WO2025069212A1 - 超硬合金および切削工具 - Google Patents

超硬合金および切削工具 Download PDF

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Publication number
WO2025069212A1
WO2025069212A1 PCT/JP2023/035008 JP2023035008W WO2025069212A1 WO 2025069212 A1 WO2025069212 A1 WO 2025069212A1 JP 2023035008 W JP2023035008 W JP 2023035008W WO 2025069212 A1 WO2025069212 A1 WO 2025069212A1
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Prior art keywords
cemented carbide
binder phase
tungsten carbide
tungsten
region
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PCT/JP2023/035008
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English (en)
French (fr)
Japanese (ja)
Inventor
保樹 城戸
好博 木村
アノンサック パサート
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to EP23954188.1A priority Critical patent/EP4692392A1/en
Priority to US18/714,829 priority patent/US12435396B2/en
Priority to JP2024516661A priority patent/JP7670234B1/ja
Priority to CN202380099943.1A priority patent/CN121464231A/zh
Priority to PCT/JP2023/035008 priority patent/WO2025069212A1/ja
Priority to TW113123540A priority patent/TW202513817A/zh
Publication of WO2025069212A1 publication Critical patent/WO2025069212A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B23B27/148—Composition of the cutting inserts
    • 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
    • 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
    • C22C29/067—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 comprising a particular metallic binder
    • 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
    • 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
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/10—Carbide
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/15—Carbonitride
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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

  • This disclosure relates to cemented carbide and cutting tools.
  • Patent Document 1 cemented carbide alloys containing multiple tungsten carbide particles and a binder phase have been used as materials for cutting tools.
  • the cemented carbide of the present disclosure is A cemented carbide comprising a plurality of tungsten carbide particles and a binder phase,
  • the cemented carbide contains 89 volume % or more of the tungsten carbide particles and the binder phase in total,
  • the cemented carbide contains 1.5% by volume or more and 23% by volume or less of the binder phase,
  • the binder phase contains 40% by mass or more of cobalt, the binder phase further comprises at least one first element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum;
  • the first element is not segregated in a first interface region between adjacent tungsten carbide particles, and
  • the cemented carbide is a hard alloy, wherein the first element does not segregate in a second interface region between adjacent tungsten carbide particles and the binder phase.
  • FIG. 1 is a schematic cross-sectional view of a cemented carbide according to a first embodiment.
  • FIG. 2 is a diagram showing an example of a first image of the cemented carbide according to the first embodiment.
  • FIG. 3 is a diagram for explaining a method for confirming that the first element is not segregated in the first interface region, and shows a first graph.
  • FIG. 4 is a diagram for explaining a method for confirming that the first element is not segregated in the second interface region, and shows a second graph.
  • FIG. 5 is a schematic diagram of a cutting tool according to the second embodiment.
  • the present disclosure therefore aims to provide a cemented carbide alloy that enables a longer service life for cutting tools, particularly when used as a material for cutting tools for drilling holes in printed circuit boards, and a cutting tool equipped with the same.
  • the cemented carbide of the present disclosure is A cemented carbide comprising a plurality of tungsten carbide particles and a binder phase,
  • the cemented carbide contains 89 volume % or more of the tungsten carbide particles and the binder phase in total,
  • the cemented carbide contains 1.5% by volume or more and 23% by volume or less of the binder phase,
  • the binder phase contains 40% by mass or more of cobalt, the binder phase further comprises at least one first element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum;
  • the first element is not segregated in a first interface region between adjacent tungsten carbide particles, and
  • the cemented carbide is a hard alloy, wherein the first element does not segregate in a second interface region between adjacent tungsten carbide particles and the binder phase.
  • the percentage of the mass M1 of the first element in the binder phase relative to the sum M1+M2 of the mass M1 of the first element and the mass M2 of cobalt, ⁇ M1/(M1+M2) ⁇ 100, may be 1% or more and 6% or less.
  • the units of the mass M1 and the mass M2 are the same. This makes it possible to provide a cemented carbide alloy that can extend the tool life of a cutting tool.
