WO2012070290A1 - 表面被覆焼結体 - Google Patents
表面被覆焼結体 Download PDFInfo
- Publication number
- WO2012070290A1 WO2012070290A1 PCT/JP2011/069546 JP2011069546W WO2012070290A1 WO 2012070290 A1 WO2012070290 A1 WO 2012070290A1 JP 2011069546 W JP2011069546 W JP 2011069546W WO 2012070290 A1 WO2012070290 A1 WO 2012070290A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sintered body
- boron nitride
- cubic boron
- adhesion layer
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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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
- B23B27/18—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing
- B23B27/20—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing with diamond bits or cutting inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
- B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
- B26D1/0006—Cutting members therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
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- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- 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
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- 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
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—Carbonitrides
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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- 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
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- 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
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2226/00—Materials of tools or workpieces not comprising a metal
- B23B2226/12—Boron nitride
- B23B2226/125—Boron nitride cubic [CBN]
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T83/00—Cutting
- Y10T83/929—Tool or tool with support
Definitions
- the present invention relates to a surface-coated sintered body including a cubic boron nitride sintered body and a surface coating layer formed on the surface thereof.
- cubic boron nitride sintered bodies have been widely used as materials for tools such as cutting tools because of their high hardness. It is also known to form a surface coating layer on the surface of a cubic boron nitride sintered body for the purpose of improving wear resistance and the like.
- Patent Document 1 JP-A-2005-047004 (Patent Document 1), an intermediate layer made of a compound such as a nitride or carbide of a group 4a, 5a, or 6a element is formed on the surface of a cubic boron nitride sintered body, A composite high hardness material for a tool in which a coating such as TiAlN is formed on the intermediate layer is disclosed.
- Patent Document 2 discloses that an intermediate layer made of at least one element selected from Group 4a, 5a, and 6a elements is formed on the surface of a boron nitride sintered body.
- Patent Document 3 discloses that a first layer made of Group 4a, 5a, 6a metal is formed on a substrate, and a second layer made of TiAlVN or the like is formed on the first layer. A layered hard coating is disclosed.
- the hard coating layer When a hard coating layer is formed on a cubic boron nitride sintered body, the hard coating layer tends to be inferior in toughness, especially when a strong impact load or a fluctuating load is applied to the hard coating layer. There was a problem that the coating layer might peel off and the tool life was shortened.
- Patent Documents 1 to 3 by forming an intermediate layer between the hard coating layer and the base material (cubic boron nitride sintered body), the adhesion of the hard coating layer to the base material is improved. It has been proposed to let
- an intermediate layer made of a compound such as a nitride or carbide of group 4a, 5a, or 6a element is said to have better adhesion than a film (hard film) such as TiAlN.
- a film hard film
- this metal diffuses into both the cubic boron nitride sintered body and the hard coating, and the diffusion Since solid solutions such as metal borides and metal nitrides are formed in the portions, stronger adhesion than Patent Document 1 can be expected.
- Patent Document 3 a metal layer is formed as an intermediate layer in the same manner as Patent Document 2, and its purpose is to relieve stress.
- stress relaxation is expected when the hard coating has high stress, but cannot be expected when the stress of the hard coating itself is low, and what kind of substrate is used? Since it is not specified, it is unclear what effect is exhibited when a cubic boron nitride sintered body is used as a base material.
- the present invention has been made in view of such a situation, and the object thereof is a surface having sufficient adhesion even when a strong impact load or a fluctuating load is applied to the surface coating layer.
- the object is to provide a surface-coated sintered body in which a coating layer is formed on a cubic boron nitride sintered body.
- the present inventor can expect a mediation of bonding between the base material and the hard coating layer or a certain degree of impact reduction when using a metal as the intermediate layer. Although it can be expected to increase the adhesion between the hard coating layer and the hard coating layer to some extent, it can be easily destroyed by a strong impact load, and the cause may be related to the melting point of the metal and the composition of the intermediate layer. Obtained. Based on this finding, the inventor has further completed the present invention as a result of examining the type of metal and the structure of the intermediate layer in more detail.
- the surface-coated sintered body of the present invention includes a cubic boron nitride sintered body and a surface coating layer formed on the surface, and the cubic boron nitride sintered body is 20 to 99.5% by volume.
- the cubic boron nitride and a binder are included, the surface coating layer includes an adhesion layer and one or more hard coating layers, and the adhesion layer is a metal layer containing at least W, and the cubic crystal
- the hard coating layer is formed so as to cover a part of the surface of the boron nitride sintered body, and the hard coating layer is formed so as to cover the cubic boron nitride sintered body and the adhesion layer.
- the ratio of cubic boron nitride particles in contact with the adhesion layer is 0.01 to 20% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the bonded body.
- the adhesion layer is preferably in an amorphous state or composed of ultrafine particles having an average particle diameter of 5 nm or less, and preferably contains 0.05 to 95 atomic% of W.
- the adhesion layer preferably contains one or both of Ti and Cr at an atomic ratio of 0.1 to 3 with respect to W, and at least one selected from the group consisting of Co, Ni, and Fe It is preferable to contain 0.1 to 20 atomic% of the seed element.
- the adhesion layer preferably has a thickness of 0.5 to 30 nm.
- the hard coating layer preferably has a stress of ⁇ 1.5 to +0.5 GPa, and includes a first coating layer as a lowermost layer in contact with the cubic boron nitride sintered body and the adhesion layer.
- One coating layer consists of group IVa elements (Ti, Zr, Hf, etc.), group Va elements (V, Nb, Ta, etc.), group VIa elements (Cr, Mo, W, etc.), Al, and Si of the periodic table It is preferably composed of a compound comprising at least one element selected from the group consisting of and at least one element selected from the group consisting of boron, carbon, nitrogen and oxygen.
- the first coating layer is composed of at least one compound selected from the group consisting of TiAlN, AlCrN and TiSiN, or a solid solution containing the compound, or an ultra-multilayer having the compound or the solid solution as a constituent layer. It is preferable to be comprised with a laminated body.
- the first coating layer is preferably composed of columnar crystals with a particle diameter of 1 to 20 nm in a region within 20 nm from the interface with the adhesion layer.
- the hard coating layer of the present invention preferably has a thickness of 0.5 to 20 ⁇ m.
- the present invention also relates to a cutting tool formed by joining the surface-coated sintered body according to any one of the above to a cutting edge portion of a cemented carbide base material.
- the surface-coated sintered body of the present invention has an extremely excellent effect that the adhesion between the cubic boron nitride sintered body and the surface coating layer is excellent by having the above-described configuration.
- the surface coating sintered body of the present invention includes a cubic boron nitride sintered body and a surface coating layer formed on the surface thereof.
- the surface coating layer may be formed so as to cover the entire surface of the cubic boron nitride sintered body, or may be formed so as to cover only a part of the surface. It may be.
- this surface-coated sintered body is used after being bonded to a base material, it is not necessary to form a surface-coating layer at the joint with the base material.
- the cubic boron nitride sintered body of the present invention includes 20 to 99.5% by volume of cubic boron nitride and a binder.
- the cubic boron nitride sintered body of the present invention may contain other optional components including inevitable impurities as long as these two components are included.
- the cubic boron nitride sintered body of the present invention is composed of a large number of cubic boron nitride particles, and the binder has an action of bonding the cubic boron nitride particles.
- a binder is not particularly limited, and for example, a binder having the following composition can be selected.
- Composition 1 at least one element selected from the group consisting of group IVa element, group Va element, group VIa element, Al, and Si in the periodic table of elements and a group consisting of boron, carbon, nitrogen, and oxygen A compound comprising at least one element.
- Composition 2 A solid solution containing the above compound.
- Composition 3 a simple metal such as Co, W, Ni, or Al.
- Composition 4 A compound containing Co, W, Ni, Al or the like.
- Composition 5 A solid solution containing the compound of composition 1 and Co, W, Ni, Al and the like.
