WO2023190525A1 - Objet fritté en nitrure de bore, procédé de production associé, support d'enfournement, et récipient - Google Patents

Objet fritté en nitrure de bore, procédé de production associé, support d'enfournement, et récipient Download PDF

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WO2023190525A1
WO2023190525A1 PCT/JP2023/012542 JP2023012542W WO2023190525A1 WO 2023190525 A1 WO2023190525 A1 WO 2023190525A1 JP 2023012542 W JP2023012542 W JP 2023012542W WO 2023190525 A1 WO2023190525 A1 WO 2023190525A1
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boron nitride
sintered body
nitride sintered
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content
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Japanese (ja)
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脩平 野中
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デンカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof

Definitions

  • the present disclosure relates to a boron nitride sintered body, a method for manufacturing the same, a setter, and a container.
  • Patent Document 1 proposes using a boron nitride sintered body as a setter when firing ceramic raw materials.
  • Patent Document 2 describes the use of a boron nitride sintered body as a firing container for holding a raw material mixture when firing the raw material mixture in a method for manufacturing a phosphor.
  • the raw material mixture contained in such a firing container is heated to 1000° C. to 1500° C., for example, in an atmosphere of hydrogen gas, ammonia gas, or inert gas. As the heating progresses, various reactions such as decarburization proceed, resulting in a fired product having desired characteristics.
  • a boron nitride sintered body When a boron nitride sintered body is used, for example, as a setter or storage container when firing raw materials, it is repeatedly used in a series of processes such as introduction into the firing furnace, heating at high temperature, and removal from the firing furnace. is normal. Therefore, from the viewpoint of work efficiency, the boron nitride sintered body is required to be difficult to break and have excellent reliability. Further, when the raw materials in the setter or the storage container are heated at high temperatures, various reactions occur, and gases may be involved in some of these reactions. In order to allow such reactions involving gas to proceed smoothly and uniformly, it is effective to ensure that the setter and the container do not obstruct the passage of gas.
  • the present disclosure provides a boron nitride sintered body that has high reliability and excellent permeability for various gases, and a method for manufacturing the same. Further, the present disclosure provides a setter and a container that have high reliability and excellent gas permeability for various gases.
  • the present disclosure provides a boron nitride sintered material having a porosity of 36 volume % or more, a bending strength of 5 MPa or more, and a pore median diameter of 0.5 ⁇ m or more as determined from the pore size distribution. Provide your body.
  • the boron nitride sintered body has a bending strength of a predetermined value or more, it is difficult to break and has high reliability. Furthermore, since it has a porosity of a predetermined value or more and a pore median diameter of a predetermined value or more, it has excellent permeability for various gases.
  • the purity of boron nitride in the boron nitride sintered body may be 97% by mass or more.
  • Such a boron nitride sintered body has sufficiently high heat resistance and stability, and when used as a setter or storage container, can sufficiently suppress reactions between components other than boron nitride and raw materials to be fired. . Therefore, the characteristics of the product obtained from the raw materials can be sufficiently improved.
  • the total content of Fe, Cr, Ni, Cu, and Mn in the boron nitride sintered body may be less than 50 mass ppm. If such a boron nitride sintered body is used, for example, in a setter or container when manufacturing a functional product such as a phosphor, the fusion between the boron nitride sintered body and the product due to the mixing of the transition element described above can be avoided. , and the deterioration of product performance can be sufficiently suppressed.
  • the content of Ca in the boron nitride sintered body may be less than 100 mass ppm. If such a boron nitride sintered body is used, for example, in a setter or a container for manufacturing functional products such as phosphors, performance deterioration due to the incorporation of Ca can be sufficiently suppressed.
  • the carbon content in the boron nitride sintered body may be less than 0.1% by mass. If such a boron nitride sintered body is used, for example, in a setter or container for manufacturing functional products such as phosphors, it is possible to sufficiently suppress performance deterioration due to the contamination of carbon.
  • the density of the boron nitride sintered body may be 0.9 to 1.4 g/cm 3 .
  • Such a boron nitride sintered body has a certain degree of strength and is lightweight, so it can be suitably used for various purposes.
  • the present disclosure provides a setter made of any of the boron nitride sintered bodies described above. Since this setter is constructed of any of the boron nitride sintered bodies described above, it has high reliability and excellent permeability for various gases.
