WO2023042777A1 - Coated ultrafine grain cemented carbide, and cutting tool or abrasion-resistant member using same - Google Patents

Coated ultrafine grain cemented carbide, and cutting tool or abrasion-resistant member using same Download PDF

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Publication number
WO2023042777A1
WO2023042777A1 PCT/JP2022/033993 JP2022033993W WO2023042777A1 WO 2023042777 A1 WO2023042777 A1 WO 2023042777A1 JP 2022033993 W JP2022033993 W JP 2022033993W WO 2023042777 A1 WO2023042777 A1 WO 2023042777A1
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Prior art keywords
cemented carbide
ultrafine
phase
coated
grained
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PCT/JP2022/033993
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French (fr)
Japanese (ja)
Inventor
友浩 堤
真之 ▲高▼田
秀彰 松原
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日本特殊合金株式会社
国立大学法人東北大学
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Publication of WO2023042777A1 publication Critical patent/WO2023042777A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B51/00—Tools for drilling machines
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • 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
    • 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
    • C23C14/08—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
    • 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
    • C23C14/34—Sputtering
    • 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
    • C23C16/32—Carbides
    • 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

Definitions

  • the present invention relates to coated ultrafine-grained cemented carbide, and cutting tools or wear-resistant members using the same.
  • Cemented carbide is used for cutting tools (drills, insert tips, etc.) used for cutting metals and wear-resistant members (molds, dies, etc.) for metal processing (Patent Document 1). Cutting tools and wear-resistant members inevitably wear out with continued use. The faster the wear, the faster the replacement cycle.
  • An object of the present invention is to provide a coated ultrafine-grained cemented carbide suitable for cutting tools or wear-resistant members with excellent wear resistance.
  • the coated ultrafine grained cemented carbide according to the present invention contains 70 to 99.4 wt% of a hard phase mainly composed of tungsten carbide (WC) having an average grain size of 1.0 ⁇ m or less with respect to the entire ultrafine grained cemented carbide,
  • a grain-growth inhibiting phase mainly composed of titanium carbonitride (Ti(C,N)) produced by carbonitriding oxide of titanium (Ti) during sintering is applied to the entire ultra-fine grained cemented carbide.
  • the binder phase containing at least one selected from the group consisting of cobalt (Co), nickel (Ni) and iron (Fe) as a main component with respect to the entire ultrafine cemented carbide
  • a hard coating is coated by PVD or CVD on an ultra-fine grained cemented carbide containing 4 to 30 wt % and the total of the hard phase, grain growth inhibiting phase and binder phase is 100 wt %.
  • Unavoidable impurities that is, impurities that exist in raw materials or are unavoidably mixed in during the manufacturing process, are originally unnecessary, but are allowed in trace amounts and do not affect the characteristics of the product. may be contained in ultrafine-grained cemented carbide.
  • the coated ultrafine-grained cemented carbide according to the present invention is composed of an ultra-fine-grained cemented carbide serving as a base material (base material) and a hard coating that coats the surface of the ultra-fine-grained cemented carbide.
  • Ultrafine-grained cemented carbide includes three types of phases: a "hard phase” (first phase), a “grain growth inhibition phase” (second phase), and a “binder phase” (third phase). The sum of these three phases is 100%.
  • the hard coating is applied to the surface of the ultra-fine grained cemented carbide using physical vapor deposition (PVD) or chemical vapor deposition (CVD).
  • the coated ultrafine-grained cemented carbide of this invention contains Ti(C,N).
  • Ti (C, N) has the effect of suppressing the grain growth of WC, which is a hard phase. It also produces an action or effect of improving the adhesion of the hard coating, thereby making it possible to obtain a coated ultrafine-grained cemented carbide with excellent wear resistance. According to cutting tests (drilling test and turning test) using drills and insert tips described later, the coated ultrafine-grained cemented carbide according to the present invention is superior to the conventional coated ultrafine-grained cemented carbide (coated ultrafine-grained cemented carbide according to the present invention).
  • the conventional ultrafine-grained cemented carbide or cemented carbide different from the ultra-fine-grained cemented carbide used as the base material is coated with a hard coating provided by the coated ultra-fine-grained cemented carbide of this invention). Exhibits abrasion resistance.
  • the ultrafine-grained cemented carbide comprises chromium (Cr) or chromium carbide (Cr 3 C 2 ) in an amount of 0.1-20 wt% relative to the total binder phase. It was confirmed that the wear resistance of the coated ultrafine-grained cemented carbide is further improved by using the ultrafine-grained cemented carbide containing Cr or Cr 3 C 2 . Furthermore, it has been confirmed by tests that the wear resistance is further improved by increasing the content of Cr 3 C 2 . Cr also functions as a grain growth inhibition phase.
  • the hard coating contains elements contained in the ultrafine grain cemented carbide. It is thought that this contributes to the improvement of the adhesion between the ultrafine cemented carbide and the hard coating.
  • the hard coating is at least one selected from carbides, nitrides, carbonitrides and oxides containing at least Ti or Cr.
  • the ultrafine grained cemented carbide used as the base material contains Ti(C, N) as a grain growth inhibition phase. It also preferably contains Cr or Cr 3 C 2 which functions as a grain growth inhibiting phase.
  • carbides, nitrides, carbonitrides or oxides of Ti or Cr which are the same elements as those contained in Ti(C, N) or Cr as the grain growth inhibiting phase, It is believed that the material is suitable for a hard coating that adheres well to the substrate constituting the coated ultrafine-grained cemented carbide according to the invention.
  • At least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN and Ti(C, N) can be used as the hard coating.
  • a plurality of types of hard coatings may be laminated on the surface of the ultrafine cemented carbide.
  • a carbide, nitride, carbonitride or oxide containing aluminum (Al) or a composite material thereof may be laminated as a base on the ultrafine cemented carbide.
  • the hard coating is deposited on an Al-containing carbide, nitride, carbonitride or oxide.
  • a hard coating may be laminated on an ultrafine cemented carbide, and then a carbide, nitride, carbonitride or oxide containing Al, or a composite material thereof may be laminated thereon.
  • the hard coating and the carbide, nitride, carbonitride or oxide containing Al may be laminated in not only two layers but also three or more layers.
  • the present invention also provides cutting tools (eg, drills, insert tips) and wear-resistant members (eg, molds, dies) composed of the above-described coated ultrafine-grained cemented carbide.
  • cutting tools eg, drills, insert tips
  • wear-resistant members eg, molds, dies
  • Fig. 1 shows an enlarged view of the tip (blade) of the drill.
  • the drill 1 has a chisel 11 at the tip, two cutting edges 12 extending on both sides of the chisel 11, a flank 13 continuing to the cutting edge 12, a chamfer 14 continuing to the flank 13, and the top of the chamfer 14. and a rake face 16 through which cutting material flows.
  • a drill 1 that rotates at high speed is pressed against the workpiece from its tip.
  • a workpiece is cut by a chisel 11 and a cutting edge 12 connected to the chisel 11 .
  • the work material is cut by sending the drill 1 toward the work material, and a hole corresponding to the diameter of the drill 1 is made in the work material.
  • the chisel 11 and the cutting edge 12 are in direct contact with the workpiece and are gradually worn. Wear of not only the chisel 11 and the cutting edge 12 but also the flank 13 and the margin 15 that are continuous with the cutting edge 12 is unavoidable.
  • FIG. 2 is a perspective view showing an enlarged insert tip.
  • the insert tip 2 has a cutting edge 21 , a flank 22 and a rake face 23 . Material is cut by the cutting edge 21 and the cut material flows along the rake face 23 . A ridge line between the flank face 22 and the rake face 23 becomes the cutting edge 21 .
  • the insert tip 2 scrapes the surface of the workpiece.
  • the surface of the workpiece is turned by moving the insert tip 2 along the axial direction of the rotating shaft of the workpiece (along the longitudinal direction of the workpiece). As for the insert tip 2, not only the cutting edge 21 but also the flank 22 continuing to the cutting edge 21 gradually wears out.
  • the coated ultra-fine grained cemented carbide drill or insert tip (development product) in which a specified coating is applied to the ultra-fine grained cemented carbide described below is a conventional cemented carbide with a specified coating. It was found that the wear resistance performance was greatly improved compared to coated cemented carbide drills or insert tips (conventional products). The compositional characteristics of the developed product and the cutting test results of the developed product and the conventional product are described below.
  • the ultrafine-grained cemented carbide that constitutes the coated ultra-fine-grained cemented carbide drill or insert tip has a first phase (hereinafter referred to as “WC phase” or generically “hard phase”) mainly composed of tungsten carbide (WC).
  • a second phase (hereinafter collectively referred to as “grain growth suppression phase”) mainly composed of titanium carbonitride (Ti (C, N)), cobalt (Co), nickel (Ni) and iron (Fe) and chromium (Cr) or chromium carbide (Cr 3 C 2 ) is added (hereinafter collectively referred to as “binder phase”); It is a so-called tungsten carbide-based cemented carbide containing The grain size of WC that forms the hard phase is 1.0 ⁇ m or less on average, and since it is ultra-fine, it can be particularly called a tungsten-based ultra-fine-grained cemented carbide.
  • Ti(C,N), which forms the grain growth inhibiting phase, is not used as the starting material, and titanium oxide (TiO 2 ) is used as the starting material.
  • TiO2 is carbonitrided to generate Ti(C,N), which is the composition of the final ultra-fine-grained cemented carbide.
  • (1) Content of hard phase (WC phase)
  • the binder phase becomes relatively large, making it difficult to control the grain growth of the WC phase.
  • the WC phase is made 70 to 99.4 wt% of the entire cemented carbide because the hardness of the ultra-fine grained cemented carbide is lowered.
  • the raw material powder should be blended in an amount falling within this range.
  • the grain growth suppression phase is to suppress the grain growth of the WC phase and maintain the WC phase as ultrafine grains as described above.
  • the WC phase growth is a phenomenon in which the WC phase dissolved in the binder phase during sintering precipitates in other WC phases and grows into particles with a large diameter.
  • Ti(C,N) as a grain growth inhibitor phase, Ti(C,N) is scattered around the WC phase. considered to be suppressed.
  • the grain-growth-suppressing phase is in an amount suitable for effectively suppressing the grain growth of the WC phase, that is, 0.1 wt % or more and 30 wt % or less with respect to the entire ultrafine-grained cemented carbide.
  • the grain growth inhibiting phases are preferably fine grains. Therefore, the grain growth inhibiting phase should preferably have an average grain size in the range of 5 to 500 nm.
  • the average grain size of the grain growth inhibiting phase exceeds 500 nm, a sufficient grain growth inhibiting effect cannot be obtained unless a large amount is added, making it difficult to achieve both high levels of strength and hardness. Also, the carbonitride phase of less than 5 nm agglomerates during powder mixing, resulting in a decrease in strength.
  • Ti(C,N) is not used as a starting material as described above, but titanium oxide (TiO 2 ) is used as a starting material, which is carbonitrided during sintering to produce Ti(C , N) are generated. This is because the ultrafine-grained cemented carbide contains a fine grain-growth-suppressing phase, and the grain growth of the WC phase is effectively suppressed with a small content.
