WO2018037625A1 - 表面被覆切削工具およびその製造方法 - Google Patents

表面被覆切削工具およびその製造方法 Download PDF

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Publication number
WO2018037625A1
WO2018037625A1 PCT/JP2017/016405 JP2017016405W WO2018037625A1 WO 2018037625 A1 WO2018037625 A1 WO 2018037625A1 JP 2017016405 W JP2017016405 W JP 2017016405W WO 2018037625 A1 WO2018037625 A1 WO 2018037625A1
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Prior art keywords
layer
atomic concentration
cutting tool
lower layer
chlorine
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PCT/JP2017/016405
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English (en)
French (fr)
Japanese (ja)
Inventor
光平 吉村
今村　晋也
秀明 金岡
アノンサック パサート
聡 小野
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Sumitomo Electric Hardmetal Corp
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Sumitomo Electric Hardmetal Corp
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Publication date
Application filed by Sumitomo Electric Hardmetal Corp filed Critical Sumitomo Electric Hardmetal Corp
Priority to US15/740,927 priority Critical patent/US10654181B2/en
Priority to EP17811821.2A priority patent/EP3308886B1/en
Priority to CN201780002260.4A priority patent/CN107980013B/zh
Priority to KR1020177037473A priority patent/KR102170166B1/ko
Publication of WO2018037625A1 publication Critical patent/WO2018037625A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26B—HAND-HELD CUTTING TOOLS NOT OTHERWISE PROVIDED FOR
    • B26B9/00—Blades for hand knives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B23B27/148—Composition of the cutting inserts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B51/00—Tools for drilling machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B23C5/16—Milling-cutters characterised by physical features other than shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23D—PLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D77/00—Reaming tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23F—MAKING GEARS OR TOOTHED RACKS
    • B23F21/00—Tools specially adapted for use in machines for manufacturing gear teeth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23G—THREAD CUTTING; WORKING OF SCREWS, BOLT HEADS, OR NUTS, IN CONJUNCTION THEREWITH
    • B23G5/00—Thread-cutting tools; Die-heads
    • B23G5/02—Thread-cutting tools; Die-heads without means for adjustment
    • B23G5/06—Taps
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/029—Graded interfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time

Definitions

  • the present invention relates to a surface-coated cutting tool and a manufacturing method thereof.
  • This application claims priority based on Japanese Patent Application No. 2016-163628, which is a Japanese patent application filed on August 24, 2016. All the descriptions described in the Japanese patent application are incorporated herein by reference.
  • Patent Document 2 In European Patent Application No. 2570510 (Patent Document 2), an ⁇ -Al 2 O 3 layer having a (0012) texture and containing 100 ppm or more of sulfur is provided on a substrate made of a cemented carbide. Thus, cutting tools with improved wear resistance have been proposed.
  • Patent Document 3 SUMMARY OF THE INVENTION In 2013-111722 (Patent Document 3), and (0001) by lowering the orientation of the base material side of the layers of ⁇ -Al 2 O 3 layer is oriented, alpha-Al 2 O 3 layer A surface-coated cutting tool has been proposed in which the adhesion between the ⁇ -Al 2 O 3 layer and the layer disposed between the substrates is enhanced.
  • JP2015-009358A European Patent Application Publication No. 2705510 JP 2013-111722 A
  • the surface-coated cutting tool is a surface-coated cutting tool comprising a substrate and a coating formed on the substrate, and the coating includes an ⁇ -Al 2 O 3 layer.
  • the ⁇ -Al 2 O 3 layer includes a plurality of ⁇ -Al 2 O 3 crystal grains and chlorine, and the TC (006) exceeds 5 in the orientation index TC (hkl).
  • the 2 O 3 layer includes a lower layer located on the substrate side in the thickness direction and an upper layer located on the opposite side of the substrate side, and the lower layer has a thickness of 1.0 ⁇ m,
  • the upper layer has a thickness of 0.5 ⁇ m or more, and the chlorine has a concentration distribution in which the atomic concentration decreases in the direction away from the substrate in the thickness direction of the lower layer.
  • the method for producing a surface-coated cutting tool includes a step of forming the coating film including the ⁇ -Al 2 O 3 layer on the base material by a CVD method,
  • the formation of the ⁇ -Al 2 O 3 layer is started by setting the amount of HCl gas contained in the gas to 6 to 10% by volume, and then the amount is decreased to 0.5 to 6% by volume.
  • FIG. 1 is a drawing-substituting photograph showing measurement points in an ⁇ -Al 2 O 3 layer set for measuring the atomic concentration of chlorine (Cl) and sulfur (S) using EDS superimposed on a micrograph. is there.
  • the surface-coated cutting tool of Patent Document 1 has room for improvement in performance such as toughness and peel resistance.
  • the cutting tool of Patent Document 2 has insufficient chipping resistance.
  • the surface-coated cutting tool of Patent Document 3 has insufficient wear resistance due to the lowered orientation of the base layer.
  • the present invention has been made in view of the above circumstances, and provides a surface-coated cutting tool that has excellent wear resistance and that can achieve a long life by preventing coating loss such as peeling and chipping, and a method for manufacturing the same. For the purpose. [Effects of the present disclosure]
  • a surface-coated cutting tool is a surface-coated cutting tool including a base material and a coating film formed on the base material, wherein the coating film is ⁇ -Al 2 O 3.
  • the ⁇ -Al 2 O 3 layer includes a plurality of ⁇ -Al 2 O 3 crystal grains and chlorine, and the orientation index TC (hkl) has a TC (006) of more than 5,
  • the ⁇ -Al 2 O 3 layer includes a lower layer located on the substrate side in the thickness direction and an upper layer located on the side opposite to the substrate side, and the lower layer has a thickness of 1.0 ⁇ m.
  • the upper layer has a thickness of 0.5 ⁇ m or more, and the chlorine has a concentration distribution in which the atomic concentration decreases in the direction away from the substrate side in the thickness direction of the lower layer.
  • the surface-coated cutting tool having such a configuration has excellent wear resistance and can prevent the loss of the coating such as peeling and chipping, thereby achieving a long life.
  • the chlorine preferably has a maximum atomic concentration of less than 0.3 atomic% in the lower layer.
  • the chlorine preferably has a maximum atomic concentration of less than 0.05 atomic% in the upper layer. Thereby, the wear resistance of the surface-coated cutting tool can be improved.
  • the TC (006) is more preferably more than 6. Thereby, the wear resistance of the surface-coated cutting tool can be improved more effectively.
