WO2023135807A1 - 超高圧発生装置用金型 - Google Patents

超高圧発生装置用金型 Download PDF

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Publication number
WO2023135807A1
WO2023135807A1 PCT/JP2022/001397 JP2022001397W WO2023135807A1 WO 2023135807 A1 WO2023135807 A1 WO 2023135807A1 JP 2022001397 W JP2022001397 W JP 2022001397W WO 2023135807 A1 WO2023135807 A1 WO 2023135807A1
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WIPO (PCT)
Prior art keywords
phase
volume
cemented carbide
less
content
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PCT/JP2022/001397
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English (en)
French (fr)
Japanese (ja)
Inventor
俊佑 山中
英司 山本
和弘 広瀬
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Sumitomo Electric Hardmetal Corp
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Sumitomo Electric Hardmetal Corp
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Application filed by Sumitomo Electric Hardmetal Corp filed Critical Sumitomo Electric Hardmetal Corp
Priority to JP2022540560A priority Critical patent/JP7540131B2/ja
Priority to US18/714,137 priority patent/US20250033309A1/en
Priority to PCT/JP2022/001397 priority patent/WO2023135807A1/ja
Priority to CN202280085075.7A priority patent/CN118451209A/zh
Priority to EP22920332.8A priority patent/EP4467260A4/en
Publication of WO2023135807A1 publication Critical patent/WO2023135807A1/ja
Priority to JP2023140801A priority patent/JP2023175721A/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B15/00—Details of, or accessories for, presses; Auxiliary measures in connection with pressing
    • B30B15/02—Dies; Inserts therefor; Mounting thereof; Moulds
    • 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
    • B22F5/007—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
    • B30B11/004—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses involving the use of very high pressures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B15/00—Details of, or accessories for, presses; Auxiliary measures in connection with pressing
    • B30B15/02—Dies; Inserts therefor; Mounting thereof; Moulds
    • B30B15/022—Moulds for compacting material in powder, granular of pasta form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B22F3/164—Partial deformation or calibration
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor

Definitions

  • the present disclosure relates to molds for ultrahigh pressure generators.
  • Tungsten carbide-cobalt (WC-Co) cemented carbide which has excellent mechanical properties, is used for molds for ultra-high pressure generators (for example, Patent Documents 1 and 2).
  • the present disclosure provides a mold for an ultrahigh pressure generator made of cemented carbide,
  • the cemented carbide has a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt, Vickers hardness of the cemented carbide is 2000Hv or more,
  • the cemented carbide has a bending strength of 2.3 GPa or more,
  • the mold for the ultrahigh pressure generator has a truncation surface,
  • the mold for an ultrahigh pressure generator, wherein the compressive residual stress of the truncation surface is 1.50 GPa or more.
  • FIG. 1 is a schematic diagram showing an example of a mold for an ultrahigh pressure generator according to Embodiment 1.
  • FIG. FIG. 2 is a schematic diagram showing another example of the mold for an ultrahigh pressure generator according to Embodiment 1.
  • FIG. FIG. 3 is a schematic diagram showing another example of the mold for an ultrahigh pressure generator according to Embodiment 1.
  • a very high pressure of up to about 20 GPa is applied to the mold for the ultra-high pressure generator when the ultra-high pressure generator is used. Under such an ultrahigh pressure, the mold for the ultrahigh pressure generator tends to be damaged, and the life of the mold for the ultrahigh pressure generator tends to be shortened. Therefore, there is a demand for a mold for an ultrahigh pressure generator that has a long life even when used under ultrahigh pressure.
  • the ultra-high pressure generator mold of the present disclosure can have a long life even when used under ultra-high pressure.
  • the present disclosure provides a mold for an ultra-high pressure generator made of cemented carbide,
  • the cemented carbide has a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt, Vickers hardness of the cemented carbide is 2000Hv or more,
  • the cemented carbide has a bending strength of 2.3 GPa or more,
  • the mold for the ultrahigh pressure generator has a truncation surface,
  • the mold for an ultrahigh pressure generator, wherein the compressive residual stress of the truncation surface is 1.50 GPa or more.
  • the mold for an ultrahigh pressure generator of the present disclosure can have a long life even when used under ultrahigh pressure.
  • the content of cobalt in the cemented carbide is preferably 3.0% by mass or more and 8.0% by mass or less. According to this, the life of the mold for the ultra-high pressure generator is further extended.
  • the average particle size of the tungsten carbide particles is preferably 0.05 ⁇ m or more and 0.50 ⁇ m or less. According to this, the life of the mold for the ultra-high pressure generator is further extended.
  • a compound or the like when represented by a chemical formula, it includes all conventionally known atomic ratios unless the atomic ratio is particularly limited, and is not necessarily limited only to those within the stoichiometric range.
  • Embodiment 1 Mold for ultra-high pressure generator
  • This embodiment is a mold for an ultrahigh pressure generator made of cemented carbide,
  • the cemented carbide comprises a first phase consisting of a plurality of tungsten carbide grains and a second phase comprising cobalt,
  • the cemented carbide has a Vickers hardness of 2000 Hv or more,
  • the cemented carbide has a bending strength of 2.3 GPa or more
  • the ultra-high pressure generator mold has a truncation surface,
  • the compressive residual stress of the truncation surface is 1.50 GPa or more, which is a mold for an ultrahigh pressure generator.