  • Binder Phase Content The binder phase is used to bind hard and ultrafine WC particles.
  • the binder phase is a metal containing these metal elements as a main component (containing 50 wt % or more of the entire binder phase).
  • the binder phase When the binder phase is less than 0.4 wt% of the entire ultrafine-grained cemented carbide, the bending strength of the ultrafine-grained cemented carbide is lowered, and when it exceeds 30wt%, the hardness of the ultrafine-grained cemented carbide is lowered. From these points of view, it is preferable that the binder phase is contained in an amount of 0.4 to 30 wt % with respect to the entire ultrafine cemented carbide. By firmly bonding the WC grains together with the binder phase, the WC grains are prevented from falling off from the ultrafine-grained cemented carbide, and the strength of the ultra-fine-grained cemented carbide can be ensured.
  • Cr or Cr 3 C 2 is used to suppress grain growth of the WC phase and growth of carbonitrides. It is also known that Cr 3 C 2 contributes to improving the hardness and oxidation resistance of the binder phase.
  • Cr or Cr 3 C 2 is contained in an amount of 0.1 wt% or more based on the entire binder phase, the hardness, strength and oxidation resistance of the binder phase are improved, grain growth of the WC phase is suppressed, and cemented carbide is improved. Improves hardness and strength.
  • Cr or Cr 3 C 2 should be 20 wt % or less with respect to the binder phase.
  • WC having an average particle diameter of 0.05 to 2.0 ⁇ m was weighed as a raw material powder so as to be 70 to 99.4 wt % with respect to the ultrafine cemented carbide, and TiO 2 was added to the ultrafine cemented carbide at 0.0%. It is weighed so as to be 1 to 30 wt%.
  • a metal containing at least one selected from the group consisting of Co, Ni and Fe as a main component and Cr or Cr 3 C 2 is used as the WC phase, the grain growth inhibition phase and the binder phase after sintering. Weigh so that the total is 100 wt%.
  • 1 wt % or less of carbon powder or 1 wt % or less of tungsten powder may be added to the raw material powder so as not to generate free carbon or a decarburized phase after sintering. These are put into a ball mill or an attritor together with an organic solvent, and mixed and pulverized for a predetermined time. After that, it is dried and formed into a predetermined shape, for example, the shape of the drill 1 .
  • the molding is sintered in a nitrogen atmosphere at a temperature of 1300-1500° C. for 60-120 minutes.
  • the TiO 2 thus added is carbonitrided by carbon in the material and nitrogen during sintering (Ti(C,N)).
  • At least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN and Ti(C, N) is used for the coating.
  • These coatings contain the same elements (that is, Ti or Cr) as Ti (C, N) and Cr contained as grain growth inhibition phases in the above-described ultrafine-grained cemented carbide. It is thought that the abrasion resistance required for cutting tools such as the drill 1 or the insert tip 2 and abrasion resistant members (tools) such as molds and dies is improved.
  • a plurality of types of TiC, TiN, TiAlN, CrAlN, TiSiN, and Ti(C, N) may be laminated on the superfine grain cemented carbide.
  • a multilayer structure of two or more layers is formed by forming an Al 2 O 3 film as a base on an ultrafine cemented carbide, and further forming one of the above-described coatings (may be more than one) on the surface of the Al 2 O 3 may form a coating.
  • Al-containing carbides, nitrides, carbonitrides, or composites thereof may be laminated instead of Al 2 O 3 , which is an Al-containing oxide.
  • an ultrafine cemented carbide is coated with at least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN, and Ti(C, N), and then Al-containing oxides, carbides, Nitrides, carbonitrides, or composites thereof may be laminated.
  • the coating is not limited to two layers, and three or more layers may be laminated.
  • PVD Physical vapor deposition
  • CVD chemical vapor deposition
  • Table 1 shows five types of coated ultrafine cemented carbide or coated cemented carbide drills 1 (Examples 1 and 2, Comparative Examples 1 to 3) used in the drilling test.
  • the composition of the alloy (amount of each component) is shown, as well as the WC grain size, hardness and average transverse rupture strength after sintering. "bal.” described in the amount of WC represents the balance amount.
  • the amount of Co as the binder phase is uniform in Examples 1-2 and Comparative Examples 1-3.
  • the intercept method was used to measure the WC grain size after sintering. Hardness was measured using a Rockwell hardness tester (A scale). The average transverse rupture strength was measured by a three-point bending test.
  • the ultrafine-grained cemented carbides of Examples 1 and 2 both contain WC as a hard phase, Ti(C,N) as a grain growth inhibiting phase, Co as a binder phase, and further Cr 3 C 2 is added. In addition, it is the above-mentioned ultrafine-grained cemented carbide.
  • Table 1 the amounts of WC, Ti(C, N), Co, and VC, which will be described later, are based on the entire cemented carbide.
  • Cr 3 C 2 indicates the amount based on the binder phase (here Co). Examples 1 and 2 differ in the amount of Cr 3 C 2 .
  • the ultrafine-grained cemented carbides of Examples 1 and 2 both contain Ti (C, N) as a grain growth inhibiting phase
  • the ultra-fine-grained cemented carbides and cemented carbides of Comparative Examples 1 to 3 contain Ti Does not contain (C, N).
  • the ultrafine-grained cemented carbide of Comparative Example 1 contains vanadium carbide (VC) as a grain growth inhibitory phase.
  • the ultrafine-grained cemented carbide of Comparative Example 2 contains neither Ti(C,N) nor VC, resulting in a rather large WC grain size after sintering (0.81 ⁇ m).
  • the cemented carbide of Comparative Example 3 also does not contain Cr 3 C 2 , resulting in a larger WC grain size after sintering (1.72 ⁇ m).
  • the ultrafine-grained cemented carbide of Example 2 and the ultra-fine-grained cemented carbide of Comparative Example 1 are relatively excellent.
  • the average transverse rupture strength of the ultrafine-grained cemented carbide of Example 2 and the ultrafine-grained cemented carbide of Comparative Example 1 focusing on hardness, the ultrafine-grained cemented carbide of Example 2 and the ultra-fine-grained cemented carbide of Comparative Example 1 are relatively excellent.
  • the average transverse rupture strength of the ultrafine-grained cemented carbide of Example 2 and the ultrafine-grained cemented carbide of Comparative Example 1 focusing on hardness, the ultrafine-grained cemented carbide of Example 2 and the ultra-fine-grained cemented carbide of Comparative Example 1 are relatively excellent.
  • the average transverse rupture strength of the ultrafine-grained cemented carbide of Example 2 and the ultrafine-grained cemented carbide of Comparative Example 1 focusing on hardness, the ultrafine-grained cemented carbide of Example 2 and the ultra-fine-g
  • FIGS. 3 to 5 show drills with a diameter of 6 mm using the five types of ultrafine cemented carbides or cemented carbides described above, which are coated with TiAlN using physical vapor deposition (PVD).
  • 1 shows the test results of a drilling test using a drill of type 1;
  • the horizontal axis represents the number of holes drilled in the workpiece using the drill 1.
  • FIG. 3 shows the wear amount (mm) of the chisel 11
  • FIG. 4 shows the wear amount (mm) of the flank 13
  • FIG. 5 shows the wear amount (mm) of the margin 15, respectively.
  • FIGS. 3 shows the wear amount (mm) of the chisel 11
  • FIG. 4 shows the wear amount (mm) of the flank 13
  • FIG. 5 shows the wear amount (mm) of the margin 15, respectively.
  • S50C HRC34
  • the workpiece was drilled in a non-step manner, and blind holes with a depth of 20 mm were drilled one after another in the workpiece.
  • Water-soluble coolant was appropriately supplied from the outside during drilling.
  • the rotational speed of the drill 1 was 4700 rpm, and the feed rate was 600 mm/min.
  • the end point of the graphs in Figures 3 to 5 indicates that the drilling test was terminated there because the drill 1 reached the end of its life.
  • the life of the drill 1 end of the drilling test
  • the occurrence of breakage of the drill 1 in addition to flank wear, the occurrence of chips of 0.5 mm or more, the occurrence of abnormal shapes of cutting waste, the occurrence of abnormal noise during cutting, etc. can be considered.
  • the number of holes at the end of the life was about 2000 for the coated ultra-fine grain cemented carbide drill 1 in which the ultra-fine grain cemented carbide was coated with TiAlN in Example 1.
  • about 2500 when using the ultrafine-grained cemented carbide of Example 2 about 1300 when using the ultrafine-grained cemented carbide of Comparative Example 1, about 1200 when using the ultrafine-grained cemented carbide of Comparative Example 2, and about 1200 when using the ultrafine-grained cemented carbide of Comparative Example 3. It was about 900 with cemented carbide.
  • coated ultrafine cemented carbide drills 1 in which the ultrafine cemented carbides of Examples 1 and 2 are coated with TiAlN are the ultrafine cemented carbide drills of Comparative Examples 1 to 3.
  • the wear resistance is considerably superior, and it was found that the coated ultra-fine-grained cemented carbide drill 1 in which the ultra-fine-grained cemented carbide is coated with TiAlN in Example 2 is particularly superior.
  • the same element (Ti) is contained in the ultrafine cemented carbide serving as the base material (base material) and the TiAlN coating, so that the adhesion between the two is improved and the life is extended.
  • Example 2 with a larger amount of Cr 3 C 2 added has a longer life than Example 1, and the amount of Cr 3 C 2 added exceeds the coating. It is also confirmed that it contributes to the improvement of the wear resistance of the fine-grain cemented carbide drill 1 . It is believed that containing 5.0 wt % or more of Cr 3 C 2 with respect to the entire binder phase sufficiently improves the wear resistance.
  • Table 2 shows the composition (amount) of the ultrafine-grained cemented carbide that constitutes the four types of coated ultra-fine-grained cemented carbide insert tips (Examples 3 and 4 and Comparative Examples 4 and 5) used in the turning test, and the sintered material. WC grain size, hardness and average transverse rupture strength after binding are shown. Comparative Examples 4 and 5 are commercially available cemented carbides, and the average transverse rupture strength could not be measured.
  • Examples 3 and 4 both contain WC as the hard phase, Ti(C,N) as the grain growth inhibiting phase, Co as the binder phase, and further the above-described ultrafine grains with the addition of Cr3C2 .
  • Cemented carbide Table 2 also shows the amount of Ti(C, N), Co and TaC described later based on the entire cemented carbide, and the amount of Cr 3 C 2 based on the binder phase.
  • Examples 3 and 4 are ultrafine-grained cemented carbides having the same composition, but are different samples (separately produced ultrafine-grained cemented carbides).
  • the ultrafine-grained cemented carbides of Examples 3 and 4 both contain Ti(C,N) as a grain growth inhibition phase, whereas the ultrafine-grained cemented carbide of Comparative Example 4 does not contain Ti(C,N). , containing tantalum carbide (TaC) as a grain growth inhibition phase. Moreover, it does not contain Cr 3 C 2 .