  • the lower layer contains sulfur
  • the lower layer is defined as C ClS
  • the sum of the atomic concentration of chlorine at a predetermined measurement point and the atomic concentration of sulfur at the measurement point is In the thickness direction, it is preferable to have a distribution in which the C ClS decreases in a direction away from the substrate side. Thereby, the improvement of chipping resistance, in particular, peeling resistance and chipping resistance can be further improved.
  • the lower layer contains sulfur, and the lower layer has a value obtained by dividing the atomic concentration of chlorine at a predetermined measurement point by the atomic concentration of sulfur at the measurement point as C Cl / S.
  • the thickness direction it is preferable to have a distribution in which the C Cl / S decreases in a direction away from the substrate side. As a result, it is possible to further improve the chipping resistance, particularly the peeling resistance and chipping resistance.
  • a surface-coated cutting tool includes a step of forming the coating film including the ⁇ -Al 2 O 3 layer on the base material by a CVD method.
  • the formation of the ⁇ -Al 2 O 3 layer is started by setting the amount of HCl gas to be 6 to 10% by volume, and then the amount is decreased to 0.5 to 6% by volume.
  • the atomic ratio when a compound or the like is represented by a chemical formula, when the atomic ratio is not particularly limited, it should include any conventionally known atomic ratio and should not necessarily be limited to a stoichiometric range.
  • metal elements such as titanium (Ti), aluminum (Al), silicon (Si), tantalum (Ta), chromium (Cr), nitrogen (N), oxygen (O), carbon (C), etc.
  • the nonmetallic element does not necessarily have to have a stoichiometric composition.
  • the surface-coated cutting tool includes a base material and a film formed on the base material.
  • the coating preferably covers the entire surface of the substrate. However, even if a part of the substrate is not coated with this coating or the configuration of the coating is partially different, it does not depart from the scope of the present invention.
  • Surface coated cutting tools include drills, end mills, drill tip changeable cutting tips, end mill tip replacement cutting tips, milling tip replacement cutting tips, turning tip replacement cutting tips, metal saws, gear cutting tools, It can be suitably used as a cutting tool such as a reamer or a tap.
  • any substrate can be used as long as it is conventionally known as this type of substrate.
  • cemented carbide for example, WC-based cemented carbide, including WC, including Co or containing carbonitride such as Ti, Ta, Nb), cermet (TiC, TiN, TiCN, etc.) Main component
  • high-speed steel ceramics (titanium carbide, silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, etc.), cubic boron nitride sintered body or diamond sintered body preferable.
  • cemented carbide especially WC-based cemented carbide
  • cermet particularly TiCN-based cermet
  • These base materials have an excellent balance between hardness and strength at high temperatures, and have excellent properties as base materials for surface-coated cutting tools for the above applications.
  • free carbon and an abnormal layer called ⁇ phase or ⁇ phase may be included in the structure.
  • the base material may have a modified surface.
  • a de- ⁇ layer may be formed on the surface, or in the case of cermet, a surface hardened layer may be formed. Even if the surface of the substrate is modified, the desired effect is exhibited.
  • the base material includes those having a chip breaker and those having no chip breaker.
  • the edge of the cutting edge is sharp edge (the ridge where the rake face and flank face intersect), honing (the sharp edge is given a radius), negative land (the chamfered), and the combination of honing and negative land Any shape may be used.
  • the coating includes an ⁇ -Al 2 O 3 layer.
  • the coating can be composed of a plurality of layers including one or more ⁇ -Al 2 O 3 layers and further including other layers.
  • TiCNO layer TiBN layer, TiC layer, TiN layer, TiAlN layer, TiSiN layer, AlCrN layer, TiAlSiN layer, TiAlNO layer, AlCrSiCN layer, TiCN layer, TiSiC layer, CrSiN layer, AlTiSiCO layer, TiSiCN layer Etc.
  • TiCNO layer TiBN layer, TiC layer, TiN layer, TiAlN layer, TiSiN layer, AlCrN layer, TiAlSiN layer, TiAlNO layer, AlCrSiCN layer, TiCN layer, TiSiC layer, CrSiN layer, AlTiSiCO layer, TiSiCN layer Etc.
  • the thickness of the coating is preferably 5 to 30 ⁇ m. More preferably, it is 10 to 25 ⁇ m. If this thickness is less than 5 ⁇ m, the wear resistance may be insufficient. When this thickness exceeds 30 ⁇ m, when a large stress is applied between the coating and the substrate in the intermittent processing, the coating may be peeled off or broken frequently.
  • the ⁇ -Al 2 O 3 layer includes crystal grains of a plurality of ⁇ -Al 2 O 3 (aluminum oxide whose crystal structure is ⁇ -type) and chlorine (Cl).
  • ⁇ -Al 2 O 3 layer contains the ⁇ -Al 2 O 3 of containing crystal grains of a plurality of ⁇ -Al 2 O 3 polycrystal.
  • ⁇ -Al 2 O 3 crystal grains have a particle size of about 0.1 to 2 ⁇ m.
  • the ⁇ -Al 2 O 3 layer is (006) oriented.
  • “(006) orientation” means that each (hkl) reflecting surface (described later in this embodiment) in the XRD data of an ⁇ -Al 2 O 3 layer obtained by analysis using an X-ray diffraction apparatus described later.
  • the orientation index TC (hkl) of (eight reflective surfaces) is compared, it means that the reflective surface showing the highest numerical value is the (006) plane.
  • the ⁇ -Al 2 O 3 layer has a TC (006) of more than 5 in the orientation index TC (hkl) represented by the following formula (1).
  • I (hkl) represents the X-ray diffraction intensity of the (hkl) reflecting surface
  • I 0 (hkl) represents the standard intensity according to ICDD PDF card number 00-042 to 1468.
  • n in Formula (1) shows the number of reflection used for calculation, and is 8 in this embodiment.
  • the (hkl) plane used for reflection is (012), (104), (110), (006), (113), (024), (116), and (300).
  • ICDD International Center for Diffraction Data (International Diffraction Data Center).
  • PDF registered trademark
  • the TC (006) of the ⁇ -Al 2 O 3 layer in the present embodiment can be expressed by the following formula (2).
  • TC (006) exceeds 5 in the orientation index TC (hkl) means that the numerical value obtained by the above equation (2) obtained by substituting TC (006) into the above equation (1) exceeds 5. means.