  • the cemented carbide is an intermetallic compound consisting of two or more elements selected from the group consisting of the first element, cobalt, and tungsten; and
  • the first element may not include a first compound consisting of at least one element selected from the group consisting of cobalt and tungsten, and at least one element selected from the group consisting of carbon, nitrogen, and oxygen.
  • the first compound does not include tungsten carbide.
  • the cutting tool of the present disclosure is a cutting tool having a cutting edge made of the cemented carbide alloy described in any one of (1) to (3) above.
  • a ⁇ B means the upper and lower limits of a range (i.e., greater than or equal to A and less than or equal to B). If no unit is stated for A and only a unit is stated for B, the units of A and B are the same.
  • any one numerical value listed as the lower limit and any one numerical value listed as the upper limit is also considered to be disclosed.
  • a1 or more, b1 or more, and c1 or more are listed as the lower limit and a2 or less, b2 or less, and c2 or less are listed as the upper limit, a1 or more and a2 or less, a1 or more and b2 or less, a1 or more and c2 or less, b1 or more and a2 or less, b1 or more and b2 or less, b1 or more and c2 or less, c1 or more and a2 or less, c1 or more and b2 or less, and c1 or more and c2 or less are considered to be disclosed.
  • the cemented carbide 3 according to one embodiment of the present disclosure (hereinafter also referred to as “embodiment 1”) is A cemented carbide (3) comprising a plurality of tungsten carbide particles (1) and a binder phase (2), The cemented carbide 3 contains tungsten carbide particles 1 and a binder phase 2 in a total amount of 89 volume % or more, The cemented carbide 3 contains a binder phase 2 of 1.5 volume % or more and 23 volume % or less, The binder phase 2 contains 40% by mass or more of cobalt, The binder phase 2 further contains at least one first element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum; In a first interface region between adjacent tungsten carbide particles 1, the first element is not segregated, and The
  • the cemented carbide of embodiment 1 can provide a cemented carbide that enables a longer life for cutting tools, particularly when used as a material for cutting tools for drilling holes in printed circuit boards, and a cutting tool equipped with the same.
  • the reason for this is unclear, but is presumed to be as follows.
  • the cemented carbide of the first embodiment comprises a plurality of tungsten carbide particles (hereinafter also referred to as "WC particles") and a binder phase, and the total content of the WC particles and binder phase in the cemented carbide is 89 volume % or more.
  • WC particles tungsten carbide particles
  • the cemented carbide has high hardness and strength, and a cutting tool comprising the cemented carbide can have excellent wear resistance and breakage resistance.
  • the cemented carbide of embodiment 1 contains a binder phase of 1.5 volume % or more and 23 volume % or less, and the binder phase contains 40 mass % or more of cobalt.
  • the cemented carbide has high hardness and strength, and a cutting tool including the cemented carbide can have excellent wear resistance and breakage resistance.
  • the binder phase contains at least one first element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum. Furthermore, the first element does not segregate in the first interface region between adjacent tungsten carbide particles, and the first element does not segregate in the second interface region between adjacent tungsten carbide particles and the binder phase. As a result, in the cemented carbide, the interface strength between the tungsten carbide particles and the interface strength between the tungsten carbide particles and the binder phase are further improved, and the tungsten carbide particles are prevented from falling off during cutting. Therefore, a cutting tool using the cemented carbide as a material can have a long tool life. Furthermore, the hole position accuracy of the cutting tool is also improved.
  • the cemented carbide of the first embodiment contains tungsten carbide particles and a binder phase in a total amount of 89% or more by volume. This can increase the hardness of the cemented carbide.
  • the cemented carbide may contain tungsten carbide particles and a binder phase in a total amount of 89% to 100% by volume, 90% to 100% by volume, 91% to 100% by volume, or 92% to 100% by volume.
  • the cemented carbide of embodiment 1 contains 1.5 vol.% or more and 23 vol.% or less of a binder phase. This allows the hardness and toughness of the cemented carbide to be increased.
  • the content of the binder phase in the cemented carbide may be 2.0 vol.% or more and 19.0 vol.% or less, 3.0 vol.% or more and 18.0 vol.% or less, or 4.0 vol.% or more and 17.0 vol.% or less.
