WO2024181015A1 - 超硬合金、被覆工具及び切削工具 - Google Patents

超硬合金、被覆工具及び切削工具 Download PDF

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Publication number
WO2024181015A1
WO2024181015A1 PCT/JP2024/003396 JP2024003396W WO2024181015A1 WO 2024181015 A1 WO2024181015 A1 WO 2024181015A1 JP 2024003396 W JP2024003396 W JP 2024003396W WO 2024181015 A1 WO2024181015 A1 WO 2024181015A1
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Prior art keywords
cemented carbide
coated tool
layer
tool
cutting
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Ceased
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PCT/JP2024/003396
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English (en)
French (fr)
Japanese (ja)
Inventor
匠 橋本
佑介 塗木
哲平 長田
洋之 金城
尚久 松田
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Kyocera Corp
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Kyocera Corp
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Priority to JP2025503677A priority Critical patent/JPWO2024181015A1/ja
Priority to CN202480005325.0A priority patent/CN120265405A/zh
Publication of WO2024181015A1 publication Critical patent/WO2024181015A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • 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

Definitions

  • This disclosure relates to cemented carbide, coated tools and cutting tools.
  • Cemented carbide containing WC (tungsten carbide) is used as the substrate for coated tools and is used in cutting tools. Such cemented carbide is required to have wear resistance.
  • Patent Document 1 As an example of a cemented carbide with excellent wear resistance, the cemented carbide (super-hard sintered body) described in International Publication No. 2018/003877 (Patent Document 1) is known.
  • the cemented carbide described in Patent Document 1 has a Vickers hardness of 1600 to 2600 HV at room temperature and a Vickers hardness of 1500 to 2500 HV at 900°C.
  • a non-limiting aspect of the present disclosure is a cemented carbide containing W, C, and an iron group metal.
  • the ratio of the average Vickers hardness at 1073K to the average Vickers hardness at 303K is 0.4 or more.
  • FIG. 1 is a perspective view of a non-limiting one-sided cemented carbide (coated tool) of the present disclosure.
  • FIG. 2 is a cross-sectional view showing the vicinity of a surface of a non-limiting one-sided coated tool of the present disclosure.
  • FIG. 2 is a cross-sectional view showing the vicinity of a surface of a non-limiting one-sided coated tool of the present disclosure.
  • FIG. 1 is a perspective view of a non-limiting one-sided cutting tool of the present disclosure.
  • cemented carbide 1 according to one aspect of the present disclosure will be described in detail with reference to the drawings.
  • the cemented carbide 1 may include any component member not shown in each of the drawings referred to.
  • the dimensions of the components in each drawing do not faithfully represent the actual dimensions of the components and the dimensional ratios of each component.
  • the cemented carbide 1 may contain W (tungsten), C (carbon), and an iron group metal.
  • the ratio of the average Vickers hardness at 1073K (800°C) to the average Vickers hardness at 303K (30°C) of the cemented carbide 1 may be 0.4 or more. In other words, the ratio (average Vickers hardness at 1073K/average Vickers hardness at 303K) may be 0.4 or more.
  • cemented carbide 1 when the above ratio is 0.4 or more, the Vickers hardness at high temperatures is maintained high even if the amount of iron group metal is large. In other words, the high temperature hardness is high in relation to the amount of iron group metal. Since the high high temperature hardness is high, the wear resistance is high. Furthermore, since the amount of iron group metal is large, toughness is easily improved and the chipping resistance is also high. Therefore, cemented carbide 1 has high wear resistance and chipping resistance. With cemented carbide 1, it is possible to achieve both high wear resistance and high chipping resistance.
  • high temperature may mean 873 to 1073 K (600 to 800°C).
  • 303 K (30°C) is a temperature equivalent to room temperature.
  • the average Vickers hardness may be a value measured in accordance with JIS Z 2244: 2009. Specific measurement conditions for the average Vickers hardness may be set, for example, as follows. Measuring device: Nikon "QM-2" Push-in strength: 1000gf Atmosphere: Argon (Ar) Measurement temperature: 303K (30°C), 1073K (800°C) Number of measurements: 5
  • the above ratio may be 0.43 or more. In this case, wear resistance and chipping resistance are likely to be improved.
