WO2023148973A1 - 切削工具 - Google Patents

切削工具 Download PDF

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Publication number
WO2023148973A1
WO2023148973A1 PCT/JP2022/004701 JP2022004701W WO2023148973A1 WO 2023148973 A1 WO2023148973 A1 WO 2023148973A1 JP 2022004701 W JP2022004701 W JP 2022004701W WO 2023148973 A1 WO2023148973 A1 WO 2023148973A1
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WIPO (PCT)
Prior art keywords
region
layer
titanium compound
less
particles
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Ceased
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PCT/JP2022/004701
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English (en)
French (fr)
Japanese (ja)
Inventor
将仁 引地
晋 奥野
貴翔 山西
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Sumitomo Electric Hardmetal Corp
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Sumitomo Electric Hardmetal Corp
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Application filed by Sumitomo Electric Hardmetal Corp filed Critical Sumitomo Electric Hardmetal Corp
Priority to JP2022530779A priority Critical patent/JP7298091B1/ja
Priority to EP22924882.8A priority patent/EP4299218A4/en
Priority to US18/284,866 priority patent/US20240189921A1/en
Priority to PCT/JP2022/004701 priority patent/WO2023148973A1/ja
Priority to CN202280025977.1A priority patent/CN117120191B/zh
Publication of WO2023148973A1 publication Critical patent/WO2023148973A1/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
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B23B27/148—Composition of the cutting inserts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2224/00—Materials of tools or workpieces composed of a compound including a metal
    • B23B2224/04—Aluminium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2224/00—Materials of tools or workpieces composed of a compound including a metal
    • B23B2224/32—Titanium carbide nitride (TiCN)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23B2228/10—Coatings
    • B23B2228/105—Coatings with specified thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23B2228/36—Multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23B2228/44—Materials having grain size less than 1 micrometre, e.g. nanocrystalline

Definitions

  • the present disclosure relates to cutting tools.
  • the cutting tools of the present disclosure are A cutting tool comprising a substrate and a coating disposed on the substrate, the coating comprises a titanium compound layer disposed on the substrate and an ⁇ -Al 2 O 3 layer disposed directly on the titanium compound layer;
  • the ⁇ -Al 2 O 3 layer is composed of a plurality of ⁇ -Al 2 O 3 particles,
  • the ⁇ -Al 2 O 3 layer includes a region A1 and a region A2,
  • the region A1 consists of a virtual plane SA2 in which the distance from the interface P1 between the titanium compound layer and the ⁇ -Al 2 O 3 layer to the surface side of the coating is 0.5 ⁇ m, and the surface of the coating from the interface P1.
  • the region A2 is a region sandwiched between the interface P1 and a virtual surface SA1 in which the distance from the interface P1 to the surface side of the coating is 0.3 ⁇ m
  • the titanium compound layer is composed of a plurality of titanium compound particles, The titanium compound particles are one selected from the group consisting of TiCN particles, TiCNO particles, TiAlCN particles and TiAlCNO particles,
  • the titanium compound layer includes a region B1 and a region B2, The region B1 is sandwiched between a virtual plane SB2 with a distance of 0.5 ⁇ m from the interface P1 to the substrate side and a virtual plane SB3 with a distance of 1.0 ⁇ m from the interface P1 to the substrate side.
  • the region B2 is a region sandwiched between the interface P1 and a virtual surface SB1 having a distance of 0.3 ⁇ m from the interface P1 to the substrate side, average particle size a1 of the ⁇ -Al 2 O 3 particles in the region A1, average particle size a2 of the ⁇ -Al 2 O 3 particles in the region A2, average particle size b1 of the titanium compound particles in the region B1, And the average particle diameter b2 of the titanium compound particles in the region B2 shows the relationship of the following formulas 1 to 3, 0.80 ⁇ a2/b2 ⁇ 1.27 Formula 1 1.50 ⁇ a1/a2 ⁇ 10 Formula 2 1.45 ⁇ b1/b2 ⁇ 5 Formula 3
  • the average particle size b1 of the cutting tool is 0.10 ⁇ m or more and 0.50 ⁇ m or less.
  • FIG. 1 is a schematic diagram showing an example of a cross section of a cutting tool according to Embodiment 1.
  • FIG. FIG. 2 is a schematic diagram showing another example of the cross section of the cutting tool according to Embodiment 1.
  • FIG. FIG. 3 is a diagram for explaining a method for measuring the particle size of ⁇ -Al 2 O 3 particles and the particle size of titanium compound particles.
  • FIG. 4 is a diagram explaining a method for measuring the particle size of ⁇ -Al 2 O 3 particles and the particle size of titanium compound particles.
  • the ⁇ -Al 2 O 3 layer has excellent mechanical properties, further improvement in adhesion to other layers and fracture resistance is required.
  • Patent Document 1 in order to improve the chipping resistance and peeling resistance of the cutting tool, at the interface between the lower layer (titanium compound layer) and the upper layer ( ⁇ -Al 2 O 3 layer), the titanium compound layer side The ratio b1/a1 between the number a1 of crystal grains and the number b1 of crystal grains on the ⁇ -Al 2 O 3 layer side was adjusted to 0.8 ⁇ b1/a1 ⁇ 1.2.
  • the ⁇ -Al 2 O 3 layer is formed after performing pretreatment on the titanium compound layer for the adjustment.
  • An object of the present disclosure is to provide a cutting tool that includes an ⁇ -Al 2 O 3 layer as a coating and has a long tool life.
  • the cutting tool of the present disclosure is a cutting tool containing an ⁇ -Al 2 O 3 layer as a coating and can have a long tool life.
  • the cutting tool of the present disclosure is A cutting tool comprising a substrate and a coating disposed on the substrate, the coating comprises a titanium compound layer disposed on the substrate and an ⁇ -Al 2 O 3 layer disposed directly on the titanium compound layer;
  • the ⁇ -Al 2 O 3 layer is composed of a plurality of ⁇ -Al 2 O 3 particles,
  • the ⁇ -Al 2 O 3 layer includes a region A1 and a region A2,
  • the region A1 consists of a virtual plane SA2 in which the distance from the interface P1 between the titanium compound layer and the ⁇ -Al 2 O 3 layer to the surface side of the coating is 0.5 ⁇ m, and the surface of the coating from the interface P1.
  • the region A2 is a region sandwiched between the interface P1 and a virtual surface SA1 in which the distance from the interface P1 to the surface side of the coating is 0.3 ⁇ m
  • the titanium compound layer is composed of a plurality of titanium compound particles, The titanium compound particles are one selected from the group consisting of TiCN particles, TiCNO particles, TiAlCN particles and TiAlCNO particles,
  • the titanium compound layer includes a region B1 and a region B2, The region B1 is sandwiched between a virtual plane SB2 with a distance of 0.5 ⁇ m from the interface P1 to the substrate side and a virtual plane SB3 with a distance of 1.0 ⁇ m from the interface P1 to the substrate side.
  • the region B2 is a region sandwiched between the interface P1 and a virtual surface SB1 having a distance of 0.3 ⁇ m from the interface P1 to the substrate side, average particle size a1 of the ⁇ -Al 2 O 3 particles in the region A1, average particle size a2 of the ⁇ -Al 2 O 3 particles in the region A2, average particle size b1 of the titanium compound particles in the region B1, And the average particle diameter b2 of the titanium compound particles in the region B2 shows the relationship of the following formulas 1 to 3, 0.80 ⁇ a2/b2 ⁇ 1.27 Formula 1 1.50 ⁇ a1/a2 ⁇ 10 Formula 2 1.45 ⁇ b1/b2 ⁇ 5 Formula 3
  • the average particle size b1 of the cutting tool is 0.10 ⁇ m or more and 0.50 ⁇ m or less.