  • Examples of the mold for the ultrahigh pressure generator of the present embodiment include anvils used for multi-anvil type high pressure generators and anvils used for belt type high pressure devices.
  • a multi-anvil type high pressure generator has a structure in which four or more anvils are synchronously driven to isotropically compress the sample.
  • An example of the anvil is shown in FIGS. 1 and 2.
  • FIG. 1 An example of the anvil is shown in FIGS. 1 and 2.
  • FIG. 1 is a schematic diagram showing an example of an anvil used in a high pressure generator using eight cubic anvils.
  • the anvil 1 in FIG. 1 has a shape in which one of the vertexes of a cube is shaved off, and the shaved surface forms a truncation surface 2 of an equilateral triangle.
  • FIG. 2 is a schematic diagram showing an example of an anvil used in a cubic anvil high pressure generator using six anvils.
  • the anvil 1 of FIG. 2 has a square truncation surface 2 .
  • the belt-type high-pressure generator has a structure in which the sample is placed in a cylinder and pressed by the opposing anvil.
  • An example of the anvil is shown in FIG.
  • the anvil 1 is frusto-conical.
  • the upper surface of the truncated cone corresponds to the truncation surface 2 .
  • the truncation surface means the surface of the mold that applies pressure to the workpiece.
  • the shape of the mold for ultra-high pressure generator and the shape of the truncation surface of this embodiment are not limited to the shapes shown in FIGS. 1 to 3, and may be any conventionally known shapes.
  • the cemented carbide forming the mold for the ultrahigh pressure generator of this embodiment comprises a first phase composed of a plurality of tungsten carbide particles and a second phase containing cobalt.
  • the first phase of the cemented carbide consists of a plurality of tungsten carbide grains (hereinafter also referred to as "WC grains").
  • the first phase corresponds to the hard phase.
  • the tungsten carbide particles of the first phase can contain unavoidable impurity elements and trace impurity elements that are mixed in the manufacturing process of WC particles, etc., as long as the effects of the present disclosure are exhibited.
  • Molybdenum (Mo) and chromium (Cr) are examples of the above inevitable impurity elements and impurity elements (hereinafter collectively referred to as "first impurity elements").
  • the content of the first impurity element in the first phase (the total content when there are two or more impurity elements) is preferably less than 0.1% by mass.
  • the content of the first impurity element in the first phase is measured by ICP (Inductively Coupled Plasma) emission spectrometry (measuring device: "ICPS-8100" (trademark) manufactured by Shimadzu Corporation).
  • the first phase preferably consists of a plurality of tungsten carbide particles, and the content of the first impurity element in the first phase is less than 0.1% by mass.
  • the first phase consists of a plurality of tungsten carbide particles, the content of tungsten carbide in the first phase is more than 99.9% by mass, and the content of the first impurity element in the first phase is less than 0.1% by mass. is preferred.
  • the first phase consists of a plurality of tungsten carbide particles, the content of tungsten carbide in the first phase is more than 99.9% by mass and not more than 100% by mass, and the content of the first impurity element in the first phase is 0% by mass. % or more and less than 0.1% by mass.
  • the average particle size of tungsten carbide particles is preferably 0.05 ⁇ m or more and 0.50 ⁇ m or less. According to this, the hardness of the cemented carbide is improved, and the life of the mold for the ultra-high pressure generator is improved.
  • the average grain size of tungsten carbide grains means the number-based arithmetic mean diameter of equivalent circle diameters of tungsten carbide grains observed in a cross section of a cemented carbide.
  • the lower limit of the average particle diameter of the tungsten carbide particles is preferably 0.05 ⁇ m or more, more preferably 0.10 ⁇ m or more, from the viewpoint of production feasibility.
  • the upper limit of the average particle size of the tungsten carbide particles is preferably 0.50 ⁇ m or less, more preferably 0.4 ⁇ m or less, and even more preferably 0.3 ⁇ m or less.
  • the average particle size of the tungsten carbide particles is preferably 0.05 ⁇ m or more and 0.50 ⁇ m or less, preferably 0.05 ⁇ m or more and 0.40 ⁇ m or less, preferably 0.05 ⁇ m or more and 0.30 ⁇ m or less, and 0.10 ⁇ m or more and 0.50 ⁇ m or less. is preferably 0.10 ⁇ m or more and 0.40 ⁇ m or less, and 0.110 ⁇ m or more and 0.30 ⁇ m or less is preferable.
  • the average particle size of the WC particles is measured by the following procedure.
  • a sample having a smooth cross section is obtained by subjecting the cemented carbide to CP (Cross Section Polisher) processing using an argon ion beam or the like.
  • CP Cross Section Polisher
  • reflected electrons of the cross section An image (SEM-BSE image) is obtained.
  • the imaging conditions are an imaging magnification of 5000 times, an acceleration voltage of 5 kV, and a work distance of 10.0 mm.
  • a measurement field of 1 mm 2 (1 mm ⁇ 1 mm rectangle) is arbitrarily set in the backscattered electron image. Identify the outer edge of each WC particle in the measurement field with image analysis software (ImageJ ver.1.51j8 (https://imagej.nih.gov/ij/)) and calculate the equivalent circle diameter of each WC particle. .
  • the number-based arithmetic mean diameter of the circle-equivalent diameters of all the WC particles in the measurement field is defined as the average particle diameter of the WC particles in the measurement field.
