WO2012153858A1 - Superhard alloy and coated superhard alloy - Google Patents

Superhard alloy and coated superhard alloy Download PDF

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Publication number
WO2012153858A1
WO2012153858A1 PCT/JP2012/062250 JP2012062250W WO2012153858A1 WO 2012153858 A1 WO2012153858 A1 WO 2012153858A1 JP 2012062250 W JP2012062250 W JP 2012062250W WO 2012153858 A1 WO2012153858 A1 WO 2012153858A1
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Prior art keywords
phase
cemented carbide
carbonitride
volume
group
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PCT/JP2012/062250
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French (fr)
Japanese (ja)
Inventor
健司 船水
木下　聡
修司 上野
幸太郎 古川
賢治 中原
真之 高田
松原　秀彰
哲志 松田
野村　浩
Original Assignee
株式会社タンガロイ
日本タングステン株式会社
日本特殊合金株式会社
一般財団法人ファインセラミックスセンター
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Publication of WO2012153858A1 publication Critical patent/WO2012153858A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • 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

Definitions

  • the present invention relates to a cemented carbide and a coated cemented carbide.
  • the present invention relates to a cemented carbide and a coated cemented carbide that exhibit excellent performance when used as a cutting tool or wear-resistant member.
  • a cemented carbide twist drill composed of a B1 type solid solution phase, a WC phase and a binder phase, 50 to 70 area% of a hard phase composed of tungsten carbide, and a hard phase composed of a B1 type solid solution phase 15 to 30% by area, 15% to 25% by weight of a binder phase made of an iron group metal, and the average particle size in the sintered body is 0.3 to 1.2 microns for the tungsten carbide phase and 0 for the B1 type solid solution phase.
  • a cemented carbide twist drill is known that has a Co lattice constant of 3.565 to 3.575 mm (for example, see Patent Document 1).
  • the ratio Db / Dp between the density Db of the bulk body measured by the gas displacement method and the density Dp of the powder after pulverizing the bulk body to a size passing through # 200 mesh is 0.95
  • a cemented carbide characterized by the above is known (for example, see Patent Document 2).
  • the cemented carbides described in Patent Document 1 and Patent Document 2 described above have larger average particle diameters of the B1 type solid solution phase and ⁇ phase particles than the average particle diameter of the WC phase. Since it is the origin of fracture, there is a problem that toughness, impact resistance and strength are low.
  • the present invention has been made to solve such problems of the prior art, and an object of the present invention is to provide a cemented carbide excellent in impact resistance and wear resistance and a coated cemented carbide with a coating on the surface thereof.
  • the present invention relates to WC phase: 55 to 95% by volume, at least one carbonitride selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W, and their mutual 3.
  • Carbonitride phase comprising at least one selected from the group consisting of solid solutions: 1 to 30% by volume, and a binder phase comprising at least one selected from the group consisting of Co, Ni and Fe as main components: 4. 2 to 22.2% by volume, provided that the total of the WC phase, the carbonitride phase, and the binder phase is 100% by volume, and the average particle size of the WC phase is 0.05 to 0.8 ⁇ m.
  • the average particle diameter of the nitride phase is 0.03 to 1.1 ⁇ m, the density DB of the cemented carbide measured by the gas displacement method and the density of the powder obtained by pulverizing the cemented carbide to a size passing through a sieve with an opening of 75 ⁇ m.
  • the ratio with DP (DB / DP) is 0.95 or more Is a cemented carbide which is characterized in Rukoto.
  • the cemented carbide and the coated cemented carbide of the present invention have the effect of being excellent in impact resistance and wear resistance.
  • the cemented carbide of the present invention has a WC phase: 55 to 94.8% by volume based on the entire cemented carbide, a carbonitride phase: 1 to 30% by volume based on the entire cemented carbide, and a binder phase:
  • the total content of the hard alloy is 4.2 to 22.2% by volume, and the total of the WC phase, the carbonitride phase, and the binder phase is 100% by volume.
  • the WC phase of the present invention is less than 55% by volume with respect to the entire cemented carbide, the carbonitride phase and the binder phase are relatively increased, and it becomes difficult to control the grain growth of the WC phase, so that the hardness of the cemented carbide is reduced. Conversely, when the WC phase exceeds 94.8% by volume with respect to the entire cemented carbide, the carbonitride phase and the binder phase are relatively decreased, and the toughness of the cemented carbide is decreased. Therefore, the WC phase was 55-94.8% by volume with respect to the entire cemented carbide. In order to achieve this requirement, an amount of raw material powder that falls within this range may be blended.
  • the WC phase is more preferably 57 to 90% by volume with respect to the entire cemented carbide, and the WC phase is more preferably 58 to 80% by volume with respect to the entire cemented carbide.
  • Making the average particle size of the WC phase of the present invention less than 0.05 ⁇ m is difficult to produce due to grain growth during sintering, and if the average particle size of the WC phase of the present invention exceeds 0.8 ⁇ m, it is too high. Since the hardness and strength of the hard alloy are lowered, the average particle size of the WC phase of the present invention is determined to be 0.05 to 0.8 ⁇ m. In order to achieve this requirement, a raw material powder having a size within this range after sintering may be used.
  • the average particle diameter of the WC phase is more preferably 0.1 to 0.7 ⁇ m.
  • the carbonitride phase of the present invention is selected from the group consisting of at least one carbonitride selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and their mutual solid solutions It is a carbonitride phase consisting of at least one kind.
  • the carbonitride phase of the present invention improves wear resistance and welding resistance, suppresses grain growth of the WC phase, and improves the hardness and strength of the cemented carbide.
  • the carbonitride phase is a double carbonitride composed of two or more selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W as the metal element.
  • the carbonitride phase is a double carbonitride composed of Ti and at least one selected from the group consisting of Zr, Hf, V, Nb, Ta, Cr, Mo and W. And more preferred.
  • the carbonitride phase of the present invention is less than 1% by volume with respect to the entire cemented carbide, the effect of improving the welding resistance and wear resistance and the effect of suppressing the grain growth of the WC phase are reduced. If the amount exceeds 1% by volume, the WC phase is relatively decreased, and the effect of suppressing the grain growth of the carbonitride phase is lowered. In order to achieve this requirement, an amount of raw material powder that falls within this range may be blended.
  • the carbonitride phase is more preferably 3 to 25% by volume with respect to the entire cemented carbide.
  • Making the average particle size of the carbonitride phase of the present invention less than 0.03 ⁇ m is difficult to suppress because grain growth during sintering is difficult to produce, and the average particle size of the carbonitride phase of the present invention is 1
  • the average particle size of the carbonitride phase of the present invention is set to 0.03 to 1.1 ⁇ m.
  • a raw material powder having a size within this range after sintering may be used.
  • the average particle size of the carbonitride phase is more preferably 0.1 to 0.7 ⁇ m.
  • the binder phase of the present invention is a metal mainly composed of at least one selected from the group consisting of Co, Ni and Fe.
  • the metal having at least one selected from the group consisting of Co, Ni and Fe as the main component is the total of at least one selected from the group consisting of Co, Ni and Fe, and the bonded phase. It means a metal containing 50% by mass or more based on the whole.
  • the binder phase of the present invention preferably contains 70 to 100% by mass of the total amount of at least one selected from the group consisting of Co, Ni and Fe, based on the total binder phase.
  • At least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, C and N is added in an amount of 0 to 30% by mass with respect to the entire binder phase. May be included.
  • the binder phase of the present invention is more preferably made of Co as a main component because it is excellent in heat resistance, toughness, and adhesion to a coating.
  • the binder phase containing Co as a main component of the present invention means a binder phase containing 50 mass% or more of Co with respect to the entire binder phase.
  • the amount of Cr element contained in the binder phase of the present invention is preferably 3 to 11% by mass with respect to the whole binder phase.
  • the binder phase of the present invention When the binder phase of the present invention is less than 4.2% by volume with respect to the entire cemented carbide, the strength and toughness of the cemented carbide are decreased, and when the content exceeds 22.2% by volume, the hardness of the cemented carbide is decreased. Therefore, the binder phase of the present invention was set to 4.2 to 22.2% by volume. In order to achieve this requirement, an amount of raw material powder that falls within this range may be blended. Of these, the binder phase is more preferably 5 to 21% by volume with respect to the entire cemented carbide.
  • the volume ratio of the WC phase, carbonitride phase, and binder phase relative to the entire cemented carbide of the present invention is the WC phase, carbonitriding obtained by observing the polished cross-sectional structure of the cemented carbide with an SEM (scanning electron microscope). It can obtain
  • the average particle size of the WC phase and the carbonitride phase can be calculated from the following Fullman equation (Equation 1) by observing the polished cross-sectional structure of the cemented carbide with an SEM.
  • Equation 1 d m average particle size, [pi is pi, N L is the number of particles per unit length which is hit by an arbitrary straight line on the cross-sectional structure, N S is in any unit area Represents the number of particles contained, and in (Expression 2), n L represents the number of particles hit by an arbitrary straight line on the cross-sectional structure, L represents the length of an arbitrary straight line on the cross-sectional structure, and (Expression 3) ), N S represents the number of particles contained in an arbitrary measurement area, and S represents the area of an arbitrary measurement region.
  • n S is preferably 1000 or more.
  • n S may be set to 1000 or more using a plurality of photos.
  • an arbitrary straight line that divides the SEM photograph into equal parts is drawn, and the number n L of particles hit by the straight line is counted.
  • nL is preferably 3000 or more.
  • n L by using a plurality of photos may be made 3,000 or more.
  • the grain boundaries of WC phase particles and carbonitride phase particles are preferentially etched, making it easy to measure the particle size of WC phase particles and carbonitride phase particles. This is preferable.
  • An example of the polished cross-sectional structure of the cemented carbide of the present invention that has been ion milled is shown in FIG. In FIG. 1, grayish white particles are WC phase particles, grayish black particles are carbonitride phase particles, and gray portions existing between these particles are binder phases.
  • the cemented carbide of the present invention has a ratio (DB / DP) between the density DB of the cemented carbide measured by the gas displacement method and the density DP of the powder obtained by pulverizing the cemented carbide to a size passing through a sieve having an opening of 75 ⁇ m.
  • This is a value for evaluating the amount of pores in the alloy. When this value is large, the pores are few and dense, and when this value is small, the pores are many and not dense.
  • DB / DP is less than 0.95, there are many pores inside the alloy, which decreases hardness and strength, and decreases wear resistance and impact resistance.
  • DB / DP is more preferably 0.98 or more. In order to achieve this requirement, it is preferable to employ the manufacturing method described below.
  • a dry-type automatic densimeter etc. can be mentioned as an apparatus which measures a density with a gas substitution method.
  • the amount of nitrogen contained in the cemented carbide of the present invention exceeds 2.6% by mass with respect to the entire cemented carbide, the sinterability tends to be low and the strength and toughness of the cemented carbide tend to be reduced.
  • the content is less than 0.1% by mass, the effect of suppressing the grain growth of the WC phase tends to be small and the hardness of the cemented carbide tends to be low. Therefore, the amount of nitrogen contained in the cemented carbide of the present invention is The content is more preferably 0.1 to 2.6% by mass with respect to the entire alloy. In order to achieve this requirement, a raw material powder containing nitrogen in an amount falling within this range may be blended. Among these, the nitrogen content is more preferably 0.1 to 2.0% by mass with respect to the entire cemented carbide.
  • a surface layer composed of a WC phase and a binder phase having an average thickness of 5 to 50 ⁇ m is formed from the surface of the cemented carbide of the present invention toward the inside.