  • the ⁇ -Al 2 O 3 layer having a TC (006) of more than 5 is superior in impact and vibration due to severe cutting conditions in hardness and Young's modulus, and can contribute to improvement in wear resistance.
  • TC (006) preferably exceeds 6. As TC (006) is larger, the wear resistance can be effectively improved.
  • the upper limit of TC (006) is not limited, but is 8 or less because there are eight reflecting surfaces used in the calculation.
  • TC (hkl) is, for example, an X-ray diffractometer (trade name: “SmartLab (registered trademark)”, manufactured by Rigaku Corporation, scan speed: 21.7 ° / min, step: 0.01 °, scan range: 15 ⁇ 140 °) can be measured under the following conditions.
  • XRD result the result of TC (hkl) measurement using an X-ray diffractometer is referred to as “XRD result”.
  • Characteristic X-ray Cu-K ⁇ Tube voltage: 45kV Tube current: 200mA
  • Filter Multi-layer mirror
  • X-ray irradiation range A pinhole collimator is used to irradiate a range of 0.3 ⁇ m in diameter.
  • the ⁇ -Al 2 O 3 layer preferably has a thickness of 2 to 15 ⁇ m. Thereby, both wear resistance and chipping resistance can be achieved. If the thickness of the ⁇ -Al 2 O 3 layer is less than 2 ⁇ m, there is a possibility that the wear easily proceeds. If this thickness exceeds 15 ⁇ m, the fracture resistance may be reduced.
  • the ⁇ -Al 2 O 3 layer includes a lower layer located on the base material side in the thickness direction and an upper layer located on the side opposite to the base material side.
  • the lower layer has a thickness of 1.0 ⁇ m. This lower layer refers to a region of 1 ⁇ m from the substrate side, which is determined for measuring the concentration distribution of Cl described later.
  • the upper layer has a thickness of 0.5 ⁇ m or more. The upper limit of the thickness of the upper layer is 14 ⁇ m.
  • the upper layer has a thickness of 0.5 ⁇ m or more, the portion of the ⁇ -Al 2 O 3 layer opposite to the base material side has a sufficiently low portion of Cl, which will be described later, having a sufficient thickness. Further, Cl does not adversely affect the wear resistance of the ⁇ -Al 2 O 3 crystal grains. However, if the thickness of the upper layer exceeds 14 ⁇ m, the entire coating including the ⁇ -Al 2 O 3 layer becomes thick. Therefore, when a large stress is applied between the coating and the substrate in intermittent processing, the coating is peeled off. Or destruction may occur frequently.
  • the thickness of the coating, the thickness of the ⁇ -Al 2 O 3 layer, and the thickness of the upper layer of the ⁇ -Al 2 O 3 layer each mean an average thickness. These thicknesses can be measured by the following method using a field emission scanning electron microscope (FE-SEM).
  • the base material coated with the coating is cut along a plane parallel to the normal line of the rake face of the base material to expose the cross section.
  • the observation cross section is polished by polishing the exposed cross section.
  • the thickness is determined by observing any five locations (5 visual fields) including the coating portion appearing on the observation polished surface at a magnification of 5000 times. Finally, an average value of the values of the five fields of view can be obtained and used as the average thickness of the film.
  • alpha-Al 2 O 3 layer as well as alpha-Al 2 when measuring the thickness of the upper layer of O 3 layer, appeared to observation polished surface alpha-Al 2 O 3 layer portion, as well as alpha-Al 2 O 3 layer
  • the arbitrary five places (5 visual fields) including the upper layer portion of each are observed at a magnification of 5000 times to obtain the thickness.
  • the average value of the five fields of view is obtained, and this can be set as the average thickness of the ⁇ -Al 2 O 3 layer and the upper layer of the ⁇ -Al 2 O 3 layer, respectively.
  • the ⁇ -Al 2 O 3 layer is a region whose lower layer is 1 ⁇ m from the substrate side, and the remaining thickness of the ⁇ -Al 2 O 3 layer excluding the lower layer is calculated as the thickness of the upper layer. It is.
  • a conventionally well-known method can be used about grinding
  • a smooth polished polishing surface can be obtained by performing ion milling using argon ions on the cross section of the substrate.
  • the conditions for the ion milling treatment with Ar ions are, for example, as follows. Accelerating voltage: 6kV Irradiation angle: 0-5 ° from the normal of the rake face of the substrate Irradiation time: 6 hours.
  • the smoothened polished surface for observation may be analyzed using FE-SEM.
  • Chlorine contained in the ⁇ -Al 2 O 3 layer (hereinafter sometimes referred to as the element symbol “Cl”) is a concentration distribution in which the atomic concentration decreases in the direction away from the substrate side in the thickness direction of the lower layer.
  • the element symbol “Cl” is a concentration distribution in which the atomic concentration decreases in the direction away from the substrate side in the thickness direction of the lower layer.
  • the “concentration distribution in which the atomic concentration decreases in the direction away from the substrate side in the thickness direction of the lower layer” of chlorine refers to the direction in which the atomic concentration of chlorine moves away from the substrate side in the thickness direction of the lower layer. It means that it is sufficient to include a decreasing part.
  • the point that touches the interface with the base material in the lower layer is the X point
  • the X point is the point in contact with the interface with the adjacent layer on the side opposite to the substrate side of the layer.
  • the Y point if the atomic concentration of Cl at these points is measured, the atomic concentration of Cl at the X point is always greater than the Y point. It means that it has a concentration distribution which becomes the atomic concentration of Cl.
  • the atomic concentration of chlorine includes a portion that decreases in the direction away from the substrate side, and the atomic concentration of Cl at the X point> the atomic concentration of Cl at the Y point, the Cl atoms in the direction away from the substrate side There may be a portion where the concentration is constant. Furthermore, there may be a portion where the atomic concentration increases in the direction away from the substrate side, or there may be a portion not containing Cl.
  • the maximum atomic concentration of chlorine in the lower layer is preferably less than 0.3 atomic%. More preferably, it is 0.02 to 0.2 atomic%.
  • the lower limit of the maximum atomic concentration in the lower layer is 0.01 atomic%.
  • the maximum atomic concentration of chlorine in the upper layer is less than 0.05 atomic%. More preferably, it is 0 to 0.04 atomic%.
  • the lower limit of the maximum atomic concentration in the upper layer is 0 atomic%. If the maximum atomic concentration in the upper layer of chlorine is 0.05 atomic% or more, the wear resistance of the coating film may be lowered due to the chlorine concentration being too high.
