WO2022137399A1 - Carbure métallique, et outil de coupe contenant celui-ci en tant que substrat - Google Patents

Carbure métallique, et outil de coupe contenant celui-ci en tant que substrat Download PDF

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WO2022137399A1
WO2022137399A1 PCT/JP2020/048247 JP2020048247W WO2022137399A1 WO 2022137399 A1 WO2022137399 A1 WO 2022137399A1 JP 2020048247 W JP2020048247 W JP 2020048247W WO 2022137399 A1 WO2022137399 A1 WO 2022137399A1
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cemented carbide
phase
particles
hard phase
elements
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PCT/JP2020/048247
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English (en)
Japanese (ja)
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貴翔 山西
晋也 今村
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住友電工ハードメタル株式会社
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Publication of WO2022137399A1 publication Critical patent/WO2022137399A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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

  • This disclosure relates to cemented carbide and cutting tools containing it as a base material.
  • cemented carbide having a hard phase containing tungsten carbide (WC) as a main component and a bonded phase containing an iron group element (for example, Fe, Co, Ni) as a main component has been used as a material for cutting tools.
  • the characteristics required for a cutting tool include strength (for example, bending force), toughness (for example, breaking toughness), hardness (for example, Vickers hardness), plastic deformation resistance, and wear resistance.
  • HSA high entropy alloys
  • Patent Document 1 describes C, Si, Al, Cr, Co, Cu, Fe, Ni, V, Mn, Ti and the like in Japanese Patent Application Laid-Open No. 2019-516007 (Patent Document 1).
  • Document 2 discloses HEA in which Co, Cr, Cu, W, Fe, Ni, Mo, Mn and the like are combined as constituent elements of a super hard alloy.
  • the cemented carbide according to the present disclosure is A cemented carbide containing a first hard phase and a bonded phase.
  • the first hard phase is composed of tungsten carbide particles.
  • the bonded phase is composed of cobalt, nickel, iron and chromium as constituent elements.
  • the average content ratio of each of the constituent elements in the bonded phase is 10 atomic% or more and 30 atomic% or less. It does not contain the second hard phase, or the content of the second hard phase is 2% by mass or less with respect to the total amount of the cemented carbide.
  • the second hard phase is one or more metal elements selected from the group consisting of group 4 elements, group 5 elements and group 6 elements excluding tungsten in the periodic table, and one selected from the group consisting of carbon, nitrogen and oxygen. It is composed of the above elements and a compound containing the above elements.
  • the cutting tool according to the present disclosure includes the cemented carbide according to the above disclosure as a base material.
  • FIG. 1 is a schematic cross-sectional view for explaining the reactivity evaluation of the cemented carbide according to the present embodiment.
  • the present disclosure has been made in view of the above circumstances, and is a cemented carbide having excellent wear resistance when processing a difficult-to-cut material, particularly an alloy containing titanium as a main component, and a cutting tool containing the same as a base material.
  • the purpose is to provide.
  • the cemented carbide according to one aspect of the present disclosure is A cemented carbide containing a first hard phase and a bonded phase.
  • the first hard phase is composed of tungsten carbide particles.
  • the bonded phase is composed of cobalt, nickel, iron and chromium as constituent elements.
  • the average content ratio of each of the constituent elements in the bonded phase is 10 atomic% or more and 30 atomic% or less. It does not contain the second hard phase, or the content of the second hard phase is 2% by mass or less with respect to the total amount of the cemented carbide.
  • the second hard phase is one or more metal elements selected from the group consisting of group 4 elements, group 5 elements and group 6 elements excluding tungsten in the periodic table, and one selected from the group consisting of carbon, nitrogen and oxygen. It is composed of the above elements and a compound containing the above elements.
  • the cemented carbide is less likely to cause mutual diffusion between Ti contained in the titanium alloy and WC or Co contained in the cemented carbide. As a result, the cemented carbide becomes a cemented carbide having excellent wear resistance against a work material containing a titanium alloy.
  • any cross section of the cemented carbide Assuming that a region in which the ratio of the content ratio of at least one of the constituent elements is 85% or less and 115% or more with respect to the average content ratio is an unevenly distributed region, it is assumed. It is preferable that the total area of the unevenly distributed regions in the bonded phase is 6% or less with respect to the total area of the bonded phase.
  • the cutting tool according to one aspect of the present disclosure contains the cemented carbide according to any one of the above [1] or [2] as a base material. Since the above-mentioned cutting tool contains a cemented carbide having excellent wear resistance with a titanium alloy as a base material, the life of the cutting tool is extended even when it is used for cutting a difficult-to-cut material containing a titanium alloy. Etc. can be realized.