  • the molded body made of the raw material powder is used in a so-called denitrification atmosphere in which the nitrogen contained in the cemented carbide is discharged out of the cemented carbide during sintering. Sintering is good.
  • the surface layer composed of the WC phase and the binder phase has a relatively large amount of binder phase compared to the inside of the cemented carbide obtained by removing the surface layer, and has an average thickness from the surface of the cemented carbide to the inside.
  • the average thickness of the surface layer is preferably 5 to 50 ⁇ m.
  • the average thickness of the surface layer is more preferably 9 to 35 ⁇ m.
  • a coated cemented carbide with improved wear resistance and surface lubricity can be obtained by coating the surface of the cemented carbide of the present invention with a coating.
  • the coating consists of at least one selected from the group consisting of metals, metal compounds, diamond and ceramics.
  • it consists of at least one selected from the group consisting of: Specifically, TiC, TiN, TiCN, Al 2 O 3 , TiAlN, TiSiN, AlCrN, (Al, Cr) 2 O 3 and the like can be mentioned.
  • the film configuration of the coating is preferably a single layer or a multilayer of two or more layers. If the total film thickness of the entire film is less than 0.1 ⁇ m in average film thickness, the effect of improving wear resistance and surface lubricity cannot be obtained sufficiently, and if it exceeds 30 ⁇ m, the chipping resistance tends to decrease. Therefore, the total film thickness of the entire film is preferably 0.1 to 30 ⁇ m as an average film thickness. Among these, the total film thickness of the entire film is more preferably 1 to 20 ⁇ m in average film thickness.
  • Examples of the method for producing the cemented carbide of the present invention include the following methods.
  • the ratio between the nitrogen content NP and the carbon content CP of the double carbonitride powder is an important factor for controlling the average particle size of the WC phase, controlling the average particle size of the carbonitride phase, and densifying the cemented carbide.
  • the ratio (NP / (CP + NP)) of the nitrogen amount NP of the double carbonitride powder to the total of the carbon amount CP of the double carbonitride powder and the nitrogen amount NP of the double carbonitride powder is less than 0.2 in atomic ratio. Further, the effect of suppressing the grain growth of the WC phase and the carbonitride phase is not sufficient, and the hardness and strength of the cemented carbide decreases.
  • NP / (CP + NP) is greater than 0.8, the sinterability is reduced and DB / DP is less than 0.95.
  • the NP / (CP + NP) ratio is more preferably 0.3 to 0.6. Also, 1 mass% or less of carbon powder or 1 mass% or less of tungsten powder is added to the raw material powder so that the sintered cemented carbide enters a healthy phase region where free carbon or tungsten cobalt carbide ( ⁇ phase) is not generated. Also good.
  • the mixed raw material powder is mixed and pulverized for 10 to 40 hours using a ball mill or an attritor mill.
  • the obtained mixed powder is formed into a predetermined shape by a method such as pressing.
  • the obtained molded body is put in a sintering furnace and sintered at a sintering temperature of 1300 to 1450 ° C. for a sintering time of 60 to 120 minutes in a vacuum, a nitrogen atmosphere or an inert gas atmosphere. preferable. If the sintering temperature is less than 1300 ° C. or the sintering time is less than 60 minutes, the cemented carbide may not be sufficiently densified and DB / DP may be less than 0.95. Conversely, when the sintering temperature is higher than 1450 ° C. or the sintering time is longer than 120 minutes, it may be difficult to suppress grain growth of the WC phase and the carbonitride phase.
  • the coated cemented carbide of the present invention is obtained by cleaning the cemented carbide of the present invention and coating the surface of the cemented carbide of the present invention with a conventionally known method such as PVD or CVD. Can do.
  • the coated cemented carbide of the present invention may be obtained by grinding the cemented carbide of the present invention and coating the surface thereof.
  • cemented carbide of the present invention and the coated cemented carbide of the present invention are suitably used for cutting tools such as inserts, end mills, drills, and reamers, and wear-resistant members such as die-cut rolls, coating tools, cutting blades, and abrasion-resistant plates. be able to.
  • These mixed powders were press-molded so as to have the shape of SEEN1203 after sintering.
  • the molded body obtained by this press molding was heated from room temperature to 450 ° C. in a nitrogen atmosphere to remove paraffin, and then heated from 450 ° C. to 1340 ° C. in a vacuum of 0.1 kPa or less to obtain 1.3 kPa.
  • the cemented carbides of the present invention products 1 to 8 and comparative products 9 to 12 were obtained by sintering at a sintering temperature of 1340 ° C. and a sintering time of 60 minutes in a nitrogen atmosphere.
  • the obtained cemented carbides of the present invention products 1 to 8 and comparative products 9 to 12 were wet-polished with a # 230 diamond grindstone, and further mirror-polished with a 1.0 ⁇ m diamond paste, and the structure was observed with an optical microscope and SEM. Was done.
  • the thickness of the surface layer composed of the WC phase and the binder phase was measured from the optical micrograph.
  • the average particle diameters of the WC phase and the carbonitride phase were measured according to Fullman's formula (Formula 1) from an SEM photograph in which the ion-milled polished cross-sectional structure was magnified 10,000 times.
  • the carbonitride phase particles are aggregated.
  • the aggregate was regarded as one particle, and the average particle size of the aggregate was measured according to Fullman's formula (Formula 1).
  • the composition of the WC phase, carbonitride phase, and binder phase was examined using EPMA (electron beam microanalyzer).
  • density DB (g / cm 3 ) of the cemented carbide was measured by a gas substitution method.
  • the density DP (g / cm 3 ) of the powder obtained by pulverizing the cemented carbide to a size passing through a sieve having an opening of 75 ⁇ m was measured by a gas displacement method.
  • the ratio of DB to DP (DB / DP) was determined.
  • the nitrogen content of the powder obtained by pulverizing the cemented carbide of the present invention was measured using a thermal conductivity method.
  • the amount of nitrogen of the product of the present invention is 0.18 to 0.74% by mass
  • the average particle size of the WC phase is 0.35 to 0.67 ⁇ m
  • carbonitriding The average particle size of the physical phase is 0.15 to 0.60 ⁇ m
  • DB / DP is 0.98 to 0.99, which is sufficiently densified.
  • the comparative products 9 to 12 have a DB / DP of 0.94 or less and are not sufficiently densified.
  • the cutting edges of the cemented carbides of the inventive products 1 to 8 and comparative products 9 to 11 are subjected to honing, and then a PVD method is used to coat a (Ti, Al) N film having an average film thickness of 3 ⁇ m. Produced.
  • Impact test material SCM440 Tool shape with hole: SEEN1203 Cutting speed: 160 m / min Cutting depth: 2.0mm Feed amount: 0.5mm / rev Tool life criterion: Machining length until chipping or chipping occurs
  • Abrasion test material SCM440 Tool shape: SEEN1203 Cutting speed: 250 m / min Cutting depth: 2.0mm Feed amount: 0.1mm / rev Tool life criteria: Machining length until corner wear reaches 0.1mm
  • the cutting tools of the products 1 to 8 of the present invention have an excellent impact resistance with a working length of 9.5 m or more until chipping or chipping occurs.
  • the cutting tools of comparative products 9 to 11 have a coarse carbonitride phase contained in the cemented carbide and the cemented carbide is not sufficiently densified. Inferior in impact.
  • the coated cemented carbides 1 to 8 of the present invention have excellent wear resistance because the processed length until the corner wear amount reaches 0.1 mm is 10.5 m or more.
  • the cutting tools of comparative products 9 to 11 were inferior in wear resistance because the machining length until the corner wear amount reached 0.1 mm was 9.9 m or less.
  • It consists of a combination of a sleeve-shaped die cutter with a three-dimensional cutting edge formed on the outer peripheral surface of the cylinder and a sleeve-shaped anvil roll having a smooth cylindrical outer peripheral surface.
  • a die-cut roll that cuts and processes a work material by rotating and pressing a die cutter onto a work material that moves on the anvil roll, and the product of the present invention was used for the die cutter and the anvil roll of the die-cut roll.
  • a die cutter and an anvil roll using the inventive products 1, 4, 6, 8 and comparative products 9 to 11 were manufactured and combined to form a die cut roll, and an abrasion resistance test was performed under the following conditions. In the wear resistance test, the same die cutter and anvil roll were combined.
  • Wear resistance test condition applied pressure 15 kN
  • Roll peripheral speed 200m / min
  • Total number of rotations The wear width of the cutting edge was measured after 100 million wear resistance tests.
  • the comparative products 9 to 11 were 20 to 65 ⁇ m, whereas the products 1, 4, 6 and 8 of the present invention were It was 5 to 20 ⁇ m, and it was confirmed that the wear resistance was excellent.
  • Coating tool tip member used for coating on film-like members, coating on panel-like members, especially the step of applying a coating solution such as a color resist on the surface of a glass substrate when manufacturing a liquid crystal display panel
  • a coating solution such as a color resist
  • the inventive product 1, 4, 6, 8 and the comparative products 9 to 11 are fixed to the stainless steel member (coating tool body) with bolts and the application tool is obtained by grinding precisely. It was.
  • the color resist was apply
  • the product of the present invention was used as a cutting blade for a sheet-like member. That is, cutting blades were produced using the inventive products 1, 4, 6, 8 and comparative products 9-11.
  • the edge angle was 30 degrees. 500 sheets of copy paper (PPC paper) were stacked and a continuous cutting test was performed in a state where moisture was present on the blade edge.
  • the comparative products 9 to 11 were 90 to 200 ⁇ m, while the inventive products 1, 4, 6 and 8 were 50 ⁇ m or less, and the cutting edge The amount of corrosive wear generated was clearly small.
  • the product of the present invention was used for a wear-resistant plate of a pulverizer. That is, abrasion resistant plates were produced using the inventive products 2, 4, 6, 7 and comparative products 9 to 11, and an abrasion resistance test (blast treatment) was performed under the following conditions.
  • Wear resistance test condition equipment Blasting equipment Blasting time: 30 seconds
  • Particle SiC Distance from nozzle to sample: 118mm
  • Blast irradiation area 20 x 20 mm
  • the comparative products 9 to 11 had an Ra of 400 to 650 nm, whereas the inventive products 2, 4, 6 and 7 had a thickness of 150 nm or less. It was confirmed that it was excellent in wear resistance.
  • cemented carbide and the coated cemented carbide of the present invention are excellent in impact resistance and wear resistance, they exhibit excellent performance particularly when used as cutting tools and wear resistant members.

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Abstract

The present invention provides a superhard alloy having excellent impact resistance and wear resistance. The superhard alloy is characterized by comprising a WC phase, a carbonitride phase comprising at least one carbonitride selected from the group consisting of both carbonitrides of at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W and solid solutions between these, and a binder phase comprising, as a main component, at least one element selected from the group consisting of Co, Ni, and Fe, the amounts of the WC phase, the carbonitride phase, and the binder phase being 55-94.8 vol.%, 1-30 vol.%, and 4.2-22.2 vol.%, respectively, of the whole superhard alloy, the sum of the WC phase, the carbonitride phase, and the binder phase being 100 vol.%. The superhard alloy is further characterized in that the WC phase has an average grain diameter of 0.05-0.8 µm and the carbonitride phase has an average grain diameter of 0.03-1.1 µm, and that the ratio of the density DB of the superhard alloy determined by a gas replacement method to the density DP of a powder obtained by pulverizing the superhard alloy to a size sufficient to enable the powder to pass through a sieve having an opening size of 75 µm, DB/DP, is 0.95 or higher.

