WO2024203158A1 - 切削工具用超硬合金と該合金を用いた切削工具 - Google Patents

切削工具用超硬合金と該合金を用いた切削工具 Download PDF

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WO2024203158A1
WO2024203158A1 PCT/JP2024/008996 JP2024008996W WO2024203158A1 WO 2024203158 A1 WO2024203158 A1 WO 2024203158A1 JP 2024008996 W JP2024008996 W JP 2024008996W WO 2024203158 A1 WO2024203158 A1 WO 2024203158A1
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avg
phase
cemented carbide
phases
cutting
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English (en)
French (fr)
Japanese (ja)
Inventor
龍 市川
佳祐 河原
万梨子 山本
誠 五十嵐
一樹 岡田
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to EP24779291.4A priority Critical patent/EP4692393A1/en
Priority to JP2025510200A priority patent/JPWO2024203158A1/ja
Publication of WO2024203158A1 publication Critical patent/WO2024203158A1/ja
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    • 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
    • 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
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware

Definitions

  • the present invention relates to a cemented carbide (WC-based sintered alloy) and a cutting tool using said alloy.
  • Cemented carbide has excellent mechanical strength and thermal fatigue resistance, and is therefore used in tools that are subjected to large impact forces and thermal cycles, such as cutting tools, drilling tools, and metal forming tools.
  • Patent Document 1 describes a cemented carbide containing a composite carbide (solid solution) of (Ti, W, Ta, Nb, Zr), and claims that by replacing part of the Ta with less expensive Nb and Zr, the production cost of the cemented carbide can be reduced and that performance will not decrease even when used for cutting purposes.
  • the present invention was made in consideration of the above circumstances and proposals, and aims to provide a cemented carbide alloy that can be used as a cutting tool with a cutting edge that has excellent resistance to plastic deformation and chipping, even when used to cut stainless steel.
  • the cemented carbide for cutting tools is Co, Ni in total 5.0 to 15.0 mass%, Ti, Zr, Nb, and Ta in total 4.0 to 12.0 mass%; Contains 5.4 to 6.5 mass% C; The balance is W and inevitable impurities.
  • the hard phase mainly contains W carbides, a binder phase mainly contains Co and Ni, and a gamma phase mainly contains Ti, Zr, Nb, Ta and W carbides,
  • the hard phase mainly composed of W carbides has an average grain size of 0.5 to 4.0 ⁇ m, and the ⁇ phase has an average grain size of 1.0 to 4.0 ⁇ m.
  • the gamma phases in which the gamma 1 phase exists which is a region in which d is 8 or more higher than d avg, account for 20 to 80% of the total gamma phases. To exist in.
  • the cutting tool according to the embodiment of the present invention uses the above-mentioned cemented carbide for cutting tools.
  • the cutting edge has excellent resistance to plastic deformation and chipping, even when used to cut stainless steel.
  • FIG. 2 is a schematic diagram showing an example of the structure of the cemented carbide for tools according to the embodiment of the present invention.
  • FIG. 1 is an explanatory diagram showing a method of line analysis. 1 is a schematic diagram showing an example of the amount of plastic deformation on the flank of a cutting edge, in which the upper diagram is a plan view of the rake face and the lower diagram is a side view of the flank.
  • the present inventors have conducted extensive research in order to obtain a cemented carbide for cutting tools that can achieve the above-mentioned object. As a result, they have found that the average grain size of the hard phase and the ⁇ phase is within a predetermined range, and When the composition of the ⁇ phase is set to a predetermined value, that is, when the average atomic ratio of the metal components contained in the ⁇ phase is within a predetermined range and the average value of the standard deviation of each metal component between the ⁇ phase particles is within a predetermined range, It has been found that the above object can be achieved.
  • a cemented carbide for cutting tools and a cutting tool using the alloy according to an embodiment of the present invention will be described.
  • composition and Structure of the Cemented Carbide for Cutting Tools The composition of the cemented carbide for cutting tools according to this embodiment and the details of the structure shown typically in FIG. 1 are as follows.
  • Co and Ni It is preferable that one or both of Co and Ni are contained, and the total content of at least one of Co and Ni is preferably 5.0 to 15.0 mass %. The reason is that when used as a cutting tool, if the content is less than 5.0% by mass, the chipping resistance is insufficient, whereas if the content exceeds 15.0% by mass, the plastic deformation resistance is reduced.
  • Co and Ni are mainly present in the binder phase (which has crystal grains with an fcc structure, and is indicated by the symbol (1) in Figure 1), and are the main components of the binder phase, i.e., the main components, with the total of Co and Ni atoms accounting for 50 atomic % or more of all the components (atoms) that make up the binder phase.
