 2021-10-22 | 北京科技大学 | 多场耦合下快速制备超细晶纯钨材料的粉末冶金方法 |
CN113614280A (zh) * | 2019-03-26 | 2021-11-05 | 日立金属株式会社 | V合金靶 |
CN115615260A (zh) * | 2022-10-24 | 2023-01-17 | 大连理工大学 | 一种高密度高放热焓难熔高熵合金破片材料 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5362709A (en) * | 1976-11-17 | 1978-06-05 | Toshiba Corp | Preparation of sintered product of metal of high melting point |
JP2003193111A (ja) * | 2001-12-27 | 2003-07-09 | Nippon Steel Corp | スパッタリング用タングステンターゲットの製造方法 |
JP2005307235A (ja) * | 2004-04-19 | 2005-11-04 | Japan New Metals Co Ltd | P含有w粉末およびこれを用いて製造されたスパッタリング焼結ターゲット |
WO2009147900A1 (ja) * | 2008-06-02 | 2009-12-10 | 日鉱金属株式会社 | タングステン焼結体スパッタリングターゲット |
WO2012042791A1 (ja) * | 2010-09-29 | 2012-04-05 | 株式会社アルバック | タングステンターゲットおよびその製造方法 |
JP2015221935A (ja) * | 2014-04-28 | 2015-12-10 | 三菱マテリアル株式会社 | 抵抗溶接用タングステン−モリブデン合金電極材料 |
JP2016049562A (ja) * | 2014-09-02 | 2016-04-11 | 三菱マテリアル株式会社 | 抵抗溶接用タングステン電極材料 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08165528A (ja) | 1994-12-09 | 1996-06-25 | Japan Energy Corp | 高純度高融点金属または合金の製造方法 |
JP3418850B2 (ja) | 1995-06-20 | 2003-06-23 | 株式会社アライドマテリアル | スパッターターゲット材及びその製造方法 |
JP3527647B2 (ja) | 1998-11-27 | 2004-05-17 | 住友電装株式会社 | 抵抗溶接用電極の製造方法および抵抗溶接用電極 |
JP2003226964A (ja) | 2002-02-05 | 2003-08-15 | Nippon Steel Corp | スパッタリング用タングステンターゲットの製造方法 |
JPWO2005073418A1 (ja) * | 2004-01-30 | 2007-09-13 | 日本タングステン株式会社 | タングステン系焼結体およびその製造方法 |
JP4916264B2 (ja) | 2006-09-20 | 2012-04-11 | 日本タングステン株式会社 | ヒュージング溶接用電極 |
AT12364U1 (de) | 2010-10-07 | 2012-04-15 | Plansee Se | Kollimator für röntgen-, gamma- oder teilchenstrahlung |
-
2016
- 2016-03-18 KR KR1020177025626A patent/KR102373916B1/ko active IP Right Grant
- 2016-03-18 WO PCT/JP2016/058713 patent/WO2016152780A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5362709A (en) * | 1976-11-17 | 1978-06-05 | Toshiba Corp | Preparation of sintered product of metal of high melting point |
JP2003193111A (ja) * | 2001-12-27 | 2003-07-09 | Nippon Steel Corp | スパッタリング用タングステンターゲットの製造方法 |
JP2005307235A (ja) * | 2004-04-19 | 2005-11-04 | Japan New Metals Co Ltd | P含有w粉末およびこれを用いて製造されたスパッタリング焼結ターゲット |
WO2009147900A1 (ja) * | 2008-06-02 | 2009-12-10 | 日鉱金属株式会社 | タングステン焼結体スパッタリングターゲット |
WO2012042791A1 (ja) * | 2010-09-29 | 2012-04-05 | 株式会社アルバック | タングステンターゲットおよびその製造方法 |
JP2015221935A (ja) * | 2014-04-28 | 2015-12-10 | 三菱マテリアル株式会社 | 抵抗溶接用タングステン−モリブデン合金電極材料 |
JP2016049562A (ja) * | 2014-09-02 | 2016-04-11 | 三菱マテリアル株式会社 | 抵抗溶接用タングステン電極材料 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113614280A (zh) * | 2019-03-26 | 2021-11-05 | 日立金属株式会社 | V合金靶 |
CN112760538A (zh) * | 2020-12-22 | 2021-05-07 | 宁波江丰电子材料股份有限公司 | 一种钒钨合金靶坯的制备方法 |
CN113523273A (zh) * | 2021-06-17 | 2021-10-22 | 北京科技大学 | 多场耦合下快速制备超细晶纯钨材料的粉末冶金方法 |
CN113523273B (zh) * | 2021-06-17 | 2022-10-21 | 北京科技大学 | 多场耦合下快速制备超细晶纯钨材料的粉末冶金方法 |
CN115615260A (zh) * | 2022-10-24 | 2023-01-17 | 大连理工大学 | 一种高密度高放热焓难熔高熵合金破片材料 |
CN115615260B (zh) * | 2022-10-24 | 2024-04-19 | 大连理工大学 | 一种高密度高放热焓难熔高熵合金破片材料 |
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