Description

超硬合金および被覆超硬合金Cemented carbide and coated cemented carbide
　本発明は超硬合金および被覆超硬合金に関する。特に切削工具、耐摩耗部材として用いたときに優れた性能を発揮する超硬合金および被覆超硬合金に関する。 The present invention relates to a cemented carbide and a coated cemented carbide. In particular, the present invention relates to a cemented carbide and a coated cemented carbide that exhibit excellent performance when used as a cutting tool or wear-resistant member.
　超硬合金の従来技術として、Ｂ１型固溶体相、ＷＣ相及び結合相からなる超硬合金製ツイストドリルにおいて、炭化タングステンからなる硬質相５０～７０面積％、Ｂ１型固溶体相からなる硬質相１５～３０面積％、鉄族金属からなる結合相１５～２５重量％からなるとともに、焼結体に於ける平均粒度が、炭化タングステン相が０．３ミクロン～１．２ミクロン、Ｂ１型固溶体相が０．３ミクロン～２ミクロンよりなり、前記Ｃｏの格子定数が３．５６５Å～３．５７５Åであることを特徴とする超硬合金製ツイストドリルが知られている（例えば、特許文献１参照。）。 As a conventional technique of cemented carbide, in a cemented carbide twist drill composed of a B1 type solid solution phase, a WC phase and a binder phase, 50 to 70 area% of a hard phase composed of tungsten carbide, and a hard phase composed of a B1 type solid solution phase 15 to 30% by area, 15% to 25% by weight of a binder phase made of an iron group metal, and the average particle size in the sintered body is 0.3 to 1.2 microns for the tungsten carbide phase and 0 for the B1 type solid solution phase. 2. Description of the Related Art A cemented carbide twist drill is known that has a Co lattice constant of 3.565 to 3.575 mm (for example, see Patent Document 1).
　また、平均粒径０．２～０．８μｍのＷＣ粒子を６０～８５体積％と、平均粒径１．２～３μｍの周期律表第４ａ，５ａ，６ａ族金属の少なくとも１種の炭化物、窒化物または炭窒化物からなるβ相粒子を５～３０体積％と、からなる硬質相と、前記硬質相の間を鉄族金属の少なくとも１種を主体とする結合相５～２０体積％にて結合してなり、ガス置換法で測定したバルク体の密度Ｄｂと、該バルク体を＃２００メッシュを通過するサイズに微粉砕した後の粉末の密度Ｄｐとの比率Ｄｂ／Ｄｐが０．９５以上であることを特徴とする超硬合金が知られている（例えば、特許文献２参照。）。 Further, WC particles having an average particle size of 0.2 to 0.8 μm, 60 to 85% by volume, and at least one carbide of Group 4a, 5a, and 6a metals in the periodic table having an average particle size of 1.2 to 3 μm, Β-phase particles made of nitride or carbonitride are 5 to 30% by volume, and a hard phase consisting of 5 to 20% by volume of a binder phase mainly composed of at least one iron group metal between the hard phases. The ratio Db / Dp between the density Db of the bulk body measured by the gas displacement method and the density Dp of the powder after pulverizing the bulk body to a size passing through # 200 mesh is 0.95 A cemented carbide characterized by the above is known (for example, see Patent Document 2).
特開２０００－１５５１４号公報JP 2000-15514 A 特開２００４－１９０１１８号公報JP 2004-190118 A
　上記の特許文献１および特許文献２に記載された超硬合金は、ＷＣ相の平均粒径よりもＢ１型固溶体相やβ相粒子の平均粒径が大きく、Ｂ１型固溶体相やβ相粒子が破壊の起源となるため、靭性、耐衝撃性および強度が低いという問題がある。本発明は、従来技術のこうした問題を解決するためになされたもので、耐衝撃性および耐摩耗性に優れた超硬合金およびその表面に被膜を被覆した被覆超硬合金を提供することを目的とする。 The cemented carbides described in Patent Document 1 and Patent Document 2 described above have larger average particle diameters of the B1 type solid solution phase and β phase particles than the average particle diameter of the WC phase. Since it is the origin of fracture, there is a problem that toughness, impact resistance and strength are low. The present invention has been made to solve such problems of the prior art, and an object of the present invention is to provide a cemented carbide excellent in impact resistance and wear resistance and a coated cemented carbide with a coating on the surface thereof. And
　発明者らは超硬合金の耐衝撃性と耐摩耗性の向上について検討した結果、ＷＣ相と炭窒化物相と結合相とからなる超硬合金において、ＷＣ相の平均粒径と炭窒化物相の平均粒径を制御することによって、耐衝撃性および耐摩耗性に優れた超硬合金を得られるという知見を得て、本発明を完成するに至った。
　すなわち本発明は、ＷＣ相：５５～９５体積％と、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された少なくとも１種の炭窒化物およびこれらの相互固溶体から成る群より選択された少なくとも１種からなる炭窒化物相：１～３０体積％と、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を主成分とする結合相：４．２～２２．２体積％とからなり、但し、ＷＣ相と炭窒化物相と結合相の合計は１００体積％であり、ＷＣ相の平均粒径が０．０５～０．８μｍであり、炭窒化物相の平均粒径が０．０３～１．１μｍであり、気体置換法で測定した超硬合金の密度ＤＢと超硬合金を目開き７５μｍのふるいを通過するサイズまで粉砕した粉末の密度ＤＰとの比率（ＤＢ／ＤＰ）が０．９５以上であることを特徴とする超硬合金である。 As a result of studying the improvement in impact resistance and wear resistance of cemented carbide, the inventors have found that in cemented carbide composed of a WC phase, a carbonitride phase, and a binder phase, the average particle size of the WC phase and the carbonitride By controlling the average particle size of the phase, the inventors have obtained the knowledge that a cemented carbide excellent in impact resistance and wear resistance can be obtained, and have completed the present invention.
That is, the present invention relates to WC phase: 55 to 95% by volume, at least one carbonitride selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W, and their mutual 3. Carbonitride phase comprising at least one selected from the group consisting of solid solutions: 1 to 30% by volume, and a binder phase comprising at least one selected from the group consisting of Co, Ni and Fe as main components: 4. 2 to 22.2% by volume, provided that the total of the WC phase, the carbonitride phase, and the binder phase is 100% by volume, and the average particle size of the WC phase is 0.05 to 0.8 μm. The average particle diameter of the nitride phase is 0.03 to 1.1 μm, the density DB of the cemented carbide measured by the gas displacement method and the density of the powder obtained by pulverizing the cemented carbide to a size passing through a sieve with an opening of 75 μm. The ratio with DP (DB / DP) is 0.95 or more Is a cemented carbide which is characterized in Rukoto.
　本発明の超硬合金および被覆超硬合金は、耐衝撃性および耐摩耗性に優れるという効果を奏する。 The cemented carbide and the coated cemented carbide of the present invention have the effect of being excellent in impact resistance and wear resistance.
本発明の超硬合金の断面組織の一例を示すＳＥＭ写真である。It is a SEM photograph which shows an example of the cross-sectional structure of the cemented carbide of this invention.
　本発明の超硬合金は、ＷＣ相：超硬合金全体に対して５５～９４．８体積％と、炭窒化物相：超硬合金全体に対して１～３０体積％と、結合相：超硬合金全体に対して４．２～２２．２体積％とからなり、ＷＣ相と炭窒化物相と結合相の合計は１００体積％である。 The cemented carbide of the present invention has a WC phase: 55 to 94.8% by volume based on the entire cemented carbide, a carbonitride phase: 1 to 30% by volume based on the entire cemented carbide, and a binder phase: The total content of the hard alloy is 4.2 to 22.2% by volume, and the total of the WC phase, the carbonitride phase, and the binder phase is 100% by volume.
　本発明のＷＣ相は、超硬合金全体に対して５５体積％未満になると、相対的に炭窒化物相と結合相とが多くなりＷＣ相の粒成長の制御が困難となり超硬合金の硬さが低下し、逆にＷＣ相が超硬合金全体に対して９４．８体積％を超えて多くなると、相対的に炭窒化物相と結合相とが少なくなり超硬合金の靭性が低下することから、ＷＣ相を超硬合金全体に対して５５～９４．８体積％とした。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相を超硬合金全体に対して５７～９０体積％とするとさらに好ましく、ＷＣ相を超硬合金全体に対して５８～８０体積％とするとさらに好ましい。本発明のＷＣ相の平均粒径を０．０５μｍ未満にすることは焼結中の粒成長により製造が困難であり、本発明のＷＣ相の平均粒径が０．８μｍを超えて大きくなると超硬合金の硬さと強度が低下することから、本発明のＷＣ相の平均粒径は０．０５～０．８μｍと定めた。この要件を達成するためには、焼結後にこの範囲に入るサイズの原料粉末を使用すれば良い。その中でも、ＷＣ相の平均粒径は０．１～０．７μｍであるとさらに好ましい。 When the WC phase of the present invention is less than 55% by volume with respect to the entire cemented carbide, the carbonitride phase and the binder phase are relatively increased, and it becomes difficult to control the grain growth of the WC phase, so that the hardness of the cemented carbide is reduced. Conversely, when the WC phase exceeds 94.8% by volume with respect to the entire cemented carbide, the carbonitride phase and the binder phase are relatively decreased, and the toughness of the cemented carbide is decreased. Therefore, the WC phase was 55-94.8% by volume with respect to the entire cemented carbide. In order to achieve this requirement, an amount of raw material powder that falls within this range may be blended. Among them, the WC phase is more preferably 57 to 90% by volume with respect to the entire cemented carbide, and the WC phase is more preferably 58 to 80% by volume with respect to the entire cemented carbide. Making the average particle size of the WC phase of the present invention less than 0.05 μm is difficult to produce due to grain growth during sintering, and if the average particle size of the WC phase of the present invention exceeds 0.8 μm, it is too high. Since the hardness and strength of the hard alloy are lowered, the average particle size of the WC phase of the present invention is determined to be 0.05 to 0.8 μm. In order to achieve this requirement, a raw material powder having a size within this range after sintering may be used. Among these, the average particle diameter of the WC phase is more preferably 0.1 to 0.7 μm.
