WO2013084749A1 - Alliage de tungstène fritté - Google Patents

Alliage de tungstène fritté Download PDF

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Publication number
WO2013084749A1
WO2013084749A1 PCT/JP2012/080565 JP2012080565W WO2013084749A1 WO 2013084749 A1 WO2013084749 A1 WO 2013084749A1 JP 2012080565 W JP2012080565 W JP 2012080565W WO 2013084749 A1 WO2013084749 A1 WO 2013084749A1
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tungsten
sintered alloy
heat treatment
flat
tungsten sintered
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PCT/JP2012/080565
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English (en)
Japanese (ja)
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剛平 豊嶋
上西　昇
胡間　紀人
智史 梅本
角倉　孝典
瀧田　朋広
一永 榊原
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株式会社アライドマテリアル
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Priority to EP12856450.7A priority Critical patent/EP2789708A4/fr
Priority to JP2013548185A priority patent/JP5805213B2/ja
Priority to US14/363,401 priority patent/US20140308536A1/en
Publication of WO2013084749A1 publication Critical patent/WO2013084749A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles

Definitions

  • the present invention generally relates to a tungsten sintered alloy, and more particularly to a tungsten sintered alloy used as a radiation shielding material in radiological medical equipment, reactor related equipment, and the like.
  • Patent Document 1 a sintered body containing 85% by weight or more of tungsten as a main component and the balance of nickel and iron or copper is subjected to plastic working, and tungsten
  • a tungsten-based alloy material for radiation shielding which has a layered structure in which particles and a nickel-containing binder layer are flattened and these flat layers overlap, is disclosed.
  • This tungsten-based alloy material is obtained by rolling a sintered body obtained by sintering a molded body at 1470 ° C. at a heating temperature of 1300 ° C. so that the total processing rate is about 60%. It is obtained by flattening the particles and the binder layer.
  • Japanese Patent Application Laid-Open No. 9-235641 discloses that tungsten is 80 to 97% by weight, nickel is 2 to 15%, and one or more of iron, copper and cobalt is 1 to 2 in total amount.
  • a tungsten polymerized gold plate containing 10%, having a thickness of 0.3 mm or less and having both sides having dimensions of 200 times or more of the thickness is disclosed.
  • This polymer metal plate is prepared by mixing raw material powders, forming a thin plate having a thickness of 0.35 mm or less with a powder rolling press, sintering in a non-oxidizing atmosphere, and performing hot rolling and / or cooling as necessary. It is obtained by carrying out hot rolling and then performing finish rolling for flattening and smoothing.
  • a tungsten sintered alloy containing 85 mass% or more of tungsten has a radiation shielding effect, and is therefore used as a radiation shielding material in radiological medical equipment, reactor related equipment, and the like. .
  • a tungsten sintered alloy for such an application it is necessary to produce a flat plate-like tungsten sintered alloy having a wide area of a certain extent or more.
  • an object of the present invention is to provide a flat tungsten sintered alloy that can be formed into a complicated shape by pressing or forging.
  • the tungsten sintered alloy according to the present invention is at least one selected from the group consisting of 85% to 98% by weight of tungsten, 1.4% to 11% by weight of nickel, iron, copper and cobalt. Is a flat plate-like tungsten sintered alloy containing 0.6 mass% or more and 6 mass% or less.
  • the flat plate-like tungsten sintered alloy has an elongation percentage in the plane direction of 20% or more.
  • the flat tungsten sintered alloy has a thickness of 1.5 mm or less.
  • the X-ray diffraction intensity ratio of the (111) plane of the Ni— (Fe, Cu, Co) phase on the flat plate surface of the flat tungsten sintered alloy (where, When the X-ray diffraction intensities of the (111) plane, (100) plane, (110) plane, and (311) plane are I (111), I (100), I (110), and I (311),
  • the X-ray diffraction intensity ratio of the (111) plane is [I (111) / ⁇ I (111) + I (100) + I (110) + I (311) ⁇ ]) of 0.68 or more and 0.9 or less. Preferably there is.
  • FIG. 1 It is a typical perspective view which shows two cross sections observed in the flat-plate-shaped tungsten sintered alloy produced as an intermediate product in the Example and comparative example of this invention. It is a scanning electron microscope (SEM) photograph which shows the cross-sectional part observed in the flat-plate-shaped tungsten sintered alloy produced as an intermediate product in Example 1 of this invention. The figure which shows typically the thickness and length of the tungsten crystal grain measured in the cross-sectional part observed in the flat-plate-shaped tungsten sintered alloy produced as an intermediate product in the Example and comparative example of this invention. is there. It is the top view (A) and side view (B) which show the dimension of the tensile test piece produced from the flat-plate-shaped tungsten sintered alloy as the final product produced by the Example and comparative example of this invention.
  • SEM scanning electron microscope
  • the flat tungsten sintered alloy as the intermediate product of the present invention is tungsten (W) 85 mass% to 98 mass%, nickel (Ni) 1.4 mass% to 11 mass%, iron (Fe ), At least one selected from the group consisting of copper (Cu) and cobalt (Co) is contained in an amount of 0.6 mass% to 6 mass%.
  • This tungsten sintered alloy has a structure in which a plurality of flat tungsten crystal grains extending along the direction in which the plane of the flat tungsten sintered alloy extends are laminated.
  • the ratio of the average length to the thickness is 9 or more and 125 or less.
  • the ratio of the average length to the average thickness of the tungsten crystal grains observed as described above is 9 or more and 125 or less. High strength can be obtained at a high temperature as compared with the prior art. If the ratio of the average length to the average thickness of the tungsten crystal grains observed as described above is less than 9, there is a possibility that a sufficiently high strength cannot be obtained at a high temperature. When the ratio of the average length to the average thickness of the tungsten crystal grains observed as described above exceeds 125, there is a possibility that cracking may occur.
  • the average thickness of tungsten crystal grains observed as described above is 2 ⁇ m or more and 10 ⁇ m or less, and the average length of tungsten crystal grains observed as described above is 30 ⁇ m or more and 250 ⁇ m or less. It is preferable that It is difficult to make the average thickness of the tungsten crystal grains less than 2 ⁇ m, or to make the average length exceed 250 ⁇ m.
  • the average thickness of tungsten crystal grains observed as described above is 2 ⁇ m or more and 3 ⁇ m or less
  • the average length of tungsten crystal grains observed as described above is preferably in the range of 30 ⁇ m or more and 250 ⁇ m or less.
  • the ratio of the average length to the average thickness is preferably 10 or more and 125 or less.
