WO2023170787A1 - 立方晶窒化硼素焼結体 - Google Patents
立方晶窒化硼素焼結体 Download PDFInfo
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- WO2023170787A1 WO2023170787A1 PCT/JP2022/010011 JP2022010011W WO2023170787A1 WO 2023170787 A1 WO2023170787 A1 WO 2023170787A1 JP 2022010011 W JP2022010011 W JP 2022010011W WO 2023170787 A1 WO2023170787 A1 WO 2023170787A1
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- boron nitride
- cubic boron
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- binder phase
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Definitions
- the present disclosure relates to a cubic boron nitride sintered body.
- a cubic boron nitride sintered body (hereinafter also referred to as "cBN sintered body") is a high-hardness material used for cutting tools and the like (Patent Document 1, Patent Document 2).
- the cubic boron nitride sintered body of the present disclosure is Comprising cubic boron nitride particles, a binder phase and voids,
- the volume-based percentage of the cubic boron nitride particles to the total of the cubic boron nitride particles and the binder phase is 40 volume % or more and 70 volume % or less
- the volume-based percentage of the binder phase with respect to the total of the cubic boron nitride particles and the binder phase is 30 volume% or more and 60 volume% or less
- the binder phase contains aluminum oxide particles at 10% by volume or more and 100% by volume or less based on the entire binder phase
- the average particle size of the aluminum oxide particles is 50 nm or more and 250 nm or less, Containing one or more first voids from 0.001% by volume to 0.100% by volume, At least a portion of each of the first voids is a cubic boron nitride sintered body in contact with the aluminum
- FIG. 1 is an example of an image showing contrast values in a backscattered electron image of the cubic boron nitride sintered body of Embodiment 1.
- FIG. 2 is an example of a backscattered electron image of the cubic boron nitride sintered body of Embodiment 1.
- FIG. 3 is another example of a backscattered electron image of the cubic boron nitride sintered body of Embodiment 1.
- an object of the present disclosure is to provide a cubic boron nitride sintered body that, when used as a tool material, can have a long tool life even in high-efficiency machining.
- the cubic boron nitride sintered body of the present disclosure is Comprising cubic boron nitride particles, a binder phase and voids,
- the volume-based percentage of the cubic boron nitride particles to the total of the cubic boron nitride particles and the binder phase is 40 volume % or more and 70 volume % or less
- the volume-based percentage of the binder phase with respect to the total of the cubic boron nitride particles and the binder phase is 30 volume% or more and 60 volume% or less
- the binder phase contains aluminum oxide particles at 10% by volume or more and 100% by volume or less based on the entire binder phase
- the average particle size of the aluminum oxide particles is 50 nm or more and 250 nm or less, Containing one or more first voids from 0.001% by volume to 0.100% by volume, At least a portion of each of the first voids
- the tool can have a long tool life even in high-efficiency machining.
- the binder phase consists of the aluminum oxide particles of 10 volume% or more and 98 volume% or less, and the first binder phase particles of 2 volume% or more and 90 volume% or less
- the first bonded phase particles are: A simple substance of one element selected from the first group consisting of Group 4 elements, Group 5 elements, Group 6 elements, aluminum, silicon, iron, cobalt and nickel of the periodic table, and a single element selected from the first group at least one element selected from the second group consisting of alloys and intermetallic compounds consisting of two or more elements, and at least one element selected from the first group, nitrogen, carbon, boron, and oxygen.
- the first compound consisting of at least one element selected from the third group, and at least one element selected from the fourth group consisting of a solid solution of the first compound;
- the first compound does not contain aluminum oxide particles. According to this, the tool life is further improved.
- the cubic boron nitride sintered body includes a plurality of the first voids;
- the average distance of the first voids is preferably 1.0 ⁇ m or more and 20 ⁇ m or less. According to this, the tool life is further improved.
- the average cross-sectional area of the first voids is preferably 0.001 ⁇ m 2 or more and 0.02 ⁇ m 2 or less. According to this, the tool life is further improved.
- the cubic boron nitride particles include first cubic boron nitride particles;
- the particle size of the first cubic boron nitride particles is 5% or more and 50% or less of the average particle size of the aluminum oxide particles,
- the volume-based percentage of the first cubic boron nitride particles to the binder phase is 1% or more and 30% or less,
- the first cubic boron nitride particles contain 30% or more and 100% or less of 1A cubic boron nitride particles on a number basis, It is preferable that at least a portion of each of the first A cubic boron nitride particles be in contact with the aluminum oxide particles. According to this, the tool life is further improved.
- the notation in the format "A to B” means the upper and lower limits of the range (i.e., from A to B), and when there is no unit described in A and only in B, The units of and the units of B are the same.
- the atomic ratio when a compound or the like is expressed by a chemical formula, unless the atomic ratio is specifically limited, it includes all conventionally known atomic ratios, and should not necessarily be limited to only those in the stoichiometric range.
- the ratio of the number of atoms constituting TiN includes all conventionally known atomic ratios.
- the cubic boron nitride sintered body of one embodiment of the present disclosure (hereinafter also referred to as "this embodiment") is Comprising cubic boron nitride particles, a binder phase and voids,
- the volume-based percentage of the cubic boron nitride particles to the total of the cubic boron nitride particles and the binder phase is 40 volume % or more and 70 volume % or less
- the volume-based percentage of the binder phase with respect to the total of the cubic boron nitride particles and the binder phase is 30 volume% or more and 60 volume% or less
- the binder phase contains aluminum oxide particles at 10% by volume or more and 100% by volume or less based on the entire binder phase
- the average particle size of the aluminum oxide particles is 50 nm or more and 250 nm or less, Containing one or more first voids from 0.001% by volume to 0.100% by volume, At
- the tool can have a long tool life even in high-efficiency machining.
- the reasons for this are presumed to be as shown in (i) to (iv) below.
- the cubic boron nitride sintered body of the present embodiment includes cubic boron nitride particles having excellent strength and toughness, and the volume of the cubic boron nitride particles relative to the total of the cubic boron nitride particles and the binder phase.
- the standard percentage is 40 volume % or more and 70 volume % or less. Therefore, the cubic boron nitride sintered body can also have excellent strength and toughness. Therefore, a tool using the cubic boron nitride sintered body has excellent wear resistance and chipping resistance, and can have a long tool life.
- the cubic boron nitride sintered body of this embodiment contains aluminum oxide particles (hereinafter also referred to as "Al 2 O 3 particles”) having excellent wear resistance at 10% by volume based on the entire binder phase. Including 100% by volume or more. Therefore, the cubic boron nitride sintered body has excellent wear resistance, and a tool using the cubic boron nitride sintered body can have a long tool life.
- Al 2 O 3 particles aluminum oxide particles
- the average particle size of the aluminum oxide particles is 50 nm or more and 250 nm or less.
- the cubic boron nitride sintered body can have excellent toughness. Therefore, a tool using the cubic boron nitride sintered body has excellent fracture resistance and can have a long tool life.
- the content of the first voids in the cubic boron nitride sintered body is 0.001 volume % or more and 0.100 volume % or less, the effect of absorbing the difference in the coefficient of thermal expansion due to the voids can be obtained, It is possible to prevent the void itself from becoming a starting point for cracks. That is, when the content of the first voids in the cubic boron nitride sintered body is 0.001 volume % or more and 0.100 volume % or less, the generation of cracks is effectively suppressed.
- the tool using the cubic boron nitride sintered body of this embodiment in which the first void content is 0.001 volume % or more and 0.10 volume % or less has excellent fracture resistance and a long tool life. can have. This is a new finding discovered by the present inventors as a result of intensive studies.
- the cubic boron nitride sintered body of this embodiment includes cubic boron nitride particles, a binder phase, and voids.
- the cubic boron nitride sintered body of this embodiment may contain unavoidable impurities resulting from the raw materials used, manufacturing conditions, etc., as long as the effects of the present disclosure are achieved.
- the cubic boron nitride sintered body of this embodiment can be composed of cubic boron nitride particles, a binder phase, voids, and unavoidable impurities.
- the content (% by mass) of unavoidable impurities in the cubic boron nitride sintered body can be 1% by mass or less.
- the content of inevitable impurities in the cubic boron nitride sintered body is measured by ICP emission spectroscopy (measurement device: Shimadzu Corporation "ICPS-8100" (trademark)).
- the volume-based percentage of the cubic boron nitride particles (hereinafter also referred to as "content rate of the cubic boron nitride particles") with respect to the total of the cubic boron nitride particles and the binder phase ) is 40 volume % or more and 70 volume % or less.
- the lower limit of the content of cubic boron nitride particles is 40 volume % or more, preferably 42 volume % or more, and more preferably 45 volume % or more from the viewpoint of improving fracture resistance.
- the upper limit of the content of cubic boron nitride particles is 70 vol% or less, preferably 68 vol% or less, and more preferably 65 vol% or less, from the viewpoint of improving sinterability.
- the content of the cubic boron nitride particles is 40 volume% or more and 70 volume% or less, preferably 42 volume% or more and 68 volume% or less, and more preferably 45 volume% or more and 65 volume% or less.
- the volume-based percentage of the binder phase (hereinafter also referred to as "bind phase content”) with respect to the total of the cubic boron nitride particles and the binder phase is 30% by volume.
- the content is 60% by volume or less.
- the lower limit of the binder phase content is 30% by volume or more, preferably 31% by volume or more, and more preferably 33% by volume or more.