  • the present disclosure provides a container made of any of the boron nitride sintered bodies described above. Since this container is constructed of any of the boron nitride sintered bodies described above, it has high reliability and excellent permeability for various gases.
  • the present disclosure includes a step of molding and firing a mixed raw material containing hexagonal boron nitride powder and amorphous boron nitride powder to obtain a boron nitride sintered body, the hexagonal boron nitride in the mixed raw material
  • the content of boron powder is higher than the content of amorphous boron nitride powder, the maximum value of the compacting pressure is less than 50 MPa, and the bending strength of the boron nitride sintered body is 5 MPa or more.
  • the boron nitride sintered body obtained by the above manufacturing method has a bending strength of a predetermined value or more, it is difficult to break and has high reliability. Furthermore, in the above manufacturing method, more hexagonal boron nitride powder is used than amorphous boron nitride powder, and the maximum value of the compacting pressure from the mixed raw material to obtain the boron nitride sintered body is less than 50 MPa. From this, a boron nitride sintered body having high porosity and containing pores (pores) having a relatively large size can be obtained. Such a boron nitride sintered body has excellent permeability for various gases.
  • the porosity of the boron nitride sintered body obtained by the above manufacturing method is 36% by volume or more, and the median diameter of pores determined from the pore size distribution of the boron nitride sintered body may be 0.5 ⁇ m or more.
  • FIG. 1 is a perspective view showing an example of a setter.
  • FIG. 2 is a perspective view showing an example of a container.
  • FIG. 3 is a diagram for explaining a method for measuring gas permeability.
  • Numerical ranges in which the upper limit or lower limit of each numerical range in each embodiment is replaced with the numerical value of any example are also included in the present disclosure.
  • the present disclosure includes both cases in which one of the plurality of materials illustrated in parallel in each embodiment is included, and cases in which two or more of the plurality of materials are included in combination.
  • the boron nitride sintered body contains boron nitride.
  • the purity of boron nitride in the boron nitride sintered body that is, the content of boron nitride in the boron nitride sintered body, may be 97% by mass or more, 98% by mass or more, and 99% by mass or more. Good too.
  • a boron nitride sintered body having such high purity has sufficiently high heat resistance and stability. When such a boron nitride sintered body is used as a setter or a storage container, reaction with the raw material to be fired can be sufficiently suppressed. Therefore, the characteristics of the product obtained from the raw materials can be sufficiently improved.
  • the upper limit of the purity of the boron nitride sintered body may be 99.8% by mass since unavoidable impurities originating from raw materials and manufacturing processes may be mixed in.
  • the purity of the boron nitride sintered body can be measured by the method described in Examples.
  • an oxygen/nitrogen analyzer (trade name: EMGA-920) manufactured by Horiba, Ltd. can be used.
  • the density of the boron nitride sintered body may be, for example, 1.4 g/cm 3 or less, 1.3 g/cm 3 or less, or 1.1 g/cm 3 or less.
  • a boron nitride sintered body having such a density is lightweight and has excellent handling properties.
  • the density of the boron nitride sintered body may be, for example, 0.9 g/cm 3 or more, or 1.0 g/cm 3 or more.
  • Such a boron nitride sintered body has high reliability.
  • the density range of the boron nitride sintered body may be, for example, 0.9 to 1.4 g/cm 3 . Density in this specification is "apparent density" measured by the Archimedes method.
  • the boron nitride sintered body is porous, and its porosity may be 36% by volume or more. In this way, the boron nitride sintered body contains pores (pores).
  • the porosity of the boron nitride sintered body may be 38 volume% or more, 40 volume% or more, 45 volume% or more, and 50 volume% or more, from the viewpoint of further increasing air permeability. It may be.
  • the porosity of the boron nitride sintered body may be 60 volume % or less, or 55 volume % or less, from the viewpoint of maintaining high bending strength.
  • the porosity range of the boron nitride sintered body may be, for example, 36 to 60% by volume.
  • the median diameter of pores determined from the pore diameter distribution of the boron nitride sintered body may be 0.5 ⁇ m or more. This median diameter may be 0.6 ⁇ m or more, 0.7 ⁇ m or more, or 0.8 ⁇ m or more from the viewpoint of increasing the permeability of gases with large molecular sizes. From the viewpoint of maintaining a certain degree of bending strength, this median diameter may be 1.5 ⁇ m or less, or may be 1.3 ⁇ m or less.
