WO2022075346A1 - ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法 - Google Patents

ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法 Download PDF

Info

Publication number
WO2022075346A1
WO2022075346A1 PCT/JP2021/036911 JP2021036911W WO2022075346A1 WO 2022075346 A1 WO2022075346 A1 WO 2022075346A1 JP 2021036911 W JP2021036911 W JP 2021036911W WO 2022075346 A1 WO2022075346 A1 WO 2022075346A1
Authority
WO
WIPO (PCT)
Prior art keywords
less
mol
zirconia
zirconia powder
sintered body
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2021/036911
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
優行 高井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daiichi Kigenso Kagaku Kogyo Co Ltd
Original Assignee
Daiichi Kigenso Kagaku Kogyo Co Ltd
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=81125996&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2022075346(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Daiichi Kigenso Kagaku Kogyo Co Ltd filed Critical Daiichi Kigenso Kagaku Kogyo Co Ltd
Priority to JP2022523220A priority Critical patent/JP7195481B2/ja
Priority to EP21877645.8A priority patent/EP4039648B1/en
Priority to CN202180006966.4A priority patent/CN114787085B/zh
Priority to US17/755,491 priority patent/US12612338B2/en
Publication of WO2022075346A1 publication Critical patent/WO2022075346A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the present invention relates to a zirconia powder, a zirconia sintered body, and a method for producing a zirconia sintered body.
  • Zirconia is used for various purposes by utilizing its mechanical strength, translucency, refractive index, etc.
  • high strength and resistance to water heat deterioration are naturally required, and further high toughness is required.
  • Patent Document 1 describes ZrO 2 powder having a particle size of 0.1 to 2.0 ⁇ m containing 2 to 4 mol% of Y 2 O 3 as a stabilizer and 2 to 4 mol% of Y 2 O 3 as a stabilizer.
  • ZrO2 fine powder having a particle size of 0.05 ⁇ m or less is mixed in an amount of 2 to 10% by weight to obtain a mixed powder, then this mixed powder is granulated, and the obtained granulated powder is molded, and then obtained.
  • Disclosed is a method for producing a zirconia sintered body, in which the molded product is pre-sintered at normal pressure to a relative density of 96 to 98%, and then hot hydrostatic pressure treatment is performed at a temperature of 1480 ° C.
  • Patent Document 1 attempts to obtain a highly tough zirconia sintered body by utilizing a microcrack strengthening mechanism. Specifically, relatively large cracks are introduced into the sintered body in the form of closed pores, and the closed pores are subjected to hot hydrostatic pressure (HIP) treatment to make the size of the fracture source smaller than the original size. , An attempt is made to obtain a highly tough zirconia sintered body by forming a defect that expresses a microcrack strengthening mechanism (see paragraph [0007]).
  • HIP hot hydrostatic pressure
  • Patent Document 1 In the manufacturing method of Patent Document 1, there is a problem that controlling the particle diameters of the two kinds of powders is complicated and difficult to control. Further, HIP sintering has a problem of low versatility.
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a zirconia powder capable of easily obtaining a highly tough zirconia sintered body. Another object of the present invention is to provide a highly tough zirconia sintered body. Another object of the present invention is to provide a method for producing the zirconia sintered body.
  • the present inventor surprisingly cracks the obtained zirconia sintered body by setting the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body to 0.2% or more and 5% or less. It has been found that while the occurrence is extremely unlikely to occur, microcracks can be easily formed and the toughness improving effect of the microcrack strengthening mechanism can be obtained. Then, in order to keep the monoclinic phase ratio within the range of 0.2% or more and 5% or less, it was found that it is preferable to include the content of the stabilizer within a specific range which is smaller than the conventional one. .. Since the microcrack strengthening mechanism is a conventionally known mechanism, detailed description thereof will be omitted here.
  • the present inventor has found that it is difficult to suitably control the monoclinic phase ratio in the zirconia sintered body only by the amount of the stabilizer.
  • the pore distribution is set within a specific range. It has been found that the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder can be easily set to 0.2% or more and 5% or less.
  • the present inventor has found that it is possible to easily obtain a highly tough zirconia sintered body by adopting the following configuration, and has completed the present invention.
