WO2025027677A1 - 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
WO2025027677A1
WO2025027677A1 PCT/JP2023/027732 JP2023027732W WO2025027677A1 WO 2025027677 A1 WO2025027677 A1 WO 2025027677A1 JP 2023027732 W JP2023027732 W JP 2023027732W WO 2025027677 A1 WO2025027677 A1 WO 2025027677A1
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Prior art keywords
cemented carbide
intensity
less
peak
tungsten
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PCT/JP2023/027732
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English (en)
French (fr)
Japanese (ja)
Inventor
好博 木村
保樹 城戸
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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Priority to PCT/JP2023/027732 priority Critical patent/WO2025027677A1/ja
Priority to JP2023577962A priority patent/JP7589839B1/ja
Priority to US18/686,491 priority patent/US12109630B1/en
Priority to CN202380047054.0A priority patent/CN119731358A/zh
Priority to EP23935623.1A priority patent/EP4527962A4/en
Priority to TW113114910A priority patent/TW202509245A/zh
Publication of WO2025027677A1 publication Critical patent/WO2025027677A1/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • 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
    • 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
    • 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
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides 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
    • 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
    • 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
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
    • B23B2222/28—Details of hard metal, i.e. cemented carbide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure

Definitions

  • This disclosure relates to cemented carbide and cutting tools.
  • cemented carbide alloys containing tungsten carbide (WC) particles and a binder phase mainly composed of cobalt, etc. have been used as materials for cutting tools (Patent Documents 1 and 2).
  • 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 80 volume % or more of the tungsten carbide particles and the binder phase in total,
  • the cemented carbide contains the binder phase in an amount of 0.1% by volume or more and 20% by volume or less,
  • the cemented carbide contains at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, cerium, yttrium, and boron;
  • the cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 20 atomic % or less,
  • the binder phase contains 50% by mass or more of cobalt,
  • a first graph showing the results of line analysis performed using an energy dispersive X-ray spectrometer attached to a transmission electron microscope along a first direction from adjacent binder phases toward the tungsten carbide particles, the results being plotted on
  • FIG. 1 is a schematic cross-sectional view of a cemented carbide according to a first embodiment.
  • FIG. 2 shows an example of a first graph of the cemented carbide according to the first embodiment.
  • FIG. 3 is a schematic diagram of a cutting tool according to a second embodiment.
  • the present disclosure therefore aims to provide a cemented carbide that, when used as a tool material, can provide a cutting tool with a long tool life, particularly in high-speed machining of difficult-to-cut materials, as well as a cutting tool with a long tool life.
  • 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 80 volume % or more of the tungsten carbide particles and the binder phase in total, The cemented carbide contains the binder phase in an amount of 0.1% by volume or more and 20% by volume or less, The cemented carbide contains at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, cerium, yttrium, and boron; The cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 20 atomic % or less, The binder phase contains 50% by mass or more of cobalt, A first graph showing the results of line analysis performed using an energy dispersive X-ray spectrometer attached to a transmission electron microscope along a first direction from adjacent binder phases
  • a cemented carbide that, when used as a cutting tool material, can provide a cutting tool with a long tool life, particularly in high-speed machining of difficult-to-cut materials, and a cutting tool with a long tool life.
  • the cemented carbide may contain 18 volume percent or less of the binder phase. This further improves the tool life.
  • the cutting tool disclosed herein is a cutting tool having a cutting edge made of the cemented carbide alloy described in (1) or (2) above.
  • the cutting tools disclosed herein can have a long tool life.
  • 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 according to one embodiment of the present disclosure (hereinafter also referred to as "embodiment 1") is A cemented carbide comprising a plurality of tungsten carbide particles and a binder phase, The cemented carbide contains 80 volume % or more of the tungsten carbide particles and the binder phase in total, The cemented carbide contains 0.1% by volume or more and 20% by volume or less of the binder phase, The cemented carbide comprises at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, cerium, yttrium, and boron; The cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 20 atomic % or less, The binder phase contains at least 50% by weight of cobalt, a first graph showing the results of line analysis performed using an energy dispersive X-ray spectrometer attached to a transmission electron microscope along a first direction from
  • the cemented carbide of embodiment 1 When used as a tool material, the cemented carbide of embodiment 1 can provide a cutting tool with a long tool life, particularly in high-speed machining of difficult-to-cut materials, and can provide a cutting tool with a long tool life. The reason for this is not clear, 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 80 volume % or more.