  • the median diameter of the pores of the boron nitride sintered body in this specification is measured based on the mercury intrusion method in accordance with JIS R 1655:2003 "Method for testing the pore distribution of fine ceramics using the mercury intrusion method.” Determined from the pore size distribution.
  • the pore size distribution can be represented, for example, by a graph in which the vertical axis is the integrated pore volume per unit mass, and the horizontal axis is the diameter of the pores (pores) on a logarithmic scale. In such a pore size distribution, the pore size when the integrated value is 50% of the total is the median diameter.
  • the boron nitride sintered body of this embodiment has a porosity and a median diameter of pores within the above-mentioned range, it can be used not only for gases with small molecular sizes such as H 2 but also for gases such as H 2 O, NH 3 , and CO. , CO 2 and other gases with large molecular sizes can also be sufficiently passed through. Therefore, it has excellent breathability for various gases.
  • the bending strength of the boron nitride sintered body is 5 MPa or more. From the viewpoint of further improving the reliability and handling properties of the boron nitride sintered body, the bending strength may be 8 MPa or more, or 10 MPa or more. This bending strength may be 40 MPa or less, 30 MPa or less, or 20 MPa or less from the viewpoint of sufficiently increasing the gas permeability of the boron nitride sintered body. The bending strength of the boron nitride sintered body may range from 5 to 40 MPa, for example.
  • the bending strength in this specification is the three-point bending strength measured in accordance with the description of JIS R 1601:2008 "Room Temperature Bending Strength Test Method for Fine Ceramics.”
  • the three-point bending strength can be measured using a commercially available bending strength meter.
  • the shore hardness of the boron nitride sintered body may be 5 or more, and may be 7 or more. Thereby, wear resistance can be improved.
  • the upper limit of the Shore hardness is not particularly limited, and the Shore hardness may be, for example, 20 or less, or 15 or less. Shore hardness in this specification is measured using a commercially available Shore hardness meter in accordance with JIS Z 2246:2000.
  • the total content of Fe, Cr, Ni, Cu, and Mn in the boron nitride sintered body may be less than 50 mass ppm.
  • a boron nitride sintered body when used as a setter or container when manufacturing a functional product such as a phosphor, the fusion between the functional product and the setter or container, and the performance of the functional product. The decrease can be sufficiently suppressed.
  • the total content of Fe, Cr, Ni, Cu, and Mn in the boron nitride sintered body may be less than 30 mass ppm, or may be less than 10 mass ppm.
  • the content of the above-mentioned transition element can be measured by high frequency inductively coupled plasma optical emission spectroscopy (ICP optical emission spectroscopy).
  • Sample decomposition can be performed by pressure acid decomposition method.
  • the content of the above-mentioned transition elements can be reduced by using boron nitride powder with high purity as a raw material.
  • the content of Ca in the boron nitride sintered body may be less than 100 mass ppm. If such a boron nitride sintered body is used, for example, in a setter or a container for manufacturing functional products such as phosphors, performance deterioration due to the incorporation of Ca can be sufficiently suppressed. From the same viewpoint, the content of Ca in the boron nitride sintered body may be less than 80 mass ppm, or may be less than 70 mass ppm.
  • the content of Ca described above can be measured by high frequency inductively coupled plasma optical emission spectroscopy (ICP optical emission spectroscopy). Sample decomposition can be performed by pressure acid decomposition method. The above-mentioned Ca content can be reduced by using boron nitride powder with high purity as a raw material.
  • the carbon content in the boron nitride sintered body may be less than 0.1% by mass. If such a boron nitride sintered body is used, for example, in a setter or container for manufacturing functional products such as phosphors, it is possible to sufficiently suppress performance deterioration due to the contamination of carbon. From the same viewpoint, the carbon content in the boron nitride sintered body may be less than 0.05% by mass, or may be less than 0.03% by mass.
  • the above carbon content can be measured using a carbon analyzer manufactured by LECO (trade name: IR-412) or the like.
  • the above-mentioned carbon content can be reduced by using boron nitride powder with high purity as a raw material. Furthermore, by manufacturing without using a graphite mold during hot pressing, the carbon content can be reduced.
  • the total amount of oxygen in the boron nitride sintered body may be less than 3% by mass. If such a boron nitride sintered body is used, for example, in a setter or container when manufacturing functional products such as phosphors, it is possible to sufficiently suppress performance deterioration due to increased oxygen content. . From the same viewpoint, the total amount of oxygen in the boron nitride sintered body may be less than 2.0% by mass, and may be less than 1.0% by mass. At least a portion of the oxygen may be contained in the boron nitride sintered body as boron oxide.