　本発明の炭窒化物相は、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された少なくとも１種の炭窒化物およびこれらの相互固溶体から成る群より選択された少なくとも１種からなる炭窒化物相である。本発明の炭窒化物相は、耐摩耗性、耐溶着性を向上させ、ＷＣ相の粒成長を抑制して超硬合金の硬さと強度を向上させる。その中でも、炭窒化物相は、金属元素がＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された２種以上からなる複炭窒化物であると、さらに好ましく、その中でも、炭窒化物相は、金属元素がＺｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された少なくとも１種とＴｉとからなる複炭窒化物であると、さらに好ましい。本発明の炭窒化物相は、超硬合金全体に対して、１体積％未満になると、耐溶着性や耐摩耗性を改善する効果とＷＣ相の粒成長を抑制する効果が低下し、３０体積％を超えて多くなると、相対的にＷＣ相が減少して炭窒化物相の粒成長を抑制する効果が低下するので、１～３０体積％とした。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、炭窒化物相を超硬合金全体に対して３～２５体積％とするとさらに好ましい。本発明の炭窒化物相の平均粒径を０．０３μｍ未満にすることは焼結中の粒成長の抑制が難しいので製造が困難であり、本発明の炭窒化物相の平均粒径が１．１μｍを超えて大きくなると硬さと強度が低下することから、本発明の炭窒化物相の平均粒径を０．０３～１．１μｍとした。この要件を達成するためには、焼結後にこの範囲に入るサイズの原料粉末を使用すれば良い。その中でも、炭窒化物相の平均粒径は０．１～０．７μｍであるとさらに好ましい。 The carbonitride phase of the present invention is selected from the group consisting of at least one carbonitride selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and their mutual solid solutions It is a carbonitride phase consisting of at least one kind. The carbonitride phase of the present invention improves wear resistance and welding resistance, suppresses grain growth of the WC phase, and improves the hardness and strength of the cemented carbide. Among them, the carbonitride phase is a double carbonitride composed of two or more selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W as the metal element. Preferably, among them, the carbonitride phase is a double carbonitride composed of Ti and at least one selected from the group consisting of Zr, Hf, V, Nb, Ta, Cr, Mo and W. And more preferred. When the carbonitride phase of the present invention is less than 1% by volume with respect to the entire cemented carbide, the effect of improving the welding resistance and wear resistance and the effect of suppressing the grain growth of the WC phase are reduced. If the amount exceeds 1% by volume, the WC phase is relatively decreased, and the effect of suppressing the grain growth of the carbonitride phase is lowered. In order to achieve this requirement, an amount of raw material powder that falls within this range may be blended. Among these, the carbonitride phase is more preferably 3 to 25% by volume with respect to the entire cemented carbide. Making the average particle size of the carbonitride phase of the present invention less than 0.03 μm is difficult to suppress because grain growth during sintering is difficult to produce, and the average particle size of the carbonitride phase of the present invention is 1 When the thickness exceeds 0.1 μm, the hardness and strength decrease, so the average particle size of the carbonitride phase of the present invention is set to 0.03 to 1.1 μm. In order to achieve this requirement, a raw material powder having a size within this range after sintering may be used. Among these, the average particle size of the carbonitride phase is more preferably 0.1 to 0.7 μm.
　本発明の結合相は、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を主成分とする金属である。本発明において、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を主成分とする金属とは、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を合計して、結合相全体に対して５０質量％以上含む金属を意味する。本発明の結合相は、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を合計して、結合相全体に対して７０～１００質量％含むことが好ましいが、主成分のＣｏ、ＮｉおよびＦｅ以外にＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、ＣおよびＮから成る群より選択された少なくとも１種を結合相全体に対して０～３０質量％の量で含んでもよい。本発明の結合相は、Ｃｏを主成分とすると耐熱性、靭性、被膜との密着性に優れるので、さらに好ましい。本発明のＣｏを主成分とする結合相とは、Ｃｏを結合相全体に対して５０質量％以上含む結合相を意味する。また、本発明の結合相にＣｒ元素が、結合相全体に対して３質量％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相と炭窒化物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。しかしながら、本発明の結合相にＣｒ元素が、結合相全体に対して１１質量％を超えて固溶することは困難である。そのため、本発明の結合相に含まれるＣｒ元素量は結合相全体に対して３～１１質量％であると好ましい。本発明の結合相は、超硬合金全体に対して４．２体積％未満になると超硬合金の強度と靭性が低下し、２２．２体積％を超えて多くなると超硬合金の硬さが低下することから、本発明の結合相を４．２～２２．２体積％とした。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、結合相を超硬合金全体に対して５～２１体積％とするとさらに好ましい。 The binder phase of the present invention is a metal mainly composed of at least one selected from the group consisting of Co, Ni and Fe. In the present invention, the metal having at least one selected from the group consisting of Co, Ni and Fe as the main component is the total of at least one selected from the group consisting of Co, Ni and Fe, and the bonded phase. It means a metal containing 50% by mass or more based on the whole. The binder phase of the present invention preferably contains 70 to 100% by mass of the total amount of at least one selected from the group consisting of Co, Ni and Fe, based on the total binder phase. In addition to Fe and Fe, at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, C and N is added in an amount of 0 to 30% by mass with respect to the entire binder phase. May be included. The binder phase of the present invention is more preferably made of Co as a main component because it is excellent in heat resistance, toughness, and adhesion to a coating. The binder phase containing Co as a main component of the present invention means a binder phase containing 50 mass% or more of Co with respect to the entire binder phase. Moreover, when Cr element is contained in the binder phase of the present invention in an amount of 3% by mass or more based on the whole binder phase, the hardness, strength and oxidation resistance of the binder phase are improved, and the grains of the WC phase and the carbonitride phase are improved. Growth is suppressed and the hardness and strength of the cemented carbide is improved. However, it is difficult for the Cr element to dissolve in the binder phase of the present invention in a solid solution exceeding 11% by mass with respect to the whole binder phase. Therefore, the amount of Cr element contained in the binder phase of the present invention is preferably 3 to 11% by mass with respect to the whole binder phase. When the binder phase of the present invention is less than 4.2% by volume with respect to the entire cemented carbide, the strength and toughness of the cemented carbide are decreased, and when the content exceeds 22.2% by volume, the hardness of the cemented carbide is decreased. Therefore, the binder phase of the present invention was set to 4.2 to 22.2% by volume. In order to achieve this requirement, an amount of raw material powder that falls within this range may be blended. Of these, the binder phase is more preferably 5 to 21% by volume with respect to the entire cemented carbide.
　本発明の超硬合金全体に対するＷＣ相、炭窒化物相および結合相の体積率は、超硬合金の研磨断面組織をＳＥＭ（走査型電子顕微鏡）で観察して得られたＷＣ相、炭窒化物相および結合相の各面積率から求めることができる。具体的には、１０面以上の研磨断面組織におけるＷＣ相、炭窒化物相および結合相の各面積率を測定し、それらを平均したものを、各相の体積率とした。 The volume ratio of the WC phase, carbonitride phase, and binder phase relative to the entire cemented carbide of the present invention is the WC phase, carbonitriding obtained by observing the polished cross-sectional structure of the cemented carbide with an SEM (scanning electron microscope). It can obtain | require from each area ratio of a physical phase and a binder phase. Specifically, the area ratios of the WC phase, carbonitride phase, and binder phase in 10 or more polished cross-sectional structures were measured, and the average of them was defined as the volume ratio of each phase.
　ＷＣ相と炭窒化物相の平均粒径は、超硬合金の研磨断面組織をＳＥＭで観察し、下記のフルマンの式（式１）から算出することができる。
Figure JPOXMLDOC01-appb-I000001
　（式１）中、ｄｍは平均粒径、πは円周率、ＮＬは断面組織上の任意の直線によってヒットされる単位長さあたりの粒子数、ＮＳは任意の単位面積内に含まれる粒子の数を表し、（式２）中、ｎＬは断面組織上の任意の直線によってヒットされる粒子の数、Ｌは断面組織上の任意の直線の長さを表し、（式３）中、ｎＳは任意の測定面積内に含まれる粒子の数、Ｓは任意の測定領域の面積を表す。 The average particle size of the WC phase and the carbonitride phase can be calculated from the following Fullman equation (Equation 1) by observing the polished cross-sectional structure of the cemented carbide with an SEM.
Figure JPOXMLDOC01-appb-I000001
(In the formula 1), d m average particle size, [pi is pi, N L is the number of particles per unit length which is hit by an arbitrary straight line on the cross-sectional structure, N S is in any unit area Represents the number of particles contained, and in (Expression 2), n L represents the number of particles hit by an arbitrary straight line on the cross-sectional structure, L represents the length of an arbitrary straight line on the cross-sectional structure, and (Expression 3) ), N S represents the number of particles contained in an arbitrary measurement area, and S represents the area of an arbitrary measurement region.
　具体的には、研磨断面組織を１００００倍でＳＥＭ観察して写真を撮影し、その写真全体を測定領域とする。得られた写真に含まれる粒子数ｎＳをカウントする。このときｎＳは１０００以上となるようにすると好ましい。１枚の写真のｎＳが１０００よりも小さいときは、複数の写真を用いてｎＳが１０００以上となるようにしてもよい。次にＳＥＭ写真を等分に分割する任意の直線を引き、その直線によってヒットされる粒子の数ｎＬをカウントする。このときｎＬは３０００以上となるようにすると好ましい。１枚の写真のｎＬが３０００よりも小さいときは、複数の写真を用いてｎＬが３０００以上となるようにしてもよい。これらの数値ｎＳおよびｎＬを、それぞれ、ＳおよびＬで除してＮＳおよびＮＬを求め、これらの値を（式１）に代入することにより平均粒径ｄｍを求めることができる。 Specifically, the polished cross-sectional structure is observed with a SEM at a magnification of 10000 to take a photograph, and the entire photograph is used as a measurement region. The number n S of particles contained in the obtained photograph is counted. At this time, n S is preferably 1000 or more. When n S of one photo is smaller than 1000, n S may be set to 1000 or more using a plurality of photos. Next, an arbitrary straight line that divides the SEM photograph into equal parts is drawn, and the number n L of particles hit by the straight line is counted. At this time, nL is preferably 3000 or more. When a photo in n L is less than 3000, n L by using a plurality of photos may be made 3,000 or more. These numbers n S and n L, respectively, determine the N S and N L is divided by the S and L, it is possible to determine the average particle diameter d m By substituting these values into equation (1) .
　なお、超硬合金の研磨断面をイオンミリングすると、ＷＣ相粒子の粒界や炭窒化物相粒子の粒界が優先的にエッチングされ、ＷＣ相粒子や炭窒化物相粒子の粒径測定が容易になるので好ましい。イオンミリングした本発明の超硬合金の研磨断面組織の一例を図１に示す。図１中、灰白色の粒子がＷＣ相粒子であり、灰黒色の粒子が炭窒化物相粒子であり、これらの粒子の間に存在する灰色の部分が結合相である。 In addition, when ion milling the polished cross-section of cemented carbide, the grain boundaries of WC phase particles and carbonitride phase particles are preferentially etched, making it easy to measure the particle size of WC phase particles and carbonitride phase particles. This is preferable. An example of the polished cross-sectional structure of the cemented carbide of the present invention that has been ion milled is shown in FIG. In FIG. 1, grayish white particles are WC phase particles, grayish black particles are carbonitride phase particles, and gray portions existing between these particles are binder phases.
　本発明の超硬合金は、気体置換法で測定した超硬合金の密度ＤＢと超硬合金を目開き７５μｍのふるいを通過するサイズまで粉砕した粉末の密度ＤＰとの比率（ＤＢ／ＤＰ）は、合金中の気孔の量を評価する値であり、この値が大きいと気孔が少なく緻密であり、この値が小さいと気孔が多く緻密でないことを示すものである。ＤＢ／ＤＰが０．９５未満であると合金内部に気孔が多く存在し、硬さと強度を低下させ、耐摩耗性や耐衝撃性が低下するため、０．９５以上とした。その中でも、ＤＢ／ＤＰが０．９８以上であるとさらに好ましい。この要件を達成するためには、以下に記載する製造方法を採用することが好ましい。なお、気体置換法で密度を測定する装置としては、乾式自動密度計などを挙げることができる。 The cemented carbide of the present invention has a ratio (DB / DP) between the density DB of the cemented carbide measured by the gas displacement method and the density DP of the powder obtained by pulverizing the cemented carbide to a size passing through a sieve having an opening of 75 μm. This is a value for evaluating the amount of pores in the alloy. When this value is large, the pores are few and dense, and when this value is small, the pores are many and not dense. When DB / DP is less than 0.95, there are many pores inside the alloy, which decreases hardness and strength, and decreases wear resistance and impact resistance. Among these, DB / DP is more preferably 0.98 or more. In order to achieve this requirement, it is preferable to employ the manufacturing method described below. In addition, as an apparatus which measures a density with a gas substitution method, a dry-type automatic densimeter etc. can be mentioned.