  • the average thickness of the tungsten crystal grains observed as described above exceeds 3 ⁇ m and is 6 ⁇ m or less, the average of the tungsten crystal grains observed as described above is required to obtain a sufficiently high strength at a high temperature.
  • the length is preferably in the range of 54 ⁇ m to 250 ⁇ m, and the ratio of the average length to the average thickness is preferably 9 to 84.
  • the average thickness of the tungsten crystal grains observed as described above exceeds 6 ⁇ m and is 10 ⁇ m or less, the average of the tungsten crystal grains observed as described above is obtained in order to obtain a sufficiently high strength at a high temperature.
  • the length is preferably in the range of 90 ⁇ m to 250 ⁇ m, and the ratio of the average length to the average thickness is preferably 9 to 42.
  • the shape of the tungsten crystal grains in the planar direction of the flat plate-like tungsten sintered alloy has various shapes such as a substantially circular shape, a substantially elliptical shape, a substantially square shape, a substantially rectangular shape, and an indefinite shape.
  • the flat tungsten sintered alloy as the intermediate product of the present invention includes (1) raw material preparation step, (2) mixing step, (3) forming step, (4) sintering step, and (5) strain described later. It is manufactured through an introduction step, (6) a heat treatment step, and (7) a hot rolling step.
  • the method for producing a flat plate-shaped tungsten sintered alloy as an intermediate product of the present invention includes tungsten in an amount of 85 to 98% by mass, nickel in an amount of 1.4 to 11% by mass, iron, A method for producing a tungsten sintered alloy containing at least one selected from the group consisting of copper and cobalt in an amount of 0.6 mass% to 6 mass%, wherein strain is introduced into the sintered body and strain is introduced. After the sintered body is heat treated, the sintered body is hot-rolled at a rolling rate of 60% or more.
  • the plate-like tungsten sintered alloy thus produced can have a structure in which the ratio of the average length to the average thickness of the tungsten crystal grains observed as described above is 9 or more and 125 or less. Higher strength than conventional can be obtained at temperature.
  • tungsten sintered alloys sintered bodies having tungsten crystal grains with a grain size of 30 to 50 ⁇ m produced by a conventionally known manufacturing method (raw material powder mixing step, molding step and sintering step).
  • a certain heat treatment after applying a certain strain, the grain size of tungsten crystal grains in the sintered tungsten alloy can be reduced to a certain value or less (5 to 20 ⁇ m).
  • the thickness of the tungsten crystal grains is reduced below a certain value and the length of the tungsten crystal grains is increased above a certain value by hot rolling the sintered body at a rolling processing rate of 60% or more.
  • tungsten sintered alloy having a structure in which a plurality of flat tungsten crystal grains extending in the planar direction of the flat tungsten sintered alloy are stacked.
  • strength compared with the former can be acquired at high temperature.
  • the flat tungsten sintered alloy according to the present invention was selected from the group consisting of 85 mass% to 98 mass% tungsten, 1.4 mass% to 11 mass% nickel, iron, copper and cobalt. At least one kind is contained in an amount of 0.6 mass% to 6 mass%.
  • the flat plate-like tungsten sintered alloy has an elongation percentage in the plane direction of 20% or more.
  • the flat plate-like tungsten sintered alloy configured as described above, the flat plate-like tungsten sintered alloy has an elongation percentage in the plane direction of 20% or more. It becomes possible to mold the bond gold into a complicated shape.
  • the flat plate-like tungsten sintered alloy has an elongation percentage of less than 20%, there is no difference in elongation rate from the conventional tungsten sintered alloy. There is a possibility that it cannot be formed into a complicated shape.
  • the upper limit of the elongation in the plane direction of the flat plate-like tungsten sintered alloy is 45%. It is difficult to obtain a flat tungsten sintered alloy having an elongation percentage in the plane direction exceeding 45%.
  • the flat plate-like tungsten sintered alloy according to the present invention has the following (1) raw material preparation step, (2) mixing step, (3) forming step, (4) sintering step, (5) strain introducing step, (6) It is manufactured through a heat treatment step, (7) a hot rolling step, and (8) a heat treatment step.
  • the method for producing a flat tungsten sintered alloy according to the present invention includes tungsten in an amount of 85 mass% to 98 mass%, nickel in an amount of 1.4 mass% to 11 mass%, iron, copper, and cobalt.
  • the flat plate-like tungsten sintered alloy thus manufactured can increase the flat plate-like tungsten sintered alloy in the planar direction by 20% or more, and is flat plate-like tungsten by pressing or forging. It becomes possible to form a sintered alloy into a complicated shape.
  • the flat tungsten sintered alloy according to the present invention can be obtained by further heat-treating the flat tungsten sintered alloy as the intermediate product of the present invention.
  • the flat tungsten sintered alloy does not have the structure of the tungsten sintered alloy as the intermediate product of the present invention, but has a structure very close to the structure of the conventional tungsten sintered alloy immediately after sintering. Have.
  • the structure of the tungsten sintered alloy as the intermediate product of the present invention is returned to the structure very close to the structure of the conventional tungsten sintered alloy. .
  • the thickness of the flat tungsten sintered alloy according to the present invention is preferably 1.5 mm or less.
  • the X-ray diffraction intensity ratio of the (111) plane of the Ni— (Fe, Cu, Co) phase on the flat plate surface of the flat tungsten sintered alloy (where, When the X-ray diffraction intensities of the (111) plane, (100) plane, (110) plane, and (311) plane are I (111), I (100), I (110), and I (311),
  • the X-ray diffraction intensity ratio of the (111) plane is [I (111) / ⁇ I (111) + I (100) + I (110) + I (311) ⁇ ]) of 0.68 or more and 0.9 or less. Preferably there is.
  • the Ni— (Fe, Cu, Co) phase that is a binder phase is also elongated in the plane direction.
  • the (111) plane that is the sliding surface of the FCC (face centered cubic) structure is oriented in parallel to the plane direction.
  • the (111) plane orientation remains in the flat tungsten sintered alloy as the final product.
  • the tungsten crystal grains can be easily slipped in the binder component.
  • the heat treatment can substantially eliminate the defects present in the tungsten sintered alloy, and can further improve the planar elongation of the tungsten sintered alloy.
  • the method for producing a tungsten sintered alloy according to the present invention strain is introduced into the sintered body, and the sintered body into which the strain has been introduced is subjected to a heat rolling process after heat treatment.
  • the sintered body can be hot-rolled at a rolling rate of at least%.
  • a flat tungsten sintered alloy having a thickness of 1.5 mm or less can be formed. Therefore, the manufacturing method of the present invention is particularly advantageous for obtaining a thin flat plate, and the manufacturing cost can be reduced.