  • the cemented carbide of embodiment 1 can be composed of a plurality of tungsten carbide particles and a binder phase.
  • the cemented carbide can contain impurities to the extent that the effect of the present disclosure is not impaired.
  • the cemented carbide may contain other phases (not shown) in addition to the tungsten carbide particles and the binder phase.
  • the other phases may include carbides, nitrides or carbonitrides containing at least one element selected from the group consisting of titanium (Ti), tantalum (Ta), niobium (Nb), zirconium (Zr), hafnium (Hf) and molybdenum (Mo).
  • the composition of the other phases may be, for example, at least one selected from the group consisting of TiCN, TaC, NbC, ZrC, HfC and Mo2C .
  • the cemented carbide of embodiment 1 can be composed of tungsten carbide particles, a binder phase, and other phases.
  • the cemented carbide can contain impurities to the extent that the effects of the present disclosure are not impaired.
  • the content of other phases in the cemented carbide is permissible within a range that does not impair the effects of the present disclosure.
  • the content of other phases in the cemented carbide may be greater than 0 vol.% and less than 11 vol.%, greater than 0 vol.% and less than 7 vol.%, or greater than 0 vol.% and less than 4 vol.%.
  • the cemented carbide of the first embodiment may contain impurities.
  • impurities include iron (Fe), calcium (Ca), silicon (Si), and sulfur (S).
  • the impurity content of the cemented carbide is acceptable within a range that does not impair the effects of the present disclosure.
  • the impurity content of the cemented carbide may be 0 mass% or more and less than 0.1 mass%.
  • the impurity content of the cemented carbide is measured by ICP optical emission spectroscopy (Inductively Coupled Plasma Emission Spectroscopy). The measuring device that can be used is Shimadzu Corporation's "ICPS-8100" (trademark).
  • the tungsten carbide particle content of the cemented carbide of embodiment 1 may be 67% by volume or more and 98.5% by volume or less, 70% by volume or more and 97% by volume or less, or 75% by volume or more and 96% by volume or less.
  • the method for measuring the tungsten carbide particle content (volume %) of the cemented carbide and the binder phase content (volume %) of the cemented carbide is as follows.
  • the mirror-finished surface of the cemented carbide is photographed with a scanning electron microscope (SEM) to obtain a backscattered electron image.
  • the photographed area is set to the center of the cross section of the cemented carbide, that is, a position that does not include any part whose properties are clearly different from the bulk part, such as the vicinity of the surface of the cemented carbide (a position where the photographed area is entirely the bulk part of the cemented carbide).
  • the observation magnification is 5000x.
  • the measurement conditions are an acceleration voltage of 3 kV, a current value of 2 nA, and a working distance (WD) of 5 mm.
  • (H1) The measurement of (G1) above is performed in five different non-overlapping measurement fields.
  • the average of the area percentages of tungsten carbide particles in the five measurement fields corresponds to the content (volume %) of tungsten carbide particles in the cemented carbide
  • the average of the area percentages of the binder phase in the five measurement fields corresponds to the content (volume %) of the binder phase in the cemented carbide.
  • the content of the other phases in the cemented carbide can be obtained by subtracting the content (volume %) of the tungsten carbide grains and the content (volume %) of the binder phase measured by the above procedure from the total cemented carbide (100 volume %).
  • the cobalt content of the cemented carbide of embodiment 1 may be 1.0% by mass or more and 20% by mass or less, 2.0% by mass or more and 15% by mass or less, or 3.0% by mass or more and 12% by mass or less.
  • the method for measuring the cobalt content of the cemented carbide is as follows. Using the same method as (A1) to (D1) of the method for measuring the tungsten carbide particle content and binder phase content of the cemented carbide, an element mapping image is obtained by performing analysis using SEM-EDX. Based on the element mapping image, the cobalt region in the cemented carbide is identified and the cobalt content is measured. The measurement is performed in five different, non-overlapping imaging regions. In the present disclosure, the average of the cobalt content in the five imaging regions corresponds to the cobalt content of the cemented carbide.
