WO2025069215A1 - 超硬合金 - Google Patents

超硬合金 Download PDF

Info

Publication number
WO2025069215A1
WO2025069215A1 PCT/JP2023/035011 JP2023035011W WO2025069215A1 WO 2025069215 A1 WO2025069215 A1 WO 2025069215A1 JP 2023035011 W JP2023035011 W JP 2023035011W WO 2025069215 A1 WO2025069215 A1 WO 2025069215A1
Authority
WO
WIPO (PCT)
Prior art keywords
cemented carbide
binder phase
less
mass
hardness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2023/035011
Other languages
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to EP23954191.5A priority Critical patent/EP4703488A1/en
Priority to US18/714,586 priority patent/US12448670B2/en
Priority to PCT/JP2023/035011 priority patent/WO2025069215A1/ja
Priority to JP2024513342A priority patent/JP7694812B1/ja
Priority to CN202380100840.2A priority patent/CN121569055A/zh
Priority to TW113122850A priority patent/TW202513815A/zh
Publication of WO2025069215A1 publication Critical patent/WO2025069215A1/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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.
  • 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 comprises 89 volume % or more of the tungsten carbide particles and the binder phase in total,
  • the cemented carbide contains 1.8 vol. % or more and 20.0 vol. % or less of the binder phase, the binder phase comprises cobalt;
  • the cemented carbide contains 1.0 mass% or more of cobalt,
  • the percentage (H2/H1) ⁇ 100 of the hardness H2GPa at 600° C. to the hardness H1GPa at 25° C. measured by a nanoindenter method of the binder phase is 25% or more.
  • FIG. 1 is a diagram illustrating a cross section of a cemented carbide according to an embodiment of the present disclosure.
  • the present disclosure therefore aims to provide a cemented carbide alloy that enables a longer tool life, particularly when used as a material for cutting tools for high-speed machining of high-hardness materials.
  • 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 the binder phase in an amount of 1.8% by volume or more and 20.0% by volume or less, the binder phase comprises cobalt; The cemented carbide contains 1.0 mass% or more of cobalt, The percentage (H2/H1) ⁇ 100 of the hardness H2GPa at 600° C. to the hardness H1GPa at 25° C. measured by a nanoindenter method of the binder phase is 25% or more.
  • the percentage (H2/H1) x 100 may be 50% or more. This makes it possible to provide a cemented carbide that can further extend the tool life of cutting tools, especially in high-speed machining of high-hardness materials.
  • the hardness H1 may be 7.0 GPa or more. This makes it possible to provide a cemented carbide that can further extend the tool life of cutting tools, especially in high-speed machining of high-hardness materials.
  • the binder phase further contains a first element
  • the first element may be at least one element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum, thereby providing a cemented carbide that can further extend the tool life of a cutting tool, particularly in high-speed machining of high-hardness materials.
  • 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. This makes it possible to provide a cemented carbide alloy that can further extend the tool life of cutting tools, especially in high-speed machining of high-hardness materials.
  • 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.
  • a cemented carbide according to one embodiment of the present disclosure will be described with reference to FIG.
  • One embodiment of the present disclosure (hereinafter also referred to as "the present embodiment") is A cemented carbide (3) comprising a plurality of tungsten carbide particles (1) and a binder phase (2),
  • the cemented carbide 3 contains the tungsten carbide particles 1 and the binder phase 2 in a total amount of 89 volume % or more,
  • the cemented carbide 3 contains the binder phase 2 in an amount of 1.8 vol.% or more and 20.0 vol.% or less,
  • the binder phase 2 contains cobalt,
  • the cemented carbide 3 contains 1.0 mass% or more of cobalt,
  • the percentage (H2/H1) ⁇ 100 of the hardness H2GPa at 600° C. to the hardness H1GPa at 25° C. measured by a nanoindenter method of the binder phase 2 is 25% or more.
