US20150203956A1 - Coated Tool - Google Patents

Coated Tool Download PDF

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Publication number
US20150203956A1
US20150203956A1 US14/420,300 US201314420300A US2015203956A1 US 20150203956 A1 US20150203956 A1 US 20150203956A1 US 201314420300 A US201314420300 A US 201314420300A US 2015203956 A1 US2015203956 A1 US 2015203956A1
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Prior art keywords
layer
stack structure
layers
metal elements
constituting
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US14/420,300
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English (en)
Inventor
Shota Asari
Masakazu Kikuchi
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Tungaloy Corp
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Tungaloy Corp
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Assigned to TUNGALOY CORPORATION reassignment TUNGALOY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ASARI, Shota, KIKUCHI, MASAKAZU
Publication of US20150203956A1 publication Critical patent/US20150203956A1/en
Abandoned legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2228/00—Properties of materials of tools or workpieces, materials of tools or workpieces applied in a specific manner
    • B23B2228/10—Coatings
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick

Definitions

  • the present invention relates to coated tools.
  • coated tools are used in which an alternate film stack of coating films is disposed on a substrate.
  • Patent Literature 1 proposes a highly wear resistant cutting tool in which a specific metal element or a compound thereof and a specific alloy compound are stacked with a stacking period of 0.4 nm to 50 nm on the surface of a base material.
  • Patent Literature 2 proposes a cutting tool exhibiting excellent wear resistance even under heavy cutting conditions.
  • This tool is such that the surface of a base is coated with 4 or more layers having an average total layer thickness of 2 to 10 pm which are in the form of an alternate stack of first thin layers of a composite nitride represented by the composition formula (Ti 1 ⁇ x Al x )N (x in atomic ratio: 0.30 to 0.70) and second thin layers containing an aluminum oxide phase in a ratio of 35 to 65 mass % relative to the total of the mass thereof and the mass of a titanium nitride phase, the average layer thickness of the individual layers being 0.2 to 1 ⁇ m.
  • Patent Literature 3 proposes a cutting tool with excellent wear resistance and welding resistance which is such that 100-5000 nm stack layers including a periodic stack of layers with thicknesses of 1 to 50 nm, and 100-5000 nm single layers are alternately stacked in 10 or more layers on top of one another on a hard base material.
  • the cutting tool of the invention of Patent Literature 1 which includes a stack of thin layers with a stacking period of 0.4 to 50 nm exhibits high wear resistance, the tool is problematically prone to be fractured under the circumstances described above.
  • the cutting tool of the invention of Patent Literature 2 which includes an alternate stack of layers with a large individual average layer thickness has a problem in that the hardness of the coating films is so insufficient that the tool exhibits poor wear resistance.
  • the fracture resistance is insufficient and the tool cannot more often satisfy the required performance described hereinabove.
  • the present invention has been made to solve these problems. It is therefore an object of the invention to provide long-life coated tools which are enhanced in fracture resistance without any decrease in wear resistance.
  • the present inventors carried out studies on the extension of the life of coated tools. The present inventors have then found that fracture resistance may be enhanced without causing a decrease in wear resistance by improving the layer configurations and the compositions of coating layers. As a result, the extension of the life of coated tools has been realized.
  • the present invention may be summarized as follows.
  • a coated tool comprising a substrate and a coating layer disposed on a surface of the substrate, the coating layer including a first stack structure and a second stack structure, the first stack structure having a structure in which two or more kinds of layers with different compositions are periodically stacked wherein the average layer thickness of each of the layers is 60 nm to 500 nm, the second stack structure having a structure in which two or more kinds of layers with different compositions are periodically stacked wherein the average layer thickness of each of the layers is 2 nm to less than 60 nm, the layers constituting the first stack structure and the layers constituting the second stack structure including at least one selected from the group consisting of a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr, Y, Sn and Bi; and compounds including at least one of these metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
  • a metal including at least one metal element selected from Ti,
  • the layers constituting the first stack structure and the layers constituting the second stack structure each include at least one selected from the group consisting of metals including at least two metal elements selected from Ti, Nb, Ta, Cr, W, Al, Si, Sr and Y; and compounds including at least two of these metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
  • the metal elements present in the layers constituting the first stack structure are identical among the layers constituting the first stack structure and include one or more metal elements having a difference in absolute value of 5 at % or more between the ratio thereof relative to the total of the metal elements present in one layer constituting the first stack structure and the ratio of the identical metal element relative to the total of the metal elements present in a layer constituting the first stack structure which layer is adjacent to the one layer.