  • the heat treatment is further performed after the hot rolling process, so that the elongation can be increased.
  • the obtained flat plate-like tungsten sintered alloy can be further thinned by rolling or the like.
  • the lower limit of the thickness of the flat tungsten sintered alloy according to the present invention is 0.05 mm. It is difficult to make the thickness of the flat tungsten sintered alloy less than 0.05 mm.
  • the tungsten sintered alloy according to the present invention contains elements other than nickel (Ni), iron (Fe), copper (Cu), and cobalt (Co) as long as the effects of the present invention are not impaired.
  • manganese (Mn), molybdenum (Mo), silicon (Si), rhenium (Re), chromium (Cr), titanium (Ti), vanadium (V), niobium (Nb), tantalum (Ta ) And the like may be contained in an amount of 0% by mass to 2% by mass.
  • Raw material preparation step Tungsten powder, nickel powder, and at least one metal powder selected from the group consisting of iron, copper, and cobalt are prepared.
  • the raw material is made from 85 mass% to 98 mass% tungsten powder, 1.4 mass% to 11 mass% nickel, and at least one metal powder selected from the group consisting of iron, copper, and cobalt is 0.6 mass%.
  • a raw material is prepared so that it may be included in a mixture ratio of not less than 6% by mass and not more than 6% by mass.
  • the strength of the obtained tungsten sintered alloy may be insufficient.
  • the binder component is insufficient, and the obtained tungsten sintered alloy may be cracked in the rolling process.
  • the obtained tungsten sintered alloy may be cracked in the rolling process. If the blending ratio of the nickel powder exceeds 11% by mass, the strength of the obtained tungsten sintered alloy may not be sufficient.
  • Iron, copper, and cobalt serve as sintering aids. If the blending ratio of at least one metal powder selected from the group consisting of iron, copper and cobalt is less than 0.6% by mass, a dense sintered body cannot be obtained. There is a risk of cracking in the rolling process. When the blending ratio of the above metal powder exceeds 6% by mass, the binder component is excessively cured, so that the toughness of the obtained tungsten sintered alloy itself may be lowered.
  • the average particle size of each of the tungsten powder, the nickel powder, and the metal powder is preferably 1 ⁇ m or more and 10 ⁇ m or less. If the average particle size of each of these powders is less than 1 ⁇ m, the production cost may increase. When the average particle diameter of each of these powders exceeds 10 ⁇ m, voids are easily formed in the obtained tungsten sintered alloy, and the tungsten sintered alloy may be cracked in the rolling process.
  • the tungsten powder prepared above, nickel powder, and at least one metal powder selected from the group consisting of iron, copper and cobalt are mixed to obtain a mixture.
  • Mixing can be performed using a Redige mixer, an attritor, a ball mill, or the like.
  • a solvent and a binder may be added to the raw material powder during mixing.
  • the binder camphor, melball, stearic acid, paraffin or the like can be used.
  • As the solvent ethanol, methanol, acetone or the like can be used.
  • Molding step A pressure is applied to the mixture obtained above and molding is performed to obtain a molded body.
  • Pressure is applied to the mixture using a cold isostatic press (CIP), dry CIP, mechanical press or the like.
  • CIP cold isostatic press
  • the pressure applied during molding is preferably 49 MPa or more and less than 294 MPa. If the pressure is less than 49 MPa, the molded body may not be obtained, and even if the molded body can be obtained, the molded body may be damaged in handling of the molded body or in a subsequent process. There is no problem even if the pressure is increased to 294 MPa or more, but it does not increase the action for obtaining a molded body.
  • the molded body obtained above is sintered to obtain a sintered body.
  • an atmosphere for sintering the compact an atmosphere of hydrogen gas, vacuum, or inert gas can be used.
  • a batch furnace, a continuous pusher furnace, or the like can be used as a sintering furnace that accommodates the compact.
  • the sintering temperature is preferably 1200 ° C. or higher and 1550 ° C. or lower. If the sintering temperature is less than 1200 ° C., a dense sintered body cannot be obtained, so that the obtained tungsten sintered alloy may break in the rolling process. If the sintering temperature exceeds 1550 ° C, the sintered body may be melted.
  • the sintering time is preferably 10 minutes to 300 minutes at the highest sintering temperature. If the sintering time is less than 10 minutes, a dense sintered body cannot be obtained, so that the obtained tungsten sintered alloy may break in the rolling process. If the sintering time exceeds 300 minutes, the tungsten crystal grains become too coarse, and there is a possibility that the tungsten crystal grains cannot be sufficiently refined in the subsequent process.
  • HIP hot isostatic press
  • an inert gas such as nitrogen gas or argon gas can be used as the atmosphere.
  • the pressure is preferably 500 MPa or more and 1500 MPa or less. If the pressure is less than 500 MPa, a dense sintered body cannot be obtained, so that the obtained tungsten sintered alloy may break in the rolling process. There is no problem even if the pressure exceeds 1500 MPa, but the action for obtaining the sintered body is not increased.
  • the temperature is preferably 1200 ° C or higher and 1550 ° C or lower. If the temperature is less than 1200 ° C., a dense sintered body cannot be obtained, so that the obtained tungsten sintered alloy may break in the rolling process. When the temperature exceeds 1550 ° C., the sintered body may be melted.
  • Strain introduction step Strain is introduced into the sintered body (tungsten sintered alloy) obtained above.
  • the temperature of the sintered body at the time of introducing strain is preferably 0 ° C. or higher and 600 ° C. or lower. If the temperature is less than 0 ° C., the sintered body becomes hard and may crack. When the temperature exceeds 600 ° C., the introduced strain is released, so that fine crystal grains may not be formed even if heat treatment is performed in a later step.
  • a method of introducing strain into the sintered body it can be performed by deforming the sintered body by forging, mechanical pressing, cold rolling, or the like.
  • an atmosphere of vacuum, hydrogen gas, nitrogen gas, argon gas, or carbon monoxide gas can be used as an atmosphere for heat-treating the sintered body.
  • the temperature of the heat treatment is preferably 900 ° C. or higher and 1400 ° C. or lower. If the temperature of the heat treatment is less than 900 ° C., the recovery of strain is insufficient and the tungsten crystal grains are not refined, so that the sintered body may break in the subsequent hot rolling process. When the temperature of the heat treatment exceeds 1400 ° C., the distortion is completely recovered and the tungsten crystal grains are coarsened, so that the sintered body may be broken in the subsequent hot rolling process.