  • the cemented carbide 3 of this embodiment comprises a plurality of tungsten carbide particles 1 (hereinafter also referred to as "WC particles 1") and a binder phase 2, and the total content of the WC particles 1 and the binder phase 2 in the cemented carbide 3 is 89 volume % or more.
  • WC particles 1 tungsten carbide particles 1
  • binder phase 2 the total content of the WC particles 1 and the binder phase 2 in the cemented carbide 3 is 89 volume % or more.
  • the cemented carbide 3 of the first embodiment contains 1.8 volume % or more and 20.0 volume % or less of the binder phase 2, the binder phase 2 contains cobalt, and the cemented carbide 3 contains 1.0 mass % or more of cobalt. Furthermore, the percentage (H2/H1) x 100 of the hardness H2GPa at 600°C to the hardness H1GPa at 25°C measured by the nanoindenter method of the binder phase 2 is 25% or more, and the "decrease in hardness of the cemented carbide 3" caused by changing from a condition of 25°C (in other words, a room temperature condition) to a condition of 600°C (in other words, a high temperature condition) can be suppressed. As a result, the "decrease in hardness of the cemented carbide 3" is suppressed, and a cutting tool using the cemented carbide 3 can have excellent wear resistance, especially in high-speed machining of high-hardness materials.
  • the cemented carbide 3 contains tungsten carbide particles 1 and binder phase 2 in a total amount of 89% or more by volume. This allows the hardness of the cemented carbide 3 to be increased.
  • the cemented carbide 3 may contain tungsten carbide particles 1 and binder phase 2 in a total amount of 90% or more by volume, 91% or more by volume, or 92% or more by volume.
  • the upper limit of the total content of the tungsten carbide particles 1 and binder phase 2 may be, for example, 100% or less by volume, 99% or less by volume, or 98% or less by volume.
  • the cemented carbide 3 may contain tungsten carbide particles 1 and binder phase 2 in a total amount of 90% or more by volume and 100% or less by volume, 91% or more by volume and 100% or less by volume, or 92% or more by volume and 100% or less by volume.
  • the cemented carbide 3 contains 1.8 volume % or more and 20.0 volume % or less of the binder phase 2. This allows the cemented carbide 3 to have increased hardness and toughness.
  • the lower limit of the content of the binder phase 2 in the cemented carbide 3 may be 2.0 volume % or more, 3.0 volume % or more, or 4.0 volume % or more.
  • the upper limit of the content of the binder phase 2 in the cemented carbide 3 may be 19.0 volume % or less, 18.0 volume % or less, or 17.0 volume % or less.
  • the cemented carbide 3 may contain 2.0 volume % or more and 19.0 volume % or less of the binder phase 2, 3.0 volume % or more and 18.0 volume % or less of the binder phase 2, or 4.0 volume % or more and 17.0 volume % or less of the binder phase 2.
  • the cemented carbide 3 of the first embodiment can be composed of a plurality of tungsten carbide particles 1 and a binder phase 2.
  • the cemented carbide 3 of the present embodiment can include other phases (not shown) in addition to the tungsten carbide particles 1 and the binder phase 2.
  • the other phases include carbides, nitrides, or carbonitrides containing at least one second 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 is, for example, TiCN, TaC, NbC, ZrC, HfC, or Mo2C .
  • the cemented carbide 3 of the first embodiment can be composed of tungsten carbide particles 1, a binder phase 2, and other phases.
  • the content of the other phases in the cemented carbide 3 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 3 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 tungsten carbide particles 1 and the binder phase 2 in the cemented carbide 3 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 3 of the first embodiment may contain impurities.
  • the impurities include iron (Fe), calcium (Ca), oxygen (O), and sulfur (S).
  • the impurity content of the cemented carbide 3 is acceptable within a range that does not impair the effects of the present disclosure.
