WO2024043230A1 - 窒化ケイ素焼結体及び窒化ケイ素焼結体の製造方法 - Google Patents

窒化ケイ素焼結体及び窒化ケイ素焼結体の製造方法 Download PDF

Info

Publication number
WO2024043230A1
WO2024043230A1 PCT/JP2023/030121 JP2023030121W WO2024043230A1 WO 2024043230 A1 WO2024043230 A1 WO 2024043230A1 JP 2023030121 W JP2023030121 W JP 2023030121W WO 2024043230 A1 WO2024043230 A1 WO 2024043230A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon nitride
sintered body
nitride sintered
less
content
Prior art date
Application number
PCT/JP2023/030121
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
貴也 矢野
修平 小川
直通 宮川
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2024542823A priority Critical patent/JPWO2024043230A1/ja
Publication of WO2024043230A1 publication Critical patent/WO2024043230A1/ja

Links

Images

Classifications

    • 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
    • C04B35/584—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 silicon nitride
    • C04B35/587—Fine ceramics
    • 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
    • C04B35/584—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 silicon nitride
    • C04B35/593—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 silicon nitride obtained by pressure sintering
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30—Parts of ball or roller bearings
    • F16C33/32—Balls

Definitions

  • the present invention relates to a silicon nitride sintered body and a method for manufacturing a silicon nitride sintered body.
  • a silicon nitride sintered body containing silicon nitride particles is known.
  • Patent Document 1 contains 7 to 18% by mass of rare earth elements in terms of oxide, and at least one element M selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W.
  • a silicon nitride sintered body is described that contains 0.1 to 3% by mass in terms of oxide and has a content of impurity cation elements of 0.3% by mass or less.
  • Patent Document 2 describes a silicon nitride sintered body containing 0.5 to 5% by weight of spinel, 0.5 to 5% by weight of titanium carbide, and the balance being silicon nitride.
  • the silicon nitride sintered body of Patent Document 1 contains a rare earth element as a sintering aid, it is required to reduce the content of the rare earth element from the viewpoint of manufacturing cost. Furthermore, silicon nitride sintered bodies are required to have good mechanical properties and high strength as products.
  • An object of the present invention is to provide a silicon nitride sintered body that has a low content of rare earth elements and good mechanical properties, and a method for manufacturing the silicon nitride sintered body.
  • the silicon nitride sintered body according to the present disclosure has a total content of Si and N of 90 wt% or more with respect to the entire silicon nitride sintered body, and a Mg content of the silicon nitride sintered body.
  • the content of Al is 0.80 wt% or more and 3.70 wt% or less based on the entire silicon nitride sintered body,
  • the content of the rare earth element is 1000 ppm or less by weight based on the entire silicon nitride sintered body, the bending strength is 900 MPa or more, and the fracture toughness value Kc is 6.5 MPa m 1/2 or more. be.
  • a method for producing a silicon nitride sintered body according to the present disclosure includes a step of producing a silicon nitride molded body containing silicon nitride, a raw material containing Mg, and a raw material containing Al, and firing the silicon nitride molded body.
  • the silicon nitride sintered body has a total content of Si and N of 90 wt% or more based on the entire silicon nitride sintered body,
  • the Mg content is 0.45 wt% or more and 1.20 wt% or less with respect to the whole silicon nitride sintered body, and the Al content is 0.45 wt% or more with respect to the whole silicon nitride sintered body.
  • the content of rare earth elements is 1000 ppm or less by weight based on the entire silicon nitride sintered body, the bending strength is 900 MPa or more, and the fracture toughness value is Kc is 6.5 MPa ⁇ m 1/2 or more.
  • a silicon nitride sintered body with a low content of rare earth elements and good mechanical properties can be provided.
  • FIG. 1 is a schematic diagram of a silicon nitride sintered body according to this embodiment.
  • FIG. 2 is a schematic diagram of a STEM image of a cross section of a silicon nitride sintered body.
  • FIG. 3 is a flowchart illustrating a method for manufacturing a silicon nitride sintered body according to this embodiment.
  • the "arbitrary cross section” in this embodiment is a cross section passing through the center of the sintered body and a cross section located 0.3 mm or more inside from the surface of the sintered body. If the sintered body is a sphere, the cross section should be a cross section passing through the center of the sphere and at least 0.3 mm inside from the surface of the sintered body. Furthermore, in the measurement using an "arbitrary cross section", the average of three observation points separated by 1 mm or more is used.
  • FIG. 1 is a schematic diagram of a silicon nitride sintered body according to this embodiment.
  • the silicon nitride sintered body 1 according to this embodiment is a sintered body of silicon nitride particles.
  • the silicon nitride sintered body 1 may be used for any purpose, and for example, may be used as a ball of a ball bearing (bearing ball, etc.), and may be used as a bearing ball for a bearing of wind power generation equipment.
  • the silicon nitride sintered body 1 may be used as a raw ball for a bearing ball.
  • the raw ball here means an intermediate product when the final product is a bearing ball. For example, by polishing the surface of the silicon nitride sintered body 1, the final product, the bearing ball, is formed.
  • the shape of the silicon nitride sintered body 1 may be arbitrary, in this embodiment, it is spherical.
  • the spherical shape here is not limited to a perfect sphere.
  • the silicon nitride sintered body 1 may have a sphericity of preferably within 3%, more preferably within 2.5%, and still more preferably within 2% of the diameter.
  • the sphericity is preferably 1.5 mm or less, more preferably 1.25 mm or less, and even more preferably 1.0 mm or less.
  • the sphericity is preferably 0.3 mm or less, more preferably 0.25 mm or less, and even more preferably 0.2 mm or less.
  • the diameter here may refer to an average diameter (arithmetic mean value of the maximum value and minimum value of the diameter).
  • the diameter of the silicon nitride sintered body 1 is preferably 0.5 mm or more and 80 mm or less, more preferably 30 mm or more and 55 mm or less, even more preferably 45 mm or more and 55 mm or less, and 49 mm or more and 51 mm or less. It is even more preferable. If the diameter is within this range, it can be suitably used, for example, as a bearing ball.
  • FIG. 2 is a schematic diagram of a STEM image of a cross section of a silicon nitride sintered body.
  • the silicon nitride sintered body 1 preferably includes silicon nitride particles 2 and a grain boundary phase 3 located around the silicon nitride particles 2.
  • the periphery here is not limited to the entire section of the outer periphery of the silicon nitride particles 2, but may refer to a part of the entire section of the outer periphery of the silicon nitride particles 2. That is, it can be said that the grain boundary phase 3 is not precipitated inside the silicon nitride particles 2, but is provided outside the silicon nitride particles 2 (adjacent to the silicon nitride particles 2).