　本発明の超硬合金に含まれる窒素量が超硬合金全体に対して２．６質量％を超えて多くなると焼結性が低く超硬合金の強度と靭性が低下する傾向を示し、窒素量が０．１質量％未満になるとＷＣ相の粒成長を抑制する効果が小さくなり超硬合金の硬さが低くなる傾向を示すことから、本発明の超硬合金に含まれる窒素量は超硬合金全体に対して０．１～２．６質量％であるとさらに好ましい。この要件を達成するためには、この範囲に入る量の窒素を含有した原料粉末を配合すれば良い。その中でも、窒素量を超硬合金全体に対して０．１～２．０質量％であるとさらに好ましい。 When the amount of nitrogen contained in the cemented carbide of the present invention exceeds 2.6% by mass with respect to the entire cemented carbide, the sinterability tends to be low and the strength and toughness of the cemented carbide tend to be reduced. When the content is less than 0.1% by mass, the effect of suppressing the grain growth of the WC phase tends to be small and the hardness of the cemented carbide tends to be low. Therefore, the amount of nitrogen contained in the cemented carbide of the present invention is The content is more preferably 0.1 to 2.6% by mass with respect to the entire alloy. In order to achieve this requirement, a raw material powder containing nitrogen in an amount falling within this range may be blended. Among these, the nitrogen content is more preferably 0.1 to 2.0% by mass with respect to the entire cemented carbide.
　本発明の超硬合金の表面から内部に向かって平均厚さ５～５０μｍのＷＣ相と結合相とからなる表面層が形成されるとさらに好ましい。この要件を達成するためには、焼結中に超硬合金に含まれる窒素が超硬合金外に排出される窒素分圧以下の雰囲気で、いわゆる脱窒雰囲気で、原料粉末からなる成形体を焼結すると良い。ＷＣ相と結合相とからなる表面層は結合相の量が、表面層を除いて得られる超硬合金の内部に比べて相対的に多く、超硬合金の表面から内部に向かって平均厚さ５μｍ以上の表面層が形成されると、耐衝撃性がさらに向上する傾向を示し、表面層の平均厚さが５０μｍを超えて厚くなると表面層における結合相の量が大きくなり、ＷＣ相が粗大になり耐塑性変形性が小さくなる傾向を示すので、表面層の平均厚さは５～５０μｍであると好ましい。その中でも、表面層の平均厚さは９～３５μｍであるとさらに好ましい。 More preferably, a surface layer composed of a WC phase and a binder phase having an average thickness of 5 to 50 μm is formed from the surface of the cemented carbide of the present invention toward the inside. In order to achieve this requirement, in a so-called denitrification atmosphere in which the nitrogen contained in the cemented carbide is discharged out of the cemented carbide during sintering, the molded body made of the raw material powder is used. Sintering is good. The surface layer composed of the WC phase and the binder phase has a relatively large amount of binder phase compared to the inside of the cemented carbide obtained by removing the surface layer, and has an average thickness from the surface of the cemented carbide to the inside. When a surface layer of 5 μm or more is formed, impact resistance tends to be further improved, and when the average thickness of the surface layer exceeds 50 μm, the amount of the binder phase in the surface layer increases and the WC phase is coarse. Therefore, the average thickness of the surface layer is preferably 5 to 50 μm. Among these, the average thickness of the surface layer is more preferably 9 to 35 μm.
　本発明の超硬合金の表面に被膜を被覆することにより、耐摩耗性や表面潤滑性を向上させた被覆超硬合金を得ることができる。被膜は、金属、金属化合物、ダイヤモンドおよびセラミックスから成る群より選択された少なくとも１種からなる。その中でもＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、ＡｌおよびＳｉから成る群より選択された少なくとも１種の炭化物、窒化物、炭窒化物、酸化物およびこれらの相互固溶体から成る群より選択された少なくとも１種からなると好ましい。具体的には、ＴｉＣ、ＴｉＮ、ＴｉＣＮ、Ａｌ２Ｏ３、ＴｉＡｌＮ、ＴｉＳｉＮ、ＡｌＣｒＮ、（Ａｌ，Ｃｒ）２Ｏ３などを挙げることができる。被膜の膜構成は単層または２層以上の多層のいずれも好ましい。被膜全体の総膜厚は平均膜厚で０．１μｍ未満であると耐摩耗性や表面潤滑性を向上させる効果が十分得られず、３０μｍを超えて厚くなると耐欠損性が低下する傾向を示すので、被膜全体の総膜厚は平均膜厚で０．１～３０μｍであると好ましい。その中でも、被膜全体の総膜厚は平均膜厚で１～２０μｍであるとさらに好ましい。 A coated cemented carbide with improved wear resistance and surface lubricity can be obtained by coating the surface of the cemented carbide of the present invention with a coating. The coating consists of at least one selected from the group consisting of metals, metal compounds, diamond and ceramics. Among them, at least one carbide, nitride, carbonitride, oxide selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al and Si, and their mutual solid solutions It is preferable that it consists of at least one selected from the group consisting of: Specifically, TiC, TiN, TiCN, Al 2 O 3 , TiAlN, TiSiN, AlCrN, (Al, Cr) 2 O 3 and the like can be mentioned. The film configuration of the coating is preferably a single layer or a multilayer of two or more layers. If the total film thickness of the entire film is less than 0.1 μm in average film thickness, the effect of improving wear resistance and surface lubricity cannot be obtained sufficiently, and if it exceeds 30 μm, the chipping resistance tends to decrease. Therefore, the total film thickness of the entire film is preferably 0.1 to 30 μm as an average film thickness. Among these, the total film thickness of the entire film is more preferably 1 to 20 μm in average film thickness.
　本発明の超硬合金の製造方法として、例えば、以下の方法を挙げることができる。平均粒径０．１～１．０μｍのＷＣ粉末：５５～９４．８体積％、好ましくは５７～９０体積％、さらに好ましくは５８～８０体積％と、金属元素がＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された２種以上からなる複炭窒化物であり、複炭窒化物の炭素量ＣＰと窒素量ＮＰの合計に対する窒素量ＮＰの比率（ＮＰ／（ＣＰ＋ＮＰ））が原子比で０．２～０．８である平均粒径０．１～１．０μｍの複炭窒化物粉末：１～３０体積％、好ましくは３～２５体積％と、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種からなる平均粒径０．１～１．０μｍの鉄族金属粉末：４．２～２２．２体積％、好ましくは５～２１体積％と、平均粒径１．０～４．０μｍのＣｒ３Ｃ２粉末：０～２．２体積％とからなり、これらの合計が１００体積％となるように配合した原料粉末を用意する。複炭窒化物粉末の窒素量ＮＰと炭素量ＣＰの比率は、ＷＣ相の平均粒径の制御や炭窒化物相の平均粒径の制御や超硬合金の緻密化に重要な因子である。複炭窒化物粉末の炭素量ＣＰと複炭窒化物粉末の窒素量ＮＰの合計に対する複炭窒化物粉末の窒素量ＮＰの比率（ＮＰ／（ＣＰ＋ＮＰ））が原子比で０．２未満であるとＷＣ相や炭窒化物相の粒成長を抑制する効果が十分でなく超硬合金の硬さや強度が低下する。逆にＮＰ／（ＣＰ＋ＮＰ）が０．８を超えて大きくなると焼結性が低下し、ＤＢ／ＤＰが０．９５未満になる。ＮＰ／（ＣＰ＋ＮＰ）比率は、０．３～０．６が更に好ましい。また焼結後の超硬合金が遊離炭素またはタングステンコバルト炭化物（η相）を生じない健全相域に入るように原料粉末に１質量％以下の炭素粉末または１質量％以下のタングステン粉末を加えてもよい。 Examples of the method for producing the cemented carbide of the present invention include the following methods. WC powder having an average particle size of 0.1 to 1.0 μm: 55 to 94.8% by volume, preferably 57 to 90% by volume, more preferably 58 to 80% by volume, and the metal elements are Ti, Zr, Hf, V , Nb, Ta, Cr, Mo and W, which is a double carbonitride selected from the group consisting of two or more, and the ratio of the nitrogen amount NP to the total of the carbon amount CP and the nitrogen amount NP of the double carbonitride ( Double carbonitride powder having an average particle size of 0.1 to 1.0 μm in which NP / (CP + NP) is an atomic ratio of 0.2 to 0.8: 1 to 30% by volume, preferably 3 to 25% by volume Iron group metal powder having an average particle size of 0.1 to 1.0 μm selected from the group consisting of Co, Ni and Fe: 4.2 to 22.2 vol%, preferably 5 to 21 vol % and, Cr 3 C 2 powder having an average particle diameter of 1.0 ~ 4.0μm: 0 ~ 2.2 body % Consists of a, these sum to prepare a raw material powder was blended so that 100% by volume. The ratio between the nitrogen content NP and the carbon content CP of the double carbonitride powder is an important factor for controlling the average particle size of the WC phase, controlling the average particle size of the carbonitride phase, and densifying the cemented carbide. The ratio (NP / (CP + NP)) of the nitrogen amount NP of the double carbonitride powder to the total of the carbon amount CP of the double carbonitride powder and the nitrogen amount NP of the double carbonitride powder is less than 0.2 in atomic ratio. Further, the effect of suppressing the grain growth of the WC phase and the carbonitride phase is not sufficient, and the hardness and strength of the cemented carbide decreases. Conversely, if NP / (CP + NP) is greater than 0.8, the sinterability is reduced and DB / DP is less than 0.95. The NP / (CP + NP) ratio is more preferably 0.3 to 0.6. Also, 1 mass% or less of carbon powder or 1 mass% or less of tungsten powder is added to the raw material powder so that the sintered cemented carbide enters a healthy phase region where free carbon or tungsten cobalt carbide (η phase) is not generated. Also good.
　配合した原料粉末をボールミルまたはアトライタミルを用いて１０～４０時間混合、及び粉砕する。得られた混合粉末をプレスなどの方法で所定の形状に成形する。得られた成形体を焼結炉に入れて焼結温度：１３００～１４５０℃にて焼結時間：６０～１２０分間、真空中、窒素雰囲気中または不活性ガス雰囲気中で焼結を行なうことが好ましい。焼結温度が１３００℃未満または焼結時間が６０分間未満であると超硬合金の緻密化が不十分でＤＢ／ＤＰが０．９５未満になる場合がある。逆に焼結温度が１４５０℃を超えて高くなるかまたは焼結時間が１２０分間を超えて長くなるとＷＣ相と炭窒化物相の粒成長を抑制することが困難になる場合がある。 The mixed raw material powder is mixed and pulverized for 10 to 40 hours using a ball mill or an attritor mill. The obtained mixed powder is formed into a predetermined shape by a method such as pressing. The obtained molded body is put in a sintering furnace and sintered at a sintering temperature of 1300 to 1450 ° C. for a sintering time of 60 to 120 minutes in a vacuum, a nitrogen atmosphere or an inert gas atmosphere. preferable. If the sintering temperature is less than 1300 ° C. or the sintering time is less than 60 minutes, the cemented carbide may not be sufficiently densified and DB / DP may be less than 0.95. Conversely, when the sintering temperature is higher than 1450 ° C. or the sintering time is longer than 120 minutes, it may be difficult to suppress grain growth of the WC phase and the carbonitride phase.
　本発明の超硬合金を洗浄し、従来から知られているＰＶＤ法やＣＶＤ法などの方法によって、本発明の超硬合金の表面に被膜を被覆して本発明の被覆超硬合金を得ることができる。なお、本発明の超硬合金を研削加工して、その表面に被膜を被覆して本発明の被覆超硬合金を得てもよい。 The coated cemented carbide of the present invention is obtained by cleaning the cemented carbide of the present invention and coating the surface of the cemented carbide of the present invention with a conventionally known method such as PVD or CVD. Can do. In addition, the coated cemented carbide of the present invention may be obtained by grinding the cemented carbide of the present invention and coating the surface thereof.