  • the binder phase may contain W and C, which are components of the hard phase, one or more of Ti, Zr, Nb, Ta, and W, which are contained in the ⁇ phase, Cr, which controls the growth of the hard phase, and unavoidable impurities.
  • W and C which are components of the hard phase
  • Ti, Zr, Nb, Ta, and W which are contained in the ⁇ phase, Cr, which controls the growth of the hard phase, and unavoidable impurities.
  • Ti, Zr, Nb, Ta It is preferable that all of Ti, Zr, Nb, and Ta are contained, and the total content of Ti, Zr, Nb, and Ta is 4.0 to 12.0 mass %. The reason is that when used as a cutting tool, if the content is less than 4.0% by mass, the plastic deformation resistance is insufficient, whereas if the content exceeds 12.0% by mass, the chipping resistance decreases.
  • Ti, Zr, Nb, Ta and W which will be described later, are contained in the ⁇ phase.
  • a avg , b avg , c avg , d avg and e avg 100.0
  • a avg + b avg + c avg + d avg + e avg 100.0
  • the average value (( ⁇ a+ ⁇ b+ ⁇ c+ ⁇ d+ ⁇ e)/4) is 0.4 or less (the lower limit may be 0.0, but in one example of the manufacturing method described below, the lower limit is about 0.1). The reason for this is that if this average value exceeds 0.4, the plastic deformation resistance and fracture resistance decrease.
  • the atomic ratio of the metal components contained in the gamma phase is within a predetermined range that is approximately equal. This is because when used as a cutting tool, it provides excellent resistance to plastic deformation and chipping.
  • the ⁇ phase may contain WC contained in the hard phase, Co and Ni contained in the binder phase, and unavoidable impurities.
  • the ⁇ phase is indicated by symbols (3) and (4), and some of the ⁇ phases (symbol (4)) contain a ⁇ 1 phase (symbol (5)) with a different composition.
  • the average grain size of the gamma phase is preferably 1.0 to 4.0 ⁇ m.
  • the reason for this is that when the cemented carbide for cutting tools is used as a cutting tool, if it is less than 1.0 ⁇ m, the resistance to chipping is insufficient, and if it exceeds 4.0 ⁇ m, the resistance to plastic deformation is insufficient.
  • the average grain size of the gamma phase refers to the circle equivalent diameter, that is, the diameter of a circle having an area equal to that of the gamma phase, and the method of measuring it will be described later.
  • the ⁇ phases containing ⁇ 1 phases which are regions in which d is 8 or more higher than davg (the upper limit is 22 in an example of the manufacturing method described later), account for 20 to 80% of all the ⁇ phases.
  • the presence of a predetermined proportion of ⁇ phases containing ⁇ 1 phases further improves plastic deformation resistance and chipping resistance.
  • C C is contained to form carbides, and is mainly contained in the hard phase, ⁇ phase, and ⁇ 1 phase.
  • the C content is preferably 5.4 to 6.5 mass%, and within this content range, a sufficient amount of carbides can be formed in the hard phase, ⁇ phase, and ⁇ 1 phase.
  • Cr Cr is an optional component and may be contained in an amount of less than 0.5 mass %, that is, the inclusion of Cr is not essential. Cr dissolves in the binder phase, suppresses the growth of W carbides contained in the hard phase, refines the W carbides, and creates a structure with a narrow grain size distribution, thereby improving the toughness of the cemented carbide and improving its resistance to plastic deformation. This function is impaired when the Cr content exceeds 0.5 mass%, causing precipitation of composite carbides of Cr and W in the binder phase, reducing toughness and possibly becoming the starting point for chipping.
  • W W is the main component of the hard phase, i.e., the main ingredient, and W carbides (mostly WC, but not limited to the stoichiometric composition) account for 50 atomic % or more of all the ingredients (atoms) that make up the hard phase (indicated by the symbol (2) in FIG. 1 ).
  • the hard phase may contain the components of the binder phase, the components of the ⁇ phase, Cr, and the inevitable impurities that are inevitably mixed in during the manufacturing process.
  • the crystal structure of the hard phase is hcp structure, so the crystal structure is different from that of the ⁇ phase that is fcc structure. The method for identifying the hard phase will be described later.
  • the average grain size of the hard phase is preferably 0.5 to 4.0 ⁇ m, because when used as a cutting tool, if the average grain size is less than 0.5 ⁇ m, the chipping resistance is insufficient, whereas if it exceeds 4.0 ⁇ m, the plastic deformation resistance is reduced.
  • the average grain size of the hard phase refers to the equivalent circle diameter, that is, the diameter of a circle having the same area as the hard phase, as in the case of the ⁇ phase, and the method of measurement will be described later.
  • the hard phase, ⁇ phase, and binder phase may contain impurities that are inevitably (unintentionally) mixed in during the manufacturing process, and the amount of such impurities is preferably 0.3% by mass or less, with the total amount of the cemented carbide being 100% by mass.
  • Measurement method (1) Measurement of composition of cemented carbide for cutting tools