  • FIG. 2 schematically shows an example of an image (STEM image) obtained when a cross section of the silicon nitride sintered body 1 is photographed using a STEM (scanning transmission electron microscope).
  • STEM image an image obtained when a cross section of the silicon nitride sintered body 1 is photographed using a STEM (scanning transmission electron microscope).
  • STEM-EDX energy dispersive X-ray spectrometer
  • an arbitrary cross section of the silicon nitride sintered body 1 is processed into a thin piece with a thickness of 100 nm or less using FIB (focused ion beam: Helios 1200 manufactured by FEI), and STEM-EDX (TEM: JEM-2010F manufactured by JEOL Ltd.) is processed.
  • FIB focused ion beam: Helios 1200 manufactured by FEI
  • STEM-EDX TEM: JEM-2010F manufactured by JEOL Ltd.
  • the range where the nitrogen concentration is relatively high is determined to be silicon nitride particle 2, and the range where the oxygen concentration is relatively high. may be determined to be grain boundary phase 3.
  • a range where the nitrogen concentration is 15 at % or more may be determined to be silicon nitride particles 2, and a range where the oxygen concentration is 30 at % or more may be determined to be the grain boundary phase 3.
  • the high-density range can be determined visually when a mapping image is created using black for the low-density areas and any color other than black for the high-density areas.
  • the silicon nitride particles 2 refer to particles of silicon nitride (Si 3 N 4 ).
  • the length of the silicon nitride particles 2 is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less, and even more preferably 3 ⁇ m or more and 12 ⁇ m or less. When the size of the silicon nitride particles 2 falls within this range, good mechanical properties can be achieved.
  • the length of the silicon nitride particles 2 is the length of the longest part of the target silicon nitride particles 2 in a unit area of 20 ⁇ m x 20 ⁇ m when an arbitrary cross section of the silicon nitride sintered body 1 is photographed (major axis ) is the average value of Only silicon nitride particles completely contained within a unit area are used to calculate the average value. That is, silicon nitride particles that exist only partially within a unit area are excluded from the calculation of the average value. Note that STEM may be used to photograph the cross section of the silicon nitride sintered body 1 here.
  • the grain boundary phase 3 is a phase formed around the silicon nitride particles 2, and can also be said to be a phase located between the silicon nitride particles 2.
  • the area ratio which is the ratio of the area of the grain boundary phase 3 to the area of the entire cross section, is preferably 10% or less, and 1% or more and 7% or less. More preferably, it is 1.5% or more and 3% or less. When the area ratio falls within this range, an appropriate amount of silicon nitride particles 2 can be included and good mechanical properties can be achieved.
  • the area ratio of the grain boundary phase 3 is the ratio of the grain boundary phase 3 included in the unit area to the unit area of 10 ⁇ m x 10 ⁇ m when an arbitrary cross section of the silicon nitride sintered body 1 is photographed. It can be calculated as a ratio of area.
  • STEM may be used to photograph the cross section of the silicon nitride sintered body 1 here.
  • the oxygen distribution in the STEM-EDX oxygen mapping image may be binarized using a predetermined brightness value as a threshold, and the range of high oxygen concentration may be taken as the area of the grain boundary phase 3 per unit area.
  • the brightness corresponding to a place where the oxygen concentration is relatively high for example, a place where the oxygen concentration is 30 at% or more
  • the area ratio can be calculated from the image.
  • the silicon nitride sintered body 1 has a total content of Si and N of 90 wt% or more, preferably 90 wt% or more and 98 wt% or less, and 92 wt% or more and 97 wt% or more, based on the entire silicon nitride sintered body. It is more preferably .5 wt% or less, and even more preferably 94 wt% or more and 96 wt% or less. When the total content of Si and N falls within this range, mechanical properties can be improved.
  • the total content of Si and N refers to the total value of the ratio of the content of Si to the entire silicon nitride sintered body and the ratio of the content of N to the entire silicon nitride sintered body.
  • Si in the Si content refers to the Si element, and may include both simple Si and Si contained in a compound (Si as ions). The same applies to other elements described below, such as N.
  • the total content of Si and N can be measured by EPMA (electron beam microanalyzer).
  • the radius of the silicon nitride sintered body 1 is r
  • a distance of 2/3 r from the center of the silicon nitride sintered body 1 to the outside in the radial direction Ten different positions are measured with EPMA.
  • each measurement (one point) is performed by analyzing a 100 ⁇ 100 ⁇ m area.
  • the average value of the measured values at 10 points may be taken as the total content of Si and N.
  • the sum of the average value of Si content at 10 points measured by EPMA and the average value of N content at 10 points measured by EPMA is calculated as the total content of Si and N.
  • the center of the silicon nitride sintered body 1 may be the center of gravity, and the radius r is the average distance from the center of the silicon nitride sintered body 1 to the outer peripheral surface. Good value. The same is true for things like substrates and rectangular parallelepipeds, if the long side is a1 and the short side is a2, the total is 10 inside (center side) from the distance 2/6a1 and 2/6a2 from the center O, respectively. Measure different positions of the points with EPMA. Note that as the EPMA device, for example, JXA-8500F manufactured by JEOL may be used.
  • the silicon nitride sintered body 1 has a total Mg content of 0.45 wt% or more and 1.20 wt% or less, and 0.60 wt% or more and 1.00 wt% or less, based on the entire silicon nitride sintered body.
  • the content is preferably 0.70 wt% or more and 0.90 wt% or less.
  • the content of Mg can be measured by EPMA. Specifically, on an arbitrary cross section of the silicon nitride sintered body 1, 10 different positions 2/3r apart in the radial direction from the center of the silicon nitride sintered body 1 are measured using EPMA. The average value of the Mg content measurements at 10 points may be taken as the Mg content.
  • the silicon nitride sintered body 1 has a total Al content of 0.80 wt% or more and 3.70 wt% or less, and 1.10 wt% or more and 2.10 wt% or less, based on the entire silicon nitride sintered body. It is preferably 1.30 wt% or more and 1.70 wt% or less. When the Al content falls within this range, mechanical properties can be improved.
  • the content of Al can be measured by EPMA. Specifically, on an arbitrary cross section of the silicon nitride sintered body 1, 10 different positions 2/3r apart in the radial direction from the center of the silicon nitride sintered body 1 are measured using EPMA. The average value of the measured values of Al content at 10 points may be taken as the Al content.
  • the silicon nitride sintered body 1 may not contain Ti or may contain any amount of Ti.