  • the tungsten carbide particles include at least one of "pure WC particles (including WC containing no impurity elements and WC containing impurity elements below the detection limit)" and "WC particles containing impurity elements intentionally or unavoidably, as long as the effect of the present disclosure is not impaired.”
  • the impurity content of the tungsten carbide particles (when the impurity elements are two or more types, the total concentration of the elements) is less than 0.1 mass%.
  • the impurity element content of the tungsten carbide particles is measured by ICP emission spectrometry.
  • the average particle size of the tungsten carbide particles is not particularly limited.
  • the average particle size of the tungsten carbide particles can be, for example, 0.1 ⁇ m or more and 3.5 ⁇ m or less. It has been confirmed that the cemented carbide of the first embodiment enables the tool to have a longer life when used as a material for cutting tools, regardless of the average particle size of the tungsten carbide particles.
  • the binder phase contains 40% by mass or more of cobalt. This allows the cemented carbide to have excellent toughness.
  • the cobalt content of the binder phase may be 40% by mass or more and less than 100% by mass, 50% by mass or more and 90% by mass or less, or 60% by mass or more and 80% by mass or less.
  • the method for measuring the cobalt content of the binder phase is as follows.
  • An element mapping image and an image after binarization are obtained by the same method as (A1) to (E1) of the above-mentioned method for measuring the tungsten carbide particle content and binder phase content of the cemented carbide.
  • the element mapping image and the image after binarization are superimposed to identify the region in which the binder phase exists in the element mapping image.
  • a rectangular measurement field of view of 24.9 ⁇ m ⁇ 18.8 ⁇ m is set in the element mapping image.
  • the cobalt content is measured in the region in which the binder phase exists in the measurement field.
  • the above measurement is performed in five different measurement fields that do not overlap each other.
  • the average of the cobalt contents in the regions in which the binder phase exists in the five measurement fields of view corresponds to the cobalt content of the binder phase.
  • the binder phase further contains at least one first element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum.
  • the inclusion of the first element in the binder phase is confirmed by the following procedure.
  • An element mapping image and an image after binarization are obtained by the same method as (A1) to (E1) of the above-mentioned method for measuring the tungsten carbide particle content and binder phase content of cemented carbide.
  • the region in which the binder phase exists is identified in the element mapping image. If the first element is present in the region in which the binder phase exists in the element mapping, it is confirmed that the binder phase contains the first element.
  • the percentage ⁇ M1/(M1+M2) ⁇ 100 of the mass M1 of the first element relative to the sum M1+M2 of the mass M1 of the first element and the mass M2 of cobalt may be 1% or more and 6% or less.
  • the units of mass M1 and mass M2 are the same.
  • the binder phase can have both superior hardness and superior toughness, and a cutting tool including a cemented carbide including the binder phase can have a longer tool life.
  • the mass M1 of the first element means the total mass of all types of the first elements when the binder phase includes two or more types of first elements.
  • the percentage ⁇ M1/(M1+M2) ⁇ 100 may be 2% or more and 5% or less, or 3% or more and 4% or less.
  • the method for measuring the percentage ⁇ M1/(M1+M2) ⁇ x 100 is as follows.
  • An element mapping image and an image after binarization are obtained by the same method as (A1) to (E1) of the method for measuring the tungsten carbide particle content and binder phase content of the cemented carbide.
  • the element mapping image and the image after binarization are superimposed to identify the region in which the binder phase exists in the element mapping image.
  • a rectangular measurement field of view of 24.9 ⁇ m x 18.8 ⁇ m is set in the element mapping image.
  • the percentage ⁇ m1/(m1+m2) ⁇ x 100 of the mass m1 of the first element relative to the sum m1+m2 of the mass m1 of the first element and the mass m2 of cobalt is calculated.
  • the above measurement is performed in five different measurement fields that do not overlap with each other.
  • the average of the percentage ⁇ m1/(m1+m2) ⁇ x 100 in the five measurement fields corresponds to the "percentage ⁇ M1/(M1+M2) ⁇ x 100" in the binder phase of the cemented carbide.