  • the cutting tool of the present disclosure is a cutting tool containing an ⁇ -Al 2 O 3 layer as a coating and can have a long tool life.
  • a ratio R1 of the number of carbon atoms to the total number of carbon, nitrogen and oxygen atoms in the region B1 and a ratio R1 of the number of carbon atoms to the total number of carbon, nitrogen and oxygen atoms in the region B2 The ratio R1/R2 to R2 is 0.9 or more and 1.1 or less, A ratio R3 of the total number of carbon and nitrogen atoms to the total number of carbon, nitrogen and oxygen atoms in the region B1 is 0.8 or more and 1.0 or less, A ratio R4 of the total number of atoms of carbon and nitrogen to the total number of atoms of carbon, nitrogen and oxygen in the region B2 is preferably 0.8 or more and 1.0 or less.
  • the composition of the titanium compound layer is substantially uniform throughout, and the generation of interfaces due to changes in composition is suppressed inside the titanium compound layer. Therefore, cracks originating from the interface are suppressed in the coating, and the peeling resistance of the cutting tool is improved.
  • the ratio a1/b1 of the average particle diameter a1 to the average particle diameter b1 is 1.50 or more and 5 or less;
  • the average particle diameter a1 is preferably 0.40 ⁇ m or more and 1.00 ⁇ m or less.
  • the chipping resistance of the cutting tool is improved.
  • the titanium compound layer has an average thickness of 1.0 ⁇ m or more and 15 ⁇ m or less;
  • the ⁇ -Al 2 O 3 layer preferably has an average thickness of 1.0 ⁇ m or more and 15 ⁇ m or less.
  • the wear resistance, chipping resistance and peeling resistance of the cutting tool are improved.
  • the ⁇ -Al 2 O 3 layer preferably has an orientation index TC (hkl) of TC (0 0 12) of 3 or more.
  • the ⁇ -Al 2 O 3 layer can have excellent wear resistance. Therefore, the cutting tool can have a long tool life.
  • the coating preferably includes a TiN layer interposed between the base material and the titanium compound layer.
  • the coating can have excellent wear resistance and chipping resistance.
  • a compound or the like when represented by a chemical formula, it shall include any conventionally known atomic ratio unless the atomic ratio is particularly limited, and should not necessarily be limited only to those within the stoichiometric range.
  • TiCN the ratio of the number of atoms constituting TiCN includes all conventionally known atomic ratios.
  • any one numerical value described in the lower limit and any one numerical value described in the upper limit shall also be disclosed.
  • a1 or more, b1 or more, c1 or more is described as the lower limit, and a2 or less, b2 or less, or c2 or less is described 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 to a2, b1 to b2, b1 to c2, c1 to a2, c1 to b2, and c1 to c2.
  • a cutting tool of one embodiment of the present disclosure (hereinafter also referred to as “this embodiment") is A cutting tool comprising a substrate and a coating disposed on the substrate, the coating comprises a titanium compound layer disposed on the substrate and an ⁇ -Al 2 O 3 layer disposed directly on the titanium compound layer;
  • the ⁇ -Al 2 O 3 layer consists of a plurality of ⁇ -Al 2 O 3 particles, the ⁇ -Al 2 O 3 layer includes a region A1 and a region A2;
  • the region A1 consists of a virtual plane SA2 where the distance from the interface P1 between the titanium compound layer and the ⁇ -Al 2 O 3 layer to the surface side of the coating is 0.5 ⁇ m, and the surface of the coating from the interface P1.
  • the region A2 is a region sandwiched between the interface P1 and a virtual surface SA1 in which the distance from the interface P1 to the surface side of the coating is 0.3 ⁇ m
  • the titanium compound layer is composed of a plurality of titanium compound particles, The titanium compound particles are one selected from the group consisting of TiCN particles, TiCNO particles, TiAlCN particles and TiAlCNO particles,
  • the titanium compound layer includes a region B1 and a region B2, The region B1 is sandwiched between a virtual plane SB2 with a distance of 0.5 ⁇ m from the interface P1 to the substrate side and a virtual plane SB3 with a distance of 1.0 ⁇ m from the interface P1 to the substrate side.
  • the region B2 is a region sandwiched between the interface P1 and a virtual surface SB1 having a distance of 0.3 ⁇ m from the interface P1 to the substrate side,
  • the average particle diameter b2 of the titanium compound particles in the region B2 shows the relationship of the following formulas 1 to 3, 0.80 ⁇ a2/b2 ⁇ 1.27 Formula 1 1.50 ⁇ a1/a2 ⁇ 10 Formula 2 1.45 ⁇ b1/b2 ⁇ 5 Formula 3
  • the average particle diameter b1 is 0.1 ⁇ m or more and 0.5 ⁇ m or less, for the cutting tool.
  • the cutting tool of this embodiment is a cutting tool containing an ⁇ -Al 2 O 3 layer as a coating, and can have a long tool life. Although the reason is not clear, it is presumed as follows (i) to (iv).
  • the ratio a2/b2 of the average grain size a2 of the region A2 of the ⁇ -Al 2 O 3 layer to the average grain size b2 of the region B2 of the titanium compound layer is 0.80 or more and 1 .27 or less. That is, in the vicinity of the interface between the ⁇ -Al 2 O 3 layer and the titanium compound layer, the difference between the average grain size a2 and the average grain size b2 is small. Therefore, the generation of an interface due to the grain size difference between the region A2 and the region B2 is suppressed. In the coating of the cutting tool, the occurrence of the interface that is the starting point of cracks is suppressed, so the adhesion between the region A2 and the region B2 is large, and the cutting tool has excellent peeling resistance and chipping resistance. .
  • the ratio a1/a2 of the average grain size a1 of the region A1 to the average grain size a2 of the region A2 of the ⁇ -Al 2 O 3 layer is 1.50 or more, and the average grain size Since the average grain size a1 is larger than a2, cracks are less likely to propagate in the thickness direction of the coating in the regions A1 and A2, and the cutting tool has excellent chipping resistance.
  • the ratio b1/b2 of the average grain size b1 in the region B1 to the average grain size b2 in the region B2 of the titanium compound layer is 1.45 or more. Since the average grain size b1 is large, cracks do not easily propagate in the thickness direction of the coating in the regions B1 and B2, and the cutting tool has excellent chipping resistance. In addition, since b1/b2 is 5 or less, and the difference between the average particle diameter b1 and the average particle diameter b2 is small, the occurrence of an interface due to the particle diameter difference is suppressed.
  • the average grain size b1 of the region B1 of the titanium compound layer is 0.10 ⁇ m or more, crack propagation from the tool surface is suppressed, and the cutting tool has excellent chipping resistance. have. Since the average grain size b1 is 0.50 ⁇ m or less, the hardness of the titanium compound layer is improved, and the cutting tool has excellent wear resistance.
  • the cutting tool 1 of this embodiment comprises a base material 10 and a coating 15 disposed on the base material 10.
  • the coating 15 comprises an ⁇ -Al 2 O 3 layer 11 and titanium compound layer 14 .
  • the coating 15 preferably covers at least a portion of the portion involved in cutting of the rake face of the substrate, preferably covers at least a portion of the portion involved in cutting of the substrate, and covers the entire surface of the substrate. Coating is more preferred.
  • the portion involved in cutting the substrate means a region within 1.5 mm from the ridgeline of the cutting edge on the surface of the substrate. It would not depart from the scope of the present disclosure if portions of the substrate were not coated with this coating or if the composition of the coating varied.
  • Cutting tools of the present disclosure include, for example, drills, end mills (e.g., ball end mills), indexable cutting inserts for drills, indexable cutting inserts for end mills, indexable cutting inserts for milling, indexable cutting inserts for turning. It can be a cutting tip, metal saw, gear cutting tool, reamer, tap, or the like.
  • the substrate 10 includes a rake face and a flank, and any conventionally known substrate of this type can be used.
