WO2024166195A1 - 超硬合金およびそれを用いた切削工具 - Google Patents

超硬合金およびそれを用いた切削工具 Download PDF

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Publication number
WO2024166195A1
WO2024166195A1 PCT/JP2023/003932 JP2023003932W WO2024166195A1 WO 2024166195 A1 WO2024166195 A1 WO 2024166195A1 JP 2023003932 W JP2023003932 W JP 2023003932W WO 2024166195 A1 WO2024166195 A1 WO 2024166195A1
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Prior art keywords
cemented carbide
less
volume
tungsten carbide
carbide
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PCT/JP2023/003932
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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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Priority to US18/844,987 priority Critical patent/US12409499B2/en
Priority to EP23921031.3A priority patent/EP4471167A4/en
Priority to CN202380026027.5A priority patent/CN118843707B/zh
Priority to JP2023546138A priority patent/JP7501800B1/ja
Priority to PCT/JP2023/003932 priority patent/WO2024166195A1/ja
Priority to TW112138884A priority patent/TW202440959A/zh
Publication of WO2024166195A1 publication Critical patent/WO2024166195A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B51/00—Tools for drilling machines
    • B23B51/02—Twist drills
    • 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
    • C22C29/02—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
    • 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
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
    • H05K3/0047—Drilling of holes