  • the cutting tool further includes a coating film provided on the base material.
  • a coating film provided on the surface of the base material. Therefore, the above-mentioned cutting tool can cope with more severe cutting conditions, further extend the life, and the like.
  • the present embodiment an embodiment of the present disclosure (hereinafter referred to as “the present embodiment”) will be described. However, this embodiment is not limited to this.
  • the cemented carbide of this embodiment is A cemented carbide containing a first hard phase and a bonded phase.
  • the first hard phase is composed of tungsten carbide particles.
  • the bonded phase is composed of cobalt, nickel, iron and chromium as constituent elements.
  • the average content ratio of each of the constituent elements in the bonded phase is 10 atomic% or more and 30 atomic% or less. It does not contain the second hard phase, or the content of the second hard phase is 2% by mass or less with respect to the total amount of the cemented carbide.
  • the second hard phase is one or more metal elements selected from the group consisting of group 4 elements, group 5 elements and group 6 elements excluding tungsten in the periodic table, and one selected from the group consisting of carbon, nitrogen and oxygen. It is composed of the above elements and a compound containing the above elements.
  • the cemented carbide of the present embodiment is a cemented carbide containing a first hard phase and a bonded phase, and may include a second hard phase. In addition, it may contain an element that does not belong to any of the first hard phase, the bonded phase and the second hard phase.
  • the first hard phase is composed of tungsten carbide (hereinafter, may be referred to as “WC”) particles.
  • the WC includes not only "pure WC (WC containing no impurity element and WC containing impurity elements below the detection limit)" but also "the inside thereof as long as the effect of the present disclosure is not impaired". Also includes the first hard phase, which intentionally or inevitably contains other impurity elements.
  • the concentration of impurities contained in WC is 1% by mass or less with respect to the total amount of the WC and the impurities.
  • the average particle size of the WC particles in the cemented carbide is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the toughness of the cemented carbide tends to be high. Therefore, the cutting tool containing the cemented carbide as a base material can suppress chipping or chipping due to mechanical impact and thermal impact.
  • the cutting tool since the cutting tool has improved crack propagation resistance, crack propagation can be suppressed, and chipping or chipping can be suppressed.
  • the cutting tool containing the cemented carbide as a base material can suppress deformation during cutting and can suppress wear or chipping.
  • the average particle size of the WC particles in the cemented carbide is obtained by mirror-processing an arbitrary surface or an arbitrary cross section of the cemented carbide, photographing the processed surface with a microscope, and analyzing the photographed image. Desired. Specifically, the particle size (Heywood diameter: equivalent area circle diameter) of each WC particle is calculated from the photographed image, and the average value thereof is taken as the average particle size of the WC particles.
  • the number of WC particles to be measured is preferably at least 100, and more preferably 200 or more. Further, it is preferable to perform the above image analysis in a plurality of fields in the same cemented carbide and use the average value as the average particle size of the WC particles.
  • the number of fields of view for image analysis is preferably 5 or more, more preferably 7 or more, still more preferably 10 or more, and even more preferably 20 or more.
  • One field of view may be, for example, a square having a length of 20 ⁇ m and a width of 20 ⁇ m.
  • Examples of the mirror surface processing method include a method of polishing with diamond paste, a method of using a focused ion beam device (FIB device), a method of using a cross section polisher device (CP device), and a method of combining these.
  • FIB device focused ion beam device
  • CP device cross section polisher device
  • a method of combining these When the machined surface is photographed with a metallurgical microscope, it is preferable to etch the machined surface with Murakami's reagent.
  • each of the WC particles constituting the first hard phase, the bonded phase described later and the second hard phase described later can be identified by the following methods.
  • the image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.) is used as the image analysis software, and the microscope image is binarized. It becomes possible by doing.
  • the binarization process refers to a process of converting the density of each pixel into two values of 1 and 0 by a constant reference value (threshold value).
  • a discriminant analysis method is used for the binarization process in the present disclosure.
  • the area ratio of the first hard phase to any surface or any cross section of the cemented carbide is preferably 70% or more and 99% or less, and 86% or more and 95%. The following is more preferable.
  • the area ratio of the first hard phase is determined, for example, by photographing an arbitrary processed surface of the cemented carbide with a microscope and analyzing the photographed image in the same manner as in the case of obtaining the average particle size of the WC particles described above. Desired. That is, the above-mentioned microscope image is binarized to recognize WC particles by using image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.) to obtain a binarized image. ..