　本発明の超硬合金および本発明の被覆超硬合金は、インサート、エンドミル、ドリル、リーマ等の切削工具およびダイカットロール、塗布工具、切断刃、耐摩板等の耐摩耗部材の用途に好適に用いることができる。 The cemented carbide of the present invention and the coated cemented carbide of the present invention are suitably used for cutting tools such as inserts, end mills, drills, and reamers, and wear-resistant members such as die-cut rolls, coating tools, cutting blades, and abrasion-resistant plates. be able to.
　原料粉末として市販の平均粒径０．５μｍのＷＣ粉末、平均粒径０．８μｍのＣｏ粉末、平均粒径１．１μｍのＣｒ３Ｃ２粉末、平均粒径０．７μｍのＴｉ（Ｃ，Ｎ）粉末、平均粒径０．８μｍの（Ｔｉ，Ｍｏ）（Ｃ，Ｎ）粉末、平均粒径０．７μｍの（Ｔｉ，Ｗ）（Ｃ，Ｎ）粉末、平均粒径０．９μｍの（Ｔｉ，Ｎｂ）（Ｃ，Ｎ）粉末、平均粒径１．０μｍの（Ｔｉ，Ｎｂ，Ｍｏ）（Ｃ，Ｎ）粉末を用意した。なお、（Ｔｉ，Ｍｏ）（Ｃ，Ｎ）粉末、（Ｔｉ，Ｗ）（Ｃ，Ｎ）粉末、（Ｔｉ，Ｎｂ）（Ｃ，Ｎ）粉末、（Ｔｉ，Ｎｂ，Ｍｏ）（Ｃ，Ｎ）粉末などの複炭窒化物粉末については、複炭窒化物粉末の炭素量ＣＰを赤外線吸収法によって測定し、複炭窒化物粉末の窒素量ＮＰを熱伝導度方式によって測定し、ＮＰ／（ＮＰ＋ＣＰ）の原子比を求め、その値を表１に記載した。 Commercially available WC powder with an average particle size of 0.5 μm, Co powder with an average particle size of 0.8 μm, Cr 3 C 2 powder with an average particle size of 1.1 μm, Ti (C, N) with an average particle size of 0.7 μm ) Powder, (Ti, Mo) (C, N) powder with an average particle diameter of 0.8 μm, (Ti, W) (C, N) powder with an average particle diameter of 0.7 μm, (Ti , Nb) (C, N) powder and (Ti, Nb, Mo) (C, N) powder having an average particle diameter of 1.0 μm were prepared. (Ti, Mo) (C, N) powder, (Ti, W) (C, N) powder, (Ti, Nb) (C, N) powder, (Ti, Nb, Mo) (C, N) For double carbonitride powder such as powder, the carbon content CP of the double carbonitride powder is measured by an infrared absorption method, the nitrogen content NP of the double carbonitride powder is measured by a thermal conductivity method, and NP / (NP + CP ) And the values are shown in Table 1.
　これらの原料粉末を、表１に示す配合組成になるように秤量した。このとき焼結後の超硬合金が遊離炭素あるいはタングステンコバルト炭化物（η相）を生じない健全相域の中央になるように１質量％以下の炭素粉末を添加した。配合した原料粉末とアセトンと超硬合金製ボールとをステンレス製容器に入れて、ボールミルによる混合及び粉砕を２４時間行なった後、加熱乾燥しながら、パラフィンを１．３質量％添加して混合粉末を得た。 These raw material powders were weighed so as to have the composition shown in Table 1. At this time, 1% by mass or less of carbon powder was added so that the cemented carbide after sintering was in the center of a healthy phase region where free carbon or tungsten cobalt carbide (η phase) was not generated. The blended raw material powder, acetone and cemented carbide balls are put into a stainless steel container, mixed and pulverized by a ball mill for 24 hours, and then mixed with 1.3% by weight of paraffin while heating and drying. Got.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　これらの混合粉末を焼結後にＳＥＥＮ１２０３の形状になるようにプレス成形した。このプレス成形により得られた成形体を窒素雰囲気中にて室温から４５０℃まで加熱してパラフィンを除去した後、０．１ｋＰａ以下の真空中で４５０℃から１３４０℃まで加熱して、１．３ｋＰａの窒素雰囲気中にて焼結温度１３４０℃、焼結時間６０分間で焼結することにより、本発明品１～８と比較品９～１２の超硬合金を得た。 These mixed powders were press-molded so as to have the shape of SEEN1203 after sintering. The molded body obtained by this press molding was heated from room temperature to 450 ° C. in a nitrogen atmosphere to remove paraffin, and then heated from 450 ° C. to 1340 ° C. in a vacuum of 0.1 kPa or less to obtain 1.3 kPa. The cemented carbides of the present invention products 1 to 8 and comparative products 9 to 12 were obtained by sintering at a sintering temperature of 1340 ° C. and a sintering time of 60 minutes in a nitrogen atmosphere.
　得られた本発明品１～８および比較品９～１２の超硬合金を＃２３０のダイヤモンド砥石で湿式研磨し、さらに１．０μｍのダイヤモンドペーストで鏡面研磨した後、光学顕微鏡とＳＥＭにより組織観察を行なった。光学顕微鏡写真からＷＣ相と結合相とからなる表面層の厚さを測定した。さらに、イオンミリングした研磨断面組織を１００００倍に拡大したＳＥＭ写真からフルマンの式（式１）によりＷＣ相と炭窒化物相の平均粒径を測定した。なお、炭窒化物相粒子が超硬合金中に均一に分散しておらず、いくつかの炭窒化物相粒子が一塊の凝集体となって存在していた場合、炭窒化物相粒子の凝集体をひとつの粒子として捉えて、フルマンの式（式１）により凝集体の平均粒径を測定した。また、ＥＰＭＡ（電子線マイクロアナライザー）を用いてＷＣ相、炭窒化物相、結合相の組成を調べた。次に気体置換法で超硬合金の密度ＤＢ（ｇ／ｃｍ３）を測定した。さらに超硬合金を目開き７５μｍのふるいを通過するサイズまで粉砕した粉末の密度ＤＰ（ｇ／ｃｍ３）を気体置換法で測定した。ＤＰに対するＤＢの比率（ＤＢ／ＤＰ）を求めた。また、本発明の超硬合金を粉砕して得られた粉末の窒素量は熱伝導度方式を用いて測定した。これらの結果を表２、３に示す。 The obtained cemented carbides of the present invention products 1 to 8 and comparative products 9 to 12 were wet-polished with a # 230 diamond grindstone, and further mirror-polished with a 1.0 μm diamond paste, and the structure was observed with an optical microscope and SEM. Was done. The thickness of the surface layer composed of the WC phase and the binder phase was measured from the optical micrograph. Furthermore, the average particle diameters of the WC phase and the carbonitride phase were measured according to Fullman's formula (Formula 1) from an SEM photograph in which the ion-milled polished cross-sectional structure was magnified 10,000 times. In addition, when the carbonitride phase particles are not uniformly dispersed in the cemented carbide and some carbonitride phase particles are present as agglomerated aggregates, the carbonitride phase particles are aggregated. The aggregate was regarded as one particle, and the average particle size of the aggregate was measured according to Fullman's formula (Formula 1). Further, the composition of the WC phase, carbonitride phase, and binder phase was examined using EPMA (electron beam microanalyzer). Next, density DB (g / cm 3 ) of the cemented carbide was measured by a gas substitution method. Further, the density DP (g / cm 3 ) of the powder obtained by pulverizing the cemented carbide to a size passing through a sieve having an opening of 75 μm was measured by a gas displacement method. The ratio of DB to DP (DB / DP) was determined. Further, the nitrogen content of the powder obtained by pulverizing the cemented carbide of the present invention was measured using a thermal conductivity method. These results are shown in Tables 2 and 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３において本発明品と比較品とを比較すると、本発明品の窒素量は０．１８～０．７４質量％であり、ＷＣ相の平均粒径は０．３５～０．６７μｍ、炭窒化物相の平均粒径は０．１５～０．６０μｍであり、ＤＢ／ＤＰは０．９８～０．９９であり、十分に緻密化されている。一方、比較品９～１２は、ＤＢ／ＤＰが０．９４以下であり、十分に緻密化されていない。 In Table 3, when the product of the present invention and the comparative product are compared, the amount of nitrogen of the product of the present invention is 0.18 to 0.74% by mass, the average particle size of the WC phase is 0.35 to 0.67 μm, and carbonitriding The average particle size of the physical phase is 0.15 to 0.60 μm, and DB / DP is 0.98 to 0.99, which is sufficiently densified. On the other hand, the comparative products 9 to 12 have a DB / DP of 0.94 or less and are not sufficiently densified.
　本発明品１～８および比較品９～１１の超硬合金の刃先部分にホーニング加工を施した後、ＰＶＤ法により、平均膜厚３μｍの（Ｔｉ，Ａｌ）Ｎ膜を被覆して切削工具を作製した。 The cutting edges of the cemented carbides of the inventive products 1 to 8 and comparative products 9 to 11 are subjected to honing, and then a PVD method is used to coat a (Ti, Al) N film having an average film thickness of 3 μm. Produced.
　この切削工具を用いて耐衝撃試験および耐摩耗試験として以下の切削を行なった。耐衝撃試験においては、切削工具に欠損またはチッピングを発生するまでの加工長さを測定し、耐摩耗試験においてはコーナー部の摩耗量が０．３ｍｍに達するまでの加工長さを測定し、各々３回試験した結果の平均を表４に示した。 Using this cutting tool, the following cutting was performed as an impact resistance test and an abrasion resistance test. In the impact resistance test, the machining length until the chipping or chipping occurs in the cutting tool is measured. In the abrasion resistance test, the machining length until the wear amount of the corner reaches 0.3 mm is measured. The average of the results of the three tests is shown in Table 4.
耐衝撃試験
被削材：ＳＣＭ４４０　穴付
工具形状：ＳＥＥＮ１２０３
切削速度：１６０ｍ／ｍｉｎ
切り込み量：２．０ｍｍ
送り量：０．５ｍｍ／ｒｅｖ
工具寿命判定基準：欠損またはチッピングが発生するまでの加工長さ Impact test material: SCM440 Tool shape with hole: SEEN1203
Cutting speed: 160 m / min
Cutting depth: 2.0mm
Feed amount: 0.5mm / rev
Tool life criterion: Machining length until chipping or chipping occurs
耐摩耗試験
被削材：ＳＣＭ４４０
工具形状：ＳＥＥＮ１２０３
切削速度：２５０ｍ／ｍｉｎ
切り込み量：２．０ｍｍ
送り量：０．１ｍｍ／ｒｅｖ
工具寿命判定基準：コーナー摩耗量が０．１ｍｍに達するまでの加工長さ Abrasion test material: SCM440
Tool shape: SEEN1203
Cutting speed: 250 m / min
Cutting depth: 2.0mm
Feed amount: 0.1mm / rev
Tool life criteria: Machining length until corner wear reaches 0.1mm
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　本発明品１～８の切削工具は、欠損またはチッピングが発生するまでの加工長さが９．５ｍ以上であり、優れた耐衝撃性を有している。一方、比較品９～１１の切削工具は超硬合金に含まれる炭窒化物相が粗大であり超硬合金の緻密化が十分でないため、加工長さ８．２以下で欠損してしまい、耐衝撃性に劣った。また、本発明品１～８の被覆超硬合金は、コーナー摩耗量が０．１ｍｍに達するまでの加工長さが１０．５ｍ以上であり、優れた耐摩耗性を有している。一方、比較品９～１１の切削工具は、コーナー摩耗量が０．１ｍｍに達するまでの加工長さが、９．９ｍ以下であり耐摩耗性に劣った。 The cutting tools of the products 1 to 8 of the present invention have an excellent impact resistance with a working length of 9.5 m or more until chipping or chipping occurs. On the other hand, the cutting tools of comparative products 9 to 11 have a coarse carbonitride phase contained in the cemented carbide and the cemented carbide is not sufficiently densified. Inferior in impact. In addition, the coated cemented carbides 1 to 8 of the present invention have excellent wear resistance because the processed length until the corner wear amount reaches 0.1 mm is 10.5 m or more. On the other hand, the cutting tools of comparative products 9 to 11 were inferior in wear resistance because the machining length until the corner wear amount reached 0.1 mm was 9.9 m or less.