  • the silicon nitride sintered body 1 preferably has a Ti content of 0.02 wt% or more and 3.5 wt% or less, and 0.05 wt% with respect to the entire silicon nitride sintered body. It is preferably 3.5 wt% or less, more preferably 0.10 wt% or more and 2.50 wt% or less, even more preferably 0.20 wt% or more and 2.00 wt% or less, and 0.30 wt%. It is more preferably 1.50 wt% or less, and even more preferably 0.50 wt% or more and 1.20 wt% or less.
  • the content of Ti can be measured by EPMA. Specifically, on an arbitrary cross section of the silicon nitride sintered body 1, 10 different positions 2/3r apart in the radial direction from the center of the silicon nitride sintered body 1 are measured using EPMA. The average value of the Ti content measurements at 10 points may be taken as the Ti content.
  • the silicon nitride sintered body 1 has a small content of rare earth elements or does not contain rare earth elements.
  • the silicon nitride sintered body 1 has a rare earth element content of 1000 ppm or less, preferably 600 ppm or less, more preferably 300 ppm or less, based on the weight ratio of the entire silicon nitride sintered body. preferable. Since the content of rare earth elements in the silicon nitride sintered body 1 is within this range, it can be said that the content of rare earth elements is low. In addition, when multiple types of rare earth elements are included, the total value of the content of each rare earth element contained in the silicon nitride sintered body 1 is treated as the content of the rare earth element.
  • the content of rare earth elements can be measured by EPMA. Specifically, on an arbitrary cross section of the silicon nitride sintered body 1, 10 different positions 2/3r apart in the radial direction from the center of the silicon nitride sintered body 1 are measured using EPMA. The average value of the rare earth element content measurements at 10 points may be taken as the rare earth element content. In addition, when a plurality of types of rare earth elements are included, the average value of the rare earth element contents at 10 points is summed for each rare earth element, and the rare earth element content is determined.
  • the silicon nitride sintered body 1 may not contain C or may contain any amount of C.
  • the content of C in the silicon nitride sintered body 1 is preferably 3500 ppm or less, more preferably 2000 ppm or less, based on the weight ratio of the entire silicon nitride sintered body. , more preferably 1000 ppm or less. With such a small content of C, mechanical properties can be improved.
  • C may not be contained, it may be, for example, 50 ppm or more, or 300 ppm or more.
  • the C content can be measured by EPMA.
  • the silicon nitride sintered body 1 may contain any amount of components other than the components explained above, but it is preferable that it does not contain any components other than the components explained above. In other words, the components explained above Other components may be included as unavoidable impurities.
  • the bending strength of the silicon nitride sintered body 1 is preferably 900 MPa or more, more preferably 1000 MPa or more, and even more preferably 1100 MPa or more.
  • the bending strength is a three-point bending strength at a span of 30 mm measured according to the method specified in JIS R 1669.
  • a bending test piece of 3 mm x 40 mm x 4 mm thickness was prepared from the silicon nitride sintered body 1, the span was 30 mm, and the load application rate was set to 0.5 mm/min.
  • the point bending strength may be taken as the bending strength of the silicon nitride sintered body 1.
  • AC-100kN-C manufactured by TSE may be used as a device for measuring bending strength.
  • the fracture toughness value Kc of the silicon nitride sintered body 1 is preferably 6.5 MPa ⁇ m 1/2 or more, more preferably 6.6 MPa ⁇ m 1/2 or more, and 6.7 MPa ⁇ m 1 It is more preferable that it is /2 or more. When the fracture toughness value Kc falls within this range, it can be confirmed that the mechanical properties were appropriately improved. The higher the fracture toughness value Kc of the silicon nitride sintered body 1 is, the more preferable it is, but the upper limit may be, for example, 7.8 MPa ⁇ m 1/2 . Note that the fracture toughness value Kc can be measured according to the IF method specified in JIS R 1607. Note that FV-800 manufactured by Futuretech may be used as a device for measuring the fracture toughness value Kc.
  • the relative density of the silicon nitride sintered body 1 is preferably 97.0% or more, more preferably 98.0% or more, even more preferably 99.0% or more, and 99.5%. It is particularly preferable that it is above. When the relative density falls within this range, mechanical properties can be appropriately improved. Relative density can be measured by the Archimedes method.
  • FIG. 3 is a flowchart illustrating a method for manufacturing a silicon nitride sintered body according to this embodiment.
  • a silicon nitride molded body is a molded body obtained by molding a raw material containing silicon nitride into a desired shape.
  • the silicon nitride molded body contains silicon nitride, Mg, and Al.
  • the silicon nitride molded body is preferably spherical.
  • silicon nitride and a sintering aid are mixed to obtain a raw material.
  • Components other than silicon nitride and sintering aids may also be mixed into the raw material.
  • silicon oxide is a compound containing silicon and oxygen, and may have any composition containing silicon and oxygen, for example, silicon oxide (SiO 2 ).
  • the sintering aid used as a raw material includes a raw material containing Mg and a raw material containing Al.
  • a spinel containing Al and Mg (magnesia alumina spinel; MgO.Al 2 O 3 ) is used as a raw material containing Mg and a raw material containing Al.
  • the raw material containing Mg and the raw material containing Al are not limited to spinel, and any material containing Al and Mg may be used.
  • a raw material containing Mg and a raw material containing Al may be prepared and mixed, and in this case, for example, MgO may be used as the raw material containing Mg, and Al 2 O 3 may be used as the raw material containing Al. .
  • the raw material containing Mg may be arbitrary, and may be, for example, at least one of MgO and MgAl 2 O 4 .
  • the raw material containing Al may be arbitrary, and may be, for example, at least one of Al 2 O 3 and MgAl 2 O 4 .
  • the blending ratio of silicon nitride and sintering aid in the raw materials may be arbitrary.
  • the amount of spinel added to the total amount of silicon nitride and spinel in the raw material is preferably 2.5 mol% or more and 5.5 mol% or less. , more preferably 3.0 mol% or more and 5.0 mol% or less, and still more preferably 3.2 mol% or more and 4.6 mol% or less.
  • the mechanical properties of the sintered body can be appropriately improved.
  • the silicon nitride sintered body 1 containing Ti when manufacturing the silicon nitride sintered body 1 containing Ti, it is preferable that the raw material containing Ti is also included in the sintering aid.
  • the silicon nitride molded body can be said to include silicon nitride, a raw material containing Mg, a raw material containing Al, and a raw material containing Ti.
  • the raw material containing Ti may be arbitrary, for example, TiO 2 may be used.
  • the amount of TiO 2 added is preferably 0 mol% or more and 6.0 mol% or less, and 0.1 mol% or more with respect to the total amount of silicon nitride and TiO 2 in the raw material.
  • It is more preferably 4.5 mol% or less, and even more preferably 0.3 mol% or more and 3.5 mol% or less. More preferably, it is 0.5 mol or more and 2.5 mol or less, most preferably 0.7 mol or more and 2 mol or less.