  • the above measurements are performed at five different measurement fields. An average value of the average particle diameters of the WC particles in the five measurement fields is calculated. This average value corresponds to the average particle size of the WC particles in this embodiment.
  • the second phase of the cemented carbide comprises cobalt (Co).
  • the second phase corresponds to the binder phase.
  • the second phase may contain chromium (Cr), vanadium (V), unavoidable impurity elements, and the like.
  • the unavoidable impurity element include iron (Fe), nickel (Ni), manganese (Mn), magnesium (Mg), calcium (Ca), molybdenum (Mo ), sulfur (S), titanium (Ti), and aluminum (Al).
  • the cobalt content of the second phase is preferably more than 99% by mass and 100% by mass or less.
  • the total content of chromium, vanadium and the second impurity element in the second phase is preferably 0% by mass or more and less than 1% by mass.
  • the total content of chromium, vanadium and the second impurity element in the second phase is measured by ICP (Inductively Coupled Plasma) emission spectrometry (measuring device: "ICPS-8100" (trademark) manufactured by Shimadzu Corporation).
  • the second phase consists of cobalt and at least one selected from the group consisting of chromium, vanadium, and second impurity elements, and the total content of chromium, vanadium, and second impurity elements in the second phase is less than 1% by mass. is preferred.
  • the second phase consists of cobalt and at least one selected from the group consisting of chromium, vanadium and second impurity elements, the cobalt content of the second phase is more than 99% by mass, the second phase chromium, The total content of vanadium and the second impurity element is preferably less than 1% by mass.
  • the second phase contains cobalt, the cobalt content of the second phase is more than 99% by mass and 100% by mass or less, and the total content of chromium, vanadium and the second impurity element in the second phase is 0% by mass or more1 It is preferably less than % by mass.
  • the cemented carbide contains other phases (also referred to as "third phase” in this specification) in addition to the first and second phases, as long as the effects of the present disclosure are exhibited. good too.
  • Components that make up the third phase include, for example, Cr 3 C 2 added as a grain growth inhibitor in the manufacturing process of cemented carbide, chromium (Cr) derived from VC, vanadium (V), carbon (C ).
  • the content of the first phase in the cemented carbide is preferably 80.0% by volume or more and 98.0% by volume or less.
  • cemented carbide can have high hardness and high bending strength.
  • the lower limit of the content of the first phase in the cemented carbide is preferably 81.0% by volume or more, more preferably 82.0% by volume or more, and 83.0% by volume or more. More preferred.
  • the upper limit of the content of the first phase in the cemented carbide is preferably 97.0% by volume or less, more preferably 96.0% by volume or less, and 95.0% by volume. More preferred are:
  • the content of the first phase in the cemented carbide is preferably 81.0% by volume or more and 97.0% by volume or less, more preferably 82.0% by volume or more and 96.0% by volume or less, and 83.0% by volume or more and 95% by volume. 0 vol % or less is more preferable.
  • the content of the second phase in the cemented carbide is preferably 2.0% by volume or more and 20.0% by volume or less.
  • cemented carbide can have high hardness and high bending strength.
  • the lower limit of the content of the second phase in the cemented carbide is preferably 3.0% by volume or more, more preferably 4.0% by volume or more, and 5.0% by volume. The above is more preferable.
  • the upper limit of the content of the second phase in the cemented carbide is preferably 19.0% by volume or less, more preferably 18.0% by volume or less, and 17.0% by volume or less. More preferred.
  • the content of the second phase in the cemented carbide is preferably 3.0% by volume or more and 19.0% by volume or less, more preferably 4.0% by volume or more and 18.0% by volume or less, and 5.0% by volume or more and 17 0 vol % or less is more preferable.
  • the cemented carbide contains the first phase and the second phase
  • the content of the first phase of the cemented carbide is 80.0% by volume or more and 98.0% by volume or less
  • the content of the second phase The ratio is preferably 2.0% by volume or more and 20.0% by volume or less
  • the content of the first phase is 81.0% by volume or more and 97.0% by volume or less
  • the content of the second phase is 3% by volume. It is more preferably 0% by volume or more and 19.0% by volume or less
  • the content of the first phase is 82.0% by volume or more and 96.0% by volume or less
  • the content of the second phase is 4.0% by volume or more. More preferably, it is vol % or more and 18.0 vol % or less.
  • the cemented carbide consists of a first phase and a second phase
  • the content of the first phase in the cemented carbide is 80.0% by volume or more and 98.0% by volume or less
  • the content of the second phase is The content is preferably 2.0% by volume or more and 20.0% by volume or less
  • the content of the first phase is 81.0% by volume or more and 97.0% by volume or less
  • the content of the second phase is It is more preferably 3.0% by volume or more and 19.0% by volume or less
  • the content of the first phase is 82.0% by volume or more and 96.0% by volume or less
  • the content of the second phase is 4.0% by volume or more. More preferably, it is 0% by volume or more and 18.0% by volume or less.
  • the cemented carbide consists of a first phase, a second phase, and unavoidable impurities, and the content of the first phase in the cemented carbide is 80.0% by volume or more and 98.0% by volume or less.