  • the binarization process is performed based on, for example, the brightness of the pixels.
  • the lightness threshold value in the binarization process is a value obtained by multiplying a value extracted from an arbitrary point near the center of the first hard phase particle that looks darkest in the image by 0.8.
  • the sum of the areas of the WC particles in the microscope image (total area) is calculated, and this is divided by the area of the entire visual field (binarized image) to obtain the first hardness in the visual field. It is possible to calculate the area ratio of the phases. Then, in the same cemented carbide, the above image analysis is performed in a plurality of fields (for example, 3 fields or more), and the average value is regarded as the area ratio of the first hard phase in the entire surface or cross section of the cemented carbide. Can be done.
  • the "predetermined field of view” may be the same as the field of view for determining the average particle size of the WC particles described above.
  • the bonded phase includes WC particles constituting the first hard phase, compound particles constituting the second hard phase described later, or WC particles constituting the first hard phase and compound particles constituting the second hard phase. Is the phase that binds.
  • the content ratio of the bonded phase is 4% by mass or more and 15% by mass or less based on the cemented carbide.
  • the bonded phase is composed of cobalt (Co), nickel (Ni), iron (Fe) and chromium (Cr) as constituent elements.
  • the average content ratio of each element of Co, Ni, Fe and Cr in the above bonded phase with respect to the total amount of Co, Ni, Fe and Cr is 10 atomic% (hereinafter referred to as “(at%”) or more and 30 at%). By doing so, it is possible to obtain a super hard alloy having no heterogeneous phase precipitation and having excellent wear resistance to the titanium alloy. Further, the content ratios of Co and Ni contained in the bonded phase are as follows. , 25 at% or more and preferably 30 at% or less, and the content ratio of Fe and Cr contained in the bonded phase is preferably 20 at% or more and 25 at% or less. The denseness of the hard alloy increases, and the hardness tends to increase.
  • the atomic concentrations of Co, Ni, Fe and Cr contained in the bonded phase are measured by using an ICP emission spectroscopic measurement method (Inductively Coupled Plasma emission spectroscopy measurement method) (hereinafter, may be referred to as "ICP measurement method"). can do.
  • ICP measurement method Inductively Coupled Plasma emission spectroscopy measurement method
  • the present inventors consider that the atomic concentration measured by the ICP measuring method is the atomic concentration obtained by averaging the entire bonded phase.
  • the area ratio of the bonded phase to any surface or any cross section of the cemented carbide according to the present embodiment is preferably 1% or more and 30% or less, and more preferably 4% or more and 15% or less. ..
  • the area ratio of the bonded phase is preferably 1% or more and 30% or less, and more preferably 4% or more and 15% or less. ..
  • the area ratio of the bonded phase is binarized using image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.) in the same manner as the measurement of the area ratio of the first hard phase. Obtain a binarized image.
  • the lightness threshold in the binarization process is a value obtained by multiplying a value extracted from an arbitrary point that does not overlap with the interface with another phase of the brightest bound phase in the image by 1.2.
  • the sum (total area) of the areas of the bonded phases (Co, Ni, Fe and Cr particles) in the microscope image is calculated, and this is calculated as the total area of the visual field (binarized image). By dividing, it is possible to calculate the area ratio of the bound phase in the field.
  • the above image analysis can be performed in a plurality of fields of view (for example, three or more fields of view), and the average value can be regarded as the area ratio of the bonded phase in the entire surface or cross section of the cemented carbide. ..
  • a region in which the ratio of the content ratio of at least one of the constituent elements is 85% or less and 115% or more with respect to the average content ratio is unevenly distributed.
  • the total area of the unevenly distributed region in the bonded phase is preferably 6% or less, more preferably 3% or less, based on the total area of the bonded phase. This indicates that the composition bias in the bonded phase in the entire cemented carbide is small. If the above ratio exceeds 6%, the wear resistance with the titanium alloy tends to deteriorate.
  • the above ratio can be calculated by the following method. That is, an arbitrary cross section obtained by using a focused ion beam device (FIB device), a cross section polisher device (CP device), or the like is imaged with a scanning transmission electron microscope (SEM) at a magnification of 5000, and an arbitrary plurality of images are taken. (For example, 10 or more) electronic images are obtained.
  • FIB device focused ion beam device
  • CP device cross section polisher device
  • SEM scanning transmission electron microscope
  • the electronic image is binarized using, for example, image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.) to obtain a binarized image.