  • the impurity content of the cemented carbide 3 may be 0 mass% or more and less than 0.1 mass%.
  • the impurity content of the cemented carbide 3 is measured by ICP optical emission spectroscopy (Inductively Coupled Plasma Emission Spectroscopy (measuring device: Shimadzu Corporation "ICPS-8100" (trademark)).
  • the method for measuring the content [volume %] of tungsten carbide particles 1 in cemented carbide 3 and the content [volume %] of binder phase 2 in cemented carbide 3 is as follows.
  • the mirror-finished surface of the cemented carbide 3 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 3, that is, a position that does not include any part whose properties are clearly different from the bulk part, such as the surface area of the cemented carbide 3 (a position where the entire photographed area is the bulk part of the cemented carbide 3).
  • 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 content of the other phases in the cemented carbide 3 can be obtained by subtracting the content [volume %] of the tungsten carbide particles 1 and the content [volume %] of the binder phase 2 measured by the above procedure from the total cemented carbide 3 (100 volume %).
  • the binder phase 2 contains cobalt, and the cemented carbide 3 contains 1.0 mass% or more of cobalt. This can impart excellent toughness to the cemented carbide 3.
  • the binder phase 2 may contain 50 mass% or more of cobalt, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more of cobalt.
  • the binder phase 2 may be made of cobalt.
  • the binder phase 2 may also be made of cobalt and a first element described later.
  • Cobalt in the cemented carbide 3 may be present only in the binder phase 2.
  • the lower limit of the content of cobalt in the cemented carbide 3 may be 2.0 mass% or more, 3.0 mass% or more, or 4.0 mass% or more.
  • the upper limit of the content of cobalt in the cemented carbide 3 may be 20 mass% or less, 15 mass% or less, 12 mass% or less, or 10 mass% or less.
  • the cemented carbide 3 may contain 1.0 mass % or more and 20 mass % or less of cobalt, 2.0 mass % or more and 15 mass % or less of cobalt, or 3.0 mass % or more and 12 mass % or less of cobalt.
  • the method for measuring the cobalt content in the cemented carbide 3 is as follows. First, a photographed area is set using the same method as (A1) to (C1) of the method for measuring the content of the tungsten carbide particles 1 and the content of the binder phase 2 in the cemented carbide 3 described above. Next, the photographed area is analyzed using SEM-EDX to identify the distribution of the elements identified in (B1) above in the photographed area, and an element mapping image is obtained, while at the same time identifying the cobalt content in the cemented carbide 3. The method for measuring the "cobalt content in the binder phase 2" is as follows.
  • a region in which the binder phase 2 exists is identified on the image after the binarization process using the same method as (A1) to (F1) of the method for measuring the content of the tungsten carbide particles 1 and the content of the binder phase 2 in the cemented carbide 3 described above.
  • the region in which the binder phase 2 exists is analyzed using SEM-EDX to measure the "cobalt content in the binder phase 2".
  • the method for determining that "cobalt in cemented carbide 3 exists only in binder phase 2" is as follows.
  • the regions where tungsten carbide particles 1 exist and the regions where binder phase 2 exist are determined on the image after binarization processing using the same method as (A1) to (F1) for measuring the content of tungsten carbide particles 1 and the content of binder phase 2 in cemented carbide 3 described above.
  • the binder phase 2 may further contain a first element, which may be at least one element selected from the group consisting of silicon, phosphorus, germanium, tin, rhenium, ruthenium, osmium, iridium, and platinum. This makes it possible to provide a cemented carbide 3 that can further extend the tool life of a cutting tool, especially in high-speed machining of high-hardness materials.
  • the content of the first element in the cemented carbide 3 may be 0.01% by mass or more and 1.0% by mass or less. This allows the binder phase 2 to have both better hardness and better toughness.
