WO2013084749A1 - Sintered tungsten alloy - Google Patents
Sintered tungsten alloy Download PDFInfo
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- 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
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- tungsten sintered
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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
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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
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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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
- 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
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- 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
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- 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
Description
タングステン粉末と、ニッケル粉末と、鉄、銅およびコバルトからなる群より選ばれた少なくとも1種の金属粉末とを準備する。原料は、タングステン粉末を85質量%以上98質量%以下、ニッケルを1.4質量%以上11質量%以下、鉄、銅およびコバルトからなる群より選ばれた少なくとも1種の金属粉末を0.6質量%以上6質量%以下の配合割合で含むように原料を準備する。 (1) 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.
上記で準備したタングステン粉末と、ニッケル粉末と、鉄、銅およびコバルトからなる群より選ばれた少なくとも1種の金属粉末とを混合して混合物を得る。混合は、レディゲミキサー、アトライター、ボールミル等を用いて行うことができる。混合時に溶媒とバインダを原料粉末に添加してもよい。バインダとしては、カンファ、メルボール、ステアリン酸、パラフィン等を用いることができる。溶媒としては、エタノール、メタノール、アセトン等を用いることができる。 (2) Mixing step 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. As 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.
上記で得られた混合物に圧力を加えて成形して成形体を得る。冷間等方圧プレス(CIP)、ドライCIP、機械プレス等を用いて混合物に圧力を加える。成形時に加えられる圧力は、49MPa以上294MPa未満であることが好ましい。圧力が49MPa未満であると、成形体を得ることができない恐れがあり、成形体を得ることができても成形体のハンドリングや後工程で成形体が破損する恐れがある。圧力を294MPa以上に高くしても問題がないが、成形体を得るための作用を増大させることはない。 (3) 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. 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.
上記で得られた成形体を焼結して焼結体を得る。成形体を焼結するための雰囲気としては、水素ガス、真空、または、不活性ガスの雰囲気を用いることができる。成形体を収容する焼結炉としては、バッチ炉、連続プッシャー炉等を用いることができる。 (4) Sintering step The molded body obtained above is sintered to obtain a sintered body. As 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.
上記で得られた焼結体(タングステン焼結合金)に歪みを導入する。たとえば、平板状の焼結体を厚み方向に20%以上50%以下の変形率で変形させることによって、焼結体に歪みを導入することが好ましい。変形率が20%未満であると、焼結体に導入される歪みの量が不十分であるため、後工程で熱処理を行っても微細な結晶粒を形成することができない恐れがある。変形率が50%を超えると、焼結体が割れてしまう恐れがある。 (5) Strain introduction step Strain is introduced into the sintered body (tungsten sintered alloy) obtained above. For example, it is preferable to introduce strain into the sintered body by deforming the flat sintered body in the thickness direction at a deformation rate of 20% to 50%. If the deformation rate is less than 20%, the amount of strain introduced into the sintered body is insufficient, so that fine crystal grains may not be formed even if heat treatment is performed in a subsequent process. If the deformation rate exceeds 50%, the sintered body may be broken.
上記で歪みが導入された焼結体(タングステン焼結合金)を熱処理する。この熱処理により、焼結体に導入された歪みを適度に回復させて、タングステン結晶粒を微細化する。 (6) Heat treatment step The sintered body (tungsten sintered alloy) in which strain is introduced as described above is heat treated. By this heat treatment, the strain introduced into the sintered body is appropriately recovered and the tungsten crystal grains are refined.
上記で熱処理された焼結体(タングステン焼結合金)を加熱した状態で、60%以上の圧延加工率で圧延加工する。焼結体を加熱するための雰囲気としては、水素ガス、窒素ガス、アルゴンガス等の雰囲気を用いることができる。 (7) 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. As an atmosphere for heating the sintered body, an atmosphere of hydrogen gas, nitrogen gas, argon gas, or the like can be used.