  • the total oxygen amount in this specification can be measured using an oxygen/nitrogen simultaneous analyzer. As the oxygen/nitrogen simultaneous analyzer, for example, an oxygen/nitrogen analyzer (trade name: EMGA-920) manufactured by Horiba, Ltd. can be used.
  • the above-mentioned total oxygen amount can be reduced by using boron nitride powder with high purity as a raw material. Further, it can be reduced by reducing the oxygen concentration in the atmosphere during firing, by reducing the amount of sintering aid used, or by manufacturing without using a sintering aid.
  • the boron nitride sintered body may include hexagonal boron nitride and amorphous boron nitride. By including both, it is possible to maintain a certain degree of bending strength and Shore hardness while increasing the porosity. Furthermore, by increasing the content of hexagonal boron nitride, the median diameter of the pores can be increased. Moreover, the Shore hardness can be increased. On the other hand, the porosity can be increased by increasing the content of amorphous boron nitride. Moreover, bending strength can be increased.
  • the gas permeability of nitrogen gas of the boron nitride sintered body may be 0.45 ⁇ 10 ⁇ 6 mol/m 2 ⁇ s ⁇ Pa or more, and may be 0.80 ⁇ 10 ⁇ 6 mol/m 2 ⁇ s ⁇ Pa. It may be more than 5.00 ⁇ 10 ⁇ 6 mol/m 2 ⁇ s ⁇ Pa or more. Such a boron nitride sintered body has even better air permeability.
  • the gas permeability of the boron nitride sintered body may be, for example, 0.45 ⁇ 10 ⁇ 6 to 5.00 ⁇ 10 ⁇ 6 mol/m 2 ⁇ s ⁇ Pa. Gas permeability is measured by the method described in Examples using a gas permeability measuring device.
  • a boron nitride sintered body has a low density and a certain degree of strength, and has excellent air permeability. Therefore, it can be used for various purposes.
  • the boron nitride sintered body may constitute a setter (setter for firing) and a container (container for firing) used for firing when obtaining ceramic products or other products.
  • the type of firing raw material and the shape of the setter and container are not particularly limited.
  • the container may be, for example, a crucible.
  • FIG. 1 is a perspective view showing an example of a setter.
  • the setter 100 in FIG. 1 has a flat plate shape.
  • the setter 100 may be, for example, a mounting table or a weight for firing raw materials.
  • the setter 100 may be an intervening plate interposed between a pair of stacked molded bodies.
  • FIG. 2 is a perspective view showing an example of a container.
  • the container 110 in FIG. 2 includes a container body 112 having a bottom plate, a frame-shaped side wall that stands up from the outer edge of the bottom plate, and an opening formed at the upper end of the side wall, and a container body 112 that has a flat plate shape to cover the opening. It has a lid body 114.
  • FIG. 2 shows the state when the container 110 is opened.
  • the container body 112 and the lid body 114 together form a housing space.
  • the housing space of the container 110 stores raw materials such as ceramics.
  • the container 110 may be introduced into the firing furnace and heated with the raw material stored in the storage space and the opening of the container body 112 covered with the lid 114. This can prevent the upper part of the raw material accommodated in the storage space from reacting excessively and the solid content of the raw material from scattering in the firing furnace.
  • the container main body 112 and the lid body 114 are made of a boron nitride sintered body, gas can be smoothly circulated between the housing space and the outside thereof. Therefore, the reaction of the raw materials can proceed smoothly.
  • the shape and configuration of the container 110 may be modified as appropriate.
  • the lid 114 may be used as a setter, and the container body 112 may be used as a lid to cover the raw material placed on the lid 114. Only one of the container body 112 and the lid 114 may be made of the above-mentioned boron nitride sintered body.
  • the container may be a crucible.
  • the setter 100 and the container 110 are made of the above-mentioned boron nitride sintered body, they are difficult to break and have high reliability. Therefore, it is easy to handle and can be used repeatedly. Boron nitride sintered bodies also have excellent air permeability, so when gas is involved in the reaction of raw materials such as ceramics, the reaction of the raw material powder composition or molded body placed or housed will not occur in the place. The process progresses with high uniformity without any distortion. For example, when a reduction reaction using H 2 gas is involved, the H 2 gas smoothly passes through the setter 100 and the container 110.