- Composition 6 A compound further containing Co, W, Ni, Al and the like with respect to the compound of composition 1 above.
- Such a binder content usually occupies the remainder other than cubic boron nitride in the cubic boron nitride sintered body.
- the cubic boron nitride particles constituting the cubic boron nitride sintered body usually have an average particle size of about 0.2 to 10 ⁇ m. It is preferable to arrange on the side (side in contact with the surface coating layer). Thereby, it can adhere more strongly to the adhesion layer described later.
- the average particle diameter of the cubic boron nitride particles can be measured by optical microscope observation or SEM (scanning electron microscope) observation of the cross section of the sintered body.
- the surface coating layer of the present invention includes an adhesion layer and one or more hard coating layers. As long as these layers are included, other arbitrary layers may be included.
- the structure of the surface coating layer of the present invention is such that the adhesion layer is first formed so as to cover a part of the surface of the cubic boron nitride sintered body, and the cubic crystal on the adhesion layer and a portion not covered by the adhesion layer.
- a hard coating layer covers the boron nitride sintered body.
- Such a surface coating layer is formed mainly for the purpose of improving the wear resistance of the cubic boron nitride sintered body.
- each layer will be described.
- the adhesion layer of the present invention is a metal layer containing at least W, and is formed so as to cover a part of the surface of the cubic boron nitride sintered body.
- the ratio of the cubic boron nitride particles in contact with the adhesion layer to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body is 0.00. It is characterized by being 01 to 20%. This ratio is more preferably 0.02 to 1%.
- the adhesive layer according to the present invention has the above-described configuration, so that it has high heat resistance, strength, and toughness, so that the cubic boron nitride sintered body and the surface coating layer are extremely strong. The excellent effect of being able to adhere is shown.
- the “metal layer” means that the main component constituting the layer is a single metal
- the surface of the cubic boron nitride sintered body means that the constituent component of the surface coating layer is cubic. When diffused in the sintered boron nitride sintered body, the diffusion portion is included.
- W contained in the adhesion layer is a metal material having a relatively high melting point, and when a high temperature is applied to the surface-coated sintered body (for example, when the surface-coated sintered body is used for a cutting tool, the cutting process is performed). The rate of softening is small even at the time of the cutting edge part. Further, W has high adhesiveness with cubic boron nitride particles constituting the cubic boron nitride sintered body, and also has high adhesiveness with the hard coating layer. For this reason, when the adhesion layer contains at least W, the surface coating layer has extremely excellent toughness.
- W has such an excellent effect because it can form a chemical bond with the cubic boron nitride, which is a covalent bond and insulating, and also has a chemical bond with a metal-bonded and conductive hard coating layer. This is probably because a bond can be formed.
- the interface where the cubic boron nitride and the hard coating layer are in contact with each other is a strong ceramic, it has a strong strength, but on the other hand, it is fragile and breaks when deformed by a high load. Further, the interface between the cubic boron nitride and the adhesion layer shows a tendency that the strength rapidly decreases at a high temperature.
- the surface-coated sintered body for example, when the surface-coated sintered body is used for a cutting tool, the cutting edge portion at the time of cutting), cubic boron nitride particles and the surface coating layer It is expected that the interface will be broken and peeled off when a strong impact load or cyclic or non-periodic repeated load (fluctuating load) is applied, resulting in low adhesion.
- the surface coating layer first, the adhesion layer is formed so as to cover a part of the surface of the cubic boron nitride sintered body, and the cubic boron nitride sintered portion on the adhesion layer and a portion not covered by the adhesion layer is formed.
- Cubic nitridation in contact with the adhesion layer with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body and having a structure in which the hard coating layer covers the bonded body By adopting a configuration in which the proportion of boron particles is 0.01 to 20%, the adhesion between the cubic boron nitride sintered body and the surface coating layer has been made extremely strong.
- a specific interface as described above includes a strong and heat-resistant interface in which cubic boron nitride particles and a hard coating layer are directly bonded, and an interface having excellent toughness in which cubic boron nitride particles and an adhesion layer are directly bonded.
- the former interface can withstand a high load, and the latter interface absorbs deformation, and this excellent effect is exhibited.
- the two kinds of interfaces are mixed in this manner, the progress of the cracks is suppressed at the boundary between the different interfaces, so that the surface coating layer is prevented from being peeled off due to the progress of the cracks. It is presumed that the adhesion between the boron sintered body and the surface coating layer is enhanced.
- the ratio of the cubic boron nitride particles in contact with the adhesion layer is less than 0.01% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. In this case, the deformation of the interface cannot be absorbed and the toughness is inferior, and if it exceeds 20%, the heat resistance and the strength are inferior.
- the adhesion layer of the present invention is preferably in an amorphous state or composed of ultrafine particles having an average particle diameter of 5 nm or less.
- the adhesion layer of the present invention is more preferably a mixed phase of both.
- a chemical bond cannot be formed directly between materials having different bonding properties or conductivity, and the interface becomes poor in adhesion.
- a metal component boride or boron nitride contained in the surface coating layer may be formed by mixing to form a compound in which elements are mixed at the interface between such materials. It will be formed as a compound.
- such borides or nitrides are brittle materials, and eventually form a covalently bonded insulating material or metal bonded conductive material, which essentially reduces the adhesion of the interface. It cannot be improved.
- W contained in the adhesion layer of the present invention is a metal-bonding and conductive metal, but since it is one of the elements with the largest number of electrons among transition metals, it can take various electron arrangements.
- the possibility of forming a chemical bond with a covalent material is also conceivable. Therefore, if the adhesion layer (especially W) is in an amorphous state or is composed of ultrafine particles having an average particle diameter of 5 nm or less, a unique electronic structure is formed, resulting in a covalent bond component and a metal bond component.
- the present inventor's research reveals that it is possible to form a strong chemical bond to both the cubic boron nitride, which is a covalent bonding material, and the metal-bonding and conductive hard coating layer. It became.
- the average particle diameter exceeds 5 nm, only the particle surface has the above-mentioned electronic structure, so the proportion of the above-mentioned preferred state in the entire adhesion layer is reduced, and most of them have normal metal binding properties. W. For this reason, the density of chemical bonds with cubic boron nitride decreases.
- the average particle size is preferably as small as possible, it is not necessary to define the lower limit value. However, when the average particle size is less than 0.5 nm, it is essentially indistinguishable from the amorphous state.
- the main phase is preferably an amorphous state or W metal composed of ultrafine particles as described above.
- adhesion layer has the above-described state, mechanical properties such as strength, hardness, and toughness of the adhesion layer itself are improved.
- the adhesion layer is in an amorphous state, the structure becomes uniform and the strength may be inferior. Further, if the entire adhesion layer is composed only of the ultrafine particles as described above, a gap may be formed at the grain boundary of the ultrafine particles, which may be inferior in strength and toughness. For this reason, it is particularly preferable that the adhesion layer is a mixed phase of both of them, whereby the amorphous phase fills the gaps between the ultrafine particles, or the presence of ultrafine particles in the parent phase of the amorphous phase, The adhesion layer is particularly excellent in strength and toughness.
- an adhesion layer having a lot of amorphous state on the cubic boron nitride sintered body side an adhesion layer having better adhesion can be obtained.
- the state of such an adhesion layer can be determined by measuring the transmission electron diffraction of the adhesion layer using a transmission electron microscope (TEM) / energy dispersive X-ray spectroscopic analysis (EDS).
- TEM transmission electron microscope
- EDS energy dispersive X-ray spectroscopic analysis
- the transmission electron beam diffraction image includes a halo component, it indicates that an amorphous state (amorphous phase) exists, and when a diffraction pattern exists, it indicates that ultrafine particles are included, both of which are observed.
- the case indicates a mixed phase of these two.
- the particle diameter of the ultrafine particles can be confirmed by a high-magnification TEM image, and the average particle diameter can be obtained by measuring the particle diameters of 10 or more particles and taking the average.