  • C Clmax-1 the maximum atomic concentration of chlorine in the lower layer, when the maximum atomic concentration of chlorine in the upper layer was C Clmax-2, satisfying the relationship C ClMAX-1 ⁇ 2C ClMAX- 2 It is preferable. Thereby, it is possible to obtain better effects of providing excellent wear resistance and preventing film defects such as peeling and chipping. More preferably, the relationship between C ClMAX-1 and C ClMAX-2 satisfies C ClMAX-1 ⁇ 3C ClMAX-2 .
  • C ClMAX-1 ⁇ 2C ClMAX-2 the chlorine concentration approaches to be equivalent in the lower layer and the upper layer, so the effect of achieving both excellent wear resistance and fracture resistance is ineffective. There is a tendency to be sufficient. If the relationship CClMAX-1 > 10CClMAX-2 is satisfied, the difference in chlorine concentration tends to be too large between the lower layer and the upper layer, and the fracture resistance tends to be insufficient.
  • the above - mentioned C ClMAX-1 is reduced from the interface between the lower layer and the base material or from the interface between the lower layer and the layer adjacent to the base material side of the lower layer (such as a TiCN layer or a TiCNO layer). It preferably appears in the region up to 5 ⁇ m.
  • the minimum atomic concentration of chlorine in the lower layer is C ClMIN-1
  • this C ClMIN-1 is 0.5 ⁇ m from the interface between the lower layer and the adjacent layer on the side opposite to the substrate side in the thickness direction. It is preferable that it appears in the region.
  • C ClMAX-1 is preferably 0.1 to 0.3 atomic%
  • C ClMIN-1 is preferably 0.01 to 0.05 atomic%.
  • the difference between C ClMAX-1 and C ClMIN-1 is more preferably 0.5 atomic% or more. This difference may be within 2 atomic%. If the difference between C ClMAX-1 and C ClMIN-1 exceeds 2 atomic%, the fracture resistance may be insufficient. Since the Cl concentration distribution as described above provides excellent adhesion between the coating and the substrate, the fracture resistance of the tool can be dramatically improved.
  • the atomic concentration of Cl contained in the lower layer and the upper layer of the ⁇ -Al 2 O 3 layer is expressed in atomic%.
  • the atomic concentration of Cl is the atomic composition percentage [Cl / (all element types) with the total number of atoms of all element types contained in the ⁇ -Al 2 O 3 layer as the denominator and the number of Cl atoms as molecules. ) ⁇ 100].
  • the element species contained in the ⁇ -Al 2 O 3 layer is Al, O, C, Cl, Ti, S
  • the atomic concentration of Cl is the number of Al atoms, the number of O atoms, the number of C atoms.
  • the atomic composition percentage [Cl / (Al + O + C + Cl + Ti + S) ⁇ 100] with the total of the number of Cl atoms, the number of Ti atoms and the number of S atoms as the denominator and the number of Cl atoms as the numerator can be expressed.
  • the atomic concentration of Cl is determined by an energy dispersive X-ray analyzer (EDS: Energy) attached with FE-SEM to the observation polished surface used for measuring the average thickness of the ⁇ -Al 2 O 3 layer. It can be measured by analyzing using Dispersive X-ray Spectroscopy).
  • EDS energy dispersive X-ray analyzer
  • the atomic concentration of Cl can be measured by EDS (trade name (model number): “SU6600”, manufactured by Hitachi High-Technologies Corporation) with FE-SEM.
  • the acceleration voltage of the FE-SEM is set to 15 kV.
  • the number of frames is set to 150 and the selected atoms are set to C, O, Al, S, Cl, and Ti, respectively.
  • FIG. 1 from the interface portion (TiCNO layer 3) of the ⁇ -Al 2 O 3 layer 1 to the base layer (TiCN layer 2) toward the surface of the coating, at a predetermined interval in the thickness direction.
  • the atomic composition percentage described above is obtained. Based on the above, the atomic concentration of Cl can be specified.
  • FIG. 1 shows measurement points 4 in the ⁇ -Al 2 O 3 layer 1 set for measuring the atomic concentration of Cl and the atomic concentration of S described later using EDS, superimposed on a micrograph.
  • a TiCN layer 2 is formed on a substrate (not shown), a TiCNO layer 3 is laminated on the TiCN layer 2, and an ⁇ -Al 2 O 3 layer 1 is formed on the TiCNO layer 3 as a coating.
  • a TiCN layer 2 is formed on a substrate (not shown)
  • a TiCNO layer 3 is laminated on the TiCN layer 2
  • an ⁇ -Al 2 O 3 layer 1 is formed on the TiCNO layer 3 as a coating.
  • Measurement points 4 were set. Thereby, at each measurement point from the first measurement point 41 to the fifth measurement point 45, the atomic concentration of Cl and the atomic concentration of S described later were calculated.
  • FIG. 1 shows only the measurement point 4 set in the lower layer.
  • the measurement points described above are plural (at least 5 points) at equal intervals so that the atomic concentration of Cl and the atomic concentration of S described later can be measured from the base material side interface to the coating surface side interface in the thickness direction of the lower layer portion. ) It is preferable to set.
  • the maximum atomic concentration of Cl in the lower layer can be calculated by obtaining the maximum value of the atomic concentration of Cl calculated at each of the measurement points described above.
  • the maximum atomic concentration of Cl in the upper layer can be calculated in the same manner as in the lower layer.
  • the lower layer preferably contains sulfur (hereinafter sometimes referred to as an element symbol “S”).
  • S sulfur
  • Lower layer when the addition value obtained by combining the atomic concentration of sulfur atom concentration of chlorine and surveying a fixed point at a predetermined measurement point and the C cls, in its thickness direction, is C cls away from the substrate side Preferably it has a decreasing distribution.
  • the lower layer when the value obtained by dividing the atomic concentration of sulfur surveying a fixed point the atomic concentration of chlorine was C Cl / S at a predetermined measuring point, in the thickness direction, C Cl in a direction away from the substrate side It is preferable to have a distribution in which / S decreases.
  • the value of C Cl / S is assumed to be 50. It is further preferable that the distribution of C Cl / S does not increase consistently in the direction away from the substrate side but decreases monotonously.
  • the surface-coated cutting tool according to the present embodiment has excellent wear resistance by having the above-described relationship between chlorine and sulfur in the lower layer, and has an effect of preventing film loss such as peeling and chipping. It can be improved dramatically.
  • “distribution in which C ClS decreases in the direction away from the substrate side in the thickness direction of the lower layer” includes a portion in which the value of C ClS decreases in the direction away from the substrate side in the thickness direction of the lower layer. It means that it should have been.
