WO2022176569A1 - ｃＢＮ焼結体 - Google Patents

ｃＢＮ焼結体 Download PDF

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WO2022176569A1
WO2022176569A1 PCT/JP2022/003315 JP2022003315W WO2022176569A1 WO 2022176569 A1 WO2022176569 A1 WO 2022176569A1 JP 2022003315 W JP2022003315 W JP 2022003315W WO 2022176569 A1 WO2022176569 A1 WO 2022176569A1
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cbn
grains
boride
sintered body
particles
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French (fr)
Japanese (ja)
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将行 越山
雅大 矢野
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to JP2023500686A priority Critical patent/JPWO2022176569A1/ja
Priority to US18/546,381 priority patent/US20240228386A9/en
Priority to EP22755892.1A priority patent/EP4296246A4/en
Publication of WO2022176569A1 publication Critical patent/WO2022176569A1/ja
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Definitions

  • the present invention relates to a cubic boron nitride sintered body (hereinafter sometimes referred to as cBN sintered body), which is a hard composite material.
  • cBN sintered body cubic boron nitride sintered body
  • the cBN sintered body is inferior in hardness to diamond, it has the property of having low reactivity with Fe-based and Ni-based materials. It is also used as a drilling tip for drilling tools in Proposals have been made to improve the performance of cBN sintered bodies.
  • Patent Document 1 one of Ti-containing boronitrides, borocarbides, borates, boronitrides, boronitrides, borocarbonates, and boronitride carbonates A first layer consisting of the above, and one of boronitrides, borocarbides, borates, boronitrides, boronitrides, borocarbonates, and boronitride carbonates containing Al on the entire surface of the first layer A cBN sintered body having a second layer formed thereon is described, and the sintered body is said to exhibit chipping resistance when used as a cutting tool.
  • the cBN particles have an average particle size of 0.5 to 3.5 ⁇ m and a content of 40 to 75 vol%, and the binder phase has an average particle size of 50 to 500 nm.
  • the Ti boride phase is dispersed and distributed, and when the amount of Ti boride phase produced is Y (vol%) and the content of cBN particles is X (vol%), (-0.05X + 4.5 ) ⁇ Y ⁇ (-0.2X + 18), and the content of the Ti boride phase not in contact with the cBN particles is 15 to 65 vol% of the total Ti boride phase cBN sintered body is described. It is said that the sintered body exhibits chipping resistance when used as a cutting tool.
  • the binding phase contains Ti boride
  • the Ti boride has an average particle size of 10 to 200 nm, and a content of 0.2 to 10 vol%.
  • a cBN sintered body is described in which the ratio (PN TB /PN BN ) of the number PN TB of cBN grains in contact with Ti borides having a long axis of 150 nm or more to the total number of PN BN is 0.05 or less. It is said that the sintered body exhibits wear resistance and chipping resistance when used as a cutting tool.
  • JP-A-5-310474 Japanese Patent No. 5804448 JP 2018-145020 A
  • the present invention has been made in view of the above circumstances and proposals, and has excellent fatigue wear resistance and abrasive wear resistance, and furthermore, even when used as a drilling tool, it can be used as a drilling tool due to impacts and vibrations for breaking rocks.
  • An object of the present invention is to provide a cBN sintered body having resistance to damage factors such as chipping.
  • the cBN sintered body according to the embodiment of the present invention is having cBN particles and a binder phase;
  • the content of the cBN particles is 40 vol% or more and 80 vol% or less, the binder phase comprises Ti-boride grains;
  • Y be the total length of the enveloping interface where each of the cBN particles contacts the binder phase, exists within 2 ⁇ m around the surface of each cBN particle, and has the following unevenness degree of 1.3 or more, 30
  • the sum of the interfacial lengths of the Ti boride grains of .0 or less is X, 3.0 ⁇ X/Y ⁇ 10.0 satisfy.