  • WC particles tungsten carbide particles
  • the cemented carbide has high hardness and strength, and a cutting tool using the cemented carbide can have excellent wear resistance and chipping resistance.
  • the cemented carbide of embodiment 1 contains a binder phase of 0.1 volume % or more and 20 volume % or less, and the binder phase contains cobalt of 50 mass % or more.
  • the cemented carbide has high hardness and strength, and a cutting tool using the cemented carbide can have excellent wear resistance and chipping resistance.
  • the cemented carbide of embodiment 1 contains at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, cerium, yttrium, and boron in a total amount of 0.01 atomic % to 20 atomic %.
  • the maximum peak M of each first element exists between the tungsten peak W1 closest to the origin and another tungsten peak W2 closest to peak W1. This indicates that a maximum concentration region of the first element exists in the surface layer portion of the tungsten carbide particle.
  • the ratio IB/IA of the intensity IB to the maximum peak intensity IA is 0.5 or less. This indicates that the first element exists only in the surface layer portion of the tungsten carbide particle and does not penetrate deep inside the tungsten carbide particle.
  • the first element is present only in the surface layer of the tungsten carbide particles, improving the adhesion resistance of the cemented carbide.
  • the cemented carbide of embodiment 1 when used in a cutting tool, the occurrence of damage such as chipping caused by adhesion during cutting is suppressed.
  • the first element does not penetrate deep into the tungsten carbide particles, so the basic physical properties of the tungsten carbide particles, such as high hardness and strength, do not change significantly and are maintained.
  • the cemented carbide 3 of the first embodiment includes a plurality of tungsten carbide particles 1 (hereinafter, also referred to as "WC particles") and a binder phase 2, and the total content of the WC particles and the binder phase of the cemented carbide 3 is 80% by volume or more.
  • the lower limit of the total content of the WC particles and the binder phase of the cemented carbide may be 82% by volume or more, 84% by volume or more, 85% by volume or more, or 86% by volume or more.
  • the upper limit of the total content of the WC particles and the binder phase of the cemented carbide may be 100% by volume or less.
  • the upper limit of the total content of the WC particles and the binder phase of the cemented carbide may be 99% by volume or less, or 98% by volume or less.
  • the total content of the WC particles and the binder phase of the cemented carbide may be 80% by volume or more and 100% by volume or less, 82% by volume or more and 100% by volume or less, or 84% by volume or more and 100% by volume or less.
  • the cemented carbide of the first embodiment can be composed of a plurality of tungsten carbide particles and a binder phase.
  • the cemented carbide of the present embodiment can include other phases in addition to the tungsten carbide particles and the binder phase.
  • the other phases can include at least one phase selected from the group consisting of TiCN, TiC, TiO 2 , TaC, Ta 2 O 5 , ZrC, ZrO 2 , CeC 2 , CeO 2 , YC, Y 2 O 3 , B 4 C and B 2 O 3 .
  • the cemented carbide of embodiment 1 may be composed of tungsten carbide particles, a binder phase, and other phases.
  • the content of other phases in the cemented carbide is acceptable within a range that does not impair the effects of the present disclosure.
  • the content of other phases in the cemented carbide may be 0 vol.% or more and 20 vol.% or less, 0 vol.% or more and 18 vol.% or less, or 0 vol.% or more and 16 vol.% or less.
  • the total content of WC particles and binder phases in the cemented carbide may be 80 vol.% or more and less than 100 vol.%, 82 vol.% or more and less than 100 vol.%, or 84 vol.% or more and less than 100 vol.%.
  • the cemented carbide of the first embodiment may contain impurities.
  • impurities include manganese (Mn), magnesium (Mg), calcium (Ca), 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 is preferably 0% by mass or more and less than 0.1% by mass.