  • the metal elements present in the layers constituting the second stack structure are identical among the layers constituting the second stack structure and include one or more metal elements having a difference in absolute value of 5 at % or more between the ratio thereof relative to the total of the metal elements present in one layer constituting the second stack structure and the ratio of the identical metal element relative to the total of the metal elements present in a layer constituting the second stack structure which layer is adjacent to the one layer.
  • coated tools of the present invention have excellent wear resistance and fracture resistance to achieve a longer tool life than heretofore possible.
  • FIG. 1 is an example of schematic views illustrating a sectional structure of a coated tool of the present invention.
  • a coated tool of the present invention includes a substrate and a coating layer disposed on a surface of the substrate.
  • the substrates in the present invention are not particularly limited, and any substrates of coated tools may be used. Examples thereof include cemented carbides, cermets, ceramics, sintered cubic boron nitrides, sintered diamonds and high-speed steels. In particular, cemented carbide substrates are more preferable due to excellent wear resistance and fracture resistance.
  • Wear resistance tends to be decreased if the average total layer thickness of the entirety of the coating layer in the coated tool of the present invention is less than 0.22 ⁇ m.
  • a decrease in fracture resistance tends to be caused if the average total layer thickness of the entirety of the coating layer exceeds 12 ⁇ m. It is therefore preferable that the average total layer thickness of the entirety of the coating layer be 0.22 to 12 ⁇ m.
  • the average total layer thickness of the entirety of the coating layer is more preferably 1.0 to 8.0 ⁇ m.
  • the coating layer in the coated tool of the present invention includes a specific first stack structure and a specific second stack structure.
  • Each of the layers constituting the first stack structure includes at least one selected from the group consisting of:
  • a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr, Y, Sn and Bi; and
  • Such layers exhibit excellent wear resistance.
  • the layers constituting the first stack structure include at least one selected from the group consisting of:
  • metals including at least two metal elements selected from Ti, Nb, Ta, Cr, W, Al, Si, Sr and Y;
  • the metals or the compounds for forming the constituent layers in the first stack structure include (Al 0.50 Ti 0.50 )N, (Al 0.60 Ti 0.40 )N, (Al 0.67 Ti 0.33 )N, (Al 0.67 Ti 0.33 )CN, (Al 0.45 Ti 0.45 Si 0.10 )N, (Al 0.45 Ti 0.45 Y 0.10 )N, (Al 0.50 Ti 0.30 Cr 0.20 )N, (Al 0.50 Ti 0.45 Nb 0.05 )N, (Al 0.50 Ti 0.45 Ta 0.05 )N, (Al 0.50 Ti 0.45 W 0.05 )N, (Ti 0.90 Si 0.10 )N and Al 0.50 Cr 0.50 )N.
  • the first stack structure has a structure in which two or more kinds of layers including any of these metals or compounds are periodically stacked on top of one another with each layer having an average layer thickness of 60 nm to 500 nm.
  • This stack structure having a specific periodicity includes two or more kinds of layers with different compositions. To prevent the penetration of cracks and to obtain enhanced fracture resistance, it is preferable that these layers with different compositions be stacked alternately each in two or more layers.
  • the thickness of the minimum unit whose repetition makes up the stack is written as the “stacking period”.
  • the stacking period will be explained below with reference to FIG. 1 which is an example of schematic views illustrating a sectional structure of a coated tool of the invention.
  • the stack consists of the repetition of Layer A1 ( 5 ), Layer B1 ( 6 ), Layer C1 and Layer D1 having different compositions in the order of Layer A1 Layer B1 ⁇ Layer C1 ⁇ Layer D1 ⁇ Layer A1 ⁇ Layer B1 ⁇ Layer C1 ⁇ Layer D1 ⁇ . . . from the substrate 1 toward the surface of the coating layer 2 , the total of the layer thicknesses of Layer A1 to Layer D1 is defined as the “stacking period”.
  • the “stacking period” indicates the total of the layer thickness of Layer A1 and the layer thickness of Layer B1.
  • the first stack structure is preferably an alternate stack structure in which Layers A1 and Layers B1 with different compositions are stacked alternately each in two or more layers in the order of Layer A1 ⁇ Layer B1 ⁇ Layer A1 ⁇ Layer B1 ⁇ . . . from the substrate toward the surface of the coating layer.