  • the average Vickers hardness at 303K may be 1200 to 1800.
  • the average Vickers hardness at 1073K may be 400 to 800.
  • the above ratio may be 0.4 to 0.5.
  • the above ratio may be 0.43 to 0.5.
  • the product of the above ratio and the amount of iron group metal may be 3 or more. In this case, wear resistance and chipping resistance are likely to be improved.
  • the above product may be 3.74 or more. In this case, wear resistance and chipping resistance are more likely to be improved.
  • the amount of iron group metal may be 5 to 15 mass%.
  • the above product may be 3 to 7.5.
  • the above product may be 3.74 to 7.5.
  • the cemented carbide 1 may have a hard phase containing W and C.
  • the hard phase may contain W and C as the main components.
  • "Main component” may mean the component with the largest mass% value compared to other components. Specifically, the top two mass% values of the components contained in the hard phase may be W and C.
  • the cemented carbide 1 (hard phase) may contain W and C in the form of WC.
  • iron group metals examples include Co and Ni (nickel).
  • the iron group metal may be cobalt.
  • the cemented carbide 1 may have a binder phase containing an iron group metal.
  • the binder phase may contain an iron group metal as a main component.
  • the binder phase may function as a phase that bonds adjacent hard phases.
  • the cemented carbide 1 may have a ⁇ phase.
  • the ⁇ phase may be a composite carbide containing at least one of Ti (titanium), Nb (niobium), Ta (tantalum), and Zr (zirconium), and W.
  • the amount of ⁇ phase may be 5 to 15 mass%.
  • the amount of ⁇ phase may be 7 to 15 mass%. If the amount of ⁇ phase is such a relatively large proportion, the above ratio tends to be 0.4 or more.
  • the composition of the cemented carbide 1 may be measured, for example, by Energy Dispersive X-ray Spectroscopy (EDS). The measurement may be performed using an EDS attached to an electron microscope. Examples of electron microscopes include a scanning electron microscope (SEM) and a transmission electron microscope (TEM).
  • WC powder, Co powder, TiC powder, TaC powder, ZrC powder, NbC powder, etc. may be prepared as raw material powders.
  • the proportion of Co powder may be 5 to 15 mass%.
  • the proportion of TiC powder may be 0.5 to 15 mass%.
  • the proportion of TaC powder may be 0 to 5 mass%.
  • the proportion of ZrC powder may be 0 to 3 mass%.
  • the proportion of NbC powder may be 0 to 5 mass%.
  • the remainder may be WC powder.
  • the average particle size of the raw material powder may be appropriately selected in the range of 0.1 to 10 ⁇ m.
  • the average particle size of the raw material powder may be a value measured by the Microtrack method.
  • the prepared raw material powders may be mixed and molded to obtain a molded body.
  • molding methods include press molding, casting, extrusion molding, and cold isostatic pressing.
  • the obtained molded body may be subjected to a binder removal treatment and then fired.
  • the firing may be performed in a non-oxidizing atmosphere such as a vacuum, an argon atmosphere, or a nitrogen atmosphere.
  • the firing temperature may be 1500 to 1600°C, or may be 1550 to 1600°C. When firing at such a relatively high firing temperature, the above ratio tends to be 0.4 or more.
  • the firing time may be 0.5 to 3 hours.
  • the material After firing, the material may be cooled to obtain a cemented carbide alloy.
  • cemented carbide is not limited to those manufactured by the above manufacturing method.
  • the coated tool 101 may have a cemented carbide 1 and a coating layer 103 located on the surface 3 of the cemented carbide 1, as in the non-limiting example shown in Figures 1 to 3.
  • the coated tool 101 may have a cemented carbide 1 as a substrate.
  • the wear resistance and chipping resistance of the cemented carbide 1 are high, so that cutting performance such as intermittent performance is likely to be improved. Therefore, the durability of the coated tool 101 is high.
  • the coating layer 103 may be located on the entire surface 3 of the cemented carbide 1, or may be located on only a portion of the surface 3. In other words, the coating layer 103 may be located on at least a portion of the surface 3 of the cemented carbide 1.