  • cemented carbide for example, WC-based cemented carbide such as WC—Co-based cemented carbide
  • the cemented carbide may contain carbonitrides such as Ti, Ta, Nb), cermet (TiC, TiN , TiCN as a main component), high-speed steel, ceramics (titanium carbide, silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, etc.), cubic boron nitride sintered body or diamond sintered body is preferred.
  • a cemented carbide especially a WC-based cemented carbide
  • a cermet especially a TiCN-based cermet
  • These base materials have an excellent balance of hardness and strength at high temperatures, and have excellent properties as base materials for cutting tools for the above applications.
  • a WC-based cemented carbide is used as the substrate, its structure may contain free carbon, an abnormal layer called ⁇ phase or ⁇ phase, and the like.
  • the base material may have its surface modified.
  • a ⁇ -free layer may be formed on the surface, and in the case of cermet, a hardened surface layer may be formed.
  • the substrate exhibits the desired effect even if its surface has been modified.
  • the substrate may or may not have a chip breaker.
  • the shape of the cutting edge ridgeline is sharp edge (the ridge where the rake face and the flank face intersect), honing (sharp edge with radius), negative land (chamfering), or a combination of honing and negative land. Any of them, such as a combination thereof, can be employed.
  • the coating 15 includes a titanium compound layer 14 and an ⁇ -Al 2 O 3 layer 11 located directly on the titanium compound layer 14 .
  • the coating can include other layers in addition to the ⁇ -Al 2 O 3 layer and the titanium compound layer.
  • the coating 15 of the cutting tool 1 may further include a TiN layer 12 positioned between the substrate 10 and the titanium compound layer 14 . It can also include a surface layer 13 disposed on the ⁇ -Al 2 O 3 layer 11 . Details of the TiN layer and the surface layer will be described later.
  • the lower limit of the average thickness of the entire coating disposed on the substrate is 2 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, 8 ⁇ m or more, 10 ⁇ m or more, 11 ⁇ m or more, 16 ⁇ m or more, 20 ⁇ m or more, and 23 ⁇ m.
  • the above is preferable.
  • the lower limit of the average thickness of the entire coating is preferably 11 ⁇ m or more, 16 ⁇ m or more, or 20 ⁇ m or more.
  • the upper limit of the average thickness of the entire coating is preferably 23 ⁇ m or less, 20 ⁇ m or less, or 16 ⁇ m or less from the viewpoint of improving peeling resistance.
  • the average thickness of the entire coating is preferably 11 ⁇ m or more and 23 ⁇ m or less, 16 ⁇ m or more and 23 ⁇ m or less, or 20 ⁇ m or more and 23 ⁇ m or less.
  • the thickness of the coating is measured, for example, by obtaining a cross-sectional sample parallel to the normal direction of the surface of the base material and observing this sample with a scanning transmission electron microscope (STEM).
  • STEM scanning transmission electron microscope
  • Examples of scanning transmission electron microscopes include JEM-2100F (trade name) manufactured by JEOL Ltd.
  • the term "thickness” means an average thickness. Specifically, the observation magnification of the cross-sectional sample is 5000 times, and a rectangular measurement field of (30 ⁇ m in the direction parallel to the substrate surface) ⁇ (distance including the entire thickness of the coating) is set in the electron microscope image, Ten thickness widths are measured in the field of view, and the average value is defined as "thickness”. The average thicknesses of the ⁇ -Al 2 O 3 layer, titanium compound layer, TiN layer and surface layer described below are similarly measured and calculated.
  • the ⁇ -Al 2 O 3 layer is composed of a plurality of ⁇ -Al 2 O 3 (aluminum oxide with ⁇ -type crystal structure) particles. That is, the ⁇ -Al 2 O 3 layer is composed of polycrystalline ⁇ -Al 2 O 3 .
  • the ⁇ -Al 2 O 3 layer can contain unavoidable impurities and the like as long as the effect of the present embodiment is exhibited.
  • the unavoidable impurities include chlorine (Cl).
  • the content of unavoidable impurities in the ⁇ -Al 2 O 3 layer is preferably 3% by mass or less.
  • the content of inevitable impurities in the ⁇ -Al 2 O 3 layer is measured by secondary ion mass spectrometry (SIMS).
  • the ⁇ -Al 2 O 3 layer 11 includes regions A1 and A2.
  • area A1 and area A2 are defined as the following areas.
  • the region A1 consists of a virtual plane SA2 where the distance from the interface P1 between the titanium compound layer 14 and the ⁇ -Al 2 O 3 layer 11 to the surface P2 side of the coating 15 is 0.5 ⁇ m, and the surface P2 of the coating 15 from the interface P1. This is an area sandwiched between the imaginary surface SA3 with a distance of 1.0 ⁇ m to the side. Virtual surface SA2 and virtual surface SA3 are included in area A1.
  • a region A2 is a region sandwiched between the interface P1 and a virtual surface SA1 in which the distance from the interface P1 to the surface P2 side of the coating 15 is 0.3 ⁇ m.
  • Virtual surface SA1 is included in area A2, and interface P1 is not included in area A2.
  • the lower limit of the average particle diameter a1 of the ⁇ -Al 2 O 3 particles in the region A1 is 0.40 ⁇ m or more and 0.40 ⁇ m or more, from the viewpoint of suppressing crack propagation from the tool surface and improving chipping resistance. 42 ⁇ m or more, 0.45 ⁇ m or more, or 0.50 ⁇ m or more is preferable.
  • the upper limit of the average particle size a1 suppresses the generation of an interface due to the difference in particle size from the average particle size a2 of the ⁇ -Al 2 O 3 particles in the region A2, suppresses crack growth originating from the interface, From the viewpoint of improving fracture resistance, it is preferably 1.00 ⁇ m or less, 0.95 ⁇ m or less, 0.90 ⁇ m or less, 0.85 ⁇ m or less, and 0.80 ⁇ m or less.
  • the average particle diameter a1 is preferably 0.40 ⁇ m or more and 1.00 ⁇ m or less, 0.45 ⁇ m or more and 0.90 ⁇ m or less, or 0.50 ⁇ m or more and 0.80 ⁇ m or less.
  • the lower limit of the average particle diameter a2 of the ⁇ -Al 2 O 3 particles in the region A2 is 0.05 ⁇ m or more, 0.06 ⁇ m or more, or 0.09 ⁇ m or more from the viewpoint of improving adhesion with the titanium compound layer. , 0.10 ⁇ m or more, preferably 0.15 ⁇ m or more.
  • the upper limit of the average particle size a2 is preferably 0.30 ⁇ m or less, 0.28 ⁇ m or less, or 0.25 ⁇ m or less from the viewpoint of improving hardness.
  • the average particle size a2 is preferably 0.05 ⁇ m or more and 0.30 ⁇ m or less, 0.10 ⁇ m or more and 0.28 ⁇ m or less, or 0.15 ⁇ m or more and 0.25 ⁇ m or less.
  • the ratio a1/a2 of the average particle diameter a1 to the average particle diameter a2 is 1.50 or more and 10 or less. According to this, the cutting tool can have excellent chipping resistance.
  • the lower limit of the ratio a1/a2 is 1.50 or more, preferably 2.00 or more, 2.50 or more, 2.67 or more, 3.00 or more, 3.33 or more, and 3.50 or more.
  • the upper limit of the ratio a1/a2 is 10 or less, preferably 9.00 or less, 8.89 or less, 8.00 or less, 7.00 or less, 6.67 or less, and 6.00 or less.
  • the ratio a1/a2 is preferably 2.00 or more and 10 or less, 2.50 or more and 8.00 or less, or 3.50 or more and 6.00 or less.
  • the average particle size a1 and the average particle size a2 are measured by the following procedures (A1) to (A6).
  • a cutting tool is cut with a diamond wire along the normal line of the rake face of the substrate to expose the cross section of the ⁇ -Al 2 O 3 layer.