上記で熱間圧延加工された焼結体(タングステン焼結合金)を熱処理する。この熱処理により、タングステン結晶粒とバインダとの界面やバインダ中に存在する欠陥をほぼ消滅させることができ、タングステン結晶粒がバインダ成分中を滑りやすくなる。その結果、タングステン焼結合金の伸びが向上する。 (8) Heat treatment step The sintered body (tungsten sintered alloy) hot-rolled as described above is heat treated. By this heat treatment, the defects present in the interface between the tungsten crystal grains and the binder and in the binder can be almost eliminated, and the tungsten crystal grains easily slip in the binder component. As a result, the elongation of the tungsten sintered alloy is improved.
本実施例では、上述の本発明の中間製造物としての平板状のタングステン焼結合金を作製した。すなわち、上記の(1)~(7)の工程を行うことによって平板状のタングステン焼結合金を作製した。 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).
熱間圧延工程後の熱処理工程において熱処理温度を1300℃にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は21μm程度であった。 (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 μm.
熱間圧延工程後の熱処理工程において熱処理温度を1550℃にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は43μm程度であった。 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 μm.
熱間圧延工程後の熱処理工程において熱処理時間を10分間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は25μm程度であった。 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 μm.
熱間圧延工程後の熱処理工程において熱処理時間を3時間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は39μm程度であった。 (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 μm.
熱間圧延工程後の熱処理工程において熱処理時間を5時間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は57μm程度であった。 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 μm.
歪導入工程において厚み方向に20%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程後の熱処理工程において熱処理温度を1500℃にしたこと以外は、実施例1と同様にして、厚みが1.1mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は19μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は39μm程度であった。 (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. In the same manner as in Example 1, a flat tungsten sintered alloy having a thickness of 1.1 mm was produced. 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 19 μm. 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 39 μm.
歪導入工程において厚み方向に40%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程後の熱処理工程において熱処理温度を1500℃にしたこと以外は、実施例1と同様にして、厚みが0.9mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は10μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は38μm程度であった。 (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. In the same manner as in Example 1, a flat tungsten sintered alloy having a thickness of 0.9 mm 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 μm. 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 38 μm.
歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程後の熱処理工程において熱処理温度を1500℃にしたこと以外は、実施例1と同様にして、厚みが0.7mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は39μm程度であった。 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. In the same manner as in Example 1, a flat tungsten sintered alloy having a thickness of 0.7 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 μm. 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 39 μm.
熱間圧延工程において合計の圧延加工率が60%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが2.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は39μm程度であった。 (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 μm.
熱間圧延工程において合計の圧延加工率が70%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが1.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は36μm程度であった。 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 μm.
熱間圧延工程において、合計の圧延加工率が85%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが0.7mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は37μm程度であった。 (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 μm.
熱間圧延工程において合計の圧延加工率が90%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は37μm程度であった。 (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 μm.
焼結工程で得られた焼結体の厚みを14mmにしたことと、熱間圧延工程において合計の圧延加工率が95%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は39μm程度であった。 (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 μm.
焼結工程で得られた焼結体の厚みを20mmにしたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が95%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は23μm程度であった。 (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. 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 μm. 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 μm.
焼結工程で得られた焼結体の厚みを20mmにしたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が95%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1450℃にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は37μm程度であった。 (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 μm. 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 μm.
焼結工程で得られた焼結体の厚みを20mmにしたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が95%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1550℃にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は47μm程度であった。 (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 μm. 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 μm.
原料準備工程において平均粒径が1μmのタングステン粉末を用い、鉄粉末の代わりに銅粉末を用いたことと、歪導入工程において厚み方向に20%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が60%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃にしたこと以外は、実施例1と同様にして、厚みが2.2mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は19μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は21μm程度であった。 (Example 18)
Using tungsten powder with an average particle diameter of 1 μm 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. 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 19 μm. 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 μm.
原料準備工程において平均粒径が5μmのタングステン粉末を用い、鉄粉末の代わりに銅粉末を用いたことと、歪導入工程において厚み方向に20%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が70%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃にしたこと以外は、実施例1と同様にして、厚みが1.7mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は19μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は23μm程度であった。 (Example 19)
Using tungsten powder with an average particle size of 5 μm 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. 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 19 μm. 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 μm.
原料準備工程において平均粒径が10μmのタングステン粉末を用い、鉄粉末の代わりに銅粉末を用いたことと、歪導入工程において厚み方向に20%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が90%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃にしたこと以外は、実施例1と同様にして、厚みが0.7mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は19μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は22μm程度であった。 (Example 20)
Using tungsten powder with an average particle size of 10 μm 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. 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 19 μm. 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 μm.