- the adhesion layer of the present invention preferably contains 0.05 to 95 atomic% of W. It is because the excellent effect as described above can be obtained by including W. Here, when the content of W is less than 0.05 atomic%, the above-described excellent effect may not be sufficiently obtained. Moreover, since the effect of W is promoted by a slight mixing of foreign elements, the content is preferably 95 atomic% or less.
- the different elements are light elements such as oxygen, carbon, nitrogen and boron, transition metals such as IVa group elements, Va group elements and VIa group elements, iron group metals such as Co, Fe and Ni, Y, Al, Si etc. can be mentioned. Note that if the W content exceeds 95 atomic%, W may crystallize and have a disadvantage that it tends to be coarse. A more preferable content of W is 5 to 70 atomic%.
- the adhesion layer preferably contains one or both of Ti and Cr in an atomic ratio of 0.1 to 3 with respect to W. More preferably, the atomic ratio is 0.8 to 2.5. When both Ti and Cr are included, the total atomic ratio is included in the above range.
- the mechanical characteristics are improved by including one or both of Ti and Cr in the above-mentioned atomic ratio. If the atomic ratio is less than 0.1, such improvement in mechanical properties may not be obtained. If the atomic ratio exceeds 3, a hard and brittle adhesion layer is obtained and the mechanical properties deteriorate. There is.
- the adhesion layer of the present invention preferably contains 0.1 to 20 atomic% of at least one element selected from the group consisting of Co, Ni, and Fe. More preferably, it is 1 to 10 atomic%. In the case where two or more of these elements are included, it is preferable that the total of them is included in the above range.
- the density of chemical bonds and mechanical properties due to W can be further improved.
- the adhesion layer can be more effectively brought into the amorphous state or ultrafine particle structure as described above, and the covalent component can be increased.
- the improvement in mechanical properties include an improvement in toughness of the adhesion layer and suppression of peeling due to fatigued destruction of the adhesion layer.
- the content is less than 0.1 atomic%, the above effects cannot be obtained, and if it exceeds 20 atomic%, the W characteristics may be lost.
- composition of such an adhesion layer can be identified by a transmission electron microscope (TEM) / energy dispersive X-ray spectroscopic analysis (EDS).
- TEM transmission electron microscope
- EDS energy dispersive X-ray spectroscopic analysis
- the adhesion layer preferably has a thickness of 0.5 to 30 nm. By setting the thickness of the adhesion layer within this range, the adhesion layer itself has high strength, and has high adhesion (affinity) to both the cubic boron nitride and the hard coating layer. More preferably, it is 2 to 20 nm.
- the thickness of the adhesion layer is less than 0.5 nm, the above effects may not be obtained.
- the thickness of the adhesion layer exceeds 30 nm, the strength of W as a metal becomes dominant, and the strength of the interface with cubic boron nitride may decrease.
- TEM transmission electron microscope
- EDS energy dispersive X-ray spectroscopy
- the surface coating layer of the present invention includes one or more hard coating layers, and the hard coating layer covers the cubic boron nitride sintered body (the portion where the adhesion layer is not formed) and the adhesion layer. It is formed.
- the hard coating layer preferably has a stress of ⁇ 1.5 to +0.5 GPa. More preferably, it is -1 to 0 GPa.
- a numerical value “+” indicates tensile stress
- a numerical value “ ⁇ ” indicates compressive stress.
- Such stress can be measured, for example, by the sin 2 ⁇ method.
- the stress of the hard coating layer exceeds 0.5 GPa, the strength and toughness are extremely lowered, and the chipping property of the tool edge may be lowered (or the wear resistance is lowered) when used as a cutting tool.
- the stress is less than ⁇ 1.5 GPa, the hard coating layer itself self-destructs, chipping and peeling occur, and the wear resistance cannot be improved (with the cubic boron nitride sintered body). (Adhesion may be reduced).
- Such a hard coating layer is composed of one or more layers, and preferably includes the first coating layer as one of them as described later.
- Such a hard coating layer is composed of at least one element selected from the group consisting of group IVa elements, group Va elements, group VIa elements, Al, and Si of the periodic table, and boron, carbon, nitrogen, and oxygen. It is preferably composed of a compound composed of at least one element selected from the group consisting of: Thereby, the outstanding abrasion resistance can be provided.
- the hard coating layer of the present invention preferably has a thickness of 0.5 to 20 ⁇ m. More preferably, it is 0.75 to 7 ⁇ m. When the thickness is less than 0.5 ⁇ m, sufficient wear resistance may not be exhibited. When the thickness exceeds 20 ⁇ m, chipping and peeling tend to occur.
- the hard coating layer of the present invention includes a first coating layer as a lowermost layer in contact with the cubic boron nitride sintered body and the adhesion layer, and the first coating layer includes a group IVa element (Ti, Zr, Hf, etc.), Group Va elements (V, Nb, Ta, etc.), Group VIa elements (Cr, Mo, W, etc.), Al, and Si, and at least one element selected from the group consisting of boron, carbon, nitrogen And a compound comprising at least one element selected from the group consisting of oxygen. Examples of such compounds include TiN, TiCN, TiB 2 , TiAlN, AlCrN, and TiSiN. In the present invention, when a compound is represented by a chemical formula such as TiCN, unless otherwise specified, all known atomic ratios are included, and the atomic ratio of Ti, C, and N is 1: 1: 1. is not.
- the first coating layer is composed of at least one compound selected from the group consisting of TiAlN, AlCrN, and TiSiN, or a solid solution containing the compound, or a superlayer having the compound or the solid solution as a constituent layer. It is preferable to be comprised with a multilayer laminated body.
- the first coating layer has the above-described configuration, the hardness is extremely high, so that the mechanical properties of the adhesion layer and the cubic boron nitride sintered body coincide with each other, and the adhesion between them is high. Sex can be obtained.
- Such a first coating layer becomes a conductive and metal-bonding coating, but if the composition contains Al nitride or Si carbide / nitride and its solid solution, these compounds are covalently bonded. Since the bonding part is partially included, the first coating layer and the adhesion layer have a stronger chemical bond in combination with the adhesion layer of the present invention including both a covalent bond and a metal bond. Therefore, extremely high adhesion can be obtained.
- the first coating layer is composed of a super multi-layer laminate
- the initial several layers formed on the adhesion layer are affected by the adhesion layer and change to an electronic structure that is more likely to form a chemical bond.
- Higher adhesion can be obtained between the adhesion layer.
- the super multi-layer laminate refers to a laminate in which about 10 to 5000 layers of nanometer layers of about 0.5 to 20 nm composed of the above compounds or solid solutions are laminated. More preferably, a structure in which two or more of the above constituent layers are repeatedly laminated is suitable.
- a region within 20 nm (referred to as a region in the thickness direction) from the interface with the adhesion layer is composed of columnar crystals having a particle diameter of 1 to 20 nm. Thereby, it will be excellent in structural consistency with an adhesion layer, and higher adhesion can be obtained.
- the particle diameter of the columnar crystal means the diameter of the columnar crystal.
- the columnar crystal can be confirmed by high-resolution SEM or TEM observation, and the particle size can also be confirmed by TEM observation.
- the surface-coated sintered body of the present invention can be used alone, but can be used as a cutting tool or the like by bonding it to a base material composed of a cemented carbide, for example.
- the present invention is suitable for use as a cutting tool in which a surface-coated sintered body is joined to a cutting edge portion of a base material made of cemented carbide.
- the cemented carbide preferably contains at least WC and Co.
- the cubic boron nitride sintered body of the present invention can be obtained by a conventionally known production method such as an ultrahigh pressure sintering method.
- the surface coating layer can be formed on the cubic boron nitride sintered body as follows, for example.
- the adhesion layer can be formed by forming the metal constituting it on the cubic boron nitride sintered body by sputtering and then partially removing it by etching. Also, by increasing the sputtering bias voltage, an adhesion layer can be formed directly on the cubic boron nitride sintered body (in this case, film formation and etching are performed simultaneously).