  • the heat treatment time is preferably 20 minutes or more and 5 hours or less. When the heat treatment time is less than 20 minutes, the recovery of strain is insufficient and the tungsten crystal grains are not refined, so that the sintered body may break in the subsequent hot rolling process. If the heat treatment time exceeds 5 hours, the distortion is completely recovered and the tungsten crystal grains are coarsened, so that the sintered body may be broken in the subsequent hot rolling process.
  • the average grain size of the tungsten crystal grains in the sintered tungsten alloy after the heat treatment is preferably 5 ⁇ m or more and 20 ⁇ m or less. It is difficult to make the average grain size of tungsten crystal grains less than 5 ⁇ m. If the average grain size of the tungsten crystal grains exceeds 20 ⁇ m, the sintered body may break in the subsequent hot rolling process.
  • Hot rolling step In the state where the sintered body (tungsten sintered alloy) heat-treated as described above is heated, it is rolled at a rolling rate of 60% or more.
  • an atmosphere for heating the sintered body an atmosphere of hydrogen gas, nitrogen gas, argon gas, or the like can be used.
  • the temperature of the rolling process is preferably 800 ° C. or higher and 1400 ° C. or lower. If the temperature of the rolling process is less than 800 ° C., the load applied to the rolling mill increases, and the rolling process cannot be performed or the sintered body may be broken. If the temperature of the rolling process exceeds 1400 ° C., the tungsten crystal grains are coarsened.
  • the rolling process rate at one time is 5% or more and 30% or less. If the rolling process rate of one time is less than 5%, the number of rolling operations for making the rolling process rate 60% or more in total increases, and the manufacturing cost increases. When the rolling processing rate of one time exceeds 30%, the load applied to the rolling mill increases, and rolling processing cannot be performed or the sintered body may be broken.
  • the total rolling rate is preferably 60% or more and 95% or less. If the total rolling ratio is less than 60%, the tungsten crystal grains do not become flat particles, so that the strength of the tungsten sintered alloy at a high temperature may not be sufficiently increased. If the total rolling ratio exceeds 95%, the sintered body may be broken by rolling.
  • the heat treatment step are performed on the sintered body (tungsten sintered alloy) obtained in the (4) sintering step ( 7)
  • the heat treatment step are performed on the sintered body (tungsten sintered alloy) obtained in the (4) sintering step ( 7)
  • the lower limit of the thickness of the tungsten sintered alloy as the intermediate product of the present invention is 0.5 mm. Obtaining a tungsten sintered alloy having a thickness of less than 0.5 mm is difficult even if (7) the hot rolling step is performed after the (5) strain introducing step and the (6) heat treatment step.
  • an atmosphere for heat-treating the hot-rolled sintered body an atmosphere of vacuum, hydrogen gas, or inert gas can be used.
  • a furnace for heat treatment a batch furnace or a continuous pusher furnace can be used.
  • the temperature of the heat treatment is preferably 1300 ° C. or higher and 1550 ° C. or lower. If the temperature of the heat treatment is lower than 1300 ° C., the coarsening of the tungsten crystal grains is insufficient, and the cold workability may not be improved. If the temperature of the heat treatment exceeds 1550 ° C., the sintered body may be melted.
  • the heat treatment time is preferably 10 minutes or more and 5 hours or less. If the heat treatment time is less than 10 minutes, the tungsten crystal grains are not sufficiently coarsened, and the cold workability may not be improved. If the heat treatment time exceeds 5 hours, the tungsten crystal grains become coarse and the workability deteriorates, so that the sintered body may be cracked when processing into a complicated shape.
  • the average grain size of tungsten crystal grains in the sintered tungsten alloy after the heat treatment is preferably 20 ⁇ m or more and 60 ⁇ m or less. If the average grain size of the tungsten crystal grains is less than 20 ⁇ m, the effect of the heat treatment is insufficient, a high elongation cannot be obtained, and cold workability may not be improved. If the average grain size of the tungsten crystal grains exceeds 60 ⁇ m, the tungsten crystal grains are coarsened and the workability is lowered, so that the sintered body may be cracked when processing into a complicated shape.
  • Example 1 In this example, a flat plate-like tungsten sintered alloy as an intermediate product of the present invention described above was produced. That is, a flat tungsten sintered alloy was produced by performing the steps (1) to (7).
  • the mixture obtained above was molded by applying a pressure of 196 MPa using a cold isostatic press (CIP) to obtain a molded body ((3) molding step).
  • the dimension of the obtained molded body was 176 mm ⁇ 176 mm ⁇ 8.2 mm.
  • the molded body obtained above was sintered at a temperature of 1460 ° C. for 80 minutes in a hydrogen gas atmosphere furnace to obtain a sintered body ((4) sintering step).
  • the size of the obtained sintered body was 150 mm ⁇ 150 mm ⁇ 7 mm.
  • the obtained flat plate-like tungsten sintered alloy was deformed at a deformation rate of 30% in the thickness direction using a forging machine at a temperature of 25 ° C., thereby introducing strain into the tungsten sintered alloy ( (5) Strain introduction step).
  • the dimension of the flat plate-like tungsten sintered alloy after introduction of strain was 177 mm ⁇ 177 mm ⁇ 5 mm.
  • the flat plate-like tungsten sintered alloy into which strain was introduced was heat-treated in a vacuum furnace at a temperature of 1200 ° C. for 3 hours ((6) heat treatment step).
  • FIG. 2 The optical microscope photograph which observed the cross section of the flat-plate-like tungsten sintered alloy obtained as mentioned above is shown in FIG. As shown in FIG. 2, it can be seen that the tungsten crystal grains are refined and the average grain size is about 10 ⁇ m.
  • the sample is taken out of the furnace and immediately rolled at a rolling rate of about 10%. The rolling process was repeated until the total rolling ratio reached 80% ((7) hot rolling process).
  • the dimension of the flat tungsten sintered alloy after hot rolling was 100 mm ⁇ 1070 mm ⁇ 1 mm.
  • the obtained flat plate-like tungsten sintered alloy as an intermediate product was heat-treated in a vacuum furnace at a temperature of 1450 ° C. for 60 minutes ((8) heat treatment step).
  • FIG. 3 shows an optical micrograph obtained by observing a cross section of a flat plate-like tungsten sintered alloy as a final product obtained as described above. As shown in FIG. 3, it can be seen that the tungsten crystal grains are coarsened and the average grain size is about 35 ⁇ m.
  • Example 2 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment temperature was 1300 ° C. in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 21 ⁇ m.
  • Example 3 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment temperature was changed to 1550 ° C. in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat plate-like tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 43 ⁇ m.