  • the surface or cross section of cemented carbide for cutting tools is mirror-finished using, for example, a focused ion beam device (FIB device), a cross-section polisher device (CP device), etc. Then, this mirror-finished surface is observed in multiple fields (e.g., 4000 times magnification, 5 fields) using a field emission scanning electron microscope (SEM) (the size of one field is, for example, a square of 25 ⁇ m (vertical) ⁇ 25 ⁇ m (horizontal)), and surface analysis is performed using an electron probe microanalyzer (EPMA) to measure the composition for each field.
  • SEM field emission scanning electron microscope
  • EPMA electron probe microanalyzer
  • the beam diameter of the EPMA can be exemplified as 1 ⁇ m.
  • the alloy composition obtained in each measurement field is averaged to determine the composition of the entire alloy.
  • the hard phase, ⁇ phase and binder phase are identified by the following measurements. 1) For the mirror-finished surface on which the composition of the entire cemented carbide for cutting tools is measured, a rectangular observation field of, for example, 24 ⁇ m (vertical) ⁇ 72 ⁇ m (horizontal) is set as one field of view on the mirror-finished surface, and an EBSD pattern and EDS data are simultaneously captured using a field emission scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDS) and an electron backscattered diffraction device (EBSD measurement device).
  • SEM field emission scanning electron microscope
  • EDS energy dispersive X-ray spectrometer
  • EBSD measurement device electron backscattered diffraction device
  • EDS and EBSD device OIM Data Collection manufactured by EDAX/TSL (now AMETEK), but is not limited thereto.
  • an example of the measurement conditions using the field emission scanning electron microscope (SEM) is an acceleration voltage of 15 kV and a measurement point interval of 50 nm, but is not limited thereto.
  • Examples of software used to analyze EBSD patterns include TSL's OIM Data Collection version 6 and TSL's OIM Analysis version 7, but are not limited to these as long as they can perform similar analyses.
  • the average value of the detected Co and Ni EDS count values is calculated, and the measurement points identified as fcc and hcp phases having Co and Ni EDS count values higher than this average value are designated as binder phases.
  • Measurement points that are judged to be phases having an hcp crystal structure other than the binder phase identified as the hcp phase are designated as hard phases, and the remaining measurement points are designated as ⁇ phases.
  • FIG. 2 the gamma phase (4) to be measured has a gamma phase (5) therein, but the gamma phase (3) shown in FIG. 1, which does not have a gamma phase (5), is also measured without distinction.
  • the size of the observation field is, for example, a rectangle of 24 ⁇ m in length and 72 ⁇ m in width, and a reference line (6) is set within the observation field that is in contact with the phase interface of the gamma phase (4) to be measured (in FIG. 2, the reference line (6) is horizontal to the observation field, but is not limited to being horizontal).
  • a measurement line (7) is set so as to be parallel to the reference line (6) at an interval of 1/10 of the average grain size of the gamma phase (average grain size determined without distinguishing whether or not it has a gamma phase) determined separately as described below.
  • the measurement lines (7) are set at the same intervals until they do not penetrate the gamma phase (4) to be measured.
  • An EPMA line analysis is performed on all measurement lines (7) in the gamma phase (4) to be measured, with the measurement point interval being 50 nm, and the atomic ratios of Ti, Zr, Nb, Ta and W to all atoms measured at each measurement point, i.e., a, b, c, d and e, are measured.
  • the EPMA beam diameter can be exemplified as 50 nm.
  • the EPMA line analysis (beam diameter can be exemplified as 50 nm) is performed on four different gamma phases per observation field to obtain the atomic ratios of Ti, Zr, Nb, Ta and W contained in the gamma phase. This atomic ratio is similarly obtained in five or more observation fields, and all the measured values of at least 20 gamma phases obtained are averaged, and a avg , b avg , c avg , d avg and e avg are calculated.
  • the number of observation fields in one observation field is less than four, the number of observation fields is increased so that the total number of ⁇ phases measured is at least 20, and a avg , b avg , c avg , d avg and e avg are calculated.
  • Average grain size of hard phase and ⁇ phase While measuring and analyzing the above-mentioned EBSD pattern, the average grain size is measured for the phases identified as the hard phase and ⁇ phase.
  • the average grain size of both phases is measured by determining the area of at least 300 phases for each type of phase, calculating the diameter of a circle equal to each area, and averaging them.
  • Examples of software used to measure the average grain size include OIM Data Collection version 6 manufactured by TSL and OIM Analysis version 7 manufactured by TSL, but are not limited to these as long as it can perform the same analysis.
  • the cemented carbide for cutting tools according to this embodiment and a cutting tool using the cemented carbide for cutting can be manufactured, for example, as follows.