  • the raw material containing C when manufacturing the silicon nitride sintered body 1 containing C, the raw material containing C will also be included in the silicon nitride molded body.
  • the silicon nitride molded body can be said to include silicon nitride, a raw material containing Mg, a raw material containing Al, and a raw material containing C.
  • the raw material containing C may be arbitrary, for example, impurities contained in resin or silicon nitride may be used as the raw material containing C.
  • the silicon nitride molded body either does not contain a rare earth element or contains a rare earth element as an unavoidable impurity.
  • a mold is filled with a raw material containing silicon nitride and a sintering aid, and then demolded to obtain a silicon nitride molded body.
  • the method for producing the molded body may be arbitrary.
  • the silicon nitride molded body may be molded by a gel casting method. The molding method using the gel casting method will be explained below.
  • silicon nitride, a sintering aid, and a solvent are mixed to produce a raw material slurry as a raw material.
  • the raw material slurry is a slurry in which silicon nitride and a sintering aid are dispersed in a solvent.
  • the method for producing the raw material slurry is not particularly limited, and at least one of a dispersant, a resin, and a resin curing agent may be added to the slurry containing silicon nitride, a sintering aid, and a solvent depending on the type of solvent. good.
  • the solvent is a liquid for uniformly mixing silicon nitride, a sintering aid, a resin, and a resin curing agent for molding.
  • the solvent is, for example, water, an organic solvent, or an alcohol, and it is preferable to use a solvent that does not remain in the silicon nitride sintered body 1 after sintering.
  • the alcohol for example, methyl alcohol and ethyl alcohol can be used.
  • the organic solvent for example, benzene, toluene, and xylene can be used. These solvents may be used alone or may be mixed as appropriate.
  • Dispersants are additives that assist in dispersing silicon nitride into a solvent.
  • Dispersants include, for example, pH adjusters such as tetramethylammonium hydroxide, polymeric dispersants such as polycarboxylic acid polymers, inorganic dispersants such as phosphates such as sodium hexametaphosphate, anionic dispersants, and cationic dispersants.
  • Organic surfactant type dispersants such as surfactants and nonionic types may be used.
  • silicon nitride, a solvent, a dispersant, and a sintering aid are first mixed to form a slurry.
  • the amount of silicon nitride added to the solvent is preferably 35 volume% or more and 65 volume% or less, more preferably 40 volume% or more and 60 volume% or less, and 45 volume% or more. More preferably, the content is 55% by volume or less. With such a blending ratio, a silicon nitride molded body can be appropriately produced.
  • the amount of dispersant added to silicon nitride is preferably 0.3% by weight or more and 3% by weight or less, and preferably 0.4% by weight or more and 2% by weight or less. More preferably, the content is 0.5% by weight or more and 1% by weight or less. With such a blending ratio, a silicon nitride molded body can be appropriately produced.
  • a resin and a resin curing agent are added to the mixed slurry to produce a raw material slurry for casting. More specifically, a resin and a resin curing agent (polymerization initiator) are added to the slurry.
  • the resin is a resin that polymerizes and hardens when a resin curing agent is added, and in this embodiment, it is preferably a resin that dissolves in the solvent of the slurry (here, a water-soluble resin).
  • the resin here is, for example, a water-soluble epoxy resin, but is not limited to an epoxy resin, and may be any resin that polymerizes and hardens when a resin curing agent is added.
  • a resin curing agent is an additive that is added to a resin to polymerize and harden the resin.
  • the resin curing agent here is, for example, a mixture of triethylenetetramine and dimethylaminomethyl, but is not limited thereto, and may be any additive that polymerizes and hardens the resin when added to the resin. .
  • a resin-added raw material slurry (hereinafter also referred to as a first raw material slurry) in which a resin is added to a slurry, and a curing agent-added raw material slurry in which a resin curing agent is added to a slurry (hereinafter also referred to as a second raw material slurry) and prepare. Then, the first raw material slurry and the second raw material slurry are mixed to obtain a mixed raw material slurry.
  • the amount of resin added to silicon nitride in the raw material slurry is preferably 1% by weight or more and 10% by weight or less, more preferably 1.5% by weight or more and 8% by weight or less. , more preferably 2% by weight or more and 5% by weight or less. With such a blending ratio, a silicon nitride molded body can be appropriately produced. Further, the amount of the resin curing agent added to the resin is preferably a stoichiometrically appropriate amount of the added resin. With such a blending ratio, a silicon nitride molded body can be appropriately produced.
  • the raw material slurry is injected into the mold.
  • the resin and the resin curing agent are separately added to the slurry and then mixed, that is, the first raw material slurry and the second raw material slurry are separately generated and mixed, but the invention is not limited thereto.
  • both a resin and a resin curing agent may be added to the slurry, and the raw material slurry to which both have been added may be poured into a mold.
  • the raw material slurry is supplied to the mold and held at a predetermined holding temperature for a predetermined holding time.
  • the holding temperature here is preferably 25°C or more and 100°C or less, more preferably 30°C or more and 80°C or less, and even more preferably 40°C or more and 60°C or less.
  • the holding time here is preferably 1 hour or more and 48 hours or less, more preferably 2 hours or more and 24 hours or less, and even more preferably 3 hours or more and 12 hours or less.
  • pressing processing is not performed on the mold to which the raw material slurry is supplied. That is, a pressure higher than atmospheric pressure is not applied to the mold to which the raw material slurry is supplied.
  • a pressure higher than atmospheric pressure may be applied to the raw material slurry.
  • the cured body obtained by hardening the raw material slurry is demolded (taken out) from the mold, and the cured body is appropriately dried and degreased to obtain a silicon nitride molded body.
  • the demolded cured body is dried to form a dry molded body, and the dried molded body is degreased to form a silicon nitride molded body.
  • the drying conditions are arbitrary, for example, a humidification drying process and a hot air drying process are performed. In the humidification and drying process, the cured product is maintained for 24 hours or more and 120 hours or less in an environment where the humidity is 30% or more and 98% or less and the temperature is 25°C or more and 50°C or less.
  • the cured product is held in a hot air drying process for 3 to 48 hours while blowing air at a temperature of 40°C to 100°C to obtain a dry molded product.