  • the content of the first element in the binder phase 2 may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less.
  • the first element in the cemented carbide 3 may be present only in the binder phase 2.
  • the lower limit of the content of the first element in the cemented carbide 3 may be 0.01% by mass or more, 0.04% by mass or more, or 0.1% by mass or more.
  • the upper limit of the content of the first element in the cemented carbide 3 may be 1.0% by mass or less, 0.8% by mass or less, or 0.6% by mass or less.
  • the content of the first element in the cemented carbide 3 may be 0.04% by mass or more and 0.8% by mass or less, or 0.1% by mass or more and 0.6% by mass or less.
  • the percentage ⁇ M1/(M1+M2) ⁇ 100 of the mass M1 of the first element relative to the total 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 binder phase 2 to have both better hardness and better toughness, and therefore it is possible to provide a cemented carbide 3 that can further extend the tool life of a cutting tool, especially in high-speed machining of high-hardness materials.
  • the mass M1 of the first element means the total mass of all types of first elements when the binder phase contains two or more types of first elements.
  • the lower limit of the percentage ⁇ M1/(M1+M2) ⁇ 100 may be 1% or more, 2% or more, or 3% or more.
  • the upper limit of the percentage ⁇ M1/(M1+M2) ⁇ 100 may be 6% or less, 5% or less, or 4% or less.
  • the percentage ⁇ M1/(M1+M2) ⁇ x 100 may be 2% or more and 5% or less, or 3% or more and 4% or less.
  • the percentage (H2/H1) ⁇ 100 of the hardness H2GPa at 600° C. relative to the hardness H1GPa at 25° C. measured by the nanoindenter method of the binder phase 2 is 25% or more. This makes it possible to suppress the "decrease in hardness of the cemented carbide 3" that accompanies a change from a condition of 25° C. (in other words, a room temperature condition) to a condition of 600° C. (in other words, a high temperature condition).
  • the lower limit of the percentage (H2/H1) ⁇ 100 may be 50% or more, 60% or more, or 70% or more.
  • the upper limit of the percentage (H2/H1) ⁇ 100 may be 85% or less, 80% or less, 75% or less, or 61% or less.
  • the percentage (H2/H1) ⁇ 100 may be 25% or more and 85% or less, 50% or more and 80% or less, or 60% or more and 75% or less.
  • Hardness H1 may be 7.0 GPa or more. This allows the cemented carbide 3 to have better wear resistance.
  • the lower limit of hardness H1 may be 7.0 GPa or more, 7.1 GPa or more, or 7.2 GPa or more.
  • the upper limit of hardness H1 may be 8.2 GPa or less, 8.0 GPa or less, or 7.8 GPa or less.
  • Hardness H1 may be 7.0 GPa or more and 8.2 GPa or less, 7.1 GPa or more and 8.0 GPa or less, or 7.2 GPa or more and 7.8 GPa or less.
  • Hardness H2 may be 1.8 GPa or more. This allows the cemented carbide 3 to have better wear resistance.
  • the lower limit of hardness H2 may be 1.8 GPa or more, 1.9 GPa or more, or 2.0 GPa or more.
  • the upper limit of hardness H2 may be 4.0 GPa or less, 3.9 GPa or less, or 3.7 GPa or less.
  • Hardness H2 may be 1.8 GPa or more and 4.0 GPa or less, 1.9 GPa or more and 3.9 GPa or less, or 2.0 GPa or more and 3.7 GPa or less.
  • the hardness H1GPa and the hardness H2GPa are measured by a nanoindenter method (Bruker's "Hysitron TI 980 Triboindenter”).
  • the nanoindenter method is a method conforming to ISO14577, and is performed under the conditions of a measurement load of 0.5 mN, a load time of 0.1 seconds, a load holding time of 0.1 seconds, and an unloading time of 0.1 seconds.
  • the measurement objects are each of a total of 10 arbitrary bonding phases 2 exposed by polishing the surface of the cemented carbide 3 using a cross-session polisher (CP) processing device (JEOL Ltd.'s "IB-19500CP Cross-Section Sample Preparation Device” (trademark)).
  • CP cross-session polisher
  • the hardness H1GPa is the average value of the hardness of each of the total 10 bonding phases 2 measured under conditions of 25°C.
  • the average hardness of each of the 10 bonding phases 2 measured under the condition of 600°C is defined as the hardness H2GPa.