  • the ultrafine-grained cemented carbide of Comparative Example 5 does not contain Ti(C,N) or TaC, but contains Cr 3 C 2 as a grain growth inhibiting phase. Also, in Comparative Example 5, a two-layer structure of TiAlN and CrAlN was adopted for the coating described below.
  • Fig. 6 shows that insert chips having the shape shown in Fig. 2 were produced using the four types of ultrafine cemented carbide described above, and TiAlN (Examples 3, 4 and Test of turning test using three types of insert tips 2 (Examples 3, 4 and Comparative Example 4) coated with Comparative Example 4) and one type of insert tip 2 (Comparative Example 5) coated with TiAlN and CrAlN shows the results.
  • the horizontal axis indicates the cutting distance
  • the vertical axis indicates the wear width (mm) of the flank 22 .
  • a polished round bar made of S45C with a diameter of 80 mm was used as the work material (work material).
  • the cutting speed was 160 m/min
  • the feed rate was 0.2 mm/rev
  • the depth of cut was 2.0 mm
  • water-soluble cutting oil was appropriately supplied during turning.
  • the life of the insert tip 2 (end of the turning test) was determined when flank wear of 0.2 mm or more occurred. In determining the life of the insert tip 2, other factors such as the occurrence of chipping, the occurrence of abnormal shape of cutting waste, and the occurrence of abnormal noise during cutting can be considered.
  • the cutting distance at the end of the life (when flank wear of 0.2 mm or more occurs) is about 22,000 m, when the coated ultrafine-grained cemented carbide obtained by coating the ultra-fine-grained cemented carbide of Example 4 with TiAlN is used, approximately 27,000 m, the coated ultra-fine-grained cemented carbide of Comparative Examples 4 and 5 coated with TiAlN. Both were about 7,000m when fine-grained cemented carbide was used.
  • the coated ultrafine-grained cemented carbide insert tip 2 in which the ultrafine-grained cemented carbide of Examples 3 and 4 is coated with TiAlN is coated with TiAlN, or TiAlN and CrAlN on the ultrafine-grained cemented carbide of Comparative Examples 4 and 5. It was found that the wear resistance was superior to that of the insert tip that had been treated.
  • the test results for the coated ultrafine-grained cemented carbide drill 1 and the coated ultrafine-grained cemented carbide insert tip 2 were explained. It is possible to obtain a result that is superior in wear resistance compared to the conventional method.
  • TiAlN is used as the hard coating. Hard coatings containing Ti other than TiAlN, specifically TiC, TiN, TiSiN and Ti(C, N) mentioned above are also considered to contribute to the same improvement in wear resistance as TiAlN. Also, it is considered that the wear resistance can be improved by using CrAlN containing Cr for the hard coating.
  • FIG. 7 shows an enlarged cross-sectional photograph of the coated ultrafine-grained cemented carbide insert chip 2 in which the ultrafine-grained cemented carbide is coated with TiAlN in Example 3 described above.

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Abstract

Provided are a tool and the like excellent in abrasion resistance. A coated ultrafine grain cemented carbide drill 1 is produced by coating an ultrafine grain cemented carbide with a hard coating film by means of PVD or CVD, said coated ultrafine grain cemented carbide containing 70 to 99.4 wt% of hard phase, which is composed mainly of WC having an average grain size of 1.0 µm or less, relative to the total ultrafine grain cemented carbide, 0.1 to 30 wt% of grain growth inhibition phase, which is composed mainly of Ti (C, N) produced by carbonitriding of Ti oxides during sintering, relative to the total ultrafine grain cemented carbide, and 0.4 to 30 wt% of binder phase, which is composed mainly of at least one kind selected from the group consisting of Co, Ni, and Fe, relative to the total ultrafine grain cemented carbide, with the total of the hard phase, the grain growth inhibition phase, and the binder phase being 100 wt%.

Description

被覆超微粒超硬合金，およびこれを用いた切削工具または耐摩耗部材Coated ultrafine-grained cemented carbide, and cutting tools or wear-resistant members using the same
　この発明は被覆超微粒超硬合金，およびこれを用いた切削工具または耐摩耗部材に関する。 The present invention relates to coated ultrafine-grained cemented carbide, and cutting tools or wear-resistant members using the same.
　金属の切削加工に用いられる切削工具（ドリル，インサートチップなど），金属加工のための耐摩耗部材（金型，ダイスなど）には超硬合金が利用されている（特許文献１）。切削工具や耐摩耗部材は使用し続けると必ず摩耗する。摩耗が早いほど交換サイクルが早くなる。 Cemented carbide is used for cutting tools (drills, insert tips, etc.) used for cutting metals and wear-resistant members (molds, dies, etc.) for metal processing (Patent Document 1). Cutting tools and wear-resistant members inevitably wear out with continued use. The faster the wear, the faster the replacement cycle.
特許第６７８６７６３号公報Japanese Patent No. 6786763
　この発明は，耐摩耗性に優れた切削工具ないし耐摩耗部材に適する被覆超微粒超硬合金を提供することを目的とする。 An object of the present invention is to provide a coated ultrafine-grained cemented carbide suitable for cutting tools or wear-resistant members with excellent wear resistance.
　この発明による被覆超微粒超硬合金は平均粒径が１．０μｍ以下である炭化タングステン（ＷＣ）を主成分とする硬質相を超微粒超硬合金全体に対して７０～９９．４ｗｔ％含み，チタン（Ｔｉ）の酸化物を焼結中に炭窒化させて生成されるチタン炭窒化物（Ｔｉ（Ｃ，Ｎ））を主成分とする粒成長抑制相を超微粒超硬合金全体に対して０．１～３０ｗｔ％含み，コバルト（Ｃｏ），ニッケル（Ｎｉ）および鉄（Ｆｅ）からなる群より選択される少なくとも１種類を主成分とする結合相を超微粒超硬合金全体に対して０．４～３０ｗｔ％含み，上記硬質相と粒成長抑制相と結合相との合計が１００ｗｔ％である超微粒超硬合金に，硬質被膜がＰＶＤまたはＣＶＤによって被覆されている。不可避不純物，すなわち原料中に存在したり，製造工程において不可避的に混入したりするもので，本来は不要なものであるが，微量であり，製品の特性に影響を及ぼさないため許容される不純物が超微粒超硬合金に含まれる場合がある。 The coated ultrafine grained cemented carbide according to the present invention contains 70 to 99.4 wt% of a hard phase mainly composed of tungsten carbide (WC) having an average grain size of 1.0 μm or less with respect to the entire ultrafine grained cemented carbide, A grain-growth inhibiting phase mainly composed of titanium carbonitride (Ti(C,N)) produced by carbonitriding oxide of titanium (Ti) during sintering is applied to the entire ultra-fine grained cemented carbide. 0.1 to 30 wt% of the binder phase containing at least one selected from the group consisting of cobalt (Co), nickel (Ni) and iron (Fe) as a main component with respect to the entire ultrafine cemented carbide A hard coating is coated by PVD or CVD on an ultra-fine grained cemented carbide containing 4 to 30 wt % and the total of the hard phase, grain growth inhibiting phase and binder phase is 100 wt %. Unavoidable impurities, that is, impurities that exist in raw materials or are unavoidably mixed in during the manufacturing process, are originally unnecessary, but are allowed in trace amounts and do not affect the characteristics of the product. may be contained in ultrafine-grained cemented carbide.
　この発明による被覆超微粒超硬合金は，基材（母材）となる超微粒超硬合金と，超微粒超硬合金の表面に被覆される硬質被膜とから構成される。超微粒超硬合金は「硬質相」（第１相）と，「粒成長抑制相」（第２相）と，「結合相」（第３相）の３種類の相を含む。これらの３つの相の合計が１００％である。硬質被膜は，物理気相蒸着法（ＰＶＤ）または化学気相蒸着法（ＣＶＤ）を用いて超微粒超硬合金の表面に被覆される。 The coated ultrafine-grained cemented carbide according to the present invention is composed of an ultra-fine-grained cemented carbide serving as a base material (base material) and a hard coating that coats the surface of the ultra-fine-grained cemented carbide. Ultrafine-grained cemented carbide includes three types of phases: a "hard phase" (first phase), a "grain growth inhibition phase" (second phase), and a "binder phase" (third phase). The sum of these three phases is 100%. The hard coating is applied to the surface of the ultra-fine grained cemented carbide using physical vapor deposition (PVD) or chemical vapor deposition (CVD).
　この発明の被覆超微粒超硬合金はＴｉ（Ｃ，Ｎ）を含む。Ｔｉ（Ｃ，Ｎ）は硬質相であるＷＣの粒成長を抑制する作用ないし効果を生じさせるが，これに加えて，ＰＶＤまたはＣＶＤを用いて硬質被膜を被覆したときに超微粒超硬合金と硬質被膜の密着性を向上させる作用ないし効果も生じさせ，これによって耐摩耗性に優れた被覆超微粒超硬合金を得ることができる。後述するドリルおよびインサートチップを用いた切削試験（穴あけ試験および旋削試験）によると，この発明による被覆超微粒超硬合金は，従来の被覆超微粒超硬合金（この発明による被覆超微粒超硬合金の基材として用いられる超微粒超硬合金と異なる従来の超微粒超硬合金または超硬合金に，この発明の被覆超微粒超硬合金が備える硬質被膜を被覆したもの）に比べて優れた耐摩耗性を発揮する。 The coated ultrafine-grained cemented carbide of this invention contains Ti(C,N). Ti (C, N) has the effect of suppressing the grain growth of WC, which is a hard phase. It also produces an action or effect of improving the adhesion of the hard coating, thereby making it possible to obtain a coated ultrafine-grained cemented carbide with excellent wear resistance. According to cutting tests (drilling test and turning test) using drills and insert tips described later, the coated ultrafine-grained cemented carbide according to the present invention is superior to the conventional coated ultrafine-grained cemented carbide (coated ultrafine-grained cemented carbide according to the present invention). The conventional ultrafine-grained cemented carbide or cemented carbide different from the ultra-fine-grained cemented carbide used as the base material is coated with a hard coating provided by the coated ultra-fine-grained cemented carbide of this invention). Exhibits abrasion resistance.
　一実施態様では，上記超微粒超硬合金が，クロム（Ｃｒ）または炭化クロム（Ｃｒ３Ｃ２）を上記結合相全体に対して０．１～２０ｗｔ％含んでいる。ＣｒまたはＣｒ３Ｃ２を含む超微粒超硬合金を用いることで被膜超微粒超硬合金の耐摩耗性がさらに向上することが確認されたものである。さらには，試験によればＣｒ３Ｃ２の含有量を増やすことによって耐摩耗性がより向上することも確認されている。Ｃｒは粒成長抑制相としても機能する。 In one embodiment, the ultrafine-grained cemented carbide comprises chromium (Cr) or chromium carbide (Cr 3 C 2 ) in an amount of 0.1-20 wt% relative to the total binder phase. It was confirmed that the wear resistance of the coated ultrafine-grained cemented carbide is further improved by using the ultrafine-grained cemented carbide containing Cr or Cr 3 C 2 . Furthermore, it has been confirmed by tests that the wear resistance is further improved by increasing the content of Cr 3 C 2 . Cr also functions as a grain growth inhibition phase.
