WO2020059755A1 - 立方晶窒化硼素焼結体、それを含む切削工具、および立方晶窒化硼素焼結体の製造方法 - Google Patents
立方晶窒化硼素焼結体、それを含む切削工具、および立方晶窒化硼素焼結体の製造方法 Download PDFInfo
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Definitions
- the present disclosure relates to a cubic boron nitride sintered body, a cutting tool including the same, and a method for producing a cubic boron nitride sintered body.
- cBN sintered body As a high-hardness material used for a cutting tool or the like, there is a cubic boron nitride sintered body (hereinafter, also referred to as “cBN sintered body”).
- a cubic boron nitride sintered body is usually composed of cubic boron nitride particles (hereinafter, also referred to as “cBN particles”) and a binder, and its characteristics tend to vary depending on the content ratio of the cubic boron nitride particles. .
- a cubic boron nitride sintered body (hereinafter, also referred to as “High-cBN sintered body”) having a high content of cubic boron nitride (hereinafter, also referred to as “cBN”) is formed by cutting a sintered alloy or the like. Can be suitably used.
- Patent Document 1 discloses a technique for suppressing the occurrence of sudden defects in a High-cBN sintered body by appropriately selecting a binder.
- a cubic boron nitride sintered body is a cubic boron nitride sintered body including cubic boron nitride particles of 85% by volume or more and less than 100% by volume, and a balance of a binder.
- the binder contains WC, Co and Al compounds
- the interface region including the interface where the cubic boron nitride particles are adjacent to each other is analyzed using TEM-EDX, all or a part of the interface is analyzed.
- Oxygen, and the width D of the region where oxygen is present is 0.1 nm or more and 10 nm or less.
- a cutting tool is a cutting tool including the above cubic boron nitride sintered body.
- a method for producing a cubic boron nitride sintered body is a method for producing a cubic boron nitride sintered body for producing the above cubic boron nitride sintered body, wherein the cubic boron nitride raw material powder Removing oxygen and attaching an organic substance to the cubic boron nitride raw material powder to produce an organic cubic boron nitride powder; and a binder raw material containing WC, Co and Al.
- FIG. 1 is an example of the second image.
- FIG. 2 is an example of a graph showing the results of line analysis, and is a graph showing the results of line analysis performed on the cubic boron nitride sintered body of Experimental Example 3.
- an object of the present disclosure is to provide a cubic boron nitride sintered body capable of extending the life, a cutting tool including the same, and a method of manufacturing a cubic boron nitride sintered body.
- the life can be prolonged, and the cutting tool including the same can also have a prolonged life.
- the present inventors first confirmed what state the cubic boron nitride raw material powder (cubic boron nitride powder to be the raw material of the cubic boron nitride sintered body) was in. Specifically, the cubic boron nitride raw material powder was observed using a transmission electron microscope (TEM). As a result, oxygen (O) exists on the surface of the cubic boron nitride raw material powder, and the oxygen exists in an amorphous state mixed with B 2 O 3 or boron (B). I knew it was there. Furthermore, when a cubic boron nitride sintered body was manufactured using the cubic boron nitride raw material powder, it was found that a large amount of oxygen remained in the cubic boron nitride sintered body.
- TEM transmission electron microscope
- the bonding between the cubic boron nitride particles in the cubic boron nitride sintered body is achieved by bonding B (boron) and / or N (nitrogen) via a binder (mainly Co) existing between the cubic boron nitride particles. It is considered that the diffusion and reprecipitation cause neck gloss between the cubic boron nitride particles.
- the present inventors have found that the presence of oxygen on the surface of the cubic boron nitride particles during sintering inhibits the generation of neck gloss between the cubic boron nitride particles. It has been hypothesized that the bonding force between the particles decreases, resulting in the dropout of the cubic boron nitride particles.
- “inhibition of generation of neck gloss” is also referred to as “neck gloss suppression”.
- the present inventors studied a method of removing oxygen from cubic boron nitride raw material powder.
- a general heat treatment specifically, a reduction treatment using hydrogen or ammonia was performed.
- these heat treatments did not properly remove oxygen.
- the present inventors focused on supercritical water. Since supercritical water has an extremely high dissolving power, it is possible to remove oxygen from cubic boron nitride raw material powder by dissolving oxygen contained in cubic boron nitride raw material powder in supercritical water. This is because he thought it might be. However, when the experiment of exposing the cubic boron nitride raw material powder to supercritical water was repeatedly performed, it was confirmed that the amount of oxygen in the cubic boron nitride raw material powder increased.
- the present inventors verified the obtained experimental results from various angles, and guessed two mechanisms based on the verification results.
- the first mechanism is that in supercritical water under an oxidizing environment, removal of oxygen from cubic boron nitride raw material powder is caused, while supercritical water is used as a source for cubic boron nitride raw material powder. Oxygen adsorption (re-oxidation) is caused.
- the second mechanism is that the cubic boron nitride raw material powder is reoxidized by handling the cubic boron nitride raw material powder after removing oxygen.
- the inventors of the present invention have conducted intensive studies on the possibility that reoxidation by the above mechanism can be prevented by performing some treatment on the surface of the cubic boron nitride raw material powder after removing oxygen.
- a cubic boron nitride sintered body includes a cubic boron nitride sintered body including 85% by volume or more and less than 100% by volume of cubic boron nitride particles, and a remaining binder.
- the binder contains WC, Co and Al compounds, and the interface region including the interface where the cubic boron nitride particles are adjacent to each other is analyzed using TEM-EDX, Alternatively, oxygen is partially present, and the width D of the region where oxygen is present is 0.1 nm or more and 10 nm or less.
- the cubic boron nitride sintered body is a “High-cBN sintered body” in which the cubic boron nitride particles are likely to fall off from the content of the cubic boron nitride particles.
- the cubic boron nitride sintered body is a cubic boron nitride sintered body in which the falling of the cubic boron nitride particles is suppressed and the life can be extended. The reason is presumed as follows.
- a conventional cubic boron nitride sintered body is analyzed by TEM-EDX for an interface region including an interface in which cubic boron nitride particles are adjacent to each other, a region where oxygen exists on the interface is analyzed.
- the width D greatly exceeded 10 nm.
- the width D is 0.1 nm or more and 10 nm or less. It is considered that such a structural difference is caused by the fact that the cubic boron nitride sintered body according to one embodiment of the present disclosure has a smaller amount of oxygen than the conventional cubic boron nitride sintered body. .
- the neck gross suppression due to oxygen is less likely to occur than in the conventional case, so that the bonding force between the cubic boron nitride particles is higher than in the conventional case.
- the falling of the cubic boron nitride particles is suppressed.
- the width D is 0.1 nm or more and 5 nm or less. In this case, the life of the cubic boron nitride sintered body can be further extended.
- the maximum value M of the oxygen content in the region where oxygen is present is 5.0 atomic% or less. In this case, the life of the cubic boron nitride sintered body can be further extended.
- a cubic boron nitride sintered body according to an embodiment of the present disclosure is a cutting tool including the above cubic boron nitride sintered body. According to the cutting tool, the life can be extended.