- the upper limit of the content of the binder phase in the cubic boron nitride sintered body is 60 vol% or less, preferably 58 vol% or less, and more preferably 54 vol% or less, from the viewpoint of improving fracture resistance.
- the content of the binder phase in the cubic boron nitride sintered body is 30 volume % or more and 60 volume % or less, preferably 31 volume % or more and 58 volume % or less, and more preferably 33 volume % or more and 54 volume % or less.
- the cubic boron nitride sintered body of the present embodiment is composed of cubic boron nitride particles, a binder phase, and voids, and the cubic boron nitride particles have a volume-based percentage of the total of the cubic boron nitride particles and the binder phase. is preferably 40% by volume or more and 70% by volume or less, and the percentage by volume of the binder phase relative to the total of the cubic boron nitride particles and the binder phase is preferably 30% by volume or more and 60% by volume or less.
- the cubic boron nitride sintered body of the present embodiment consists of cubic boron nitride particles, a binder phase, voids, and unavoidable impurities, and the volume of the cubic boron nitride particles relative to the total of the cubic boron nitride particles and the binder phase.
- the reference percentage is preferably 40 volume % or more and 70 volume % or less, and the volume percentage of the binder phase relative to the total of the cubic boron nitride particles and the binder phase is preferably 30 volume % or more and 60 volume % or less.
- the cubic boron nitride sintered body of this embodiment contains one or more first voids of 0.001% by volume or more and 0.100% by volume or less.
- the first voids are voids in which at least a portion of the voids is in contact with the aluminum oxide particles.
- the lower limit of the content of the first voids in the cubic boron nitride sintered body is 0.001% by volume or more from the viewpoint of obtaining the effect of absorbing the difference in thermal expansion coefficient between the cubic boron nitride particles and the binder phase. Yes, preferably 0.003% by volume or more, and preferably 0.005% by volume or more.
- the upper limit of the content of the first voids in the cubic boron nitride sintered body is 0.100% by volume or less, preferably 0.080% by volume or less, from the viewpoint of suppressing the formation of crack starting points. It is preferably 0.060% by volume or less.
- the content of the first voids in the cubic boron nitride sintered body is 0.001 volume% or more and 0.100 volume% or less, preferably 0.003 volume% or more and 0.080 volume% or less, and 0.005 volume% or more. It is preferably at least 0.060 vol% by volume.
- the cubic boron nitride sintered body of this embodiment can include voids (hereinafter also referred to as "second voids") that are not in contact with the aluminum oxide particles, as long as the effects of the present disclosure are achieved.
- the content of the second voids in the cubic boron nitride sintered body is preferably 0 volume% or more and 0.002 volume% or less, more preferably 0 volume% or more and 0.001 volume% or less, and most preferably 0 volume%. . That is, it is most preferable that the second void is not included.
- the first void and the second void will also be collectively referred to as a "void.”
- Content rate of voids (volume%) of cubic boron nitride sintered body, content rate of binder phase (volume%), content rate of cubic boron nitride particles (volume%), content rate of first voids (volume%) ) and the content rate (volume %) of the second voids are measured by the following procedures (A1) to (G1).
- a cubic boron nitride sintered body is cut at an arbitrary position to prepare a sample including a cross section of the cubic boron nitride sintered body.
- a focused ion beam device, a cross-section polisher device, or the like is used to prepare the cross section.
- FIG. 1 shows a backscattered electron image of the cubic boron nitride sintered body of this embodiment showing brightness values.
- the region where the voids 1 exist is a black region
- the region where the cubic boron nitride particles 2 are present is a dark gray region
- the region where the binder phase 3 is present is a light gray region. area or white area.
- the vertical axis direction (not shown) perpendicular to the horizontal straight line X1 of the image indicates the brightness value.
- FIG. 1 shows that the luminance value in the vertical axis direction on the straight line X1 fluctuates between 8 and 149.
- the void content (total content (volume %) of first voids and second voids) of the cubic boron nitride sintered body is measured by the following procedure.
- the backscattered electron image whose brightness value has been adjusted is binarized using image analysis software ("WinROOF” manufactured by Mitani Shoji Co., Ltd.) under conditions preset in the image analysis software.
- a measurement area of 12 ⁇ m x 9 ⁇ m is set in the image after the binarization process.
- the area ratio of the area where voids exist is calculated.
- the calculated area ratio as volume %, the void content (volume %) of the cubic boron nitride sintered body can be determined.
- the content (volume %) of cubic boron nitride particles is measured by the following procedure.
- the backscattered electron image whose brightness value has been adjusted is binarized using image analysis software ("WinROOF” manufactured by Mitani Shoji Co., Ltd.) under conditions preset in the image analysis software.
- WinROOF image analysis software manufactured by Mitani Shoji Co., Ltd.
- a measurement area of 12 ⁇ m x 9 ⁇ m is set in the image after the binarization process.
- the area ratio of pixels originating from the dark field (black area and dark gray area) (pixels originating from voids and cBN particles) to the area of the measurement field of view is calculated.
- the area ratio of the cubic boron nitride particles is calculated by subtracting the area ratio of the voids (the total area ratio of the first voids and the second voids) from this area ratio.
- the content rate (volume %) of cubic boron nitride particles in the cubic boron nitride sintered body is calculated.
- the content (volume %) of the binder phase is calculated by the following procedure.
- the area ratio of the bonding phase is calculated by subtracting the dark field (pixels derived from voids and cBN particles) from the area ratio of the entire measurement field of view (D1), which is 100 area %.
- the content rate (volume %) of the binder phase of the cubic boron nitride sintered body is calculated.
- the first void content (volume %) and the second void content (volume %) of the cubic boron nitride sintered body are measured by the following procedure. Color separation is performed on the backscattered electron image whose brightness value has been adjusted using image analysis software ("WinROOF” manufactured by Mitani Shoji Co., Ltd.), and voids are shown in blue and aluminum oxide particles are shown in green.
- the aluminum oxide particles in the backscattered electron image are identified by SEM-EDX (energy dispersive X-ray spectroscopy). Specifically, regions where Al and O are detected by SEM-EDX are regarded as aluminum oxide particles.
- FIG. 2 shows an example of a backscattered electron image of the cubic boron nitride sintered body of this embodiment.
- the region where the voids 1 exist is a black region
- the region where the cubic boron nitride particles 2 are present is a dark gray region
- the region where the binder phase is present is a light gray region. Or it becomes a white area.
- the light gray region corresponds to the aluminum oxide particles 5.
- the blue (void) region and the green (Al 2 O 3 particles) region are in contact, and the length of the interface between the blue region and the green region is 5 nm or more.
- the voids shown in the blue region are determined to be first voids at least partially in contact with the aluminum oxide particles. Note that even if the blue (void) region and the green (Al 2 O 3 particles) region are in contact with each other, if the length of the interface between the blue region and the green region is less than 5 nm, it is indicated by the blue region. The area does not correspond to the first gap and is determined to be the second gap.
- the area ratio of the first void and the area ratio of the second void are calculated in the measurement area.
- the calculated area ratio as volume %, the first void content (volume %) and the second void content (volume %) of the cubic boron nitride sintered body can be determined.
- (G1) Perform the above (A1) to (F1) in five different measurement regions, and in each measurement region, the content of voids (volume %), cubic boron nitride particle content (volume %), binder phase
- the content rate (volume %) of the first void, the content rate (volume %) of the second void, and the content rate (volume %) of the second void are measured.
- the average of the measured values of the five measurement areas is calculated based on the void content (volume %) of the cubic boron nitride sintered body of this embodiment, the cubic boron nitride particle content (volume %), and the binder phase content (volume %).
- the binder phase contains aluminum oxide particles in an amount of 10% by volume or more and 100% by volume or less based on the entire binder phase, and the average particle size of the aluminum oxide particles is 50 nm or more and 250 nm or less.
- the lower limit of the content of aluminum oxide particles in the entire binder phase is 10% by volume or more, preferably 13% by volume or more, and more preferably 15% by volume or more.
- the upper limit of the content of aluminum oxide particles in the entire binder phase is 100% by volume or less, preferably 98% by volume or less, and more preferably 95% by volume or less, from the viewpoint of improving fracture resistance.
- the content of aluminum oxide particles in the entire binder phase is 10 volume% or more and 100 volume% or less, preferably 10 volume% or more and 98 volume% or less, more preferably 13 volume% or more and 98 volume% or less, and 15 volume% or more. More preferably, it is 95% by volume or less.
- the content rate (volume %) of aluminum oxide particles in the entire binder phase is measured by the following method.
- the binder phase content (volume %) of the cubic boron nitride sintered body is calculated using the same procedure as the method (E1) for measuring the binder phase content of the cubic boron nitride sintered body.
- aluminum oxide particles were identified and their area ratios were measured according to the procedure described in the method (F1) for measuring the first void content of the cubic boron nitride sintered body. do.
- this area ratio as volume %, the content rate (volume %) of aluminum oxide particles in the cubic boron nitride sintered body can be obtained.
- the percentage of the aluminum oxide particle content (volume %) of the cubic boron nitride sintered body to the binder phase content (volume %) of the cubic boron nitride sintered body is calculated. This percentage corresponds to the content (volume %) of aluminum oxide particles in the entire binder phase.
- the content rate (volume %) of aluminum oxide particles in the entire binder phase is measured in five different measurement areas. The average of the measured values of the five measurement areas is taken as the content rate (volume %) of aluminum oxide particles in the entire binder phase in the cubic boron nitride sintered body of this embodiment.