  • any average layer thickness of each layer that is less than 60 nm results in a decrease in the effect of preventing the penetration of cracks to the substrate.
  • fracture resistance is reduced if the average layer thickness exceeds 500 nm.
  • the average layer thickness of each of the layers constituting the first stack structure is limited to 60 nm to 500 nm. More preferably, the average layer thickness of each of the layers constituting the first stack structure is 60 nm to 250 nm.
  • the average thickness of the first stack structure is less than 0.2 ⁇ m, the first stack structure has so small a number of repetitions of the periodic stacking of the layers with different compositions that the first stack structure tends to decrease the effect of suppressing the penetration of cracks to the substrate.
  • any average thickness exceeding 6 ⁇ m results in an increase in the residual compressive stress in the entirety of the coating layer, and consequently the coating layer is prone to be separated or fractured, namely, tends to exhibit poor fracture resistance.
  • the average thickness of the first stack structure in the present invention is more preferably 0.2 to 6 ⁇ m.
  • the coating layer in the coated tool of the invention includes a second stack structure.
  • the layers constituting the second stack structure include at least one selected from the group consisting of:
  • a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr, Y, Sn and Bi; and
  • Such layers exhibit excellent wear resistance.
  • the layers constituting the second stack structure include at least one selected from the group consisting of:
  • metals including at least two metal elements selected from Ti, Nb, Ta, Cr, W, Al, Si, Sr and Y;
  • the metals or the compounds for forming the constituent layers in the second stack structure include (Al 0.50 Ti 0.50 )N, (Al 0.60 Ti 0.40 )N, (Al 0.67 Ti 0.33 )N, (Al 0.67 Ti 0.33 )CN, (Al 0.45 Ti 0.45 Si 0.10 )N, (Al 0.45 Ti 0.45 Y 0.10 )N, (Al 0.50 Ti 0.30 Cr 0.20 )N, (Al 0.50 Ti 0.45 Nb 0.05 )N, (Al 0.50 Ti 0.45 Ta 0.05 )N, (Al 0.50 Ti 0.45 W 0.05 )N, (Ti 0.90 Si 0.10 )N and (Al 0.50 Cr 0.50 )N.
  • the second stack structure in the present invention has a structure in which two or more kinds of layers including any of these metals or compounds are periodically stacked on top of one another with each layer having an average layer thickness of 2 nm to less than 60 nm.
  • This stack structure having a specific periodicity includes two or more kinds of layers with different compositions.
  • the second stack structure be an alternate stack structure in which these layers with different compositions are stacked alternately each in two or more layers.
  • the thickness of the minimum unit whose repetition makes up the stack is written as the “stacking period”.
  • the stack consists of the repetition of Layer A2 ( 7 ), Layer B2 ( 8 ), Layer C2 and Layer D2 having different compositions in the order of Layer A2 ⁇ Layer B2 ⁇ Layer C2 ⁇ Layer D2 ⁇ Layer A2 ⁇ Layer B2 ⁇ Layer C2 ⁇ Layer D2 ⁇ . . . from the substrate 1 toward the surface of the coating layer 2 , the total of the layer thicknesses of Layer A2 to Layer D2 is defined as the “stacking period”.
  • the “stacking period” indicates the total of the layer thickness of Layer A2 and the layer thickness of Layer B2.
  • the second stack structure in the coated tool of the present invention attains high hardness to achieve an enhancement in wear resistance.
  • this effect is further enhanced when an alternate stack structure is adopted in which two kinds of layers having different compositions are stacked alternately each in two or more layers.
  • the second stack structure is more preferably an alternate stack structure in which Layers A2 and Layers B2 with different compositions are stacked alternately each in two or more layers in the order of Layer A2 ⁇ Layer B2 ⁇ Layer A2 ⁇ Layer B2 ⁇ . . . from the substrate toward the surface of the coating layer.
  • the average layer thickness of each of the layers constituting the second stack structure is less than 2 nm, a difficulty is encountered in forming the layer with a uniform thickness. If the average layer thickness of each of the layers constituting the second stack structure is 60 nm or more, hardness is reduced to cause a decrease in wear resistance. Further, such a second stack structure has little difference in layer thickness from the first stack structure with the result that it is hard to fully achieve the effect of suppressing the penetration of cracks to the substrate by causing a crack to advance in a direction parallel to the interface between the first stack structure and the second stack structure. Thus, the average layer thickness of each of the layers constituting the second stack structure in the present invention is limited to 2 nm to less than 60 nm. From the above viewpoints, the average layer thickness of each of the layers constituting the second stack structure is more preferably 5 nm to 30 nm.