- a method for producing a cubic boron nitride sintered body is a method for producing a cubic boron nitride sintered body for producing the above cubic boron nitride sintered body, the method comprising: A step of preparing an organic cubic boron nitride powder by removing oxygen from the boron raw material powder and attaching an organic substance to the cubic boron nitride raw powder (preparation step); an organic cubic boron nitride powder; For preparing a mixed powder composed of 85% by volume or more and less than 100% by volume of organic cubic boron nitride powder and the balance of the binder material powder by mixing the binder material powder containing Al and Al And a step of sintering the mixed powder to obtain a cubic boron nitride sintered body (sintering step).
- the manufacturing process removes oxygen from the cubic boron nitride raw material powder and attaches an organic substance to the cubic boron nitride raw material powder from which oxygen has been removed. This makes it possible to remove oxygen from the cubic boron nitride raw material powder and suppress reoxidation. That is, according to the above-described manufacturing method, an organic cubic boron nitride powder having a smaller amount of oxygen as compared with the conventional one is used as the cubic boron nitride raw material powder used in the sintering step.
- the producing step includes a step of charging the cubic boron nitride raw material powder and the organic substance into supercritical water.
- oxygen on the surface of the cubic boron nitride raw material powder dissolves in the supercritical water and is discharged from the surface of the cubic boron nitride raw material powder. This cleans the surface of the cubic boron nitride raw material powder.
- an organic substance can efficiently adhere to the cleaned surface of the cubic boron nitride raw material powder (hereinafter, also referred to as “clean surface”). As a result, it becomes easy to prepare an organic cubic boron nitride powder in which organic substances are uniformly adhered to the surface (clean surface from which oxygen has been removed).
- the organic substance is an amine or a hydrocarbon compound having 5 or more carbon atoms.
- the organic substance is hexylamine, hexylnitrile, paraffin, or hexane.
- the manufacturing step includes a step of etching the surface of the cubic boron nitride raw material powder by plasma treatment and then attaching an organic substance to the surface.
- the surface of the cubic boron nitride raw material powder is etched to form a clean surface from which oxygen has been removed, and organic substances adhere to the clean surface. This facilitates the preparation of an organic cubic boron nitride powder in which organic substances are uniformly adhered to the surface (clean surface from which oxygen has been removed).
- the organic substance is an amine or fluorocarbon.
- the present embodiment is not limited to these.
- the notation in the form of “A to Z” means the upper and lower limits of the range (that is, A or more and Z or less), in which the unit is not described in A and the unit is described only in Z. , A and Z are the same.
- the cubic boron nitride sintered body according to the present embodiment includes 85% by volume or more and less than 100% by volume of cubic boron nitride particles, and the remaining binder. That is, the cubic boron nitride sintered body according to the present embodiment is a so-called High-cBN sintered body. Note that the cubic boron nitride sintered body may contain unavoidable impurities due to raw materials used, manufacturing conditions, and the like. At this time, it can be understood that the inevitable impurities are contained in the binder.
- the content (vol%) of the cubic boron nitride particles in the cubic boron nitride sintered body is substantially the same as the content (vol%) of the cubic boron nitride raw material powder used in the mixed powder described later. Become. This is because the amount of change in volume caused by the adhesion of organic substances is extremely small with respect to the volume of the cubic boron nitride powder itself. Therefore, by controlling the content ratio of the cubic boron nitride raw material powder used in the mixed powder, the content (content ratio) of the cubic boron nitride particles in the cubic boron nitride sintered body is adjusted to a desired range. can do.
- the content (volume%) of the cubic boron nitride particles in the cubic boron nitride sintered body was determined by quantitative analysis by inductively coupled high frequency plasma spectroscopy (ICP) and energy dispersive X-rays provided with a scanning electron microscope (SEM). It can also be confirmed by observing the structure and performing elemental analysis on the cubic boron nitride sintered body using an analyzer (EDX) or an EDX attached to a transmission electron microscope (TEM).
- EDX analyzer
- TEM transmission electron microscope
- the content of cubic boron nitride particles in the cubic boron nitride sintered body is determined by a method using an SEM described below.
- the content ratio (volume%) of cubic boron nitride particles can be determined as follows. First, an arbitrary position of the cubic boron nitride sintered body is cut to prepare a sample including a cross section of the cubic boron nitride sintered body. For producing the cross section, a focused ion beam device, a cross section polisher device, or the like can be used. Next, the cross section is observed with a SEM at a magnification of 2000 to obtain a reflected electron image. In the backscattered electron image, the region where the cubic boron nitride particles exist is a black region, and the region where the binder is present is a gray region or a white region.
- binarization processing is performed on the reflected electron image using image analysis software (for example, “WinROOF” of Mitani Corporation), and each area ratio is calculated from the image after the binarization processing. .
- image analysis software for example, “WinROOF” of Mitani Corporation
- the calculated area ratio as volume%, the content ratio (vol%) of the cubic boron nitride particles can be obtained.
- the volume% of the binder can be determined at the same time.
- the cubic boron nitride particles have high hardness, strength, and toughness, and serve as a skeleton in the cubic boron nitride sintered body.
- the D 50 (average particle size) of the cubic boron nitride particles is not particularly limited, and may be, for example, 0.1 to 10.0 ⁇ m. Usually, there is a tendency that people D 50 is less increases the hardness of cubic boron nitride sintered body. Also, the smaller the variation of the particle size, the more the properties of the cubic boron nitride sintered body tend to be uniform.
- the cubic boron nitride particles preferably have a D 50 of, for example, 0.5 to 4.0 ⁇ m.
- D 50 of the cubic boron nitride particles is determined as follows. First, a sample including a cross section of a cubic boron nitride sintered body is prepared according to the above-described method for determining the content of cubic boron nitride particles, and a reflected electron image is obtained. Next, the equivalent circle diameter of each black region in the reflected electron image is calculated using image analysis software. It is preferable to calculate the equivalent circle diameter of 100 or more cubic boron nitride particles by observing 5 or more visual fields.
- the cumulative distribution is obtained by arranging the circle equivalent diameters in ascending order from the minimum value to the maximum value.
- Particle diameter at a cumulative area of 50% in the cumulative distribution is D 50.
- the equivalent circle diameter means the diameter of a circle having the same area as the measured area of the cubic boron nitride particles.
- the binder plays a role in enabling sintering of cubic boron nitride particles, which are difficult-to-sinter materials, at an industrial-level pressure temperature. Further, since reactivity with iron is lower than that of cubic boron nitride, a function of suppressing chemical wear and thermal wear in cutting hardened hardened steel is added to the cubic boron nitride sintered body. Further, when the cubic boron nitride sintered body contains a binder, the wear resistance in high-efficiency working of hardened steel with high hardness is improved.
- the binder contains WC (tungsten carbide), Co (cobalt), and an Al compound.
- Al compound means a compound containing Al (aluminum) as a constituent element.
- Al compound include CoAl, Al 2 O 3 , AlN, and AlB 2 , and composite compounds thereof.
- the binder containing WC, Co and Al compounds is considered to be particularly effective for extending the life of the cubic boron nitride sintered body according to the present embodiment.
- WC is presumed to be effective in making the thermal expansion coefficient of the binder close to that of the cubic boron nitride particles.