  • the lightness threshold in the binarization process is a value obtained by multiplying a value extracted from an arbitrary point that does not overlap with the interface with another phase of the brightest bound phase in the image by 1.2.
  • the bound phase is detected based on the above binarized image.
  • the detected bound phase is subjected to element mapping for a predetermined region (for example, 12 ⁇ m ⁇ 9 ⁇ m) using an electron probe microanalyzer (EPMA) or energy dispersive X-ray spectroscopy (EDS) attached to the SEM. ..
  • EPMA electron probe microanalyzer
  • EDS energy dispersive X-ray spectroscopy
  • the phase containing WC is regarded as the first hard phase
  • the phase containing Co, Ni, Fe and Cr is regarded as the bonded phase.
  • the first hard phase and the bonded phase have a clear interface and light and dark in the image captured by SEM, and the bright phase can be regarded as the first hard phase and the dark phase can be regarded as the bonded phase.
  • the cemented carbide according to the present embodiment does not contain the second hard phase, or the content of the second hard phase is 2% by mass or less with respect to the total amount of the cemented carbide, and the second hard phase is described. It is preferable that it does not contain a phase.
  • the cemented carbide contains the second hard phase, it is not added to the extent that the effect of the present disclosure is not impaired, or the second hard phase is added as a raw material, and it is inevitably generated in the manufacturing process. It is considered to be a thing.
  • the second hard phase includes "one or more metal elements selected from the group consisting of group 4 elements, group 5 elements and group 6 elements excluding tungsten" in the periodic table, and "carbon (C), nitrogen (N) and oxygen. It is composed of a compound (complex compound) containing "one or more elements selected from the group consisting of (O)".
  • Examples of the Group 4 element of the periodic table include titanium (Ti), zirconium (Zr), hafnium (Hf) and the like.
  • Examples of the Group 5 element of the periodic table include vanadium (V), niobium (Nb), tantalum (Ta) and the like.
  • Examples of the Group 6 element of the periodic table include chromium (Cr) and molybdenum (Mo).
  • the compound is mainly a carbide, a nitride, a carbonitride, an oxide or the like of the above-mentioned metal element.
  • the second hard phase is a compound phase or a solid solution phase composed of one or more of the above compounds.
  • the "compound phase or solid solution phase” indicates that the compounds constituting the phase may form a solid solution or may exist as individual compounds without forming a solid solution.
  • the second hard phase include compounds such as TaC, NbC, TiC, TiCN, Cr 3 C 2 , Cr 7 C 3 , Al 2 O 3 and SiO 2 .
  • the area ratio of the second hard phase to any surface or any cross section of the cemented carbide is preferably 1.5% or less.
  • the area ratio of the second hard phase is binarized using image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.) in the same manner as the measurement of the area ratio of the first hard phase.
  • the lightness threshold value in the binarization process is a value obtained by multiplying the value extracted from the particulate phase that was not detected during the binarization process of the first hard phase by 0.8.
  • the sum (total area) of the areas of the second hard phase in the microscope image is calculated, and this is divided by the area of the entire visual field (binarized image) to obtain the second in the visual field. It is possible to calculate the area ratio of the two hard phases.
  • the above image analysis is performed in a plurality of fields of view (for example, three or more fields of view), and the average value is regarded as the area ratio of the second hard phase in the entire surface or cross section of the cemented carbide.
  • the predetermined position is, for example, a portion 50% with respect to the thickness of the measurement sample, specifically, a portion 500 ⁇ m from the surface.
  • the area ratio of the second hard phase may change on the surface portion of the cemented carbide, it is obvious to those skilled in the art to avoid the surface for measurement.
  • the cemented carbide of the present embodiment can be typically produced through a raw material powder preparation step, a mixing step, a molding step, and a sintering step in this order. Hereinafter, each step will be described.
  • the preparation step is a step of preparing all the raw material powders of the materials constituting the cemented carbide.
  • examples of the raw material powder of the first hard phase include WC particles.
  • (i) particles obtained by alloying Co, Ni, Fe and Cr with a predetermined compounding composition hereinafter, may be referred to as “CoNiFeCr alloy particles”
  • (ii) Co examples include the use of particles obtained by alloying particles with Ni, Fe, and Cr with a predetermined compounding composition (hereinafter, may be referred to as “NiFeCr alloy particles”).