原料準備工程においてタングステン粉末を85質量%、ニッケル粉末を10.5質量%、鉄粉末を4.5質量%の配合割合で含むように準備したこと、熱間圧延工程において合計の圧延加工率が90%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃、熱処理時間を3時間にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は9μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は24μm程度であった。 (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. 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 9 μm. 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 24 μm.
原料準備工程においてタングステン粉末を90質量%、ニッケル粉末を7質量%、鉄粉末を3質量%の配合割合で含むように準備したこと、熱間圧延工程において合計の圧延加工率が90%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃、熱処理時間を3時間にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は10μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は24μm程度であった。 (Example 22)
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 flat plate having a thickness of 0.5 mm in the same manner as in Example 1 except that the rolling process was performed until 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 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 μm. 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 24 μm.
原料準備工程においてタングステン粉末を98質量%、ニッケル粉末を1.4質量%、鉄粉末を0.6質量%の配合割合で含むように準備したこと、熱間圧延工程において合計の圧延加工率が90%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃、熱処理時間を3時間にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は10μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は26μm程度であった。 (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 μm. 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 μm.
原料準備工程において平均粒径が1μmのニッケル粉末を用い、鉄粉末の代わりにコバルト粉末を用いたことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃、熱処理時間を5時間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は11μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は28μm程度であった。 (Example 24)
Nickel powder with an average particle size of 1 μm 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. 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 11 μm. 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 28 μm.
原料準備工程において平均粒径が5μmのニッケル粉末を用い、鉄粉末の代わりにコバルト粉末を用いたことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃、熱処理時間を5時間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は10μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は30μm程度であった。 (Example 25)
Nickel powder having an average particle size of 5 μm 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 μm. 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 μm.
原料準備工程において平均粒径が10μmのニッケル粉末を用い、鉄粉末の代わりにコバルト粉末を用いたことと、熱間圧延工程後の熱処理工程において熱処理温度を1300℃、熱処理時間を5時間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は10μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は27μm程度であった。 (Example 26)
Nickel powder having an average particle size of 10 μm 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 μm. 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 μm.
原料準備工程において平均粒径が1μmの鉄粉末を用いたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が60%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は32μm程度であった。 (Example 27)
The use of iron powder having an average particle size of 1 μm 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. 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 μm. 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 32 μm.
原料準備工程において平均粒径が5μmの鉄粉末を用いたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が60%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は35μm程度であった。 (Example 28)
The use of iron powder having an average particle size of 5 μm 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. 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 μm. 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 35 μm.
原料準備工程において平均粒径が10μmの鉄粉末を用いたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が60%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は33μm程度であった。 (Example 29)
The use of iron powder having an average particle size of 10 μm 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. 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 μm. Moreover, 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 33 μm.
上記の(1)~(4)の工程を行うことによって作製された従来のタングステン焼結合金を、研削と研磨により、厚みが1mmになるまで加工した。 (Comparative Example 1)
A conventional tungsten sintered alloy produced by performing the above steps (1) to (4) was processed to a thickness of 1 mm by grinding and polishing.
上記の(1)~(4)の工程を行うことによって作製された従来のタングステン焼結合金に対して、(5)(6)の工程を行わずに、焼結直後に圧延加工率が60%になるまで(厚みが2mmになるまで)(7)の熱間圧延工程を行った。その後、圧延加工されたタングステン焼結合金を、研削と研磨により、厚みが1mmになるまで加工した。 (Comparative Example 2)
With respect to the conventional tungsten sintered alloy produced by performing the above steps (1) to (4), the rolling processing rate is 60 immediately after sintering without performing the steps (5) and (6). The hot rolling process of (7) was performed until the content became% (until the thickness became 2 mm). Then, the rolled tungsten sintered alloy was processed by grinding and polishing until the thickness became 1 mm.
熱間圧延工程後の熱処理工程において熱処理温度を1200℃にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は18μm程度であった。 (Comparative 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 μm.