- the above-mentioned catalytic function means that B (boron) and / or N (nitrogen) constituting the cubic boron nitride particles diffuse or precipitate through Co or Al.
- the composition of the binder contained in the cubic boron nitride sintered body can be specified by combining XRD (X-ray diffraction measurement) and ICP. Specifically, first, a test piece having a thickness of about 0.45 to 0.50 mm is cut out from the cubic boron nitride sintered body, XRD analysis is performed on the test piece, and the test piece is determined from the X-ray diffraction peak. Compounds, metals, etc. are determined.
- ICP analysis is performed on the acid-treated solution, and quantitative analysis of each metal element is performed.
- the composition of the binder is determined by analyzing the result of the XRD and the result of the ICP analysis.
- the binder in the present embodiment may include other binders in addition to the WC, Co and Al compounds. Suitable elements constituting the other binder include Ni, Fe, Cr, Mn, Ti, V, Zr, Nb, Mo, Hf, Ta, and Re.
- the cubic boron nitride sintered body according to the present embodiment has the following (1) and (2) when the interface region including the interface where the cubic boron nitride particles are adjacent to each other is analyzed using TEM-EDX. Is satisfied. (1) oxygen is present on the interface; (2) The width D of the region where oxygen exists is 0.1 to 10 nm.
- TEM-EDX The above analysis by TEM-EDX is performed as follows. First, a sample is collected from a cubic boron nitride sintered body, and the sample is sliced into a thickness of 30 to 100 nm using an argon ion slicer to prepare a section. Next, a first image is obtained by observing the section with a TEM (transmission electron microscope) at a magnification of 50,000. As the transmission electron microscope used at this time, for example, “JEM-2100F / Cs” (trade name) manufactured by JEOL Ltd. can be mentioned. In the first image, one interface where the cubic boron nitride particles are adjacent to each other is arbitrarily selected.
- the interface exists so as to extend from one end of the image, pass near the center of the image, and extend to another end facing the one end.
- an element mapping analysis by EDX is performed on the second image to analyze the distribution of oxygen in the second image, that is, in the interface region including the interface.
- An example of the energy dispersive X-ray analyzer used at this time is “EDAX” (trade name) manufactured by AMETEK.
- the extension direction of the interface (the extension direction in which the region with high oxygen concentration extends) is confirmed, and the element line analysis is performed in a direction substantially perpendicular to the extension direction.
- the beam diameter is set to 0.3 nm or less, and the scan interval is set to 0.1 to 0.7 nm.
- the width D of the region where oxygen is present is calculated.
- the width D is 0.1 to 10 nm, the cubic boron nitride sintered body satisfies the above (2).
- the cubic boron nitride sintered body is It can be regarded as the cubic boron nitride sintered body according to the embodiment.
- the condition (1) can be grasped as "oxygen is present on all or a part of the interface".
- FIG. 1 is an example of the second image.
- a black region is a region (BN region) having B and N as main constituent elements, and a white region or a gray region corresponds to a region (SF region) recognized as an interface in the first image. I do.
- the SF region in the second image corresponds to “an interface where cubic boron nitride particles are adjacent to each other”, and the entire second image is “an interface region including an interface”. Is equivalent to
- the process returns to the first image and another interface is selected again. This is because when the width of the SF region exceeds 10 nm, it is difficult to say that the SF region corresponds to “an interface in which cubic boron nitride particles are adjacent to each other”.
- FIG. 2 is an example of a graph based on the result of the line analysis.
- the solid line shows the result of the distance (nm) at which the line analysis was performed on the horizontal axis and the value of the oxygen content (atomic%) in the spot calculated from the line analysis result on the vertical axis.
- the portion where the peak is observed is the “region where oxygen exists”, and the width D of the peak is “the width D of the region where oxygen exists”.
- the life can be extended.
- the reason is as follows.
- the width D exceeds 10 nm, whereas in the cubic boron nitride sintered body according to the present embodiment, the width D is 10 nm or less. That is, in the cubic boron nitride sintered body according to the present embodiment, the region where oxygen is present is smaller and the amount of oxygen is smaller than in the conventional cubic boron nitride sintered body.
- the cubic boron nitride sintered body according to the present embodiment is less susceptible to neck gloss suppression due to oxygen during the manufacturing process, and therefore has a better neck gloss than the conventional cubic boron nitride sintered body. Will have. Therefore, the cubic boron nitride sintered body according to the present embodiment has a remarkably improved bonding force between the cubic boron nitride particles as compared with the conventional cubic boron nitride sintered body. The service life can be extended. According to various studies, it has been confirmed that it is preferable to satisfy the above (1) and (2) in three or more visual fields among the six visual fields observed in the above method.
- the cubic boron nitride sintered body when oxygen is completely removed from the cubic boron nitride particles constituting the cubic boron nitride sintered body, the cubic boron nitride sintered body does not have a region where oxygen exists, and therefore, The width D is 0 nm. However, at this stage, it is difficult to completely remove oxygen from the surface of the cubic boron nitride particles. Therefore, in the cubic boron nitride sintered body according to the present embodiment, the width D is less than 0.1 nm. There is no fact.
- the width D is preferably 0.1 to 5 nm. In this case, the life of the cubic boron nitride sintered body can be further extended.
- the maximum value M of the oxygen content in the region where oxygen is present is preferably 5.0 atomic% or less. In this case, the life of the cubic boron nitride sintered body can be further extended.
- the maximum value M of the oxygen content is the maximum value of the oxygen content ratio (atomic%) in each spot calculated from the line analysis result. For example, in FIG. 2, the maximum value M is about 2.4 atomic%.
- the maximum value M is more than 5.0 atomic%, the oxygen content in the cubic boron nitride particles may not be sufficiently reduced. In this case, the bonding force between the cubic boron nitride particles is not sufficiently high, and as a result, the degree of life extension may be insufficient.
- the maximum value M is 0 atomic%. However, it is difficult to completely remove oxygen.
- the life is particularly prolonged. It becomes possible.
- the cutting tool according to the present embodiment includes the cubic boron nitride sintered body.
- the cutting tool includes the cubic boron nitride sintered body as a base material. Further, the cutting tool according to the present embodiment may have a coating on a part or the whole of the surface of the cubic boron nitride sintered body serving as the base material.
- the shape and application of the cutting tool according to the present embodiment are not particularly limited.
- a pin milling tip for a shaft may be used.
- the cutting tool according to the present embodiment is not limited to the one in which the entire tool is made of a cubic boron nitride sintered body, and only a part of the tool (particularly, a cutting edge portion (cutting edge portion) or the like) is cubic nitrided. Also includes those made of a boron sintered body.
- a cutting tool according to the present embodiment includes a substrate (support) made of a cemented carbide or the like in which only the cutting edge portion is formed of a cubic boron nitride sintered body.
- the cutting edge portion is regarded as a cutting tool in terms of words.
- the cubic boron nitride sintered body is referred to as a cutting tool.
- the life of the cutting tool can be extended because the cutting tool includes the cubic boron nitride sintered body.
- a method for manufacturing a cubic boron nitride sintered body according to the present embodiment will be described.