  • the cBN sintered body has excellent fatigue wear resistance, abrasive wear resistance, and high toughness, and when used as a drilling tool, it is resistant to damage factors such as fracture due to impact and vibration for breaking rocks. Tolerant.
  • FIG. 2 is a diagram schematically showing cBN grains and surrounding Ti borides in the cBN sintered body according to the embodiment of the present invention.
  • FIG. 4 is a diagram schematically showing the enveloping interface length of one cBN particle according to an embodiment of the present invention.
  • the inventor of the present invention proposes that these cBN sintered bodies are mainly used as cutting tools by pressing them against a work material of uniform composition.
  • a work material of uniform composition it was recognized that, as a material for cutting tools, the resistance to the main damage factor, which is the contact part with the work material and frictional wear with chips, is improved.
  • a digging tool is a tool for digging into the ground or bedrock.
  • rocks in the ground are not uniform in composition and strength, and are brittle materials. Therefore, unlike cutting, which focuses on cutting and chipping performance, the drilling tool must withstand the impact and vibration to break the rock, as well as the rotation caused by the excavator to efficiently remove this broken rock.
  • materials for excavating tools suffer from fatigue wear due to repeated impacts, and abrasive wear due to minute cutting action that occurs when the hard components of rocks enter between the cutting edge of the tool and the rock when crushed rock surrounds the drilling tool. Furthermore, resistance to damage factors such as damage due to impact and vibration for breaking rocks is required.
  • the inventors of the present invention have found that the fatigue wear resistance and abrasive wear resistance are excellent, and when used as a drilling tool, it is resistant to damage factors such as chipping due to impact and vibration for breaking rocks. Intensive studies were conducted to obtain a cBN sintered body having resistance.
  • Ti-boride crystal grains contained in the binder phase and having elongated plate-like shapes (the degree of plate-likeness is expressed by the degree of unevenness described later) are present in a specific form near the cBN grains. It was found that there is the following effect. (1) Ti-boride grains divert crack propagation near the interface between the cBN grains and the binder phase. (2) By detouring in (1) above, chipping of cBN particles on the surface of the cBN sintered body is suppressed, and chipping resistance is improved inside the cBN sintered body. (3) Whether the Ti boride crystal grains exist singly or in a state in which a plurality of Ti boride crystal grains are intertwined, the item (2) is satisfied.
  • cBN Cubic boron nitride
  • the average particle size of the cBN particles used in the present embodiment is not particularly limited, but is preferably in the range of 0.5 ⁇ m or more and 30.0 ⁇ m or less.
  • the inclusion of cBN particles in the sintered body improves chipping resistance, and in addition, if the average particle size is 0.5 ⁇ m or more and 30.0 ⁇ m or less, it can be used as a drilling tool. It more reliably suppresses chipping and chipping originating from the uneven shape of the cutting edge caused by cBN particles falling off the tool surface, and furthermore, progresses from the interface between the cBN particles and the binder phase caused by the stress applied to the cutting edge during use. This is because the propagation of cracks or cracks developed by splitting cBN grains can be reliably suppressed, and better chipping resistance can be obtained. More preferably, the average particle diameter is 1.0 ⁇ m or more and 25.0 ⁇ m or less.
  • the average particle diameter of cBN particles can be determined as follows.
  • the cross section of the cBN sintered body is mirror-finished, and the mirror-finished surface is subjected to structural observation with a scanning electron microscope (hereinafter referred to as SEM) to obtain a secondary electron image.
  • SEM scanning electron microscope
  • the cBN grain portion in the obtained image is extracted by image processing, and the average grain size, which will be described later, is calculated based on the maximum length of each grain determined by image analysis.
  • the image is displayed in monochrome with 256 gradations, 0 being black and 255 being white.
  • the peak value (v) of the pixel value of the cBN particle portion and the peak value (w) of the pixel value of the bonded phase portion are binarized using the value calculated by (w ⁇ v)/2+v as the threshold value. .