- the hard coating layer can be formed by an arc discharge ion plating method or a sputtering method.
- the arc discharge ion plating method conventionally known conditions are employed using a metal evaporation source of the metal species that will constitute the hard coating layer and a reactive gas such as CH 4 , N 2 , O 2, etc. By doing so, a hard coating layer can be formed.
- a metal evaporation source of a metal species constituting the hard coating layer a reaction gas such as CH 4 , N 2 , O 2 , and Ar, Kr, Xe, He, Ne, etc.
- a hard coating layer can be formed by employing a conventionally known condition using a sputtering gas.
- the surface-coated sintered body of the present invention can be produced. And when obtaining this cutting tool by joining this surface covering sintered compact to the base material made from a cemented carbide, for example, it can manufacture as follows.
- a substrate made of cemented carbide can be manufactured by a conventionally known sintering method and molding method. And it can be set as a cutting tool by joining a surface covering sintered compact to the suitable site
- the hard coating layer refers to the first coating layer unless otherwise specified.
- a cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a raw material powder for a binder (the composition of the binder is TiN and the content of the cubic boron nitride as shown in Table 1 below). (Ti is used so as to be TiB 2 ) and sintered under conditions of 1450 ° C. and 5.5 GPa (note that the mixing ratio of the raw material powder is cubic unless otherwise specified) The composition ratio of the boron nitride sintered body is reflected (the same applies to the following examples).
- this sintered body tool was put into a film forming apparatus, vacuumed, heated to 500 ° C., and etched with Ar ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition containing 25 atomic% of W, 50 atomic% of Cr, 12.5 atomic% of Co, and 12.5 atomic% of Fe was prepared, and 1 Pa and sputtering power of 5 kW were introduced while introducing Ar. The film was formed by sputtering until the thickness reached 20 nm under the conditions.
- the coating ratio of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 1 nm using Ar ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the thickness of the adhesion layer formed in advance by sputtering and the amount of etching with Ar ions.
- the state of the said adhesion layer was made into the amorphous state by adjusting the temperature at the time of said sputtering to 300 degreeC.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is Ti 0.9 Si 0.1 N, and it is evaporated and ionized by cold cathode arc discharge using an evaporation source prepared to have the film composition as a cathode, and continues for a time until the thickness reaches 2 ⁇ m.
- a hard coating layer of 0.9 Si 0.1 N was formed.
- the stress of the hard coating layer is ⁇ 1.1 GPa, and the region within 20 nm from the interface with the adhesion layer is 2 nm. It was composed of columnar crystals with a particle size of.
- Example 101 to 109> A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (a carbide having a composition of W and a carbide of W and Co so that the content of cubic boron nitride is 92% by volume). Or it was produced by sintering under conditions of 1500 ° C. and 5.5 GPa by mixing boride and W, Co, B, and C so as to form a solid solution of W—Co.
- this sintered body tool was put into a film forming apparatus, vacuumed, heated to 500 ° C., and etched with Ar ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a W target and a target having a composition ratio of Al and Si of 2: 1 were prepared. While introducing Ar, the composition shown in Table 2 was applied under the conditions of 1 Pa and sputtering power of each target of 0.1 to 10 kW. It adjusted so that it might become, and it formed by performing sputtering until the thickness became 30 nm. However, only the adhesion layer of Example 109 and only the W target were set to 5 kW.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 2 nm using Kr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by the Kr gas flow rate, the bias voltage, the degree of vacuum, and the substrate temperature. The temperature at the time of sputtering was adjusted to 350 ° C.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is Ti 0.65 Cr 0.2 Al 0.1 Si 0.05 N, and it is evaporated and ionized by cold cathode arc discharge using an evaporation source prepared to be the film composition as a cathode until the thickness becomes 1.1 ⁇ m.
- the hard coating layer of Ti 0.65 Cr 0.2 Al 0.1 Si 0.05 N was formed.
- the substrate temperature was 600 ° C.
- the pressure was 4 Pa
- the bias voltage was ⁇ 30 V
- the stress of the hard coating layer was ⁇ 0.5 GPa.
- a region within 20 nm from the interface with the adhesion layer was composed of columnar crystals having a particle diameter of 4 nm.
- the adhesion layers of Examples 101 to 108 were in the form of ultrafine particles having an average particle size of 2 nm, but only Example 109 was formed of coarse particles in a crystalline state having a particle size of 10 nm.
- a cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiCN, TiB 2 , AlN, AlB 2 so that the content of cubic boron nitride is 70% by volume. It was produced by sintering under the conditions of 1400 ° C. and 5.0 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 10 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- the etching was performed with an arc current of 100 A, a pressure of Ar introduced to 1 Pa, and a bias voltage of 600 V.
- This adjustment can be performed by further adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 1 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer was Ti 0.5 Al 0.5 N, and it was evaporated and ionized by cold cathode arc discharge using an evaporation source prepared to have the film composition as a cathode, and continued for a time until the thickness became 3 ⁇ m.
- a hard coating layer of 0.5 Al 0.5 N was formed.
- the stress of the hard coating layer was -1 GPa.
- a region within 20 nm from the interface with the adhesion layer was composed of columnar crystals having a particle diameter of 4 nm.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (so that the composition of the binder is TiWN, WC, and TiB 2 so that the content of cubic boron nitride is 50% by volume. And using Ti, W, and C) and sintering under conditions of 1350 ° C. and 5.5 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- the adhesion ratio of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 7 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 3 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is Al 0.7 Cr 0.23 Si 0.07 N, and the time until the thickness becomes 1.8 ⁇ m by evaporation and ionization by cold cathode arc discharge using the evaporation source prepared to be the film composition as the cathode Continuing, a hard coating layer of Al 0.7 Cr 0.23 Si 0.07 N was formed.
- the stress of the hard coating layer was ⁇ 1.3 GPa. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., a region within 20 nm from the interface with the adhesion layer was constituted by columnar crystals having a particle diameter of 1.5 nm.
- Example 301 to 307 were produced.
- Examples 401 to 409> A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiHfCN, TiB 2 , HfB 2 , AlN so that the cubic boron nitride content is 60% by volume. And Ti, Hf, and Al were used so as to be AlB 2 ), and sintering was performed at 1400 ° C. and 5.5 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition such that W is 53 atomic%, Cr is 5 atomic%, and Co is 42 atomic% is prepared.
- the thickness is 1. Pa under the conditions of 1 Pa and sputtering power of 5 kW while introducing Ar. It was formed by adjusting the sputtering time so that the thickness was 5 to 180 nm.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to the thickness shown in Table 5 using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 0.7 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is a super multi-layer laminate in which 50 layers of Ti 0.4 Al 0.6 N and Al 0.6 Cr 0.3 Si 0.1 N are alternately stacked, and two types of Ti 0.4 Al 0.6 and Al 0.6 Cr 0.3 Si 0.1 are provided. It was produced by simultaneously discharging the evaporation sources and rotating the sintered body tool so as to pass between the evaporation sources. The film formation time was continued until the thickness of the hard coating layer became 1 ⁇ m.
- the stress of the hard coating layer was +0.4 GPa by changing the bias voltage from -50 V to +15 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 550 ° C., the region within 20 nm from the interface with the adhesion layer was constituted by columnar crystals having a particle diameter of 2 nm.
- a cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiCN, TiB 2 , AlN, AlB 2 so that the content of cubic boron nitride is 85% by volume. , Using Ti, Al, and Zr so as to be ZrO 2 ), and sintering under conditions of 1450 ° C. and 5.5 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- the adhesion layer has a composition of W 33.3 atomic%, Cr 33.3 atomic%, Co 33.3 atomic%, and W and Co by sputtering, Cr is arc discharge ion plating. It was formed by simultaneous vapor deposition by the method. The formation time continued until the thickness of the adhesion layer reached 40 nm.