- the method for manufacturing a cubic boron nitride sintered body according to the present embodiment is a method for manufacturing the cubic boron nitride sintered body according to the first embodiment.
- the method for producing a cubic boron nitride sintered body includes, at least, removing oxygen from the cubic boron nitride raw material powder and attaching an organic substance to the cubic boron nitride raw material powder, A step of preparing an organic cubic boron nitride powder (preparation step); mixing the organic cubic boron nitride powder with a binder raw material powder containing WC, Co and Al; A step of preparing a mixed powder composed of the organic cubic boron nitride powder and the remaining binder raw material powder (preparation step); and a step of sintering the mixed powder to obtain a cubic boron nitride sintered body (sintering step) ).
- preparation step mixing the organic cubic boron nitride powder with a binder raw material powder containing WC, Co and Al
- This step is a step of preparing an organic cubic boron nitride powder by removing oxygen from the cubic boron nitride raw material powder and attaching an organic substance to the cubic boron nitride raw material powder.
- the cubic boron nitride raw material powder is a raw material powder of the cubic boron nitride particles contained in the cubic boron nitride sintered body.
- the present inventors have confirmed that an oxide is present on the surface of the cubic boron nitride raw material powder. This is presumably because the cubic boron nitride raw material powder synthesized by ultra-high pressure is subjected to a cleaning treatment or exposed to the atmosphere. Therefore, “removing oxygen from the cubic boron nitride raw material powder” includes both meaning of removing an oxide from the cubic boron nitride raw material powder and removing oxygen atoms.
- a method of charging the cubic boron nitride raw material powder and the organic substance to supercritical water for example, a method of charging the cubic boron nitride raw material powder and the organic substance to supercritical water in this order, an organic substance and cubic nitride There is a method in which the boron raw material powder is charged in this order, and a method in which the cubic boron nitride raw material powder and the organic substance are simultaneously charged.
- the oxygen located on the surface of the cubic boron nitride raw material powder is dissolved in the supercritical water due to the contact between the cubic boron nitride raw material powder and the supercritical water, so that the oxygen on the surface is removed.
- a clean surface is formed. This is because supercritical water has high solubility. Further, the organic matter put into the supercritical water efficiently adheres to the clean surface of the organic cubic boron nitride powder. This is because the clean surface is activated in the supercritical water, and the adhesion to organic substances is enhanced.
- a method in which a cubic boron nitride raw material powder and an organic substance are charged in this order into supercritical water is preferable. This is because an organic substance is unlikely to adhere to the cubic boron nitride raw material powder before oxygen is removed, and the organic substance can be efficiently adhered to a clean surface.
- a method for performing the plasma processing will be described.
- a step of attaching an organic substance to the surface is performed.
- a cubic boron nitride raw material powder is exposed to a first gas atmosphere containing carbon and then exposed to a second gas atmosphere containing ammonia in a plasma generator.
- a first gas CF 4 , CH 4 , C 2 H 2 or the like can be used.
- a second gas a mixed gas of NH 3 , N 2 and H 2 or the like can be used.
- the organic cubic boron nitride powder can be efficiently produced by either the method using supercritical water or the method of performing plasma treatment. In this step, it is preferable to adopt a method using supercritical water. This is because the organic substances adhering to the cubic boron nitride raw material powder can be easily made uniform, and thus the organic cubic boron nitride powder can be easily made uniform.
- the average particle size of the cubic boron nitride raw material powder is not particularly limited.
- the thickness is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5.0 ⁇ m.
- the organic substance used is preferably an amine or a hydrocarbon compound having 5 or more carbon atoms.
- hexylamine, hexylnitrile, paraffin, and hexane are more preferred, and hexylamine is still more preferred.
- the present inventors have confirmed that when these organic substances are used, falling off of cubic boron nitride particles in the cubic boron nitride sintered body is drastically reduced.
- the organic substance to be attached includes amine, fluorocarbon, and the like.
- the preferred amount of the organic substance attached to the cubic boron nitride raw material powder varies depending on the particle size of the cubic boron nitride raw material powder.
- hexylamine it is preferable that hexylamine of 50 to 2000 ppm adheres to the cubic boron nitride raw material powder having an average particle diameter of 1 to 10 ⁇ m, and the average particle diameter is 0.1 to 1 ⁇ m. It is preferable that 100 to 5000 ppm of hexylamine adhere to the cubic boron nitride raw material powder. In such a case, a desired cubic boron nitride sintered body tends to be efficiently manufactured.
- the amount of organic substances attached to the organic cubic boron nitride powder can be measured, for example, by gas chromatography mass spectrometry.
- the organic cubic boron nitride powder used in the second step of the sintering step described later contains carbon to such an extent that it reacts with the remaining oxygen.
- the amount of organic substances attached to the cubic boron nitride raw material powder tends to decrease in subsequent steps (for example, a purification step, a preparation step, and the like described later). For this reason, even if the amount of the organic substance adhering to the cubic boron nitride raw material powder is other than the above, for example, an excessive amount, the organic cubic crystal to be supplied to the second step can be appropriately prepared in each of the subsequent steps. It is considered that a suitable amount of carbon can be left in the boron nitride powder.
- the organic cubic boron nitride powder is obtained as a slurry.
- the organic cubic boron nitride powder and unreacted organic substances can be separated.
- the organic cubic boron nitride raw material powder taken out of the supercritical water or the organic cubic boron nitride raw material powder taken out of the supercritical water and subjected to the above-described centrifugation and the like is further subjected to a heat treatment (for example, under vacuum).
- a heat treatment for example, under vacuum.
- impurities such as moisture adsorbed on the surface of the organic cubic boron nitride powder can be removed.
- the present inventors initially anticipated that when heat treatment was performed on the organic cubic boron nitride powder, all of the organic substances attached to the cubic boron nitride raw material powder would volatilize and / or disappear. Surprisingly, as a result of observing the organic cubic boron nitride powder by Auger electron spectroscopy, the organic matter is decomposed by the heat treatment, but the carbon remains uniformly on the surface of the organic cubic boron nitride powder. It was confirmed that. This carbon is considered to be organic.
- ⁇ Preparation process In this step, the organic cubic boron nitride powder and the binder raw material powder containing WC, Co and Al are mixed, and the organic cubic boron nitride powder of 85% by volume or more and less than 100% by volume is mixed with the remaining binder.
- This is a step of preparing a mixed powder composed of the raw material powder.
- the organic cubic boron nitride powder is the organic cubic boron nitride powder obtained by the above-described manufacturing process
- the binder raw material powder is the raw material of the binder contained in the cubic boron nitride sintered body.
- the binder raw material powder can be prepared as follows. First, WC powder, Co powder and Al powder are prepared. Next, each powder is mixed so as to have a predetermined ratio, and this is heat-treated (for example, at 1200 ° C.) under vacuum to produce an intermetallic compound. By pulverizing the intermetallic compound with a wet ball mill, wet bead mill, or the like, a binder raw material powder containing WC, Co, and Al is prepared.
- the method of mixing the powders is not particularly limited, but from the viewpoint of efficient and homogeneous mixing, ball mill mixing, bead mill mixing, planetary mill mixing, jet mill mixing, and the like are preferable. Each mixing method may be wet or dry.