  • a region of about 0.5 ⁇ m ⁇ 0.5 ⁇ m is selected as the region for obtaining the pixel value of the cBN grain portion, and the average value obtained from at least three different locations within the same image region is calculated as the above-described cBN It is desirable to set the pixel value to Then, a region of about 0.2 ⁇ m ⁇ 0.2 ⁇ m to about 0.5 ⁇ m ⁇ 0.5 ⁇ m is selected as a region for obtaining the pixel value of the bonded phase portion, and similarly, from at least three different locations within the same image region.
  • the determined average value is taken as the peak value of the aforementioned pixel values of the combined phase.
  • a process for separating the portions where the cBN grains are considered to be in contact with each other such as watershed image processing, is used to separate the cBN grains that are considered to be in contact. do.
  • the part (black part) corresponding to the cBN particles in the image obtained after the above-mentioned binarization processing is subjected to particle analysis, and the obtained maximum length of each cBN particle is taken as the diameter of each cBN particle.
  • particle analysis for determining the maximum length the value of the larger length from the two lengths obtained by calculating the Feret diameter for one cBN particle is the maximum length, and that value is the diameter of each cBN particle. .
  • the volume obtained by calculation is the volume of each particle, and the cumulative volume is obtained. Based on this cumulative volume, the vertical axis is the volume percentage (%) and the horizontal axis is the diameter. ( ⁇ m), and the diameter when the volume percentage is 50% is taken as the average particle diameter of the cBN particles. This is performed for three observation areas, and the average value is defined as the average particle size ( ⁇ m) of the cBN particles.
  • the length ( ⁇ m) per pixel is set using the scale value known from the SEM in advance.
  • the observation area at least 30 or more cBN particles are observed in the observation area, that is, if the average particle size of the cBN particles is about 3 ⁇ m, the observation area is preferably about 15 ⁇ m ⁇ 15 ⁇ m, for example.
  • the content (vol%) of cBN particles in the cBN sintered body is preferably 40vol% or more and 80vol% or less.
  • the reason for this is that if the content is less than 40 vol%, there are few hard substances in the cBN sintered body, and, for example, when used as a drilling tool, the chipping resistance may decrease. This is because voids that act as starting points for cracks are generated in the sintered body, and chipping resistance may be lowered.
  • the content of cBN particles is more preferably 65 vol % or more and 78 vol % or less.
  • the content of cBN particles in the cBN sintered body can be obtained as follows. That is, the cross-sectional structure of the cBN sintered body is observed by SEM, the portion of cBN grains in the obtained secondary electron image is extracted by image processing, and the area occupied by the cBN grains is calculated by image analysis. This is performed for at least three observation regions, and the average value of the obtained area values is defined as the content (vol %) of the cBN grains.
  • the observation area used for this image processing is an area where at least 30 cBN particles are observed in the observation area, that is, when the average particle size of the cBN particles is 3 ⁇ m, for example, an observation area of about 15 ⁇ m ⁇ 15 ⁇ m is used. desirable.
  • Binder Phase The binder phase of the present embodiments preferably includes Ti - boride grains, eg TiB2.
  • the Ti boride grains referred to in this specification and claims are obtained by mirror-finishing the cross section of the cBN sintered body, and by element mapping the cross-sectional structure by Auger Electron Spectroscopy (AES). and B elements are particles that overlap in the mapping image.
  • the area per piece is not particularly limited, but is preferably 0.01 ⁇ m 2 or more and 5.00 ⁇ m 2 or less.
  • the observation magnification is about 20,000 times.
  • regions 2 ⁇ m apart are included. Therefore, the observation area is preferably about 3.5 ⁇ m ⁇ 4.5 ⁇ m in size, and three or more fields of view are preferably observed.
  • the entire grain may not be present in the image. not considered as an interface to use. Also, when Ti boride grains overlap, they are treated as one grain including the overlapping regions.