  • Co, Ni, Fe and Cr which are constituent elements of the bonded phase, can use (i) CoNiFeCr alloy particles or (ii) Co particles and NiFeCr alloy particles as raw material powders, and can be used as CoNiFeCr. It is preferable to use alloy particles.
  • Co, Ni, Fe and Cr are added as elemental raw material powders, the temperature of the liquid phase in the sintering step is different, so that the above-mentioned cemented carbide cannot be produced.
  • Cr easily bonds with carbon and precipitates a second hard phase such as Cr 3 C 2 and Cr 7 C 3 , so elemental Cr cannot be used as a raw material powder.
  • the WC particles as a raw material are not particularly limited, and WC particles usually used for producing cemented carbide may be used. Commercially available products may be used as the WC particles. Examples of commercially available WC particles include the "uniform-grained tungsten carbide powder" series manufactured by Allied Materials.
  • the average particle size of the WC particles as a raw material is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the toughness tends to be high when a cemented carbide is formed. Therefore, the cutting tool containing the cemented carbide as a base material can suppress chipping and chipping due to mechanical impact and thermal impact. In addition, since the cutting tool has improved crack propagation resistance, crack propagation can be suppressed, and chipping and chipping can be suppressed.
  • the cutting tool containing the cemented carbide as a base material can suppress deformation during cutting, and can suppress wear and chipping.
  • CoNiFeCr alloy particles Using each of the following particles, particles (CoNiFeCr alloy particles) in which Co, Ni, Fe and Cr are alloyed with a predetermined compounding composition are produced.
  • the method for producing CoNiFeCr alloy particles include a mechanical method, a chemical method, an atomizing method, and the like, and it is preferable to use the atomizing method.
  • the metal to be alloyed is melted, and the melted metal (molten metal) is scattered and solidified to form a powder.
  • An alloy can be obtained by preparing the above powder to a desired particle size and mixing them uniformly.
  • the Co particles used as a raw material are not particularly limited, and Co particles usually used for producing cemented carbide may be used.
  • Examples of the Co particles include particles composed of a simple substance of Co. Commercially available products may be used as the Co particles.
  • Ni particles as a raw material are not particularly limited, and Ni particles usually used for producing cemented carbide may be used.
  • Examples of the Ni particles include particles made of Ni alone. Commercially available products may be used as the Ni particles.
  • the Fe particles as a raw material are not particularly limited, and Fe particles usually used for producing cemented carbide may be used.
  • Fe particles include particles made of Fe alone. Commercially available products may be used as the Fe particles.
  • the Cr particles as a raw material are not particularly limited, and Cr particles usually used for producing cemented carbide may be used.
  • Examples of the Cr particles include particles composed of a simple substance of Cr. Commercially available products may be used as the Cr particles.
  • the concentration of impurities contained in the Co particles, Ni particles, Fe particles and Cr particles is the total amount of each of the particles and the impurities. It is 2% by mass or less.
  • the FSSS particle diameter (average particle diameter measured by the Fisher method) of the CoNiFeCr alloy particles obtained by the above production method is preferably 0.5 ⁇ m or more and 50 ⁇ m or less.
  • the Fisher method is a method of measuring the specific surface area of particles using the flow resistance of air to obtain the particle size of the particles.
  • the FSSS particle size can be measured using, for example, Fisher Sub-Seve Sizer Model 95 (manufactured by Fisher Scientific).
  • NiFeCr alloy particles Using each of the above-mentioned particles, particles (NiFeCr alloy particles) in which Ni, Fe and Cr are alloyed with a predetermined compounding composition are produced.
  • the method for producing NiFeCr alloy particles include the above-mentioned mechanical method, chemical method, atomizing method and the like, and it is preferable to use the atomizing method.
  • the FSSS particle size of the NiFeCr alloy particles obtained by the above production method is preferably 0.5 ⁇ m or more and 50 ⁇ m or less.
  • the FSSS particle diameter of the Co particles, the Ni particles, the Fe particles, and the Cr particles is preferably 0.5 ⁇ m or more and 50 ⁇ m or less.
  • the mixing step is a step of mixing each raw material powder prepared in the preparation step.
  • a mixed powder in which each raw material powder is mixed is obtained.
  • the mass ratio of the raw material powder (for example, WC particles, CoNiFeCr alloy particles, NiFeCr alloy particles, etc.) at the time of mixing is a ratio corresponding to the area ratio of the first hard phase and the area ratio of the bonded phase described above.
  • a known device can be used as the device used in the mixing step. For example, an attritor, a rolling ball mill, a Kalman mixer, a bead mill and the like can be used.