  • the point of contact with the interface with the base material in the lower layer if there is a layer adjacent to the base material side of the lower layer (TiCN layer, TiCNO layer, etc.) is the T point,
  • the value of C ClS at these points is always the value of C ClS at the T point> C at the U point. It has a distribution of ClS values.
  • the value of C cls is included the portion decreases in a direction away from the substrate side, and as long as the value of C cls value> U point C cls the T point, the value of C cls in a direction away from the substrate side There may be a portion where becomes constant. Furthermore, there may be a portion where the value of C ClS increases in the direction away from the substrate side.
  • C value of Cl / S is included the portion decreases in a direction away from the substrate side, and as long as the values of the C Cl / S values> U point C Cl / S of T point, the substrate side There may be a portion where the value of C Cl / S is constant in the direction away from the substrate, and there may be a portion where the value of C Cl / S increases in the direction away from the substrate side.
  • the distribution of C Cl / S has a distribution that always decreases in the direction away from the substrate side in the thickness direction of the lower layer. In that case, the distribution of C Cl / S has a portion which the value of C Cl / S in a direction away from the substrate side is the value of C Cl / S in a direction away from the portion and the substrate side becomes constant increases Not.
  • C ClS and C Cl / S will be described from the viewpoint of the concentration distribution of sulfur. That is, for example, sulfur contained in the lower layer may or may not have a constant atomic concentration in a direction away from the substrate in the thickness direction.
  • the atomic concentration of sulfur is not constant, for example, it decreases when the atomic concentration of Cl decreases in the direction away from the substrate side, and increases when the atomic concentration of Cl increases. It is preferable to have a distribution that increases or decreases.
  • the increase / decrease width of the sulfur atomic concentration is preferably smaller than the increase / decrease width of the Cl atomic concentration.
  • the atomic concentration of S contained in the lower layer is expressed in atomic% similarly to the atomic concentration of Cl. Therefore, the atomic concentration of S is the atomic composition percentage [S / (all element species) ⁇ 100 with the total number of atoms of all element species contained in the ⁇ -Al 2 O 3 layer as the denominator and the number of S atoms as the molecule. ].
  • the atomic concentration of S can be expressed by [S / (Al + O + C + Cl + Ti + S) ⁇ 100].
  • the atomic concentration of S can also be measured by the same method as the measuring method of the atomic concentration of Cl. Accordingly, by specifying the atomic concentration of S and the atomic concentration of Cl at each predetermined measurement point (for example, the first measurement point 41 to the fifth measurement point 45 in FIG. 1), the values of C ClS and C Cl / S are determined. Will also be determined.
  • the grain size of ⁇ -Al 2 O 3 crystal grains in the ⁇ -Al 2 O 3 layer can be measured using the above-described observation polished surface. Specifically, the surface of the ⁇ -Al 2 O 3 layer appearing on the polishing surface for observation (if there is a layer adjacent to the side opposite to the substrate side of the Al 2 O 3 layer, A part 0.5 ⁇ m away from the interface) to the substrate side of the ⁇ -Al 2 O 3 layer is observed with a FE-SEM at a magnification of 5000 times.
  • the grain size of the ⁇ -Al 2 O 3 crystal grains can be measured from the microscopic image using the intercept method.
  • the intercept method used in the present embodiment is a method of calculating the particle diameter by counting the number of particles crossing a specific width and dividing the width by the number of particles.
  • the ⁇ -Al 2 O 3 layer is measured parallel to the interface with the adjacent layer on the surface or on the side opposite to the substrate side and located at a depth of 0.5 ⁇ m from the surface or the interface.
  • ⁇ -Al 2 O 3 crystal grains having a grain size of 0.2 to 2 ⁇ m occupy 20 to 80 area%. If the grain size of ⁇ -Al 2 O 3 occupying 20 to 80 area% on this measurement surface is less than 0.2 ⁇ m, the fracture resistance may be lowered. If this particle diameter exceeds 2 ⁇ m, the wear resistance may be reduced.
  • the upper limit of the grain size of ⁇ -Al 2 O 3 crystal grains is preferably 1.85 ⁇ m or less.
  • the lower limit of the particle size is 0.2 ⁇ m, which is a preferable value as long as it is not less than 0.2 ⁇ m.
  • the wear resistance and the fracture resistance can be improved.
  • the proportion of ⁇ -Al 2 O 3 crystal grains having a grain size of 0.2 to 2 ⁇ m on the measurement surface is less than 20 area% or 80 area% or more, the chipping resistance and It is impossible to achieve both wear characteristics.
  • a more preferable ratio of ⁇ -Al 2 O 3 crystal grains having a grain size of 0.2 to 2 ⁇ m is 50 to 70 area%.
  • the coating can include other layers in addition to the ⁇ -Al 2 O 3 layer.
  • examples of such other layers include a TiCN layer. Since this TiCN layer is excellent in wear resistance, it is possible to impart suitable wear resistance to the coating.
  • the TiCN layer is particularly preferably formed by MT-CVD (medium temperature CVD).
  • the MT-CVD method can form a film at a relatively low temperature among the CVD methods of about 800 to 1000 ° C., and can reduce damage to the substrate due to heating during film formation.
  • the TiCN layer can be disposed, for example, between the ⁇ -Al 2 O 3 layer and the base material (intermediate layer described later).
  • the coating can include an outermost surface layer, an intermediate layer, and the like, which will be described later, as other layers.
  • the coating may have an outermost surface layer mainly composed of Ti carbide, nitride or boride on the surface thereof.
  • the outermost surface layer is a layer disposed on the most surface side in the coating. However, it may not be formed in the region including the edge of the cutting edge. For example, when no other layer is formed on the ⁇ -Al 2 O 3 layer, the outermost surface layer is disposed directly on the ⁇ -Al 2 O 3 layer.
  • the main component is any one of Ti carbide, nitride, and boride” means that 90% by mass or more of any of Ti carbide, nitride, and boride is included. Furthermore, it means that it consists of any one of Ti carbide, nitride and boride except for inevitable impurities.
  • the corner identification (identification of the used part) of the cutting tip after cutting is facilitated by the effect of exhibiting a clear color.
  • the outermost layer preferably has an average thickness of 0.05 to 1 ⁇ m.
  • the upper limit of the average thickness of the outermost surface layer is preferably 0.8 ⁇ m, more preferably 0.6 ⁇ m.