熱間圧延工程後の熱処理工程において熱処理温度を1600℃にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製することを試みたが、平板状のタングステン焼結合金が溶融した。 (Comparative Example 4)
Except that the heat treatment temperature was 1600 ° C. in the heat treatment step after the hot rolling step, an attempt was made to produce a flat plate-like tungsten sintered alloy having a thickness of 1.0 mm in the same manner as in Example 1. The flat tungsten sintered alloy melted.
熱間圧延工程後の熱処理工程において熱処理時間を6分間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は17μm程度であった。 (Comparative 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 μm.
熱間圧延工程後の熱処理工程において熱処理時間を6時間にしたこと以外は、実施例1と同様にして、厚みが1.0mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は64μm程度であった。 (Comparative 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 μm.
歪導入工程において厚み方向に17%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程後の熱処理工程において熱処理温度を1500℃にしたこと以外は、実施例1と同様にして、平板状のタングステン焼結合金を作製することを試みたが、熱間圧延工程後に割れが発生した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は24.3μm程度であった。 (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 μm. .
歪導入工程において厚み方向に60%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程後の熱処理工程において熱処理温度を1500℃にしたこと以外は、実施例1と同様にして、平板状のタングステン焼結合金を作製することを試みたが、歪導入工程において割れが発生した。 (Comparative Example 8)
Except that the strain was introduced into the sintered tungsten alloy by deforming at a deformation rate of 60% 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 in the strain introduction process.
熱間圧延工程において合計の圧延加工率が50%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、厚みが2.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は37μm程度であった。 (Comparative 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 μm.
熱間圧延工程において合計の圧延加工率が97%になるまで圧延加工を行ったこと以外は、実施例1と同様にして、平板状のタングステン焼結合金を作製することを試みたが、熱間圧延工程後に割れが発生した。 (Comparative Example 10)
An attempt was made to produce a flat tungsten sintered alloy in the same manner as in Example 1 except that the rolling process was performed until the total rolling ratio reached 97% in the hot rolling process. Cracks occurred after the hot rolling process.
焼結工程で得られた焼結体の厚みを20mmにしたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が95%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1200℃にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。また、実施例1と同様にして、最終製造物としての平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は17μm程度であった。 (Comparative 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 μm. 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 μm.
焼結工程で得られた焼結体の厚みを20mmにしたことと、歪導入工程において厚み方向に50%の変形率で変形させることによってタングステン焼結合金に歪みを導入したことと、熱間圧延工程において合計の圧延加工率が95%になるまで圧延加工を行ったことと、熱間圧延工程後の熱処理工程において熱処理温度を1600℃にしたこと以外は、実施例1と同様にして、厚みが0.5mmの平板状のタングステン焼結合金を作製することを試みたが、平板状のタングステン焼結合金が溶融した。なお、実施例1と同様にして、歪導入工程後の熱処理後の平板状のタングステン焼結合金の断面を光学顕微鏡で観察したところ、タングステン結晶粒の平均粒径は5μm程度であった。 (Comparative 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 μm.
上記の実施例1における(1)~(4)の工程を行うことによって作製された従来のタングステン焼結合金に対して、焼結直後に圧延加工率が65%になるまで(7)の熱間圧延工程を行った場合には、タングステン焼結合金に割れが発生した。 (Comparative Example 13)
With respect to the conventional tungsten sintered alloy produced by performing the steps (1) to (4) in Example 1, the heat of (7) is applied until the rolling rate reaches 65% immediately after sintering. When the hot rolling process was performed, cracks occurred in the tungsten sintered alloy.
図5に示すように、実施例1~29と比較例1~6、9、11、12の中間製造物として得られた平板状のタングステン焼結合金1の平面100が延在する方向と直交する厚みT0(1mm)の方向に沿った第1の断面101と、平板状のタングステン焼結合金1の平面100が延在する方向と直交する厚みT0の方向に沿った断面であって第1の断面と直交する第2の断面102とを、走査型電子顕微鏡(SEM)で観察した。 (Measurement of average thickness and average length of tungsten crystal grains)
As shown in FIG. 5, the
実施例1~29と比較例1~3、5、6、9、11、12で最終製造物として得られた平板状のタングステン焼結合金から、図8に示すように厚みTの引張試験片10を作製した。標点間距離は、中心線20を中心にして8mmとした。 (Measurement of elongation of tungsten sintered alloy)
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
実施例1~29と比較例1~3、5、6、9、11、12で最終製造物として得られた平板状のタングステン焼結合金から、厚みが0.5mmで8mm×8mmの平面を有する試験片を作製した。 (Measurement of X-ray diffraction intensity ratio of (111) plane of Ni- (Fe, Cu, Co) phase)
From a flat plate-like 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, a flat surface having a thickness of 0.5 mm and 8 mm × 8 mm was obtained. A test piece was prepared.