  • the impurity content of the cemented carbide is measured by ICP optical emission spectroscopy (measuring device: Shimadzu Corporation "ICPS-8100" (trademark)).
  • the lower limit of the content of tungsten carbide particles in the cemented carbide of embodiment 1 may be 60 volume% or more, 65 volume% or more, 66 volume% or more, or 68 volume% or more.
  • the upper limit of the content of tungsten carbide particles in the cemented carbide may be 99.9 volume% or less, 99.8 volume% or less, 99 volume% or less, 98 volume% or less, 96 volume% or less, or 94 volume% or less.
  • the content of tungsten carbide particles in the cemented carbide may be 60 volume% or more and 99.9 volume% or less, 65 volume% or more and 99.8 volume% or less, 66 volume% or more and 99 volume% or less, or 68 volume% or more and 98 volume% or less.
  • the cemented carbide of embodiment 1 contains a binder phase of 0.1 volume % or more and 20 volume % or less.
  • the lower limit of the binder phase content of the cemented carbide is 0.1 volume % or more, 1 volume % or more, 2 volume % or more, 3 volume % or more, 5 volume % or more, or 8 volume % or more, from the viewpoint of improving toughness.
  • the upper limit of the binder phase content of the cemented carbide is 20 volume % or less, 19 volume % or less, 18 volume % or less, 17 volume % or less, 16 volume % or less, or 15 volume % or less, from the viewpoint of improving hardness.
  • the binder phase content of the cemented carbide may be 0.1 volume % or more and 18 volume % or less, 1 volume % or more and 18 volume % or less, 3 volume % or more and 17 volume % or less, 5 volume % or more and 16 volume % or less, or 8 volume % or more and 15 volume % or less.
  • content of the binder phase in the cemented carbide is 18 volume percent or less, the hardness and wear resistance of the cemented carbide are further improved, and the tool life of cutting tools using the cemented carbide as a material is further improved.
  • 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 area photographed for the image is set to the center of the cross section of the cemented carbide, that is, a position that does not include areas with properties that are clearly different from the bulk part, such as near the surface of the cemented carbide (a position where the entire imaged area is 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.
  • (D1) The photographed area of (C1) above is analyzed using an energy dispersive X-ray analyzer (SEM-EDX) attached to a SEM to determine the distribution of the elements identified in (B1) above in the photographed area, and an element mapping image is obtained.
  • SEM-EDX energy dispersive X-ray analyzer
  • the above measurement (G1) 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 cut-out location of the cemented carbide cross section, the photographed area described in (C1) above, and the measurement field described in (G1) above can be arbitrarily set, and even when the tungsten carbide particle content and binder phase content of the cemented carbide are measured multiple times according to the above procedure, there is little variation in the measurement results, and it has been confirmed that the cut-out location of the cemented carbide cross section, the photographed area, and the measurement field can be arbitrarily set without being arbitrary.
  • the tungsten carbide particles include tungsten carbide and a first element.
  • the inclusion of the first element in the tungsten carbide particles is indicated by confirming that the maximum peak M of each of the first elements is between the tungsten peak W1 closest to the origin and another tungsten peak W2 closest to the peak W1 in a first graph obtained by performing line analysis on the cemented carbide.
  • the tungsten carbide particles may contain impurity elements other than carbon, tungsten, and the first element.
  • the impurity content of the tungsten carbide particles (if 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 can have a long tool life regardless of the average particle size of the tungsten carbide particles.
  • the binder phase contains 50% by mass or more of cobalt. This can impart excellent toughness to the cemented carbide.
  • the lower limit of the cobalt content of the binder phase may be 55% by mass or more, 60% by mass or more, or 65% by mass or more.
  • the upper limit of the cobalt content of the binder phase may be 100% by mass or less, less than 100% by mass, 99% by mass or less, 98% by mass or less, 95% by mass or less, or 90% by mass or less.
  • the cobalt content of the binder phase may be 50% by mass or more and less than 100% by mass, 60% by mass or more and 99% by mass or less, 65% by mass or more and 98% by mass or less, 65% by mass or more and 95% by mass or less, or 65% by mass or more and 90% by mass or less.