  • the average thickness of the second stack structure is less than 0.02 ⁇ m, the second stack structure has so small a number of repetitions of the periodic stacking of the layers that the enhancement in hardness cannot be obtained.
  • any average thickness of the second stack structure exceeding 6 ⁇ m results in an increase in the residual compressive stress in the second stack structure, and consequently the coating layer is prone to be separated or fractured, namely, tends to exhibit poor fracture resistance.
  • the average thickness of the second stack structure is preferably 0.02 to 6 ⁇ m.
  • the coated tool of the present invention preferably has a difference between T 1 and T 2 (T 1 -T 2 ) of 20 to 996 nm wherein T 1 is the average value of the stacking periods in the first stack structure and T 2 is the average value of the stacking periods in the second stack structure. If the difference (T 1 -T 2 ) is less than 20 nm, the coated tool tends to decrease its effect of suppressing the penetration of cracks to the substrate by causing a crack to advance in a direction parallel to the interface between the first stack structure and the second stack structure. If, on the other hand, the difference between T 1 and T 2 (T 1 -T 2 ) exceeds 996 nm, the average thickness of the first stack structure is so large that fracture resistance tends to be decreased. In particular, the difference between T 1 and T 2 (T 1 -T 2 ) is more preferably 20 to 500 nm, and still more preferably 20 to 250 nm.
  • the average value of the stacking periods is calculated by obtaining the total of the stacking periods of the 100 repeating units “Layer A2 ⁇ Layer B2 ⁇ Layer A2 ⁇ Layer B2 ⁇ Layer A2 ⁇ Layer B2 ⁇ . . . ” and dividing the total of the stacking periods by the number of repetitions, namely, 100.
  • the metal elements present in the layers constituting the first stack structure are identical among the layers constituting the first stack structure and include one or more metal elements having a difference in absolute value of 5 at % or more between the ratio thereof relative to the total of the metal elements present in one layer constituting the first stack structure and the ratio of the identical metal element relative to the total of the metal elements present in another layer constituting the first stack structure which is adjacent to the one layer.
  • misalignment of crystal lattices may be obtained at the interface between adjacent layers constituting the first stack structure without causing any decrease in adhesion between the layers. Consequently, the structure may easily cause a crack to advance in a direction parallel to the interface between the layers constituting the first stack structure, and is therefore more advantageous in that the effect of suppressing the penetration of cracks to the substrate is enhanced.
  • the metal elements “include one or more metal elements which have a difference in absolute value of 5 at % or more” will be described.
  • the first stack structure includes (Al 0.55 Ti 0.45 )N layers and (Al 0.67 Ti 0.33 )N layers
  • the two kinds of layers include identical metal elements, namely, Al element and Ti element.
  • the ratio of the Al element present in the (Al 0.55 Ti 0.45 )N layer is 55 at % relative to the total of the metal elements
  • the ratio of the Al element present in the (Al 0.67 Ti 0.33 )N layer is 67 at % relative to the total of the metal elements.
  • the difference in the ratio of the Al element between the two layers is 12 at %, satisfying the above requirement.
  • (Al 0.49 Ti 0.39 Cr 0.12 )N layers and (Al 0.56 Ti 0.36 Cr 0.08 )N layers will be discussed. These two kinds of layers include identical metal elements, namely, Al element, Ti element and Cr element. Although the difference in the ratio of the Ti element between the two layers is 3 at % and the difference in the ratio of the Cr element between the two layers is 4 at %, namely, the differences for both elements are less than 5 at %, the structure satisfies the requirement because the difference in the Al ratio between the two layers is 7 at %.
  • nitrides are sometimes written as (M a L b )N with the letter a indicating the atomic ratio of the element M and the letter b indicating the atomic ratio of the element L relative to the total of the metal elements.
  • (Al 0.55 Ti 0.45 )N means that the atomic ratio of the Al element relative to the total of the metal elements is 0.55 and the atomic ratio of the Ti element relative to the total of the metal elements is 0.45, namely, the ratio of the Al element relative to the total of the metal elements is 55 at % and the ratio of the Ti element relative to the total of the metal elements is 45 at %.