  • the exposed cross section is subjected to ion milling with Ar ions to make the cross section into a mirror surface state.
  • the ion milling conditions are as follows. Accelerating voltage: 6 kV
  • Irradiation time 6 hours
  • FIG. 3 is a diagram for explaining a method for measuring the particle size of ⁇ -Al 2 O 3 particles, and schematically shows an example of the cross section.
  • the difference D1 of the distance along the normal direction of the rake face between the valley bottom B1 and the peak T1 of the irregularities at the interface P1 on the substrate side of the ⁇ -Al 2 O 3 layer is 0.5 ⁇ m or less.
  • a region is identified and a measurement range is set to include the region.
  • the measurement range is a rectangle of (horizontal direction (direction parallel to the rake face): 30 ⁇ m) ⁇ (longitudinal direction (normal direction to the rake face): length including the entire coating).
  • a reference line LS1 is set at an intermediate position between the valley bottom B1 and the peak T1 of the interface P1 within the above measurement range.
  • (A6) Measure the lateral grain size of the ⁇ -Al 2 O 3 particles on a line L2 which is 0.8 ⁇ m away from the reference line LS1 in the surface direction of the cutting tool. The particle diameters of all the ⁇ -Al 2 O 3 particles within the measurement range are measured, and the average value of these is taken as the average particle diameter a1 of the ⁇ -Al 2 O 3 particles in the region A1.
  • the present inventors determined that in the area A2, the distance along the normal direction of the rake face from the reference line LS1 is in the range of 0 ⁇ m or more and 0.3 ⁇ m or less, and the distance is 0.05 ⁇ m intervals.
  • a plurality of measurement lines passing through the position for example, a line at a distance of 0.05 ⁇ m from the reference line LS1, a line at a distance of 0.10 ⁇ m from the reference line LS1, and a line at a distance of 0.15 ⁇ m from the reference line LS1).
  • the particle size of all ⁇ -Al 2 O 3 particles in the measurement range was measured on each line, and the average value of these was calculated.
  • the average particle size of the ⁇ -Al 2 O 3 particles on the line corresponding to the line L1, which is 0.2 ⁇ m from the reference line LS1 is the average particle size of the ⁇ -Al 2 O 3 particles on the plurality of measurement lines. It was confirmed that the diameter was almost the same. The reason for this is that the initial stage of nucleation is greatly affected by the orientation and unevenness of the substrate, so the Al 2 O 3 crystals are not columnar (or a state in which the cross-sectional grain size increases toward the surface), but are granular (at the interface). It is presumed that this is due to the fact that the growth is even to some extent perpendicular to and parallel to the surface. From the above, the average particle size of the ⁇ -Al 2 O 3 particles on the line L1 can be regarded as the average particle size a2 of the ⁇ -Al 2 O 3 particles in the region A2.
  • the present inventors determined that the distance along the normal direction of the rake face from the reference line LS1 in the region A1 is in the range of 0.5 ⁇ m or more and 1.0 ⁇ m or less, and 0.05 ⁇ m
  • a plurality of measurement lines passing through the spaced positions e.g., a line at a distance of 0.50 ⁇ m from the reference line LS1, a line at a distance of 0.55 ⁇ m from the reference line LS1, a line at a distance of 0.60 ⁇ m from the reference line LS1)
  • the particle diameters of all ⁇ -Al 2 O 3 particles in the measurement range were measured on each line, and the average value of these was calculated.
  • the average particle size of the ⁇ -Al 2 O 3 particles on the line corresponding to the line L2, which is 0.8 ⁇ m from the reference line LS1 is the average particle size of the ⁇ -Al 2 O 3 particles on the plurality of measurement lines. It was confirmed that the diameter was almost the same. The reason for this is presumed to be as follows.
  • Region A1 is the transition region from nucleation to crystal growth.
  • nucleation occurred due to the influence of the orientation, unevenness, etc. of the substrate in addition to the gas conditions. etc.) take precedence. While crystals produced by nucleation are eliminated, stable nuclei are generated under new gas conditions, so it is speculated that the total number of particles does not change significantly and the change in grain size is not large.
  • the gas conditions during the formation of the regions A2 and A1 are adjusted to moderately transition crystal selection and nucleation, thereby expanding the region A1 in the thickness direction and maintaining the grain size.
  • the average particle size of the ⁇ -Al 2 O 3 particles on the line L2 can be regarded as the average particle size a1 of the ⁇ -Al 2 O 3 particles in the region A1.
  • the average thickness of the ⁇ -Al 2 O 3 layer is preferably 1.0 ⁇ m or more and 15 ⁇ m or less. According to this, the cutting tool can achieve both excellent wear resistance and chipping resistance.
  • the lower limit of the average thickness of the ⁇ -Al 2 O 3 layer is preferably 1.0 ⁇ m or more, 2.0 ⁇ m or more, 3.0 ⁇ m or more, or 5.0 ⁇ m or more from the viewpoint of improving wear resistance.
  • the upper limit of the average thickness of the ⁇ -Al 2 O 3 layer is preferably 15 ⁇ m or less, 10 ⁇ m or less, 9 ⁇ m or less, or 8 ⁇ m or less from the viewpoint of improving fracture resistance.
  • the average thickness of the ⁇ -Al 2 O 3 layer is preferably 1.0 ⁇ m or more and 15 ⁇ m or less, 2.0 ⁇ m or more and 10 ⁇ m or less, 3.0 ⁇ m or more and 9 ⁇ m or less, or 5.0 ⁇ m or more and 8 ⁇ m or less.
  • the thickness of the ⁇ -Al 2 O 3 layer can be confirmed by observing a cross-sectional sample of the cutting tool using a scanning transmission electron microscope (STEM) or the like as described above.
  • the observation field is the measurement range set when measuring the particle size of the ⁇ -Al 2 O 3 particles.
  • the same results can be obtained by selecting multiple measurement ranges including the coating on the rake face or the coating on the flank face of the same sample and performing the above measurements for each measurement range. confirmed.
  • the ⁇ -Al 2 O 3 layer preferably has a TC (0 0 12) of 3 or more in the orientation index TC (hkl) represented by the following formula (1). According to this, the ⁇ -Al 2 O 3 layer can have excellent wear resistance. Therefore, the cutting tool can have a long tool life.
  • I(hkl) indicates the X-ray diffraction intensity of the (hkl) reflecting surface
  • I 0 (hkl) indicates the standard intensity according to ICDD PDF card number 00-010-0173.
  • n in equation (1) indicates the number of reflections used in the calculation, which is 8 in this embodiment.
  • the (hkl) planes used for reflection are (012), (104), (110), (0 0 12), (113), (024), (116) and (300).
  • ICDD International Center for Diffraction Data
  • PDF registered trademark
  • Powder Diffraction File is an abbreviation for Powder Diffraction File.
  • TC (0 0 12) of the ⁇ -Al 2 O 3 layer of this embodiment can be expressed by the following formula (2).
  • TC (0 0 12) is 3 or more in the orientation index TC (hkl)" means that the numerical value obtained by the above formula (2) obtained by substituting TC (0 0 12) into the above formula (1) is It means 3 or more.
  • the value of TC (0 0 12) is more preferably 4 or more, and even more preferably 5 or more. Wear resistance can be effectively improved as the value of TC (0 0 12) increases.
  • the upper limit of the value of TC (0 0 12) is not limited, but since the number of reflecting surfaces used in the calculation is 8, it should be 8 or less.
  • the value of TC(0 0 12) can be 3 or more and 8 or less, 4 or more and 8 or less, or 5 or more and 8 or less.
  • the ⁇ -Al 2 O 3 layer preferably has a TC (110) of 2 or more in the orientation index TC (hkl) represented by the above formula (1). According to this, the ⁇ -Al 2 O 3 layer can have excellent fracture resistance. Therefore, the cutting tool can have a long tool life.