  • H 2 gas is also smoothly supplied to the portions of the powder composition or molded body that are in contact with the upper surface of the setter 100 and the inner surface of the container 110 .
  • the reduction reaction proceeds smoothly with high uniformity, and variations in the degree of reaction progress can be sufficiently reduced.
  • the product produced by the reduction reaction is a gas
  • the produced gas passes through the setter 100 and the container 110 and is smoothly released to the outside.
  • boron nitride sintered bodies is not limited to setters and containers. Furthermore, the shapes and structures of the setter and container are not limited to those shown in FIGS. 1 and 2.
  • the manufacturing method of this embodiment includes the steps of forming and firing a mixed raw material containing hexagonal boron nitride powder and amorphous boron nitride powder to obtain a boron nitride sintered body.
  • the content of hexagonal boron nitride powder is higher than the content of amorphous boron nitride powder.
  • the content of hexagonal boron nitride powder may be 55 parts by mass or more, and may be 60 parts by mass or more. It's okay.
  • the content range of the hexagonal boron nitride powder may be, for example, 50 to 85 parts by mass.
  • the content of the amorphous boron nitride powder may be 15 parts by mass or more, and may be 25 parts by mass or more. , 30 parts by mass or more.
  • the content range of the amorphous boron nitride powder may be, for example, 15 parts by mass or more and less than 50 parts by mass.
  • the mixed raw material may also contain a sintering aid.
  • the sintering aid include oxides of rare earth elements such as yttria oxide, oxides such as alumina oxide, magnesium oxide, and calcium oxide, carbonates of alkali metals such as lithium carbonate and sodium carbonate, and boron oxide. It will be done. From the viewpoint of sufficiently increasing the purity of boron nitride in the boron nitride sintered body, the boron nitride sintered body may be manufactured without using such a sintering aid. That is, the mixed raw material does not need to contain a sintering aid.
  • the amount of the sintering aid added may be 1 part by mass or less, and may be 0.5 part by mass or less when the total of the amorphous boron nitride powder and hexagonal boron nitride powder is 100 parts by mass. , 0.1 part by mass or less.
  • the average particle diameter (D50) of both the hexagonal boron nitride powder and the amorphous boron nitride powder may be 1 to 30 ⁇ m.
  • the particle size distribution of each powder is measured according to the method described in JIS Z 8825:2013 "Particle size analysis - laser diffraction/scattering method". In the cumulative distribution of number-based particle size distribution measured in this way, the particle size when the integrated value from small particle sizes reaches 50% of the total is the average particle size (D50).
  • Microtrack manufactured by Nikkiso Co., Ltd., trade name: MT3300EXII
  • the total oxygen content of the hexagonal boron nitride powder may be 0.5% by mass or less, 0.3% by mass or less, and 0.5% by mass or less, and 0.3% by mass or less. It may be 2% by mass or less.
  • the method for measuring the total oxygen content of the hexagonal boron nitride powder is the same as described in the embodiment of the boron nitride sintered body.
  • the total oxygen content of the amorphous boron nitride powder may be, for example, 0.3% by mass or more, 0.5% by mass or more, and 1.0% by mass. % or more.
  • the total oxygen content of the amorphous boron nitride powder may be, for example, 3.0% by mass or less, and may be 2.5% by mass or less. , 2.0% by mass or less.
  • the total oxygen content of the amorphous boron nitride powder may be higher than the total oxygen content of the hexagonal boron nitride powder.
  • the method for measuring the total oxygen content of the amorphous boron nitride powder is the same as described in the embodiment of the boron nitride sintered body.
  • the mixed raw materials may be prepared by dry grinding and dry mixing.
  • wet pulverization and wet mixing may be performed using a ball mill or the like.
  • a device having high dispersion power such as a bead mill may also be used.
  • the liquid medium used for wet grinding and wet mixing may be an organic solvent, for example, an alcohol.
  • an organic binder may be blended in a proportion of 3% by mass or less based on the solid content, and granulation may be performed using a spray dryer. The obtained granules may be sieved to remove coarse particles. Thereby, variations in bending strength of the boron nitride sintered body can be suppressed.
  • the obtained mixed raw material may be pressure-molded into a predetermined shape in advance. Mold molding (uniaxial pressure molding) may be performed using a mold, or CIP molding may be performed using a cold isostatic press device. If the bulk density of the mixed raw material is high and the moldability is low, molding may be performed before CIP molding.
  • the shape of the molded body is not particularly limited.