  • the tungsten carbide particles 1 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 therein, as long as the effect of the present disclosure is not impaired.”
  • the content of impurities in the tungsten carbide particles (when the impurity elements are two or more types, the total content of the elements) is less than 0.1 mass%.
  • the content of impurities in the tungsten carbide particles is measured by ICP emission spectroscopy (Inductively Coupled Plasma Emission Spectroscopy, measuring device: "ICPS-8100" (trademark) manufactured by Shimadzu Corporation).
  • the average particle size of the tungsten carbide particles 1 is not particularly limited.
  • the average particle size of the tungsten carbide particles 1 can be, for example, 0.5 ⁇ m or more and 3 ⁇ m or less. It has been confirmed that the cemented carbide 3 of the first embodiment can have a long tool life regardless of the average particle size of the tungsten carbide particles 1.
  • the cemented carbide 3 of this embodiment can be used for cutting tools.
  • the cutting tools include cutting tools for general-purpose machining. More specifically, cutting tools such as drills, end mills, indexable cutting tips for drills, indexable cutting tips for end mills, indexable cutting tips for milling, indexable cutting tips for turning, metal saws, gear cutting tools, reamers, taps, etc. can be used.
  • the cemented carbide of this embodiment can be manufactured by carrying out the steps of preparing raw material powder, mixing, molding, sintering, first cooling, heating, HIP (Hot Isostatic Pressing), and second cooling in the above order. Each step will be described below.
  • the preparation step is a step of preparing raw material powders of materials constituting the cemented carbide.
  • raw material powders include tungsten carbide powder (hereinafter also referred to as "WC powder") and cobalt (Co) powder.
  • first element powder, niobium carbide (NbC) powder, tungsten carbide (TaC) powder, titanium carbonitride (TiCN) powder, and zirconium carbide (ZrC) powder 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, 0.5 to 2 ⁇ 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 at a predetermined ratio.
  • the mixing step produces a mixed powder in which the raw material powders are mixed.
  • the mixing ratio of the raw material powders is adjusted appropriately according to the composition of the target cemented carbide.
  • the first element powder may be used as the raw material powder. This makes it easier to provide the cemented carbide with the desired "hardness at 25°C measured by the nanoindenter method of the binder phase" since the first element is sufficiently dissolved in the binder phase.
  • the total content of the powders other than the WC powder, Co powder, and the first element powder in the mixed powder may be less than 5% by mass.
  • the binder phase content and the WC particle content can each be within a desired range.
  • 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 body.
  • the sintering conditions in this embodiment are as follows: The compact is heated to 1360° C. and held at 1360° C. for 1 hour.
  • the first cooling step is a step of cooling the cemented carbide intermediate body. More specifically, the cemented carbide intermediate body is cooled to 1000° C.
  • the cooling rate is not particularly limited, and may be, for example, 20° C./min.
  • the heating step is a step of heating the cemented carbide intermediate body. More specifically, the heating temperature is 1200° C., and the temperature is maintained for 0.25 hours.
  • the HIP process is a process of performing HIP treatment on the cemented carbide intermediate body.
  • the conditions of the HIP process in this embodiment are as follows: The cemented carbide intermediate body is held under a pressure of 100 MPa for 2 hours.
  • the second cooling step is a step of cooling the cemented carbide intermediate body. More specifically, the cemented carbide intermediate body is cooled to 800° C. The cooling rate is 20° C./min. In this way, the cemented carbide of the first embodiment can be obtained.