  • the mixing time is not particularly limited, and for example, it may be set to 0.1 hours or more and 48 hours or less. From the viewpoint of uniformly mixing the raw material powder, the above-mentioned mixing time is preferably set to 2 hours or more and 15 hours or less.
  • the mixing conditions by the attritor may be wet mixing or dry mixing. Further, the mixing may be carried out in a solvent such as water, ethanol, acetone or isopropyl alcohol. The mixing may be carried out with a binder such as polyethylene glycol or paraffin wax.
  • the mixed powder may be granulated as needed.
  • a known granulation method can be applied to the granulation, and for example, a commercially available granulator such as a spray dryer can be used.
  • the molding step is a step of molding the mixed powder obtained in the mixing step into a predetermined shape to obtain a molded product.
  • a mixed powder may be placed in a Ta capsule and pressed to obtain a molded product.
  • the press pressure at this time may be set to 10 MPa or more and 16 GPa or less.
  • the predetermined shape include a cutting tool shape (for example, a shape of a cutting tip with a replaceable cutting edge).
  • the sintering step is a step of sintering a molded body obtained in the molding step to obtain a sintered body.
  • the sintering temperature is preferably 1400 ° C. or higher and 1600 ° C. or lower.
  • the sintering time is preferably 0.5 hours or more and 2 hours or less.
  • the atmosphere at the time of sintering is not particularly limited, and examples thereof include an N2 gas atmosphere, an inert gas atmosphere such as Ar, or a hydrogen gas atmosphere.
  • the degree of vacuum (pressure) at the time of sintering is preferably 0.1 kPa or more and 10 kPa or less.
  • a sintering HIP (sinter hip) treatment that can be pressurized at the time of sintering may be performed.
  • the HIP conditions include, for example, a temperature of 1300 ° C. or higher and 1350 ° C. or lower, and a pressure of 5 MPa or higher and 200 MPa or lower in an N2 gas atmosphere or an inert gas atmosphere such as Ar.
  • the temperature lowering rate from the maximum temperature to room temperature is preferably 2 ° C./min to 50 ° C./min.
  • the temperature lowering rate is 2 ° C./min
  • the atmosphere at the time of cooling is not particularly limited, and may be an N2 gas atmosphere or an inert gas atmosphere such as Ar.
  • the cooling pressure is not particularly limited and may be pressurized or reduced.
  • the pressure at the time of the pressurization is, for example, 400 kPa or more and 500 kPa or less.
  • the pressure at the time of the reduced pressure is, for example, 100 kPa or less, preferably 10 kPa or more and 50 kPa or less.
  • the cemented carbide of this embodiment has excellent wear resistance as described above, it can be used as a cutting tool and a base material. That is, the cutting tool of the present embodiment contains the above-mentioned cemented carbide as a base material. Further, the cemented carbide of the present embodiment can also be used as an abrasion resistant tool and a grinding tool, and the abrasion resistant tool and the grinding tool include the cemented carbide as a base material.
  • the cemented carbide of the present embodiment can be widely applied to conventionally known cutting tools, for example, a cutting tool, a drill, an end mill, a cutting tip with a replaceable cutting edge for milling, a cutting tip with a replaceable cutting edge for turning, a metal saw, and the like. Examples thereof include a gear cutting tool, a reamer, a tap, and the like.
  • the cemented carbide of the present embodiment can be widely applied to conventionally known wear-resistant tools and grinding tools. Examples of the wear-resistant tool include a die, a scriber, a scribing wheel, a dresser, and the like, and examples of the grinding tool include a grinding wheel and the like.
  • the cemented carbide of this embodiment may constitute the whole of these tools.
  • the cemented carbide may form a part of these tools.
  • "partially constituting” indicates, for example, in the case of a cutting tool, an embodiment in which the cemented carbide of the present embodiment is brazed to a predetermined position of an arbitrary base material to form a cutting edge portion.
  • the cutting tool according to the present embodiment may further include a coating film provided on the base material.
  • the wear-resistant tool and the grinding tool according to the present embodiment may further include a coating film provided on the base material.
  • the composition of the coating film is one or more elements selected from the group consisting of a metal element of Group 4 of the Periodic Table, a metal element of Group 5 of the Periodic Table, a metal element of Group 6 of the Periodic Table, and aluminum (Al) and silicon (Si). And compounds with one or more elements selected from the group consisting of nitrogen (N), oxygen (O), carbon (C) and boron (B). Examples of the compound include TiCN, Al2O3 , TiAlN, TiN, TiC, AlCrN and the like.