  • the binder phase can contain, in addition to cobalt and the first element, at least one second element selected from the group consisting of iron (Fe), nickel (Ni) and chromium (Cr).
  • the binder phase can consist of cobalt, the first element and the second element.
  • the binder phase can consist of cobalt, the first element, the second element and unavoidable impurities. Examples of the unavoidable impurities include iron (Fe), nickel (Ni) and sulfur (S).
  • the first element does not segregate in the first interface region between adjacent tungsten carbide particles, and the first element does not segregate in the second interface region between adjacent tungsten carbide particles and the binder phase, thereby improving the interface strength between the tungsten carbide particles and between the tungsten carbide particles and the binder phase, and improving the wear resistance and breakage resistance of the cemented carbide.
  • the tungsten carbide particles 1 are observed as white to gray regions, the bonding phase 2 is observed as black regions, and the interfaces 4 located between adjacent tungsten carbide particles 1 are observed as black regions.
  • the width of the interfaces 4 is, for example, 2 nm or less.
  • the interfaces between adjacent tungsten carbide particles are arbitrarily selected.
  • the adjacent tungsten carbide particles are also referred to as the first tungsten carbide particles and the second tungsten carbide particles.
  • the selected interface is positioned so as to pass through the vicinity of the center of the image, and the observation magnification is adjusted so that the field of view size is 5 nm x 5 nm, and a second image is obtained.
  • the extension direction of the interface is confirmed.
  • Line analysis is performed with an energy dispersive X-ray analyzer (TEM-EDX) attached to the TEM in a direction perpendicular to the extension direction and from the first tungsten carbide particle to the second tungsten carbide particle, and a graph (hereinafter also referred to as the first graph) is obtained that measures the distribution of cobalt, tungsten, and the first element.
  • TEM-EDX energy dispersive X-ray analyzer
  • the distribution of each element is measured.
  • the direction perpendicular to the extension direction of the interface means the direction along a straight line that intersects with the tangent to the extension direction at an angle of 90° ⁇ 5°.
  • the direction indicated by the arrow corresponds to the direction perpendicular to the extension direction of the interface.
  • the measurement conditions for acquiring the second image were: acceleration voltage 200 kV, camera length 10 cm, pixel count 128 x 128 pixels, and dwell time 0.02 to 3 s/pixel.
  • Figure 3 is an example of the first graph.
  • the horizontal axis (X axis) indicates the distance (nm) from the measurement start point
  • the vertical axis (Y axis) indicates the content (atomic %) of each element.
  • the first element is silicon (Si).
  • the first interface is formed between a first tungsten carbide particle and a second tungsten carbide particle that are adjacent to each other. In the first graph of FIG. 3, the first interface is located at 5.98 nm on the X-axis.
  • a first A region is identified in which the distance from the first interface to the first tungsten carbide particle side is within 1.20 nm
  • a first B region is identified in which the distance from the first interface to the second tungsten carbide particle side is within 1.20 nm.
  • the region consisting of the first A region and the first B region is the first interface region.
  • the first interface region is located in the region of 4.78 to 7.18 nm on the X-axis.
  • the first interface region between adjacent tungsten carbide particles can also be expressed as a first interface region located between adjacent tungsten carbide particles.
  • a second A region is identified in which the distance from the first interface to the first tungsten carbide particle side is 1.50 nm or more and 3.50 nm or less
  • a second B region is identified in which the distance from the first interface to the second tungsten carbide particle side is 1.50 nm or more and 3.50 nm or less.
  • the second A region is located in the region of 2.48 to 4.48 nm on the X-axis
  • the second B region is located in the region of 7.48 to 9.48 nm on the X-axis.
  • the average content B of silicon (first element) in the baseline region consisting of the second A region and the second B region is 7.68 atomic %
  • the maximum content A of silicon (first element) in the first interface region is 6.75 atomic %.
  • A/B is 0.9, so it is confirmed that the first element does not segregate in the first interface region between adjacent tungsten carbide particles of the cemented carbide.
  • a first image is obtained in the above-mentioned first interface region by the same method as (A2) described in the method for confirming that the first element is not segregated.