  • the zirconia powder according to the present invention is Contains stabilizers
  • the stabilizer is CaO , Y2O3 , Er2O3 , or Yb2O3 .
  • the stabilizer is Y 2 O 3
  • the content of the Y 2 O 3 in the entire zirconia powder is 1.4 mol% or more and less than 2.0 mol%.
  • the stabilizer is Er 2 O 3
  • the content of Er 2 O 3 in the entire zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the stabilizer is Yb 2 O 3
  • the content of Yb 2 O 3 in the entire zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the content of the CaO in the entire zirconia powder is 3.5 mol% or more and 4.5 mol% or less.
  • the peak top diameter of the pore volume distribution is 20 nm or more and 120 nm or less, and the pore volume is 0.2 ml / g or more and less than 0.5 ml / g. It is characterized in that the pore distribution width is 30 nm or more and 170 nm or less.
  • the zirconia powder when the stabilizer is Y 2 O 3 , the zirconia powder is baked when the Y 2 O 3 is contained in the range of 1.4 mol% or more and less than 2.0 mol%.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by binding is likely to be 0.2% or more and 5% or less.
  • the stabilizer when the stabilizer is Er 2 O 3 , when the Stabilizer is contained in the range of 1.4 mol% or more and 1.8 mol% or less, the zirconia baking obtained by sintering the zirconia powder is obtained.
  • the monoclinic phase ratio contained in the crystal phase of the body is likely to be 0.2% or more and 5% or less.
  • the stabilizer when the stabilizer is Yb 2 O 3 , when the Yb 2 O 3 is contained in the range of 1.4 mol% or more and 1.8 mol% or less, the zirconia baking obtained by sintering the zirconia powder is obtained.
  • the monoclinic phase ratio contained in the crystal phase of the body is likely to be 0.2% or more and 5% or less.
  • the stabilizer when the stabilizer is CaO, when the CaO is contained in the range of 3.5 mol% or more and 4.5 mol% or less, the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is obtained. It is easy to set the contained monoclinic phase ratio to 0.2% or more and 5% or less.
  • the peak top diameter of the pore volume distribution is 20 nm or more and 120 nm or less in the range of 10 nm or more and 200 nm or less in the pore distribution based on the mercury intrusion method, and the pore volume is 0. .Since it is 2 ml / g or more and less than 0.5 ml / g and the pore distribution width is 30 nm or more and 170 nm or less, monoclinic crystals contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder. It is easy to set the phase ratio to 0.2% or more and 5% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is 0.2% or more and 5% or less.
  • the present inventor presumes that low-temperature sintering is possible by controlling the physical characteristics of the powder (pore volume / pore distribution width). That is, under the sintering conditions at a high temperature exceeding 1350 ° C., when the stabilizer is reduced in order to obtain high toughness, the phase transition from the square crystal phase to the monoclinic crystal phase at the time of temperature reduction for sintering is performed.
  • the peak top diameter, the pore volume, and the pore distribution width are controlled within the numerical range, the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is 0.2% or more 5 It is clear from the comparison of Examples and Comparative Examples that it is easy to make it less than%.
  • the zirconia powder according to the above constitution it is not necessary to mix the two kinds of powders, and sintering by HIP is not essential, so that a highly tough zirconia sintered body can be easily obtained.
  • the specific surface area is 10 m 2 / g or more and 50 m 2 / g or less.
  • the particle size D 50 is preferably 0.1 ⁇ m or more and 0.7 ⁇ m or less.
  • the sinterability is excellent. Further, when the particle diameter D 50 is 0.1 ⁇ m or more and 0.7 ⁇ m or less, the sinterability is excellent.
  • the peak top diameter is 20 nm or more and 70 nm or less.
  • the pore distribution width is preferably 40 nm or more and 105 nm or less.
  • the peak top diameter is 20 nm or more and 70 nm or less and the pore distribution width is 40 nm or more and 105 nm or less
  • the monoclinic phase contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder It is easy to set the rate to 0.2% or more and 5% or less.
  • the content of Y 2 O 3 is preferably 1.4 mol% or more and 1.9 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is determined. It is easier to make it 0.2% or more and 5% or less.