  • the method for measuring the cobalt content of the binder phase is as follows. Using the same method as (A1) to (F1) for measuring the tungsten carbide particle content and binder phase content of the cemented carbide above, the area where the binder phase exists is identified on the image after binarization processing. The area where the binder phase exists is analyzed using SEM-EDX to measure the cobalt content of the binder phase.
  • the bonding phase may contain, in addition to cobalt, at least one second element selected from the group consisting of boron (B), aluminum (Al), silicon (Si), iron (Fe), nickel (Ni), germanium (Ge), ruthenium (Ru), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), tantalum (Ta) and niobium (Nb).
  • the bonding phase may be composed of cobalt, a second element and unavoidable impurities. Examples of the unavoidable impurities include manganese (Mn), magnesium (Mg), calcium (Ca) and sulfur (S).
  • the content of the unavoidable impurities in the bonding phase is less than 0.1% by mass.
  • the content of the impurity elements in the bonding phase is measured by ICP emission spectrometry.
  • the cemented carbide of the first embodiment contains at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, cerium, yttrium, and boron.
  • the total content of the first elements in the cemented carbide is 0.01 atomic % or more and 20 atomic % or less.
  • the total content of the first elements means the content of one type of first element when the cemented carbide contains one type of first element, and means the total content of all first elements contained in the cemented carbide when the cemented carbide contains two or more types of first elements.
  • the lower limit of the total content of the first element in the cemented carbide is 0.01 atomic % or more, may be 0.07 atomic % or more, may be 0.09 atomic % or more, may be 0.10 atomic % or more, may be 0.50 atomic % or more, may be 1.0 atomic % or more, may be 3.0 atomic % or more, may be 5.0 atomic % or more, or may be 7.0 atomic % or more, from the viewpoint of improving adhesion resistance.
  • the upper limit of the content of the first element in the cemented carbide is 20.0 atomic % or less, may be 17.0 atomic % or less, may be 15.0 atomic % or less, may be 14.0 atomic % or less, or may be 10.0 atomic % or less, from the viewpoint of suppressing deterioration of the basic physical properties of the cemented carbide.
  • the total content of the first element in the cemented carbide may be 0.07 atomic % or more and 17.0 atomic % or less, 0.09 atomic % or more and 15.0 atomic % or less, 0.10 atomic % or more and 15.0 atomic % or less, 0.50 atomic % or more and 15.0 atomic % or less, 1.0 atomic % or more and 14.0 atomic % or less, 3.0 atomic % or more and 14.0 atomic % or less, 5.0 atomic % or more and 10.0 atomic % or less, or 7.0 atomic % or more and 10.0 atomic % or less.
  • the type of the first element contained in the cemented carbide and the content of the first element contained in the cemented carbide are determined by ICP optical emission spectrometry.
  • FIG. 2 is an example of a first graph showing the results obtained by performing line analysis on the cemented carbide of the first embodiment, tungsten, cobalt, and the first element (titanium in FIG. 2), which are elements contained in the cemented carbide, in a coordinate system in which the X axis is the distance [nm] from the position where cobalt shows the maximum intensity, and the Y axis is the normalized intensity (normalized intensity) [a.u.].
  • the binder phase is cobalt.
  • the origin O is 0 nm away from the X axis, and corresponds to the position where cobalt shows the maximum intensity in the line analysis results.
  • the normalized intensity is the intensity shown relatively to the maximum intensity in the area where the line analysis was performed, which is 100.
  • the maximum peak M of the first element is between the peak W1 of tungsten closest to the origin O of the first graph and another peak W2 of tungsten closest to the peak W1.
  • the peak W2 is located farther from the origin O than the peak W1. That is, the distance Pw1 at the maximum peak intensity Iw1 of the peak W1, the distance Pw2 at the maximum peak intensity Iw2 of the peak W2, and the distance P1 at the maximum peak intensity IA of the maximum peak M show a relationship of Pw1 ⁇ P1 ⁇ Pw2 .