  • an interface between adjacent tungsten carbide particles and a binder phase is arbitrarily selected.
  • the selected interface is positioned so that it passes through the center of the image, and the observation magnification is adjusted so that the field of view size is 5 nm x 5 nm, and the third image is obtained.
  • the extension direction of the interface is confirmed.
  • Line analysis is performed with TEM-EDX perpendicular to the extension direction and in the direction from the tungsten carbide particle toward the bonding phase, and a graph (hereinafter also referred to as the second graph) is obtained that measures the distribution of cobalt, tungsten, and the first element. If the cemented carbide contains two or more types of first elements, the distribution of each element is measured.
  • the direction perpendicular to the extension direction of the interface means the direction along a straight line that intersects with the tangent of the extension direction at an angle of 90° ⁇ 5°.
  • the measurement conditions for obtaining the third image are an acceleration voltage of 200 kV, a camera length of 10 cm, a pixel count of 128 x 128 pixels, and a dwell time of 0.02 to 3 s/pixel.
  • FIG. 4 is an example of the second graph.
  • the horizontal axis (X axis) indicates the distance (nm) from the measurement start point
  • the vertical axis (Y axis) indicates the content (atomic %) of each element.
  • the first element is silicon (Si).
  • the position where the tungsten content and the cobalt content intersect is identified.
  • the position where the tungsten content and the cobalt content intersect is referred to as the second interface.
  • the second interface is formed between adjacent tungsten carbide particles and the binder phase. In the second graph of FIG. 4, the second interface is located at 5.97 nm on the x-axis.
  • a first C region is identified that is within 1.20 nm of the distance from the second interface to the tungsten carbide particle side
  • a first D region is identified that is within 1.20 nm of the distance from the second interface to the binder phase side.
  • the region consisting of the first C region and the first D region is the second interface region.
  • the second interface region is located in the region of 4.76 to 7.16 nm on the X-axis.
  • the second interface region between adjacent tungsten carbide particles and the binder phase can also be expressed as a second interface region located between adjacent tungsten carbide particles and the binder phase.
  • a second C region is identified in which the distance from the second interface to the tungsten particle side is 1.50 nm or more and 3.50 nm or less
  • a second D region is identified in which the distance from the second interface to the bonding phase side is 1.50 nm or more and 3.50 nm or less.
  • the second C region is located in the region of 2.46 to 4.46 nm on the X-axis
  • the second D region is located in the region of 7.46 to 9.46 nm on the X-axis.
  • cemented carbide alloy For a cemented carbide alloy, five mutually non-overlapping first images are randomly obtained, a second graph is obtained based on each of the first images, and the above-mentioned analysis is repeated. If no segregation of the first element is confirmed in the second interface region in four or more of the second graphs, it is determined that the first element is not segregated in the second interface region between adjacent tungsten carbide particles and the binder phase of the cemented carbide alloy.
  • the cut-out location of the cemented carbide cross section is arbitrarily set, the first image is arbitrarily obtained on the cross section, and the presence or absence of segregation of the first element in the first interface region and the second interface region is confirmed multiple times according to the above procedure by changing the line analysis region, and it has been confirmed that there is almost no variation in the results of the presence or absence of segregation of the first element in the first interface region and the second interface region.
  • the cemented carbide of the first embodiment may not include an intermetallic compound (hereinafter also referred to as "first interalloy compound") consisting of two or more elements selected from the group consisting of the first element, cobalt, and tungsten, and a first compound consisting of at least one element selected from the group consisting of the first element, cobalt, and tungsten, and at least one element selected from the group consisting of carbon, nitrogen, and oxygen.
  • first compound does not include tungsten carbide. This suppresses the decrease in strength of the cemented carbide.
  • Examples of the first intermetallic compound include Co 2 Si, Co 3 Si, and CoSi.
  • Examples of the first compound include Co3W3C and Co6W6C .
  • the fact that the cemented carbide does not contain either the first intermetallic compound or the first compound is confirmed by structural observation and EDX analysis of a cross section of the cemented carbide.