  • Raw material powders such as WC powder, Co powder, and carbide powders containing Ti, Zr, Nb, and Ta are prepared, wet-mixed, dried, and press-molded into the desired cutting tool shape, and then sintered.
  • Sintering is performed by holding at a given temperature of 1440 to 1470°C for 1 to 3 hours, cooling to 1200°C, and then holding at 1200°C for 0 to 24 hours (holding for 0 hours means not holding).
  • the carbide powder containing Ti, Zr, Nb, and Ta may be a powder of each of Ti carbide, Zr carbide, Nb carbide, and Ta carbide, or a powder of multiple composite carbides containing two or more of Ti, Zr, Nb, and Ta, so long as the cemented carbide for cutting tools contains all of Ti, Zr, Nb, and Ta.
  • powders were then mixed to obtain the composition shown in Table 1 to prepare powder for sintering.
  • the powder was then wet mixed in a ball mill for 72 hours, dried, and then pressed at a pressure of 100 MPa to produce a powder compact.
  • these powder compacts were subjected to a liquid phase sintering (main sintering) process in which they were held at a predetermined temperature for a predetermined time.
  • the main sintering was performed under the conditions shown in Table 2, that is, in a vacuum atmosphere of 0.1 Pa or less, by heating to a holding temperature range of 1440°C and holding at that holding temperature for 2 hours, or by heating to a holding temperature range of 1470°C and holding at that holding temperature for 1 hour.
  • Comparative Examples 1' to 9' comparative cemented carbide alloys 1' to 9' (hereinafter referred to as Comparative Examples 1' to 9') were produced.
  • the manufacturing process is one in which the alloy composition is outside the above-mentioned range in the manufacturing processes of Examples 1 to 10, the holding temperature is 1360°C or 1470°C, the cooling rate is more than 20°C/min, and/or the holding time at 1200°C is 0 to 1 hour.
  • the sintering powders which were mixed according to the composition shown in Table 1, were wet mixed in a ball mill for 72 hours, dried, and then pressed at a pressure of 100 MPa to produce a green compact.
  • the green compact was then sintered under the conditions shown in Table 2, that is, in a vacuum atmosphere of 0.1 Pa or less, heated to a holding temperature range of 1360°C or 1470°C, and held at that temperature for 1 hour. Thereafter, the inside of the furnace was kept in a vacuum atmosphere of 0.1 Pa or less, cooled to 1200°C at 70°C/min, and held at 1200°C for 0 to 1 hour to produce Comparative Examples 1' to 9' shown in Table 4.
  • the coating layer is formed by vapor deposition in a three-layer laminate structure here, the number of layers in this laminate structure is not limited to three, and may be one, two, or four or more layers.
  • the vapor deposition conditions for the hard coating layer but the chemical vapor deposition conditions for TiN, TiCN, and Al 2 O 3 in the above-mentioned Examples 6 to 10 and Comparative Examples 6' to 9' were as follows.
  • Reactant gas (volume %): AlCl3 2.2%, CO2 5.5%, HCl 2.2%, H2S 0.2%, H2 balance Reaction pressure: 7 kPa Reaction temperature: 1000°C
  • cutting test 1 was performed on Examples 1 to 5 and Comparative Examples 1' to 5' in which no coating layer was formed
  • cutting test 2 was performed on Examples 6 to 10 and Comparative Examples 6' to 9' in which a coating layer was formed, to measure the amount of plastic deformation on the flank of the cutting edge and to observe the state of wear on the cutting edge.
  • Cutting test 1 Wet external diameter turning of alloy steel (JIS, SUS304) round bar (diameter 200 mm) Workpiece: JIS, SUS304 Cutting speed: 250m/min Cut: 1.8 mm Feed: 0.18 mm/rev Cutting time: 5 minutes (cutting was interrupted every 20 seconds to observe the cutting edge) Uses wet water-soluble cutting oil
  • Cutting test 2 Dry external diameter turning of alloy steel (JIS, SUS304) round bar (diameter 200 mm) Workpiece: JIS, SUS304 Cutting speed: 55m/min Cut: 1.1 mm Feed: 0.12 mm/rev Cutting time: 5 minutes (cutting was interrupted every 20 seconds to observe the cutting edge) Uses wet water-soluble cutting oil
  • the amount of plastic deformation on the cutting edge flank was measured and the state of wear on the cutting edge was observed.
  • the amount of plastic deformation on the cutting edge flank was measured by drawing a line segment on the ridge where the flank (9) on the main cutting edge side of the tool intersects with the rake face (8) at a position sufficiently distant from the cutting edge (10), extending the line segment toward the cutting edge, and measuring the maximum distance between the extended line segment (12) and the cutting edge ridge (perpendicular to the extended line segment), which was taken as the amount of plastic deformation on the cutting edge flank (11).
  • the amount of plastic deformation on the flank was 0.100 mm or more, the state of wear was taken as cutting edge deformation (see Figure 3).
  • Binder phase 2 Hard phase 3 ⁇ phase 4 ⁇ phase ( ⁇ phase with ⁇ 1 phase) 5 ⁇ 1 phase 6 Reference line 7 Measurement line 8 Rake face 9 Main cutting edge side flank 10 Cutting edge 11 Amount of plastic deformation on the flank of the cutting edge 12 Extending line segment