  • the metal elements present in the layers constituting the second stack structure are identical among the layers constituting the second stack structure and include one or more metal elements having a difference in absolute value of 5 at % or more between the ratio thereof relative to the total of the metal elements present in one layer constituting the second stack structure and the ratio of the identical metal element relative to the total of the metal elements present in another layer constituting the second stack structure which is adjacent to the one layer.
  • the structure may easily cause a crack to advance in a direction parallel to the interface between the layers constituting the second stack structure, and is therefore more advantageous in that the effect of suppressing the penetration of cracks to the substrate is enhanced.
  • the metal elements “include one or more metal elements which have a difference in absolute value of 5 at % or more” is the same as described above with respect to the first stack structure.
  • one layer constituting the first stack structure and another layer constituting the first stack structure which is adjacent to the one layer include one or more metal elements different between the layers.
  • the first stack structure includes (Al 0.50 Ti 0.50 )N layers and (Al 0.50 Ti 0.30 Cr 0.20 )N layers
  • the comparison of the metal elements present in these two kinds of layers shows that the Al element and the Ti element are contained in the two layers while the Cr element is present only in one of the layers. That is, the above requirement is satisfied.
  • the first stack structure includes (Al 0.50 Cr 0.50 )N layers and (Al 0.67 Ti 0.33 )N layers
  • the comparison of the metal elements present in these two kinds of layers shows that the Al element is contained in the two layers while the Cr element is present only in one of the layers and the Ti element is present only in the other of the layers.
  • the above requirement is satisfied.
  • one layer constituting the second stack structure and another layer constituting the second stack structure which is adjacent to the one layer include one or more metal elements different between the layers.
  • the coating layer includes the first stack structure having excellent fracture resistance and the second stack structure having excellent wear resistance. As a result, the coated tool exhibits excellent fracture resistance and wear resistance.
  • the coating layer may include an upper layer on the surface of the coating layer on the side opposite to the substrate through the first stack structure and the second stack structure. Further, the coating layer may include a lower layer at a closer side to the substrate than the first and second stack structures. Furthermore, the coating layer may include an intermediate layer between the first stack structure and the second stack structure.
  • the configurations of these upper layers, intermediate layers and lower layers are not particularly limited and any of coating layers provided in coated tools may be used.
  • enhanced wear resistance may be advantageously obtained by adopting a single layer configuration or a non-periodic multilayer configuration including at least one selected from the group consisting of a metal including at least one metal element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Si, Sr, Y, Sn and Bi; and compounds including at least one of these metal elements and at least one non-metal element selected from carbon, nitrogen, oxygen and boron.
  • the first stack structures and the second stack structures are stacked alternately and continuously each in two or more layers.
  • the structure may easily cause a crack to advance in a direction parallel to the interface between the first stack structure and the second stack structure, and thus effectively suppresses the penetration of cracks to the substrate, namely, achieves enhanced fracture resistance.
  • the positional relationship between the first stack structure and the second stack structure is not limited and may be such that the first stack structure is closest to the substrate and the second stack structure is closest to the surface of the coating layer on the side opposite to the substrate or may be such that the second stack structure is closest to the substrate and the first stack structure is closest to the surface of the coating layer on the side opposite to the substrate.
  • the first stack structure or the second stack structure may be disposed closest to both the substrate and the surface of the coating layer on the side opposite to the substrate. Based on the fact that the residual compressive stress in the first stack structure is lower than the residual compressive stress in the second stack structure, it is more preferable that the first stack structure be disposed closest to the substrate and the second stack structure be disposed closest to the surface. In this case, the coating layer tends to exhibit enhanced separation resistance.
  • the coating layer in the coated tool of the present invention may be produced by any methods without limitation.
  • a physical deposition method such as an ion plating method, an arc ion plating method, a sputtering method or an ion mixing method may be used to form layers such as the aforementioned first stack structure and second stack structure onto the substrate.
  • the arc ion plating method is more preferable because of excellent adhesion between the coating layer and the substrate.
  • the coated tool of the present invention may be obtained by forming the layers onto the surface of the substrate by a conventional coating method.
  • An exemplary production method is described below.