  • the maximum value of molding pressure during mold molding and CIP molding is less than 50 MPa.
  • the maximum value of the molding pressure may be 40 MPa or less, or 30 MPa or less. This makes it possible to sufficiently increase the porosity and increase the median diameter of the pores. Therefore, the air permeability of the boron nitride sintered body can be further increased.
  • the maximum value of molding pressure during mold molding and CIP molding may be 3 MPa or more, and may be 5 MPa or more. Thereby, the strength of the boron nitride sintered body can be increased.
  • the maximum value of molding pressure during mold molding and CIP molding may be 3 MPa or more and less than 50 MPa.
  • a batch type furnace, a continuous type furnace, etc. can be used.
  • batch furnaces include muffle furnaces, tube furnaces, and atmospheric furnaces.
  • continuous furnaces include tunnel furnaces, belt furnaces, pusher furnaces, and harp-shaped continuous furnaces.
  • Firing may be performed at normal pressure (atmospheric pressure).
  • the maximum molding pressure during hot pressing is also less than 50 MPa. In this way, by setting the maximum value of the pressure during molding and firing (molding pressure) within the above range, it is possible to obtain a boron nitride sintered body with sufficiently high porosity and a large median pore diameter. can.
  • Firing consists of a first firing step in which the molded body (mixed raw materials in the case of hot press) is heat-treated at a heating temperature of 1800°C or less for a predetermined time to obtain a heated product, and a first firing step in which a heated product is obtained by heating at a heating temperature of 1900 to 2300°C for a predetermined time. It may include a second firing step of processing to obtain a fired body from the heat-treated product.
  • a degreasing step for decomposing and removing the organic binder may be performed before the first firing step and the second firing step.
  • heat treatment may be performed at a heating temperature of 600° C. or lower for 1 to 5 hours to decompose and remove the organic binder component from the mixture.
  • the mixture that has undergone the degreasing process is also referred to below as a degreased body.
  • the firing can be performed in an atmosphere containing at least one selected from the group consisting of rare gases and inert gases (excluding rare gases).
  • the rare gas may contain, for example, argon gas, helium gas, etc., may contain argon gas, or may be composed of argon gas.
  • the inert gas may be, for example, nitrogen gas.
  • a heated product is obtained from the molded body or degreased body by heating at a temperature of 1800° C. or lower for a predetermined period of time.
  • the heating temperature in the first firing step may be, for example, 1200°C or higher, or 1300°C or higher.
  • the heating temperature in the first firing step may be, for example, 1750° C. or lower.
  • the firing time in the first firing step may be, for example, 1 to 10 hours.
  • a boron nitride sintered body is obtained from the above heat-treated product by heat treatment at a temperature of 1900 to 2300°C for a predetermined time.
  • the first firing step and the second firing step may be performed continuously.
  • the heating temperature in the second firing step may be, for example, 1950°C or higher, or 2000°C or higher.
  • the heating temperature in the second firing step may be, for example, 2200°C or lower, or 2100°C or lower.
  • the firing time in the second firing step may be, for example, 1 to 15 hours.
  • the structure and properties of the obtained boron nitride sintered body are as described above.
  • the bending strength of a boron nitride sintered body is 5 MPa or more.
  • the porosity of the boron nitride sintered body is 36% by volume or more, and the median diameter of pores determined from the pore size distribution of the boron nitride sintered body is 0.5 ⁇ m or more.
  • the content described in the embodiment of the boron nitride sintered body is applied to the boron nitride sintered body obtained by the manufacturing method of this embodiment.
  • the content described in the embodiment of the manufacturing method is applied to the embodiment of the boron nitride sintered body.
  • [4] The boron nitride sintered body according to any one of [1] to [3], wherein the Ca content is less than 100 mass ppm.
  • [5] The boron nitride sintered body according to any one of [1] to [4], wherein the carbon content is less than 0.1% by mass.
  • [6] The boron nitride sintered body according to any one of [1] to [5], which has a density of 0.9 to 1.4 g/cm 3 .
  • a setter comprising the boron nitride sintered body according to any one of [1] to [6] above.
  • the content of the hexagonal boron nitride powder is higher than the content of the amorphous boron nitride powder,
  • the maximum value of molding pressure is less than 50 MPa
  • the porosity of the boron nitride sintered body is 36% by volume or more, and the median diameter of pores determined from the pore size distribution of the boron nitride sintered body is 0.5 ⁇ m or more, [9] The method for manufacturing the boron nitride sintered body described above. [11] The method for producing a boron nitride sintered body according to [9] or [10], wherein the purity of boron nitride in the boron nitride sintered body is 97% by mass or more.