  • Example 4 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment time was 10 minutes in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 25 ⁇ m.
  • Example 5 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment time was 3 hours in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 39 ⁇ m.
  • Example 6 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment time was 5 hours in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 57 ⁇ m.
  • Example 7 Except that the strain was introduced into the sintered tungsten alloy by deforming at a deformation rate of 20% in the thickness direction in the strain introduction step, and that the heat treatment temperature was 1500 ° C. in the heat treatment step after the hot rolling step.
  • a flat tungsten sintered alloy having a thickness of 1.1 mm was produced.
  • the average grain size of the tungsten crystal grains was about 19 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 39 ⁇ m.
  • Example 8 Except that the strain was introduced into the sintered tungsten alloy by deforming at a deformation rate of 40% in the thickness direction in the strain introduction step, and that the heat treatment temperature was 1500 ° C. in the heat treatment step after the hot rolling step.
  • a flat tungsten sintered alloy having a thickness of 0.9 mm was produced.
  • the average grain size of the tungsten crystal grains was about 10 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 38 ⁇ m.
  • Example 9 Except that the strain was introduced into the sintered tungsten alloy by deforming at a deformation rate of 50% in the thickness direction in the strain introduction step, and that the heat treatment temperature was 1500 ° C. in the heat treatment step after the hot rolling step.
  • a flat tungsten sintered alloy having a thickness of 0.7 mm was produced.
  • the average grain size of the tungsten crystal grains was about 5 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 39 ⁇ m.
  • Example 10 A flat plate-like tungsten sintered alloy having a thickness of 2.0 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling ratio reached 60% in the hot rolling process. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 39 ⁇ m.
  • Example 11 A flat plate-like tungsten sintered alloy having a thickness of 1.5 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling process rate reached 70% in the hot rolling process. In addition, when the cross section of the flat-plate-like tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 36 ⁇ m.
  • Example 12 In the hot rolling process, a flat plate-like tungsten sintered alloy having a thickness of 0.7 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling ratio reached 85%. . In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 37 ⁇ m.
  • Example 13 A flat plate-like tungsten sintered alloy having a thickness of 0.5 mm was manufactured in the same manner as in Example 1 except that the rolling process was performed until the total rolling process rate reached 90% in the hot rolling process. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 37 ⁇ m.
  • Example 14 The same as in Example 1 except that the thickness of the sintered body obtained in the sintering process was 14 mm and that the rolling process was performed until the total rolling ratio in the hot rolling process reached 95%. Then, a flat tungsten sintered alloy having a thickness of 0.5 mm was produced. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 39 ⁇ m.
  • Example 15 The thickness of the sintered body obtained in the sintering step was 20 mm, the strain was introduced into the tungsten sintered alloy by being deformed at a deformation rate of 50% in the thickness direction in the strain introducing step, In the same manner as in Example 1, except that the rolling process was performed until the total rolling ratio became 95% in the rolling process, and the heat treatment temperature was set to 1300 ° C. in the heat treatment process after the hot rolling process, A flat tungsten sintered alloy having a thickness of 0.5 mm was produced.
  • the average grain size of the tungsten crystal grains was about 5 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 23 ⁇ m.
  • Example 16 The thickness of the sintered body obtained in the sintering step was 20 mm, the strain was introduced into the tungsten sintered alloy by being deformed at a deformation rate of 50% in the thickness direction in the strain introducing step, In the same manner as in Example 1 except that the rolling process was performed until the total rolling ratio reached 95% in the rolling process and that the heat treatment temperature was 1450 ° C. in the heat treatment process after the hot rolling process, A flat tungsten sintered alloy having a thickness of 0.5 mm was produced. As in Example 1, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 5 ⁇ m. Further, in the same manner as in Example 1, when the cross section of the flat plate-like tungsten sintered alloy as the final product was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 37 ⁇ m.
  • Example 17 The thickness of the sintered body obtained in the sintering step was 20 mm, the strain was introduced into the tungsten sintered alloy by being deformed at a deformation rate of 50% in the thickness direction in the strain introducing step, In the same manner as in Example 1, except that the rolling process was performed until the total rolling ratio became 95% in the rolling process, and the heat treatment temperature was set to 1550 ° C. in the heat treatment process after the hot rolling process, A flat tungsten sintered alloy having a thickness of 0.5 mm was produced. As in Example 1, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 5 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 47 ⁇ m.
  • Example 18 Using tungsten powder with an average particle diameter of 1 ⁇ m in the raw material preparation process, using copper powder instead of iron powder, and deforming at a deformation rate of 20% in the thickness direction in the strain introduction process, the tungsten sintered alloy Except for introducing strain, performing rolling until the total rolling rate reaches 60% in the hot rolling step, and setting the heat treatment temperature to 1300 ° C. in the heat treatment step after the hot rolling step. In the same manner as in Example 1, a flat plate-like tungsten sintered alloy having a thickness of 2.2 mm was produced.
  • the average grain size of the tungsten crystal grains was about 19 ⁇ m. Further, in the same manner as in Example 1, when the cross section of the flat plate-like tungsten sintered alloy as the final product was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 21 ⁇ m.
  • Example 19 Using tungsten powder with an average particle size of 5 ⁇ m in the raw material preparation step, using copper powder instead of iron powder, and deforming at a deformation rate of 20% in the thickness direction in the strain introduction step, the tungsten sintered alloy Except for introducing strain, performing rolling until the total rolling ratio reaches 70% in the hot rolling step, and setting the heat treatment temperature to 1300 ° C. in the heat treatment step after the hot rolling step. In the same manner as in Example 1, a flat plate-like tungsten sintered alloy having a thickness of 1.7 mm was produced.
  • the average grain size of the tungsten crystal grains was about 19 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 23 ⁇ m.
  • Example 20 Using tungsten powder with an average particle size of 10 ⁇ m in the raw material preparation process, using copper powder instead of iron powder, and deforming at a deformation rate of 20% in the thickness direction in the strain introduction process, the tungsten sintered alloy Except for introducing strain, performing rolling until the total rolling ratio reaches 90% in the hot rolling step, and setting the heat treatment temperature to 1300 ° C. in the heat treatment step after the hot rolling step. In the same manner as in Example 1, a flat plate-like tungsten sintered alloy having a thickness of 0.7 mm was produced.
  • the average grain size of the tungsten crystal grains was about 19 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 22 ⁇ m.