  • the degreasing method is also arbitrary, but for example, the dried molded body is held in an environment with a temperature of 550° C. or more and 750° C. or less for 2 hours or more and 12 hours or less to degrease and obtain a silicon nitride molded body.
  • drying is a process of removing the solvent in the cured body
  • degreasing is a process of removing the resin in the cured body (dried molded body).
  • the silicon nitride molded body formed by this manufacturing method preferably has a relative density of 40% or more, more preferably 45% or more, and even more preferably 50% or more. Although a higher relative density is preferable, it may be 65% or less, 60% or less, or 55% or less.
  • the relative density here refers to the value obtained by dividing the molded body density by the material density.
  • the compact density is a value obtained by dividing the volume obtained from the dimensions of the silicon nitride compact by the weight of the silicon nitride compact.
  • the material density is calculated from the composition ratio of silicon nitride and sintering aid and the theoretical density of each material.
  • the material density of silicon nitride (molar mass ag/mol, theoretical density Ag/cm 3 ) and sintering aid (molar mass bg/mol, theoretical density Bg/cm 3 ) is X mol % and Y mol %, respectively. %, it can be calculated from the following equation (1).
  • a silicon nitride molded body is prepared using the gel casting method as described above.
  • the method for producing the silicon nitride molded body is not limited to the gel casting method, and may be any method.
  • a powder press method may be used in which silicon nitride and a sintering aid filled in a mold are pressurized to form a silicon nitride molded body.
  • heat treatment In this production method, a silicon nitride molded body is fired to produce a silicon nitride sintered body.
  • the firing conditions (heat treatment conditions) for the silicon nitride molded body may be arbitrary, it is preferable to perform the heat treatment in at least two stages: heat treatment under the first conditions and heat treatment under the second conditions. This will be explained in detail below.
  • the produced silicon nitride molded body is heat-treated (fired) under the first conditions (step S12).
  • the temperature at which the silicon nitride molded body is heated is the first heating temperature
  • the pressure applied to the silicon nitride molded body is the first pressure
  • the time for maintaining the silicon nitride molded body at the first heating temperature is the first heating temperature. This is the first heating time.
  • the first conditions, that is, the first heating temperature, the first pressure, and the first heating time may be set as appropriate, and may be set within the following ranges, for example.
  • the first heating temperature is preferably 1600°C or higher, more preferably 1600°C or higher and 1800°C or lower, even more preferably 1620°C or higher and 1780°C or lower, and 1650°C or higher and 1750°C or lower. is even more preferable.
  • the first pressure is preferably 0.01 MPa or more and 5 MPa or less, more preferably 0.05 MPa or more and 3 MPa or less, and even more preferably 0.1 MPa or more and 1 MPa or less.
  • the heat treatment under the first condition is most preferably performed at normal pressure (atmospheric pressure), that is, 0.1 MPa, from the viewpoint of mass productivity and ease of operation.
  • the first heating time is preferably 1 hour or more and 24 hours or less, more preferably 2 hours or more and 20 hours or less, and even more preferably 5 hours or more and 15 hours or less.
  • each parameter under the first condition falls within this range, the relative density of the molded body can be appropriately increased and the sinterability can be improved.
  • the heat treatment under the first condition is preferably performed under an inert gas atmosphere.
  • silicon nitride can be appropriately sintered.
  • the inert gas here refers to nitrogen or rare gas. In this embodiment, it is preferable to use nitrogen as the inert gas, and a mixed gas of nitrogen and a rare gas (eg, argon, etc.) may be used. Note that it is preferable that the heat treatment under the second and third conditions described below is also performed under an inert gas atmosphere, similarly to the first condition.
  • the silicon nitride molded body is thus subjected to the heat treatment under the first conditions, thereby performing the first sintering, that is, the primary sintering.
  • the first sintering that is, the primary sintering.
  • the primary sintered body (silicon nitride molded body heat-treated under the first conditions) is heat-treated (fired) under the second conditions (step S14).
  • silicon nitride sintered body 1 is obtained.
  • the heat treatment under the second conditions is heat treatment in a higher pressure environment than the heat treatment under the first conditions, and HIP (Hot Isostatic Pressing) treatment may be applied.
  • the temperature at which the primary sintered body (silicon nitride molded body heat-treated under the first condition) is heated is the second heating temperature
  • the pressure applied to the primary sintered body is the second pressure
  • the time to maintain the temperature at the second heating temperature (heating time) is the second heating time
  • the rate at which the temperature is raised to the second heating temperature is the second heating rate
  • the temperature decreasing rate from the second heating temperature after heating is the second cooling rate.
  • the second conditions that is, the second heating temperature, the second pressure, the second heating time, the second temperature increase rate, and the second temperature decrease rate may be set as appropriate, and may be set, for example, in the following ranges.
  • the second heating temperature is preferably 1700°C or higher, preferably 1600°C or higher and 1900°C or lower, more preferably 1680°C or higher and 1850°C or lower, and preferably 1700°C or higher and 1800°C or lower. More preferred.
  • the second pressure is higher than the first pressure, preferably 50 MPa or more and 200 MPa or less, more preferably 80 MPa or more and 195 MPa or less, and even more preferably 100 MPa or more and 190 MPa or less.
  • the difference between the first pressure and the second pressure is preferably 50 MPa or more, more preferably 80 MPa or more, and most preferably 100 MPa or more.
  • the second heating time is preferably 0.1 hours or more and 10 hours or less, more preferably 1 hour or more and 7 hours or less, and even more preferably 3 hours or more and 5 hours or less.
  • the first heating time and the second heating time are preferably the first heating time ⁇ the second heating time.
  • the second temperature increase rate is preferably 200°C/h or more and 1000°C/h or less, more preferably 300°C/h or more and 800°C/h or less, and 400°C/h or more and 600°C/h or less. It is more preferable that The temperature increase rate is an average temperature increase rate from a predetermined temperature to a predetermined temperature.
  • the second temperature increase rate is an average temperature increase rate from room temperature to the second heating temperature.
  • the second temperature reduction rate is preferably 800°C/h or more, more preferably 800°C/h or more and 10,000°C/h or less, and even more preferably 1,500°C/h or more and 5,000°C/h or less.
  • the second temperature decreasing rate refers to the temperature decreasing rate from the second heating temperature to 800° C.