  • the content of the two phases is preferably 2.0% by volume or more and 20.0% by volume or less
  • the content of the first phase is 81.0% by volume or more and 97.0% by volume or less
  • the content of the second phase is More preferably, the content is 3.0% by volume or more and 19.0% by volume or less
  • the content of the first phase is 82.0% by volume or more and 96.0% by volume or less
  • the content of the second phase is is more preferably 4.0% by volume or more and 18.0% by volume or less.
  • the content of the third phase in the cemented carbide is 0% by volume or more and 0.5% by volume from the viewpoint of suppressing the occurrence of fracture originating from the third phase and improving the transverse rupture strength of the cemented carbide.
  • 5% by volume or less is preferable, 0% by volume or more and 0.3% by volume or less is more preferable, and 0% by volume is most preferable. That is, it is preferable that the cemented carbide does not contain the third phase and consists of the first phase and the second phase.
  • the cemented carbide includes a first phase, a second phase and a third phase
  • the content of the first phase of the cemented carbide is 80.0% by volume or more and less than 98.0% by volume.
  • the content of the two phases is 2.0% by volume or more and less than 20.0% by volume
  • the content of the third phase is preferably more than 0% by volume and 0.5% by volume or less
  • the content of the first phase is is 80.0% by volume or more and less than 98.0% by volume
  • the content of the second phase is 2.0% by volume or more and less than 20.0% by volume
  • the content of the third phase is more than 0% by volume.
  • the content of the first phase is 80.0 vol% or more and less than 98.0 vol%
  • the content of the second phase is 2.0 vol% or more and 20.0 % by volume
  • the content of the third phase is more preferably more than 0% by volume and 0.1% by volume or less.
  • the cemented carbide is composed of a first phase, a second phase, and a third phase
  • the content of the first phase of the cemented carbide is 80.0% by volume or more and less than 98.0% by volume.
  • the content of the phase is 2.0% by volume or more and less than 20.0% by volume
  • the content of the third phase is preferably more than 0% by volume and 0.5% by volume or less
  • the content of the first phase is 80.0% by volume or more and less than 98.0% by volume
  • the content of the second phase is 2.0% by volume or more and less than 20.0% by volume
  • the content of the third phase is more than 0% by volume.
  • the content of the first phase is 80.0% by volume or more and less than 98.0% by volume
  • the content of the second phase is 2.0% by volume or more and 20.0% by volume %
  • the content of the third phase is more preferably more than 0% by volume and 0.1% by volume or less.
  • the cemented carbide consists of the first phase, the second phase, the third phase, and unavoidable impurities, and the content of the first phase in the cemented carbide is 80.0% by volume or more and less than 98.0% by volume.
  • the content of the second phase is 2.0% by volume or more and less than 20.0% by volume, and the content of the third phase is preferably more than 0% by volume and 0.5% by volume or less, and the first phase
  • the content of is 80.0% by volume or more and less than 98.0% by volume
  • the content of the second phase is 2.0% by volume or more and less than 20.0% by volume
  • the content of the third phase is 0 volume % is more than 0.3% by volume
  • the content of the first phase is 80.0% by volume or more and less than 98.0% by volume
  • the content of the second phase is 2.0% by volume or more. It is less than 20.0% by volume
  • the content of the third phase is more preferably more than 0% by volume and 0.1% by volume or less.
  • the methods for measuring the content of the first phase, the content of the second phase, and the content of the third phase of the cemented carbide are as follows.
  • a sample with a smooth cross section is obtained by CP (Cross Section Polisher) processing of the cemented carbide using an argon ion beam or the like.
  • CP Cross Section Polisher
  • FE-SEM field emission scanning electron microscope
  • JSM-7800F a field emission scanning electron microscope
  • reflected electrons of the cross section An image (SEM-BSE image) is obtained.
  • the imaging conditions are an imaging magnification of 10,000 times, an acceleration voltage of 5 kV, and a work distance of 10.0 mm.
  • the first phase is shown in light gray and the second phase is shown in dark gray.
  • the third phase is indistinguishable from the second phase because it has almost the same color.
  • both the 2nd and 3rd phases are shown in dark gray.
  • a measurement field of 101 ⁇ m 2 (11.88 ⁇ m ⁇ 8.5 ⁇ m rectangle) is set in the backscattered electron image.
  • binarization processing is performed using image analysis software (ImageJ ver.1.51j8 (https://imagej.nih.gov/ij/)).
  • the binarization process is performed in the following procedures (a) to (d) in the initial setting state of the image analysis software.
  • (a) Edit ⁇ Invert (b) After above (a), Process ⁇ Binary ⁇ MakeBinary (c) After the above (b), Process ⁇ Noise ⁇ Despeckle. Repeat (c) three times.
  • the first phase is shown in light gray and the second phase is shown in dark gray. If the cemented carbide contains a tertiary phase, the tertiary phase is shown in dark gray as is the secondary phase. It was confirmed by SEM-EDX (Energy Dispersive X-ray Spectroscopy ) can be confirmed.
  • the image analysis software is used to calculate the sum (total area) of the areas of all the first phases (light gray areas) in the measurement visual field. Calculate the percentage of the total area of the first phase in the measurement field to obtain the area ratio of the first phase in the measurement field.
  • the image analysis software is used to calculate the sum (total area) of the areas of all the second phases (dark gray areas) in the measurement visual field. Calculate the percentage of the total area of the second phase in the measurement field to obtain the area ratio of the second phase in the measurement field.