  • Example 21 In the raw material preparation step, the tungsten powder was prepared to contain 85% by mass, the nickel powder was 10.5% by mass, and the iron powder was prepared to contain 4.5% by mass, and the total rolling ratio in the hot rolling step was The thickness was 0 as in Example 1, except that the rolling process was performed until 90% and that the heat treatment temperature was 1300 ° C. and the heat treatment time was 3 hours in the heat treatment step after the hot rolling step.
  • a 5 mm flat plate-like tungsten sintered alloy was produced.
  • the average grain size of the tungsten crystal grains was about 9 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 24 ⁇ m.
  • the raw material preparation step was prepared so as to include 90% by mass of tungsten powder, 7% by mass of nickel powder, and 3% by mass of iron powder, and the total rolling ratio in the hot rolling step was 90%.
  • a tungsten sintered alloy was produced.
  • the average grain size of the tungsten crystal grains was about 10 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 24 ⁇ m.
  • Example 23 In the raw material preparation step, the tungsten powder was prepared to contain 98% by mass, the nickel powder was 1.4% by mass, and the iron powder was prepared to contain 0.6% by mass, and the total rolling ratio in the hot rolling step was The thickness was 0 as in Example 1, except that the rolling process was performed until 90% and that the heat treatment temperature was 1300 ° C. and the heat treatment time was 3 hours in the heat treatment step after the hot rolling step. A 5 mm flat plate-like tungsten sintered alloy was produced. In addition, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 10 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 26 ⁇ m.
  • Example 24 Nickel powder with an average particle size of 1 ⁇ m was used in the raw material preparation step, cobalt powder was used instead of iron powder, and the heat treatment temperature was 1300 ° C. and the heat treatment time was 5 hours in the heat treatment step after the hot rolling step. Except for this, a flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1.
  • the average grain size of the tungsten crystal grains was about 11 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 28 ⁇ m.
  • Example 25 Nickel powder having an average particle size of 5 ⁇ m was used in the raw material preparation step, cobalt powder was used instead of iron powder, and the heat treatment temperature was 1300 ° C. and the heat treatment time was 5 hours in the heat treatment step after the hot rolling step. Except for this, a flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1. In addition, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 10 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 30 ⁇ m.
  • Example 26 Nickel powder having an average particle size of 10 ⁇ m was used in the raw material preparation step, cobalt powder was used instead of iron powder, and the heat treatment temperature was 1300 ° C. and the heat treatment time was 5 hours in the heat treatment step after the hot rolling step. Except for this, a flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1. In addition, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 10 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 27 ⁇ m.
  • Example 27 The use of iron powder having an average particle size of 1 ⁇ m in the raw material preparation step, the introduction of strain into the tungsten sintered alloy by deformation at a deformation rate of 50% in the thickness direction in the strain introduction step, and hot rolling A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling process rate reached 60% in the process.
  • the average grain size of the tungsten crystal grains was about 5 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 32 ⁇ m.
  • Example 28 The use of iron powder having an average particle size of 5 ⁇ m in the raw material preparation step, the introduction of strain into the tungsten sintered alloy by deformation at a deformation rate of 50% in the thickness direction in the strain introduction step, and hot rolling A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling process rate reached 60% in the process.
  • the average grain size of the tungsten crystal grains was about 5 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 35 ⁇ m.
  • Example 29 The use of iron powder having an average particle size of 10 ⁇ m in the raw material preparation step, the introduction of strain into the tungsten sintered alloy by deformation at a deformation rate of 50% in the thickness direction in the strain introduction step, and hot rolling A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling process rate reached 60% in the process.
  • the average grain size of the tungsten crystal grains was about 5 ⁇ m.
  • the average grain size of the tungsten crystal grains was about 33 ⁇ m.
  • FIG. 4 shows an optical micrograph obtained by observing a cross section of the flat plate-like tungsten sintered alloy obtained as described above.
  • Example 3 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment temperature was 1200 ° C. in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 18 ⁇ m.
  • Example 5 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment time was 6 minutes in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 17 ⁇ m.
  • Example 6 A flat plate-like tungsten sintered alloy having a thickness of 1.0 mm was produced in the same manner as in Example 1 except that the heat treatment time was 6 hours in the heat treatment step after the hot rolling step. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 64 ⁇ m.
  • Example 7 Comparative Example 7 Except that the strain was introduced into the sintered tungsten alloy by deformation at a deformation rate of 17% in the thickness direction in the strain introduction step, and that the heat treatment temperature was 1500 ° C. in the heat treatment step after the hot rolling step. In the same manner as in Example 1, an attempt was made to produce a flat tungsten sintered alloy, but cracking occurred after the hot rolling step. As in Example 1, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 24.3 ⁇ m. .
  • Example 9 A flat plate-like tungsten sintered alloy having a thickness of 2.5 mm was produced in the same manner as in Example 1 except that the rolling process was performed until the total rolling process rate reached 50% in the hot rolling process. In addition, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 37 ⁇ m.
  • Example 11 The thickness of the sintered body obtained in the sintering step was 20 mm, the strain was introduced into the tungsten sintered alloy by being deformed at a deformation rate of 50% in the thickness direction in the strain introducing step, In the same manner as in Example 1, except that the rolling process was performed until the total rolling ratio reached 95% in the rolling process and that the heat treatment temperature was 1200 ° C. in the heat treatment process after the hot rolling process, A flat tungsten sintered alloy having a thickness of 0.5 mm was produced. As in Example 1, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 5 ⁇ m. Moreover, when the cross section of the flat tungsten sintered alloy as the final product was observed with an optical microscope in the same manner as in Example 1, the average grain size of the tungsten crystal grains was about 17 ⁇ m.
  • Example 12 The thickness of the sintered body obtained in the sintering step was 20 mm, the strain was introduced into the tungsten sintered alloy by being deformed at a deformation rate of 50% in the thickness direction in the strain introducing step, In the same manner as in Example 1, except that the rolling process was performed until the total rolling ratio reached 95% in the rolling process, and that the heat treatment temperature was 1600 ° C. in the heat treatment process after the hot rolling process, An attempt was made to produce a flat tungsten sintered alloy having a thickness of 0.5 mm, but the flat tungsten sintered alloy melted. As in Example 1, when the cross section of the flat plate-like tungsten sintered alloy after the heat treatment after the strain introducing step was observed with an optical microscope, the average grain size of the tungsten crystal grains was about 5 ⁇ m.
  • the plane 100 of the flat plate-like tungsten sintered alloy 1 obtained as an intermediate product of Examples 1 to 29 and Comparative Examples 1 to 6, 9, 11, and 12 is orthogonal to the extending direction.
  • a second cross section 102 perpendicular to the first cross section was observed with a scanning electron microscope (SEM).