  • the lower limit of this average thickness is preferably 0.1 ⁇ m, more preferably 0.2 ⁇ m. If this average thickness is less than 0.05 ⁇ m, the chipping resistance may not be sufficiently obtained. If this average thickness exceeds 1 ⁇ m, the adhesion with the layer adjacent to the outermost surface layer may be reduced.
  • the coating preferably has an intermediate layer between the ⁇ -Al 2 O 3 layer and the substrate.
  • the intermediate layer include a TiN layer, a TiCN layer, a TiCNO layer, and a TiBN layer.
  • the intermediate layer is disposed between the ⁇ -Al 2 O 3 layer, the ⁇ -Al 2 O 3 layer, and the base material, whereby the adhesion of the ⁇ -Al 2 O 3 layer in the coating can be improved.
  • the intermediate layer can be formed by a known method.
  • the average thickness of the TiCN layer and the TiBN layer is preferably 2 to 20 ⁇ m. If the average thickness is less than 2 ⁇ m, the wear may easily proceed. If this average thickness exceeds 20 ⁇ m, the chipping resistance may be lowered.
  • the TiN layer preferably has an average thickness of 0.3 to 1 ⁇ m. With a thickness in this range, the adhesion of the ⁇ -Al 2 O 3 layer in the coating can be further enhanced.
  • the TiN layer is more preferably 0.4 to 0.8 ⁇ m.
  • the thickness of an intermediate layer such as a TiN layer, a TiCN layer, a TiCNO layer, or a TiBN layer can be measured by the same method as that used for measuring the thickness of the ⁇ -Al 2 O 3 layer.
  • the surface-coated cutting tool according to the present embodiment has excellent wear resistance, and can prevent the film from being lost such as peeling and chipping, thereby achieving a long life.
  • the method for manufacturing a surface-coated cutting tool includes a step of forming a coating film containing an ⁇ -Al 2 O 3 layer on a base material by a CVD method.
  • the formation of the ⁇ -Al 2 O 3 layer is started by setting the amount of HCl gas contained in the raw material gas to 6 to 10% by volume, and then the amount is reduced to 0.5 to 6% by volume.
  • the surface-coated cutting tool can be preferably manufactured by forming a film on a substrate by a chemical vapor deposition (CVD) method.
  • CVD chemical vapor deposition
  • the film forming temperature is 800 to 1200 ° C., which is higher than the physical vapor deposition method, and the adhesion to the substrate is improved.
  • other layers other than the ⁇ -Al 2 O 3 layer are formed, these layers can be formed by a conventionally known method.
  • the thickness of the ⁇ -Al 2 O 3 layer and other layers can be adjusted by appropriately adjusting the film formation time (the film formation speed of each layer is about 0.5 to 2.0 ⁇ m / hour). .
  • the ⁇ -Al 2 O 3 layer can be formed by the following method using a CVD method.
  • a TiCN layer is formed on the substrate by a known method with or without another layer, and a TiCNO layer is formed on the surface of the TiCN layer. Further, the surface of the TiCNO layer is oxidized to nucleate ⁇ -Al 2 O 3 crystal grains. Subsequently, an ⁇ -Al 2 O 3 crystal is grown to form an ⁇ -Al 2 O 3 layer, and a lower layer and an upper layer of the ⁇ -Al 2 O 3 layer are formed.
  • the blending amount of HCl gas blended in the raw material gas is started at 6 to 10% by volume, and then the blending amount is 0.5 to 6%. Reduce to volume percent.
  • the blending amount of the HCl gas blended in the raw material gas may be constant at 0.5 to 6% by volume.
  • the compounding amount of each composition gas other than HCl gas of the raw material gas is 1.3 to 2.5% by volume for AlCl 3 , 1 to 5% by volume for CO, 0.4 to 3% by volume for CO 2 , H 2 S Is 0.4 to 3% by volume, and the balance is H 2 .
  • the variation amount of the HCl gas may be adjusted by adjusting the amount of H 2 gas occupying the remainder of the raw material gas.
  • the compounding quantity of other gas, the furnace temperature of a CVD apparatus, and the furnace pressure can be made unchanged.
  • the furnace temperature of the CVD apparatus is 970 to 1020 ° C.
  • the furnace pressure is 70 to 110 hPa.
  • the surface of the TiCNO layer is oxidized by CO and CO 2 in the composition of the source gas.
  • the variation in the amount of HCl gas added when the lower layer of the ⁇ -Al 2 O 3 layer is formed will be described.
  • the amount of HCl gas in the starting material gas is 6 to 10% by volume.
  • it is 8 to 10% by volume.
  • the blending amount is lowered to 0.5 to 6% by volume, and then the formation of the lower layer is completed.
  • the blending amount is preferably lowered to 0.5 to 4% by volume.
  • the variation in the amount of HCl gas may take a form in which the amount is continuously reduced over time, or may be in a stepwise (multi-stage) manner in which the amount is reduced at regular intervals.
  • the blending amount may be decreased instantaneously (rapidly) from 0.5% to 6% by volume.
  • an ⁇ -Al 2 O 3 layer having a concentration distribution in which the atomic concentration of Cl decreases in the thickness direction away from the substrate side can be formed.
  • the time required to reduce the compounding amount of HCl gas from 6 to 10% by volume to 0.5 to 6% by volume is appropriately determined according to the ⁇ -Al 2 O 3 layer to be formed and the thickness of the lower layer. Adjust it.
  • the amount of HCl gas contained in the raw material gas for forming the ⁇ -Al 2 O 3 layer was about 0.5 to 2% by volume during the formation start the ⁇ -Al 2 O 3 layer. This is because it was considered that a low Cl component was preferable for nucleation of ⁇ -Al 2 O 3 crystal grains.
  • the ⁇ -Al 2 O 3 layer formed under these conditions has insufficient adhesion, and there is room for improvement in chipping resistance and chipping resistance.
  • the blending amount of HCl gas is about 5 to 8% by volume, which is more blending amount than the present embodiment. Tended to be more.
  • the amount of HCl gas added is large, a large amount of Cl impurities are contained in the ⁇ -Al 2 O 3 crystal grains or in the crystal grain boundaries, leading to a decrease in wear resistance.
  • the ⁇ -Al 2 O 3 layer is formed under the above-described conditions for these problems, and includes a lower layer having a concentration distribution in which the Cl atomic concentration decreases in the direction away from the substrate side in the thickness direction. Therefore, it has become possible to achieve a long service life by providing excellent wear resistance and preventing film loss such as peeling and chipping.