  • Five measurement fields are arbitrarily set so that there is no overlap in the backscattered electron image, and the area ratio of the second phase is measured in each measurement field.
  • the average value of the area ratio of the second phase in the five measurement fields is calculated.
  • the average value corresponds to the second phase content (% by volume) of the cemented carbide in this embodiment.
  • the contents of the second and third phases are measured and calculated according to the following procedure.
  • Five measurement fields are arbitrarily set so that there is no overlap in the backscattered electron image, and the area ratio of the second phase and the third phase is measured in each measurement field.
  • the average value of the area ratios of the second phase and the third phase in five measurement fields is calculated.
  • the average value corresponds to the total content (% by volume) of the second and third phases of the cemented carbide in this embodiment.
  • the content (% by volume) of the third phase of the cemented carbide is obtained by measuring the solid solution amount of the atoms constituting the third phase in the cobalt constituting the second phase and calculating the amount of precipitation of the atoms. can get.
  • the amount of solid solution in cobalt is 5% for chromium (Cr) and 0.2% for vanadium (V).
  • the content of cobalt in the second phase is assumed to be 100% by mass.
  • the solid solution amount of atoms constituting the third phase in cobalt is measured by the following method. Cemented carbide is pulverized to obtain cemented carbide powder (hereinafter referred to as “measurement sample”).
  • 0.2 g of the sample for measurement is dissolved in 20 ml of a solution in which 35% hydrochloric acid and water are mixed at a volume ratio of 1:1 (220° C. ⁇ 1 h) to obtain a solution.
  • the Cr and V concentrations are analyzed by ICP.
  • the Cr concentration corresponds to the solid solution amount of Cr in cobalt.
  • the concentration of V corresponds to the solid solution amount of V in cobalt.
  • the content rate (% by volume) of the third phase is obtained. be done.
  • the content of cobalt in the cemented carbide is preferably 3.0% by mass or more and 8.0% by mass or less.
  • cemented carbide can have excellent toughness.
  • the lower limit of the cobalt content of the cemented carbide is preferably 3.0% by mass or more, more preferably 4.0% by mass or more, and even more preferably 5.0% by mass or more.
  • the upper limit of the cobalt content of the cemented carbide is preferably 8.0% by mass or less, more preferably 7.5% by mass or less, and even more preferably 7.0% by mass or less.
  • the cobalt content of the cemented carbide is preferably 3.0% by mass or more and 8.0% by mass or less, more preferably 4.0% by mass or more and 7.5% by mass or less. , more preferably 5.0% by mass or more and 7.0% by mass or less.
  • the cobalt content of the above cemented carbide can be obtained by analyzing TAS 0054:2017 by the cobalt potentiometric titration method for cemented carbide.
  • the cemented carbide has a Vickers hardness of 2000 Hv or more. According to this, the life of the mold for the ultra-high pressure generator is improved.
  • the lower limit of the Vickers hardness is 2000 Hv or more, more preferably 2050 Hv or more, and still more preferably 2100 Hv or more, from the viewpoint of improving the life of the mold for an ultrahigh pressure generator.
  • the upper limit of the Vickers hardness is not particularly limited, it can be 3000 Hv or less from the viewpoint of manufacturing.
  • the Vickers hardness of the cemented carbide is preferably from 2000 Hv to 3000 Hv, more preferably from 2050 Hv to 3000 Hv, and more preferably from 2100 Hv to 3000 Hv, from the viewpoint of improving the life of the mold for an ultra-high pressure generator.
  • the method for measuring the Vickers hardness is as follows. By CP (Cross Section Polisher) machining a mold for ultra-high pressure generator made of cemented carbide using an argon ion beam or the like, the mold for ultra-high pressure generator is roughly divided into two parts, exposing a smooth cross-section. Let the central part of this cross section be a measuring point. The central portion of the cross section means a region within 5 mm from the center of gravity of the cross section.
  • the Vickers hardness of the measurement point is measured according to JIS Z 2244:2009 Vickers hardness test-test method. The measurement conditions are room temperature (23° C. ⁇ 5° C.), test load of 294.2 N (30 kgf, Hv30), and holding time of 20 seconds.
  • the bending strength of the cemented carbide is 2.3 GPa or more. According to this, the life of the mold for the ultra-high pressure generator is improved.
  • the lower limit of the bending strength is 2.3 GPa or more, preferably 2.7 GPa or more, and still more preferably 3.0 GPa or more, from the viewpoint of improving the life of the mold for an ultrahigh pressure generator.
  • the upper limit of the bending strength is not particularly limited, it can be 6.0 GPa or less from the viewpoint of manufacturing.
  • the bending strength of the cemented carbide is preferably 2.3 GPa or more and 6.0 GPa or less, more preferably 2.7 GPa or more and 6.0 GPa or less, and 3.0 GPa or more, from the viewpoint of improving the life of the mold for an ultrahigh pressure generator. 6.0 GPa or less is more preferable.
  • the above bending strength is measured according to CIS026B-2007 Cemented Carbide Alloy Bending Strength (Bending Strength) Test Method.
  • the test piece size is 4 mm ⁇ 8 mm ⁇ 25 mm, the load point/fulcrum size is R2.0 mm, and the fulcrum span is 20 mm.