　一実施態様では，上記硬質被膜は上記超微粒超硬合金に含まれる元素を含む。超微粒超硬合金と硬質被膜との間の密着性の向上に寄与すると考えられる。 In one embodiment, the hard coating contains elements contained in the ultrafine grain cemented carbide. It is thought that this contributes to the improvement of the adhesion between the ultrafine cemented carbide and the hard coating.
　好ましくは，上記硬質被膜は，少なくともＴｉまたはＣｒを含む炭化物，窒化物，炭窒化物または酸化物から選択される少なくとも１種類である。上述のように基材（母材）となる超微粒超硬合金は粒成長抑制相としてＴｉ（Ｃ，Ｎ）を含む。また，好ましくは，粒成長抑制相として機能するＣｒまたはＣｒ３Ｃ２も含む。以下に詳述する切削試験結果に基づくと，粒成長抑制相としてのＴｉ（Ｃ，Ｎ）ないしＣｒに含まれる元素と同一の元素であるＴｉまたはＣｒの炭化物，窒化物，炭窒化物または酸化物が，この発明による被覆超微粒超硬合金を構成する基材に良好に密着する硬質被膜に適すると考えられる。 Preferably, the hard coating is at least one selected from carbides, nitrides, carbonitrides and oxides containing at least Ti or Cr. As described above, the ultrafine grained cemented carbide used as the base material (base material) contains Ti(C, N) as a grain growth inhibition phase. It also preferably contains Cr or Cr 3 C 2 which functions as a grain growth inhibiting phase. Based on the cutting test results detailed below, carbides, nitrides, carbonitrides or oxides of Ti or Cr, which are the same elements as those contained in Ti(C, N) or Cr as the grain growth inhibiting phase, It is believed that the material is suitable for a hard coating that adheres well to the substrate constituting the coated ultrafine-grained cemented carbide according to the invention.
　具体的には，上記硬質被膜としては，ＴｉＣ，ＴｉＮ，ＴｉＡｌＮ，ＣｒＡｌＮ，ＴｉＳｉＮ，Ｔｉ（Ｃ，Ｎ）からなる群より選択される少なくとも１種類を用いることができる。複数種類の硬質被膜を超微粒超硬合金の表面に積層させてもよい。 Specifically, at least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN and Ti(C, N) can be used as the hard coating. A plurality of types of hard coatings may be laminated on the surface of the ultrafine cemented carbide.
　超微粒超硬合金に下地としてアルミニウム（Ａｌ）を含有する炭化物，窒化物，炭窒化物もしくは酸化物，またはそれらの複合材を積層してもよい。この場合，硬質被膜は，Ａｌを含有する炭化物，窒化物，炭窒化物または酸化物の上に積層される。逆に，超微粒超硬合金に硬質被膜を積層し，その上からＡｌを含有する炭化物，窒化物，炭窒化物もしくは酸化物，またはそれらの複合材を積層してもよい。硬質被膜およびＡｌを含有する炭化物，窒化物，炭窒化物または酸化物は，２層に限らずに３層以上に積層してもよい。 A carbide, nitride, carbonitride or oxide containing aluminum (Al) or a composite material thereof may be laminated as a base on the ultrafine cemented carbide. In this case, the hard coating is deposited on an Al-containing carbide, nitride, carbonitride or oxide. Conversely, a hard coating may be laminated on an ultrafine cemented carbide, and then a carbide, nitride, carbonitride or oxide containing Al, or a composite material thereof may be laminated thereon. The hard coating and the carbide, nitride, carbonitride or oxide containing Al may be laminated in not only two layers but also three or more layers.
　この発明は，上述した被覆超微粒超硬合金から構成される切削工具（たとえばドリル，インサートチップ）および耐摩耗部材（たとえば金型，ダイス）も提供する。 The present invention also provides cutting tools (eg, drills, insert tips) and wear-resistant members (eg, molds, dies) composed of the above-described coated ultrafine-grained cemented carbide.
ドリルの先端部分の拡大図である。It is an enlarged view of the tip portion of the drill. インサートチップの拡大斜視図である。It is an expansion perspective view of an insert tip. 穴あけ試験の結果を示すもので，被加工材にあけた穴の数とドリルのチゼル摩耗量との関係を示すグラフである。It is a graph showing the results of a drilling test and showing the relationship between the number of holes drilled in a work material and the amount of chisel wear of a drill. 穴あけ試験の結果を示すもので，被加工材にあけた穴の数とドリルの逃げ面摩耗量との関係を示すグラフである。It is a graph showing the results of a drilling test and showing the relationship between the number of holes drilled in a work material and the amount of flank wear of a drill. 穴あけ試験の結果を示すもので，被加工材にあけた穴の数とドリルのマージン摩耗量との関係を示すグラフである。It is a graph showing the results of a drilling test and showing the relationship between the number of holes drilled in a work material and the amount of marginal wear of a drill. 旋削試験の結果を示すもので，切削距離とインサートチップの逃げ面摩耗幅との関係を示すグラフである。It is a graph showing the results of a turning test and showing the relationship between the cutting distance and the flank wear width of the insert tip. インサートチップの拡大断面写真である。It is an enlarged cross-sectional photograph of an insert chip.
　図１はドリルの先端部分（刃部）を拡大して示している。 Fig. 1 shows an enlarged view of the tip (blade) of the drill.
　ドリル１は，先端のチゼル１１，チゼル１１の両側にのびる２つの切れ刃１２，切れ刃１２に連続する逃げ面１３，逃げ面１３に連続する二番取り面１４，二番取り面１４の頂部を形成するマージン１５，および切削材料が流れるすくい面１６を備えている。 The drill 1 has a chisel 11 at the tip, two cutting edges 12 extending on both sides of the chisel 11, a flank 13 continuing to the cutting edge 12, a chamfer 14 continuing to the flank 13, and the top of the chamfer 14. and a rake face 16 through which cutting material flows.
　高速回転するドリル１がその先端から被加工材に押し当てられる。被加工材はチゼル１１およびチゼル１１につながる切れ刃１２によって切削される。ドリル１を被加工材に向けて送り出すことで被加工材が切削され，被加工材にはドリル１の直径に相当する孔があく。 A drill 1 that rotates at high speed is pressed against the workpiece from its tip. A workpiece is cut by a chisel 11 and a cutting edge 12 connected to the chisel 11 . The work material is cut by sending the drill 1 toward the work material, and a hole corresponding to the diameter of the drill 1 is made in the work material.
　チゼル１１および切れ刃１２は被加工材に直接に接触するので次第に摩耗する。チゼル１１および切れ刃１２のみならず，切れ刃１２に連続する逃げ面１３およびマージン１５の摩耗も避けられない。 The chisel 11 and the cutting edge 12 are in direct contact with the workpiece and are gradually worn. Wear of not only the chisel 11 and the cutting edge 12 but also the flank 13 and the margin 15 that are continuous with the cutting edge 12 is unavoidable.
　図２はインサートチップを拡大して示す斜視図である。 FIG. 2 is a perspective view showing an enlarged insert tip.
　インサートチップ２は，切れ刃２１，逃げ面２２およびすくい面２３を備えている。切れ刃２１によって材料が切削され，切削された材料はすくい面２３に沿って流れる。逃げ面２２とすくい面２３の稜線が切れ刃２１となる。高速回転する被加工材の表面にインサートチップ２の切れ刃２１が押し当てられると，被加工材の表面がインサートチップ２によって削り取られる。被加工材の回転軸の軸方向に沿って（被加工材の長手方向に沿って）インサートチップ２を移動させることで，被加工材の表面が旋削される。インサートチップ２についても，切れ刃２１のみならず，切れ刃２１に連続する逃げ面２２も次第に摩耗する。 The insert tip 2 has a cutting edge 21 , a flank 22 and a rake face 23 . Material is cut by the cutting edge 21 and the cut material flows along the rake face 23 . A ridge line between the flank face 22 and the rake face 23 becomes the cutting edge 21 . When the cutting edge 21 of the insert tip 2 is pressed against the surface of the workpiece rotating at high speed, the insert tip 2 scrapes the surface of the workpiece. The surface of the workpiece is turned by moving the insert tip 2 along the axial direction of the rotating shaft of the workpiece (along the longitudinal direction of the workpiece). As for the insert tip 2, not only the cutting edge 21 but also the flank 22 continuing to the cutting edge 21 gradually wears out.
　発明者の検討によれば，以下に説明する超微粒超硬合金に所定の被膜を施した被覆超微粒超硬合金製ドリルないしインサートチップ（開発品）は，従来の超硬合金に所定の被膜を施した被覆超硬合金製ドリルないしインサートチップ（従来品）に比べて耐摩耗性能が大幅に向上することが分かった。以下では，開発品の組成上の特徴を説明するとともに，開発品と従来品のそれぞれについての切削試験結果を説明する。 According to the study of the inventor, the coated ultra-fine grained cemented carbide drill or insert tip (development product) in which a specified coating is applied to the ultra-fine grained cemented carbide described below is a conventional cemented carbide with a specified coating. It was found that the wear resistance performance was greatly improved compared to coated cemented carbide drills or insert tips (conventional products). The compositional characteristics of the developed product and the cutting test results of the developed product and the conventional product are described below.
（超微粒超硬合金について）
　被覆超微粒超硬合金製ドリルないしインサートチップを構成する超微粒超硬合金は，炭化タングステン（ＷＣ）を主成分とする第１相（以下，「ＷＣ相」または包括的に「硬質相」という）と，チタン炭窒化物（Ｔｉ（Ｃ，Ｎ））を主成分とする第２相（以下，包括的に「粒成長抑制相」という）と，コバルト（Ｃｏ），ニッケル（Ｎｉ）および鉄（Ｆｅ）からなる群から選択される少なくとも１種類を含み，かつクロム（Ｃｒ）または炭化クロム（Ｃｒ３Ｃ２）が添加された第３相（以下，包括的に「結合相」という）とを含む，いわゆる炭化タングステン基超硬合金である。硬質相を形成するＷＣの粒径は平均１．０μｍ以下であり，超微粒であるので，特にタングステン基超微粒超硬合金と呼ぶことができる。 (Regarding ultrafine grain cemented carbide)
The ultrafine-grained cemented carbide that constitutes the coated ultra-fine-grained cemented carbide drill or insert tip has a first phase (hereinafter referred to as “WC phase” or generically “hard phase”) mainly composed of tungsten carbide (WC). ), a second phase (hereinafter collectively referred to as “grain growth suppression phase”) mainly composed of titanium carbonitride (Ti (C, N)), cobalt (Co), nickel (Ni) and iron (Fe) and chromium (Cr) or chromium carbide (Cr 3 C 2 ) is added (hereinafter collectively referred to as “binder phase”); It is a so-called tungsten carbide-based cemented carbide containing The grain size of WC that forms the hard phase is 1.0 μm or less on average, and since it is ultra-fine, it can be particularly called a tungsten-based ultra-fine-grained cemented carbide.
