WO2023042777A1 - 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 - Google Patents

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 Download PDF

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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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English (en)
French (fr)
Japanese (ja)
Inventor
友浩 堤
真之 ▲高▼田
秀彰 松原
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Tohoku University NUC
Nippon Tokushu Goukin Co Ltd
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Tohoku University NUC
Nippon Tokushu Goukin Co Ltd
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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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WO2012153858A1 (ja) * 2011-05-12 2012-11-15 株式会社タンガロイ 超硬合金および被覆超硬合金
JP6227517B2 (ja) * 2014-11-20 2017-11-08 日本特殊合金株式会社 超硬合金
JP2017164859A (ja) * 2016-03-17 2017-09-21 三菱マテリアル株式会社 硬質被覆層がすぐれた耐チッピング性、耐剥離性を発揮する表面被覆切削工具
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CN118166258A (zh) * 2024-02-27 2024-06-11 无锡市标准件厂有限公司 一种高强度耐高温合金紧固件及其制备方法

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