  • the mold 1 for ultrahigh pressure generator has a truncation surface 2, and the compressive residual stress of the truncation surface is 1.50 GPa or more. According to this, the strength of the truncation surface is increased, and the generation of cracks is suppressed, so that the life of the mold for the ultrahigh pressure generator is improved.
  • the lower limit of the compressive residual stress is 1.50 GPa or more, preferably 1.80 GPa or more, and still more preferably 2.00 GPa or more, from the viewpoint of improving the life of the mold for an ultrahigh pressure generator.
  • the upper limit of the compressive residual stress is not particularly limited, it can be 3.00 GPa or less from the viewpoint of manufacturing.
  • the compressive residual stress on the truncation surface of the ultrahigh pressure generator mold is preferably 1.50 GPa or more and 3.00 GPa or less, and 1.80 GPa or more and 3.00 GPa or less, from the viewpoint of improving the life of the ultrahigh pressure generator mold. More preferably, 2.00 GPa or more and 3.00 GPa or less is even more preferable.
  • the compressive residual stress on the truncation surface of the mold for the ultrahigh pressure generator is measured using the cos ⁇ method.
  • the compressive residual stress on the truncation surface is measured by irradiating the truncation surface of the mold for the ultrahigh pressure generator with X-rays and measuring the distortion of the crystal lattice using the diffraction phenomenon.
  • “portable X-ray residual stress measuring device ⁇ -X360s” manufactured by Pulstec Industrial Co., Ltd. can be used.
  • the measurement conditions are as follows.
  • the parameters in the above measuring device are Young's modulus of 534.4 GPa and Poisson's ratio of 0.220.
  • the mold for an ultrahigh pressure generator of this embodiment can be manufactured, for example, by the following method.
  • the mold for an ultrahigh pressure generator of this embodiment may be manufactured by a method other than the method described below.
  • the mold for the ultra-high pressure generator of the present embodiment can be manufactured by performing the raw material powder preparation step, mixing step, molding step, sintering step, cooling step, and compressive residual stress imparting step in the above order. . Each step will be described below.
  • the preparation step is a step of preparing a raw material powder of the cemented carbide.
  • raw material powders tungsten carbide powder as the raw material of the first phase, cobalt (Co) powder as the raw material of the second phase, and chromium carbide (Cr 3 C 2 ) powder and vanadium carbide (VC) as grain growth inhibitors.
  • tungsten carbide powder, cobalt powder, chromium carbide powder, and vanadium carbide powder can be used.
  • the tungsten carbide powder it is preferable to use tungsten carbide powder carbonized at a temperature of 1400°C or higher and 1600°C or lower.
  • the particle size of the tungsten carbide powder is preferably about 0.1 to 0.3 ⁇ m. According to this, the stability of WC grains is increased in the liquid phase appearance stage during sintering, the dissolution and reprecipitation of tungsten carbide are suppressed, the cemented carbide structure is refined, and the hardness and strength are improved.
  • the average particle size of the raw material powder is the average particle size measured by the FSSS (Fisher Sub-Sieve Sizer) method (measuring device: "Fisher Sub-Sieve Sizer Model 95" (trademark) manufactured by Fisher Scientific). means diameter.
  • the average particle size of the cobalt powder can be 0.4 ⁇ m or more and 1.0 ⁇ m or less (FSSS method).
  • the average particle size of the chromium carbide powder can be 0.5 ⁇ m or more and 3 ⁇ m or less (FSSS method).
  • the vanadium carbide powder can have an average particle size of 0.5 ⁇ m or more and 3 ⁇ m or less (FSSS method).
  • the mixing step is a step of mixing each raw material powder prepared in the preparation step.
  • a mixed powder in which each raw material powder is mixed is obtained by the mixing step.
  • the content of the tungsten carbide powder in the mixed powder can be, for example, 89.0% by mass or more and 96.9% by mass or less.
  • the content of cobalt powder in the mixed powder can be, for example, 3.0% by mass or more and 8.0% by mass or less.
  • the content of chromium carbide powder in the mixed powder can be, for example, 0.1% by mass or more and 2.0% by mass or less.
  • the content of the vanadium carbide powder in the mixed powder can be, for example, 0.02% by mass or more and 1.0% by mass or less.
  • the mixed powder is mixed using a ball mill.
  • the media diameter can be 1 mm to 10 mm.
  • the rotation speed can be 10-120 rpm.
  • Mixing time can be from 20 hours to 48 hours.
  • the mixed powder may be granulated as needed.
  • it is easy to fill the mixed powder into a die or mold during the molding process described below.
  • a known granulation method can be applied for granulation, and for example, a commercially available granulator such as a spray dryer can be used.
  • the molding step is a step of molding the mixed powder obtained in the mixing step into a predetermined shape to obtain a compact.
  • General methods and conditions may be adopted for the molding method and molding conditions in the molding step, and are not particularly limited.
  • Examples of the predetermined shape include a cubic shape, a truncated cone, and the like, which are shapes of the anvil.
  • the sintering step is a step of sintering the compact obtained in the forming step to obtain a cemented carbide.
  • the sintering conditions can be a vacuum, a sintering temperature of 1340 to 1450° C., and a sintering time of 30 to 180 minutes. According to this, generation of coarse tungsten carbide particles is suppressed.
  • a HIP treatment hot isostatic pressing method
  • a cooling process is a process of cooling the cemented carbide after completion of sintering.