  • the coating layer 103 may be formed by a chemical vapor deposition (CVD) method.
  • the coating layer 103 may be a CVD film.
  • the coating layer 103 may also be a physical vapor deposition (PVD) film formed by a PVD method.
  • the coating layer 103 may be a single layer or a laminate of multiple layers.
  • Examples of the composition of the coating layer 103 include TiCN (titanium carbonitride), Al2O3 ( alumina), and TiN (titanium nitride).
  • the coating layer 103 may have a TiCN layer 105 and an Al2O3 layer 107, in this order, from the cemented carbide 1 side.
  • the TiCN layer 105 may be in contact with the cemented carbide 1.
  • the Al2O3 layer 107 may be in contact with the TiCN layer 105.
  • the coating layer 103 may have a TiN layer 109, a TiCN layer 105, and an Al2O3 layer 107, in that order from the cemented carbide 1.
  • the TiN layer 109 may be in contact with the cemented carbide 1.
  • the TiCN layer 105 may be in contact with the TiN layer 109.
  • the Al2O3 layer 107 may be in contact with the TiCN layer 105.
  • the coating layer 103 is not limited to a specific thickness.
  • the TiCN layer 105 may have an average thickness of about 1 to 15 ⁇ m.
  • the Al 2 O 3 layer 107 may have an average thickness of about 1 to 15 ⁇ m.
  • the TiN layer 109 may have an average thickness of about 0.1 to 5 ⁇ m.
  • the thickness of the coating layer 103 may be measured by cross-sectional observation using an electron microscope. For example, the thickness may be measured at 10 or more measurement points at any position of each layer, and the average value may be calculated.
  • a cutting insert is shown as a non-limiting example of the coated tool 101. Note that the form of the coated tool 101 is not limited to a cutting insert.
  • the coated tool 101 may have a first surface 111 (top surface), a second surface 113 (side surface) adjacent to the first surface 111, and a cutting edge 115 located at the intersection of the first surface 111 and the second surface 113.
  • the first surface 111 may be a rake surface.
  • the first surface 111 may be a rake surface in its entirety, or only a portion of the first surface 111 may be a rake surface.
  • the area of the first surface 111 along the cutting edge 115 may be a rake surface.
  • the second surface 113 may be a flank surface.
  • the second surface 113 may be a flank surface entirely, or only a portion of the second surface 113 may be a flank surface.
  • the area of the second surface 113 along the cutting edge 115 may be a flank surface.
  • the cutting edge 115 may be located over the entire intersection of the first surface 111 and the second surface 113, or may be located over only a portion of this intersection.
  • the cutting edge 115 can be used to cut a workpiece when manufacturing a machined product using the coated tool 101.
  • the coated tool 101 may have a through hole 117.
  • the through hole 117 can be used to attach a screw or a clamp member when fixing the coated tool 101 to a holder.
  • the through hole 117 may be formed from the first surface 111 to the surface (lower surface) located opposite the first surface 111, and may open in these surfaces. Note that there is no problem even if the through holes 117 are configured to open in opposing areas of the second surface 113.
  • the coated tool 101 may have a rectangular plate shape. Note that the shape of the coated tool 101 is not limited to a rectangular plate shape.
  • the first surface 111 may have a triangular, pentagonal, hexagonal, or circular shape.
  • the coated tool 101 is not limited to a specific size.
  • the length of one side of the first surface 111 may be set to approximately 3 to 20 mm.
  • the height from the first surface 111 to the surface (lower surface) located on the opposite side of the first surface 111 may be set to approximately 5 to 20 mm.
  • a coating layer may be formed on the surface of the cemented carbide alloy by the CVD method to obtain a coated tool.
  • the TiCN layer may be formed as follows. First, a mixed gas containing 0.1 to 10 volume % titanium tetrachloride (TiCl 4 ) gas, 10 to 60 volume % nitrogen (N 2 ) gas, 0.1 to 15 volume % methane (CH 4 ) gas, and the remainder hydrogen (H 2 ) gas may be prepared as the reaction gas composition. Then, this mixed gas may be introduced into a chamber, and the temperature may be set to 800 to 1100° C. and the pressure may be set to 5 to 30 kPa to form the TiCN layer.