  • a substrate processed into a shape of a tool is placed in a reaction vessel of a physical deposition apparatus, and a vacuum is produced by evacuating the inside of the reaction vessel to a pressure of 1 ⁇ 10 ⁇ 2 Pa or below. After the vacuum has been generated, the temperature of the substrate is raised to 200 to 800° C. with a heater disposed in the reaction vessel. After the heating, Ar gas is introduced into the reaction vessel to raise the pressure to 0.5 to 5.0 Pa.
  • a bias voltage of ⁇ 200 to ⁇ 1000 V is applied to the substrate and a current of 5 to 20 A is passed through a tungsten filament disposed in the reaction vessel, thereby treating the surface of the substrate by ion bombardment of the Ar gas.
  • a vacuum is drawn to a pressure of 1 ⁇ 10 ⁇ 2 Pa or below.
  • a reaction gas such as nitrogen gas is introduced into the reaction vessel to increase the pressure inside the reaction vessel to 0.5 to 5.0 Pa.
  • a bias voltage of ⁇ 10 to ⁇ 150 V is applied to the substrate, and metal deposition sources in accordance with the metal components of the respective layers are vaporized by arc discharge, thereby forming layers on the surface of the substrate.
  • the layer thicknesses of the respective layers for constituting the first stack structure or the second stack structure may be controlled by adjusting the rotational speed of the rotatable table supporting the substrate in the reaction vessel.
  • the layer thicknesses of the respective layers for constituting the first stack structure or the second stack structure may be controlled by adjusting the arc discharge time for the respective metal deposition sources.
  • the layer thicknesses of the respective layers constituting the coating layer in the coated tool of the present invention may be measured by analyzing the sectional structure of the coated tool with a device such as an optical microscope, a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
  • the average layer thickness of each of the layers in the coated tool of the present invention may be obtained by measuring the layer thickness of each layer with respect to cross sections sampled from 3 or more regions approximately 50 ⁇ m from the cutting edge of the surface opposed to the metal deposition source toward the center of the surface, and calculating the average value of the obtained layer thicknesses.
  • composition of each of the layers in the coated tool of the present invention may be measured by analyzing the sectional structure of the coated tool of the present invention with a device such as an energy dispersive X-ray spectrometer (EDS) or a wavelength dispersive X-ray spectrometer (WDS).
  • EDS energy dispersive X-ray spectrometer
  • WDS wavelength dispersive X-ray spectrometer
  • coated tools of the present invention include cutting inserts, drills and end mills.
  • a cemented carbide corresponding to P10 in the shape of ISO SEEN 1203 insert was provided as a substrate.
  • Metal deposition sources were arranged in a reaction vessel of an arc ion plating apparatus so as to design layers having compositions described in any of Tables 1 to 3.
  • the substrate was fixed to a fixing hardware of a rotatable table disposed in the reaction vessel.
  • a vacuum was produced by evacuating the inside of the reaction vessel to a pressure of 5.0 ⁇ 10 ⁇ 3 Pa or below. After the vacuum had been generated, the substrate was heated to a temperature of 500° C. with a heater disposed in the reaction vessel. After the heating, Ar gas was introduced into the reaction vessel to raise the pressure to 5.0 Pa.
  • a bias voltage of ⁇ 1000 V was applied to the substrate and a current of 10 A was passed through a tungsten filament disposed in the reaction vessel, thereby treating the surface of the substrate by ion bombardment of the Ar gas for 30 minutes.
  • the inside of the reaction vessel was evacuated to draw a vacuum to a pressure of 5.0 ⁇ 10 ⁇ 3 Pa or below.
  • nitrogen gas was introduced into the reaction vessel to create a nitrogen gas atmosphere having a pressure of 2.7 Pa.
  • a bias voltage of ⁇ 50 V was applied to the substrate, and an arc current of 200 A was passed to produce arc discharge and thereby to vaporize the metal deposition sources, thus forming the respective layers.
  • Layers A1 and Layers B1 in Inventive Products 1 to 11 the metal deposition source for Layers A1 and the metal deposition source for Layers B1 were alternately vaporized by arc discharge to form Layers A1 and Layers B1. During this process, the layer thicknesses of Layers A1 and Layers B1 were controlled by adjusting the respective arc discharge times.
  • Layers X and Layers Y with large layer thicknesses were formed in the similar manner by alternately vaporizing the metal deposition source for Layers X and the metal deposition source for Layers Y by arc discharge. During this process, the layer thicknesses of Layers X and Layers Y were controlled by adjusting the respective arc discharge times.