　後述するように，上述した粒成長抑制相を形成するＴｉ（Ｃ，Ｎ）は出発材料としては用いられず，出発材料としてはチタン酸化物（ＴｉＯ２）が用いられる。超微粒超硬合金の製造工程の一つである焼結処理においてＴｉＯ２が炭窒化されることによってＴｉ（Ｃ，Ｎ）が生成され，これが最終的に作製される超微粒超硬合金の組成の一つとなる。 As will be described later, Ti(C,N), which forms the grain growth inhibiting phase, is not used as the starting material, and titanium oxide (TiO 2 ) is used as the starting material. In the sintering process, which is one of the manufacturing processes for ultrafine-grained cemented carbide, TiO2 is carbonitrided to generate Ti(C,N), which is the composition of the final ultra-fine-grained cemented carbide. be one of
（１）硬質相（ＷＣ相）の含有量
　ＷＣ相は，超微粒超硬合金全体に対して７０ｗｔ％未満になると，相対的に結合相が多くなり，ＷＣ相の粒成長の制御が困難となり，超微粒超硬合金の硬さが低下することから，ＷＣ相は超硬合金全体に対して７０～９９．４ｗｔ％とされる。この要件を達成するためにはこの範囲に入る量の原料粉末を配合すれば良い。その中でもＷＣ相を超微粒超硬合金全体に対して８０～９５ｗｔ％とするとさらに好ましい。ＷＣ平均粒径が大きいと超微粒超硬合金の硬さと強度が低下することから，ＷＣ平均粒径は１．０μｍ以下であるのが好ましい。 (1) Content of hard phase (WC phase) When the content of the WC phase is less than 70 wt% in the entire ultrafine-grained cemented carbide, the binder phase becomes relatively large, making it difficult to control the grain growth of the WC phase. , the WC phase is made 70 to 99.4 wt% of the entire cemented carbide because the hardness of the ultra-fine grained cemented carbide is lowered. In order to achieve this requirement, the raw material powder should be blended in an amount falling within this range. Among them, it is more preferable to make the WC phase 80 to 95 wt% of the entire ultrafine cemented carbide. If the WC average grain size is large, the hardness and strength of the ultrafine cemented carbide are lowered, so the WC average grain size is preferably 1.0 μm or less.
（２）粒成長抑制相の含有量
　粒成長抑制相を含ませる理由の一つは，上述したようにＷＣ相の粒成長を抑制し，ＷＣ相を超微粒に維持するためである。ＷＣ相の成長とは焼結時に結合相に溶解したＷＣ相が他のＷＣ相に析出することによって直径の大きな粒子に成長する現象である。粒成長抑制相としてのＴｉ（Ｃ，Ｎ）を添加することによってＷＣ相の周囲にＴｉ（Ｃ，Ｎ）が点在し，これによってＷＣ相析出量が減少することでＷＣ相の粒成長が抑制されると考えられている。 (2) Content of Grain Growth Suppression Phase One of the reasons for including the grain growth suppression phase is to suppress the grain growth of the WC phase and maintain the WC phase as ultrafine grains as described above. The WC phase growth is a phenomenon in which the WC phase dissolved in the binder phase during sintering precipitates in other WC phases and grows into particles with a large diameter. By adding Ti(C,N) as a grain growth inhibitor phase, Ti(C,N) is scattered around the WC phase. considered to be suppressed.
　粒成長抑制相は，ＷＣ相の粒成長を効果的に抑制するのに適する量，すなわち超微粒超硬合金中全体に対して，０．１ｗｔ％以上３０ｗｔ％以下とされる。十分な粒成長抑制効果を得るためには少ない添加量で多数の粒成長抑制相が必要であり，この要求を満たすために粒成長抑制相は微粒であることが好ましい。このため，粒成長抑制相は平均粒径が５～５００ｎｍの範囲がよい。粒成長抑制相の平均粒径が５００ｎｍを越えると，多量に添加しなければ十分な粒成長抑制効果が得られず，強度と硬度を高い水準で両立することが困難となる。また５ｎｍ未満の炭窒化物相は粉末混合中に凝集してしまい強度の低下を招く。 The grain-growth-suppressing phase is in an amount suitable for effectively suppressing the grain growth of the WC phase, that is, 0.1 wt % or more and 30 wt % or less with respect to the entire ultrafine-grained cemented carbide. In order to obtain a sufficient grain growth inhibiting effect, a large number of grain growth inhibiting phases are required with a small amount of addition, and in order to satisfy this requirement, the grain growth inhibiting phases are preferably fine grains. Therefore, the grain growth inhibiting phase should preferably have an average grain size in the range of 5 to 500 nm. If the average grain size of the grain growth inhibiting phase exceeds 500 nm, a sufficient grain growth inhibiting effect cannot be obtained unless a large amount is added, making it difficult to achieve both high levels of strength and hardness. Also, the carbonitride phase of less than 5 nm agglomerates during powder mixing, resulting in a decrease in strength.
　Ｔｉ（Ｃ，Ｎ）については，上述のように出発材料としては用いられず，出発材料としてはチタン酸化物（ＴｉＯ２）が用いられ，これを焼結中に炭窒化させることによってＴｉ（Ｃ，Ｎ）が生成される。これは，超微粒超硬合金に微細な粒成長抑制相を含有させ，少ない含有量でＷＣ相の粒成長を効果的に抑制するためである。 Ti(C,N) is not used as a starting material as described above, but titanium oxide (TiO 2 ) is used as a starting material, which is carbonitrided during sintering to produce Ti(C , N) are generated. This is because the ultrafine-grained cemented carbide contains a fine grain-growth-suppressing phase, and the grain growth of the WC phase is effectively suppressed with a small content.
（３）結合相の含有量
　結合相は硬くかつ超微粒のＷＣ粒子を結合するために用いられる。 (3) Binder Phase Content The binder phase is used to bind hard and ultrafine WC particles.
　結合相にはＣｏ，ＮｉまたはＦｅを用いることができ，これらを混合した合金を用いることもできる。結合相はこれらの金属元素を主成分（結合相全体に対して５０ｗｔ％以上含む）とする金属である。 　Co, Ni or Fe can be used for the binder phase, and an alloy in which these are mixed can also be used. The binder phase is a metal containing these metal elements as a main component (containing 50 wt % or more of the entire binder phase).
　結合相が超微粒超硬合金全体に対して０．４ｗｔ％未満になると超微粒超硬合金の抗折力が低下し，３０ｗｔ％を超えると超微粒超硬合金の硬さが低下する。これらの観点から結合相は超微粒超硬合金全体に対して０．４～３０ｗｔ％含むのが好ましい。結合相によってＷＣ粒子同士をしっかりと結合させることで，超微粒超硬合金からのＷＣ粒子の脱落が防止され，超微粒超硬合金の強度を確保することができる。 When the binder phase is less than 0.4 wt% of the entire ultrafine-grained cemented carbide, the bending strength of the ultrafine-grained cemented carbide is lowered, and when it exceeds 30wt%, the hardness of the ultrafine-grained cemented carbide is lowered. From these points of view, it is preferable that the binder phase is contained in an amount of 0.4 to 30 wt % with respect to the entire ultrafine cemented carbide. By firmly bonding the WC grains together with the binder phase, the WC grains are prevented from falling off from the ultrafine-grained cemented carbide, and the strength of the ultra-fine-grained cemented carbide can be ensured.
（４）ＣｒまたはＣｒ３Ｃ２の含有量
　ＣｒまたはＣｒ３Ｃ２は，ＷＣ相の粒成長抑制および炭窒化物の成長抑制のために用いられる。また，Ｃｒ３Ｃ２は結合相の硬さおよび耐酸化性の向上にも寄与することが知られている。ＣｒまたはＣｒ３Ｃ２が結合相全体に対して０．１ｗｔ％以上含まれると，結合相の硬さ，強度および耐酸化性が向上し，ＷＣ相の粒成長が抑制され，超硬合金の硬さおよび強度が向上する。結合相にＣｒまたはＣｒ３Ｃ２を十分に溶解するために，ＣｒまたはＣｒ３Ｃ２は結合相に対して２０ｗｔ％以下とされる。 (4) Content of Cr or Cr 3 C 2 Cr or Cr 3 C 2 is used to suppress grain growth of the WC phase and growth of carbonitrides. It is also known that Cr 3 C 2 contributes to improving the hardness and oxidation resistance of the binder phase. When Cr or Cr 3 C 2 is contained in an amount of 0.1 wt% or more based on the entire binder phase, the hardness, strength and oxidation resistance of the binder phase are improved, grain growth of the WC phase is suppressed, and cemented carbide is improved. Improves hardness and strength. In order to sufficiently dissolve Cr or Cr 3 C 2 in the binder phase, Cr or Cr 3 C 2 should be 20 wt % or less with respect to the binder phase.
　超微粒超硬合金の製造方法の一例を説明する。原料粉として平均粒径０．０５～２．０μｍのＷＣを超微粒超硬合金に対して７０～９９．４ｗｔ％になるように秤量し，ＴｉＯ２を超微粒超硬合金に対して０．１～３０ｗｔ％になるように秤量する。また結合相として，Ｃｏ，ＮｉおよびＦｅから成る群より選択された少なくとも１種類を主成分とする金属およびＣｒまたはＣｒ３Ｃ２を，焼結後のＷＣ相と粒成長抑制相と結合相の合計が１００ｗｔ％となるように秤量する。焼結後に遊離炭素や脱炭相を生じないように原料粉末に１ｗｔ％以下の炭素粉末または１ｗｔ％以下のタングステン粉末を加えてもよい。これらを有機溶剤とともにボールミルまたはアトライタに投入し，所定の時間にわたって混合および粉砕する。その後，乾燥を経て所定の形状，たとえばドリル１の形状に成形する。 An example of a method for producing an ultrafine cemented carbide will be described. WC having an average particle diameter of 0.05 to 2.0 μm was weighed as a raw material powder so as to be 70 to 99.4 wt % with respect to the ultrafine cemented carbide, and TiO 2 was added to the ultrafine cemented carbide at 0.0%. It is weighed so as to be 1 to 30 wt%. In addition, as a binder phase, a metal containing at least one selected from the group consisting of Co, Ni and Fe as a main component and Cr or Cr 3 C 2 is used as the WC phase, the grain growth inhibition phase and the binder phase after sintering. Weigh so that the total is 100 wt%. 1 wt % or less of carbon powder or 1 wt % or less of tungsten powder may be added to the raw material powder so as not to generate free carbon or a decarburized phase after sintering. These are put into a ball mill or an attritor together with an organic solvent, and mixed and pulverized for a predetermined time. After that, it is dried and formed into a predetermined shape, for example, the shape of the drill 1 .