  • Ti borides are preferably present around the cBN grains, as schematically shown in FIG. Specifically, the total length of the enveloping interface where each of the cBN particles contacts the binder phase is Y, and the unevenness present within 2 ⁇ m around the surface of each cBN particle is 1.3 or more and 30.0 or less. When the sum of the interfacial lengths of the Ti boride grains of is X, 3.0 ⁇ X/Y ⁇ 10.0 is preferably satisfied.
  • the enveloping interface length of the cBN particle is the interface length of the cBN particle indicated by the dotted line in FIG. Y is the sum of the interfacial lengths where each cBN grain present contacts the binder phase. If there is an interface where cBN grains are in contact with each other, for example, they are separated using the watershed image processing described above, first, after obtaining the enveloping interface length of each cBN grain, cBN grains are in contact with each other. Y is calculated by subtracting the interface length.
  • the method of determining the enveloping interface is as follows. 1) A rectangular observation area of 3.5 ⁇ m ⁇ 4.5 ⁇ m (observation magnification is 20,000 times) is set. 2) When a straight line perpendicular to the diagonal from the upper left end to the lower right end of the rectangular observation area is translated toward the cBN particle in the same observation area, the surface of the particle and the first Let P0 be the point of contact. 3) Draw a half straight line L0 parallel to the horizontal line of the observation area from P0 to the outside of the cBN particle, rotate the half straight line L0 counterclockwise around P0, and first the surface of the cBN particle Let P1 be the point of contact.
  • the reason for using the enveloping interface length is as follows. Since Ti boride grains are generated from the B element of cBN grains, when tabular Ti boride grains are formed, the surfaces of the cBN grains often become uneven. If the unevenness of the cBN grains is used as the interface length between the cBN grains and the binder phase, the value of Y will be estimated high, and the value of X/Y will be small. It will be taken away. Therefore, we decided to use the enveloping interface length Y, which does not depend on the unevenness of the cBN grains.
  • the interface length of Ti boride grains refers to the length around the Ti boride grains, that is, the interface length (L) along the unevenness of the surface of the Ti boride grains, and the cBN grains present in the observation area.
  • X is the sum of all interfacial lengths (L) of Ti-boride particles having an unevenness of 1.3 or more and 30.0 or less existing within 2 ⁇ m around the surface.
  • X/Y is more preferably 4.0 or more and 7.0 or less.
  • the unevenness is represented by L 2 /(4 ⁇ S) (where L is the interface length of the Ti boride grains, and S is the area of the Ti boride grains), and defines the shape of the Ti boride grains. do.
  • the shape of the Ti boride grains preferably has an irregularity of 1.3 or more and 30.0 or less.
  • the reason why the unevenness is preferably 1.3 or more and 30.0 or less is as follows. That is, the degree of unevenness approaches 1 as the shape is closer to a circle, and is 1 in the case of a perfect circle. , more than 30.0, the Ti boride grains are too long and the strength is low, so that cracks are difficult to bypass and their progress cannot be suppressed, so that they do not contribute to chipping resistance.
  • the unevenness is more preferably 1.5 or more and 25.0 or less.
  • the Ti boride grains present within 2 ⁇ m from the surface of the cBN grains are defined as Ti boride grains in a circle with a radius of 2 ⁇ m centered at an arbitrary point between the cBN grain and the bonding phase interface. It refers to the part of the grain (it may be in contact with one point) that includes it. At this time, the Ti boride may be in contact with the cBN grains.
  • the reason why the cBN particle surface is within 2 ⁇ m around it is that when the cBN particle is separated from the cBN particle by more than 2 ⁇ m around it, the cBN particle is easily reached without going through the Ti boride grain when the crack develops. This is because the cBN particles cannot be prevented from falling off from the surface of the sintered body, and cracks propagate along the cBN particle interfaces inside the sintered body, thereby lowering the resistance to chipping of the cBN sintered body. More preferably, the Ti-boride grains are present within 1 ⁇ m from the surface of the cBN grains.