- the adhesion ratio of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 9 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did. This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the conditions of the above-mentioned sputtering method and arc discharge ion plating method are adjusted such that the substrate temperature is 350 ° C. to 650 ° C. and the bias voltage is ⁇ 50 V to ⁇ 500 V, so that the state of the adhesion layer is shown in Table 6. It was changed as follows.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is Al 0.65 Ti 0.3 Si 0.05 C 0.05 N 0.95, and the thickness is 4.5 ⁇ m by evaporation and ionization by cold cathode arc discharge using the evaporation source prepared to be the film composition as the cathode.
- the stress of the hard coating layer was -0.2 GPa by changing the bias voltage from -50V to 0V at 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 250 to 550 ° C., the region within 20 nm from the interface with the adhesion layer was composed of columnar crystals having a particle diameter of 1.5 nm.
- Examples 601 to 605 and Comparative Examples 601 to 602> A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is W, Co such as WC or WCoB 2) so that the content of cubic boron nitride is 95% by volume. And W, Co, B, and C are used so as to form a compound of B, C), and sintered under conditions of 1450 ° C. and 6.0 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- the adhesion layer was formed by sputtering with W and Co so that the composition of W was 29 atomic%, Cr was 58 atomic%, and Co was 13 atomic%, and Cr was formed by arc discharge ion plating. .
- the formation time was continued until the thickness of the adhesion layer became 75 nm.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 15 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body is as shown in Table 7.
- Etching conditions were adjusted by adjusting the arc current to 50 A, the pressure to Ar and N 2 at a ratio of 9: 1, 1 Pa, and the bias voltage to 300 to 900 V.
- the above-described sputtering method and arc discharge ion plating method were simultaneously formed to configure the state of the adhesion layer as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 0.6 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is Al 0.7 Ti 0.3 N, which is evaporated and ionized by cold cathode arc discharge using an evaporation source prepared to have the film composition as a cathode, and continues for a time until the thickness reaches 4 ⁇ m.
- a hard coating layer of 0.7 Ti 0.3 N was formed.
- the stress of the hard coating layer was ⁇ 0 GPa by changing the bias voltage from -20 V to 0 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., a region within 20 nm from the interface with the adhesion layer was constituted by columnar crystals having a particle diameter of 15 nm.
- a cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (so that the composition of the binder is TiZrCN, Al 2 O 3 so that the cubic boron nitride content is 45% by volume. And using Ti, Zr, and Al) and sintering under conditions of 1350 ° C. and 5.5 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition such that W is 70 atomic% and Fe is 30 atomic% is prepared, and sputtering is performed for a time until the thickness reaches 70 nm under the conditions of 1 Pa and sputtering power of 5 kW while introducing Ar. was formed.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 15 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 4.5 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is a super multi-layer laminate in which Ti 0.93 Si 0.07 N and Ti 0.5 Al 0.3 Cr 0.1 Si 0.1 N are alternately laminated by 1050 layers, and Ti 0.93 Si 0.07 N and Ti 0.5 Al 0.3 Cr 0.1 Si 0.1
- the two types of evaporation sources N and N were simultaneously discharged, and the sintered body tool was rotated so as to pass between the respective evaporation sources. The film formation time was continued until the thickness of the hard coating layer became 6.3 ⁇ m.
- the stress of the hard coating layer was changed as shown in Table 8 by changing the bias voltage to + 20V, + 10V, -10V, -25V, -50V, -80V, -100V to 0V at 50 kHz. . Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., the region within 20 nm from the interface with the adhesion layer was composed of columnar crystals having a particle diameter of 3 nm.
- Examples 801 to 807> A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (so that the composition of the binder is Al, AlN, and AlB 2 so that the content of cubic boron nitride is 98% by volume. And Al was used), and sintering was performed under conditions of 1450 ° C. and 6.0 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- the adhesion layer is formed by preparing a target having a composition containing 90 atomic% of W and 10 atomic% of Ti, and performing sputtering until the thickness reaches 100 nm under the conditions of 1 Pa and sputtering power of 5 kW while introducing Ar. did.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 22 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the said adhesion layer was made into the amorphous state by adjusting the temperature at the time of said sputtering to 300 degreeC.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is Al 0.8 Cr 0.2 N, and it is evaporated and ionized by cold cathode arc discharge using an evaporation source prepared to be the film composition as a cathode so that the thickness becomes the thickness described in Table 9.
- the time was adjusted and a hard coating layer of Al 0.8 Cr 0.2 N was formed.
- the stress of the hard coating layer was -0.2 GPa by changing the bias voltage from -50 V to +30 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., a region within 20 nm from the interface with the adhesion layer was constituted by columnar crystals having a particle diameter of 18 nm.
- Examples 901 to 906> A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a raw material powder for binder (the composition of the binder is TiC, TiCN, TiB 2 , AlN, so that the content of cubic boron nitride is 65% by volume. It was prepared by sintering under the conditions of 1350 ° C. and 6.0 GPa by mixing Ti and Al so as to be AlB 2 .
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition containing 76 atomic% W, 8 atomic% Co, 8 atomic% Ni, and 8 atomic% Fe was prepared, and sputtered under conditions of 1 Pa and sputtering power of 5 kW while introducing Ar.
- Ti was evaporated by arc discharge ion plating while applying a bias voltage of ⁇ 750 V to the sintered body tool, and mixing was performed, so that W was 45 atomic%, Ti was 40 atomic%, and Co was 5 atomic%.
- An adhesion layer composed of 5 atomic% Ni and 5 atomic% Fe was formed to 35 nm.
- the adhesion ratio of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 7 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 1.8 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the composition of the hard coating layer is a super multi-layer laminate in which 800 layers of Al 0.7 Cr 0.3 N and Ti 0.5 Al 0.4 Si 0.1 N are alternately stacked, and 2 of Al 0.7 Cr 0.3 N and Ti 0.5 Al 0.4 Si 0.1 N.
- the various types of evaporation sources were simultaneously discharged, and the sintered body tool was rotated so as to pass between the evaporation sources. The film formation time was continued until the thickness of the hard coating layer reached 8 ⁇ m.
- the stress of the hard coating layer was +1.4 GPa by changing the bias voltage from -25 V to 0 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 300 to 600 ° C., the particle diameter of the columnar crystals in the region within 20 nm from the interface with the adhesion layer was changed as shown in Table 10.
- Example 1001 A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiCN, TiB 2 , AlN, AlB 2 so that the content of cubic boron nitride is 65% by volume. And using TiAl 2 N and W so as to be WC), and sintering under conditions of 1300 ° C. and 6.0 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition such that W is 40 atomic%, Cr is 40 atomic%, and Co is 20 atomic% is prepared.
- the thickness is 60 nm under the conditions of 1 Pa and sputtering power of 5 kW while introducing Ar. It was formed by adjusting the sputtering time.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 11 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 1.1 nm.
- the hard coating layer is composed of a first coating layer made of TiN having a thickness of 0.3 ⁇ m and a layer having a thickness of 2.7 ⁇ m made of Ti 0.5 Al 0.5 N on the first coating layer (hereinafter referred to as “second coating layer”). ).
- first coating layer made of TiN having a thickness of 0.3 ⁇ m and a layer having a thickness of 2.7 ⁇ m made of Ti 0.5 Al 0.5 N on the first coating layer (hereinafter referred to as “second coating layer”).
- second coating layer a layer having a thickness of Ti 0.5 Al 0.5 N on the first coating layer
- the stress of the hard coating layer was -0.6 GPa by changing the bias voltage from -50 V to 0 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., the region within 20 nm from the interface with the adhesion layer in the first coating layer was composed of columnar crystals having a particle diameter of 1.5 nm.
- Example 1001 The cutting tool of Example 1001 was produced.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiCN, TiB 2 , AlN, AlB 2 so that the content of cubic boron nitride is 50% by volume. And using Ti, Al, and W so as to be WC), and sintering under conditions of 1300 ° C. and 6 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition of 45 atomic% W, 32 atomic% Ti, and 23 atomic% Co was prepared, and the thickness was 40 nm under the conditions of 1 Pa and sputtering power of 5 kW while introducing Ar. It was formed by adjusting the sputtering time.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 8 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 1.2 nm.