  • TiCl 4 titanium tetrachloride
  • N 2 nitrogen
  • CH 4 0.1 to 15 volume % methane
  • H 2 hydrogen
  • the Al 2 O 3 layer may be formed as follows. First, a mixed gas may be prepared as a reaction gas composition, which is 0.5 to 5 volume % aluminum trichloride (AlCl 3 ) gas, 0.5 to 3.5 volume % hydrogen chloride (HCl) gas, 0.5 to 5 volume % carbon dioxide (CO 2 ) gas, 0.5 volume % or less hydrogen sulfide (H 2 S) gas, and the remainder hydrogen (H 2 ) gas. Then, this mixed gas may be introduced into a chamber, and the temperature may be set to 930 to 1010° C. and the pressure may be set to 5 to 10 kPa, to form the Al 2 O 3 layer.
  • AlCl 3 aluminum trichloride
  • HCl hydrogen chloride
  • CO 2 carbon dioxide
  • H 2 S hydrogen sulfide
  • H 2 S hydrogen sulfide
  • the TiN layer may be formed as follows. First, a mixed gas containing 0.1 to 10 volume % titanium tetrachloride (TiCl 4 ) gas, 10 to 60 volume % nitrogen (N 2 ) gas, and the remainder hydrogen (H 2 ) gas may be prepared as the reaction gas composition. Then, this mixed gas may be introduced into a chamber, and the temperature may be set to 800 to 1010° C. and the pressure may be set to 10 to 85 kPa to form the TiN layer.
  • TiCl 4 titanium tetrachloride
  • N 2 nitrogen
  • H 2 hydrogen
  • coated tools are not limited to those manufactured by the above manufacturing method.
  • the cutting tool 201 may include a holder 203 and a coated tool 101, as shown in a non-limiting example in FIG. 4.
  • the holder 203 may extend from a first end 203a toward a second end 203b, and may have a pocket 205 on the side of the first end 203a.
  • the coated tool 101 may be located in the pocket 205.
  • the coated tool 101 has high durability, enabling stable cutting.
  • the pocket 205 may be a portion in which the coated tool 101 is attached.
  • the pocket 205 may be open on the outer peripheral surface of the holder 203 and on the end surface on the side of the first end 203a.
  • the coated tool 101 may be attached to the pocket 205 so that at least a part of the cutting edge 115 protrudes from the holder 203.
  • the coated tool 101 may also be attached to the pocket 205 by a screw 207. That is, the coated tool 101 may be attached to the pocket 205 by inserting the screw 207 into the through hole 117 of the coated tool 101, inserting the tip of the screw 207 into a screw hole formed in the pocket 205, and fixing the screw 207 to the screw hole. At this time, the bottom surface of the coated tool 101 may be in direct contact with the pocket 205, or a sheet may be sandwiched between the coated tool 101 and the pocket 205.
  • the material of the holder 203 may be, for example, steel or cast iron. If the material of the holder 203 is steel, the holder 203 has high toughness.
  • a cutting tool 201 used for so-called turning is illustrated.
  • Examples of turning include internal diameter machining, external diameter machining, and groove machining.
  • the cutting tool 201 (coated tool 101) is not limited to use for turning. For example, there is no problem in using the coated tool 101 as the cutting tool 201 used for turning.
  • the cemented carbide 1 is used for the coated tool 101 and the cutting tool 201, but the cemented carbide 1 can also be used for other applications.
  • other applications include wear-resistant parts such as sliding parts or dies, tools such as drilling tools and blades, and impact-resistant parts.
  • the cemented carbide 1, the coated tool 101 and the cutting tool 201 may have the following configurations.
  • the cemented carbide is a cemented carbide containing W, C, and an iron-group metal, and has a ratio of the average Vickers hardness at 1073 K to the average Vickers hardness at 303 K of 0.4 or more.
  • the ratio may be 0.43 or more.
  • the product of the ratio and the amount of the iron-group metal may be 3 or more.
  • the product In the cemented carbide of (3) above, the product may be 3.74 or more.
  • the iron group metal may be cobalt.