  • the sintering step is performed by heating the compact to 1360°C and holding it at 1360°C for 1 hour.
  • the first cooling step is performed by cooling the cemented carbide intermediate to 1000°C.
  • the heating step is performed under conditions of a temperature of 1200°C and a holding time of 0.25 hours.
  • the HIP step is performed under conditions of a pressure of 100 MPa and a time of 2 hours.
  • the second cooling step is performed by setting the cooling rate to 800°C at 20°C/min.
  • a cemented carbide can be produced in which the percentage (H2/H1) x 100 of the hardness H2GPa at 600°C relative to the hardness H1GPa at 25°C measured by the nanoindenter method of the binder phase is 25% or more.
  • the fact that the cemented carbide of the present disclosure can be realized by such sintering conditions, the first cooling step, the heating step, the HIP step, and the second cooling step was newly discovered by the present inventors as a result of intensive research.
  • the nanoindenter method can be performed in accordance with ISO 14577 under conditions of a measurement load of 0.5 mN, a loading time of 0.1 seconds, a load holding time of 0.1 seconds, and an unloading time of 0.1 seconds.
  • WC powder (average particle size: 1 ⁇ m), Co powder (average particle size: 1 ⁇ m), first element powder, and TiCN powder (average particle size: 1 ⁇ m) were prepared.
  • first element powders Si powder (average particle size: 1 ⁇ m), Ge powder (average particle size: 1 ⁇ m), Sn powder (average particle size: 1 ⁇ m), Os powder (average particle size: 1 ⁇ m), Ir powder (average particle size: 1 ⁇ m), Pt powder (average particle size: 1 ⁇ m), P powder (average particle size: 1 ⁇ m), Re powder (average particle size: 1 ⁇ m), and Ru powder (average particle size: 1 ⁇ m) were prepared.
  • ⁇ Mixing step> The raw material powders were mixed in the ratios shown in Tables 1 and 2 for 10 hours using an attritor to obtain mixed powders.
  • ⁇ Second cooling step> The cemented carbide intermediate body after the HIP process was cooled to 800° C. at the cooling rates shown in Tables 3 and 4 to obtain a cemented carbide.
  • ⁇ M1/(M1+M2) ⁇ 100> For each cemented carbide sample, ⁇ M1/(M1+M2) ⁇ 100 was determined by the method described in embodiment 1. The results are shown in the column " ⁇ M1/(M1+M2) ⁇ 100[%]" in Tables 5 and 6.
  • ⁇ Cutting test> First, three end mills (GSXB20000 type) with a blade diameter of ⁇ 8 mm were prepared as cutting tools for each sample by machining round bars made of cemented carbide for each sample. Next, the end mills of each sample were used to perform cutting under the following cutting conditions, and the cutting distance until the end mills were worn down to 0.05 mm was measured. For each sample, the cutting length was obtained by calculating the average cutting distance of each of the three end mills. The obtained results are shown in the "Cutting Length [m]" column of Tables 5 and 6, respectively. Note that the longer the cutting length, the longer the tool life.
  • the cemented carbide alloys of samples 1 to 20 correspond to the examples.
  • the cemented carbide alloys of samples 101 to 114 correspond to the comparative examples. From the results in Tables 5 and 6, it was found that the cemented carbide alloys of samples 1 to 20 enable a longer tool life than the cemented carbide alloys of samples 101 to 114, even when used as materials for cutting tools for high-speed machining of high-hardness materials.
  • cemented carbide alloys of samples 1 to 20 can extend the tool life even when used as materials for cutting tools for high-speed machining of high-hardness materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
PCT/JP2023/035011 2023-09-26 2023-09-26 超硬合金 Pending WO2025069215A1 (ja)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP23954191.5A EP4703488A1 (en) 2023-09-26 2023-09-26 Cemented carbide
US18/714,586 US12448670B2 (en) 2023-09-26 2023-09-26 Cemented carbide
PCT/JP2023/035011 WO2025069215A1 (ja) 2023-09-26 2023-09-26 超硬合金
JP2024513342A JP7694812B1 (ja) 2023-09-26 2023-09-26 超硬合金
CN202380100840.2A CN121569055A (zh) 2023-09-26 2023-09-26 硬质合金
TW113122850A TW202513815A (zh) 2023-09-26 2024-06-20 超硬合金