  • Layers A2 and Layers B2 in Inventive Products 1 to 11 the metal deposition source for Layers A2 and the metal deposition source for Layers B2 were simultaneously vaporized by arc discharge to form Layers A2 and Layers B2. During this process, the layer thicknesses of Layers A2 and Layers B2 were controlled by adjusting the rotational speed of the rotatable table in the range of 0.2 to 10 min ⁇ 1 .
  • Layers X and Layers Y with small layer thicknesses were formed in the similar manner by simultaneously vaporizing the metal deposition source for Layers X and the metal deposition source for Layers Y by arc discharge. During this process, the layer thicknesses of Layers X and Layers Y were controlled by adjusting the rotational speed of the rotatable table in the range of 0.2 to 10 min ⁇ 1 .
  • the heater was turned off. After the sample temperature had decreased to 100° C. or below, the sample was collected from the reaction vessel.
  • Second stack structure Layers A2 + Layers B2 Layers B2 Average Average value of layer stacking Number of Average Sample thickness periods repetitions thickness T 1 ⁇ T 2 No. Composition (nm) T 2 (nm) (times) ( ⁇ m) (nm) Inv. (Al 0.67 Ti 0.33 )N 10 20 50 1.0 180 Prod. 1 Inv. (Al 0.67 Ti 0.33 )N 10 20 25 0.5 100 Prod. 2 Inv. (Al 0.67 Ti 0.33 )N 10 20 100 2.0 480 Prod. 3 Inv.
  • the respective average layer thicknesses of the layers in the samples obtained were determined by measuring the layer thickness of each layer by TEM observation with respect to cross sections sampled from 3 regions approximately 50 ⁇ m from the cutting edge of the surface of the coated tool opposed to the metal deposition source toward the center of the surface, and calculating the average value of the obtained layer thicknesses.
  • the respective compositions of the layers in the samples obtained were determined by analyzing a cross section sampled from a region of from the cutting edge of the surface of the coated tool opposed to the metal deposition source to a distance of 50 ⁇ m toward the center using an EDS.
  • the results are described in Tables 1 to 3.
  • the compositional ratios of the metal elements in the layers described in Tables 1 to 3 indicate the atomic ratios of the metal elements relative to the total of the metal elements in the metal compounds forming the respective layers.
  • Evaluation item The length of cutting to the occurrence of fracture of the sample (the occurrence of fracture in the cutting blade of the sample) was measured.
  • a cemented carbide corresponding to P10 in the shape of ISO SEEN 1203 insert was provided as a substrate.
  • Metal deposition sources were arranged in a reaction vessel of an arc ion plating apparatus so as to design layers having compositions described in Table 5. Samples having layer configurations described in Tables 5 and 6 were fabricated by the same production method as in Example 1.
  • Second stack structure Layers A2 + Layers B2 Layers B2 Average Average value of layer stacking Number of Average Sample thickness periods repetitions thickness T 1 ⁇ T 2 No. Composition (nm) T 2 (nm) (times) ( ⁇ m) (nm) Inv. (Al 0.67 Ti 0.33 )N 2 4 125 0.5 116 Prod. 12 Inv. (Al 0.67 Ti 0.33 )N 10 20 100 2.0 180 Prod. 13 Inv. (Al 0.67 Ti 0.33 )N 10 20 300 6.0 480 Prod. 14 Inv.
  • a cemented carbide corresponding to P10 in the shape of ISO SEEN 1203 insert was provided as a substrate.
  • metal deposition sources were arranged in a reaction vessel of an arc ion plating apparatus so as to design layers having compositions described in Tables 8 and 10, and samples having layer configurations described in Tables 9 and 10 were fabricated by the same production method as in Example 1.
  • the respective layer thicknesses and the respective compositions of the layers in the samples obtained were determined in the same manner as in Example 1, the results being described in Tables 8 to 10.
  • the compositional ratios of the metal elements in the layers described in Tables 8 and 10 indicate the atomic ratios of the metal elements relative to the total of the metal elements in the metal compounds forming the respective layers.
  • the fracture resistance of the samples obtained was evaluated by using the samples in face milling under the same test conditions as in Example 1. The evaluation results are described in Tables 11 and 12.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Drilling Tools (AREA)
  • Physical Vapour Deposition (AREA)
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US10501842B2 (en) 2019-12-10
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