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
PCT/JP2024/008996 2023-03-30 2024-03-08 切削工具用超硬合金と該合金を用いた切削工具 Ceased WO2024203158A1 (ja)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025205593A1 (ja) * 2024-03-25 2025-10-02 三菱マテリアル株式会社 表面被覆切削工具
WO2025205594A1 (ja) * 2024-03-25 2025-10-02 三菱マテリアル株式会社 表面被覆切削工具

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001179507A (ja) * 1999-12-24 2001-07-03 Kyocera Corp 切削工具
CN1425787A (zh) 2002-10-10 2003-06-25 株洲硬质合金集团有限公司 碳化钨基硬质合金
WO2021193159A1 (ja) * 2020-03-26 2021-09-30 三菱マテリアル株式会社 Ｗｃ基超硬合金製切削工具
JP2023056798A (ja) 2021-10-08 2023-04-20 富士通株式会社 機械学習プログラム、検索プログラム、機械学習装置、及び方法
WO2023166900A1 (ja) * 2022-03-03 2023-09-07 京セラ株式会社 超硬合金およびこれを用いた被覆工具、切削工具

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001179507A (ja) * 1999-12-24 2001-07-03 Kyocera Corp 切削工具
CN1425787A (zh) 2002-10-10 2003-06-25 株洲硬质合金集团有限公司 碳化钨基硬质合金
WO2021193159A1 (ja) * 2020-03-26 2021-09-30 三菱マテリアル株式会社 Ｗｃ基超硬合金製切削工具
JP2023056798A (ja) 2021-10-08 2023-04-20 富士通株式会社 機械学習プログラム、検索プログラム、機械学習装置、及び方法
WO2023166900A1 (ja) * 2022-03-03 2023-09-07 京セラ株式会社 超硬合金およびこれを用いた被覆工具、切削工具

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025205593A1 (ja) * 2024-03-25 2025-10-02 三菱マテリアル株式会社 表面被覆切削工具
WO2025205594A1 (ja) * 2024-03-25 2025-10-02 三菱マテリアル株式会社 表面被覆切削工具

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