- the average particle size of the aluminum oxide particles is 50 nm or more and 250 nm or less.
- the average particle diameter of the aluminum oxide particles means the arithmetic mean diameter based on the number of circle-equivalent diameters of the aluminum oxide particles observed in any cross section of the cubic boron nitride sintered body.
- the lower limit of the average particle size of the aluminum oxide particles is 50 nm or more, preferably 60 nm or more, and more preferably 70 nm or more.
- the average particle size (arithmetic mean) of aluminum oxide particles is measured by the following method.
- the aluminum oxide particles are identified by the procedure described in the method (F1) for measuring the content of the first voids in the cubic boron nitride sintered body.
- the equivalent circle diameter of each aluminum oxide particle is measured using the image analysis software.
- the average particle size (number-based arithmetic mean) of the aluminum oxide particles is calculated based on the circle-equivalent diameter of each aluminum oxide particle in the measurement area.
- the above measurements are performed in five different measurement areas.
- the average particle size of the aluminum oxide particles in the five measurement areas is defined as the average particle size of the aluminum oxide particles in the cubic boron nitride sintered body of this embodiment.
- the binder phase consists of aluminum oxide particles of 10 volume% or more and 98 volume% or less, and first binder phase particles of 2 volume% or more and 90 volume% or less
- the first bonded phase particles are A simple substance of one element selected from the first group consisting of Group 4 elements, Group 5 elements, Group 6 elements, aluminum, silicon, iron, cobalt and nickel of the periodic table, and a single element selected from the first group at least one element selected from the second group consisting of alloys and intermetallic compounds consisting of two or more elements, and at least one element selected from the first group, nitrogen, carbon, boron, and oxygen.
- the first compound does not contain aluminum oxide particles.
- the first binder phase particles described above have particularly high bonding strength to cubic boron nitride particles. Therefore, the cubic boron nitride sintered body containing the first binder phase particles has excellent wear resistance and chipping resistance, and a tool using the cubic boron nitride sintered body is a long tool. It can have a long lifespan.
- the first bonded phase particles can have any of the following forms (a) to (f).
- Consists of at least one species selected from the second group (a) Consists of at least one species selected from the second group. (b) Contains at least one species selected from the second group. (c) Consists of at least one species selected from Group 4. (d) Contains at least one species selected from Group 4. (e) At least one type selected from the second group and at least one type selected from the fourth group. (f) At least one type selected from the second group and at least one type selected from the fourth group.
- the Group 4 elements of the periodic table include, for example, titanium (Ti), zirconium (Zr), and hafnium (Hf).
- Group 5 elements include, for example, vanadium (V), niobium (Nb), and tantalum (Ta).
- Group 6 elements include, for example, chromium (Cr), molybdenum (Mo), and tungsten (W).
- first elements the elements of the first group consisting of Group 4 elements, Group 5 elements, Group 6 elements, aluminum, silicon, iron, cobalt, and nickel will also be referred to as "first elements.”
- Examples of the alloy of the first element include Ti-Zr, Ti-Hf, Ti-V, Ti-Nb, Ti-Ta, Ti-Cr, and Ti-Mo.
- Examples of the intermetallic compound of the first element include TiCr 2 , Ti 3 Al, and Co--Al.
- Examples of the first compound (nitride) containing the first element and nitrogen include titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN), vanadium nitride (VN), and niobium nitride (NbN).
- Examples of the first compound (carbide) containing the first metal and carbon include titanium carbide (TiC), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), and niobium carbide (NbC). , tantalum carbide (TaC), chromium carbide (Cr 3 C 2 ), molybdenum carbide (MoC), tungsten carbide (WC), silicon carbide (SiC), tungsten cobalt carbide (W 2 Co 3 C), titanium aluminum carbide (Ti 2 AlC).
- Examples of the first compound (boride) containing the first element and boron include titanium boride (TiB 2 ), zirconium boride (ZrB 2 ), hafnium boride (HfB 2 ), and vanadium boride ( VB 2 ), niobium boride (NbB 2 ), tantalum boride (TaB 2 ), chromium boride (CrB), molybdenum boride (MoB), tungsten boride (WB), aluminum boride (AlB 2 ), boron
- Examples include cobalt oxide (Co 2 B), nickel boride (Ni 2 B), and tungsten cobalt boride (W 2 Co 21 B 6 ).
- Examples of the first compound (carbonitride) containing the first element, carbon, and nitrogen include titanium carbonitride (TiCN), zirconium carbonitride (ZrCN), hafnium carbonitride (HfCN), titanium niobium carbonitride ( TiNbCN), titanium zirconium carbonitride (TiZrCN), titanium hafnium carbonitride (TiHfCN), titanium tantalum carbonitride (TiTaCN), and titanium chromium carbonitride (TiCrCN).
- TiCN titanium carbonitride
- ZrCN zirconium carbonitride
- HfCN hafnium carbonitride
- TiNbCN titanium niobium carbonitride
- TiZrCN titanium zirconium carbonitride
- TiHfCN titanium tantalum carbonitride
- TiCrCN titanium chromium carbonitride
- Examples of the first compound (oxynitride) consisting of the first element, oxygen, and nitrogen include titanium oxynitride (TiON), zirconium oxynitride (ZrON), hafnium oxynitride (HfON), and vanadium oxynitride ( VON), niobium oxynitride (NbON), tantalum oxynitride (TaON), chromium oxynitride (CrON), molybdenum oxynitride (MoON), tungsten oxynitride (WON), aluminum oxynitride (AlON), aluminum silicon oxynitride ( SiAlON).
- TiON titanium oxynitride
- ZrON zirconium oxynitride
- HfON hafnium oxynitride
- VON vanadium oxynitride
- NbON niobium oxynitride
- TaON
- the solid solution of the first compound means a state in which two or more types of these first compounds are dissolved in each other's crystal structure, and means an interstitial solid solution or a substitutional solid solution.
- an interstitial solid solution or a substitutional solid solution for example, mention may be made of Al 2 O 3 -ZrO 2 solid solution.
- the first compound may be used alone or in combination of two or more types.
- the content of the first binder phase particles in the binder phase is preferably 2% by volume or more and 90% by volume or less. According to this, the fracture resistance of the cubic boron nitride sintered body is improved.
- the lower limit of the content of the first binder phase particles in the binder phase is preferably 2% by volume or more, preferably 3% by volume or more, and more preferably 5% by volume or more.
- the upper limit of the content of the first binder phase particles in the binder phase is preferably 90% by volume or less, more preferably 87% by volume or less, and even more preferably 85% by volume or less.
- the total content of first binder phase particles in the binder phase is calculated by the following procedure.
- the content rate (volume %) of aluminum oxide particles in the entire binder phase is measured using the same procedure as the method for measuring the content rate of aluminum oxide particles in the entire binder phase.
- the total content (volume %) of the first binder phase particles in the binder phase is calculated by subtracting the content (volume %) of aluminum oxide particles relative to the entire binder phase from the entire binder phase (100 volume %). .
- composition of the bonded phase can be determined by XRD (X-ray diffraction measurement).
- the cubic boron nitride sintered body of this embodiment includes a plurality of first voids, and the average distance of the first voids is preferably 1.0 ⁇ m or more and 20 ⁇ m or less. According to this, the tool life is further improved. The reason for this is presumed to be that the first voids exist dispersedly in the cubic boron nitride sintered body, and the generation of cracks is suppressed substantially uniformly over the entire area of the cubic boron nitride sintered body.
- the lower limit of the average distance of the first voids is preferably 1.0 ⁇ m or more, more preferably 1.5 ⁇ m or more, from the viewpoint of suppressing the first voids from becoming densely packed and becoming the starting point of defects. More preferably, it is 0 ⁇ m or more.
- the upper limit of the average distance of the first voids is preferably 20 ⁇ m or less, preferably 15 ⁇ m or less, and preferably 10 ⁇ m or less, from the viewpoint of improving the stress relaxation effect of the first voids.
- the average distance of the first voids is preferably 1.0 ⁇ m or more and 20 ⁇ m or less, more preferably 1.5 ⁇ m or more and 15 ⁇ m or less, and even more preferably 2.0 ⁇ m or more and 10 ⁇ m or less.
- the average distance of the first void is measured by the following method.
- the first voids are extracted from the backscattered electron image using the same procedure as (F1) of the method for measuring the content of the first voids in the cubic boron nitride sintered body.
- a measurement area (12 ⁇ m ⁇ 9 ⁇ m) is set in the image after the binarization process.
- the center of gravity position of each first gap is derived using the image processing software.
- the obtained barycenter coordinates are regarded as generating points, and Voronoi division processing is performed to calculate each Voronoi region. For adjacent Voronoi regions, calculate the line segment connecting the barycentric coordinates of the generating points. The straight length of the calculated line segment is defined as the distance of the first gap.
- the average distance of the first gap is calculated.
- the average distance of the first gap is measured in five different measurement areas.
- the average of the measured values of the five measurement areas is taken as the average of the distances of the first voids in the cubic boron nitride sintered body of this embodiment.
- the average cross-sectional area of the first voids is preferably 0.001 ⁇ m 2 or more and 0.02 ⁇ m 2 or less. According to this, the tool life is further improved. The reason for this is presumed to be that the thermal stress relaxation effect of the first voids is improved and the first voids are inhibited from becoming the starting point of cracks.