- a hard coating layer was formed by arc discharge ion plating on the adhesion layer and on the cubic boron nitride sintered body where the adhesion layer was not formed.
- the hard coating layer is composed of a first coating layer 0.7 ⁇ m thick made of Ti 0.2 Al 0.7 Si 0.1 N, and a 1.3 ⁇ m layer made of Ti 0.92 Si 0.08 C 0.2 N 0.8 on the first coating layer. (Hereinafter referred to as “second coating layer”).
- second coating layer Specifically, evaporation and ionization were performed by cold cathode arc discharge using an evaporation source prepared to have such a film composition as a cathode, and the film formation time was adjusted to achieve the above thickness.
- the stress of the hard coating layer was -0.4 GPa by changing the bias voltage from -60 V to 0 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., the region within 20 nm from the interface with the adhesion layer in the first coating layer was composed of columnar crystals having a particle diameter of 1.2 nm.
- Example 1003 A cutting tool was prepared by joining a surface-coated sintered body to the cutting edge of a cemented carbide substrate.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiCN, TiB 2 , AlN, AlB 2 so that the cubic boron nitride content is 42% by volume. And using TiN, AlN, and W so as to be WC), and sintering under conditions of 1300 ° C. and 5.0 GPa.
- the sintered body tool was put into a film forming apparatus, vacuumed, heated to 620 ° C., and etched with Xe ions. Thereafter, an adhesion layer was formed on the cubic boron nitride sintered body in the same film forming apparatus.
- a target having a composition such that W is 85 atomic% and Ni is 15 atomic% is prepared.
- Sputtering time is 30 nm under the conditions of 1 Pa and sputtering power of 5 kW while introducing Ar. It was formed by adjusting.
- the coating rate of the adhesion layer was adjusted as follows by etching the adhesion layer to a thickness of 6 nm using Cr ions. That is, the ratio of the cubic boron nitride particles in contact with the adhesion layer is adjusted to 15% with respect to the total number of cubic boron nitride particles in contact with the adhesion layer or the hard coating layer on the surface of the cubic boron nitride sintered body. did.
- This adjustment can be performed by adjusting the arc current, bias voltage, degree of vacuum, gas type (N 2 , Ar) and the ratio of the Cr evaporation source.
- the state of the adhesion layer was configured as a mixed phase of an amorphous state and ultrafine particles having an average particle diameter of 1.3 nm.
- the hard coating layer consists of a first coating layer made of Ti 0.7 Zr 0.1 Si 0.2 N and having a thickness of 0.5 ⁇ m, and 25 layers of Ti 0.7 Zr 0.1 Si 0.2 N and Al 0.7 Ti 0.3 N on the first coating layer.
- a layer having a thickness of 1 ⁇ m (hereinafter referred to as “second coating layer”) made of super multi-layer laminates laminated one by one was used.
- the first coating layer is evaporated and ionized by cold cathode arc discharge using an evaporation source prepared to have the film composition as described above as a cathode, and the film formation time is set to have the above thickness. It was adjusted.
- the second coating layer was produced by rotating the sintered body tool as to simultaneously discharge the two evaporation sources of Ti 0.7 Zr 0.1 Si 0.2 and Al 0.7 Ti 0.3, it passes between the respective evaporation sources.
- the stress of the hard coating layer was -1.2 GPa by changing the bias voltage from -50 V to 0 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., the region within 20 nm from the interface with the adhesion layer in the first coating layer was composed of columnar crystals having a particle diameter of 1.4 nm.
- Example 1003 the cutting tool of Example 1003 was produced.
- a cemented carbide alloy (equivalent to K10) having a shape of ISO CNMA120408 is prepared, and a cubic boron nitride sintered body produced as described later on its blade edge portion (corner portion) (Shape: Triangular prism shape with a thickness of 2 mm with an isosceles triangle of 2 mm each on both sides sandwiching the apex angle) and a brazing material made of Ti—Zr—Cu. Then, the outer periphery and upper and lower surfaces of the joined body were ground to form a negative land (width 150 ⁇ m, angle 25 °) shape at the blade edge (hereinafter referred to as a sintered body tool).
- the cubic boron nitride sintered body has a cubic boron nitride powder and a binder raw material powder (the composition of the binder is TiCN, TiB 2 , AlN, AlB 2 so that the cubic boron nitride content is 40% by volume. And using Ti, Al, and W so as to be WC), and sintering under conditions of 1350 ° C. and 5 GPa.
- this sintered body tool was put into a film forming apparatus, vacuumed, and then heated to 620 ° C. and etched with Xe ions. Thereafter, a hard coating layer was directly formed by an arc discharge ion plating method without forming an adhesion layer on the cubic boron nitride sintered body in the film forming apparatus.
- the configuration of the hard coating layer was a 3 ⁇ m thick layer made of Ti 0.5 Al 0.5 N. Specifically, evaporation and ionization were performed by cold cathode arc discharge using an evaporation source prepared to have such a film composition as a cathode, and the film formation time was adjusted to achieve the above thickness.
- the stress of the hard coating layer was ⁇ 1 GPa by changing the bias voltage from ⁇ 70 V to 0 V at a pulse bias of 50 kHz. Further, by setting the substrate temperature at the initial stage of film formation to 600 ° C., the region within 20 nm from the interface with the adhesion layer in the hard coating layer was composed of columnar crystals having a particle diameter of 10 nm.
- the state evaluation (structure evaluation) including the thickness, composition, crystallinity, and average particle size of the ultrafine particles was measured as follows. That is, first, one cross section including the cubic boron nitride sintered body and the surface coating layer was formed by the FIB (Focused Ion Beam) method. Next, in the cross section, the interface between the cubic boron nitride sintered body and the adhesion layer was observed by a scanning transmission electron microscope (STEM) / energy dispersive X-ray spectroscopic analysis (EDS).
- STEM scanning transmission electron microscope
- EDS energy dispersive X-ray spectroscopic analysis
- the thickness and composition of the hard coating layer were determined in the same manner as in the adhesion layer.
- the sample was adjusted to a thickness of about 100 nm by ion beam processing, the STEM electron beam diameter was 1 nm ⁇ , and the observation magnification was 100000 times or more.
- the incident angle of the electron beam was adjusted so that the contrast of the adhesion layer or the contrast of W was maximized compared to other metal element components (including the metal element constituting the hard coating layer) and B.
- the adhesion layer has irregularities, when the composition of the adhesion layer is observed, the element of the hard coating layer or the element of the cubic boron nitride sintered body may be detected.
- the adhesion layer or the hard coating layer it is possible to mix the adhesion layer and the cubic boron nitride sintered body or the hard coating layer by controlling the energy of the film forming species. The analysis result is as described above. The detected result including such a case was defined as the composition of the adhesion layer.
- one cross section including the cubic boron nitride sintered body formed in the same manner as described above and the surface coating layer was flattened by ion beam treatment.
- the interface between the cubic boron nitride particles and the surface coating layer is observed using a high resolution scanning electron microscope (SEM), and W is observed at the interface using EDS.
- SEM high resolution scanning electron microscope
- the adhesion layer containing W is observed as a layer having particularly high brightness, it can be determined simply by the presence or absence of this bright layer.
- Cutting test A can mainly evaluate defects due to adhesion of the hard coating layer, wear resistance and chipping
- cutting test B shows adhesion resistance and wear resistance of the hard coating layer as well as fracture resistance due to relatively large chipping. Can be evaluated.
- the time required for the flank wear amount (Vb) to reach 0.2 mm is defined as the tool life, and the longer the time, the greater the adhesion between the cubic boron nitride sintered body and the surface coating layer. Excellent (that is, excellent in both wear resistance and toughness).