  • TC(110) of the ⁇ -Al 2 O 3 layer of this embodiment can be expressed by the following formula (3).
  • TC (110) is 2 or more in the orientation index TC (hkl)
  • TC (hkl) means that the numerical value obtained by the above formula (3) obtained by substituting TC (110) into the above formula (1) is 2 or more.
  • the value of TC(110) above is more preferably 2.5 or more, and even more preferably 3 or more. Fracture resistance can be effectively improved as the value of TC(110) increases.
  • the upper limit of the value of TC(110) is not limited, it may be set to 8 or less because the number of reflecting surfaces used in the calculation is 8.
  • the value of TC(110) can be 2 or more and 8 or less, 2.5 or more and 8 or less, or 3 or more and 8 or less.
  • TC (hkl) is determined using, for example, SmartLb/a (registered trademark) manufactured by Rigaku Corporation (scan speed: 21.7°/min, step: 0.01°, scan range: 15 to 140°) as follows. It can be measured under such conditions.
  • XRD result the result of the measurement of TC(hkl) using the X-ray diffractometer is referred to as "XRD result”.
  • X-ray diffraction method ⁇ -2 ⁇ method
  • the flank of the cutting tool is irradiated with X-rays. Since the rake face is usually uneven and the flank face is flat, it is preferable to irradiate the flank face with X-rays in order to eliminate disturbance factors.
  • X-rays are applied to a portion on the flank extending over a range of about 2 to 4 mm from the ridgeline of the cutting edge. This increases the reproducibility of the results.
  • the value of TC (hkl) of the ⁇ -Al 2 O 3 layer on the flank face of the substrate is the TC (hkl) of the ⁇ -Al 2 O 3 layer on the rake face of the substrate. is the same as the value
  • the titanium compound layer is composed of a plurality of titanium compound particles, and the titanium compound particles are one selected from the group consisting of TiCN particles, TiCNO particles, TiAlCN particles and TiAlCNO particles. That is, the titanium compound layer is composed of a polycrystalline titanium compound.
  • the titanium compound layer can contain unavoidable impurities and the like as long as the effect of the present embodiment is exhibited.
  • the unavoidable impurities include chlorine (Cl).
  • the content of unavoidable impurities in the titanium compound layer is preferably 3% by mass or less.
  • the content of unavoidable impurities in the titanium compound layer is measured by secondary ion mass spectrometry (SIMS).
  • the titanium compound layer 14 includes regions B1 and B2.
  • the area B1 and the area B2 are defined as the following areas.
  • the region B1 is a region sandwiched between a virtual plane SB2 with a distance of 0.5 ⁇ m from the interface P1 to the substrate 10 side and a virtual plane SB3 with a distance of 1.0 ⁇ m from the interface P1 to the substrate 10 side. be.
  • Virtual surface SB2 and virtual surface SB3 are included in area B1.
  • a region B2 is a region sandwiched between the interface P1 and a virtual surface SB1 having a distance of 0.3 ⁇ m from the interface P1 to the substrate 10 side.
  • Virtual surface SB1 is included in region B2, and interface P1 is not included in region B2.
  • the average particle diameter b1 of the titanium compound particles in the region B1 is 0.10 ⁇ m or more and 0.50 ⁇ m or less. According to this, the cutting tool can have excellent fracture resistance and wear resistance.
  • the lower limit of the average particle size b1 is 0.10 ⁇ m or more, preferably 0.15 ⁇ m or more, 0.17 ⁇ m or more, or 0.20 ⁇ m or more, from the viewpoint of improving chipping resistance.
  • the upper limit of the average particle size b1 is 0.50 ⁇ m or less, preferably 0.45 ⁇ m or less, 0.40 ⁇ m or less, 0.35 ⁇ m or less, or 0.32 ⁇ m or less, from the viewpoint of improving wear resistance.
  • the average particle size b1 is preferably 0.15 ⁇ m or more and 0.50 ⁇ m or less, 0.20 ⁇ m or more and 0.40 ⁇ m or less, and 0.20 ⁇ m or more and 0.32 ⁇ m or less.
  • the lower limit of the average particle diameter b2 of the titanium compound particles in the region B2 is 0.05 ⁇ m or more, 0.06 ⁇ m or more, or 0.08 ⁇ m or more from the viewpoint of improving adhesion with the ⁇ -Al 2 O 3 layer. , is preferably 0.10 ⁇ m or more.
  • the upper limit of the average particle diameter b2 is preferably 0.22 ⁇ m or less and 0.20 ⁇ m or less from the viewpoint of improving hardness.
  • the average particle diameter b2 is preferably 0.05 ⁇ m or more and 0.22 ⁇ m or less, 0.06 ⁇ m or more and 0.20 ⁇ m or less, or 0.10 ⁇ m or more and 0.20 ⁇ m or less.
  • the ratio b1/b2 of the average particle size b1 to the average particle size b2 is 1.45 or more and 5 or less. According to this, the cutting tool can have excellent chipping resistance.
  • the lower limit of the ratio b1/b2 is 1.45 or more, preferably 1.50 or more, 1.60 or more, 1.67 or more, 1.70 or more, and 2.00 or more.
  • the upper limit of the ratio b1/b2 is 5 or less, preferably 4.50 or less, 4.00 or less, 3.50 or less, and 3.33 or less.
  • the ratio b1/b2 is preferably 1.50 or more and 5 or less, and 2.00 or more and 4.00 or less.
  • the average particle size b1 and the average particle size b2 are measured by the following procedures (B1) to (B3).
  • (B1) Perform the same procedures as the procedures (A1) to (A4) described in the method for measuring the average particle diameter a1 and the average particle diameter a2, and set the reference line LS1 within the measurement range of the EBSD image.
  • the grain size of the titanium compound particles in the lateral direction is measured on a line L3 that is 0.2 ⁇ m away from the reference line LS1 in the direction of the base material of the cutting tool.
  • the particle diameters of all the titanium compound particles in the measurement range are measured, and the average value thereof is taken as the average particle diameter b2 of the titanium compound particles in the region B2.
  • the grain size of the titanium compound particles in the lateral direction is measured on a line L4 that is 0.8 ⁇ m away from the reference line LS1 in the direction of the base material of the cutting tool.
  • the particle diameters of all the titanium compound particles in the measurement range are measured, and the average value thereof is taken as the average particle diameter b1 of the titanium compound particles in the region B1.
  • the difference between the valley bottom B1 and the peak T1 of the interface is large (for example, more than 0.5 ⁇ m), and as shown in FIG.
  • the grain size of the titanium compound particles is not measured on the line L3 inside the ⁇ -Al 2 O 3 layer 11 (for example, the region indicated by y in FIG. 4), and the grain size of the titanium compound particles is measured only within the titanium compound layer. The diameter is measured and the average particle diameter b2 is calculated.
  • the present inventors determined that in the region B2, the distance along the normal direction of the rake face from the reference line LS1 is in the range of 0 ⁇ m or more and 0.3 ⁇ m or less, and the distance is 0.05 ⁇ m intervals.
  • a plurality of measurement lines passing through the position for example, a line at a distance of 0.05 ⁇ m from the reference line LS1, a line at a distance of 0.10 ⁇ m from the reference line LS1, and a line at a distance of 0.15 ⁇ m from the reference line LS1). On each line, the particle diameters of all the titanium compound particles within the measurement range were measured, and the average value of these was calculated.
  • the average particle size of the titanium compound particles on the line corresponding to the line L3, which is 0.2 ⁇ m from the reference line LS1 is substantially the same as the average particle size of the titanium compound particles on the plurality of measurement lines. confirmed. The reason for this is presumed to be as follows.
  • Region B2 is the transition region from nucleation to crystal growth.