  • the temperature decreasing rate from 800° C. to room temperature may be, for example, 300° C./h or more and 1500° C./h or less.
  • the temperature decreasing rate is an average temperature decreasing rate from a predetermined temperature to a predetermined temperature.
  • the second temperature decreasing rate is an average temperature decreasing rate from the second heating temperature to 800°C.
  • the temperature decreasing rate from 800°C to room temperature is the average temperature decreasing rate from 800°C to room temperature.
  • the primary sintered body can be appropriately sintered and the mechanical properties of the sintered body can be appropriately improved.
  • the second cooling rate is set to 800° C./h or more, compressive stress can be applied to the surface of the primary sintered body, thereby suppressing cracking during cooling.
  • the temperature decreasing rate is as high as 800° C./h or more, the manufacturing process can be shortened.
  • the silicon nitride molded body is subjected to two stages of heat treatment, that is, heat treatment under the first condition and heat treatment under the second condition.
  • Heat treatment under the third condition may be performed between the heat treatment under the second condition and the heat treatment under the second condition. That is, in this case, the silicon nitride molded body heat-treated under the first condition is heat-treated under the third condition, and the silicon nitride molded body heat-treated under the third condition is heat-treated under the second condition to obtain silicon nitride sintered body 1.
  • heat treatment may also be performed under other conditions.
  • the heat treatment under the third condition is heat treatment under a higher pressure environment than the heat treatment under the first condition, and is heat treatment under a lower pressure environment than the heat treatment under the second condition.
  • the temperature at which the primary sintered body (the silicon nitride molded body heat-treated under the first condition) is heated is the third heating temperature
  • the pressure applied to the primary sintered body is the third pressure
  • the third conditions, that is, the third heating temperature, the third pressure, and the third heating time may be set as appropriate, and may be in the following ranges, for example.
  • the third heating temperature is preferably 1650°C or more and 1900°C or less, more preferably 1680°C or more and 1850°C or less, and even more preferably 1700°C or more and 1800°C or less.
  • the third pressure is higher than the first pressure and lower than the second pressure.
  • the third pressure is preferably 0.5 MPa or more and 20 MPa or less, more preferably 0.6 MPa or more and 15 MPa or less, and even more preferably 0.7 MPa or more and 10 MPa or less.
  • the third heating time is preferably 0.1 hours or more and 10 hours or less, more preferably 1 hour or more and 7 hours or less, and even more preferably 3 hours or more and 5 hours or less.
  • the first condition in the case where the heat treatment is not performed in three stages is as follows.
  • the first heating temperature is more preferably 1700°C or more and 1750°C or less
  • the first pressure is preferably 0.1 MPa or more and 1 MPa or less
  • the first heating time is 10 The duration is preferably at least 20 hours.
  • the first condition in the case of performing heat treatment in three stages is as follows.
  • the first heating temperature is more preferably 1650°C or more and 1750°C or less
  • the first pressure is preferably 0.1 MPa or more and 1 MPa or less
  • the first heating time is 5 The duration is preferably at least 10 hours.
  • the silicon nitride sintered body 1 according to the first aspect of the present disclosure has a total content of Si and N of 90 wt% or more with respect to the entire silicon nitride sintered body 1, and Mg
  • the content of Al is 0.45 wt% or more and 1.20 wt% or less with respect to the whole silicon nitride sintered body 1, and the content of Al is 0.45 wt% or more with respect to the whole silicon nitride sintered body 1.
  • the content of rare earth elements is 1000 ppm or less by weight relative to the entire silicon nitride sintered body 1, the bending strength is 900 MPa or more, and the fracture toughness value Kc is 6.5 MPa ⁇ m 1/2 or more. It can be seen that the silicon nitride sintered body 1 according to the present disclosure has a rare earth element content of 1000 ppm or less, and is made with a low rare earth element content. Furthermore, if the amount of rare earth elements is small, proper sintering may not be possible and mechanical properties may deteriorate.
  • the silicon nitride sintered body 1 of the present disclosure has Al and Mg contents within the above ranges, and has bending strength and fracture toughness values within the above ranges, so even if the rare earth elements are small, the silicon nitride sintered body 1 is mechanically The characteristics become better.
  • the silicon nitride sintered body 1 according to the second aspect of the present disclosure is the silicon nitride sintered body 1 according to the first aspect, in which the Ti content is 0 with respect to the entire silicon nitride sintered body 1.
  • the content is preferably .02 wt% or more and 3.5 wt% or less. By setting the Ti content within this range, mechanical properties can be further improved.
  • the silicon nitride sintered body 1 according to the third aspect of the present disclosure is the silicon nitride sintered body 1 according to the first aspect or the second aspect, in which the content of C is throughout the silicon nitride sintered body 1.
  • the weight ratio is 3500 ppm or less.
  • the silicon nitride sintered body 1 according to the fourth aspect of the present disclosure is the silicon nitride sintered body 1 according to any one of the first to third aspects, and is used as a raw ball for a bearing ball.
  • the silicon nitride sintered body 1 can be suitably applied to bearing balls.
  • the silicon nitride sintered body 1 according to the fifth aspect of the present disclosure is the silicon nitride sintered body 1 according to the fourth aspect, and is used as a bearing ball for a bearing of wind power generation equipment.
  • the silicon nitride sintered body 1 can be suitably applied to bearing balls for bearings of wind power generation equipment.
  • a method for producing a silicon nitride sintered body includes the steps of producing a silicon nitride molded body containing silicon nitride, a raw material containing Mg, and a raw material containing Al; and firing to produce a silicon nitride sintered body 1.
  • the silicon nitride sintered body 1 to be manufactured has a total content of Si and N of 90 wt% or more based on the entire silicon nitride sintered body 1, and a Mg content of 90 wt% or more based on the entire silicon nitride sintered body 1.
  • the content of Al is 0.80 wt% or more and 3.70 wt% or less with respect to the entire silicon nitride sintered body 1
  • the content of the rare earth element is 1000 ppm or less by weight relative to the entire silicon nitride sintered body 1
  • the bending strength is 900 MPa or more
  • the fracture toughness value Kc is 6.5 MPa m 1/2 or more.
  • a method for manufacturing a silicon nitride sintered body according to a seventh aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to the sixth aspect, in which the step of producing a silicon nitride molded body uses a gel casting method. , it is preferred to produce a silicon nitride compact. By molding using the gel casting method, better mechanical properties can be achieved.