- the lower limit of the average cross-sectional area of the first voids is preferably 0.001 ⁇ m 2 or more, more preferably 0.002 ⁇ m 2 or more, and 0.003 ⁇ m from the viewpoint of improving the thermal stress relaxation effect of the first voids. More preferably 2 or more.
- the average upper limit of the cross-sectional area of the first voids is preferably 0.02 ⁇ m 2 or less, more preferably 0.015 ⁇ m 2 or less, and 0.010 ⁇ m from the viewpoint of suppressing the first voids from becoming crack starting points. 2 or less is more preferable.
- the average cross-sectional area of the first voids is preferably 0.001 ⁇ m 2 or more and 0.02 ⁇ m 2 or less, more preferably 0.002 ⁇ m 2 or more and 0.015 ⁇ m 2 or less, and even more preferably 0.003 ⁇ m 2 or more and 0.010 ⁇ m 2 or less. preferable.
- the average cross-sectional area of the first voids is measured by the following method.
- the first voids are extracted from the backscattered electron image using the same procedure as (F1) of the method for measuring the content of the first voids in the cubic boron nitride sintered body.
- a measurement area (12 ⁇ m ⁇ 9 ⁇ m) is set in the image after the binarization process.
- the cross-sectional area of each first void is measured using the image processing software. If two or more first voids are close to each other, and if even one pixel indicating each first void is adjacent, the two or more first voids where the pixels are adjacent The cross-sectional area is calculated by regarding it as one void.
- the average cross-sectional area of all the first voids within the measurement area is calculated.
- the average of cross-sectional areas means the arithmetic mean of the number of cross-sectional areas.
- the cross-sectional area of the one first void is regarded as the average cross-sectional area.
- the average cross-sectional area is measured in five different measurement areas. The average of the measured values of the five measurement areas is taken as the average of the cross-sectional area of the first void in the cubic boron nitride sintered body of this embodiment.
- the cubic boron nitride particles consist of cubic boron nitride.
- the cubic boron nitride particles can contain unavoidable impurities as long as the effects of the present disclosure are achieved.
- the cubic boron nitride particles include first cubic boron nitride particles, and the particle size of the first cubic boron nitride particles is the average particle size of the aluminum oxide particles.
- the diameter of the first cubic boron nitride particles is 5% or more and 50% or less, and the volume-based percentage of the first cubic boron nitride particles with respect to the binder phase is 1% or more and 30% or less, and the first cubic boron nitride particles are It is preferable that the first A cubic boron nitride particles contain 30% or more and 100% or less of the cubic boron nitride particles, and at least a portion of each of the 1A cubic boron nitride particles is in contact with the aluminum oxide particles. According to this, the life of the cutting tool using the cubic boron nitride sintered body is further improved.
- the first cubic boron nitride particles mean cubic boron nitride particles whose particle size is 5% or more and 50% or less of the average particle size of the aluminum oxide particles.
- the particle size of the first cubic boron nitride particles means the equivalent circle diameter of the first cubic boron nitride particles observed in an arbitrary cross section of the cubic boron nitride sintered body. It is presumed that the first cubic boron nitride particles are likely to be arranged between the aluminum oxide particles, and that the first cubic boron nitride particles tend to have the effect of suppressing grain growth of the aluminum oxide particles.
- the particle size of the first cubic boron nitride particles is 5% or more of the average particle size of the aluminum oxide particles, a decrease in fracture resistance due to a decrease in toughness is suppressed in the cubic boron nitride sintered body.
- the particle size of the first cubic boron nitride particles is preferably 2.5 nm or more and 125 nm or less, more preferably 5 nm or more and 100 nm or less, and even more preferably 10 nm or more and 80 nm or less.
- the first cubic boron nitride particles are identified by the following steps (A2) to (E2).
- a focused ion beam device, a cross-section polisher device, or the like is used to prepare the cross section.
- (B2) Observe the above cross section with a SEM at a magnification of 30,000 times to obtain a backscattered electron image and a secondary electron image.
- the observation area is set so that the area percentage of the binder phase is 50 area % or more.
- regions where voids exist are black regions
- regions where cubic boron nitride particles are present are dark gray regions
- regions where the binder phase is present are light gray regions or white regions.
- the region where the void exists becomes a concave region.
- FIG. 3 shows an example of a backscattered electron image in the observation area of the cubic boron nitride sintered body of this embodiment.
- the region where the cubic boron nitride particles exist becomes the dark gray region 2
- the region where the binder phase exists becomes the light gray region or white region.
- the light gray region corresponds to the aluminum oxide particles 5
- the white region corresponds to the first binder phase particles 6.
- the first cubic boron nitride particles are identified by comparing the equivalent circle diameter of each cubic boron nitride particle with the average particle size (arithmetic mean) of the aluminum oxide particles.
- the volume-based percentage of the first cubic boron nitride particles to the binder phase is preferably 1% or more and 30% or less.
- the volume-based percentage of the first cubic boron nitride particles to the binder phase is preferably 1% or more and 30% or less, more preferably 2% or more and 25% or less, and even more preferably 3% or more and 20% or less.
- the volume-based percentage of the first cubic boron nitride particles to the binder phase is measured by the following steps (A3) to (D3).
- (A3) Identify the first cubic boron nitride particles in the measurement region using the same procedure as (A2) to (D2) of the method for identifying the first cubic boron nitride particles.
- the area ratio (area %) of the first cubic boron nitride particles in the measurement area is measured using the image processing software.
- the content rate (volume %) of the first cubic boron nitride particles in the cubic boron nitride sintered body is calculated.
- the first The volumetric percentage of cubic boron nitride particles to the binder phase is calculated.
- the volumetric percentage of the first cubic boron nitride particles relative to the binder phase is measured in five different measurement areas. The average of the measured values of the five measurement areas is taken as the volume-based percentage of the first cubic boron nitride particles to the binder phase in the cubic boron nitride sintered body of this embodiment.
- the 1A cubic boron nitride particles mean cubic boron nitride particles at least partially in contact with aluminum oxide particles among the first cubic boron nitride particles.
- the first cubic boron nitride particles contain 30% or more and 100% or less of the 1A cubic boron nitride particles on a number basis, and at least a portion of each of the 1A cubic boron nitride particles is in contact with the aluminum oxide particles. is preferred. According to this, it is inferred that the effect of suppressing grain growth of aluminum oxide particles by the first cubic boron nitride particles is likely to be obtained.
- the lower limit of the number-based content of the 1A cubic boron nitride particles in the first cubic boron nitride particles is determined by: It is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
- the upper limit of the number-based content of the 1A cubic boron nitride particles in the first cubic boron nitride particles is preferably 100% or less, and from a manufacturing standpoint, 98% or less, 95%. It can be as follows.
- the number-based content of the 1A cubic boron nitride particles in the first cubic boron nitride particles is preferably 30% or more and 100% or less, preferably 40% or more and 98% or less, and preferably 50% or more and 95% or less. .
- the number-based content of the 1A cubic boron nitride particles in the first cubic boron nitride particles is measured by the following steps (A4) to (C4). be done.
- (A4) Identify the first cubic boron nitride particles in the measurement area using the same method as (A3) to (D3) of the method for identifying the first cubic boron nitride particles.
- the number of first cubic boron nitride particles in the measurement area is measured using the image analysis software described above. When two or more first cubic boron nitride particles are adjacent to each other, if even one pixel indicating the adjacent first cubic boron nitride particles is adjacent to each other, the pixels are adjacent to each other. Two or more first cubic boron nitride particles that match are regarded as one first cubic boron nitride particle and counted.
- (B4) In the measurement area, color separation is performed, and cubic boron nitride particles are shown in green, and aluminum oxide particles are shown in red. Based on the color classification, 1A cubic boron nitride particles, at least a part of which is in contact with the aluminum oxide particles, are extracted from the first cubic boron nitride particles.
- the aluminum oxide particles and the first cubic boron nitride particles are in contact with each other when the length of their interface is 5 nm or more.
- the cubic boron nitride particles correspond to the 1A cubic boron nitride particles. do not.
- the number of 1A cubic boron nitride particles in the measurement area is measured using the image analysis software described above. When two or more 1A cubic boron nitride particles are close to each other, if even one pixel indicating adjacent 1A cubic boron nitride particles is adjacent to each other, the pixels are adjacent to each other. The number of the two or more 1A cubic boron nitride particles in the sample is counted as one particle.
- the first cubic boron nitride particles are The number-based content of the 1A cubic boron nitride particles is calculated.
- the number-based content of the 1A cubic boron nitride particles in the first cubic boron nitride particles is measured in five different measurement regions. The average of the measured values of the five measurement areas is taken as the number-based content of the 1A cubic boron nitride particles of the first cubic boron nitride particles in the cubic boron nitride sintered body of this embodiment.
- the cubic boron nitride sintered body of the present disclosure is suitable for use in cutting tools, wear-resistant tools, grinding tools, and the like.
- a cutting tool, a wear-resistant tool, and a grinding tool using the cubic boron nitride sintered body of the present disclosure may each be entirely composed of the cubic boron nitride sintered body, or a part thereof (for example, a cutting tool In this case, only the cutting edge portion) may be composed of cubic boron nitride sintered body. Furthermore, a coating film may be formed on the surface of each tool.
- Cutting tools include drills, end mills, indexable cutting tips for drills, indexable cutting tips for end mills, indexable cutting tips for milling, indexable cutting tips for turning, metal saws, gear cutting tools, and reamers. , taps, cutting tools, etc.