  • the peak intensity of the peak of each element in the first graph means the normalized intensity of the peak of each element.
  • the ratio IB/IA of the intensity IB to the maximum peak intensity IA of the maximum peak M is 0.5 or less.
  • the intensity IB is the intensity of the first element at position P2, which is 0.2 nm away from the position P1 of the maximum peak intensity toward the opposite side of the origin.
  • the first element is one type of element (titanium), so there is one peak M.
  • the maximum peaks of the first element exist in the same number as the types of elements, all peaks exist between peaks W1 and W2, and the ratio IB/IA for each peak is 0.5 or less.
  • the upper limit of the ratio IB/IA is 0.5 or less, and may be 0.4 or less, 0.3 or less, 0.2 or less, or 0.1 or less.
  • the lower limit of the ratio IB/IA may be 0 or more, 0.001 or more, 0.002 or more, 0.003 or more, 0.005 or more, 0.01 or more, 0.02 or more, or 0.05 or more.
  • the ratio IB/IA may be 0 or more and 0.5 or less, 0.001 or more and 0.5 or less, 0.005 or more and 0.4 or less, 0.01 or more and 0.3 or less, or 0.05 or more and 0.2 or less.
  • the line analysis of the cemented carbide and the acquisition of the first graph based on the analysis results are performed as follows.
  • the cemented carbide is sliced to a thickness of 30 to 100 nm using an argon ion slicer ("Cryo Ion Slicer IB-09060BCIS” (trademark) manufactured by JEOL Ltd.) at an accelerating voltage of 6 kV and finishing voltage of 2 kV to prepare a measurement sample.
  • the measurement sample is then observed at 200,000 times magnification using a TEM (Transmission Electron Microscopy) ("JEM-ARM300F2" (trademark) manufactured by JEOL Ltd.) at an accelerating voltage of 200 V to obtain a first image (not shown).
  • TEM Transmission Electron Microscopy
  • the tungsten carbide particles are observed as white areas and the binder phase is observed as black areas.
  • the interface between the tungsten carbide particles and the binder phase is arbitrarily selected.
  • the selected interface is positioned so as to pass through the center of the image, and the observation magnification is adjusted so that the field of view size is 10 nm x 10 nm, and a second image is obtained (not shown).
  • the extension direction of the interface is confirmed.
  • Line analysis is performed using an energy dispersive X-ray spectrometer (TEM-EDX) attached to a transmission electron microscope along a first direction perpendicular to the extension direction and extending from a position X1 in the bonding phase to a position X2 in a tungsten carbide particle adjacent to the bonding phase, and the distribution of tungsten, cobalt, and the first element is measured.
  • TEM-EDX energy dispersive X-ray spectrometer
  • 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 position X1 in the bonding phase is set to a position in the first graph where the distance from the distance P1 of the peak M to the origin side is 0.5 nm or more and 5 nm or less, and where the peak of cobalt can be confirmed.
  • Position X2 in the tungsten carbide particle is set to a position in the first graph where the distance from the distance P1 of the peak M to the opposite side of the origin is 2 nm or more and 5 nm or less.
  • the conditions for performing EDX 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.
  • the first graph is obtained by plotting the measurement results for tungsten, cobalt, and the first element in a coordinate system in which the X-axis represents the distance from the position where cobalt shows the maximum intensity, and the Y-axis represents the normalized intensity.
  • first images of non-overlapping fields of view are arbitrarily obtained for a cemented carbide, and the above-mentioned analysis is performed based on each of the first images to obtain five first graphs. If, in four or more first graphs, "the maximum peak M of each of the first elements is between peak W1 and peak W2, and the ratio IB/IA is 0.5 or less," it is determined that, in the first graph of the cemented carbide, "the maximum peak M of each of the first elements is between peak W1 and peak W2, and the ratio IB/IA is 0.5 or less.” In order to obtain this judgment criterion, the inventors performed multiple line analyses for each of multiple cemented carbide.
  • the cemented carbide exhibits the effect of the present disclosure.
  • the manufacturing method of cemented carbide it is presumed that the presence of tungsten and the first element in the interface region between the WC grains and the binder phase will be roughly the same within the same cemented carbide.