Definitions

  • This disclosure relates to cemented carbide alloys and cutting tools using the same.
  • 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 present disclosure provides 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 comprises at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium and molybdenum;
  • the cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 10.0 atomic % or less,
  • the binder phase contains 50% by mass or more of cobalt,
  • the cemented carbide is a hard alloy in which the first element does not segregate in a first interface region between adjacent tungsten carbide particles.
  • FIG. 1 is a schematic cross-sectional view of a cemented carbide according to a first embodiment.
  • FIG. 2 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. 3 is a schematic diagram of a cutting tool according to a second embodiment.
  • the present disclosure therefore aims to provide a cemented carbide alloy and a cutting tool equipped with the same that can extend the tool's life, particularly when used as a material for cutting tools for drilling holes in printed circuit boards.
  • the present disclosure provides 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 comprises at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium and molybdenum;
  • the cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 10.0 atomic % or less,
  • the binder phase contains 50% by mass or more of cobalt,
  • the cemented carbide is one in which the first element does not segregate in a first interface region between adjacent tungsten carbide particles.
  • a cemented carbide alloy and a cutting tool having the same that can extend the tool's life, particularly when used as a material for cutting tools for drilling holes in printed circuit boards.
  • the total content of the first element in the cemented carbide may be 0.1 atomic % or more and 5 atomic % or less. This further improves the tool life.
  • the cemented carbide may contain 18 volume percent or less of the binder phase. This further improves the tool life.
  • the first tungsten carbide particle and the second tungsten carbide particle form a first interface
  • the first interface region is composed of a first A region within 1.2 nm of the first interface toward the first tungsten carbide particle side, and a first B region within 1.2 nm of the first interface toward the second tungsten carbide particle side.
  • the cutting tool disclosed herein is a cutting tool having a cutting edge made of the cemented carbide alloy described in any one of (1) to (4) above.
  • the cutting tools disclosed herein can have a long tool life, especially when used to drill holes in printed circuit boards.
  • notations in the format "A ⁇ B" refer to 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, hafnium and molybdenum; The cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 10.0 atomic % or less, The binder phase contains at least 50% by weight of cobalt, The cemented carbide has a first interface region between adjacent tungsten carbide particles, in which the first element does not segregate.
  • the cemented carbide of embodiment 1 can provide a cemented carbide that enables a longer tool life, 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 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 breakage 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 50 mass % or more of cobalt.
  • the cemented carbide has high hardness and strength, and a cutting tool using the cemented carbide can have excellent wear resistance and breakage resistance.
  • the cemented carbide of embodiment 1 contains at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium, and molybdenum, and the cemented carbide contains the first element in a total amount of 0.01 atomic % or more and 10.0 atomic % or less. This improves the heat resistance and reactivity resistance of the cemented carbide.
  • the first element does not segregate in the first interface region between adjacent tungsten carbide particles. This improves the interface strength between the tungsten carbide particles in the cemented carbide, and prevents the tungsten carbide particles from falling off during cutting. Therefore, a cutting tool using the cemented carbide as its material can have a long tool life. Furthermore, the hole position accuracy of the cutting tool is also improved.
  • 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 may be composed of a plurality of tungsten carbide particles and a binder phase.
  • the cemented carbide of the present embodiment may include other phases in addition to the tungsten carbide particles and the binder phase.
  • the other phases may include carbides, nitrides, or carbonitrides containing at least one first 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, TiCN, TaC, NbC, ZrC, HfC, or Mo2C .
  • the cemented carbide of embodiment 1 may be composed of tungsten carbide particles, a binder phase, and other phases.
  • the content of the other phases in the cemented carbide is acceptable within a range that does not impair the effects of the present disclosure.
  • the content of the other phases in the cemented carbide may be more than 0 vol% and less than 20 vol%, more than 0 vol% and less than 18 vol%, or more than 0 vol% and less than 16 vol%.
  • the total content of the WC particles and binder phase 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 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 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 (Inductively Coupled Plasma 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, 62 volume% or more, 64 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, 99.2 volume% or less, 99 volume% or less, 98 volume% or less, 97 volume% or less, or 90 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, 60 volume% or more and 99.2 volume% or less, 64 volume% or more and 97 volume% or less, or 68 volume% or more and 90 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, 0.4 volume % or more, 1 volume % or more, 1.5 volume % or more, 2 volume % or more, 3 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, 18 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, 0.4 volume % or more and 18 volume % or less, 1.5 volume % or more and 16 volume % or less, or 8 volume % or more and 14 volume % or less.
  • the Rockwell hardness (HRC) of the cemented carbide in this embodiment may be, for example, 90 or more and 95 or less, or 91 or more and 95 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 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 (G1) measurement 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 measurements of the tungsten carbide particle content and binder phase content of the cemented carbide are performed multiple times according to the above procedure, there is little variation in the measurement results, and it has been confirmed that arbitrarily setting the cut-out location of the cemented carbide cross section, the photographed area, and the measurement field is not arbitrary.
  • 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 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 52% by mass or more, 60% by mass or more, 66% by mass or more, or 70% 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, 95% by mass or less, 93% 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 95% by mass or less, or 70% 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, binder phase content, and hard phase particle content of the cemented carbide described 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 first element selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium, and molybdenum.
  • the bonding phase may further contain at least one second element selected from the group consisting of nickel (Ni), chromium (Cr), iron (Fe), aluminum (Al), ruthenium (Ru), and rhenium (Re).
  • the bonding phase may consist of cobalt and the first element.
  • the bonding phase may consist of cobalt, the first element, and the second element.
  • the bonding phase may consist of cobalt, the first element, the second element, and unavoidable impurities. Examples of the unavoidable impurities include manganese (Mn), magnesium (Mg), calcium (Ca), and sulfur (S).
  • the cemented carbide of the first embodiment includes at least one first element selected from the group consisting of titanium, tantalum, niobium, zirconium, hafnium and molybdenum, and the cemented carbide includes the first element in a total amount of 0.01 atomic % or more and 10 atomic % or less.
  • the lower limit of the content of the first element of the cemented carbide is 0.01 atomic % or more, 0.03 atomic % or more, 0.1 atomic % or more, 0.8 atomic % or more, 1 atomic % or more, 2 atomic % or more, or 2.3 atomic % or more from the viewpoint of improving the tool life.
  • the upper limit of the content of the first element of the cemented carbide is 10.0 atomic % or less, 9 atomic % or less, 8.2 atomic % or less, 8 atomic % or less, 7.7 atomic % or less, or 5 atomic % or less from the viewpoint of maintaining the strength.
  • the content of the first element of the cemented carbide may be 0.1 atomic % or more and 5 atomic % or less.