- wear-resistant tools include dies, scribers, scribing wheels, dressers, etc.
- the grinding tool include a grinding wheel.
- Emodiment 2 Method for manufacturing cubic boron nitride sintered body
- the cubic boron nitride sintered body of the present disclosure can be produced, for example, by the method below.
- Cubic boron nitride powder (hereinafter also referred to as "cBN powder”) and aluminum oxide powder are prepared.
- cBN powder Cubic boron nitride powder
- first binder phase raw material powder prepare a raw material powder for the first binder phase particles (hereinafter also referred to as “first binder phase raw material powder”). do.
- the cBN powder is not particularly limited, and any known cBN powder can be used.
- the D 50 (average particle size) of the cBN powder is not particularly limited, and can be, for example, 0.1 to 12.0 ⁇ m.
- the average particle size of the raw material powder means the median diameter D50 of the equivalent circle diameter.
- the average particle size is measured using a particle size distribution analyzer (trade name: MT3300EX) manufactured by Microtrac.
- the average particle size of the cBN powder having a large average particle size is preferably 0.5 to 5 ⁇ m.
- the average particle size of the cBN powder having a small average particle size is preferably 0.01 to 0.3 ⁇ m.
- the aluminum oxide powder is not particularly limited, and any known aluminum oxide powder can be used.
- the D 50 (average particle size) of the aluminum oxide powder is not particularly limited, and can be, for example, 0.05 to 0.25 ⁇ m.
- the first binder phase raw material powder can have the same composition as at least some of the components constituting the first binder phase.
- the binder phase raw material powder a simple substance of one element selected from the first group consisting of Group 4 elements, Group 5 elements, Group 6 elements, aluminum, silicon, iron, cobalt and nickel of the periodic table; Alloys and intermetallic compounds consisting of two or more elements selected from the first group, at least one element selected from the first group, and at least one element selected from the third group consisting of nitrogen, carbon, boron, and oxygen.
- a first compound consisting of a seed element and a powder consisting of a solid solution of the first compound can be used.
- ⁇ Mixing process> the cBN powder and aluminum oxide powder prepared above are mixed and stirred using a planetary stirring device (hereinafter also referred to as "primary mixing") to obtain a primary mixed powder.
- a planetary stirring device hereinafter also referred to as "primary mixing”
- the mixing and stirring method may be either wet or dry.
- the mixing time of the primary mixing can be 0.1 hour or more and less than 2 hours, and can also be 0.1 hour or more and 1.5 hours or less.
- the mixing method shall be a method that does not involve pulverization. Examples include jet mills, planetary mixing without media, and the like.
- the secondary mixed powder is filled into a tantalum (Ta) container in contact with a WC-6% Co cemented carbide disk and a Co (cobalt) foil, and vacuum sealed.
- the mixed powder filled in a container made of Ta is pressurized to a pressure of 5 GPa or more and 7 GPa or less using a belt-type ultra-high pressure and high temperature generator, and then heated to a temperature of 1300°C or more and 1500°C or less, and the pressure after pressurization and heating is and temperature conditions for 15 minutes or more and 30 minutes or less to sinter.
- the void content of the cubic boron nitride sintered body can be controlled. This is a new finding discovered by the present inventors. In this way, the cubic boron nitride sintered body of this embodiment is produced.
- the present inventors found that by employing the above-mentioned mixing step and sintering step in the manufacturing method of cubic boron nitride sintered bodies, the void content can be controlled, and aluminum oxide particles can be It has been newly discovered that by containing C, it is possible to obtain a cubic boron nitride sintered body having excellent wear resistance and chipping resistance.
- the cubic boron nitride sintered body of the present embodiment is composed of cubic boron nitride particles, a binder phase, and voids, and the cubic boron nitride particles have a volume-based percentage of the total of the cubic boron nitride particles and the binder phase. is preferably 40% by volume or more and 70% by volume or less, and the percentage by volume of the binder phase relative to the total of the cubic boron nitride particles and the binder phase is preferably 30% by volume or more and 60% by volume or less.
- the cubic boron nitride sintered body of the present embodiment consists of cubic boron nitride particles, a binder phase, voids, and unavoidable impurities, and the volume of the cubic boron nitride particles relative to the total of the cubic boron nitride particles and the binder phase.
- the reference percentage is preferably 40 volume % or more and 70 volume % or less, and the volume percentage of the binder phase relative to the total of the cubic boron nitride particles and the binder phase is preferably 30 volume % or more and 60 volume % or less.
- Example 1 [Preparation of cubic boron nitride sintered body] Each sample No. shown in Tables 1 to 4. A cubic boron nitride sintered body was produced using the following procedure.
- ⁇ Raw material preparation process Two types of cBN powder with different known average particle sizes (average particle size 2 ⁇ m (indicated as “cBN powder large particle size” in Table 1), average particle size 0.1 ⁇ m (in Table 1, “cBN powder small particle size”) )), a known aluminum oxide powder (average particle size: 0.1 ⁇ m, referred to as "Al 2 O 3 powder” in Table 1), and a known first binder phase raw material powder were prepared.
- the first binder phase powders include ZrO 2 powder (average particle size 1 ⁇ m), Al 2 O 3 -ZrO 2 solid solution powder (average particle size 1 ⁇ m), ZrB 2 powder (average particle size 2 ⁇ m), and TiC powder (average particle size 1 ⁇ m).
- cBN powder, aluminum oxide powder, and first binder phase raw material powder were prepared so as to have the blending ratio (by volume) shown in Table 1.
- Table 1 the notation "-" indicates that the corresponding raw material powder was not used.
- cBN powder and aluminum oxide powder were mixed under the conditions described in the "Method", “Time” and “Media” columns of "Primary Mixing” in Table 2 to obtain a primary mixed powder ( primary mixture).
- Sample 1 was mixed for 0.25 hours using alumina media with a diameter of 0.5 mm using a planetary stirrer.
- the primary mixed powder and the first binder phase powder are mixed under the conditions described in the "Method", “Time/Number of Times", and “Media” columns of "Secondary Mixing” in Table 2, and the A mixed powder was obtained.
- sample 1 a wet jet mill was used and the number of passes was 30.
- Sample 9 was mixed for 20 hours in a ball mill using cemented carbide media with a diameter of 5 mm.
- the secondary mixed powder is filled into a tantalum (Ta) container in contact with a WC-6% Co cemented carbide disk and a Co (cobalt) foil, and vacuum sealed.
- the mixed powder filled in a container made of Ta was pressurized to a pressure of 6 GPa using a belt-type ultra-high pressure and high temperature generator, and then heated to the temperature listed in the "Temperature” column of "Sintering conditions” in Table 2. After pressurization and heating, the product was sintered under the pressure and temperature conditions for the time indicated in the "Time” column to obtain a cubic boron nitride sintered body.
- sample 1 was sintered at a pressure of 6 GPa and a temperature of 1350° C. for 0.25 hours to obtain a cubic boron nitride sintered body.
- the content rate (volume %) of the first void and the content rate (volume %) of the second void are shown in the "First void content” and "Second void content” columns of Tables 3 and 4. .
- the cubic boron nitride sintered body consisted of cubic boron nitride particles, a binder phase, and voids. That is, the total content (volume %) of cubic boron nitride particles and the binder phase in the cubic boron nitride sintered body is the content of the first voids from the entire cubic boron nitride sintered body (100 volume %).
- the volume ratio of the cubic boron nitride particles to the binder phase in the cubic boron nitride sintered body is the same as the cBN powder as the raw material (the sum of these if two types are used) and the binder phase raw material. It was confirmed that the blending ratio with the powder (total of aluminum oxide powder and first binder phase raw material powder) was maintained.
- composition of the binder phase For each cubic boron nitride sintered body, the composition of the binder phase and the content (volume %) of aluminum oxide particles in the entire binder phase were measured. Since the specific measurement method is shown in Embodiment 1, its description will not be repeated. It was confirmed that the binder phase of Sample 1 consisted of 100% by volume of aluminum oxide particles. It was confirmed that the binder phase of the other samples consisted of aluminum oxide particles and the first binder phase. That is, the total of the aluminum oxide particles and the first binder phase particles in the binder phase was 100% by volume. The composition of the first binder phase of each sample is shown in the "First binder phase composition" column of Tables 3 and 4.
- the content ratio (volume %) of aluminum oxide particles to the entire binder phase is shown in the "Al 2 O 3 /Binder Phase" column of Tables 3 and 4. In all samples, the value obtained by subtracting the content (volume %) of aluminum oxide particles to the entire binder phase from the entire binder phase (100 volume %) corresponds to the content of the first binder phase particles in the binder phase. .
- First cubic boron nitride particles For the cubic boron nitride sintered body of each sample, first cubic boron nitride particles having a particle size of 5% or more and 50% or less of the average particle size of the aluminum oxide particles are identified, and the first cubic boron nitride particles are The volumetric percentage of particles to binder phase was determined. Since the specific measurement method is shown in Embodiment 1, its description will not be repeated. The results are shown in the "first cBN/bonded phase" column of Tables 3 and 4.
- Cutting tools (shape: TCGW110208) were produced using the cBN sintered bodies of Samples 1 to 48. A cutting test was conducted using a machining center under the following cutting conditions. The cutting conditions below apply to high-efficiency, high-load cutting of cast iron. Work material: Centrifugal cast iron Cutting speed Vc: 1000m/min Feed speed f: 0.35mm/rev Depth of cut Ap: 0.2mm Coolant: WET Cutting method: 50 bits/0.8km, cutting in which collision occurs between the tool and the workpiece 50 times to finish cutting a cutting length of 0.8km with a constant depth of cut.Evaluation method: Cutting distance until fracture (km) Derive. The longer the cutting distance, the longer the tool life. The results are shown in the "life span" column of Tables 3 and 4.