  • nucleation occurs under the influence of the orientation, unevenness, etc. of the underlying layer in addition to the gas conditions. takes precedence. While crystals produced by nucleation are eliminated, stable nuclei are generated under new gas conditions, so it is speculated that the total number of particles does not change significantly and the change in grain size is not large.
  • the gas conditions during the formation of the regions B1 and B2 are adjusted to moderately transition crystal selection and nucleation, thereby expanding the region B2 in the thickness direction and maintaining the grain size.
  • the average particle size of the titanium compound particles on the line L3 can be regarded as the average particle size b2 of the titanium compound particles in the region B2.
  • the present inventors determined that the distance along the normal direction of the rake face from the reference line LS1 is 0.05 ⁇ m in the range of 0.5 ⁇ m or more and 1.0 ⁇ m or less in the region B1.
  • a plurality of measurement lines passing through the spaced positions e.g., a line at a distance of 0.50 ⁇ m from the reference line LS1, a line at a distance of 0.55 ⁇ m from the reference line LS1, a line at a distance of 0.60 ⁇ m from the reference line LS1) ) were set, the particle diameters of all the titanium compound particles in the measurement range were measured on each line, and the average value of these was calculated.
  • the average particle size of the titanium compound particles on the line corresponding to the line L4, which is 0.8 ⁇ m from the reference line LS1 is substantially the same as the average particle size of the titanium compound particles on the plurality of measurement lines. confirmed.
  • the reason for this is that the initial stage of nucleation is greatly affected by the orientation and unevenness of the substrate, so the titanium compound crystals are not columnar (or a state in which the cross-sectional grain size increases toward the surface), but granular (with respect to the interface). It is presumed that this is because the growth is even to some extent in the vertical and parallel directions. From the above, the average particle size of the titanium compound particles on the line L4 can be regarded as the average particle size b1 of the titanium compound particles in the region B1.
  • the ratio R1 of the number of carbon atoms to the total number of carbon, nitrogen and oxygen atoms in the region B1 and the ratio R2 of the number of carbon atoms to the total number of carbon, nitrogen and oxygen atoms in the region B2 The ratio R1/R2 is 0.9 or more and 1.1 or less, and the ratio R3 of the total number of carbon and nitrogen atoms to the total number of carbon, nitrogen and oxygen atoms in region B1 is 0.8 or more and 1 0.0 or less, and the ratio R4 of the total number of carbon and nitrogen atoms to the total number of carbon, nitrogen and oxygen atoms in region B2 is preferably 0.8 or more and 1.0 or less.
  • the composition of the titanium compound layer is substantially uniform throughout, and the generation of interfaces due to changes in the composition is suppressed inside the titanium compound layer. Therefore, cracks originating from the interface are suppressed in the coating, and the chipping resistance of the cutting tool is improved.
  • the lower limit of R1 is preferably 0.4 or more, 0.45 or more, or 0.5 or more.
  • the upper limit of R1 is preferably 0.7 or less, 0.65 or less, or 0.6 or less.
  • R1 is preferably 0.4 or more and 0.7 or less, 0.45 or more and 0.65 or less, and 0.5 or more and 0.6 or less.
  • the lower limit of R2 is preferably 0.3 or more, 0.35 or more, or 0.4 or more.
  • the upper limit of R1 is preferably 0.6 or less, 0.55 or less, or 0.5 or less.
  • R1 is preferably 0.3 or more and 0.6 or less, 0.35 or more and 0.55 or less, and 0.4 or more and 0.5 or less.
  • the lower limit of the ratio R1/R2 is preferably 0.9 or more and 0.95 or more.
  • the upper limit of the ratio R1/R2 is preferably 1.1 or less and 1.05 or less.
  • the ratio R1/R2 is preferably 0.9 or more and 1.1 or less, and 0.95 or more and 1.05 or less.
  • the lower limit of R3 is preferably 0.8 or more, 0.85 or more, or 0.87 or more.
  • the upper limit of R3 is preferably 1.0 or less, 0.95 or less, or 0.92 or less.
  • R3 is preferably 0.8 or more and 1.0 or less, 0.85 or more and 0.95 or less, or 0.87 or more and 0.92 or less.
  • the lower limit of R4 is preferably 0.8 or more, 0.85 or more, or 0.87 or more.
  • the upper limit of R4 is preferably 1.0 or less, 0.95 or less, or 0.92 or less.
  • R4 is preferably 0.8 or more and 1.0 or less, 0.85 or more and 0.95 or less, and 0.87 or more and 0.92 or less.
  • R1, R2, R3, and R4 are measured according to the following procedures (C1) to (C4).
  • a cutting tool is cut with a diamond wire along the normal line of the rake face of the base material to prepare a thin sample (about 100 nm thick) in which the cross section of the titanium compound layer is exposed.
  • Focused ion beam processing (hereinafter also referred to as “FIB processing”) is performed on the exposed cross section to make the cross section into a mirror surface state.
  • C2 Observe the FIB-processed cross section using a scanning transmission electron microscope (STEM) to identify the titanium compound layer. The observation magnification is 500,000 times.
  • a BF-STEM image of the titanium compound layer is obtained.
  • a region B1 and a region B2 are identified in the BF-STEM image.
  • Regions B1 and B2 in the BF-STEM image are identified by grain boundary analysis using EBSD.
  • a rectangular measurement area of 100 nm ⁇ 100 nm is set in each of the areas B1 and B2. As far as the applicant measures, as long as the measurement area is located in area B1 or area B2, there is almost no variation in measurement results even if rectangular analysis is performed in different measurement areas, and measurement points can be arbitrarily set. is not arbitrary.
  • the ratio of the number of carbon atoms to the total number of carbon, nitrogen, and oxygen atoms in the measurement region set in region B1 (hereinafter also referred to as R1′), the measurement region set in region B2
  • the ratio of the number of carbon atoms to the total number of carbon, nitrogen and oxygen atoms in (hereinafter also referred to as R2 '), carbon to the total number of carbon, nitrogen and oxygen atoms in the measurement area set in area B1 and
  • the ratio of the total number of nitrogen atoms hereinafter also referred to as R3 '
  • the ratio of the total number of carbon and nitrogen atoms to the total number of carbon, nitrogen and oxygen atoms in the measurement region set in region B2 (hereinafter , R4′) are calculated.
  • R1', R2', R3', and R4' are performed in five different measurement regions.
  • the average value of R1' in the five measurement regions is defined as R1 in region B1.
  • the average value of R2' of the five measurement regions is defined as R2 in region B2.
  • the average value of R3' in the five measurement regions is defined as R3 in region B1.
  • the average value of R4' in the five measurement regions is defined as R4 in region B2.
  • the average thickness of the titanium compound layer is preferably 1.0 ⁇ m or more and 15 ⁇ m or less. According to this, the cutting tool can achieve both excellent wear resistance and chipping resistance. From the viewpoint of improving wear resistance, the lower limit of the average thickness of the titanium compound layer is preferably 1.0 ⁇ m or more, 2.0 ⁇ m or more, 3.0 ⁇ m or more, and 5.0 ⁇ m or more. The upper limit of the average thickness of the titanium compound layer is preferably 15 ⁇ m or less, 10 ⁇ m or less, 9 ⁇ m or less, or 8 ⁇ m or less from the viewpoint of improving fracture resistance. The average thickness of the titanium compound layer is preferably 1.0 ⁇ m to 15 ⁇ m, 2.0 ⁇ m to 10 ⁇ m, 3.0 ⁇ m to 9 ⁇ m, and 5.0 ⁇ m to 8 ⁇ m.
  • the thickness of the titanium compound layer can be confirmed by observing a cross-sectional sample of the cutting tool using a scanning transmission electron microscope (STEM) or the like as described above.
  • the observation field of view is the measurement range set when measuring the particle size of the titanium compound particles.