  • the atomic number content of the first element in the cemented carbide is measured by ICP (Inductively Coupled Plasma) emission spectrometry (measuring device: Shimadzu Corporation's "ICPS-8100" (trademark)).
  • ICP Inductively Coupled Plasma
  • the first element does not segregate in the first interface region between adjacent tungsten carbide particles. This improves the interface strength between the tungsten carbide particles, and the cemented carbide can have excellent wear resistance and breakage resistance.
  • the cemented carbide is sliced to a thickness of 30 to 100 nm using an argon ion slicer (JEOL Ltd.'s "Cryo Ion Slicer IB-09060BCIS” (trademark)) at an accelerating voltage of 6 kV and a 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) (JEOL Ltd.'s "JEM-ARM300F2" (trademark)) 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 regions, the bonding phase is observed as black regions, and the interfaces are observed as black regions.
  • interfaces between the tungsten carbide particles are arbitrarily selected.
  • the adjacent tungsten carbide particles that form an interface are also referred to as the first tungsten carbide particle and the second tungsten carbide particle.
  • the selected interface is positioned so that it passes near 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 (not shown).
  • the extension direction of the interface is confirmed. Line analysis is performed perpendicular to the extension direction and in a direction from the first tungsten carbide particle to the second tungsten carbide particle to obtain a graph (hereinafter also referred to as the first graph) measuring 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 to the extension direction at an angle of 90° ⁇ 5°.
  • the measurement conditions for obtaining the second 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. 2 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 NET strength (unitless).
  • the first element is tantalum (Ta).
  • 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 position of the first interface region is 2.95 to 5.35 nm on the X-axis.
  • 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 position of the second A region is 0.65 to 2.65 nm on the X-axis
  • the position of the second B region is 5.65 to 7.65 nm on the X-axis.
  • the average NET strength B in the baseline region consisting of the second A region and the second B region of tantalum (first element) is 78.7 (the average NET strength of the second A region is 97.6, and the average NET strength of the second B region is 59.7), and the maximum NET strength A in the first interface region of tantalum (first element) is 112.6.
  • A/B is 1.43, 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.
  • the cemented carbide In the cemented carbide, five non-overlapping first images are randomly obtained, and the above-described analysis is repeatedly performed based on each of the first images. If no segregation of the first element is confirmed in the first interface region in four or more fields, it is determined that the first element is not segregated in the first interface region between adjacent tungsten carbide particles in the cemented carbide.
  • 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 is confirmed multiple times according to the above procedure while changing the area of line analysis, with almost no variation in the results regarding the presence or absence of segregation of the first element in the first interface region. Therefore, it is inferred that the interfacial strength between the tungsten carbide particles of the cemented carbide is improved as long as the above method for confirming the segregation of the first element is performed on the cemented carbide and it is confirmed that the first element is not segregated in the first interface region.
  • the first element can be present in the other phases mentioned above or in cobalt.
  • the cemented carbide of this embodiment can be manufactured by carrying out the steps of preparing raw material powder, mixing, molding, sintering, and cooling 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.
  • the raw material powders include tungsten carbide powder (hereinafter also referred to as "WC powder"), cobalt (Co) powder, and a powder containing a first metal element.
  • the powder containing a first metal element include titanium carbonitride (TiCN) powder, tantalum carbide (TaC) powder, niobium carbide (NbC) powder, zirconium carbide (ZrC) powder, hafnium carbide (HfC) powder, and molybdenum carbide (Mo2C) powder. 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 Co.
  • the particle size distribution of the WC powder is measured using a particle size distribution measuring device manufactured by Microtrac (product name: MT3300EX).
  • 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 a conventionally known mixing method such as an attritor, ball mill, or bead mill.
  • a conventionally known mixing method such as an attritor, ball mill, or bead mill.
  • Conventional known conditions can also be used for the mixing conditions.
  • 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 (e.g., a round bar shape) 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 in which the compact obtained through the molding step is sintered by a sintering HIP (Hot Isostatic Pressing) treatment, which can simultaneously perform sintering and pressing, to obtain a cemented carbide intermediate.
  • a sintering HIP Hot Isostatic Pressing
  • the sintering process can include a first sintering process and a second sintering process.
  • first sintering process the sintering temperature is kept at 1300°C and the sintering pressure is kept at 7 MPa for 240 minutes.
  • second sintering process the temperature is raised to 1360°C while maintaining the sintering pressure at 7 MPa, and the carbide intermediate is kept at 1360°C for 15 minutes to obtain the carbide intermediate.
  • the atmosphere during sintering is not particularly limited, but for example, an N2 gas atmosphere or an inert gas atmosphere such as Ar can be used.
  • 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 to obtain a cemented carbide.
  • the sintering temperature of 1300°C in the first sintering step is lower than the sintering temperature of a general cemented carbide. Furthermore, the sintering time of 240 minutes in the first sintering step is longer than the sintering time of 30 to 60 minutes for a general cemented carbide. It is presumed that this advances the diffusion and rearrangement of atoms during sintering, and that the cemented carbide of the present disclosure can be obtained in which the first element is not segregated in the first interface region between adjacent tungsten carbide particles.
  • cemented carbide of the present disclosure can be realized under such sintering conditions is a new discovery made by the present inventors as a result of intensive research. Note that the sintering temperature and sintering time of the first sintering step were not adopted by those skilled in the art because they would reduce production efficiency.
  • the cutting tool of this embodiment 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 an imaginary surface that is 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.
  • the hard film may be made of, for example, diamond-like carbon or diamond.
  • 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 0.3 ⁇ m), Co powder (average particle size 1.0 ⁇ m), TiCN powder (average particle size 1.0 ⁇ m), TaC powder (average particle size 1.0 ⁇ m), NbC powder (average particle size 1.0 ⁇ m), ZrC powder (average particle size 1.0 ⁇ m), HfC powder (average particle size 1.0 ⁇ m), and Mo 2 C powder (average particle size 1.0 ⁇ m) were prepared in the ratios shown in the "raw powder" column of Table 1, and mixed to obtain a mixed powder.
  • WC powder, Co powder, and TiCN powder were prepared in a mass ratio of 81.8:11.7:6.5, and mixed to obtain a mixed powder. In all samples, mixing was performed for 10 hours using an attritor.
  • the mixed powder was then press-molded to produce a round bar-shaped compact.
  • the compact was then subjected to a first sintering process in Ar gas.
  • the temperature, pressure, and time in the first sintering process are as shown in the "First sintering process” column of Table 2.
  • the temperature was changed to 1360°C and a second sintering process was performed to obtain a cemented carbide intermediate.
  • the holding time in the second sintering process is as shown in the "Second sintering process” column of Table 2.
  • the cemented carbide intermediate was quenched in Ar gas at a pressure of 200 MPaG to obtain each sample of cemented carbide.
  • the cemented carbide and cutting tools of Samples 1 to 13 correspond to Examples.
  • the cemented carbide and cutting tools of Samples 1-1 to 1-8 correspond to Comparative Examples. It was confirmed that the cutting tools of Samples 1 to 13 (Examples) had better hole position accuracy and longer tool life than the cutting tools of Samples 1-1 to 1-8 (Comparative Examples). This is presumably because the cemented carbide of Samples 1 to 13 has excellent wear resistance and breakage resistance.