- the cubic boron nitride sintered body of Sample 3 has aluminum oxide particles with an average particle size of less than 50 nm, and falls under a comparative example.
- the cubic boron nitride sintered body of Sample 7 has an average grain size of aluminum oxide particles of more than 250 nm, and corresponds to a comparative example.
- the cubic boron nitride sintered body of Sample 8 has a first void content of more than 0.10% by volume and corresponds to a comparative example.
- the cubic boron nitride sintered body of Sample 9 has a first void content of less than 0.001% by volume and corresponds to a comparative example.
- the volume-based percentage of cubic boron nitride particles with respect to the total of cubic boron nitride particles and the binder phase is more than 70% by volume, and the content of the first voids is It is more than 0.10% by volume and corresponds to a comparative example.
- the content of cubic boron nitride particles relative to the total of the cubic boron nitride particles and the binder phase is less than 39% by volume, and the content of the first voids is 0. It is less than 0.001% by volume and corresponds to a comparative example.
- the cubic boron nitride sintered bodies of Sample 1, Sample 2, Sample 4 to Sample 6, Sample 10, Sample 11, Sample 14 to Sample 48 (Example) are Sample 3, Sample 7 to Sample 9, Sample 12 and Sample It was confirmed that the tool life was longer than that of the cubic boron nitride sintered body No. 13 (comparative example). This is presumably because the samples corresponding to Examples have excellent fracture resistance even in high-efficiency, high-load cutting of cast iron.
- Voids 1. Cubic boron nitride particles, 3. Binding phase, 4. Cubic boron nitride sintered body, 5. Aluminum oxide particles, 6. First binding phase particles.
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Abstract
Description
立方晶窒化硼素粒子と結合相と空隙とを備え、
前記立方晶窒化硼素粒子と前記結合相との合計に対する前記立方晶窒化硼素粒子の体積基準の百分率は40体積%以上70体積%以下であり、
前記立方晶窒化硼素粒子と前記結合相との合計に対する前記結合相の体積基準の百分率は30体積%以上60体積%以下であり、
前記結合相は、前記結合相全体に対して酸化アルミニウム粒子を10体積%以上100体積%以下含み、
前記酸化アルミニウム粒子の平均粒径は、50nm以上250nm以下であり、
1つ以上の第1の空隙を0.001体積%以上0.100体積%以下含み、
前記第1の空隙のそれぞれの少なくとも一部は、前記酸化アルミニウム粒子に接する、立方晶窒化硼素焼結体である。
近年、高能率加工への要求が高まっている。立方晶窒化硼素を用いた工具で高能率加工を行った場合、欠損により工具寿命が短くなる場合がある。よって、工具材料として用いた場合、該工具が高能率加工においても長い工具寿命を有することができる立方晶窒化硼素焼結体が求められている。
本開示の立方晶窒化硼素焼結体を工具材料として用いた場合、該工具は高能率加工においても長い工具寿命を有することができる。
最初に本開示の実施態様を列記して説明する。
(1)本開示の立方晶窒化硼素焼結体は、
立方晶窒化硼素粒子と結合相と空隙とを備え、
前記立方晶窒化硼素粒子と前記結合相との合計に対する前記立方晶窒化硼素粒子の体積基準の百分率は40体積%以上70体積%以下であり、
前記立方晶窒化硼素粒子と前記結合相との合計に対する前記結合相の体積基準の百分率は30体積%以上60体積%以下であり、
前記結合相は、前記結合相全体に対して酸化アルミニウム粒子を10体積%以上100体積%以下含み、
前記酸化アルミニウム粒子の平均粒径は、50nm以上250nm以下であり、
1つ以上の第1の空隙を0.001体積%以上0.100体積%以下含み、
前記第1の空隙のそれぞれの少なくとも一部は、前記酸化アルミニウム粒子に接する、立方晶窒化硼素焼結体である。
前記第1の結合相粒子は、
周期表の第4族元素、第5族元素、第6族元素、アルミニウム、珪素、鉄、コバルト及びニッケルからなる第1群より選ばれる1種の元素の単体、並びに、前記第1群より選ばれる2種以上の元素からなる合金及び金属間化合物、からなる第2群より選ばれる少なくとも1種、及び
前記第1群より選ばれる少なくとも1種の元素と、窒素、炭素、硼素及び酸素からなる第3群より選ばれる少なくとも1種の元素とからなる第1化合物、並びに、前記第1化合物の固溶体、からなる第4群より選ばれる少なくとも1種、の一方又は両方を含み、
前記第1化合物は、酸化アルミニウム粒子を含まないことが好ましい。
これによると、工具寿命が更に向上する。
前記第1の空隙間の距離の平均は、1.0μm以上20μm以下であることが好ましい。
これによると、工具寿命が更に向上する。
前記第1の立方晶窒化硼素粒子の粒径は、前記酸化アルミニウム粒子の平均粒径の5%以上50%以下であり、
前記第1の立方晶窒化硼素粒子の前記結合相に対する体積基準の百分率は、1%以上30%以下であり、
前記第1の立方晶窒化硼素粒子は、第1A立方晶窒化硼素粒子を個数基準で30%以上100%以下含み、
前記第1A立方晶窒化硼素粒子のそれぞれの少なくとも一部は、前記酸化アルミニウム粒子に接することが好ましい。
これによると、工具寿命が更に向上する。
本開示の立方晶窒化硼素焼結体の具体例を、以下に図面を参照しつつ説明する。本開示の図面において、同一の参照符号は、同一部分または相当部分を表すものである。また、長さ、幅、厚さ、深さなどの寸法関係は図面の明瞭化と簡略化のために適宜変更されており、必ずしも実際の寸法関係を表すものではない。
本開示の一実施形態(以下、「本実施形態」とも記す。)の立方晶窒化硼素焼結体は、
立方晶窒化硼素粒子と結合相と空隙とを備え、
該立方晶窒化硼素粒子と該結合相の合計に対する該立方晶窒化硼素粒子の体積基準の百分率は40体積%以上70体積%以下であり、
該立方晶窒化硼素粒子と該結合相の合計に対する該結合相の体積基準の百分率は30体積%以上60体積%以下であり、
該結合相は、該結合相全体に対して酸化アルミニウム粒子を10体積%以上100体積%以下含み、
該酸化アルミニウム粒子の平均粒径は、50nm以上250nm以下であり、
1つ以上の第1の空隙を0.001体積%以上0.100体積%以下含み、
該第1の空隙のそれぞれの少なくとも一部は、該酸化アルミニウム粒子に接する、立方晶窒化硼素焼結体である。
本実施形態の立方晶窒化硼素焼結体は、立方晶窒化硼素粒子と結合相と空隙とを備える。本実施形態の立方晶窒化硼素焼結体は、本開示の効果を奏する限り、使用する原材料、製造条件等に起因する不可避不純物を含み得る。本実施形態の立方晶窒化硼素焼結体は、立方晶窒化硼素粒子と結合相と空隙と不可避不純物とからなることができる。立方晶窒化硼素焼結体の不可避不純物の含有率(質量%)は、1質量%以下とすることができる。立方晶窒化硼素焼結体の不可避不純物の含有率は、ICP発光分析(Inductively Coupled Plasma)Emission Spectroscopy(測定装置:島津製作所「ICPS-8100」(商標))により測定される。
≪酸化アルミニウム粒子≫
本実施形態において、結合相は、該結合相全体に対して酸化アルミニウム粒子を10体積%以上100体積%以下含み、該酸化アルミニウム粒子の平均粒径は、50nm以上250nm以下である。
本実施形態において、結合相は、10体積%以上98体積%以下の酸化アルミニウム粒子と、2体積%以上90体積%以下の第1の結合相粒子と、からなり、
該第1の結合相粒子は、