  • the ⁇ -Al 2 O 3 layer by varying the amount of H 2 S gas contained in the source gas in addition to the variation of the HCl gas described above.
  • the variation form of the H 2 S gas content is the same as the variation of the HCl gas, for example. Specifically, when the amount of HCl gas is continuously reduced, the amount of H 2 S gas is also continuously reduced. When the amount of HCl gas decreases stepwise, the amount of H 2 S gas is also decreased stepwise. Or if the amount of the HCl gas is reduced momentarily (descent), the amount of H 2 S gas also reduces instantaneously.
  • the decreasing rate of the H 2 S gas content is set smaller than the decreasing rate of the HCl gas content.
  • both C Cl / S and C Cl / S have a distribution that decreases in the direction away from the substrate side in the thickness direction of the lower layer. Therefore, it is possible to manufacture a surface-coated cutting tool that has excellent wear resistance and can further prevent coating loss such as peeling and chipping.
  • Example 1 Preparation of substrate>
  • the base material which consists of the cemented carbide base material (made by Sumitomo Electric Industries) which has the shape of CNMG120408 prescribed
  • the prepared substrates were classified into 8 groups named Samples A1 to A8. There are four substrates in one group. These substrates have a composition comprising 90.0 wt% WC, 5.0 wt% Co, 1.0% TaC, 2.0 wt% NbC, and 2.0 wt% TiC. .
  • samples A1 to A6 are examples
  • samples A7 to A8 are comparative examples.
  • the coating was formed so as to be a 0.3 ⁇ m TiN layer, an 8 ⁇ m TiCN layer, a 0.3 ⁇ m TiCNO layer, and a 6 ⁇ m ⁇ -Al 2 O 3 layer in this order from the substrate side.
  • Table 2 shows the layer structures and thicknesses ( ⁇ m) of Samples A1 to A8. Table 2 also shows the thickness ( ⁇ m) of the upper layer of the ⁇ -Al 2 O 3 layer.
  • the ⁇ -Al 2 O 3 layer oxidizes the surface of the TiCNO layer formed on the surface of the TiCN layer by CVD to nucleate ⁇ -Al 2 O 3 crystal grains, and then continues to ⁇ -Al 2 O 3 The crystal grains were grown and formed.
  • Table 3 shows the blending amount of each component of the raw material gas for forming the ⁇ -Al 2 O 3 layer, the variation of the blending amount of the HCl gas, and the variation form.
  • stepped means a form in which the amount of HCl gas is lowered stepwise at regular intervals
  • continuous means the passage of time.
  • it refers to a form in which the amount of HCl gas is continuously reduced
  • suffi drop refers to a form in which the amount of HCl gas is instantaneously reduced from 10% to 4 or 6% by volume.
  • the amount of HCl gas is constant.
  • Example 1 ⁇ Content of the test>
  • four surface-coated cutting tools are manufactured for each of the samples A1 to A8.
  • the flank face was irradiated with X-rays on the first of the four tools, and the TC (006) of the ⁇ -Al 2 O 3 layer was measured using the X-ray diffraction method under the conditions described above.
  • the atomic concentration of Cl and the atomic concentration of S in the ⁇ -Al 2 O 3 layer were measured using EDS by the measurement method described above.
  • the wear resistance was evaluated for the third piece, and the fracture resistance was evaluated for the fourth piece.
  • the atomic concentration of Cl and the atomic concentration of S in the lower layer of the ⁇ -Al 2 O 3 layer were measured at equal intervals in the thickness direction. Specifically, because of its thickness from the interface 1.0 ⁇ m of the TiCNO layer lower portion is adjacent to the substrate side of the ⁇ -Al 2 O 3 layer, the substrate of ⁇ -Al 2 O 3 layer in the coating section Measurement points (first measurement point to fifth measurement point) were set every 0.2 ⁇ m from the point in contact with the interface with the adjacent TiCNO layer to the coating surface side. Thereby, the atomic concentration of Cl and the atomic concentration of S in the lower layer were calculated (see FIG. 1).
  • the evaluation methods for wear resistance and fracture resistance are as follows.
  • Table 4 the TC (006) of the ⁇ -Al 2 O 3 layer for samples A1 to A8, the atomic concentration of Cl at each measurement point, the maximum atomic concentration of Cl at the lower layer and the upper layer, and at each measurement point The atomic concentration of S is shown.
  • Table 5 the added value C ClS and the numerical value C Cl / S at each measurement point for the samples A1 to A8, and the evaluation of wear resistance and fracture resistance are shown together with the performance rank.
  • the above-mentioned surface-coated cutting tool is set on an NC lathe and the cutting of the above-mentioned work material is started.
  • the time until the maximum width of the exposed portion of the material exceeded 0.1 mm was evaluated. It can be evaluated that the longer this time is, the better the wear resistance is.
  • each of the above surface-coated cutting tools was set on an NC lathe, the work material was cut for 5 minutes under the above conditions, and the chipping state at that time was compared visually. did.
  • the time to that point was evaluated. It can be evaluated that the chipping state after cutting for 5 minutes remains in wear (normal wear), and that chipping or chipping is not observed, the chip is excellent in chipping resistance. Furthermore, it can be evaluated that the longer the time until chipping or chipping is, the better the chipping resistance.
  • the performance rank indicated by symbol A or the like is defined as follows.
  • B Excellent wear resistance and fracture resistance (time (min) until the maximum width of the exposed portion of the substrate exceeds 0.1 mm is more than 10 minutes and 15 minutes or less, and the fracture resistance is The condition is normal wear or wear disturbance due to minute chipping)
  • C Insufficient wear resistance or fracture resistance (at least the time (minutes) until the maximum width of the exposed portion of the substrate exceeds 0.1 mm is 10 minutes or less, or the fracture resistance is The state is chipping or chipping (including the case where cutting cannot be continued and the time is indicated).
  • the maximum atomic concentration in the lower layer of chlorine is less than 0.3 atomic%
  • the maximum atomic concentration in the upper layer is less than 0.05 atomic%
  • the maximum atomic concentration of chlorine in the lower layer is C ClMAX- 1.
  • the wear resistance of samples A1 to A3 satisfying at least one of the requirements of satisfying the relationship of C ClMAX-1 ⁇ 2C ClMAX-2 was even better.
  • C ClS had a distribution that decreased in the direction away from the substrate side in the thickness direction of the lower layer.
  • C Cl / S also had a distribution that decreased in the direction away from the substrate side in the thickness direction of the lower layer.