　切断すべき製品の形状に合わせて形成した３次元の切刃を円筒外周表面に設けたスリーブ状のダイカッターと、平滑な円筒外周表面を有するスリーブ状のアンビルロールの組合せとからなり、回転するアンビルロール上を移動するワーク材上にダイカッターを回転押圧してワーク材を切断加工するダイカットロールであって、ダイカットロールのダイカッターおよびアンビルロールに本発明品を使用した。 It consists of a combination of a sleeve-shaped die cutter with a three-dimensional cutting edge formed on the outer peripheral surface of the cylinder and a sleeve-shaped anvil roll having a smooth cylindrical outer peripheral surface. A die-cut roll that cuts and processes a work material by rotating and pressing a die cutter onto a work material that moves on the anvil roll, and the product of the present invention was used for the die cutter and the anvil roll of the die-cut roll.
　本発明品１、４、６、８および比較品９～１１を用いたダイカッターおよびアンビルロールを製作し、組み合わせてダイカットロールを構成させて、以下の条件で耐摩耗試験を実施した。なお、耐摩耗試験においてダイカッターおよびアンビルロールは同じものを組み合わせた。 A die cutter and an anvil roll using the inventive products 1, 4, 6, 8 and comparative products 9 to 11 were manufactured and combined to form a die cut roll, and an abrasion resistance test was performed under the following conditions. In the wear resistance test, the same die cutter and anvil roll were combined.
耐摩耗試験条件
加圧力（押圧する総荷重）：１５ｋＮ
ロール周速：２００ｍ／ｍｉｎ
総回転数：１００百万回
耐摩耗試験後、刃先の摩耗幅を測定したところ、比較品９～１１は２０～６５μｍであったのに対して、本発明品１、４、６および８は５～２０μｍであり、耐摩耗性に優れることが確認された。 Wear resistance test condition applied pressure (total load to be pressed): 15 kN
Roll peripheral speed: 200m / min
Total number of rotations: The wear width of the cutting edge was measured after 100 million wear resistance tests. The comparative products 9 to 11 were 20 to 65 μm, whereas the products 1, 4, 6 and 8 of the present invention were It was 5 to 20 μm, and it was confirmed that the wear resistance was excellent.
　フィルム状部材への塗布、パネル状部材への塗布、特に液晶ディスプレイパネルを製造するときのガラス基板表面にカラーレジスト等の塗布液を塗布する工程等に用いられる塗布工具用先端部材（ヘッド部）に本発明品を使用した。 Coating tool tip member (head part) used for coating on film-like members, coating on panel-like members, especially the step of applying a coating solution such as a color resist on the surface of a glass substrate when manufacturing a liquid crystal display panel The product of the present invention was used.
　本発明品１、４、６、８および比較品９～１１を、塗布工具用先端部材をステンレス製部材（塗布工具本体）へボルトで固定し、精密に研削加工をすることで塗布工具を得た。得られた塗布工具で３．２ｍ×２．４ｍの大きさの液晶ディスプレイパネルを製造するときのガラス基板表面にカラーレジストを塗布した。 The inventive product 1, 4, 6, 8 and the comparative products 9 to 11 are fixed to the stainless steel member (coating tool body) with bolts and the application tool is obtained by grinding precisely. It was. The color resist was apply | coated to the glass substrate surface when manufacturing the liquid crystal display panel of a magnitude | size of 3.2 m x 2.4 m with the obtained application tool.
　本発明品１、４、６および８を用いて塗布、乾燥後に膜厚を測定したところ一定であり、比較品９～１１のいずれに対しても２５％以上バラツキが小さく、非常に良好な塗布膜を形成することができた。また、本発明品１、４、６および８を用いて塗布した膜には塗布によるスジ、ムラも全く見られなかった。このほか、脂肪酸、防錆剤、含金属皮膜部剤、含磁性粉末塗布剤、含セラミックス粉末塗布剤などでも同様の塗布を行ったが、本発明品１、４、６および８は、比較品９～１１に比較していずれも塗布膜の厚さのバラツキは同等もしくは小さく、スジやムラは全く見られなかった。さらに、これらのいずれの用途についても、１０００時間の加速耐久使用に対して、面荒れやチッピング、摩耗、腐食などが起こらず、比較品９～１１のいずれと比較しても、経時的な性能の劣化が１０％以上改善された。 When the film thickness was measured after coating and drying using the inventive products 1, 4, 6 and 8, it was constant, and the variation was 25% or more small compared to any of the comparative products 9 to 11, and very good coating. A film could be formed. In addition, no streaks or unevenness due to the application were observed in the films applied using the products 1, 4, 6 and 8 of the present invention. In addition, the same application was performed with fatty acid, rust preventive agent, metal-containing film coating agent, magnetic-containing powder coating agent, ceramic-containing powder coating agent, etc., but the products 1, 4, 6 and 8 of the present invention were comparative products. Compared with 9 to 11, the thickness variation of the coating film was the same or small, and no streak or unevenness was observed. Furthermore, for any of these applications, surface roughness, chipping, wear, corrosion, etc. do not occur with respect to 1000 hours of accelerated durability use, and performance over time compared to any of comparative products 9-11. Degradation of 10% or more was improved.
　本発明品を、シート状部材の切断刃に使用した。すなわち、本発明品１、４、６、８および比較品９～１１を使用して切断刃を作製した。刃先角度は３０度とした。コピー用紙（ＰＰＣ紙）を５００枚重ねて、刃先に水分がある状況で連続裁断テストを行った。 The product of the present invention was used as a cutting blade for a sheet-like member. That is, cutting blades were produced using the inventive products 1, 4, 6, 8 and comparative products 9-11. The edge angle was 30 degrees. 500 sheets of copy paper (PPC paper) were stacked and a continuous cutting test was performed in a state where moisture was present on the blade edge.
　１０００回の裁断を実施した後に刃先摩耗幅を計測したところ、比較品９～１１が９０～２００μｍであったのに対して、本発明品１、４、６および８は５０μｍ以下であり、刃先に発生する腐食摩耗量が明らかに小さかった。 When the cutting edge wear width was measured after cutting 1000 times, the comparative products 9 to 11 were 90 to 200 μm, while the inventive products 1, 4, 6 and 8 were 50 μm or less, and the cutting edge The amount of corrosive wear generated was clearly small.
　本発明品を、粉砕機の耐摩板に使用した。すなわち、本発明品２、４、６、７および比較品９～１１を使用して耐摩板を作製し、以下の条件で耐摩耗試験（ブラスト処理）を実施した。 The product of the present invention was used for a wear-resistant plate of a pulverizer. That is, abrasion resistant plates were produced using the inventive products 2, 4, 6, 7 and comparative products 9 to 11, and an abrasion resistance test (blast treatment) was performed under the following conditions.
耐摩耗試験条件
設備：ブラスト装置
ブラスト時間：３０秒
粒子：ＳｉＣ
ノズルから試料までの距離：１１８ｍｍ
ブラスト照射面積：２０×２０ｍｍ Wear resistance test condition equipment: Blasting equipment Blasting time: 30 seconds Particle: SiC
Distance from nozzle to sample: 118mm
Blast irradiation area: 20 x 20 mm
ブラスト処理後に試料表面の算術平均粗さＲａを測定したところ、比較品９～１１のＲａが４００～６５０ｎｍであったのに対して、本発明品２、４、６および７は１５０ｎｍ以下であり、耐摩耗性に優れることが確認された。 When the arithmetic average roughness Ra of the sample surface was measured after the blast treatment, the comparative products 9 to 11 had an Ra of 400 to 650 nm, whereas the inventive products 2, 4, 6 and 7 had a thickness of 150 nm or less. It was confirmed that it was excellent in wear resistance.
　本発明の超硬合金および被覆超硬合金は、耐衝撃性および耐摩耗性に優れるため、特に切削工具、耐摩耗部材として用いたときに優れた性能を発揮する。
　 Since the cemented carbide and the coated cemented carbide of the present invention are excellent in impact resistance and wear resistance, they exhibit excellent performance particularly when used as cutting tools and wear resistant members.

Claims (21)

  1. 　ＷＣ相：超硬合金全体に対して５５～９４．８体積％と、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された少なくとも１種の炭窒化物およびこれらの相互固溶体から成る群より選択された少なくとも１種からなる炭窒化物相：超硬合金全体に対して１～３０体積％と、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を主成分とする結合相：超硬合金全体に対して４．２～２２．２体積％とからなり、但し、ＷＣ相と炭窒化物相と結合相の合計は１００体積％であり、ＷＣ相の平均粒径が０．０５～０．８μｍであり、炭窒化物相の平均粒径が０．０３～１．１μｍであり、気体置換法で測定した超硬合金の密度ＤＢと、超硬合金を目開き７５μｍのふるいを通過するサイズまで粉砕した粉末の密度ＤＰとの比率（ＤＢ／ＤＰ）が０．９５以上であることを特徴とする超硬合金。 WC phase: 55-94.8% by volume with respect to the entire cemented carbide, and at least one carbonitride selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W And at least one carbon nitride phase selected from the group consisting of these mutual solid solutions: 1 to 30% by volume based on the total cemented carbide, and at least one selected from the group consisting of Co, Ni and Fe A binder phase mainly composed of seeds: 4.2 to 22.2% by volume with respect to the entire cemented carbide, provided that the total of the WC phase, the carbonitride phase and the binder phase is 100% by volume, The average particle size of the WC phase is 0.05 to 0.8 μm, the average particle size of the carbonitride phase is 0.03 to 1.1 μm, and the density DB of the cemented carbide measured by the gas displacement method; Powder obtained by grinding cemented carbide to a size that passes through a 75 μm sieve Cemented carbide ratio of the density DP of (DB / DP) is equal to or is less than 0.95.
  2. 　炭窒化物相は、金属元素がＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された２種以上からなる複炭窒化物である請求項１に記載の超硬合金。 The carbonitride phase is a double carbonitride composed of two or more selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W as a metal element. Cemented carbide.
  3. 　炭窒化物相は、金属元素がＺｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された１種以上とＴｉとからなる複炭窒化物である請求項１または２に記載の超硬合金。 The carbonitride phase is a double carbonitride composed of Ti and at least one selected from the group consisting of Zr, Hf, V, Nb, Ta, Cr, Mo and W as a metal element. The cemented carbide described in 1.
  4. 　超硬合金全体に含まれる窒素量が０．１～２．６質量％である請求項１～３のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 3, wherein an amount of nitrogen contained in the entire cemented carbide is 0.1 to 2.6 mass%.
  5. 　超硬合金全体に含まれる窒素量が０．１～２．０質量％である請求項１～４のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 4, wherein an amount of nitrogen contained in the entire cemented carbide is 0.1 to 2.0 mass%.