  • the coating film may be a simple substance of metal.
  • cubic boron nitride (cBN), diamond-like carbon and the like are also suitable as the composition of the coating film.
  • a film can be formed by a vapor phase method such as a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the film is formed by the CVD method, it is easy to obtain a film having excellent adhesion to the substrate.
  • the CVD method include a thermal CVD method and the like.
  • the coating film is formed by the PVD method, compressive residual stress is applied, and it is easy to increase the toughness of a cutting tool or the like.
  • the coating film in the cutting tool according to the present embodiment is provided in the vicinity of the cutting edge portion of the base material.
  • the coating film may be provided on the entire surface of the base material. Further, the coating film may be a single layer or a multi-layered film.
  • the thickness of the coating film may be 1 ⁇ m or more and 20 ⁇ m or less, or 1.5 ⁇ m or more and 15 ⁇ m or less.
  • CoNiFeCr alloy powder A powder of CoNiFeCr alloy (hereinafter, may be referred to as "CoNiFeCr alloy powder"), which is a raw material of the bonded phase, was produced by the following method.
  • the CoNiFeCr alloy powder corresponds to the above-mentioned "CoNiFeCr alloy particles”.
  • the raw material powder was blended with the blending composition shown in Table 1 to prepare a CoNiFeCr alloy by an atomizing method.
  • the obtained CoNiFeCr alloy was pulverized by a bead mill under the following conditions.
  • the slurry containing the CoNiFeCr alloy obtained by the pulverization treatment was dried in vacuum.
  • a CoNiFeCr alloy powder having an FSSS particle size of 1.5 ⁇ m was obtained.
  • Beads Particle size 1.0 mm
  • Dispersion medium Ethanol or acetone
  • Treatment time 8 hours (Preparation of other raw material powder)
  • As the raw material powder a powder having the composition shown in Table 1 was prepared.
  • sample No. 107 is a HEA powder containing Al, Cr, Cu, Fe, Mn, Ti and V as a bonding phase at a molar ratio of 1: 1: 1: 1: 1: 1 (corresponding to Example 1 of Patent Document 1).
  • Sample No. for 108 HEA powder containing Co, Cr, Cu, Fe and Ni in an atomic ratio of 1: 1: 1: 1: 1 (corresponding to Example 2 of Patent Document 2) was used as a bonding phase, respectively.
  • Sample No. Commercially available particles were used for the particles of each element of 107 and 108.
  • WC FSSS particle size: 2.0 ⁇ m (Sample No. 9: 0.7 ⁇ m, Sample No. 10: 5.0 ⁇ m)
  • Co FSSS particle size: 1.1 ⁇ m
  • Ni FSSS particle size: 3.3 ⁇ m
  • Fe FSSS particle size: 3.0 ⁇ m
  • Cr FSSS particle size: 5.0 ⁇ m
  • TaC FSSS particle size: 1.8 ⁇ m
  • ⁇ Mixing process> Each of the prepared raw material powders was added in the blending ratios shown in Table 1 and mixed using an attritor to prepare a mixed powder. The mixing conditions are shown below. After mixing, the obtained slurry was dried in the air to obtain a mixed powder.
  • sample No. 1 to 15 cemented carbide and sample No. Cemented carbides of 101 to 108 were prepared. Sample No. 1 to 15 cemented carbides correspond to the examples. Sample No. The cemented carbides 101 to 108 correspond to the comparative examples.
  • sample No. 101 and 105 are cemented carbides in which the composition of the bonded phase consists of a simple substance of Co.
  • Sample No. Reference numeral 102 is a cemented carbide in which TaC is added to the raw material powder as the second hard phase.
  • Sample No. 103 and 104 are cemented carbides in which the composition of the bonded phase consists of Co, Ni, Fe and Cr, but the atomic concentration of each element does not meet the requirements of the present disclosure.
  • Sample No. Reference numeral 106 is a cemented carbide in which the composition of the bonded phase is composed of Co, Ni, Fe and Cr, and the powder of the elemental metal of each element is used as the raw material powder.
  • Reference numeral 107 is a cemented carbide containing HEA having a bonded phase composition of Al, Cr, Cu, Fe, Mn, Ti and V, which corresponds to Example 1 of Patent Document 1.
  • Sample No. Reference numeral 108 denotes a cemented carbide containing HEA having a bonded phase composition of Co, Cr, Cu, Fe and Ni, which corresponds to Example 2 of Patent Document 2.