  • the cemented carbide of the first embodiment can be manufactured by carrying out a raw material powder preparation step, a mixing step, a molding step, a sintering step, a first cooling step, a HIP (Hot Isostatic Pressing) step, and a second cooling 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.
  • the raw material powder include tungsten carbide powder (hereinafter also referred to as "WC powder"), cobalt (Co) powder, first element powder, and alloy powder of the first element and cobalt.
  • the first element powder include silicon (Si) powder, phosphorus (P) powder, germanium (Ge) powder, tin (Sn) powder, rhenium (Re) powder, ruthenium (Ru) powder, osmium (Os) powder, iridium (Ir) powder, and platinum (Pt) powder.
  • nickel (Ni) powder, niobium carbide (NbC) powder, tungsten carbide (TaC) powder, titanium carbonitride (TiCN) powder, and the like can be further prepared.
  • These raw material powders can be commercially available.
  • the average particle size of these raw material powders is not particularly limited and can be, for example, 0.5 to 5 ⁇ m.
  • the average particle size of the raw material powder refers to the average particle size measured by the Fisher Sub-Sieve Sizer (FSSS) method using a "Sub-Sieve Sizer Model 95" (trademark) manufactured by Fisher Scientific.
  • the mixing step is a step of mixing the raw material powders prepared in the preparation step in a predetermined ratio.
  • a mixed powder in which the raw material powders are mixed is obtained by the mixing step.
  • the mixing ratio of the raw material powders is appropriately adjusted depending on the composition of the target cemented carbide.
  • the raw material powders can be mixed using conventional mixing methods such as an attritor, ball mill, or bead mill. Conventional mixing conditions can also be used.
  • the mixing time can be, for example, 2 hours or more and 20 hours or less.
  • the mixed powder may be granulated as necessary. Granulating the mixed powder makes it easier to fill the mixed powder into a die or mold during the molding step described below.
  • a known granulation method can be used 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 shape for a cutting tool to obtain a molded body.
  • the molding method and molding conditions in the molding step are not particularly limited and may be general methods and conditions.
  • the sintering step is a step of sintering the compact obtained in the compacting step to obtain a cemented carbide intermediate.
  • the sintering conditions in the first embodiment are as follows: The compact is heated to 1360° C. at a heating rate of 30° C./min and held at 1360° C. for 15 minutes.
  • the first cooling step is a step of cooling the cemented carbide intermediate body after the sintering step. Specifically, the cemented carbide intermediate body is cooled to 800° C. The temperature drop rate is ⁇ 20° C./min.
  • the HIP process is a process of performing a HIP treatment on the cemented carbide intermediate body after the first cooling process.
  • the conditions of the HIP process are as follows: The cemented carbide intermediate body is held under conditions of 200 MPa and 1310° C. for 15 minutes.
  • the second cooling step is a step of cooling the cemented carbide intermediate body after the HIP step. Specifically, the cemented carbide intermediate body is cooled to 800° C. The temperature drop rate is ⁇ 30° C./min. Then, the cemented carbide of the first embodiment is obtained by slow cooling.
  • the temperature drop rate during slow cooling may be any general condition and is not particularly limited.
  • the heating rate in the sintering step is 30° C./min, which is higher than a general heating rate.
  • the cooling rate in the second cooling step is ⁇ 30° C./min, which is higher than a general cooling rate.
  • the cemented carbide of the first embodiment can be produced, in which the binder phase contains 40 mass % or more of cobalt and at least one first element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum, and the first element is not segregated in the first interface region and the second interface region.
  • the present inventors have found, as a result of intensive research, that the cemented carbide of the present disclosure can be realized by adopting such a heating rate in the sintering step and a heating rate in the second cooling step.
  • a cutting tool according to an embodiment of the present disclosure includes a cutting edge made of the cemented carbide of embodiment 1.
  • the cutting edge refers to a portion involved in cutting. More specifically, the cutting edge refers to a region surrounded by a cutting edge ridge and a virtual surface that is 0.5 mm or 2 mm away from the cutting edge ridge toward the cemented carbide side.
  • Cutting tools include, for example, cutting tools, drills, end mills, indexable cutting tips for milling, indexable cutting tips for turning, metal saws, gear cutting tools, reamers, taps, etc.