周期表の第4族元素、第5族元素、第6族元素、アルミニウム、珪素、鉄、コバルト及びニッケルからなる第1群より選ばれる1種の元素の単体、並びに、該第1群より選ばれる2種以上の元素からなる合金及び金属間化合物、からなる第2群より選ばれる少なくとも1種、及び
該第1群より選ばれる少なくとも1種の元素と、窒素、炭素、硼素及び酸素からなる第3群より選ばれる少なくとも1種の元素とからなる第1化合物、並びに、該第1化合物の固溶体、からなる第4群より選ばれる少なくとも1種、の一方又は両方を含み、
該第1化合物は、酸化アルミニウム粒子を含まないことが好ましい。
(b)第2群より選ばれる少なくとも1種を含む。
(c)第4群より選ばれる少なくとも1種からなる。
(d)第4群より選ばれる少なくとも1種を含む。
(e)第2群より選ばれる少なくとも1種、並びに、第4群より選ばれる少なくとも1種からなる。
(f)第2群より選ばれる少なくとも1種、並びに、第4群より選ばれる少なくとも1種を含む。
本実施形態の立方晶窒化硼素焼結体は、複数の第1の空隙を含み、第1の空隙間の距離の平均は、1.0μm以上20μm以下が好ましい。これによると、工具寿命が更に向上する。この理由は、立方晶窒化硼素焼結体において第1の空隙が分散して存在し、立方晶窒化硼素焼結体の全領域で略均一に亀裂の発生が抑制されるためと推察される。
本実施形態の立方晶窒化硼素焼結体において、第1の空隙の断面積の平均は、0.001μm2以上0.02μm2以下であることが好ましい。これによると、工具寿命が更に向上する。この理由は、第1の空隙による熱応力の緩和効果が向上し、かつ、第1の空隙が亀裂の起点となることが抑制されるためと推察される。
立方晶窒化硼素粒子は、立方晶窒化硼素からなる。立方晶窒化硼素粒子は、本開示の効果を奏する限り、不可避不純物を含むことができる。
本実施形態において、第1の立方晶窒化硼素粒子とは、その粒径が酸化アルミニウム粒子の平均粒径の5%以上50%以下である立方晶窒化硼素粒子を意味する。ここで、第1の立方晶窒化硼素粒子の粒径とは、立方晶窒化硼素焼結体の任意の断面で観察される第1の立方晶窒化硼素粒子の円相当径を意味する。該第1の立方晶窒化硼素粒子は、酸化アルミニウム粒子間に配置されやすく、第1の立方晶窒化硼素粒子による酸化アルミニウム粒子の粒成長の抑制効果が得られやすいと推察される。第1の立方晶窒化硼素粒子の粒径が、酸化アルミニウム粒子の平均粒径の5%以上であると、立方晶窒化硼素焼結体において靭性の低下による耐欠損性の低下が抑制される。
本実施形態において、第1A立方晶窒化硼素粒子とは、第1の立方晶窒化硼素粒子のうち、その少なくとも一部が酸化アルミニウム粒子に接している立方晶窒化硼素粒子を意味する。第1の立方晶窒化硼素粒子は、第1A立方晶窒化硼素粒子を個数基準で30%以上100%以下含み、第1A立方晶窒化硼素粒子のそれぞれの少なくとも一部は、酸化アルミニウム粒子に接することが好ましい。これによると、第1の立方晶窒化硼素粒子による酸化アルミニウム粒子の粒成長の抑制効果が得られやすいと推察される。
本開示の立方晶窒化硼素焼結体は、切削工具、耐摩工具、研削工具などに用いることが好適である。
本開示の立方晶窒化硼素焼結体は、例えば、下記の方法で作製することができる。
立方晶窒化硼素粉末(以下、「cBN粉末」ともいう。)と、酸化アルミニウム粉末を準備する。結合相が、酸化アルミニウム粒子に加えて、第1の結合相粒子を含む場合は、該第1の結合相粒子の原料粉末(以下、「第1の結合相原料粉末」とも記す。)を準備する。
次に、上記で準備したcBN粉末と酸化アルミニウム粉末とを遊星攪拌装置で混合攪拌して(以下、「1次混合」とも記す)、1次混合粉末を得る。cBN粉末として、粒径の異なる2種類のcBN粉末を用いる場合は、2種類とも混合する。攪拌の際は、アルミナメディアを用いる。混合攪拌方法は、湿式又は乾式のいずれでもよい。1次混合の混合時間は、0.1時間以上2時間未満とすることができ、0.1時間以上1.5時間以下とすることもできる。アルミナメディアを用い、前記の混合時間とすることにより、立方晶窒化硼素焼結体の空隙含有率を制御することができる。これは本発明者らが新たに見出した知見である。
2次混合粉末をWC-6%Coの超硬合金製円盤とCo(コバルト)箔とに接した状態で、Ta(タンタル)製の容器に充填して真空シールする。Ta製容器に充填された混合粉末を、ベルト型超高圧高温発生装置を用いて、圧力5GPa以上7GPa以下に加圧した後、温度1300℃以上1500℃以下に加熱し、加圧加熱後の圧力及び温度条件下で15分以上30分以下保持して焼結させる。前記の焼結条件とすることにより、立方晶窒化硼素焼結体の空隙含有率を制御することができる。これは本発明者らが新たに見出した知見である。これにより、本実施形態の立方晶窒化硼素焼結体が作製される。
従来、酸化アルミニウム粒子を含む立方晶窒化硼素焼結体の製造において、酸化アルミニウム粒子の焼結性の低さに起因して亀裂の起点となる空隙が生じやすく、立方晶窒化硼素焼結体の耐欠損性が低下する傾向があった。空隙を低減させるためには、焼結温度を上昇させることが考えられる。しかし、焼結温度を上昇させると酸化アルミニウム粒子が粒成長して粒径が増加し、強度及び耐摩耗性が低下する。よって、酸化アルミニウム粒子を含む立方晶窒化硼素焼結体では、耐摩耗性及び耐欠損性の両立が困難であった。
本実施形態の立方晶窒化硼素焼結体は、立方晶窒化硼素粒子と結合相と空隙とからなり、立方晶窒化硼素粒子と結合相との合計に対する前記立方晶窒化硼素粒子の体積基準の百分率は40体積%以上70体積%以下であり、立方晶窒化硼素粒子と結合相との合計に対する前記結合相の体積基準の百分率は30体積%以上60体積%以下であることが好ましい。
本実施形態の立方晶窒化硼素焼結体は、立方晶窒化硼素粒子と結合相と空隙と不可避不純物とからなり、立方晶窒化硼素粒子と結合相との合計に対する前記立方晶窒化硼素粒子の体積基準の百分率は40体積%以上70体積%以下であり、立方晶窒化硼素粒子と結合相との合計に対する前記結合相の体積基準の百分率は30体積%以上60体積%以下であることが好ましい。
[立方晶窒化硼素焼結体の作製]
表1~表4に示される各試料No.の立方晶窒化硼素焼結体を以下の手順で作製した。
公知の平均粒径の異なる2種類のcBN粉末(平均粒径2μm(表1において、「cBN粉末 粒径大」と記す)、平均粒径0.1μm(表1において、「cBN粉末 粒径小」と記す。))、公知の酸化アルミニウム粉末(平均粒径0.1μm、表1において、「Al2O3粉末」と記す。)及び、公知の第1の結合相原料粉末を準備した。第1の結合相粉末としては、ZrO2粉末(平均粒径1μm)、Al2O3-ZrO2固溶体粉末(平均粒径1μm)、ZrB2粉末(平均粒径2μm)、TiC粉末(平均粒径1.2μm)、TiN粉末(平均粒径0.5μm)、Ti2AlN粉末(平均粒径0.4μm)、Ti2AlC粉末(平均粒径0.5μm)、WC-Co粉末(平均粒径2μm)、Al粉末(平均粒径2μm)、NbN粉末(平均粒径2μm)、HfC粉末(平均粒径2μm)、Mo2N粉末(平均粒径2μm)、Si3N4粉末(平均粒径2μm)、VC粉末(平均粒径2μm)を準備した。
次に、cBN粉末と酸化アルミニウム粉末とを、表2の「1次混合」記載の「方法」、「時間」及び「メディア」欄に記載の条件で混合して1次混合粉末を得た(1次混合)。例えば、試料1では、遊星攪拌装置で径0.5mmのアルミナメディアを用いて、0.25時間混合した。
2次混合粉末をWC-6%Coの超硬合金製円盤とCo(コバルト)箔とに接した状態で、Ta(タンタル)製の容器に充填して真空シールする。Ta製容器に充填された混合粉末を、ベルト型超高圧高温発生装置を用いて、圧力6GPaまで加圧した後、表2の「焼結条件」の「温度」欄に記載の温度まで加熱し、加圧加熱後の圧力及び温度条件下で「時間」欄に記載の時間保持して焼結し、立方晶窒化硼素焼結体を得た。例えば、試料1では圧力6GPa、温度1350℃で0.25時間保持して焼結して立方晶窒化硼素焼結体を得た。
≪立方晶窒化硼素粒子の含有率(体積%)、結合相の含有率(体積%)、第1の空隙の含有率(体積%)及び第2の空隙の含有率(体積%)≫
各立方晶窒化硼素焼結体について、立方晶窒化硼素粒子の含有率(体積%)、結合相の含有率(体積%)、第1の空隙の含有率(体積%)及び第2の空隙の含有率(体積%)を測定した。具体的な測定方法は実施形態1に示されているため、その説明は繰り返さない。第1の空隙の含有率(体積%)及び第2の空隙の含有率(体積%)を表3及び表4の「第1の空隙含有率」及び「第2の空隙含有率」欄に示す。全ての試料において、立方晶窒化硼素焼結体は立方晶窒化硼素粒子、結合相及び空隙からなることが確認された。すなわち、立方晶窒化硼素焼結体における立方晶窒化硼素粒子と結合相との含有率(体積%)の合計は、立方晶窒化硼素焼結体全体(100体積%)から第1の空隙の含有率(体積%)及び第2の空隙の含有率(体積%)を減じて求められる。全ての試料において、立方晶窒化硼素焼結体中の立方晶窒化硼素粒子と結合相との体積比率は、原料のcBN粉末(2種類を用いている場合はこれらの合計)と、結合相原料粉末(酸化アルミニウム粉末及び第1の結合相原料粉末の合計)との配合比率を維持していることが確認された。
各立方晶窒化硼素焼結体について、結合相の組成、結合相全体に対する酸化アルミニウム粒子の含有率(体積%)を測定した。具体的な測定方法は実施形態1に示されているため、その説明は繰り返さない。試料1の結合相は酸化アルミニウム粒子100体積%からなることが確認された。その他の試料の結合相は、酸化アルミニウム粒子と第1の結合相とからなることが確認された。すなわち、結合相における酸化アルミニウム粒子と第1の結合相粒子との合計は100体積%であった。各試料の第1の結合相の組成を表3及び表4の「第1の結合相組成」欄に示す。結合相全体に対する酸化アルミニウム粒子の含有率(体積%)を表3及び表4の「Al2O3/結合相」欄に示す。全ての試料において、結合相全体(100体積%)から、結合相全体に対する酸化アルミニウム粒子の含有率(体積%)を減じた値が、結合相の第1の結合相粒子の含有率に相当する。