　窒素雰囲気中で，１３００～１５００℃の温度で６０～１２０分成形品を焼結する。これにより添加したＴｉＯ２は材料中の炭素と焼結時の窒素とによって炭窒化される（Ｔｉ（Ｃ，Ｎ））。 The molding is sintered in a nitrogen atmosphere at a temperature of 1300-1500° C. for 60-120 minutes. The TiO 2 thus added is carbonitrided by carbon in the material and nitrogen during sintering (Ti(C,N)).
（被膜について）
　上述の工程を経ることで作られた超微粒超硬合金製成形品，たとえばドリル１またはインサートチップ２に被膜が被覆される。被膜には，少なくともＴｉまたはＣｒを含む炭化物，窒化物，炭窒化物および酸化物からなる群より選択される少なくとも１種類が用いられる。 (About coating)
A super-fine cemented carbide molded product, such as a drill 1 or an insert tip 2, which has been produced through the above steps, is coated with a coating. At least one selected from the group consisting of carbides, nitrides, carbonitrides and oxides containing at least Ti or Cr is used for the coating.
　より具体的には，ＴｉＣ，ＴｉＮ，ＴｉＡｌＮ，ＣｒＡｌＮ，ＴｉＳｉＮ，Ｔｉ（Ｃ，Ｎ）からなる群より選択される少なくとも１種類が被膜に用いられる。これらの被膜は，上述した超微粒超硬合金に粒成長抑制相として含まれるＴｉ（Ｃ，Ｎ），Ｃｒと同一元素（すなわちＴｉまたはＣｒ）を含み，このために上述した超微粒超硬合金との密着性に優れ，ドリル１またはインサートチップ２に代表される切削工具，金型やダイスに代表される耐摩耗部材（工具）に必要とされる耐摩耗性が向上すると考えられる。ＴｉＣ，ＴｉＮ，ＴｉＡｌＮ，ＣｒＡｌＮ，ＴｉＳｉＮ，Ｔｉ（Ｃ，Ｎ）のうちの複数種類を，超微粒超硬合金に積層してもよい。また，超微粒超硬合金に下地としてＡｌ２Ｏ３を成膜し，Ａｌ２Ｏ３の表面にさらに上述した被膜のいずれか（複数でもよい）を成膜することで２層以上の多層構造の被膜を形成してもよい。Ａｌを含有する酸化物であるＡｌ２Ｏ３に代えて，Ａｌを含有する炭化物，窒化物もしくは炭窒化物，またはそれらの複合材を積層してもよい。逆に超微粒超硬合金にＴｉＣ，ＴｉＮ，ＴｉＡｌＮ，ＣｒＡｌＮ，ＴｉＳｉＮ，Ｔｉ（Ｃ，Ｎ）からなる群より選択される少なくとも１種類を被膜し，その上からＡｌを含有する酸化物，炭化物，窒化物もしくは炭窒化物，またはそれらの複合材を積層してもよい。被膜は２層に限らず３層以上に積層することもできる。 More specifically, at least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN and Ti(C, N) is used for the coating. These coatings contain the same elements (that is, Ti or Cr) as Ti (C, N) and Cr contained as grain growth inhibition phases in the above-described ultrafine-grained cemented carbide. It is thought that the abrasion resistance required for cutting tools such as the drill 1 or the insert tip 2 and abrasion resistant members (tools) such as molds and dies is improved. A plurality of types of TiC, TiN, TiAlN, CrAlN, TiSiN, and Ti(C, N) may be laminated on the superfine grain cemented carbide. In addition, a multilayer structure of two or more layers is formed by forming an Al 2 O 3 film as a base on an ultrafine cemented carbide, and further forming one of the above-described coatings (may be more than one) on the surface of the Al 2 O 3 may form a coating. Al-containing carbides, nitrides, carbonitrides, or composites thereof may be laminated instead of Al 2 O 3 , which is an Al-containing oxide. Conversely, an ultrafine cemented carbide is coated with at least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN, and Ti(C, N), and then Al-containing oxides, carbides, Nitrides, carbonitrides, or composites thereof may be laminated. The coating is not limited to two layers, and three or more layers may be laminated.
　上述した被膜（下地を含む）の成膜には，物理気相蒸着法（ＰＶＤ）（たとえば，イオンプレーティング法，スパッタリング法）を用いてもよいし，化学気相蒸着法（ＣＶＤ）を用いてもよい。いずれにしても全体に均等な厚さの被膜が成膜される。典型的には１μｍ～２０μｍ程度の層厚により被膜は成膜される。 Physical vapor deposition (PVD) (e.g., ion plating, sputtering) may be used to form the coating (including the base) described above, or chemical vapor deposition (CVD) may be used. may In any case, a coating having a uniform thickness is formed over the entire surface. The coating is typically deposited with a layer thickness of the order of 1 μm to 20 μm.
（穴あけ試験）
　表１は穴あけ試験に使用した５種類の被覆超微粒超硬合金製または被覆超硬合金製ドリル１（実施例１および２，比較例１～３）を構成する超微粒超硬合金または超硬合金の組成（成分ごとの量），ならびに焼結後のＷＣ粒径，硬さおよび平均抗折力を示している。ＷＣの量に記載の「bal.」は残部量であることを表す。結合相としてのＣｏの量は実施例１～２および比較例１～３において統一している。 (Drilling test)
Table 1 shows five types of coated ultrafine cemented carbide or coated cemented carbide drills 1 (Examples 1 and 2, Comparative Examples 1 to 3) used in the drilling test. The composition of the alloy (amount of each component) is shown, as well as the WC grain size, hardness and average transverse rupture strength after sintering. "bal." described in the amount of WC represents the balance amount. The amount of Co as the binder phase is uniform in Examples 1-2 and Comparative Examples 1-3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　焼結後のＷＣ粒径の測定にはインターセプト法を用いた。硬さはロックウェル硬度計（Ａスケール）を用いて測定した。平均抗折力は３点曲げ試験により測定した。 The intercept method was used to measure the WC grain size after sintering. Hardness was measured using a Rockwell hardness tester (A scale). The average transverse rupture strength was measured by a three-point bending test.
　実施例１および２の超微粒超硬合金はいずれも硬質相としてＷＣを含み，粒成長抑制相としてＴｉ（Ｃ，Ｎ）を含み，結合相としてＣｏを含み，さらにＣｒ３Ｃ２が添加された，上述した超微粒超硬合金である。表１において，ＷＣ，Ｔｉ（Ｃ，Ｎ），Ｃｏ，および後述するＶＣについては超硬合金全体を基準とする量を示している。Ｃｒ３Ｃ２は結合相（ここではＣｏ）を基準とする量を示している。実施例１と実施例２ではＣｒ３Ｃ２の量が異なっている。 The ultrafine-grained cemented carbides of Examples 1 and 2 both contain WC as a hard phase, Ti(C,N) as a grain growth inhibiting phase, Co as a binder phase, and further Cr 3 C 2 is added. In addition, it is the above-mentioned ultrafine-grained cemented carbide. In Table 1, the amounts of WC, Ti(C, N), Co, and VC, which will be described later, are based on the entire cemented carbide. Cr 3 C 2 indicates the amount based on the binder phase (here Co). Examples 1 and 2 differ in the amount of Cr 3 C 2 .
　実施例１および２の超微粒超硬合金がいずれも粒成長抑制相としてＴｉ（Ｃ，Ｎ）を含むのに対し，比較例１～比較例３の超微粒超硬合金ないし超硬合金はＴｉ（Ｃ，Ｎ）を含まない。比較例１の超微粒超硬合金は粒成長抑制相として炭化バナジウム（ＶＣ）を含む。比較例２の超微粒超硬合金はＴｉ（Ｃ，Ｎ）およびＶＣのいずれも含まず，その結果として焼結後のＷＣ粒径がやや大きい（０．８１μｍ）。比較例３の超硬合金はさらにＣｒ３Ｃ２も含まず，その結果焼結後のＷＣ粒径がさらに大きいものとなっている（１．７２μｍ）。 While the ultrafine-grained cemented carbides of Examples 1 and 2 both contain Ti (C, N) as a grain growth inhibiting phase, the ultra-fine-grained cemented carbides and cemented carbides of Comparative Examples 1 to 3 contain Ti Does not contain (C, N). The ultrafine-grained cemented carbide of Comparative Example 1 contains vanadium carbide (VC) as a grain growth inhibitory phase. The ultrafine-grained cemented carbide of Comparative Example 2 contains neither Ti(C,N) nor VC, resulting in a rather large WC grain size after sintering (0.81 μm). The cemented carbide of Comparative Example 3 also does not contain Cr 3 C 2 , resulting in a larger WC grain size after sintering (1.72 μm).
　硬さに着目すると，実施例２の超微粒超硬合金および比較例１の超微粒超硬合金が比較的優れている。他方，実施例２の超微粒超硬合金と比較例１の超微粒超硬合金の平均抗折力に着目すると，実施例２の超微粒超硬合金の平均抗折力が大きく，実施例２の超微粒超硬合金の方が比較例１に比べてバランスのよい超硬合金となっている。 Focusing on hardness, the ultrafine-grained cemented carbide of Example 2 and the ultra-fine-grained cemented carbide of Comparative Example 1 are relatively excellent. On the other hand, focusing on the average transverse rupture strength of the ultrafine-grained cemented carbide of Example 2 and the ultrafine-grained cemented carbide of Comparative Example 1, the average transverse rupture strength of the ultrafine-grained cemented carbide of Example 2 is large, and the average transverse rupture strength of Example 2 is large. The ultra-fine grained cemented carbide has a better balance than Comparative Example 1.
　図３～図５は，上述した５種類の超微粒超硬合金または超硬合金を用いて直径６ｍｍのドリルを作製し，これに物理気相蒸着法（ＰＶＤ）を用いてＴｉＡｌＮを被覆した５種類のドリル１を用いた穴あけ試験の試験結果を示している。図３～図５に示すグラフにおいて横軸はドリル１を用いて被加工材に開けた穴の数である。縦軸については，図３はチゼル１１の摩耗量（ｍｍ）を，図４は逃げ面１３の摩耗量（ｍｍ）を，図５はマージン１５の摩耗量（ｍｍ）を，それぞれ示している。図３～図５のグラフには，実施例１および実施例２の超微粒超硬合金を用いて作製した被覆超微粒超硬合金製ドリル１（開発品）のグラフが実線により，比較例１～３の超微粒超硬合金ないし超硬合金を用いて作製した被覆超硬合金製ドリル（従来品）のグラフが破線によって，それぞれ示されている。 3 to 5 show drills with a diameter of 6 mm using the five types of ultrafine cemented carbides or cemented carbides described above, which are coated with TiAlN using physical vapor deposition (PVD). 1 shows the test results of a drilling test using a drill of type 1; In the graphs shown in FIGS. 3 to 5, the horizontal axis represents the number of holes drilled in the workpiece using the drill 1. FIG. 3 shows the wear amount (mm) of the chisel 11, FIG. 4 shows the wear amount (mm) of the flank 13, and FIG. 5 shows the wear amount (mm) of the margin 15, respectively. In the graphs of FIGS. 3 to 5, the graphs of coated ultrafine-grained cemented carbide drill 1 (developed product) produced using the ultrafine-grained cemented carbide of Examples 1 and 2 are shown by solid lines, and the graphs of Comparative Example 1 are shown by solid lines. Graphs of coated cemented carbide drills (conventional products) made using ultrafine cemented carbide or cemented carbide of No. 1 to 3 are indicated by dashed lines, respectively.