  • the same results can be obtained by selecting multiple measurement ranges including the coating on the rake face or the coating on the flank face of the same sample and performing the above measurements for each measurement range. confirmed.
  • the ratio a2/b2 of the average particle size a2 to the average particle size b2 is 0.80 or more and 1.27 or less. According to this, the cutting tool can have excellent delamination resistance and chipping resistance.
  • the lower limit of the ratio a2/b2 is 0.80 or more, preferably 0.90 or more, and 1.00 or more.
  • the upper limit of the ratio a2/b2 is 1.27 or less, preferably 1.20 or less, 1.15 or less, 1.13 or less, and 1.10 or less.
  • the ratio a2/b2 is preferably 0.90 or more and 1.15 or less, and 1.00 or more and 1.10 or less.
  • the ratio a1/b1 of the average particle size a1 to the average particle size b1 is preferably 1.50 or more and 5 or less. According to this, chipping resistance is improved.
  • the lower limit of the ratio a1/b1 is 1.50 or more, preferably 2.00 or more, 2.27 or more, 2.33 or more, and 2.50 or more.
  • the upper limit of the ratio a1/b1 is 5 or less, preferably 4.50 or less, 4.00 or less, 3.50 or less, and 3.00 or less.
  • the ratio a1/b1 is preferably 2.00 or more and 4.50 or less, and 2.50 or more and 4.00 or less.
  • the coating can contain other layers besides the ⁇ -Al 2 O 3 layer and the titanium compound layer. As shown in FIG. 2, other layers include a TiN layer 12, a surface layer 13, an intermediate layer (not shown), and the like.
  • TiN layer is arranged between the substrate and the titanium compound layer and corresponds to the underlayer.
  • the TiN layer preferably has an average thickness of 0.1 ⁇ m or more and 20 ⁇ m or less. According to this, the coating can have excellent wear resistance and chipping resistance.
  • a TiN layer can be placed directly on the substrate.
  • a TiN layer can be placed in contact with the titanium compound layer.
  • the TiN layer can be placed directly on the substrate and in contact with the titanium compound layer.
  • the surface layer preferably contains, for example, Ti (titanium) carbide, nitride, or boride as a main component.
  • the surface layer is the layer located closest to the surface side in the coating. However, it may not be formed at the cutting edge ridge.
  • the surface layer is for example arranged directly on the ⁇ -Al 2 O 3 layer.
  • Consists mainly of Ti carbide, nitride, or boride means containing 90% by mass or more of Ti carbide, nitride, or boride. Moreover, it means that it preferably consists of any one of carbide, nitride and boride of Ti except for inevitable impurities.
  • Ti carbides nitrides, and carbonitrides
  • the surface layer mainly from Ti nitrides (that is, compounds represented by TiN).
  • TiN has the clearest color (exhibits a gold color), so it has the advantage of facilitating identification of the corners of the cutting tip after use for cutting (identification of used portions).
  • the surface layer preferably consists of a TiN layer.
  • the surface layer preferably has an average thickness of 0.05 ⁇ m or more and 1 ⁇ m or less. According to this, the adhesion between the surface layer and the adjacent layer is improved.
  • the upper limit of the average thickness of the surface layer can be 0.8 ⁇ m or less and 0.6 ⁇ m or less.
  • the lower limit of the average thickness can be 0.1 ⁇ m or more and 0.2 ⁇ m or more.
  • An intermediate layer is arranged between the TiN layer and the titanium compound layer.
  • the intermediate layer include a TiCN layer and a TiCNO layer having compositions different from those of the titanium compound layer. Since the TiCN layer and the TiCNO layer are excellent in wear resistance, it is possible to impart more suitable wear resistance to the coating.
  • the intermediate layer preferably has an average thickness of 1 ⁇ m or more and 20 ⁇ m or less. Here, the average thickness of the intermediate layer means the average total thickness of the two or more layers when the intermediate layer is formed of two or more layers.
  • An intermediate layer may be arranged in contact with the TiN layer.
  • the intermediate layer can be arranged in contact with the titanium compound layer.
  • An intermediate layer may be disposed in contact with each of the TiN layer and the titanium compound layer.
  • the cutting tool of this embodiment can be manufactured by forming a coating on a substrate by a chemical vapor deposition (CVD) method.
  • CVD chemical vapor deposition
  • the ⁇ -Al 2 O 3 layer and the titanium compound layer can be formed, for example, by the following method.
  • Layers other than the titanium compound layer and the ⁇ -Al 2 O 3 layer of the coating can be formed under conventionally known conditions.
  • the deposition conditions for the titanium compound layer can be, for example, a temperature of 950 to 1050° C., a pressure of 90 to 130 hPa, and a gas flow rate (total gas flow rate) of 50 to 100 L/min.
  • total gas flow rate refers to the total volumetric flow rate introduced into the CVD furnace per unit time, assuming that the gas under standard conditions (0° C., 1 atm) is an ideal gas.
  • CH 3 CN, CH 4 , TiCl 4 , CO, N 2 , AlCl 3 and H 2 are used as source gases. From the start of film formation, the blending amounts of CH 3 CN, CH 4 , N 2 and H 2 in the raw material gas are changed according to changes in the thickness of the formed titanium compound layer. Specifically, it is as follows.
  • region B1 When forming a region (region B1) at a distance of 0.5 ⁇ m or more and 1.0 ⁇ m or less from the interface P1 between the titanium compound layer and the ⁇ -Al 2 O 3 layer formed immediately above it, the blending of the source gas CH 3 CN: 0.2 vol% or more and 1.0 vol% or less, CH 4: 1.0 vol% or more and 2.5 vol% or less, TiCl 4 : 8.0 vol% or more and 9.0 vol% or less , CO: 0% by volume or more and 1.5% by volume or less, N 2 : 10.0% by volume or more and 15% by volume or less, AlCl 3 : 0% by volume or more and 1.5% by volume or less, and H 2 : 100% by volume of the entire source gas It is the remaining volume % when it is set to volume %.
  • the blending amount of the raw material gas is changed from the blending amount in the region B1 to The blending amount is changed so as to be in the region B2 described later.
  • each raw material gas is adjusted so that the amount of change per hour is constant.
  • the compounding of the source gas is CH 3 CN: 0.4 vol % or more and 2.0 vol % or less, CH 4 : 0.8% by volume or more and 2.02% by volume or less, N : 8.0% by volume or more and 12.0% by volume or less, and compared with the time of forming the region B1, CH 3 CN, CH 4 and In accordance with the increase or decrease in the total content of N2 , H2 is increased or decreased so that the total gas flow rate becomes the same as when forming region B1, and the composition of other gases is the same as when forming region B1.
  • the compounding amount of CH 3 CN in the raw material gas when forming the region B2 is made larger than the compounding amount of CH 3 CN in the raw material gas when forming the region B1. Also, the amount of CH4 mixed in the raw material gas when forming the region B2 is made smaller than the amount of CH4 mixed in the raw material gas when forming the region B1. As a result, the average particle size b2 of the titanium compound particles in the region B2 is smaller than the average particle size b1 of the titanium compound particles in the region B1.
  • CH 4 and CH 3 CN are used simultaneously as raw material gases, and by changing the compounding amounts of CH 4 and CH 3 CN together with N 2 , In the thickness direction of the titanium compound layer, only the particle size of the titanium compound particles can be adjusted without causing a large change in composition. This is a finding newly discovered by the present inventors.
  • the deposition conditions for the ⁇ -Al 2 O 3 layer can be, for example, a temperature of 950 to 1050° C., a pressure of 60 to 90 hPa, and a gas flow rate (total gas flow rate) of 50 to 100 L/min.
  • AlCl 3 , HCl, CO 2 , H 2 S and H 2 are used as source gases. From the start of film formation, the blending amounts of HCl and H 2 in the source gas are changed according to changes in the thickness of the formed ⁇ -Al 2 O 3 layer. Specifically, it is as follows.