  • each of the first cross-section 101 and the second cross-section 102 a photograph of an arbitrary location (field of view) is taken at 1000 times, and the cross-section is taken along the direction in which the plane 100 extends from the location.
  • a photograph of a portion (field of view) shifted in position is taken, and photographs of seven fields of view obtained by sequentially shifting are connected in the direction in which the plane 100 extends, and the thickness T is 70 ⁇ m and the width W is 500 ⁇ m.
  • a photograph of the cross section was obtained.
  • the first cross-section portion having the constant width W (500 ⁇ m) and the constant thickness T (70 ⁇ m) selected from the first cross-section 101 and the constant cross-section selected from the second cross-section 102 are selected.
  • a photograph of a second cross-sectional portion having a width W (500 ⁇ m) and a constant thickness T (70 ⁇ m) was obtained.
  • An example (Example 1) of a scanning electron microscope (SEM) photograph of the cross section is shown in FIG.
  • FIG. 7 schematically shows the above cross-sectional portion.
  • the first cross-section portion 101a and the second cross-section portion 102a obtained as described above, it passes through the center of a constant width W (500 ⁇ m) and has a constant thickness T (70 ⁇ m).
  • the thickness t and the length s of the plurality of tungsten crystal grains G1 to G4 intersecting the center line 200 extending in the direction were measured.
  • the average value of these measured values was determined and used as the average thickness and average length of the tungsten crystal grains.
  • the ratio of the average length with respect to the average thickness of a tungsten crystal grain was computed.
  • Table 1 shows the average thickness and average length of the tungsten crystal grains calculated as described above, and the ratio of the average length to the average thickness.
  • a tensile test piece having a thickness T as shown in FIG. 8 was obtained from the flat tungsten sintered alloy obtained as a final product in Examples 1 to 29 and Comparative Examples 1 to 3, 5, 6, 9, 11, and 12. 10 was produced.
  • the distance between the gauge points was 8 mm with the center line 20 as the center.
  • the produced tensile test piece 10 is set in a tensile tester of model number 5867 manufactured by INSTRON Co., Ltd. at a test temperature of 20 ° C. and 300 mm / min. Tensile tests were conducted until rupture at a tensile rate of. The increase rate of the distance between the gauge points of the test piece until it broke was defined as the elongation rate. In addition, also about the flat-plate-shaped tungsten sintered alloy obtained as an intermediate product in Example 1, the elongation rate was measured similarly to the above.
  • Table 1 shows the measurement results of the elongation obtained as described above.
  • Example 1 the numerical value in parentheses indicates the elongation of the flat tungsten sintered alloy obtained as an intermediate product in Example 1.
  • the X-ray diffraction intensity ratio of the (111) plane (here, (111) plane, (100) plane, (110) plane and (311) plane each) If the X-ray diffraction intensity is I (111), I (100), I (110), I (311), the X-ray diffraction intensity ratio of the (111) plane is [I (111) / ⁇ I (111) + I (100) + I (110) + I (311) ⁇ ]).
  • Table 1 shows the measurement results of the X-ray diffraction intensity ratio of the (111) plane of the Ni— (Fe, Cu, Co) phase obtained as described above.
  • the X-ray diffraction intensity ratio of the (111) plane of the Ni— (Fe, Cu, Co) phase shows a value of 0.68 or more and 0.9 or less.
  • the tungsten sintered alloy of the present invention is used as a radiation shielding material in radiological medical equipment, reactor related equipment, and the like.
  • tungsten sintered alloy 100: plane
  • G1 to G4 Tungsten crystal grains
  • T, T 0 thickness
  • W width
  • t thickness
  • s length.

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Abstract

　L'invention concerne un alliage de tungstène fritté sous forme de plaque, lequel peut être façonné en formes complexes par traitement à la presse ou à la forge. Cet alliage de tungstène fritté sous forme de plaque contient: 85 à 90 % en masse de W; 1,4 à 11 % en masse de Ni; 0,6 à 6 % en masse d'au moins un élément choisi dans un groupe contenant Fe, Cu et Co. Le coefficient d'extension de cet alliage de tungstène fritté sous forme de plaque est supérieur ou égal à 20 %.
PCT/JP2012/080565 2011-12-07 2012-11-27 Alliage de tungstène fritté WO2013084749A1 (fr)

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CN111910112B (zh) * 2020-07-01 2022-02-11 昆山家锐电子科技有限公司 一种钨铜合金材料及其制备方法、应用
CN113817944B (zh) * 2021-09-13 2022-10-11 安泰天龙(北京)钨钼科技有限公司 一种高性能钨合金棒材及其制备方法
CN115478236B (zh) * 2022-08-30 2023-02-28 广州市华司特合金制品有限公司 一种高比重钨合金的热处理方法

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5237503A (en) * 1975-09-18 1977-03-23 Us Government Method of producing articles made of tungstennnickell iron alloy
JPH01142048A (ja) * 1987-10-23 1989-06-02 Cime Bocuze:Soc 極めて高い機械的特性値をもつタングステン―ニツケル―鉄重合金及びかかる合金の製造方法