　穴あけ試験では被加工材（被削材）としてＳ５０Ｃ（ＨＲＣ３４）を用いた。被加工材をノンステップで穿孔し，被加工材に深さ２０ｍｍの止まり穴を次々とあけた。穿孔中，外部から水溶性クーラントを適宜供給した。ドリル１の回転数は４７００ｒｐｍ，送り量は６００ｍｍ／ｍｉｎとした。 In the drilling test, S50C (HRC34) was used as the work material (work material). The workpiece was drilled in a non-step manner, and blind holes with a depth of 20 mm were drilled one after another in the workpiece. Water-soluble coolant was appropriately supplied from the outside during drilling. The rotational speed of the drill 1 was 4700 rpm, and the feed rate was 600 mm/min.
　図３～図５のグラフの終点はドリル１が寿命に達したためにそこで穴あけ試験を終了したことを示している。ここではドリル１の寿命（穴あけ試験の終了）を０．３ｍｍ以上の逃げ面摩耗が発生したときとした（図４）。ドリル１の寿命判断には，逃げ面摩耗の他，ドリル１の折損発生，０．５ｍｍ以上のカケ発生，切削くずの形状異常の発生，切削時の異音発生なども考えられる。 　The end point of the graphs in Figures 3 to 5 indicates that the drilling test was terminated there because the drill 1 reached the end of its life. Here, the life of the drill 1 (end of the drilling test) was determined when 0.3 mm or more of flank wear occurred (Fig. 4). In determining the life of the drill 1, in addition to flank wear, the occurrence of breakage of the drill 1, the occurrence of chips of 0.5 mm or more, the occurrence of abnormal shapes of cutting waste, the occurrence of abnormal noise during cutting, etc. can be considered.
　寿命に達したとき（０．３ｍｍ以上の逃げ面摩耗が発生したとき）の穴数は，実施例１の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金製ドリル１は約２０００，実施例２の超微粒超硬合金を用いると約２５００，比較例１の超微粒超硬合金を用いると約１３００，比較例２の超微粒超硬合金を用いると約１２００，比較例３の超硬合金を用いると約９００であった。 The number of holes at the end of the life (when flank wear of 0.3 mm or more occurs) was about 2000 for the coated ultra-fine grain cemented carbide drill 1 in which the ultra-fine grain cemented carbide was coated with TiAlN in Example 1. , about 2500 when using the ultrafine-grained cemented carbide of Example 2, about 1300 when using the ultrafine-grained cemented carbide of Comparative Example 1, about 1200 when using the ultrafine-grained cemented carbide of Comparative Example 2, and about 1200 when using the ultrafine-grained cemented carbide of Comparative Example 3. It was about 900 with cemented carbide.
　図３～図５を参照して，実施例１，２の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金製ドリル１は，比較例１～３の超微粒超硬合金ないし超硬合金にＴｉＡｌＮを被覆したドリルに比べて耐摩耗性にかなり優れ，特に実施例２の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金製ドリル１が優れていることが分かった。基材（母材）となる超微粒超硬合金と被覆されるＴｉＡｌＮとに同一元素（Ｔｉ）が含まれるために両者の密着性が良好になって寿命が伸びたと考えられる。また，実施例１と実施例２とを比較すると，Ｃｒ３Ｃ２の添加量が多い実施例２の方が実施例１よりも寿命が伸びており，Ｃｒ３Ｃ２の添加量が被覆超微粒超硬合金製ドリル１の耐摩耗性の向上に寄与することも確認される。結合相全体に対して５．０ｗｔ％以上のＣｒ３Ｃ２を含有させることで耐摩耗性が十分に向上すると考えられる。 3 to 5, coated ultrafine cemented carbide drills 1 in which the ultrafine cemented carbides of Examples 1 and 2 are coated with TiAlN are the ultrafine cemented carbide drills of Comparative Examples 1 to 3. Compared to the hard alloy TiAlN-coated drill, the wear resistance is considerably superior, and it was found that the coated ultra-fine-grained cemented carbide drill 1 in which the ultra-fine-grained cemented carbide is coated with TiAlN in Example 2 is particularly superior. . It is considered that the same element (Ti) is contained in the ultrafine cemented carbide serving as the base material (base material) and the TiAlN coating, so that the adhesion between the two is improved and the life is extended. Further, when comparing Example 1 and Example 2, Example 2 with a larger amount of Cr 3 C 2 added has a longer life than Example 1, and the amount of Cr 3 C 2 added exceeds the coating. It is also confirmed that it contributes to the improvement of the wear resistance of the fine-grain cemented carbide drill 1 . It is believed that containing 5.0 wt % or more of Cr 3 C 2 with respect to the entire binder phase sufficiently improves the wear resistance.
（旋削試験）
　表２は，旋削試験に使用した４種類の被覆超微粒超硬合金製インサートチップ（実施例３，４および比較例４，５）を構成する超微粒超硬合金の組成（量），ならびに焼結後のＷＣ粒径，硬さおよび平均抗折力を示している。比較例４，５は市販の超硬合金であり，平均抗折力は測定できていない。 (Turning test)
Table 2 shows the composition (amount) of the ultrafine-grained cemented carbide that constitutes the four types of coated ultra-fine-grained cemented carbide insert tips (Examples 3 and 4 and Comparative Examples 4 and 5) used in the turning test, and the sintered material. WC grain size, hardness and average transverse rupture strength after binding are shown. Comparative Examples 4 and 5 are commercially available cemented carbides, and the average transverse rupture strength could not be measured.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例３および４はいずれも硬質相としてＷＣを含み，粒成長抑制相としてＴｉ（Ｃ，Ｎ）を含み，結合相としてＣｏを含み，さらにＣｒ３Ｃ２が添加された，上述した超微粒超硬合金である。表２においてもＴｉ（Ｃ，Ｎ），Ｃｏおよび後述するＴａＣについては超硬合金全体を基準とする量を示し，Ｃｒ３Ｃ２については結合相を基準とする量を示している。実施例３と実施例４は同一組成を持つ超微粒超硬合金であるが，別サンプル（別々に製造した超微粒超硬合金）である。 Examples 3 and 4 both contain WC as the hard phase, Ti(C,N) as the grain growth inhibiting phase, Co as the binder phase, and further the above-described ultrafine grains with the addition of Cr3C2 . Cemented carbide. Table 2 also shows the amount of Ti(C, N), Co and TaC described later based on the entire cemented carbide, and the amount of Cr 3 C 2 based on the binder phase. Examples 3 and 4 are ultrafine-grained cemented carbides having the same composition, but are different samples (separately produced ultrafine-grained cemented carbides).
　実施例３および４の超微粒超硬合金がいずれも粒成長抑制相としてＴｉ（Ｃ，Ｎ）を含むのに対し，比較例４の超微粒超硬合金はＴｉ（Ｃ，Ｎ）を含まず，粒成長抑制相として炭化タンタル（ＴａＣ）を含む。また，Ｃｒ３Ｃ２を含まない。比較例５の超微粒超硬合金はＴｉ（Ｃ，Ｎ）もＴａＣも含まずに粒成長抑制相としてＣｒ３Ｃ２を含む。また，比較例５については，次に説明する被膜についてＴｉＡｌＮとＣｒＡｌＮの２層構造を採用した。 The ultrafine-grained cemented carbides of Examples 3 and 4 both contain Ti(C,N) as a grain growth inhibition phase, whereas the ultrafine-grained cemented carbide of Comparative Example 4 does not contain Ti(C,N). , containing tantalum carbide (TaC) as a grain growth inhibition phase. Moreover, it does not contain Cr 3 C 2 . The ultrafine-grained cemented carbide of Comparative Example 5 does not contain Ti(C,N) or TaC, but contains Cr 3 C 2 as a grain growth inhibiting phase. Also, in Comparative Example 5, a two-layer structure of TiAlN and CrAlN was adopted for the coating described below.
　図６は，上述の４種類の超微粒超硬合金を用いて図２に示す形状のインサートチップを作製し，これに物理気相蒸着法（ＰＶＤ）を用いてＴｉＡｌＮ（実施例３，４および比較例４）を被覆した３種類のインサートチップ２（実施例３，４および比較例４）と，ＴｉＡｌＮおよびＣｒＡｌＮを被覆した１種類のインサートチップ２（比較例５）を用いた旋削試験の試験結果を示している。図６のグラフにおいて横軸は切削距離を，縦軸は逃げ面２２の摩耗幅（ｍｍ）を示している。図６のグラフには，実施例３および４の超微粒超硬合金を用いて作製した被覆超微粒超硬合金製インサートチップ２（開発品）のグラフが実線によって，比較例４および５の超微粒超硬合金を用いて作製した被覆超微粒超硬合金製インサートチップ（従来品）のグラフが破線によって，それぞれ示されている。 Fig. 6 shows that insert chips having the shape shown in Fig. 2 were produced using the four types of ultrafine cemented carbide described above, and TiAlN (Examples 3, 4 and Test of turning test using three types of insert tips 2 (Examples 3, 4 and Comparative Example 4) coated with Comparative Example 4) and one type of insert tip 2 (Comparative Example 5) coated with TiAlN and CrAlN shows the results. In the graph of FIG. 6, the horizontal axis indicates the cutting distance, and the vertical axis indicates the wear width (mm) of the flank 22 . In the graph of FIG. 6, the graph of the coated ultrafine-grained cemented carbide insert tip 2 (development product) produced using the ultrafine-grained cemented carbide of Examples 3 and 4 is shown by the solid line, and the graph of the ultrafine-grained cemented carbide of Comparative Examples 4 and 5 is shown by the solid line. Graphs of a coated ultrafine-grained cemented carbide insert chip (conventional product) manufactured using a fine-grained cemented carbide are indicated by dashed lines.
　旋削試験では，被加工材（被削材）として直径８０ｍｍのＳ４５Ｃ製のみがき丸棒を用いた。切削速度は１６０ｍ／ｍｉｎ，送り量は０．２ｍｍ／ｒｅｖ，切込み量は２．０ｍｍとし，旋削中に水溶性切削油を適宜供給した。 In the turning test, a polished round bar made of S45C with a diameter of 80 mm was used as the work material (work material). The cutting speed was 160 m/min, the feed rate was 0.2 mm/rev, and the depth of cut was 2.0 mm, and water-soluble cutting oil was appropriately supplied during turning.