  • the cooling rate is preferably 2° C./min to 4° C./min. According to this, abnormal grain growth is suppressed.
  • the compressive residual stress imparting step is a step of imparting compressive residual stress to the truncation surface of the high pressure generator mold made of cemented carbide. If the shape of the cemented carbide after the cooling step is a cube or the like and it does not have a truncation plane, one of the vertices is cut off using an electrical discharge machine to form a truncation plane. When the shape of the cemented carbide is a truncated cone, the upper surface corresponds to the truncation surface.
  • the methods of applying compressive residual stress to the truncation surface include grinding, shot blasting, and shot peening of the truncation surface.
  • a diamond grindstone (for example, #200) is used to grind the truncation surface at an ultra-high speed under conditions of a depth of cut of 6 ⁇ m or more and a feed rate of 400 mm/min or more. Thereby, a compressive residual stress of 1.50 GPa or more can be applied to the truncation surface.
  • the truncation surface is ground under the conditions of a depth of cut of 2 ⁇ m to 3 ⁇ m and a feed rate of 50 mm/min to 100 mm/min due to the limitations of the shape of the workpiece (mold for high pressure generator) and the shape of the grinding device. processing was taking place. According to the above conditions, the compressive residual stress applied to the truncation surface is less than 1.50 GPa.
  • the inventors realized grinding conditions of a peripheral speed of 60 m/s or more by using a grinding machine that enables the above-mentioned ultra-high-speed grinding.
  • the temperature of the workpiece rises, causing a reduction in compressive residual stress and generation of tensile residual stress, leading to breakage.
  • the inventors set the cooling water flow rate to 100 L/min, which is more than five times the conventional rate, in order to suppress the temperature rise of the workpiece.
  • ultra-high-speed grinding can be performed on the truncation surface under the conditions of a depth of cut of 6 ⁇ m or more and a feed rate of 400 mm/min or more without increasing the temperature of the workpiece.
  • the ultra-high speed grinding process can impart a compressive residual stress of 1.50 GPa or more to the truncation surface of the mold for high pressure generator.
  • the method for processing the truncation surface described above was newly discovered by the present inventors. As a result, a compressive residual stress of 1.50 GPa or more can be applied to the truncation surface, completing the present disclosure.
  • a shot blasting device or a shot peening device is used to inject hard powder onto the truncation surface to impart compressive residual stress to the truncation surface.
  • the hard powder fine cemented carbide or amorphous alloy particles having an average particle size of 0.05 mm to 1 mm are used.
  • the injection pressure is 0.6 MPa or more, and the treatment time is 30 seconds or more.
  • Shot particles with a Vickers hardness of 13 Hv or more are used for cemented carbide particles, and shot particles with a Vickers hardness of 18 Hv or more are used for amorphous alloy particles. Thereby, a compressive residual stress of 1.50 GPa or more can be applied to the truncation surface.
  • the injection pressure is less than 0.6 MPa, a compressive residual stress of 1.5 GPa or more cannot be applied. If the hard powder has an average particle size of more than 1 mm, a compressive residual stress of 1.5 GPa or more cannot be imparted.
  • shot particles made of steel or oxide ceramics such as mullite, alumina, and silica are used from the viewpoint of economy. These particles have a Vickers hardness of 10 Hv or less, or a material specific gravity of 5 g/cm 3 or less, and the kinetic energy of the particles during projection is small, so a compressive residual stress of 1.50 GPa or more can be applied to the truncation surface. I didn't.
  • the present inventors have found that by using fine cemented carbide or amorphous alloy particles with an average particle size of 0.05 mm to 1 mm, shot blasting or shot peening is performed to impart high compressive residual stress to the truncation surface. Found a new way to do it. As a result, a compressive residual stress of 1.50 GPa or more can be applied to the truncation surface, completing the present disclosure.
  • the cemented carbide includes a first phase and a second phase, and the content of the first phase of the cemented carbide is 80.0% by volume or more and 98.0% by volume or less. and the content of the second phase is preferably 2.0% by volume or more and 20.0% by volume or less.
  • the cemented carbide includes a first phase, a second phase and a third phase, and the content of the first phase of the cemented carbide is 80.0% by volume or more and 98.0 % by volume, the content of the second phase is 2.0% by volume or more and less than 20.0% by volume, and the content of the third phase is preferably more than 0% by volume and 0.5% by volume or less. .
  • Tungsten carbide powder (average particle size (FSSS method) 0.1 to 0.2 ⁇ m, carbonization temperature 1400° C.), cobalt (Co) powder (average particle size 0.8 ⁇ m), chromium carbide (Cr 3 C 2 ) powder (average 1.0 ⁇ m in particle size) and vanadium carbide (VC) powder (average particle size of 0.9 ⁇ m) are mixed in a ball mill to obtain a mixed powder.
  • the mixing conditions were a media diameter of 6 mm, a rotation speed of 60 rpm, a mixing time of 20 hours, and wet mixing.
  • the content of each powder in the mixed powder is the first phase, the second phase, the third phase and the Co content in the cemented carbide after sintering are shown in Table 1 as “first phase (% by volume)”, “Second phase (volume %)", “third phase (volume %)", and “Co (mass %)” were adjusted.
  • the average particle size of the tungsten carbide powder is selected so that the average particle size of the tungsten carbide particles in the cemented carbide after sintering is the "WC particle average particle size ( ⁇ m)" of "Cemented Carbide” in Table 1. bottom.