  6. 　結合相が、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を合計して、結合相全体に対して５０質量％以上含む請求項１～５のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 5, wherein the binder phase comprises at least one selected from the group consisting of Co, Ni, and Fe in a total amount of 50% by mass or more based on the total binder phase. alloy.
  7. 　結合相が、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種を合計して、結合相全体に対して７０～１００質量％、およびＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、ＣおよびＮから成る群より選択された少なくとも１種を結合相全体に対して０～３０質量％含むものからなる請求項１～６のいずれか１項に記載の超硬合金。 The binder phase is a total of at least one selected from the group consisting of Co, Ni and Fe, and is 70 to 100% by mass with respect to the total binder phase, and Ti, Zr, Hf, V, Nb, Ta, Cr The cemented carbide according to any one of claims 1 to 6, wherein the cemented carbide contains 0 to 30% by mass of at least one selected from the group consisting of Mo, W, C, and N based on the entire binder phase. .
  8. 　結合相に含まれるＣｒ元素量が結合相全体に対して３～１１質量％である請求項１～７のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 7, wherein the amount of Cr element contained in the binder phase is 3 to 11 mass% with respect to the whole binder phase.
  9. 　超硬合金の表面から内部に向かって平均厚さ５～５０μｍのＷＣ相と結合相とからなる表面層が形成された請求項１～８のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 8, wherein a surface layer composed of a WC phase and a binder phase having an average thickness of 5 to 50 µm is formed from the surface of the cemented carbide to the inside.
  10. 　表面層の平均厚さが９～３５μｍである請求項１～９のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 9, wherein the average thickness of the surface layer is 9 to 35 µm.
  11. 　ＤＢ／ＤＰが、０．９８以上である請求項１～１０のいずれか１項に記載の超硬合金。 The cemented carbide according to any one of claims 1 to 10, wherein DB / DP is 0.98 or more.
  12. 　ＷＣ相：５７～９０体積％、炭窒化物相：３～２５体積％および結合相：５～２１体積％とからなり、ＷＣ相と炭窒化物相と結合相の合計は１００体積％である請求項１～１１のいずれか１項に記載の超硬合金。 WC phase: 57 to 90% by volume, carbonitride phase: 3 to 25% by volume, and binder phase: 5 to 21% by volume. The total of the WC phase, the carbonitride phase, and the binder phase is 100% by volume. The cemented carbide according to any one of claims 1 to 11.
  13. 　ＷＣ相：５８～８０体積％、炭窒化物相：３～２５体積％および結合相：５～２１体積％とからなり、ＷＣ相と炭窒化物相と結合相の合計は１００体積％である請求項１～１２のいずれか１項に記載の超硬合金。 WC phase: 58 to 80% by volume, carbonitride phase: 3 to 25% by volume, and binder phase: 5 to 21% by volume. The total of the WC phase, the carbonitride phase, and the binder phase is 100% by volume. The cemented carbide according to any one of claims 1 to 12.
  14. 　超硬合金が、平均粒径０．１～１．０μｍのＷＣ粉末：５５～９４．８体積％と、金属元素がＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、ＭｏおよびＷから成る群より選択された２種以上からなる複炭窒化物であり、複炭窒化物の炭素量ＣＰと窒素量ＮＰの合計に対する窒素量ＮＰの比率（ＮＰ／（ＣＰ＋ＮＰ））が原子比で０．２～０．８である平均粒径０．１～１．０μｍの複炭窒化物粉末：１～３０体積％と、Ｃｏ、ＮｉおよびＦｅから成る群より選択された少なくとも１種からなる平均粒径０．１～１．０μｍの鉄族金属粉末：４．２～２２．２体積％と、平均粒径１．０～４．０μｍのＣｒ３Ｃ２粉末：０～２．２体積％とからなり、これらの合計が１００体積％となるように配合した原料粉末を、混合、粉砕し、得られた混合粉末を成形後、焼結を行なうことにより得られたものである請求項請求項１～１３のいずれか１項に記載の超硬合金。 Cemented carbide is WC powder with an average particle size of 0.1 to 1.0 μm: 55 to 94.8% by volume, and metal elements are composed of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W It is a double carbonitride composed of two or more selected from the group, and the ratio (NP / (CP + NP)) of the nitrogen amount NP to the total of the carbon amount CP and the nitrogen amount NP of the double carbonitride is 0. Double carbonitride powder with an average particle size of 0.1 to 1.0 μm being 2 to 0.8: 1 to 30% by volume, and an average particle consisting of at least one selected from the group consisting of Co, Ni and Fe Iron group metal powder having a diameter of 0.1 to 1.0 μm: 4.2 to 22.2% by volume, and Cr 3 C 2 powder having an average particle diameter of 1.0 to 4.0 μm: 0 to 2.2% by volume Mixed powder obtained by mixing and pulverizing the raw material powder blended so that the total of these is 100% by volume After molding, the cemented carbide according to any one of claims claims 1 to 13, is obtained by conducting the sintering.
  15. 　請求項１～１４のいずれか１項に記載の超硬合金の表面に被膜が被覆された被覆超硬合金。 15. A coated cemented carbide in which the surface of the cemented carbide according to any one of claims 1 to 14 is coated with a coating.
  16. 　被膜が、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、ＡｌおよびＳｉから成る群より選択された少なくとも１種の炭化物、窒化物、炭窒化物、酸化物およびこれらの相互固溶体から成る群より選択された少なくとも１種からなる請求項１５に記載の被覆超硬合金。 The coating is at least one carbide, nitride, carbonitride, oxide selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al and Si and their mutual The coated cemented carbide according to claim 15, comprising at least one selected from the group consisting of solid solutions.
  17. 　被膜が、ＴｉＣ、ＴｉＮ、ＴｉＣＮ、Ａｌ２Ｏ３、ＴｉＡｌＮ、ＴｉＳｉＮ、ＡｌＣｒＮおよび（Ａｌ，Ｃｒ）２Ｏ３から成る群より選択された少なくとも１種からなる請求項１５または１６に記載の被覆超硬合金。 Coating, TiC, TiN, TiCN, Al 2 O 3, TiAlN, TiSiN, AlCrN and (Al, Cr) coating than of claim 15 or 16 comprising at least one member selected from the group consisting of 2 O 3 Hard alloy.
  18. 　請求項１～１４のいずれか１項に記載された超硬合金からなる切削工具。 A cutting tool made of the cemented carbide according to any one of claims 1 to 14.
  19. 　請求項１５～１７のいずれか１項に記載された被覆超硬合金からなる切削工具。 A cutting tool made of the coated cemented carbide according to any one of claims 15 to 17.
  20. 　請求項１～１４のいずれか１項に記載された超硬合金からなる耐摩耗部材。 A wear-resistant member made of the cemented carbide according to any one of claims 1 to 14.
  21. 　請求項１５～１７のいずれか１項に記載された被覆超硬合金からなる耐摩耗部材。 A wear-resistant member made of the coated cemented carbide according to any one of claims 15 to 17.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017186624A (en) * 2016-04-06 2017-10-12 サンアロイ工業株式会社 Hard metal alloy and manufacturing method therefor and carbide tool
US10262819B2 (en) 2015-09-03 2019-04-16 Meidensha Corporation Vacuum circuit breaker
EP4006199A1 (en) * 2020-11-26 2022-06-01 AB Sandvik Coromant A coated cutting tool
WO2023042777A1 (en) * 2021-09-17 2023-03-23 日本特殊合金株式会社 Coated ultrafine grain cemented carbide, and cutting tool or abrasion-resistant member using same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018193659A1 (en) * 2017-04-19 2018-10-25 住友電気工業株式会社 Cemented carbide, cutting tool including cemented carbide, method for producing cemented carbide
JP7388431B2 (en) * 2019-11-26 2023-11-29 住友電気工業株式会社 Cemented carbide and cutting tools containing it as a base material
JP7383498B2 (en) * 2020-01-14 2023-11-20 日本特殊合金株式会社 Manufacturing method of ultrafine cemented carbide
CN117677724A (en) 2022-01-19 2024-03-08 住友电气工业株式会社 Cemented carbide and tool comprising the same
WO2024105882A1 (en) 2022-11-18 2024-05-23 住友電気工業株式会社 Cemented carbide and tool containing same

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5487719A (en) * 1977-12-23 1979-07-12 Sumitomo Electric Industries Super hard alloy and method of making same
JPS6176646A (en) * 1984-09-21 1986-04-19 Mitsubishi Metal Corp Tungsten carbide-base sintered hard alloy
JPS6479340A (en) * 1987-09-22 1989-03-24 Kyocera Corp Hard alloy
JPH10110235A (en) * 1996-10-04 1998-04-28 Sumitomo Electric Ind Ltd Hard alloy having high hardness and its production
JPH10324943A (en) * 1997-05-27 1998-12-08 Tokyo Tungsten Co Ltd Ultra-fine cemented carbide, and its manufacture
JP2000015514A (en) * 1998-06-30 2000-01-18 Hitachi Tool Engineering Ltd Twisted drill made of cemented carbide
JP2001049378A (en) * 1999-06-03 2001-02-20 Ngk Spark Plug Co Ltd Wear resistant cemented carbide sintered compact and its manufacture
JP2004190118A (en) * 2002-12-13 2004-07-08 Kyocera Corp Cemented carbide, its production method, and cutting tool using the same
JP2004232042A (en) * 2003-01-31 2004-08-19 Allied Material Corp Hard metal
JP2006131974A (en) * 2004-11-08 2006-05-25 Sumitomo Electric Ind Ltd Cemented carbide

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5487719A (en) * 1977-12-23 1979-07-12 Sumitomo Electric Industries Super hard alloy and method of making same
JPS6176646A (en) * 1984-09-21 1986-04-19 Mitsubishi Metal Corp Tungsten carbide-base sintered hard alloy
JPS6479340A (en) * 1987-09-22 1989-03-24 Kyocera Corp Hard alloy
JPH10110235A (en) * 1996-10-04 1998-04-28 Sumitomo Electric Ind Ltd Hard alloy having high hardness and its production
JPH10324943A (en) * 1997-05-27 1998-12-08 Tokyo Tungsten Co Ltd Ultra-fine cemented carbide, and its manufacture
JP2000015514A (en) * 1998-06-30 2000-01-18 Hitachi Tool Engineering Ltd Twisted drill made of cemented carbide
JP2001049378A (en) * 1999-06-03 2001-02-20 Ngk Spark Plug Co Ltd Wear resistant cemented carbide sintered compact and its manufacture
JP2004190118A (en) * 2002-12-13 2004-07-08 Kyocera Corp Cemented carbide, its production method, and cutting tool using the same
JP2004232042A (en) * 2003-01-31 2004-08-19 Allied Material Corp Hard metal
JP2006131974A (en) * 2004-11-08 2006-05-25 Sumitomo Electric Ind Ltd Cemented carbide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10262819B2 (en) 2015-09-03 2019-04-16 Meidensha Corporation Vacuum circuit breaker
JP2017186624A (en) * 2016-04-06 2017-10-12 サンアロイ工業株式会社 Hard metal alloy and manufacturing method therefor and carbide tool
EP4006199A1 (en) * 2020-11-26 2022-06-01 AB Sandvik Coromant A coated cutting tool
WO2022112162A1 (en) * 2020-11-26 2022-06-02 Ab Sandvik Coromant A coated cutting tool
WO2023042777A1 (en) * 2021-09-17 2023-03-23 日本特殊合金株式会社 Coated ultrafine grain cemented carbide, and cutting tool or abrasion-resistant member using same

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