  • Example 1 ⁇ Preparation of boron nitride sintered body> Amorphous boron nitride powder (manufactured by Denka Corporation, hereinafter referred to as "amorphous BN”) and hexagonal boron nitride powder (manufactured by Denka Corporation, hereinafter referred to as "h-BN”) were prepared. The purity, average particle diameter (D50), BET specific surface area, and impurity concentration of each were as shown in Table 1. The purity of boron nitride was determined by a neutralization titration method after a sample was melted in an alkali. The content of B 2 O 3 was measured according to the following procedure.
  • Methyl alcohol was added to boron nitride powder to form methyl borate, which was volatilized by heating.
  • the content of B 2 O 3 was determined from the amount of mass decrease at this time.
  • the total oxygen amount (TO) was measured using an oxygen/nitrogen analyzer (trade name: EMGA-920).
  • the carbon content (TC) was measured using a carbon analyzer manufactured by LECO (trade name: IR-412).
  • the respective concentrations of Fe, Cr, Ni, Cu, Mn, and Ca were determined by ICP emission spectrometry after each powder was dissolved by a pressure acid decomposition method. These powders, an organic binder, and water were blended and mixed. No sintering aid was used.
  • the blending ratio (based on mass) of amorphous BN and h-BN was as shown in Table 2.
  • amorphous BN and h-BN After mixing amorphous BN and h-BN, they were dried and granulated to obtain a mixed raw material.
  • the molded body was further pressurized using a cold isostatic pressing device (manufactured by Kobe Steel, Ltd., trade name: ADW800) to obtain a CIP molded body.
  • the pressure at this time (CIP pressure) was as shown in Table 2.
  • the obtained molded body was heat-treated at a heating temperature of 600° C. for 5 hours to decompose and remove the organic binder component from the molded body to obtain a degreased body.
  • a batch-type high frequency furnace manufactured by Fuji Denpa Kogyo Co., Ltd.
  • the degreased body was held at 1400°C for 2 hours (first firing process), and then held at 2050°C for 10 hours (second firing process). In this way, a flat plate-shaped boron nitride sintered body was obtained. Note that during firing, nitrogen gas was flowed into the furnace at a rate of 10 L/min to create a nitrogen atmosphere (atmospheric pressure) inside the furnace.
  • the three-point bending strength of the boron nitride sintered body was measured in accordance with the description of JIS R 1601:2008 "Room Temperature Bending Strength Test Method for Fine Ceramics”. Specifically, a boron nitride sintered body was processed into a predetermined shape to prepare a test piece for measuring bending strength. Three-point bending strength was measured using a commercially available universal testing machine (manufactured by Shimadzu Corporation, device name: Autograph AG2000D). The measurement results were as shown in Table 2.
  • the Shore hardness of the boron nitride sintered body was measured in accordance with JIS Z 2246:2000. Specifically, a boron nitride sintered body was processed into a predetermined shape to prepare a test piece for Shore hardness measurement. Shore hardness was measured using a commercially available Shore hardness meter (manufactured by Shimadzu Corporation, device name: Shore hardness meter D type). The measurement results were as shown in Table 2.
  • the pore size distribution of the boron nitride sintered body was measured using a mercury intrusion porosimeter in accordance with JIS R 1655:2003. The median diameter of the pores (pores) was determined from this pore diameter distribution. The results were as shown in Table 2.
  • the gas permeability of the boron nitride sintered body was measured by the reduced pressure method using the following procedure.
  • a cylindrical jig 10 for a gas permeability measuring device as shown in FIG. 3 was prepared.
  • the diameter of the disk-shaped boron nitride sintered body 20 (thickness: 2 mm) processed so as to be fixed to the cylindrical jig 10 was measured, and the surface area (A) of the main surface 22a was measured. .
  • the side surface (peripheral surface) of the boron nitride sintered body and the inner wall surface of the cylindrical jig 10 are adhered and sealed with an epoxy adhesive, and the boron nitride sintered body 20 is fixed inside the cylindrical jig 10.