- the results are shown in Tables 1-11. In the table, “peeling / deleting” means that the surface coating layer was peeled off during the cutting test, or the cutting tool was damaged, and the cutting time could not be measured.
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Abstract
Description
<表面被覆焼結体>
本発明の表面被覆焼結体は、立方晶窒化硼素焼結体とその表面に形成された表面被覆層とを含む。本発明の表面被覆焼結体において、表面被覆層は、立方晶窒化硼素焼結体の全表面を覆うように形成されていてもよいし、その一部の表面のみを覆うようにして形成されていてもよい。特に、後述のように、この表面被覆焼結体を基材に接合して用いる場合は、その基材との接合部に表面被覆層を形成する必要はない。
本発明の立方晶窒化硼素焼結体は、20~99.5体積%の立方晶窒化硼素と、結合材とを含む。本発明の立方晶窒化硼素焼結体は、これら2成分を含む限り、不可避不純物を含め他の任意の成分を含んでいても差し支えない。
組成1:元素周期律表のIVa族元素、Va族元素、VIa族元素、Al、およびSiからなる群より選ばれる少なくとも1種の元素と、硼素、炭素、窒素および酸素からなる群より選ばれる少なくとも1種の元素とからなる化合物。
組成2:上記化合物を含む固溶体。
組成3:Co、W、Ni、Al等の金属単体。
組成4:Co、W、Ni、Al等を含む化合物。
組成5:上記組成1の化合物とCo、W、Ni、Al等とを含む固溶体。
組成6:上記組成1の化合物に対しさらにCo、W、Ni、Al等を含む化合物。
本発明の表面被覆層は、密着層と1層以上の硬質被膜層とを含む。これらの層を含む限り、他の任意の層が含まれていても差し支えない。
本発明の密着層は、少なくともWを含む金属層であり、該立方晶窒化硼素焼結体の表面の一部を被覆するように形成される。そして、本発明においては、立方晶窒化硼素焼結体の表面において密着層または硬質被膜層と接する立方晶窒化硼素粒子の総数に対して、密着層と接する立方晶窒化硼素粒子の割合が0.01~20%であることを特徴とする。この割合は、さらに好ましくは、0.02~1%である。このように本発明の密着層を上記のような構成とすることにより、耐熱性、強度、および靭性を高度に兼ね備え、以って立方晶窒化硼素焼結体と表面被覆層とを極めて強力に密着することができるという優れた効果を示す。
本発明の密着層は、アモルファス状態であるかまたは平均粒径が5nm以下の超微粒子により構成されることが好ましい。そして、本発明の密着層は、これら両者の混合相となることがより好ましい。
本発明の密着層は、Wを0.05~95原子%含むことが好ましい。Wを含むことにより、上記のように優れた効果を得ることができるからである。ここで、Wの含有量が0.05原子%未満の場合は、上記の優れた効果を十分に得られない場合がある。また、Wの効果は、わずかな異元素の混入により促進されるため、95原子%以下とすることが好ましい。ここで異元素とは、酸素、炭素、窒素、硼素などの軽元素、IVa族元素、Va族元素、VIa族元素などの遷移金属、Co、Fe、Niなどの鉄族金属、Y、Al、Siなどを挙げることができる。なお、Wの含有量が95原子%を超えるとWが結晶化し、粗粒化しやすいという不都合を有する場合がある。Wのより好ましい含有量は、5~70原子%である。
上記密着層は、0.5~30nmの厚みを有することが好ましい。密着層の厚みをこの範囲とすることにより、密着層自体の強度が高く、また立方晶窒化硼素および硬質被膜層の両者に対して高い密着性(親和性)を有したものとなる。より好ましくは、2~20nmである。
本発明の表面被覆層は、1層以上の硬質被膜層を含み、当該硬質被膜層は、立方晶窒化硼素焼結体(の密着層が形成されていない部分)および密着層を被覆するように形成される。そして、この硬質被膜層は、-1.5~+0.5GPaの応力を有することが好ましい。より好ましくは、-1~0GPaである。
本発明の硬質被膜層は、立方晶窒化硼素焼結体および密着層と接する最下層として第1被膜層を含み、該第1被膜層は、元素周期律表のIVa族元素(Ti、Zr、Hf等)、Va族元素(V、Nb、Ta等)、VIa族元素(Cr、Mo、W等)、Al、およびSiからなる群より選ばれる少なくとも1種の元素と、硼素、炭素、窒素および酸素からなる群より選ばれる少なくとも1種の元素とからなる化合物で構成されることが好ましい。このような化合物としては、たとえばTiN、TiCN、TiB2、TiAlN、AlCrN、TiSiN等を挙げることができる。なお、本発明において、化合物をTiCN等の化学式で表わす場合、特に断りのない限り従来公知のあらゆる原子比を含むものとし、TiとCとNの原子比が1:1:1の場合を示すものではない。
本発明の表面被覆焼結体は、それ単独で用いることも可能であるが、たとえば超硬合金等で構成される基材に接合することにより、切削工具等として用いることができる。特に、本発明は、表面被覆焼結体を超硬合金製の基材の刃先部に接合してなる切削工具としての使用に適したものである。
<製造方法>
本発明の立方晶窒化硼素焼結体は、超高圧焼結法等の従来公知の製法により得ることができる。また、表面被覆層は、たとえば下記のようにして立方晶窒化硼素焼結体上に形成することができる。
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例101~109>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例301~307>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例401~409>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例501~507>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例601~605および比較例601~602>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例801~807>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例901~906>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例1001>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例1002>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<実施例1003>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<比較例1001>
超硬合金製の基材の刃先部に表面被覆焼結体を接合することにより切削工具を作製した。
<測定条件>
上記の実施例および比較例における数値は以下のようにして測定した。
密着層の厚み、組成、結晶性および超微粒子の平均粒径を含む状態評価(組織評価)は、次のようにして測定した。すなわち、まず立方晶窒化硼素焼結体と表面被覆層とを含む一断面をFIB(Focused Ion Beam)法により形成した。次いで、その断面において、立方晶窒化硼素焼結体と密着層との界面を走査透過型電子顕微鏡(STEM)/エネルギ分散型X線分光分析(EDS)により観察した。
立方晶窒化硼素焼結体の表面における、密着層または硬質被膜層と接する立方晶窒化硼素粒子の総数に対する、密着層と接する立方晶窒化硼素粒子の割合は次のようにして測定した。
上記で得た実施例および比較例の切削工具を用いて以下の切削条件により切削試験を2種行なった。切削試験Aは硬質被膜層の密着性、耐摩耗性とチッピングの集積による欠損を主に評価でき、切削試験Bは硬質被膜層の密着性、耐摩耗性とともに比較的大きな欠けによる耐欠損性を評価できる。両試験とも、逃げ面摩耗量(Vb)が0.2mmとなるまでに要する時間(切削時間)を工具寿命とし、時間が長くなるほど立方晶窒化硼素焼結体と表面被覆層との密着性が優れること(すなわち耐摩耗性と靭性の両者に優れること)を示す。その結果を表1~11に示す。なお、表中、「剥離・欠損」とは、切削試験の途中で表面被覆層が剥離したり、切削工具が欠損し、切削時間を測定できなかったことを示す。
切削速度:V=170m/min.
送 り:f=0.1mm/rev.
切り込み:d=0.2mm
湿式乾式:乾式(Dry)
被削材 :SCM435浸炭材(HRC62)であって、1つの溝を有し、黒皮付きの丸棒。
切削速度:V=200m/min.
送 り:f=0.05mm/rev.