- the organic cubic boron nitride powder and the prepared binder raw material powder are preferably mixed by wet ball mill mixing using ethanol, acetone or the like as a solvent. After the mixing, the solvent is removed by natural drying. Thereafter, it is preferable to remove impurities such as moisture adsorbed on the surface by heat treatment (for example, at 850 ° C. or more under vacuum). Thereby, as described above, on the surface of the organic cubic boron nitride powder, the organic substance is decomposed, and the carbon derived from the organic substance can remain uniformly, and thus, the organic cubic boron nitride surface-modified. A powder can be obtained. Thus, a mixed powder is prepared.
- the binder raw material powder may contain other elements in addition to WC, Co and Al.
- Preferred as other elements are Ni, Fe, Cr, Mn, Ti, V, Zr, Nb, Mo, Hf, Ta, Re and the like.
- This step is a step of sintering the mixed powder to obtain a cubic boron nitride sintered body.
- the mixed powder is exposed to high temperature and high pressure and sintered to produce a cubic boron nitride sintered body.
- the mixed powder is filled in a container and vacuum-sealed.
- the temperature of the vacuum seal is preferably 850 ° C. or higher. This is a temperature exceeding the melting point of the sealing material, and the organic substances adhering to the organic cubic boron nitride powder are decomposed, and the carbon derived from the organic substances remains uniformly on the surface of the organic cubic boron nitride powder. Temperature is sufficient.
- the vacuum-sealed mixed powder is sintered using an ultra-high temperature and high pressure apparatus.
- the sintering conditions are not particularly limited, but are preferably 5.5-8 GPa and 1500 ° C. or more and less than 2000 ° C. Particularly, from the viewpoint of the balance between cost and sintering performance, 6 to 7 GPa and 1600 to 1900 ° C. are preferable.
- the surface-modified organic cubic crystal in which carbon remains uniformly on the surface of the organic cubic boron nitride powder will be subjected to the first step. If the heat treatment has not been performed before this step, the surface-modified organic cubic boron nitride powder is prepared in the first step. Therefore, carbon is uniformly present on the surface of the organic cubic boron nitride powder used in the second step.
- oxygen existing in the cubic boron nitride raw material powder is removed and reoxidation is suppressed, so that the amount of oxygen is reduced as compared with the conventional cubic boron nitride raw material powder.
- An organic cubic boron nitride powder is produced.
- oxygen remaining on the surface of the organic cubic boron nitride powder reacts with carbon remaining on the surface of the organic cubic boron nitride powder, and the reactant is converted into organic cubic boron nitride.
- Oxygen remaining on the surface of the cubic boron nitride raw material powder is further removed because it is discharged outside the powder.
- oxygen is removed by the same action as in the sintering step. This is because some heat is applied to the mixed powder also in the preparation process.
- the amount of oxygen in the organic cubic boron nitride powder used for sintering is significantly reduced as compared with conventional cubic boron nitride particles. Therefore, the generation of neck gloss between the cubic boron nitride particles is improved, the bonding force between the cubic boron nitride particles is increased, and a cubic boron nitride sintered body capable of extending the life is obtained.
- (Appendix 1) A cubic boron nitride sintered body comprising 85% by volume or more and less than 100% by volume of cBN particles and the balance of a binder.
- the binder comprises WC, Co and Al compounds;
- Oxygen is present on the interface
- a cubic boron nitride sintered body, wherein the width D of the region where oxygen is present is 0.1 nm or more and 10 nm or less.
- (Appendix 2) The cubic boron nitride sintered body according to claim 1, wherein the width D is 0.1 nm or more and 5 nm or less.
- the organic cBN powder is mixed with a binder raw material powder containing WC, Co and Al to obtain a mixed powder composed of the organic cBN powder in an amount of 85% by volume or more and less than 100% by volume and the remaining binder raw material powder.
- the slurry was centrifuged (9000 rpm, 8 minutes) to separate excess hexylamine not adhering to the cubic boron nitride raw material powder.
- the concentrated slurry after the separation was dried ( ⁇ 90 ° C., 10 hours), and about 15 g of the powder after the supercritical water treatment was recovered.
- an organic cubic boron nitride powder was produced.
- the prepared organic cubic boron nitride powder was subjected to gas chromatography mass spectrometry, and it was confirmed that 782 ppm of hexylamine was present (attached) to the cubic boron nitride powder.
- a cubic boron nitride sintered body was produced by sintering the obtained mixed powder. Specifically, the mixed powder was filled in a Ta container while being in contact with a WC-6% Co cemented carbide disc and a Co foil, and vacuum sealed. This was sintered at 6.5 GPa and 1650 ° C. for 15 minutes using a belt-type ultra-high pressure and high temperature generator. Thus, a cubic boron nitride sintered body was produced.
- a cubic boron nitride sintered body was produced in the same manner as in Experimental Example 1 except that the above operation was performed.
- the organic cubic boron nitride powder was subjected to gas chromatography mass spectrometry, it was confirmed that 607 ppm of hexylamine was present relative to the cubic boron nitride.
- ⁇ Experimental example 3> The concentration of hexylamine to be administered was 5.0% by weight, and the organic cubic boron nitride powder and the binder raw material powder were mixed in a volume ratio of organic cubic boron nitride powder: binder raw material powder 92: 8. Then, the mixture was uniformly mixed by a wet ball mill method using ethanol. Thereafter, a cubic boron nitride sintered body was produced in the same manner as in Experimental Example 1, except that heat treatment was performed on the powder mixed at 250 ° C. under vacuum. When the organic cubic boron nitride powder was subjected to gas chromatography mass spectrometry, it was confirmed that 350 ppm of hexylamine was present relative to the cubic boron nitride.
- a cubic boron nitride sintered body was produced in the same manner as in Experimental Example 1 except that the above operation was performed.
- the organic cubic boron nitride powder was subjected to gas chromatography mass spectrometry, it was confirmed that 1016 ppm of hexylamine was present with respect to the cubic boron nitride.
- an organic cubic boron nitride powder was produced by plasma treatment. Specifically, after etching the surface of the cubic boron nitride raw material powder in a CF 4 atmosphere using a plasma reforming apparatus (low-pressure plasma apparatus FEMTO, manufactured by Dienner), the inside of the apparatus is switched to an NH 3 atmosphere, The cubic boron nitride raw material powder after the etching was treated. Except for the above, a cubic boron nitride sintered body was manufactured in the same manner as in Experimental Example 1.
- a plasma reforming apparatus low-pressure plasma apparatus FEMTO, manufactured by Dienner
- Example 7 A cubic boron nitride sintered body was manufactured in the same manner as in Experimental Example 2 except that the above-described plasma treatment was performed instead of the method using supercritical water.
- Example 8 A cubic boron nitride sintered body was manufactured in the same manner as in Experimental Example 3 except that the above-described plasma treatment was performed instead of the method using supercritical water.
- Example 9 A cubic boron nitride sintered body was manufactured in the same manner as in Experimental Example 4 except that the above-described plasma treatment was performed instead of the method using supercritical water.
- Example 10 A cubic boron nitride sintered body was manufactured in the same manner as in Experimental Example 5 except that the above-described plasma treatment was used instead of the method using supercritical water.