  • a measurement sample was obtained. This measurement sample was set in a gas permeability measuring device, the flow rate of the supply gas (N 2 ) was set at 500 ml/min, and then held at room temperature (25° C.) for 50 minutes. Thereafter, the pressure change per unit time due to N 2 gas passing through the boron nitride sintered body 20 fixed inside the cylindrical jig 10 was measured. From the measurement results, gas permeability P was calculated using the following formula.
  • Examples 2 to 4, Comparative Examples 1 and 2 A boron nitride sintered body was produced and evaluated in the same manner as in Example 1, except that the pressure used to obtain the CIP compact was changed as shown in Table 2. Each evaluation result was as shown in Table 2. Note that the CIP pressure in Example 4 was lower than the pressure during uniaxial pressurization. Therefore, the maximum molding pressure in Example 4 was 7.5 MPa. The maximum value of the molding pressure in other Examples and Comparative Examples was equal to the CIP pressure.
  • Examples 1 to 4 had a porosity of 38% by volume or more, a bending strength of 5 MPa or more, and a pore median diameter of 0.5 ⁇ m or more.
  • the gas permeability of these boron nitride sintered bodies was all 0.45 ⁇ 10 ⁇ 6 mol/m 2 ⁇ s ⁇ Pa or more. Note that the purity of boron nitride in Examples 1 to 4 and Comparative Examples 1 to 2 was 97% by mass or more.
  • Amorphous boron nitride powder manufactured by Denka Corporation, hereinafter referred to as "amorphous BN”
  • hexagonal boron nitride powder manufactured by Denka Corporation, hereinafter referred to as "h-BN”
  • the respective purity, average particle diameter (D50), BET specific surface area, and each impurity concentration were as shown in Table 3. These measurement methods are the same as in Example 1.
  • the procedure was the same as Comparative Example 1, except that these h-BN and amorphous BN were used, and the blending ratio (mass basis) of h-BN and amorphous BN was as shown in Table 4.
  • a boron nitride sintered body was prepared and evaluated. The evaluation results are as shown in Table 4.
  • a boron nitride sintered body that has high reliability and excellent permeability for various gases, and a method for manufacturing the same. Further, a setter and a container that are reliable and have excellent gas permeability for various gases are provided.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne un objet fritté en nitrure de bore qui présente une porosité de 36 % en volume ou plus, une résistance à la flexion de 5 MPa ou plus, et un diamètre médian de pore déterminé à partir d'une distribution de diamètres de pore de 0,5 µm ou plus. L'invention concerne également un procédé de production de l'objet fritté en nitrure de bore présentant une résistance à la flexion de 5 MPa ou plus, le procédé comportant une étape dans laquelle un mélange de matières premières comprenant une poudre de nitrure de bore hexagonal et une poudre de nitrure de bore amorphe est moulé et brûlé, la teneur en poudre de nitrure de bore amorphe dans le mélange de matières premières étant supérieure à la teneur en poudre de nitrure de bore hexagonal et une pression maximale dans le moulage étant inférieure à 50 MPa.
PCT/JP2023/012542 2022-03-31 2023-03-28 Objet fritté en nitrure de bore, procédé de production associé, support d'enfournement, et récipient WO2023190525A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000119068A (ja) * 1998-10-14 2000-04-25 Denki Kagaku Kogyo Kk 窒化アルミニウム成形体の脱脂・焼成用器具
JP2013543834A (ja) * 2010-11-10 2013-12-09 イーエスケイ セラミクス ゲーエムベーハー アンド カンパニー カーゲー 窒化ホウ素凝集体、その製造方法およびその使用
WO2014196496A1 (fr) * 2013-06-03 2014-12-11 電気化学工業株式会社 Corps fritté en nitrure de bore imprégné de résine, et application de celui-ci
WO2022210555A1 (fr) * 2021-03-31 2022-10-06 デンカ株式会社 Moyen de réglage pour cuisson de céramique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000119068A (ja) * 1998-10-14 2000-04-25 Denki Kagaku Kogyo Kk 窒化アルミニウム成形体の脱脂・焼成用器具
JP2013543834A (ja) * 2010-11-10 2013-12-09 イーエスケイ セラミクス ゲーエムベーハー アンド カンパニー カーゲー 窒化ホウ素凝集体、その製造方法およびその使用
WO2014196496A1 (fr) * 2013-06-03 2014-12-11 電気化学工業株式会社 Corps fritté en nitrure de bore imprégné de résine, et application de celui-ci
WO2022210555A1 (fr) * 2021-03-31 2022-10-06 デンカ株式会社 Moyen de réglage pour cuisson de céramique

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