切り込み:d=0.2mm
湿式乾式:乾式(Dry)
被削材 :SUJ2(HRC60)であって、長手方向に6つの溝を有する丸棒。
Claims (12)
- 立方晶窒化硼素焼結体とその表面に形成された表面被覆層とを含み、
前記立方晶窒化硼素焼結体は、20~99.5体積%の立方晶窒化硼素と、結合材とを含み、
前記表面被覆層は、密着層と1層以上の硬質被膜層とを含み、
前記密着層は、少なくともWを含む金属層であり、前記立方晶窒化硼素焼結体の表面の一部を被覆するように形成され、
前記硬質被膜層は、前記立方晶窒化硼素焼結体および前記密着層を被覆するように形成され、
前記立方晶窒化硼素焼結体の表面において前記密着層または前記硬質被膜層と接する立方晶窒化硼素粒子の総数に対して、前記密着層と接する立方晶窒化硼素粒子の割合が0.01~20%である、表面被覆焼結体。 - 前記密着層は、アモルファス状態であるかまたは平均粒径が5nm以下の超微粒子により構成される、請求項1記載の表面被覆焼結体。
- 前記密着層は、Wを0.05~95原子%含む、請求項1記載の表面被覆焼結体。
- 前記密着層は、TiまたはCrのいずれか一方または両方を、Wに対し原子比で0.1~3含む、請求項1記載の表面被覆焼結体。
- 前記密着層は、Co、Ni、およびFeからなる群より選ばれる少なくとも1種の元素を、0.1~20原子%含む、請求項1記載の表面被覆焼結体。
- 前記密着層は、0.5~30nmの厚みを有する、請求項1記載の表面被覆焼結体。
- 前記硬質被膜層は、-1.5~+0.5GPaの応力を有する、請求項1記載の表面被覆焼結体。
- 前記硬質被膜層は、前記立方晶窒化硼素焼結体および前記密着層と接する最下層として第1被膜層を含み、
前記第1被膜層は、元素周期律表のIVa族元素、Va族元素、VIa族元素、Al、およびSiからなる群より選ばれる少なくとも1種の元素と、硼素、炭素、窒素および酸素からなる群より選ばれる少なくとも1種の元素とからなる化合物で構成される、請求項1記載の表面被覆焼結体。 - 前記第1被膜層は、TiAlN、AlCrNおよびTiSiNからなる群より選ばれる少なくとも1種の化合物またはその化合物を含む固溶体で構成されるか、あるいは前記化合物または前記固溶体を構成層とする超多層積層体で構成される、請求項8記載の表面被覆焼結体。
- 前記第1被膜層は、前記密着層との界面から20nm以内の領域が1~20nmの粒径の柱状晶で構成されている、請求項8記載の表面被覆焼結体。
- 前記硬質被膜層は、0.5~20μmの厚みを有する、請求項1記載の表面被覆焼結体。
- 請求項1記載の表面被覆焼結体を超硬合金製の基材の刃先部に接合してなる、切削工具。
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| JP2012545638A JP5776125B2 (ja) | 2010-11-26 | 2011-08-30 | 表面被覆焼結体 |
| MX2013003469A MX346949B (es) | 2010-11-26 | 2011-08-30 | Cuerpo sinterizado de superficie revestida. |
| KR1020137014405A KR20140002661A (ko) | 2010-11-26 | 2011-08-30 | 표면 피복 소결체 |
| CN201180056084.5A CN103228383B (zh) | 2010-11-26 | 2011-08-30 | 表面被覆烧结体 |
| US13/877,372 US9056437B2 (en) | 2010-11-26 | 2011-08-30 | Surface-coated sintered body |
| EP11843929.8A EP2644300B1 (en) | 2010-11-26 | 2011-08-30 | Surface coated sintered body |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014195859A (ja) * | 2013-03-29 | 2014-10-16 | 住友電工ハードメタル株式会社 | 表面被覆窒化硼素焼結体工具 |
| JP2014195858A (ja) * | 2013-03-29 | 2014-10-16 | 住友電工ハードメタル株式会社 | 表面被覆窒化硼素焼結体工具 |
| JP2014195857A (ja) * | 2013-03-29 | 2014-10-16 | 住友電工ハードメタル株式会社 | 表面被覆窒化硼素焼結体工具 |
| JP2017077599A (ja) * | 2015-10-20 | 2017-04-27 | 三菱マテリアル株式会社 | 硬質被覆層がすぐれた耐欠損性と耐摩耗性を備える表面被覆切削工具およびその製造方法 |
| WO2021193876A1 (ja) * | 2020-03-27 | 2021-09-30 | 京セラ株式会社 | 被覆工具および切削工具 |
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| KR102178189B1 (ko) | 2013-07-03 | 2020-11-13 | 외를리콘 서피스 솔루션즈 아게, 페피콘 | TixSi1-xN 층 및 그의 생산 |
| DE102013011073A1 (de) * | 2013-07-03 | 2015-01-08 | Oerlikon Trading Ag, Trübbach | TlxSi1-xN Schichten und ihre Herstellung |
| MX2018009605A (es) * | 2016-03-30 | 2018-09-11 | Sumitomo Electric Hardmetal Corp | Cuerpo sinterizado de nitruro de boro cubico recubierto en la superficie y herramienta de corte que se proporciona con el mismo. |
| WO2018097280A1 (ja) * | 2016-11-28 | 2018-05-31 | パナソニックIpマネジメント株式会社 | 鉄系焼結体の基材の表面に形成される酸化被膜、およびこの酸化被膜を形成した摺動部材、並びに、この摺動部材を備える機器 |
| EP3730470A1 (de) * | 2018-08-21 | 2020-10-28 | Refractory Intellectual Property GmbH & Co. KG | Feuerfestes erzeugnis, ein versatz zur herstellung des erzeugnisses, ein verfahren zur herstellung des erzeugnisses sowie eine verwendung des erzeugnisses |
| EP3960341A4 (en) * | 2019-08-06 | 2022-06-29 | Sumitomo Electric Hardmetal Corp. | Cutting tool |
| JP7214680B2 (ja) * | 2020-04-06 | 2023-01-30 | 株式会社神戸製鋼所 | 硬質皮膜および耐土砂摩耗性硬質皮膜被覆部材 |
| JP7346751B1 (ja) * | 2022-03-08 | 2023-09-19 | 住友電工ハードメタル株式会社 | 立方晶窒化硼素焼結体 |
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- 2011-08-30 KR KR1020137014405A patent/KR20140002661A/ko not_active Ceased
- 2011-08-30 US US13/877,372 patent/US9056437B2/en active Active
- 2011-08-30 EP EP11843929.8A patent/EP2644300B1/en active Active
- 2011-08-30 CN CN201180056084.5A patent/CN103228383B/zh active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014195859A (ja) * | 2013-03-29 | 2014-10-16 | 住友電工ハードメタル株式会社 | 表面被覆窒化硼素焼結体工具 |
| JP2014195858A (ja) * | 2013-03-29 | 2014-10-16 | 住友電工ハードメタル株式会社 | 表面被覆窒化硼素焼結体工具 |
| JP2014195857A (ja) * | 2013-03-29 | 2014-10-16 | 住友電工ハードメタル株式会社 | 表面被覆窒化硼素焼結体工具 |
| JP2017077599A (ja) * | 2015-10-20 | 2017-04-27 | 三菱マテリアル株式会社 | 硬質被覆層がすぐれた耐欠損性と耐摩耗性を備える表面被覆切削工具およびその製造方法 |
| WO2021193876A1 (ja) * | 2020-03-27 | 2021-09-30 | 京セラ株式会社 | 被覆工具および切削工具 |
| JPWO2021193876A1 (ja) * | 2020-03-27 | 2021-09-30 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130199351A1 (en) | 2013-08-08 |
| JPWO2012070290A1 (ja) | 2014-05-19 |
| KR20140002661A (ko) | 2014-01-08 |
| MX346949B (es) | 2017-04-06 |
| EP2644300A4 (en) | 2016-05-25 |
| EP2644300B1 (en) | 2018-03-07 |
| EP2644300A1 (en) | 2013-10-02 |
| CN103228383B (zh) | 2016-08-03 |
| US9056437B2 (en) | 2015-06-16 |
| JP5776125B2 (ja) | 2015-09-09 |
| CN103228383A (zh) | 2013-07-31 |
| MX2013003469A (es) | 2013-06-24 |
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