JPH02122026A (ja) * 1988-10-31 1990-05-09 Nippon Yakin Kogyo Co Ltd タングステン焼結合金の製造方法
JPH02122048A (ja) * 1988-10-31 1990-05-09 Nippon Yakin Kogyo Co Ltd 低温で高延性を有するタングステン焼結合金
JPH03173738A (ja) * 1989-11-30 1991-07-29 Nippon Yakin Kogyo Co Ltd 高強度，高靭性タングステン焼結合金
JPH03173727A (ja) * 1989-11-30 1991-07-29 Nippon Yakin Kogyo Co Ltd タングステン焼結合金の製造方法
JPH03226541A (ja) * 1990-01-30 1991-10-07 Mitsubishi Materials Corp パッケージ型半導体装置の高強度放熱性構造部材
JPH042736A (ja) * 1990-04-18 1992-01-07 Japan Steel Works Ltd:The 高靭性Ｗ―Ｎｉ―Ｆｅ焼結合金の製造方法
JPH0436436A (ja) * 1990-05-31 1992-02-06 Nippon Yakin Kogyo Co Ltd 高靭性タングステン焼結合金
JPH0436428A (ja) * 1990-05-31 1992-02-06 Nippon Yakin Kogyo Co Ltd 高靭性タングステン焼結合金の製造方法
JPH0436437A (ja) * 1990-05-31 1992-02-06 Nippon Yakin Kogyo Co Ltd 高靭性タングステン焼結合金
JPH05263163A (ja) * 1992-03-18 1993-10-12 Japan Steel Works Ltd:The Ｗ−Ｎｉ −Ｆｅ 焼結合金の製造方法
JPH06192804A (ja) * 1992-08-06 1994-07-12 Hosan:Kk タングステン基合金の熱処理方法
JPH06316706A (ja) * 1993-04-30 1994-11-15 Japan Steel Works Ltd:The 高強度Ｗ−Ｎｉ−Ｆｅ合金焼結体の製造方法
JPH0971828A (ja) 1995-08-31 1997-03-18 Toho Kinzoku Kk 放射線遮蔽用タングステン基合金材料
JPH09235641A (ja) 1996-02-28 1997-09-09 Toho Kinzoku Kk タングステン重合金板及びその製法
JPH10219414A (ja) * 1997-02-03 1998-08-18 Japan Steel Works Ltd:The 高強度高延性タングステン合金の製造方法
JP2002030372A (ja) * 2000-07-12 2002-01-31 Allied Material Corp 薄物・異形状超重合金板及びその製造方法
JP2005163112A (ja) * 2003-12-02 2005-06-23 Nippon Paint Co Ltd 重合金シート、塗装重合金シート及び重合金シートの製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3254995A (en) * 1962-04-13 1966-06-07 Powder Alloys Corp Heavy metal alloys
US4332617A (en) * 1979-09-18 1982-06-01 The United States Of America As Represented By The United States Department Of Energy Method of fabricating thin-walled articles of tungsten-nickel-iron alloy
DE3446334A1 (de) * 1984-12-19 1986-06-19 Philips Patentverwaltung Gmbh, 2000 Hamburg Verfahren zur herstellung von <111>-vorzugsorientiertem wolfram
US4749410A (en) * 1985-07-10 1988-06-07 Gte Products Corporation Elongated tungsten heavy metal aritcle and method for producing same
US4801330A (en) * 1987-05-12 1989-01-31 Rensselaer Polytechnic Institute High strength, high hardness tungsten heavy alloys with molybdenum additions and method
US4851042A (en) * 1987-05-12 1989-07-25 Rensselaer Polytechnic Institute Hardness and strength of heavy alloys by addition of tantalum
US4743512A (en) * 1987-06-30 1988-05-10 Carpenter Technology Corporation Method of manufacturing flat forms from metal powder and product formed therefrom
US4768365A (en) * 1987-11-23 1988-09-06 Gte Products Corporation Process for producing tungsten heavy alloy sheet
JPH02259053A (ja) * 1989-03-31 1990-10-19 Mitsubishi Metal Corp 硬質タングステン基焼結合金部材の製造法
JP2819906B2 (ja) * 1991-12-27 1998-11-05 住友金属工業株式会社 室温および高温強度に優れた工具用Ｎｉ基合金
DE19824078C2 (de) * 1998-05-29 2001-05-31 Zinser Textilmaschinen Gmbh Verfahren beim Herstellen von verdichtetem Garn und Einrichtung hierfür
US6136105A (en) * 1998-06-12 2000-10-24 Lockheed Martin Corporation Process for imparting high strength, ductility, and toughness to tungsten heavy alloy (WHA) materials
CN101473054B (zh) * 2006-06-22 2012-07-04 H.C.施塔克有限公司 制备成型的耐火金属主体的方法
CN100582267C (zh) * 2008-02-22 2010-01-20 中南大学 一种含稀土的细晶W-Ni-Fe合金的制备方法

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5237503A (en) * 1975-09-18 1977-03-23 Us Government Method of producing articles made of tungstennnickell iron alloy
JPH01142048A (ja) * 1987-10-23 1989-06-02 Cime Bocuze:Soc 極めて高い機械的特性値をもつタングステン―ニツケル―鉄重合金及びかかる合金の製造方法
JPH02122026A (ja) * 1988-10-31 1990-05-09 Nippon Yakin Kogyo Co Ltd タングステン焼結合金の製造方法
JPH02122048A (ja) * 1988-10-31 1990-05-09 Nippon Yakin Kogyo Co Ltd 低温で高延性を有するタングステン焼結合金
JPH03173738A (ja) * 1989-11-30 1991-07-29 Nippon Yakin Kogyo Co Ltd 高強度，高靭性タングステン焼結合金
JPH03173727A (ja) * 1989-11-30 1991-07-29 Nippon Yakin Kogyo Co Ltd タングステン焼結合金の製造方法
JPH03226541A (ja) * 1990-01-30 1991-10-07 Mitsubishi Materials Corp パッケージ型半導体装置の高強度放熱性構造部材
JPH042736A (ja) * 1990-04-18 1992-01-07 Japan Steel Works Ltd:The 高靭性Ｗ―Ｎｉ―Ｆｅ焼結合金の製造方法
JPH0436436A (ja) * 1990-05-31 1992-02-06 Nippon Yakin Kogyo Co Ltd 高靭性タングステン焼結合金
JPH0436428A (ja) * 1990-05-31 1992-02-06 Nippon Yakin Kogyo Co Ltd 高靭性タングステン焼結合金の製造方法
JPH0436437A (ja) * 1990-05-31 1992-02-06 Nippon Yakin Kogyo Co Ltd 高靭性タングステン焼結合金
JPH05263163A (ja) * 1992-03-18 1993-10-12 Japan Steel Works Ltd:The Ｗ−Ｎｉ −Ｆｅ 焼結合金の製造方法
JPH06192804A (ja) * 1992-08-06 1994-07-12 Hosan:Kk タングステン基合金の熱処理方法
JPH06316706A (ja) * 1993-04-30 1994-11-15 Japan Steel Works Ltd:The 高強度Ｗ−Ｎｉ−Ｆｅ合金焼結体の製造方法
JPH0971828A (ja) 1995-08-31 1997-03-18 Toho Kinzoku Kk 放射線遮蔽用タングステン基合金材料
JPH09235641A (ja) 1996-02-28 1997-09-09 Toho Kinzoku Kk タングステン重合金板及びその製法
JPH10219414A (ja) * 1997-02-03 1998-08-18 Japan Steel Works Ltd:The 高強度高延性タングステン合金の製造方法
JP2002030372A (ja) * 2000-07-12 2002-01-31 Allied Material Corp 薄物・異形状超重合金板及びその製造方法
JP2005163112A (ja) * 2003-12-02 2005-06-23 Nippon Paint Co Ltd 重合金シート、塗装重合金シート及び重合金シートの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2789708A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115341125A (zh) * 2022-08-12 2022-11-15 广州市华司特合金制品有限公司 一种钨合金医疗屏蔽板及其制备方法

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