- Example 21 A cubic boron nitride sintered body was manufactured in the same manner as in Experimental Example 3, except that a mixed powder was prepared using a cubic boron nitride raw material powder without performing the treatment using supercritical water.
- Example 23 A cubic boron nitride powder was prepared in the same manner as in Experimental Example 1, except that only the cubic boron nitride raw material powder was used without performing the treatment using supercritical water and without blending the binder raw material powder. A body was produced.
- Experimental Examples 1 to 10 correspond to Examples.
- Experimental examples 21 to 23 correspond to comparative examples.
- the energy dispersive X-ray analyzer used was "EDAX" (trade name) manufactured by AMETEK.
- the beam diameter in EDX was 0.2 nm, and the scan interval was 0.6 nm.
- the software used for element mapping analysis and element line analysis by EDX was Analysis Station manufactured by JEOL Ltd. Table 1 shows the results. For reference, a graph showing the results of the line analysis in Experimental Example 3 is shown in FIG.
- Each value shown in Table 1 is an average value of the visual fields satisfying the above (1) and (2) when there are visual fields satisfying the above (1) and (2) among the six visual fields.
- the above (1) and (2) were satisfied in all of the six interface regions arbitrarily extracted.
- Experimental Example 3 (1) and (2) were satisfied in one visual field among the six interface regions arbitrarily extracted.
- Experimental Example 4 (1) and (2) were satisfied in three visual fields among the six interface regions arbitrarily extracted.
- a cutting tool (substrate shape: DNGA150408, blade edge treatment T01225) was produced using each of the produced cubic boron nitride sintered bodies. Using this, a cutting test was performed under the following cutting conditions. Cutting speed: 200 m / min. Feed speed: 0.1 mm / rev. Cut: 0.1mm Coolant: DRY Cutting method: Intermittent cutting lathe: LB400 (manufactured by Okuma Corporation) Work material: sintered part (quenched sintered alloy D-40 manufactured by Sumitomo Electric Industries, hardness of hardened cut part: 40 HRC).
- the cutting edge was observed at a cutting distance of 0.5 km, and the amount of the falling edge was measured.
- the falling-off amount of the cutting edge was defined as a retreat width due to wear from the position of the cutting edge ridge line before cutting.
- the size of the deficiency was defined as the shedding amount.
- the cutting distance at the time when the falling amount of the cutting edge became 0.1 mm or more was measured. The cutting distance was used as an index of the life of the cutting tool. Table 1 shows the results.
- Table 1 also shows the volume percentage of cubic boron nitride particles in the cubic boron nitride sintered body.
- composition of the binder it was confirmed in Experimental Examples 1 to 10 and Experimental Examples 21 to 22 that at least WC, Co, and Al compounds were present. Since no clear peak was detected in XRD for the Al compound, it was inferred that the Al compound was a composite compound composed of a plurality of Al compounds.
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Abstract
Description
本開示の一態様に係る立方晶窒化硼素焼結体の製造方法は、上記立方晶窒化硼素焼結体を製造する立方晶窒化硼素焼結体の製造方法であって、立方晶窒化硼素原料粉末の酸素を除去するとともに、立方晶窒化硼素原料粉末に有機物を付着させて、有機立方晶窒化硼素粉末を作製する工程と、有機立方晶窒化硼素粉末と、WC、CoおよびAlを含む結合材原料粉末とを混合して、85体積%以上100体積%未満の有機立方晶窒化硼素粉末と、残部の結合材原料粉末とからなる混合粉末を調製する工程と、混合粉末を焼結して立方晶窒化硼素焼結体を得る工程と、を含む。
近年、機械部品の急速な高機能化に伴い、機械部品となる被削材の難削化が加速している。これに伴い、切削工具の短寿命化によるコスト増という問題が顕在化している。このため、High-cBN焼結体のさらなる改良が望まれる。この点に鑑み、本開示では、長寿命化を可能とする立方晶窒化硼素焼結体、それを含む切削工具、および立方晶窒化硼素焼結体の製造方法を提供することを目的とする。