  • the cemented carbide of this embodiment can be manufactured by carrying out the steps of preparing raw material powder, mixing, molding, sintering, cooling and HIP in the above-mentioned order. Each step will be described below.
  • the preparation step is a step of preparing raw material powders of materials constituting the cemented carbide material.
  • raw material powders include tungsten carbide powder (hereinafter also referred to as "WC powder"), cobalt (Co) powder, and first element-containing powder.
  • first element-containing powders include TiCN powder, TaC powder, NbC powder , ZrC powder, CeC2 powder, Y2O3 powder, and B4C powder .
  • nickel (Ni) powder and the like can be 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, 0.1 to 3.0 ⁇ m.
  • the average particle size of the raw material powder means the average particle size measured by the FSSS (Fisher Sub-Sieve Sizer) method. The average particle size is measured 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.
  • a ball mill can be used to mix the raw material powders.
  • the mixing conditions can be, for example, a media diameter of 6 mm, a rotation speed of 100 rpm, and a mixing time of 20 hours.
  • 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 compact obtained in the molding step is sintered to obtain a cemented carbide.
  • the compact is first sintered in Ar gas at a pressure of 0.1 MPa and a temperature of 1400° C. for 400 minutes (hereinafter also referred to as the “first sintering step”), and then sintered in Ar gas at a pressure of 5 MPa and a temperature of 1350° C. for 300 minutes (hereinafter also referred to as the “second sintering step”) to obtain a cemented carbide intermediate.
  • the cooling step is a step of cooling the cemented carbide intermediate body after the sintering step.
  • the cemented carbide intermediate body can be quenched in Ar gas under a pressure condition of 100 to 400 MPaG.
  • ⁇ HIP process> The cooled cemented carbide intermediate is subjected to a pressure of 10 MPa for 60 minutes in a hot isostatic pressing (HIP) apparatus, thereby obtaining a cemented carbide.
  • HIP hot isostatic pressing
  • the mixing step is performed using a ball mill for 20 hours, and the sintering step is performed in two stages, firstly by holding at a pressure of 0.1 MPa and a temperature of 1400°C for 400 minutes (first sintering step), and then by holding at a pressure of 5 MPa and a temperature of 1350°C for 300 minutes (second sintering step).
  • first sintering step a pressure of 0.1 MPa and a temperature of 1400°C for 400 minutes
  • second sintering step a pressure of 5 MPa and a temperature of 1350°C for 300 minutes
  • the inventors have newly found that the cemented carbide of the present disclosure can be realized under such mixing and sintering conditions as a result of intensive research. Note that the mixing and sintering conditions used in this embodiment would not have been adopted by those skilled in the art because they would reduce production efficiency.
  • the mixing time is about 10 hours, and the sintering process is carried out in one step by raising the temperature to a specified temperature and maintaining it for a specified time.
  • the first element is randomly arranged in the interface region between the WC particles and the binder phase, and in the first graph, there is no maximum peak M of each of the first elements between peaks W1 and W2.
  • the cutting tool of this embodiment includes a cutting edge made of the cemented carbide of embodiment 1.
  • the cutting edge means a portion involved in cutting. More specifically, the cutting edge means a region surrounded by a cutting edge ridge and a virtual surface that is 0.5 nm 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 this 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. 3 is made of the cemented carbide of embodiment 1.
  • the cemented carbide of this embodiment may constitute the entirety of these tools, or may constitute only a part of them.
  • "constitute a part” refers to a mode in which the cemented carbide of this embodiment is brazed to a predetermined position of any substrate to form a cutting edge.
  • the cutting tool of this embodiment may further include a hard film that covers at least a portion of the surface of the substrate made of cemented carbide.
  • a hard film that covers at least a portion of the surface of the substrate made of cemented carbide.
  • diamond-like carbon or diamond can be used as the hard film.
  • the cutting tool of this embodiment can be obtained by forming the cemented carbide of embodiment 1 into a desired shape.