  • a method for manufacturing a silicon nitride sintered body according to an eighth aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to the sixth aspect or the seventh aspect, in which the step of producing a silicon nitride molded body includes: It is preferable to use at least one of MgO and MgAl 2 O 4 as the raw material containing Mg. By using such raw materials, a silicon nitride sintered body with good mechanical properties can be appropriately manufactured.
  • a method for manufacturing a silicon nitride sintered body according to a ninth aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to any one of the sixth to eighth aspects, comprising the step of producing a silicon nitride molded body.
  • a method for manufacturing a silicon nitride sintered body according to a tenth aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to any one of the sixth to ninth aspects, comprising the step of producing a silicon nitride molded body.
  • a method for manufacturing a silicon nitride sintered body according to an eleventh aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to any one of the sixth to tenth aspects, comprising a step of producing a silicon nitride molded body.
  • a raw material containing C is contained in a silicon nitride molded body, and impurities contained in the resin or silicon nitride are used as the raw material containing C.
  • a method for manufacturing a silicon nitride sintered body according to a twelfth aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to any one of the sixth to eleventh aspects, comprising the step of producing a silicon nitride molded body.
  • the silicon nitride molded body is made into a spherical shape.
  • a method for manufacturing a silicon nitride sintered body according to a thirteenth aspect of the present disclosure is a method for manufacturing a silicon nitride sintered body according to any one of the sixth to twelfth aspects, which comprises manufacturing a silicon nitride sintered body 1.
  • the step includes heat-treating the silicon nitride molded body under a first condition, and heat-treating the silicon nitride molded body heat-treated under the first condition under a second condition having a higher pressure than the first condition. .
  • the first condition is that the heating temperature of the silicon nitride molded body is 1600° C.
  • the pressure applied to the silicon nitride molded body is 0.1 MPa or more and 1 MPa or less, and it is preferable that the heating temperature is in an inert gas atmosphere.
  • the second condition is that the heating temperature of the silicon nitride molded body is 1700° C. or more, the pressure applied to the silicon nitride molded body is 50 MPa or more and 200 MPa or less, and it is preferable that the heating temperature is in an inert gas atmosphere.
  • Table 1 is a table showing the sintered bodies of each example.
  • Example 1 In Example 1, silicon nitride (manufactured by Denka: SN-9FWS), spinel powder and TiO 2 powder as sintering aids, ion exchange water as a solvent, and tetramethylammonium hydroxide as a dispersant, The mixture was put into a bead mill and mixed and pulverized for 1.5 hours to produce a slurry. The ratio of the amount of spinel powder added to silicon nitride was 3.6 mol%, and the ratio of the amount of TiO 2 powder added to silicon nitride was 1.0 mol%.
  • a water-soluble epoxy resin manufactured by Nagase ChemteX: EX614B, EX512
  • a resin is added and mixed to a part of the slurry to produce a first raw material slurry, and another part of the slurry is mixed with a water-soluble epoxy resin as a resin.
  • the first silicon nitride slurry and the second silicon nitride slurry are depressurized and degassed in separate tanks, and while being stirred in the tanks, they are simultaneously sent to a mixing mixer and mixed to form a raw material slurry. and supplied to a mold connected to the mixer outlet. Then, the mold filled with the raw material slurry (a mixture of the first raw material slurry and the second raw material slurry) was held at 50° C. for 5 hours to cure the raw material slurry and obtain a cured body. Then, the cured product was removed from the mold, humidified and dried at 30°C for 4 days, and then dried with hot air at 50°C to obtain a dry molded product.
  • the raw material slurry a mixture of the first raw material slurry and the second raw material slurry
  • the dried molded body was then heated at 600° C. for 3 hours to degrease it to obtain a silicon nitride molded body.
  • the obtained silicon nitride molded body was heat treated under the first conditions and then heat treated under the second conditions to obtain a silicon nitride sintered body.
  • the heating temperature (first heating temperature) was 1650° C.
  • the holding time (first holding time) was 15 h
  • the pressure (first pressure) was 0.1 MPa.
  • the heating temperature (second heating temperature) was 1750°C
  • the holding time (second holding time) was 5 hours
  • the pressure (second pressure) was 190 MPa
  • the cooling rate (second cooling rate) was 600°C/ It was set as h.
  • the obtained silicon nitride sintered body is subjected to the method described in this embodiment to determine the total content (wt%) of Si and N with respect to the whole silicon nitride sintered body, and the total content (wt%) of Si and N with respect to the whole silicon nitride sintered body.
  • the content of rare earth elements (ppm by weight) relative to the entire body and the content of C (ppm by weight) relative to the entire silicon nitride sintered body were measured.
  • the fracture toughness value Kc (MPa ⁇ m 1/2 ), bending strength (MPa), and relative density of the obtained silicon nitride sintered body were measured by the method described in this embodiment. . The results of each measurement are shown in Table 1.
  • Example 2 to Example 13 silicon nitride sintered bodies were obtained in the same manner as in Example 1, except that the contents of spinel powder and TiO 2 powder were as shown in Table 1. Table 1 shows the measurement results of the obtained silicon nitride sintered body.
  • Example 1 passed the test, indicating that the rare earth element content was low and the mechanical properties were good. Further, as shown in Example 11 and Examples 1 to 10, it can be seen that the inclusion of Ti increases the Weibull coefficient, which is more preferable. On the other hand, Examples 12 and 13, which are comparative examples, failed, indicating that the mechanical properties could not be improved. In Example 13, many snowflakes were observed over the entire cross section, and their width was also larger than 600 ⁇ m.
  • the embodiment of the present invention has been described above, the embodiment is not limited by the content of this embodiment. Furthermore, the above-mentioned components include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those that are in a so-called equivalent range. Furthermore, the aforementioned components can be combined as appropriate. Furthermore, various omissions, substitutions, or modifications of the constituent elements can be made without departing from the gist of the embodiments described above.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Products (AREA)
PCT/JP2023/030121 2022-08-24 2023-08-22 窒化ケイ素焼結体及び窒化ケイ素焼結体の製造方法 WO2024043230A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024542823A JPWO2024043230A1 (enrdf_load_stackoverflow) 2022-08-24 2023-08-22