  • the mirrored surface of this observation sample was photographed with a scanning transmission electron microscope (SEM) (manufactured by JEOL Ltd.) at a magnification of 2000 times. This imaging was performed for each sample by 10 fields of view on the outside of the mirror-processed surface and the center of the mirror-processed surface.
  • SEM scanning transmission electron microscope
  • the particle size (Heywood diameter) of each particle was determined using image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.). The average particle size of the sintered tungsten carbide particles in a total of 10 fields was calculated. As a result, it was found that the average particle size of the tungsten carbide particles after sintering was substantially equal to the average particle size of the WC particles used as the raw material. The results are shown in the column of "Average particle size of the first hard phase" in Table 1. When measuring the particle size, the particles containing W and C were identified as tungsten carbide particles by performing element mapping using an energy dispersive X-ray spectroscopic analysis (EDS) device attached to the SEM.
  • EDS energy dispersive X-ray spectroscopic analysis
  • ⁇ Area ratio of each element of Co, Ni, Fe and Cr in the bonded phase> First, a cross section obtained by using a cross-section polisher device (CP device) was imaged by SEM at a magnification of 5000 to obtain 10 electronic images. Using the image analysis type particle size distribution software (“Mac-View” manufactured by Mountech Co., Ltd.), the above electronic image is subjected to the above-mentioned “ ⁇ Calculation of area ratio of first hard phase, bonded phase and second hard phase>”. The binarization process was performed under the same conditions as in the above case, and a binarization image was obtained. The bound phase was detected based on the above binarized image.
  • CP device cross-section polisher device
  • the detected bound phase was subjected to element mapping for a plurality of regions of 12 ⁇ m ⁇ 9 ⁇ m using the energy dispersive X-ray spectroscopy (EDS) attached to the SEM.
  • EDS energy dispersive X-ray spectroscopy
  • FIG. 1 shows an example of the SEM image taken in this way.
  • SEM scanning transmission electron microscope
  • the point 4 farthest from the work material 5 and the point 4 drawn vertically toward the contact surface 2.
  • the length of the line was defined as the thickness T of the diffusion layer, and the average value of the thickness T of the diffusion layers having three or more visual fields in which the contact surface 2 with the work material 5 was captured was measured.
  • the results are shown in the column of "Average thickness of diffusion phase" in Table 1. The smaller the average value of the thickness T of the diffusion layer, the more the cemented carbide 1 can be evaluated as having excellent reactivity with titanium.
  • the cemented carbide according to the example does not contain the second hard phase (TaC) as a compounding composition, or the content of TaC is 2% by mass or less with respect to the total amount of the cemented carbide.
  • Sample No. containing 4% by mass of TaC It is also suggested that the reaction resistance is superior to that of the cemented carbide according to 102.
  • Example No. 1 cutting tool A cutting tool using the cemented carbide of No. 1 as a base material is referred to as "Sample No. 1 cutting tool" or the like. Sample No. The same applies to samples other than 1.
  • the cemented carbide according to the example does not contain the second hard phase (TaC) as a compounding composition, or the content of TaC is 2% by mass or less with respect to the total amount of the cemented carbide.
  • Sample No. containing 4% by mass of TaC It is also suggested that it is superior in wear resistance and heat resistance to the cemented carbide according to 102.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un carbure métallique qui contient une première phase dure et une phase liaison. Ladite première phase dure est constituée de particules de carbure de tungstène. Ladite phase liaison est constituée d'un cobalt, d'un nickel, d'un fer et d'un chrome en tant qu'éléments constitutifs. La proportion en teneur moyenne de chacun desdits éléments constitutifs dans ladite phase liaison, est supérieure ou égale à 10%at. et inférieure ou égale à 30%at. pour tous lesdits éléments constitutifs. Soit le carbure métallique de l'invention ne contient pas de seconde phase dure, soit sa teneur en seconde phase dure est inférieure ou égale à 2% en masse pour sa masse totale. Ladite seconde phase dure est constituée d'un composé qui contient : au moins une sorte d'élément métallique choisie dans un groupe constitué des éléments du quatrième groupe du tableau de classification périodique, des éléments du cinquième groupe et des éléments du sixième groupe à l'exclusion du tungstène ; et au moins une sorte d'élément choisie dans un groupe constitué d'un carbone, d'un azote et d'un oxygène.
PCT/JP2020/048247 2020-12-23 2020-12-23 Carbure métallique, et outil de coupe contenant celui-ci en tant que substrat WO2022137399A1 (fr)

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