上記により得られる立方晶窒化硼素焼結体によれば、長寿命化が可能となり、それを含む切削工具もまた、長寿命化が可能となる。
本発明者らは、立方晶窒化硼素焼結体のさらなる長寿命化を実現するためには、High-cBN焼結体における立方晶窒化硼素粒子の脱落をさらに抑制する必要があると考えた。しかしながら、これを実現し、かつブレイクスルーを図るためには、従来の手法とは異なるアプローチが必要と考えた。
以下、本開示の一実施形態(以下「本実施形態」と記す)について説明する。ただし、本実施形態はこれらに限定されるものではない。なお、本明細書において「A~Z」という形式の表記は、範囲の上限下限(すなわちA以上Z以下)を意味し、Aにおいて単位の記載がなく、Zにおいてのみ単位が記載されている場合、Aの単位とZの単位とは同じである。
本実施形態に係る立方晶窒化硼素焼結体は、85体積%以上100体積%未満の立方晶窒化硼素粒子と、残部の結合材と、を備える。すなわち本実施形態に係る立方晶窒化硼素焼結体は、いわゆるHigh-cBN焼結体である。なお立方晶窒化硼素焼結体は、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。このとき、当該不可避不純物は結合材に含まれていると把握することができる。
立方晶窒化硼素粒子は、硬度、強度、靱性が高く、立方晶窒化硼素焼結体中の骨格としての役割を果たす。立方晶窒化硼素粒子のD50(平均粒径)は特に限定されず、例えば、0.1~10.0μmとすることができる。通常、D50が小さい方が立方晶窒化硼素焼結体の硬度が高くなる傾向がある。また、粒径のばらつきが小さい方が、立方晶窒化硼素焼結体の性質が均質となる傾向がある。立方晶窒化硼素粒子のD50は、例えば、0.5~4.0μmとすることが好ましい。
結合材は、難焼結性材料である立方晶窒化硼素粒子を工業レベルの圧力温度で焼結可能とする役割を果たす。また、鉄との反応性が立方晶窒化硼素より低いため、高硬度焼入鋼の切削においての化学的摩耗及び熱的摩耗を抑制する働きを立方晶窒化硼素焼結体に付加する。また、立方晶窒化硼素焼結体が結合材を含有すると、高硬度焼入鋼の高能率加工における耐摩耗性が向上する。
本実施形態における立方晶窒化硼素焼結体は、TEM-EDXを用いて、立方晶窒化硼素粒子同士が隣接してなる界面を含む界面領域を分析した場合に、以下(1)および(2)を満たすことを特徴とする。
(1)界面上に酸素が存在しており;
(2)酸素が存在する領域の幅Dは、0.1~10nmである。
上述の本実施形態に係る立方晶窒化硼素焼結体によれば、長寿命化が可能となる。その理由は、次のとおりである。従来の立方晶窒化硼素焼結体においては、幅Dが10nm超となるのに対し、本実施形態に係る立方晶窒化硼素焼結体においては、幅Dが10nm以下である。すなわち、本実施形態に係る立方晶窒化硼素焼結体においては、従来の立方晶窒化硼素焼結体と比して、酸素の存在領域が狭く、かつ酸素量が少ない。
本実施形態に係る切削工具は、上記立方晶窒化硼素焼結体を含む。本実施形態の一側面において、上記切削工具は、基材として上記立方晶窒化硼素焼結体を含む。また本実施形態に係る切削工具は、基材となる立方晶窒化硼素焼結体の表面の一部または全部に被膜を有していてもよい。
本実施形態に係る立方晶窒化硼素焼結体の製造方法について説明する。本実施形態に係る立方晶窒化硼素焼結体の製造方法は、第1の実施形態に係る立方晶窒化硼素焼結体を製造する方法である。
本工程は、立方晶窒化硼素原料粉末の酸素を除去するとともに、立方晶窒化硼素原料粉末に有機物を付着させて、有機立方晶窒化硼素粉末を作製する工程である。
超臨界水を用いる方法について説明する。当該方法においては、立方晶窒化硼素原料粉末と有機物とを超臨界水に投入する工程が実施される。これにより、有機立方晶窒化硼素粉末を作製することができる。なお本明細書において、超臨界水とは、超臨界状態または亜臨界状態の水を意味する。
プラズマ処理を実施する方法について説明する。当該方法においては、プラズマ処理により、立方晶窒化硼素原料粉末の表面をエッチングした後、該表面に有機物を付着させる工程が実施される。具体的には、プラズマ発生装置内において、立方晶窒化硼素原料粉末を、炭素を含む第1ガス雰囲気に曝した後、アンモニアを含む第2ガス雰囲気下に曝す方法が挙げられる。第1ガスとしては、CF4、CH4、C2H2等を用いることができる。第2ガスとしては、NH3、N2およびH2の混合ガス等を用いることができる。
上記作製工程により得られた有機立方晶窒化硼素粉末を、下記調製工程に用いるにあたって、有機立方晶窒化硼素粉末から不純物を除去することが好ましい。不純物としては、たとえば未反応の有機物が挙げられる。未反応の有機物を除去することにより、調製工程および/または焼結工程における意図しない反応を抑制することができる。
本工程は、有機立方晶窒化硼素粉末と、WC、CoおよびAlを含む結合材原料粉末とを混合して、85体積%以上100体積%未満の有機立方晶窒化硼素粉末と、残部の結合材原料粉末とからなる混合粉末を調製する工程である。有機立方晶窒化硼素粉末は、上述の作製工程により得られた有機立方晶窒化硼素粉末であり、結合材原料粉末は、立方晶窒化硼素焼結体に含まれる結合材の原料である。
本工程は、混合粉末を焼結して立方晶窒化硼素焼結体を得る工程である。本工程において、混合粉末が高温高圧条件下に曝されて焼結されることにより、立方晶窒化硼素焼結体が製造される。
上述の本実施形態に係る立方晶窒化硼素焼結体の製造方法によれば、長寿命化が可能な立方晶窒化硼素焼結体を製造することができる。その理由は次のとおりである。
(付記1)
85体積%以上100体積%未満のcBN粒子と、残部の結合材と、を備える立方晶窒化硼素焼結体であって、
前記結合材は、WC、CoおよびAl化合物を含み、
TEM-EDXを用いて、cBN粒子同士が隣接してなる界面を含む界面領域を分析した場合に、
前記界面上に酸素が存在し、
前記酸素が存在する領域の幅Dは、0.1nm以上10nm以下である、立方晶窒化硼素焼結体。
(付記2)
前記幅Dは、0.1nm以上5nm以下である、付記1に記載の立方晶窒化硼素焼結体。
(付記3)
前記酸素が存在する領域における前記酸素の含有量の最大値Mは5.0原子%以下である、付記1または付記2に記載の立方晶窒化硼素焼結体。
(付記4)
付記1から付記3のいずれかに記載の立方晶窒化硼素焼結体を含む切削工具。
(付記5)
cBN原料粉末の酸素を除去するとともに、前記cBN原料粉末に有機物を付着させて、有機cBN粉末を作製する工程と、
前記有機cBN粉末と、WC、CoおよびAlを含む結合材原料粉末とを混合して、85体積%以上100体積%未満の前記有機cBN粉末と、残部の結合材原料粉末とからなる混合粉末を調製する工程と、
前記混合粉末を焼結してcBN焼結体を得る工程と、を含む、立方晶窒化硼素焼結体の製造方法。
(付記6)
前記作製する工程は、
前記cBN原料粉末と前記有機物とを、超臨界水に投入する工程を含む、付記5に記載の立方晶窒化硼素焼結体の製造方法。
(付記7)
前記作製する工程は、
プラズマ処理により、前記cBN原料粉末の表面をエッチングした後、前記表面に前記有機物を付着させる工程を含む、付記5に記載の立方晶窒化硼素焼結体の製造方法。
まず、有機立方晶窒化硼素粉末を作製した。具体的には、まず、超臨界水合成装置(株式会社アイテック社製、「MOMI超mini」)を用いて、以下の条件下で超臨界水を作製した。
圧力:38MPa
温度:390℃
流速:2ml/分。
投与するヘキシルアミンの濃度を7.5重量%とし、有機立方晶窒化硼素粉末と結合材原料粉末とを、体積%で有機立方晶窒化硼素粉末:結合材原料粉末=94:6の比率で配合すること以外は、実験例1と同様の方法により、立方晶窒化硼素焼結体を作製した。有機立方晶窒化硼素粉末をガスクロマトグラフ質量分析法に供したところ、立方晶窒化硼素に対して607ppmのヘキシルアミンが存在することが確認された。