  • Example 2 >> ⁇ Preparation of substrate> A base material made of a cemented carbide base material (manufactured by Sumitomo Electric Industries) having the same composition and the same shape (CNMG120408) as in Example 1 was prepared. The prepared substrates were classified into 8 groups named Samples B1 to B8. There are four substrates in one group. As will be described later, samples B1 to B6 are examples, and samples B7 to B8 are comparative examples.
  • the coating was formed so as to be a 0.3 ⁇ m TiN layer, an 8 ⁇ m TiCN layer, a 0.3 ⁇ m TiCNO layer, and a 10 ⁇ m ⁇ -Al 2 O 3 layer in this order from the substrate side.
  • Table 6 shows the layer structures and thicknesses ( ⁇ m) of Samples B1 to B8. Table 6 also shows the thickness ( ⁇ m) of the upper layer of the ⁇ -Al 2 O 3 layer.
  • the ⁇ -Al 2 O 3 layer oxidizes the surface of the TiCNO layer formed on the surface of the TiCN layer by CVD to nucleate ⁇ -Al 2 O 3 crystal grains, and then continues to ⁇ -Al 2 O 3 The crystal grains were grown and formed.
  • Table 7 shows the blending amount of each component of the raw material gas for forming the ⁇ -Al 2 O 3 layer, the variation amount of the blending amount of the HCl gas, and the variation form thereof.
  • Example 2 includes an example in which the blending amount of the H 2 S gas contained in the raw material gas is also varied along with the above-described variation of the HCl gas.
  • the amount of change in the blending amount of H 2 S gas is shown in Table 7.
  • the amount of HCl gas contained in the source gas is lowered in three steps (stepped) like the sample B1, while the amount of H 2 S gas contained in the source gas is reduced.
  • the amount of H 2 S gas contained in the source gas was reduced.
  • the blending amount of 0.5% by volume is started and the blending amount is increased in three stages (stepped), specifically, H 2 S in the order of 0.7% by volume, 0.8% by volume, and 1% by volume. After increasing the amount of gas, the formation of the lower layer was completed.
  • Example 2 ⁇ Content of the test>
  • four surface-coated cutting tools are produced for each of the samples B1 to B8.
  • the flank face was irradiated with X-rays on the first of the four tools, and the TC (006) of the ⁇ -Al 2 O 3 layer was measured using the X-ray diffraction method under the conditions described above.
  • the atomic concentration of Cl and the atomic concentration of S in the ⁇ -Al 2 O 3 layer were measured using EDS by the measurement method described above.
  • the wear resistance was evaluated for the third piece, and the fracture resistance was evaluated for the fourth piece.
  • the atomic concentration of Cl and the atomic concentration of S in the lower layer of the ⁇ -Al 2 O 3 layer were measured at equal intervals in the thickness direction. Specifically, because of its thickness from the interface 1.0 ⁇ m of the TiCNO layer lower portion is adjacent to the substrate side of the ⁇ -Al 2 O 3 layer, the substrate of ⁇ -Al 2 O 3 layer in the coating section Measurement points (first measurement point to fifth measurement point) were set every 0.2 ⁇ m from the point in contact with the interface with the adjacent TiCNO layer to the coating surface side. Thereby, the atomic concentration of Cl and the atomic concentration of S in the lower layer were calculated (see FIG. 1).
  • Example 1 The methods for evaluating wear resistance, chipping resistance and performance rank are the same as those in Example 1.
  • Table 8 TC of the ⁇ -Al 2 O 3 layer for samples B1 to B8 (006), the atomic concentration of Cl at each measurement point, the maximum atomic concentration of Cl at the lower layer and the upper layer, and at each measurement point The atomic concentration of S is shown. Further, in Table 9, the added value C ClS and the numerical value C Cl / S at each measurement point regarding the samples B1 to B8, and the evaluation of wear resistance and fracture resistance are shown together with the performance rank.
  • the maximum atomic concentration in the lower layer of chlorine is less than 0.3 atomic%
  • the maximum atomic concentration in the upper layer is less than 0.05 atomic%
  • the maximum atomic concentration of chlorine in the lower layer is C ClMAX- 1.
  • the maximum atomic concentration of chlorine in the upper layer is C ClMAX-2
  • samples B1, B2, and B3 satisfying at least one of the requirements of satisfying the relationship of C ClMAX-1 ⁇ 2C ClMAX-2
  • the abrasion resistance and fracture resistance evaluation was further excellent.
  • the sample has a distribution in which C ClS decreases in the direction away from the substrate side and the distribution in which C Cl / S decreases in the direction away from the substrate side.
  • B2 and B3 were found to have much more excellent wear resistance and fracture resistance than the sample B1.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Forests & Forestry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Chemical Vapour Deposition (AREA)
  • Drilling Tools (AREA)
  • Milling, Broaching, Filing, Reaming, And Others (AREA)
PCT/JP2017/016405 2016-08-24 2017-04-25 表面被覆切削工具およびその製造方法 Ceased WO2018037625A1 (ja)

Priority Applications (4)

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US15/740,927 US10654181B2 (en) 2016-08-24 2017-04-25 Surface-coated cutting tool and method of manufacturing the same
EP17811821.2A EP3308886B1 (en) 2016-08-24 2017-04-25 Surface-coated cutting tool and manufacturing method therefor
CN201780002260.4A CN107980013B (zh) 2016-08-24 2017-04-25 表面被覆切削工具及其制造方法
KR1020177037473A KR102170166B1 (ko) 2016-08-24 2017-04-25 표면 피복 절삭 공구 및 그 제조방법

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CN115397586A (zh) * 2021-03-22 2022-11-25 住友电工硬质合金株式会社 切削工具
CN115397587A (zh) * 2021-03-22 2022-11-25 住友电工硬质合金株式会社 切削工具

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CN115397587A (zh) * 2021-03-22 2022-11-25 住友电工硬质合金株式会社 切削工具

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KR20190041885A (ko) 2019-04-23
EP3308886A4 (en) 2019-07-31
JP2018030193A (ja) 2018-03-01
JP6635340B2 (ja) 2020-01-22
EP3308886A1 (en) 2018-04-18
CN107980013B (zh) 2019-07-05
US20180339415A1 (en) 2018-11-29
CN107980013A (zh) 2018-05-01
US10654181B2 (en) 2020-05-19
KR102170166B1 (ko) 2020-10-26
EP3308886B1 (en) 2022-07-20

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