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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)
  • Drilling Tools (AREA)
PCT/JP2023/003932 2023-02-07 2023-02-07 超硬合金およびそれを用いた切削工具 Ceased WO2024166195A1 (ja)

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US18/844,987 US12409499B2 (en) 2023-02-07 2023-02-07 Cemented carbide and cutting tool using the same
EP23921031.3A EP4471167A4 (en) 2023-02-07 2023-02-07 Super hard alloy and cutting tool using same
CN202380026027.5A CN118843707B (zh) 2023-02-07 2023-02-07 硬质合金以及使用了该硬质合金的切削工具
JP2023546138A JP7501800B1 (ja) 2023-02-07 2023-02-07 超硬合金およびそれを用いた切削工具
PCT/JP2023/003932 WO2024166195A1 (ja) 2023-02-07 2023-02-07 超硬合金およびそれを用いた切削工具
TW112138884A TW202440959A (zh) 2023-02-07 2023-10-12 超硬合金及使用其之切削工具

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US20250100057A1 (en) 2025-03-27
JP7501800B1 (ja) 2024-06-18
CN118843707A (zh) 2024-10-25
EP4471167A1 (en) 2024-12-04
TW202440959A (zh) 2024-10-16
CN118843707B (zh) 2025-05-27
US12409499B2 (en) 2025-09-09
JPWO2024166195A1 (https=) 2024-08-15

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