  • the above mixed powder was press molded at a pressure of 1000 kg/cm 2 to obtain a compact.
  • the compact was heated to 1350° C. in vacuum and sintered for 1 hour. After that, it was subjected to HIP treatment under the conditions of 1350° C., 100 MPa, and 1 hour, and then cooled to obtain a cemented carbide.
  • the cemented carbide has the shape shown in FIG. Specifically, it has a 15 mm width ⁇ 15 mm length ⁇ 15 mm thickness cube shape in which one of the vertexes is cut off, and has a truncation surface.
  • the truncation surface of the obtained cemented carbide was ground or shot blasted to obtain a mold for an ultrahigh pressure generator for each sample.
  • a plurality of molds for the ultrahigh pressure generator were prepared.
  • Samples 1, 2, and 4 to 14 were ground.
  • a diamond grindstone eg, #200
  • a diamond grindstone for example, #200
  • samples 8 and 9 a diamond grindstone (for example, #200) was used with a depth of cut of 1 ⁇ m and a feed rate of 70 mm/min.
  • shot blasting was performed.
  • the shot blasting conditions were as follows: cemented carbide particles with an average particle size of 0.1 mm were used as the hard powder, the injection pressure was 1 MPa, and the treatment time was 5 minutes.
  • ⁇ Average particle size of tungsten carbide particles The average particle size of the tungsten carbide particles was measured in each sample. Since a specific measuring method is described in Embodiment 1, the description thereof will not be repeated. The results are shown in the "WC particle average particle size ( ⁇ m)" column of Table 1.
  • a multi-anvil was made using eight ultra-high pressure generator molds. Using the multi-anvil, a high-temperature and high-pressure treatment was performed on the graphite powder under conditions of 16 GPa and 2200° C. by a multi-anvil type high pressure generator to produce diamond. For each sample, the same multi-anvil was used to produce the above-described diamond a plurality of times, and the number of production times when one or more molds for an ultrahigh pressure generator were damaged was evaluated as the life. For example, if one or more ultra-high pressure generator molds break during the fifth diamond production, the life of the multi-anvil is five.
  • the "Lifetime” column in Table 1 shows the ratio of the lifetime of each sample when the lifetime of Sample 8 is assumed to be 1.0.
  • Sample 1 has a lifetime of "1.8". This means that the lifetime of sample 1 is 1.8 times that of sample 8. A larger value in the life column indicates a longer life.
  • Samples 1 to 3, 6, and 10 to 14 correspond to examples.
  • Samples 4, 5, and 7 to 9 correspond to comparative examples. It was confirmed that Samples 1 to 3, 6, and 10 to 14 (Examples) had longer lives than Samples 4, 5, and 7 to 9 (Comparative Examples).

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  • Organic Chemistry (AREA)
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PCT/JP2022/001397 2022-01-17 2022-01-17 超高圧発生装置用金型 Ceased WO2023135807A1 (ja)

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US18/714,137 US20250033309A1 (en) 2022-01-17 2022-01-17 Mold for ultra-high pressure generator
PCT/JP2022/001397 WO2023135807A1 (ja) 2022-01-17 2022-01-17 超高圧発生装置用金型
CN202280085075.7A CN118451209A (zh) 2022-01-17 2022-01-17 超高压发生装置用模具
EP22920332.8A EP4467260A4 (en) 2022-01-17 2022-01-17 MOLD FOR AN ULTRA-HIGH PRESSURE GENERATOR
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JPH1029160A (ja) * 1996-07-12 1998-02-03 Sintokogio Ltd 高硬度金属製品のショットピ−ニング方法及び高硬度金属製品
JP2001181777A (ja) 1999-12-24 2001-07-03 Fuji Dies Kk 超高圧発生装置用シリンダーコアおよびアンビルコア
JP2008038242A (ja) 2006-08-08 2008-02-21 Fuji Dies Kk 超微粒超硬合金
JP2015506818A (ja) * 2011-11-29 2015-03-05 スミス インターナショナル インコーポレイテッド 勾配構造を組み込んだ高圧炭化物構成要素

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JPS461911Y1 (https=) * 1967-04-03 1971-01-22
JP4801033B2 (ja) 2007-10-31 2011-10-26 住友重機械テクノフォート株式会社 超高圧発生装置
JP6896229B2 (ja) * 2017-09-29 2021-06-30 三菱マテリアル株式会社 耐溶着チッピング性にすぐれた切削工具
CN110328372B (zh) * 2019-08-06 2021-07-02 金华中烨超硬材料有限公司 聚晶复合刀具及3c刀具用聚晶金刚石复合片制备工艺

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JPH1029160A (ja) * 1996-07-12 1998-02-03 Sintokogio Ltd 高硬度金属製品のショットピ−ニング方法及び高硬度金属製品
JP2001181777A (ja) 1999-12-24 2001-07-03 Fuji Dies Kk 超高圧発生装置用シリンダーコアおよびアンビルコア
JP2008038242A (ja) 2006-08-08 2008-02-21 Fuji Dies Kk 超微粒超硬合金
JP2015506818A (ja) * 2011-11-29 2015-03-05 スミス インターナショナル インコーポレイテッド 勾配構造を組み込んだ高圧炭化物構成要素

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