  • a coated tool may have any one of the cemented carbide alloys described above in (1) to (5) and a coating layer located on the surface of the cemented carbide alloy.
  • the coating layer may have, from the cemented carbide side, a TiCN layer and an Al2O3 layer in this order.
  • the coating layer may have, from the cemented carbide side, a TiN layer, a TiCN layer, and an Al2O3 layer in this order.
  • the cutting tool may include a holder extending from a first end toward a second end and having a pocket on the side of the first end, and a coated tool according to any one of (6) to (8) above, positioned in the pocket.
  • the raw material powders were then mixed so that the Co and ⁇ phase in the sintered body had the ratios shown in Table 1, and pressed into a cutting tool shape (CNMG120408) to obtain a green body.
  • the resulting green body was subjected to a binder removal process, and then sintered by holding it at the sintering temperature shown in Table 1 for 1 hour. After sintering, it was cooled to obtain the cemented carbide shown in Table 1.
  • the composition of the resulting cemented carbide was measured using EDS. Specifically, cross-sections were observed using an EDS attached to an SEM at a magnification of 5,000 to 20,000 times, and the average value of measurements at five locations was measured.
  • the results of EDS measurements showed that all of the obtained cemented carbide alloys contained W, C, and an iron group metal (Co). More specifically, all of the obtained cemented carbide alloys had a hard phase containing W and C as the main components, and a binder phase containing an iron group metal (Co) as the main component. In addition, all of the obtained cemented carbide alloys had a ⁇ phase. The composition of the ⁇ phase was measured by EDS, and the ⁇ phase was found to be (W, Ti, Nb, Ta, Zr)C.
  • the average Vickers hardness of the obtained cemented carbide was measured according to the method exemplified above. The measurement results are shown in Table 1.
  • the ratio of the average Vickers hardness at 1073 K to the average Vickers hardness at 303 K is shown in the "Ratio” column of Table 1.
  • the product of this ratio and the amount of iron group metal (Co) is shown in the "Product” column of Table 1.
  • the obtained cemented carbide was subjected to a cutting evaluation. Specifically, a TiN layer having an average thickness of 1 ⁇ m, a TiCN layer having an average thickness of 10 ⁇ m, and an Al 2 O 3 layer having an average thickness of 6 ⁇ m were formed by CVD in this order from the cemented carbide (substrate) to prepare a coated tool, and the cutting evaluation was performed under the following conditions.
  • the evaluation results are shown in Table 1. Note that the "number of impacts until the cutting edge is chipped" in the evaluation results in Table 1 indicates the number of impacts until the cutting edge is chipped when cutting, and can also be called the intermittent performance evaluation.
  • REFERENCE SIGNS LIST 1 Carbide alloy 3: Surface 101: Coated tool 103: Coating layer 105: TiCN layer 107: Al2O3 layer 109 : TiN layer 111: First surface (upper surface) 113...Second side (side) 115...Cutting blade 117...Through hole 201...Cutting tool 203...Holder 203a...First end 203b...Second end 205...Pocket 207...Screw

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
PCT/JP2024/003396 2023-03-02 2024-02-02 超硬合金、被覆工具及び切削工具 Ceased WO2024181015A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51103914A (en) * 1975-03-12 1976-09-14 Mitsubishi Metal Corp Kyojinsaametsuto
WO2013002270A1 (ja) * 2011-06-27 2013-01-03 京セラ株式会社 硬質合金および切削工具
JP2014208889A (ja) * 2013-03-22 2014-11-06 住友電気工業株式会社 焼結体およびその製造方法
JP2023148484A (ja) * 2022-03-30 2023-10-13 Ｎｔｋカッティングツールズ株式会社 焼結体、及び切削工具

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51103914A (en) * 1975-03-12 1976-09-14 Mitsubishi Metal Corp Kyojinsaametsuto
WO2013002270A1 (ja) * 2011-06-27 2013-01-03 京セラ株式会社 硬質合金および切削工具
JP2014208889A (ja) * 2013-03-22 2014-11-06 住友電気工業株式会社 焼結体およびその製造方法
JP2023148484A (ja) * 2022-03-30 2023-10-13 Ｎｔｋカッティングツールズ株式会社 焼結体、及び切削工具

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