  • the composition of the source gas is HCl: 7.5% by volume or more and 11% by volume or less.
  • AlCl 3 2% by volume or more and 5% by volume or less, CO 2 : 0.1% by volume or more and 6% by volume or less, H 2 S: 0.1% by volume or more and 1% by volume or less, and H 2 : 100 volumes of the entire source gas It is the remaining volume % when it is set as %.
  • the raw material gas is mixed in the region A2. is changed so as to be the blending amount in the area A1 which will be described later. At this time, each raw material gas is adjusted so that the amount of change per hour is constant.
  • the composition of the raw material gas is changed to HCl: 3.2% by volume or more and 7.0% by volume. % by volume or less, H2 is increased by the amount of HCl decrease in the raw material gas compared to the formation of the region A2, and the composition of the other gases is the same as that of the formation of the region A2.
  • HCl has been used to suppress the excessive production of ⁇ -Al 2 O 3 during film formation and the formation of ⁇ -Al 2 O 3 particles in the gas phase.
  • Formation of ⁇ -Al 2 O 3 particles in the gas phase makes it difficult to form an ⁇ -Al 2 O 3 layer on the substrate.
  • the amount of HCl is changed in order to control the particle size of the ⁇ -Al 2 O 3 particles. Furthermore, the amount of HCl in the source gas when forming the region A2 is the same as the amount of HCl in the source gas used when forming the conventional ⁇ -Al 2 O 3 layer (for example, 2.8% by volume or more). less than 6% by volume). This reduces the average grain size of the ⁇ -Al 2 O 3 grains in the regions A1 and A2. This is a finding newly discovered by the present inventors.
  • the ratio R3 of the total number of atoms of carbon and nitrogen to the total number of atoms of carbon, nitrogen and oxygen in region B1 can be 0.9 or more and 1.0 or less.
  • a cutting tool was produced by forming a film on the surface of the base material obtained above. Specifically, the substrate was set in a CVD apparatus, and a coating was formed on the substrate by CVD. The composition of the coating of each sample is shown in Tables 2 and 3. "None" in Tables 2 and 3 indicates that the layer was not formed in the sample.
  • a TiN layer (underlying layer), a titanium compound layer, an ⁇ -Al 2 O 3 layer, and a TiN layer (surface layer) are formed in the above order on the substrate.
  • the thickness of the TiN layer (underlying layer) is 0.4 ⁇ m, and the thickness of the TiN (surface layer) is 0.7 ⁇ m.
  • Table 4 shows the deposition conditions for the TiN layer (base layer) and the TiN layer (surface layer).
  • Tables 5 to 8 show the deposition conditions and source gas composition of the titanium compound layer of each sample.
  • "Remainder” in the “H 2 " column in Tables 5 to 8 indicates that H 2 gas accounts for the remainder of the raw material gas composition (% by volume).
  • the base material was fixed and the gas pipe for ejecting the raw material gas was rotated at 2 rpm.
  • the total thickness of the titanium compound layer is as shown in the "Thickness" column of Tables 5-8.
  • the raw material gas composition for forming the titanium compound layer of Sample 1 is as follows.
  • a region B1 is thereby formed.
  • the blending amount of the raw material gas is changed from the blending amount in the region B1 to The blending amount is changed so as to be in the region B2 described later.
  • each raw material gas is adjusted so that the amount of change per hour is constant.
  • the composition of the raw material gas is CH 3 CN: 1.00 vol %, CH 4 : 1.50 vol %. , TiCl 4 : 8.5% by volume, CO: 1.4% by volume, N 2 : 10.0% by volume, and compared to when the region B1 was formed, the total of CH 3 CN, CH 4 and N 2 in the source gas As the content decreases, H2 is increased so that the total gas flow remains constant.
  • the total thickness of the formed titanium compound layer is 8 ⁇ m.
  • the raw material gas composition at the time of forming the titanium compound layer is as follows.
  • the composition of the source gas was CH3CN : 0.60% by volume, TiCl4 : 8.0% by volume, CO: 2.0% by volume, N2 : 20.0% by volume, and H2. : Remaining volume % when the whole source gas is taken as 100 volume %.
  • the pressure during formation of the region 1 is set to 70 hPa. A region B1 is thereby formed.
  • the composition of the source gas was CH4 : 4.00% by volume, TiCl4 : 8.0% by volume, CO: 2.0% by volume, N2 : 10.0% by volume, and H2 : It is the remaining volume % when the entire raw material gas is 100 volume %.
  • the pressure during formation of the region 1 is set to 200 hPa. A region B1 is thereby formed. Samples 1-10 do not use CH 3 CN and CH 4 simultaneously.
  • Tables 9 and 10 show the raw material gas composition and deposition conditions for the ⁇ -Al 2 O 3 layer of each sample. “Remainder” in the “H 2 ” column in Tables 9 and 10 indicates that H 2 gas accounts for the remainder of the source gas composition (% by volume).
  • the base material was fixed and the gas pipe for ejecting the raw material gas was rotated at 2 rpm.
  • the total thickness of the ⁇ -Al 2 O 3 layer is as shown in Tables 9-10 in the "Thickness" column.
  • the deposition conditions for the ⁇ -Al 2 O 3 layer of Sample 1 are as follows.
  • the composition of the source gas is AlCl 3 : 2.2% by volume, HCl: 9.0% by volume, CO 2 : 3.0% by volume, H 2 S: 0.6% by volume, and H 2 : Remaining volume% when the entire raw material gas is taken as 100% by volume.
  • the raw material gas is mixed in the region A2. is changed so as to be the blending amount in the area A1 which will be described later. At this time, each raw material gas is adjusted so that the amount of change per hour is constant.
  • the mixture of the raw material gas is HCl: 5.5 volumes, and the region A2 is formed.
  • H2 is increased so that the total gas flow rate remains constant according to the decrease in the HCl content in the raw material gas compared to the time, and the composition of the other gases is the same as when forming the region A2.
  • the total thickness of the formed ⁇ -Al 2 O 3 layer is 8 ⁇ m.
  • the ratio R4 of the total number of atoms of carbon and nitrogen to the total number of atoms of carbon, nitrogen and oxygen in the region B2 and the composition of the titanium compound particles were measured.
  • breakage rate (%) (number of broken cutting edges/20) ⁇ 100.
  • breakage rate is less than 65%, the chipping resistance of the cutting tool is good.
  • the results are shown in the "cutting evaluation 1 failure rate (%)" column of Tables 11 to 14.
  • samples 1-1 to 1-10 correspond to comparative examples.
  • Samples 1-4 and 1-9 had insufficient fracture resistance.
  • Samples 1-1 to 1-3, 1-5, 1-6 and 1-8 to 1-10 had insufficient peel resistance.
  • Samples 1-7 had insufficient wear resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Chemical Vapour Deposition (AREA)
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US18/284,866 US20240189921A1 (en) 2022-02-07 2022-02-07 Cutting tools
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JP6210348B1 (ja) * 2016-11-08 2017-10-11 株式会社タンガロイ 被覆切削工具
JP2019025615A (ja) * 2017-08-01 2019-02-21 京セラ株式会社 被覆工具、切削工具及び切削加工物の製造方法

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JP2012096303A (ja) 2010-03-23 2012-05-24 Mitsubishi Materials Corp 耐チッピング性にすぐれた表面被覆切削工具
JP5872748B1 (ja) * 2015-08-28 2016-03-01 住友電工ハードメタル株式会社 表面被覆切削工具
JP6210348B1 (ja) * 2016-11-08 2017-10-11 株式会社タンガロイ 被覆切削工具
JP2019025615A (ja) * 2017-08-01 2019-02-21 京セラ株式会社 被覆工具、切削工具及び切削加工物の製造方法

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