  • WC powder (average particle size 0.5 ⁇ m), Co powder (average particle size 1.0 ⁇ m), TiCN powder (average particle size 0.1 ⁇ m), TaC powder (average particle size 0.3 ⁇ m), NbC powder (average particle size 0.3 ⁇ m), ZrC powder (average particle size 0.5 ⁇ m), CeC2 powder (average particle size 0.5 ⁇ m), Y2O3 powder (average particle size 0.5 ⁇ m), and B4C powder (average particle size 0.5 ⁇ m) were prepared in the proportions shown in the "Raw Powder" column of Tables 1 to 3.
  • the raw material powders were mixed in a bead mill to obtain a mixed powder.
  • the mixing conditions were as follows.
  • "Packing ratio” refers to the bead packing ratio. ⁇ Samples 1 to 48> Media diameter 6 mm, rotation speed 100 rpm, filling rate 40%, mixing time 20 hours. ⁇ Samples 49 to 76> Media diameter 6 mm, rotation speed 100 rpm, filling rate 40%, mixing time 10 hours.
  • the sintering conditions for each sample were as follows: ⁇ Samples 1 to 48> First sintering step: maintained in Ar gas at a pressure of 0.1 MPa and a temperature of 1400° C. for 400 minutes. Second sintering step: maintained in Ar gas at a pressure of 5 MPa and a temperature of 1,350° C. for 300 minutes. ⁇ Samples 49 to 76> First sintering step: maintained in Ar gas at a pressure of 0.1 MPa and a temperature of 1400° C. for 60 minutes. Second sintering step: None.
  • the "first sintering step” refers to the sintering step carried out immediately after the start of sintering.
  • the “second sintering step” refers to the second sintering step carried out after the first sintering step.
  • the entry “none" for the second sintering step indicates that the second sintering step was not carried out.
  • the cemented carbide intermediate was quenched in Ar gas at a pressure of 200 MPaG. After cooling, a pressure of 10 MPa was applied to the cemented carbide intermediate for 60 minutes in a hot isostatic pressing (HIP) device. This resulted in the cemented carbide samples.
  • HIP hot isostatic pressing
  • ⁇ Total content of first element in cemented carbide The type and total content of the first element in each sample of cemented carbide were measured. The specific measurement method is as described in embodiment 1. The results are shown in the "Type of first element” and “Total content of first element” columns of "Cemented carbide” in Tables 7 to 9.
  • Damage width refers to the maximum length of damage on the flank caused by wear or chipping. In the case of wear, the maximum length corresponds to the maximum amount of wear, and in the case of chipping, it corresponds to the maximum loss length.
  • the cutting distance at which the damage width reaches 0.1 mm is taken as the tool life. The results are shown in the "Cutting test" column of Tables 7 to 9. A longer cutting distance indicates a longer tool life.
  • the cemented carbide and cutting tools of Samples 1 to 48 correspond to Examples.
  • the cemented carbide and cutting tools of Samples 49 to 76 correspond to Comparative Examples. It was confirmed that the cutting tools of Samples 1 to 48 (Examples) exhibited longer tool life in high-speed machining of difficult-to-cut materials than the cutting tools of Samples 49 to 76 (Comparative Examples). This is presumably because the cemented carbide of Samples 1 to 48 (Examples) has a peak M and a ratio IB/IA of 0.5 or less, improving adhesion resistance and suppressing the occurrence of wear and chipping due to adhesion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
PCT/JP2023/027732 2023-07-28 2023-07-28 超硬合金および切削工具 Pending WO2025027677A1 (ja)

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US18/686,491 US12109630B1 (en) 2023-07-28 2023-07-28 Cemented carbide and cutting tool
CN202380047054.0A CN119731358A (zh) 2023-07-28 2023-07-28 硬质合金以及切削工具
EP23935623.1A EP4527962A4 (en) 2023-07-28 2023-07-28 CEMENTED CARBIDE AND CUTTING TOOL
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JP2021110010A (ja) 2020-01-14 2021-08-02 日本特殊合金株式会社 超微粒超硬合金，およびこれを用いた切断用もしくは切削用工具または耐摩耗用工具
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