  • the cutting tool 10 of the second embodiment can be highly effective in the case of a small diameter drill for machining printed circuit boards.
  • the cutting edge 11 of the cutting tool 10 shown in FIG. 5 is made of the cemented carbide of the first embodiment.
  • the cemented carbide of embodiment 1 may constitute the entire tool or may constitute only a part of the tool.
  • "constitute a part” refers to a mode in which the cemented carbide of embodiment 1 is brazed to a predetermined position of any substrate to form a cutting edge.
  • the cutting tool of the second embodiment may further include a hard film that covers at least a portion of the surface of the substrate made of cemented carbide.
  • the hard film may be made of, for example, diamond-like carbon or diamond.
  • the cutting tool of embodiment 2 can be obtained by forming the cemented carbide of embodiment 1 into a desired shape.
  • a first interface is formed between the first tungsten carbide particle and the second tungsten carbide particle
  • the first interface region may be composed of a first A region within 1.2 nm from the first interface to the first tungsten carbide particle side, and a first B region within 1.2 nm from the first interface to the second tungsten carbide particle side.
  • a second interface is formed between adjacent tungsten carbide particles and a binder phase,
  • the second interface region may be composed of a first C region within 1.2 nm of the second interface toward the tungsten carbide particle side, and a first D region within 1.2 nm of the second interface toward the binder phase side.
  • silicon (Si) powder (average particle size: 1 ⁇ m), phosphorus (P) powder (average particle size: 1 ⁇ m), germanium (Ge) powder (average particle size: 1 ⁇ m), tin (Sn) powder (average particle size: 1 ⁇ m), rhenium (Re) powder (average particle size: 1 ⁇ m), ruthenium (Ru) powder (average particle size: 1 ⁇ m), osmium (Os) powder (average particle size: 1 ⁇ m), iridium (Ir) powder (average particle size: 1 ⁇ m), and platinum (Pt) powder (average particle size: 1 ⁇ m) were prepared.
  • ⁇ Mixing step> A mixed powder was obtained by mixing the raw material powders for 10 hours using an attritor in the ratios shown in Table 1.
  • the ratio (mass %) of each raw material powder shown in Table 1 is the ratio when the total mixed powder is taken as 100 mass %.
  • HIP process The cemented carbide intermediate body after the first cooling step was subjected to HIP treatment.
  • HIP treatment the pressure and the temperature shown in the "Pressure” column and the “Temperature” column of the "HIP step” in Table 3 were maintained for the time shown in the "Time” column.
  • ⁇ Second cooling step> The cemented carbide intermediate body after the HIP process was cooled to 800° C. at the temperature decreasing rate shown in the “Temperature decreasing rate” column of the “Second cooling process” in Table 3. Then, the cemented carbide intermediate body was slowly cooled to obtain each sample of the cemented carbide.
  • the cemented carbide and cutting tools of Samples 1 to 17 correspond to Examples.
  • the cemented carbide and cutting tools of Samples 101 to 104 correspond to Comparative Examples. It was confirmed that the cutting tools of Samples 1 to 17 had better hole position accuracy and longer tool life than the cutting tools of Samples 101 to 104.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
PCT/JP2023/035008 2023-09-26 2023-09-26 超硬合金および切削工具 Pending WO2025069212A1 (ja)

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US18/714,829 US12435396B2 (en) 2023-09-26 2023-09-26 Cemented carbide and cutting tool
JP2024516661A JP7670234B1 (ja) 2023-09-26 2023-09-26 超硬合金および切削工具
CN202380099943.1A CN121464231A (zh) 2023-09-26 2023-09-26 硬质合金以及切削工具
PCT/JP2023/035008 WO2025069212A1 (ja) 2023-09-26 2023-09-26 超硬合金および切削工具
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WO2015178484A1 (ja) * 2014-05-23 2015-11-26 株式会社タンガロイ 超硬合金および被覆超硬合金
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JP2010012552A (ja) * 2008-07-03 2010-01-21 Mitsubishi Materials Corp 耐折損性に優れた超硬合金製ミニチュアドリル
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