  • the raw material powder contained a small amount of unavoidable impurities.
  • cBN raw material having an average particle size after sintering of 0.5 to 30.0 ⁇ m as shown in Table 2, and Ti 2 AlC as a raw material powder constituting a binder phase and Ti 3 AlC 2 raw materials were prepared respectively.
  • the average particle size of the raw material the particle size D50 at which the cumulative frequency becomes 50% in the particle size distribution graph consisting of the frequency [%] with respect to the particle size was taken as the average particle size.
  • TiCN powder and TiAl3 powder were separately prepared as binder phase forming raw material powders.
  • the average particle size of these separately prepared powders was 0.6 ⁇ m. Table 1 shows the composition of these raw materials.
  • this mixed raw material powder was preliminarily heat-treated at 600°C in a vacuum atmosphere of 1 Pa or less to evaporate the adsorbed water from the powder surface.
  • the provisional heat treatment temperature is preferably 250 to 900° C. in a vacuum atmosphere of 1 Pa or less, which includes the treatment conditions of this example.
  • the reason for this is that if the temperature is less than 250° C., the evaporation of the adsorbed water is not sufficient, and Ti 2 AlC and Ti 3 AlC 2 react with the remaining moisture during ultra-high pressure and high temperature sintering to form TiO 2 and Al 2 .
  • Ti 2 AlC and Ti 3 AlC 2 react with oxygen during the preliminary heat treatment and similarly decompose into TiO 2 and Al 2 O 3 , which are raw materials constituting the binder phase. This is because the content of certain Ti 2 AlC and Ti 3 AlC 2 decreases and the toughness of the cBN sintered body decreases.
  • cBN sintered bodies (referred to as example sintered bodies) 1 to 10 of the present invention shown in Table 2 were produced.
  • the content and average particle diameter of cBN particles in Table 2 were measured by the method described above.
  • the average particle diameter and the content of cBN particles were measured using an observation area where at least 30 cBN particles were observed in the observation area, and the other observation fields were measured using the sizes given as examples.
  • Raw material powders include cBN raw material having an average particle size of 1.5 to 8.8 ⁇ m after sintering as shown in Table 4 as a hard raw material, and Ti 2 AlC powder, TiCN powder, TiAl 3 powder and Co powder were prepared.
  • Ti 2 AlC raw materials were prepared, one having an average particle size of 5 ⁇ m and the other having an average particle size of 50 ⁇ m.
  • the TiCN and TiAl 3 raw materials had an average grain size of 0.6 ⁇ m.
  • the Co raw material had an average particle size of 1 ⁇ m.
  • comparative example cBN sintered bodies (referred to as comparative example sintered bodies) 1 to 4 shown in Table 4 were produced. Each value in Table 4 was obtained in the same manner as in the example.
  • Example tools 1 to 10 (referred to as Examples 1 to 10) and Comparative example tools 1 to 1 having the shape of ISO standard RNGN090300, respectively 4 (referred to as Comparative Examples 1 to 4) were prepared, mounted on an NC lathe, and subjected to the following wet cutting test.
  • Cutting speed 150m/min Cutting depth: 0.3mm Feed rate: 0.1mm/rev Work Material: Granite (produced in Takine) Shape ⁇ 150mm ⁇ 200mmL
  • Cutting oil material Water-soluble cutting oil (NEOCOOL manufactured by MORESCO Co., Ltd.) The amount of wear of the cutting edge and the state of the cutting edge were confirmed when the cutting length (cutting distance) was 800 m. However, the cutting edge was observed every 100 m of cutting length, and the presence or absence of chipping and the amount of wear were measured. If the amount of wear exceeded 2000 ⁇ m, the cutting test was stopped at that point. Table 5 shows the results.

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