1: tungsten sintered alloy, 100: plane, 101: first cross section, 101a: first cross section, 102: second cross section, 102a: second cross section, 200: center line, G1 to G4: Tungsten crystal grains, T, T 0 : thickness, W: width, t: thickness, s: length.
Claims (3)
- タングステンを85質量%以上98質量%以下、ニッケルを1.4質量%以上11質量%以下、鉄、銅およびコバルトからなる群より選ばれた少なくとも1種を0.6質量%以上6質量%以下、含む平板状のタングステン焼結合金であって、
当該平板状のタングステン焼結合金の平面方向の伸び率が20%以上である、タングステン焼結合金。 85% by mass to 98% by mass of tungsten, 1.4% by mass to 11% by mass of nickel, and 0.6% by mass to 6% by mass of at least one selected from the group consisting of iron, copper and cobalt A flat plate-like tungsten sintered alloy comprising:
A tungsten sintered alloy in which the flat plate-like tungsten sintered alloy has an elongation in the plane direction of 20% or more. - 当該平板状のタングステン焼結合金の厚みが1.5mm以下である、請求項1に記載のタングステン焼結合金。 The tungsten sintered alloy according to claim 1, wherein the thickness of the flat plate-like tungsten sintered alloy is 1.5 mm or less.
- 当該平板状のタングステン焼結合金の平板面におけるNi-(Fe、Cu、Co)相の(111)面のX線回折強度比(ここで、(111)面、(100)面、(110)面および(311)面のそれぞれのX線回折強度をI(111)、I(100)、I(110)、I(311)とすると、(111)面のX線回折強度比は[I(111)/{I(111)+I(100)+I(110)+I(311)}]の値である)が0.68以上0.9以下である、請求項1に記載のタングステン焼結合金。
X-ray diffraction intensity ratio of the (111) plane of the Ni— (Fe, Cu, Co) phase on the flat plate surface of the flat plate-like tungsten sintered alloy (where (111) plane, (100) plane, (110) If the X-ray diffraction intensities of the 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)}] is 0.68 or more and 0.9 or less.
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JP5818045B1 (en) * | 2014-12-05 | 2015-11-18 | 株式会社半導体熱研究所 | Heat dissipation board and semiconductor package and semiconductor module using it |
RU2623566C1 (en) * | 2016-09-15 | 2017-06-27 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of manufacture of sintered porous products from tungsten-based pseudoalloy |
CN106756379B (en) * | 2017-01-10 | 2019-01-25 | 广州市华司特合金制品有限公司 | Tungsten alloy barricade and the electronic information card for being provided with tungsten alloy barricade |
CN110172598A (en) * | 2018-12-13 | 2019-08-27 | 苏州赛特锐精密机械配件有限公司 | A kind of method of co-injection preparation bi-component tungsten-copper alloy |
CN111910112B (en) * | 2020-07-01 | 2022-02-11 | 昆山家锐电子科技有限公司 | Tungsten-copper alloy material and preparation method and application thereof |
CN113817944B (en) * | 2021-09-13 | 2022-10-11 | 安泰天龙(北京)钨钼科技有限公司 | High-performance tungsten alloy bar and preparation method thereof |
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JP5847196B2 (en) | 2016-01-20 |
JP5805213B2 (en) | 2015-11-04 |
JPWO2013084749A1 (en) | 2015-04-27 |
EP2789708A1 (en) | 2014-10-15 |
US20140308536A1 (en) | 2014-10-16 |
JPWO2013084748A1 (en) | 2015-04-27 |
EP2789708A4 (en) | 2015-10-14 |
WO2013084748A1 (en) | 2013-06-13 |
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