投与するヘキシルアミンの濃度を5.0重量%とし、有機立方晶窒化硼素粉末と結合材原料粉末とを、体積%で有機立方晶窒化硼素粉末:結合材原料粉末=92:8の比率で配合し、エタノールを用いた湿式ボールミル法により均一に混合した。その後、真空下にて250℃で混合した粉末に熱処理を実施したこと以外は、実験例1と同様の方法により、立方晶窒化硼素焼結体を作製した。有機立方晶窒化硼素粉末をガスクロマトグラフ質量分析法に供したところ、立方晶窒化硼素に対して350ppmのヘキシルアミンが存在することが確認された。
投与するヘキシルアミンの濃度を3.5重量%とし、有機立方晶窒化硼素粉末と結合材原料粉末とを、体積%で有機立方晶窒化硼素粉末:結合材原料粉末=92:8の比率で配合し、エタノールを用いた湿式ボールミル法により均一に混合した。その後、真空下にて400℃で混合した粉末に熱処理を実施したこと以外は、実験例1と同様の方法により、立方晶窒化硼素焼結体を作製した。有機立方晶窒化硼素粉末をガスクロマトグラフ質量分析法に供したところ、立方晶窒化硼素に対して212ppmのヘキシルアミンが存在することが確認された。
投与するヘキシルアミンの濃度を12.5重量%とし、有機立方晶窒化硼素粉末と結合材原料粉末とを、体積%で有機立方晶窒化硼素粉末:結合材原料粉末=92:8の比率で配合すること以外は、実験例1と同様の方法により、立方晶窒化硼素焼結体を作製した。有機立方晶窒化硼素粉末をガスクロマトグラフ質量分析法に供したところ、立方晶窒化硼素に対して1016ppmのヘキシルアミンが存在することが確認された。
超臨界水を用いる方法に代えて、プラズマ処理により有機立方晶窒化硼素粉末を作製した。具体的には、プラズマ改質装置(低圧プラズマ装置FEMTO、Dienner社製)を用いて、CF4雰囲気下で立方晶窒化硼素原料粉末の表面をエッチングした後、装置内をNH3雰囲気に切り替え、エッチング後の立方晶窒化硼素原料粉末を処理した。上記以外は、実験例1と同様の方法により、立方晶窒化硼素焼結体を製造した。
超臨界水を用いる方法に代えて、上述のプラズマ処理を実施した以外は、実験例2と同様の方法により、立方晶窒化硼素焼結体を製造した。
超臨界水を用いる方法に代えて、上述のプラズマ処理を実施した以外は、実験例3と同様の方法により、立方晶窒化硼素焼結体を製造した。
超臨界水を用いる方法に代えて、上述のプラズマ処理を実施した以外は、実験例4と同様の方法により、立方晶窒化硼素焼結体を製造した。
超臨界水を用いる方法に代えて、上述のプラズマ処理を用いた以外は、実験例5と同様の方法により、立方晶窒化硼素焼結体を製造した。
超臨界水を用いた処理を実施せずに、立方晶窒化硼素原料粉末を用いて混合粉末を調製した以外は、実験例3と同様の方法により、立方晶窒化硼素焼結体を製造した。
有機立方晶窒化硼素粉末と結合材原料粉末とを、体積%で有機立方晶窒化硼素粉末:結合材原料粉末=65:35の比率で配合した以外は、実験例4と同様の方法により、立方晶窒化硼素焼結体を作製した。
超臨界水を用いた処理を実施せずに、かつ結合材原料粉末を配合せずに立方晶窒化硼素原料粉末のみを用いた以外は、実験例1と同様の方法により、立方晶窒化硼素焼結体を作製した。
《幅Dおよび最大値M》
作製された各立方晶窒化硼素焼結体に関し、任意の位置で切断した後、露出した面を研磨して平滑面を作製した。その後、アルゴンイオンスライサーを用いて、50nmの厚みに薄片化して切片を作製した。次いで、上述の方法に従って、第2画像(100nm×100nm)に対して、EDXによる元素マッピング分析および元素ライン分析を実施した。このとき、透過型電子顕微鏡は、日本電子株式会社製の「JEM-2100F/Cs」(商品名)を用いた。また、エネルギー分散型X線分析装置は、AMETEK社製の「EDAX」(商品名)を用いた。EDXにおけるビーム径は0.2nmとし、スキャン間隔は0.6nmとした。EDXによる元素マッピング分析および元素ライン分析に用いたソフトは日本電子株式会社社製のAnalysis Stationであった。これらの結果を表1に示す。また、参考として、実験例3におけるライン分析の結果を示すグラフを、図2に示す。
作製された各立方晶窒化硼素焼結体から、長さ6mm、幅3mm、厚さ0.45~0.50mmの試験片を切り出し、該試験片に対してXRD分析を実施した。次に、密閉容器内において、各試験片を140℃の弗硝酸(濃硝酸(60%):蒸留水:濃弗酸(47%)=2:2:1の体積比混合の混合酸)に48時間浸漬し、結合材が溶解された酸処理液を得た。当該酸処理液に対してICP分析を実施した。そして、XRD分析の結果およびICP分析の結果から、結合材の組成を特定した。
上述の酸処理後の各試験片に対し、3点曲げ試験機を用いて、4mmスパン、ストローク速度0.5mm/minで抗折強度(GPa)を測定した。その結果を表1に示す。
作製された各立方晶窒化硼素焼結体を用いて切削工具(基材形状:DNGA150408、刃先処理T01225)を作製した。これを用いて、以下の切削条件下で切削試験を実施した。
切削速度:200m/min.
送り速度:0.1mm/rev.
切込み:0.1mm
クーラント:DRY
切削方法:断続切削
旋盤:LB400(オークマ株式会社製)
被削材:焼結部品(住友電気工業社製の焼入焼結合金D-40、焼入れされた切削部の硬度:40HRC)。
Claims (10)
- 85体積%以上100体積%未満の立方晶窒化硼素粒子と、残部の結合材と、を備える立方晶窒化硼素焼結体であって、
前記結合材は、WC、CoおよびAl化合物を含み、
TEM-EDXを用いて、立方晶窒化硼素粒子同士が隣接してなる界面を含む界面領域を分析した場合に、
前記界面上の全て又は一部に酸素が存在し、
前記酸素が存在する領域の幅Dは、0.1nm以上10nm以下である、立方晶窒化硼素焼結体。 - 前記幅Dは、0.1nm以上5nm以下である、請求項1に記載の立方晶窒化硼素焼結体。
- 前記酸素が存在する領域における前記酸素の含有量の最大値Mは5.0原子%以下である、請求項1または請求項2に記載の立方晶窒化硼素焼結体。
- 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を含む切削工具。
- 立方晶窒化硼素原料粉末の酸素を除去するとともに、前記立方晶窒化硼素原料粉末に有機物を付着させて、有機立方晶窒化硼素粉末を作製する工程と、
前記有機立方晶窒化硼素粉末と、WC、CoおよびAlを含む結合材原料粉末とを混合して、85体積%以上100体積%未満の前記有機立方晶窒化硼素粉末と、残部の結合材原料粉末とからなる混合粉末を調製する工程と、
前記混合粉末を焼結して立方晶窒化硼素焼結体を得る工程と、を含む、立方晶窒化硼素焼結体の製造方法。 - 前記作製する工程は、
前記立方晶窒化硼素原料粉末と前記有機物とを、超臨界水に投入する工程を含む、請求項5に記載の立方晶窒化硼素焼結体の製造方法。 - 前記有機物は、アミン又は炭素数が5以上の炭化水素化合物である、請求項6に記載の立方晶窒化硼素焼結体の製造方法。
- 前記有機物は、ヘキシルアミン、ヘキシルニトリル、パラフィン又はヘキサンである、請求項7に記載の立方晶窒化硼素焼結体の製造方法。
- 前記作製する工程は、
プラズマ処理により、前記立方晶窒化硼素原料粉末の表面をエッチングした後、前記表面に前記有機物を付着させる工程を含む、請求項5に記載の立方晶窒化硼素焼結体の製造方法。 - 前記有機物は、アミン又はフッ化炭素である、請求項9に記載の立方晶窒化硼素焼結体の製造方法。
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EP3854898A4 (en) | 2022-06-22 |
EP3854898A1 (en) | 2021-07-28 |
CN112714801A (zh) | 2021-04-27 |
CN112714801B (zh) | 2022-08-12 |
JPWO2020059755A1 (ja) | 2021-01-07 |
KR20210060569A (ko) | 2021-05-26 |
KR102605373B1 (ko) | 2023-11-23 |
US11396482B2 (en) | 2022-07-26 |
US20210246078A1 (en) | 2021-08-12 |
JP6744519B1 (ja) | 2020-08-19 |
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