各立方晶窒化硼素焼結体について、酸化アルミニウム粒子の平均粒径(円相当径の個数基準の算術平均径)を測定した。具体的な測定方法は実施形態1に示されているため、その説明は繰り返さない。結果を表3及び表4の「Al2O3平均粒径」欄に示す。
各試料の立方晶窒化硼素焼結体について、第1の空隙間の距離の平均を測定した。具体的な測定方法は実施形態1に示されているため、その説明は繰り返さない。結果を表3及び表4の「第1の空隙間距離」欄に示す。
各試料の立方晶窒化硼素焼結体について、第1の空隙の断面積の平均を測定した。具体的な測定方法は実施形態1に示されているため、その説明は繰り返さない。結果を表3及び表4の「第1の空隙断面積」欄に示す。
各試料の立方晶窒化硼素焼結体について、酸化アルミニウム粒子の平均粒径の5%以上50%以下の粒径を有する第1の立方晶窒化硼素粒子を特定し、第1の立方晶窒化硼素粒子の結合相に対する体積基準の百分率を測定した。具体的な測定方法は実施形態1に示されているため、その説明は繰り返さない。結果を表3及び表4の「第1のcBN/結合相」欄に示す。
試料1~試料48のcBN焼結体を用いて切削工具(形状:TCGW110208)を作製した。これをマシニングセンタを用いて、以下の切削条件下で切削試験を実施した。下記の切削条件は、鋳鉄の高能率高負荷切削に該当する。
被削材:遠心鋳造鋳鉄
切削速度Vc:1000m/min
送り速度f:0.35mm/rev
切込みAp:0.2mm
クーラント:WET
切削方法:50食いつき/0.8km、切削長0.8kmを一定の切り込みで削りきるのに50回工具と被削材間の衝突が起きる切削
評価方法:欠損に至るまでの切削距離(km)を導出する。切削距離が長いほど、工具寿命が長いことを示す。
結果を表3及び表4の「寿命」欄に示す。
今回開示された実施の形態および実施例はすべての点で例示であって、制限的なものではないと考えられるべきである。本発明の範囲は上記した実施の形態および実施例ではなく請求の範囲によって示され、請求の範囲と均等の意味、および範囲内でのすべての変更が含まれることが意図される。
Claims (5)
- 立方晶窒化硼素粒子と結合相と空隙とを備え、
前記立方晶窒化硼素粒子と前記結合相との合計に対する前記立方晶窒化硼素粒子の体積基準の百分率は40体積%以上70体積%以下であり、
前記立方晶窒化硼素粒子と前記結合相との合計に対する前記結合相の体積基準の百分率は30体積%以上60体積%以下であり、
前記結合相は、前記結合相全体に対して酸化アルミニウム粒子を10体積%以上100体積%以下含み、
前記酸化アルミニウム粒子の平均粒径は、50nm以上250nm以下であり、
1つ以上の第1の空隙を0.001体積%以上0.100体積%以下含み、
前記第1の空隙のそれぞれの少なくとも一部は、前記酸化アルミニウム粒子に接する、立方晶窒化硼素焼結体。 - 前記結合相は、10体積%以上98体積%以下の前記酸化アルミニウム粒子と、2体積%以上90体積%以下の第1の結合相粒子と、からなり、
前記第1の結合相粒子は、
周期表の第4族元素、第5族元素、第6族元素、アルミニウム、珪素、鉄、コバルト及びニッケルからなる第1群より選ばれる1種の元素の単体、並びに、前記第1群より選ばれる2種以上の元素からなる合金及び金属間化合物、からなる第2群より選ばれる少なくとも1種、及び
前記第1群より選ばれる少なくとも1種の元素と、窒素、炭素、硼素及び酸素からなる第3群より選ばれる少なくとも1種の元素とからなる第1化合物、並びに、前記第1化合物の固溶体、からなる第4群より選ばれる少なくとも1種、の一方又は両方を含み、
前記第1化合物は、酸化アルミニウム粒子を含まない、請求項1に記載の立方晶窒化硼素焼結体。 - 前記立方晶窒化硼素焼結体は、複数の前記第1の空隙を含み、
前記第1の空隙間の距離の平均は、1.0μm以上20μm以下である、請求項1又は請求項2に記載の立方晶窒化硼素焼結体。 - 前記第1の空隙の断面積の平均は、0.001μm2以上0.02μm2以下である、請求項1から請求項3のいずれか1項に記載の立方晶窒化硼素焼結体。
- 前記立方晶窒化硼素粒子は、第1の立方晶窒化硼素粒子を含み、
前記第1の立方晶窒化硼素粒子の粒径は、前記酸化アルミニウム粒子の平均粒径の5%以上50%以下であり、
前記第1の立方晶窒化硼素粒子の前記結合相に対する体積基準の百分率は、1%以上30%以下であり、
前記第1の立方晶窒化硼素粒子は、第1A立方晶窒化硼素粒子を個数基準で30%以上100%以下含み、
前記第1A立方晶窒化硼素粒子のそれぞれの少なくとも一部は、前記酸化アルミニウム粒子に接する、請求項1から請求項4のいずれか1項に記載の立方晶窒化硼素焼結体。
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| WO2012057183A1 (ja) * | 2010-10-27 | 2012-05-03 | 住友電工ハードメタル株式会社 | 立方晶窒化硼素焼結体及び立方晶窒化硼素焼結体工具 |
| JP2013255986A (ja) * | 2012-05-16 | 2013-12-26 | Mitsubishi Materials Corp | 立方晶窒化ほう素基焼結体製切削工具 |
| JP2016107396A (ja) | 2014-11-27 | 2016-06-20 | 三菱マテリアル株式会社 | 耐チッピング性、耐摩耗性にすぐれた表面被覆切削工具 |
| WO2016194416A1 (ja) * | 2015-05-29 | 2016-12-08 | 住友電工ハードメタル株式会社 | 焼結体および切削工具 |
| WO2017168841A1 (ja) * | 2016-03-30 | 2017-10-05 | 住友電工ハードメタル株式会社 | 表面被覆立方晶窒化硼素焼結体およびこれを備える切削工具 |
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| MX346949B (es) * | 2010-11-26 | 2017-04-06 | Sumitomo Electric Hardmetal Corp | Cuerpo sinterizado de superficie revestida. |
| JP6637664B2 (ja) * | 2014-03-28 | 2020-01-29 | 三菱マテリアル株式会社 | 立方晶窒化硼素焼結体切削工具 |
| JP2018505839A (ja) * | 2014-12-31 | 2018-03-01 | ダイヤモンド イノヴェーションズ インコーポレイテッド | 微結晶立方晶窒化ホウ素(CBN)を含む多結晶立方晶窒化ホウ素(PcBN)及び作製方法 |
| JP6048522B2 (ja) * | 2015-02-26 | 2016-12-21 | 住友電気工業株式会社 | 焼結体および切削工具 |
| JP6928218B2 (ja) * | 2015-12-25 | 2021-09-01 | 三菱マテリアル株式会社 | 表面被覆立方晶窒化ホウ素焼結体工具 |
| JP2017210383A (ja) * | 2016-05-23 | 2017-11-30 | 株式会社栗本鐵工所 | 窒化ホウ素顆粒体の製造方法 |
| GB201622458D0 (en) * | 2016-12-31 | 2017-02-15 | Element Six Ltd | Superhard constructions & methods of making same |
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|---|---|---|---|---|
| JPS49109231A (ja) * | 1973-02-21 | 1974-10-17 | ||
| WO2012057183A1 (ja) * | 2010-10-27 | 2012-05-03 | 住友電工ハードメタル株式会社 | 立方晶窒化硼素焼結体及び立方晶窒化硼素焼結体工具 |
| JP2013255986A (ja) * | 2012-05-16 | 2013-12-26 | Mitsubishi Materials Corp | 立方晶窒化ほう素基焼結体製切削工具 |
| JP2016107396A (ja) | 2014-11-27 | 2016-06-20 | 三菱マテリアル株式会社 | 耐チッピング性、耐摩耗性にすぐれた表面被覆切削工具 |
| WO2016194416A1 (ja) * | 2015-05-29 | 2016-12-08 | 住友電工ハードメタル株式会社 | 焼結体および切削工具 |
| WO2017168841A1 (ja) * | 2016-03-30 | 2017-10-05 | 住友電工ハードメタル株式会社 | 表面被覆立方晶窒化硼素焼結体およびこれを備える切削工具 |
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Also Published As
| Publication number | Publication date |
|---|---|
| US11958782B2 (en) | 2024-04-16 |
| CN118510737A (zh) | 2024-08-16 |
| US20230286869A1 (en) | 2023-09-14 |
| JP7346751B1 (ja) | 2023-09-19 |
| EP4491601A4 (en) | 2025-05-07 |
| JPWO2023170787A1 (ja) | 2023-09-14 |
| EP4491601A1 (en) | 2025-01-15 |
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