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2023/035011 WO2025069215A1 (ja) 2023-09-26 2023-09-26 超硬合金

Publications (1)

Publication Number Publication Date
WO2025069215A1 true WO2025069215A1 (ja) 2025-04-03

Family

ID=95067751

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/035011 Pending WO2025069215A1 (ja) 2023-09-26 2023-09-26 超硬合金

Country Status (6)

Country Link
US (1) US12448670B2 (https=)
EP (1) EP4703488A1 (https=)
JP (1) JP7694812B1 (https=)
CN (1) CN121569055A (https=)
TW (1) TW202513815A (https=)
WO (1) WO2025069215A1 (https=)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6514456B1 (en) * 1999-10-12 2003-02-04 Plansee Tizit Aktiengesellschaft Cutting metal alloy for shaping by electrical discharge machining methods
JP2004131769A (ja) 2002-10-09 2004-04-30 Toshiba Tungaloy Co Ltd 超微粒超硬合金
JP2006037160A (ja) * 2004-07-27 2006-02-09 Tungaloy Corp 焼結体
WO2011002008A1 (ja) * 2009-06-30 2011-01-06 株式会社タンガロイ サーメットおよび被覆サーメット
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
US20190345589A1 (en) * 2017-08-23 2019-11-14 Element Six Gmbh Cemented carbide material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111386158B (zh) * 2018-01-31 2022-08-19 日立金属株式会社 复合硬质合金轧辊以及复合硬质合金轧辊的制造方法
JP7131738B1 (ja) * 2021-04-28 2022-09-06 住友電工ハードメタル株式会社 超硬合金及びそれを用いた超高圧発生装置用金型

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6514456B1 (en) * 1999-10-12 2003-02-04 Plansee Tizit Aktiengesellschaft Cutting metal alloy for shaping by electrical discharge machining methods
JP2004131769A (ja) 2002-10-09 2004-04-30 Toshiba Tungaloy Co Ltd 超微粒超硬合金
JP2006037160A (ja) * 2004-07-27 2006-02-09 Tungaloy Corp 焼結体
WO2011002008A1 (ja) * 2009-06-30 2011-01-06 株式会社タンガロイ サーメットおよび被覆サーメット
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
US20190345589A1 (en) * 2017-08-23 2019-11-14 Element Six Gmbh Cemented carbide material

Also Published As

Publication number Publication date
EP4703488A1 (en) 2026-03-04
CN121569055A (zh) 2026-02-24
US20250101548A1 (en) 2025-03-27
TW202513815A (zh) 2025-04-01
JPWO2025069215A1 (https=) 2025-04-03
JP7694812B1 (ja) 2025-06-18
US12448670B2 (en) 2025-10-21

Similar Documents

Publication Publication Date Title
JP7666745B1 (ja) 超硬合金および切削工具
JP7694812B1 (ja) 超硬合金
JP7694813B1 (ja) 超硬合金
JP7694819B1 (ja) 超硬合金
JP7694811B1 (ja) 超硬合金
JP7666744B1 (ja) 超硬合金および切削工具
JP7670234B1 (ja) 超硬合金および切削工具
JP7501800B1 (ja) 超硬合金およびそれを用いた切削工具
JP7616426B1 (ja) 超硬合金およびそれを用いた切削工具
WO2026088289A1 (ja) 超硬合金および切削工具
WO2026033733A1 (ja) 超硬合金および切削工具
WO2026088290A1 (ja) 超硬合金および切削工具
WO2026088288A1 (ja) 超硬合金および切削工具
JP2025076775A (ja) 超硬合金および切削工具
WO2026033732A1 (ja) 超硬合金および切削工具

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2024513342

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2024513342

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23954191

Country of ref document: EP

Kind code of ref document: A1

WWG Wipo information: grant in national office

Ref document number: 18714586

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2023954191

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

ENP Entry into the national phase

Ref document number: 2023954191

Country of ref document: EP

Effective date: 20251126

WWP Wipo information: published in national office

Ref document number: 2023954191

Country of ref document: EP