　インサートチップ２の寿命（旋削試験の終了）を０．２ｍｍ以上の逃げ面摩耗が発生したときとした。インサートチップ２の寿命判断には，その他，カケ発生，切削くずの形状異常の発生，切削時の異音発生なども考えられる。 The life of the insert tip 2 (end of the turning test) was determined when flank wear of 0.2 mm or more occurred. In determining the life of the insert tip 2, other factors such as the occurrence of chipping, the occurrence of abnormal shape of cutting waste, and the occurrence of abnormal noise during cutting can be considered.
　寿命に到達したとき（０．２ｍｍ以上の逃げ面摩耗が発生したとき）の切削距離は，実施例３の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金製インサートチップ２は約２２，０００ｍ，実施例４の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金を用いると約２７，０００ｍ，比較例４，５の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金を用いると，いずれも約７，０００ｍであった。実施例３および実施例４の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金製インサートチップ２は，比較例４および５の超微粒超硬合金にＴｉＡｌＮ，またはＴｉＡｌＮおよびＣｒＡｌＮを被覆したインサートチップに比べて耐摩耗性に優れることが分かった。 The cutting distance at the end of the life (when flank wear of 0.2 mm or more occurs) is about 22,000 m, when the coated ultrafine-grained cemented carbide obtained by coating the ultra-fine-grained cemented carbide of Example 4 with TiAlN is used, approximately 27,000 m, the coated ultra-fine-grained cemented carbide of Comparative Examples 4 and 5 coated with TiAlN. Both were about 7,000m when fine-grained cemented carbide was used. The coated ultrafine-grained cemented carbide insert tip 2 in which the ultrafine-grained cemented carbide of Examples 3 and 4 is coated with TiAlN is coated with TiAlN, or TiAlN and CrAlN on the ultrafine-grained cemented carbide of Comparative Examples 4 and 5. It was found that the wear resistance was superior to that of the insert tip that had been treated.
　上述した実施例では被覆超微粒超硬合金製ドリル１および被覆超微粒超硬合金製インサートチップ２に関する試験結果を説明したが，ドリルまたはインサートチップ以外の切削工具または耐摩耗部材についても，従来に比べて耐摩耗性に優れる結果が得ることができる。また，上述した実施例ではＴｉＡｌＮを硬質被膜として用いている。ＴｉＡｌＮ以外のＴｉを含む硬質被膜，具体的には上述したＴｉＣ，ＴｉＮ，ＴｉＳｉＮおよびＴｉ（Ｃ，Ｎ）についても，ＴｉＡｌＮと同等の耐摩耗性の向上に寄与すると考えられる。また，Ｃｒを含むＣｒＡｌＮを硬質被膜に用いても耐摩耗性の向上を図ることができると考えられる。さらには複数種類の硬質被膜を超微粒超合金に積層することも考えられる。なお，ＴｉＡｌＮ，ＴｉＮおよびＴｉ（Ｃ，Ｎ）の３種類の硬質被膜についてそれぞれ同一条件のもとでスクラッチ試験をしたところ，いずれについても膜剥がれは発生せず，これらの３種類について性能差は確認することができなかった。いずれにしても，少なくともＴｉまたはＣｒを元素に含む炭化物，窒化物，炭窒化物または酸化物を硬質被膜として用いれば，上述した超微粒超硬合金と良好に密着し，切削工具ないし耐摩耗部材として用いた場合の寿命が大幅に伸びると考えられる。 In the above-described embodiment, the test results for the coated ultrafine-grained cemented carbide drill 1 and the coated ultrafine-grained cemented carbide insert tip 2 were explained. It is possible to obtain a result that is superior in wear resistance compared to the conventional method. Also, in the above-described embodiment, TiAlN is used as the hard coating. Hard coatings containing Ti other than TiAlN, specifically TiC, TiN, TiSiN and Ti(C, N) mentioned above are also considered to contribute to the same improvement in wear resistance as TiAlN. Also, it is considered that the wear resistance can be improved by using CrAlN containing Cr for the hard coating. Furthermore, it is conceivable to laminate a plurality of types of hard coatings on an ultrafine grained superalloy. In addition, when a scratch test was performed under the same conditions for three types of hard coatings, TiAlN, TiN, and Ti(C, N), no film peeling occurred in any of them, and there was no difference in performance between these three types. could not confirm. In any case, when a carbide, nitride, carbonitride or oxide containing at least Ti or Cr as an element is used as a hard coating, it adheres well to the above-mentioned ultra-fine cemented carbide, cutting tools or wear-resistant members. It is thought that the life when used as a material is greatly extended.
　図７に，上述した実施例３の超微粒超硬合金にＴｉＡｌＮを被覆した被覆超微粒超硬合金製インサートチップ２の拡大断面写真を示しておく。 FIG. 7 shows an enlarged cross-sectional photograph of the coated ultrafine-grained cemented carbide insert chip 2 in which the ultrafine-grained cemented carbide is coated with TiAlN in Example 3 described above.
１　ドリル
２　インサートチップ 1 drill 2 insert tip

Claims (8)

  1. 　平均粒径が１．０μｍ以下であるＷＣを主成分とする硬質相を超微粒超硬合金全体に対して７０～９９．４ｗｔ％含み，
    　Ｔｉの酸化物を焼結中に炭窒化させて生成されるＴｉ（Ｃ，Ｎ）を主成分とする粒成長抑制相を超微粒超硬合金全体に対して０．１～３０ｗｔ％含み，
    　Ｃｏ，ＮｉおよびＦｅからなる群より選択される少なくとも１種類を主成分とする結合相を超微粒超硬合金全体に対して０．４～３０ｗｔ％含み，
    　上記硬質相と粒成長抑制相と結合相との合計が１００ｗｔ％である超微粒超硬合金に，硬質被膜がＰＶＤまたはＣＶＤによって被覆されている，
    　被覆超微粒超硬合金。     70 to 99.4 wt% of a hard phase mainly composed of WC having an average grain size of 1.0 μm or less with respect to the entire ultrafine grain cemented carbide,
    0.1 to 30 wt% of the grain growth inhibiting phase containing Ti (C, N) as a main component produced by carbonitriding Ti oxide during sintering with respect to the entire ultrafine cemented carbide,
    0.4 to 30 wt% of a binder phase mainly composed of at least one selected from the group consisting of Co, Ni and Fe with respect to the entire ultrafine cemented carbide,
    A hard coating is coated by PVD or CVD on the ultrafine grained cemented carbide in which the total of the hard phase, the grain growth suppression phase and the binder phase is 100 wt%,
    Coated ultra-fine grain cemented carbide.
  2. 　ＣｒまたはＣｒ３Ｃ２を上記結合相全体に対して０．１～２０ｗｔ％含む，
    　請求項１に記載の被覆超微粒超硬合金。     Cr or Cr 3 C 2 in an amount of 0.1 to 20 wt% with respect to the entire bonding phase,
    The coated ultrafine-grained cemented carbide according to claim 1.
  3. 　上記硬質被膜が上記超微粒超硬合金に含まれる元素と同一の元素を含む，
    　請求項１または２に記載の被覆超微粒超硬合金。     The hard coating contains the same elements as those contained in the ultrafine-grained cemented carbide,
    The coated ultrafine-grained cemented carbide according to claim 1 or 2.
  4. 　上記硬質被膜が少なくともＴｉまたはＣｒを含む炭化物，窒化物，炭窒化物または酸化物から選択される少なくとも１種類である，
    　請求項１または２に記載の被覆超微粒超硬合金。     The hard coating is at least one selected from carbides, nitrides, carbonitrides or oxides containing at least Ti or Cr,
    The coated ultrafine-grained cemented carbide according to claim 1 or 2.
  5. 　上記硬質被膜が，ＴｉＣ，ＴｉＮ，ＴｉＡｌＮ，ＣｒＡｌＮ，ＴｉＳｉＮ，Ｔｉ（Ｃ，Ｎ）からなる群より選択される少なくとも１種類である，
    　請求項１または２に記載の被覆超微粒超硬合金。     The hard coating is at least one selected from the group consisting of TiC, TiN, TiAlN, CrAlN, TiSiN, and Ti(C, N).
    The coated ultrafine-grained cemented carbide according to claim 1 or 2.
  6. 　上記硬質被膜の下地にまたは上記硬質被膜の表面に，Ａｌを含有する炭化物，窒化物，炭窒化物もしくは酸化物，またはそれらの複合材が積層されている，
    　請求項５に記載の被覆超微粒超硬合金。     Al-containing carbides, nitrides, carbonitrides or oxides, or composites thereof, are laminated on the base of the hard coating or on the surface of the hard coating.
    The coated ultrafine-grained cemented carbide according to claim 5.
  7. 　請求項１に記載の被覆超微粒超硬合金から構成される切削工具。 A cutting tool composed of the coated ultrafine-grained cemented carbide according to claim 1.
  8. 　請求項１に記載の被覆超微粒超硬合金から構成される耐摩耗部材。 A wear-resistant member composed of the coated ultrafine-grained cemented carbide according to claim 1.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153858A1 (en) * 2011-05-12 2012-11-15 株式会社タンガロイ Superhard alloy and coated superhard alloy
JP2017164859A (en) * 2016-03-17 2017-09-21 三菱マテリアル株式会社 Surface coated cutting tool whose hard coating layer exerts excellent chipping resistance and peeling resistance
JP6227517B2 (en) * 2014-11-20 2017-11-08 日本特殊合金株式会社 Cemented carbide
JP2019181586A (en) * 2018-04-03 2019-10-24 株式会社タンガロイ Coated cutting tool
WO2020070978A1 (en) * 2018-10-04 2020-04-09 住友電工ハードメタル株式会社 Cemented carbide alloy, cutting tool containing same, and method for producing cemented carbide alloy
JP6786763B1 (en) * 2019-02-26 2020-11-18 住友電工ハードメタル株式会社 Cutting tools
WO2021144998A1 (en) * 2020-01-14 2021-07-22 日本特殊合金株式会社 Ultrafine cemented carbide, and shearing tool, cutting tool, or abrasion-resistant tool using ultrafine cemented carbide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012153858A1 (en) * 2011-05-12 2012-11-15 株式会社タンガロイ Superhard alloy and coated superhard alloy
JP6227517B2 (en) * 2014-11-20 2017-11-08 日本特殊合金株式会社 Cemented carbide
JP2017164859A (en) * 2016-03-17 2017-09-21 三菱マテリアル株式会社 Surface coated cutting tool whose hard coating layer exerts excellent chipping resistance and peeling resistance
JP2019181586A (en) * 2018-04-03 2019-10-24 株式会社タンガロイ Coated cutting tool
WO2020070978A1 (en) * 2018-10-04 2020-04-09 住友電工ハードメタル株式会社 Cemented carbide alloy, cutting tool containing same, and method for producing cemented carbide alloy
JP6786763B1 (en) * 2019-02-26 2020-11-18 住友電工ハードメタル株式会社 Cutting tools
WO2021144998A1 (en) * 2020-01-14 2021-07-22 日本特殊合金株式会社 Ultrafine cemented carbide, and shearing tool, cutting tool, or abrasion-resistant tool using ultrafine cemented carbide

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