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-133456 2022-08-24
JP2022133456 2022-08-24

Publications (1)

Publication Number Publication Date
WO2024043230A1 true WO2024043230A1 (ja) 2024-02-29

Family

ID=90013426

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/030121 WO2024043230A1 (ja) 2022-08-24 2023-08-22 窒化ケイ素焼結体及び窒化ケイ素焼結体の製造方法

Country Status (2)

Country Link
JP (1) JPWO2024043230A1 (enrdf_load_stackoverflow)
WO (1) WO2024043230A1 (enrdf_load_stackoverflow)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05294730A (ja) * 1992-04-16 1993-11-09 Toshiba Corp 窒化けい素セラミックス焼結体
JPH07118070A (ja) * 1993-10-25 1995-05-09 Toshiba Corp 窒化ケイ素系セラミックス焼結体
JPH07206526A (ja) * 1994-01-10 1995-08-08 Toyota Motor Corp 窒化珪素焼結体の製造方法
WO2003010113A1 (en) * 2001-07-24 2003-02-06 Kabushiki Kaisha Toshiba Wear-resistant silicon nitride member and method for manufacture thereof
WO2021225158A1 (ja) * 2020-05-07 2021-11-11 Ａｇｃ株式会社 セラミックス焼結体の製造方法及びセラミックス焼結体
WO2022163730A1 (ja) * 2021-01-27 2022-08-04 Ａｇｃ株式会社 窒化ケイ素焼結体および窒化ケイ素焼結体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05294730A (ja) * 1992-04-16 1993-11-09 Toshiba Corp 窒化けい素セラミックス焼結体
JPH07118070A (ja) * 1993-10-25 1995-05-09 Toshiba Corp 窒化ケイ素系セラミックス焼結体
JPH07206526A (ja) * 1994-01-10 1995-08-08 Toyota Motor Corp 窒化珪素焼結体の製造方法
WO2003010113A1 (en) * 2001-07-24 2003-02-06 Kabushiki Kaisha Toshiba Wear-resistant silicon nitride member and method for manufacture thereof
WO2021225158A1 (ja) * 2020-05-07 2021-11-11 Ａｇｃ株式会社 セラミックス焼結体の製造方法及びセラミックス焼結体
WO2022163730A1 (ja) * 2021-01-27 2022-08-04 Ａｇｃ株式会社 窒化ケイ素焼結体および窒化ケイ素焼結体の製造方法

Also Published As

Publication number Publication date
JPWO2024043230A1 (enrdf_load_stackoverflow) 2024-02-29

Similar Documents

Publication Publication Date Title
EP4148031A1 (en) Method for producing ceramic sintered body, and ceramic sintered body
CN102482162B (zh) 氧化锆烧结体和氧化锆烧结体的烧结用混合体、烧结前成形体以及烧结前假烧体
JP7062229B2 (ja) 板状の窒化ケイ素質焼結体およびその製造方法
KR20150114616A (ko) 블랙 알루미나의 제조방법
US11524924B2 (en) SiC composite and method for manufacturing the same
CN110540429B (zh) 一种氮化铝烧结体及应用
KR20220062050A (ko) 지르코니아 세라믹, 지르코니아 세라믹을 제조하는 방법, 및 그의 적용 및 조성물
JP2013256397A (ja) 転動体及びその製造方法
WO2024043230A1 (ja) 窒化ケイ素焼結体及び窒化ケイ素焼結体の製造方法
US5401450A (en) β-silicon nitride sintered body and method of producing same
JP6720053B2 (ja) 窒化ケイ素焼結体の製造方法
WO2019059641A2 (ko) 질화규소 소결체 제조를 위한 테이프 캐스팅용 슬러리 조성물
WO2024019143A1 (ja) 窒化ケイ素焼結体及び窒化ケイ素焼結体の製造方法
JP4859267B2 (ja) 窒化アルミニウム焼結体とその製造方法
WO2022163730A1 (ja) 窒化ケイ素焼結体および窒化ケイ素焼結体の製造方法
JP2006327924A (ja) セラミック製刃物およびその製造方法
JP5945382B2 (ja) 窒化珪素質焼結体および耐摩耗部材
JP5312523B2 (ja) セラミック製刃物およびその製造方法
JP7728692B2 (ja) Ｙａｇ質焼結体、および半導体製造装置用部材
KR102702952B1 (ko) 가공이 용이한 수용성 바인더를 이용한 세라믹 소재의 제조방법 및 이에 따라 제조된 세라믹 물품
JP7579432B2 (ja) 窒化アルミニウム焼結体、回路基板、並びに、積層基板
JPH10279365A (ja) 緻密質窒化珪素焼結体
CN112030028A (zh) 氧化铝基金属复合陶瓷及制备方法、氧化铝基金属复合陶瓷骨植入假体及应用
WO2020189428A1 (ja) 酸化タングステンスパッタリングターゲット
Yeung et al. Design and fabrication of anisotropic SiO2 gyroid bioscaffolds with tunable properties

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23857339

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024542823

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23857339

Country of ref document: EP

Kind code of ref document: A1