  • the content of Y 2 O 3 is preferably 1.4 mol% or more and less than 1.8 mol%.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is determined. Further, it is easy to make it 0.2% or more and 5% or less.
  • the specific surface area is preferably 20 m 2 / g or more and 40 m 2 / g or less.
  • the sinterability is more excellent.
  • the particle diameter D 50 is 0.1 ⁇ m or more and less than 0.3 ⁇ m.
  • the particle size D 50 is 0.1 ⁇ m or more and less than 0.3 ⁇ m, the sinterability is more excellent.
  • one or more selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or less may be contained in an amount of 0.005% by mass or more and 2% by mass or less.
  • alumina When at least one selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or lower is contained within the above numerical range, it functions as a sintering aid and is excellent in low-temperature sinterability.
  • alumina functions as a sintering aid by removing pores by inhibiting the grain growth of zirconia by being present at the grain boundaries of the primary particles and the secondary particles.
  • the metal oxide having a Tanman temperature of 1200 ° C. or lower absolute temperature: 1473.15 K or lower
  • Td Tanman temperature expressed in absolute temperature
  • Tm melting point of a solid expressed in absolute temperature
  • Td 0.33 Tm for metals
  • Td 0.757 Tm for oxides
  • covalent bond compounds 0.90Tm (these are called Tanman's law). Therefore, in the present specification, the "Tanman temperature” means a value according to this Tanman's law.
  • one or more selected from the group consisting of Fe, V, Er, Mn, Co, Tb, Zn, Cu, and Ti may be contained.
  • coloring can be preferably performed.
  • the zirconia sintered body according to the present invention is The monoclinic phase ratio contained in the crystal phase is 0.2% or more and 5% or less.
  • the crack length generated in the sintered body is 1 ⁇ m or more and 90 ⁇ m or less when the load is 50 kgf.
  • the three-point bending strength is 80 kg / mm 2 or more and 150 kg / mm 2 or less.
  • the zirconia sintered body according to the above configuration since the monoclinic phase ratio contained in the crystal phase is 0.2% or more and 5% or less, it is possible to develop the microcrack strengthening mechanism.
  • One of the features of the present invention is that the expression of the microcrack strengthening mechanism is controlled by the monoclinic phase ratio. Further, since the crack length is 1 ⁇ m or more and 90 ⁇ m or less, the toughness is excellent. Further, since the three-point bending strength is 80 kg / mm 2 or more and 150 kg / mm 2 or less, the strength is excellent.
  • the relative sintering density is preferably 98.5% or more.
  • the zirconia sintered body has higher strength.
  • the toughness value when the weight is 50 kgf in the toughness measurement by the IF method is preferably 10 MPa ⁇ m 0.5 or more and 40 MPa ⁇ m 0.5 or less.
  • the toughness value is 10 MPa / m 0.5 or more and 40 MPa / m 0.5 or less, it can be said that the toughness is sufficiently high.
  • a stabilizer is included and It is preferable that the stabilizer is at least one selected from the group consisting of CaO , Y2O3 , Er2O3 , and Yb2O3.
  • the stabilizer is at least one selected from the group consisting of CaO , Y2O3 , Er2O3 , and Yb2O3, monoclinic crystals contained in the crystal phase of the zirconia sintered body. It is easy to set the phase ratio to 0.2% or more and 5% or less.
  • the content of the Y 2 O 3 in the entire zirconia powder is 1.4 mol% or more and less than 2.0 mol%.
  • the content of Er 2 O 3 in the whole zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the content of Yb 2 O 3 in the whole zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the content of the CaO in the entire zirconia powder is preferably 3.5 mol% or more and 4.5 mol% or less.
  • the stabilizer When the stabilizer is only Y 2 O 3 , when the Y 2 O 3 is contained in the range of 1.4 mol% or more and less than 2.0 mol%, the uniclinic crystal phase contained in the crystal phase of the zirconia sintered body is contained. It is easy to set the crystal phase ratio to 0.2% or more and 5% or less. Similarly, when the stabilizer is only Er 2 O 3 , if the Er 2 O 3 is contained in the range of 1.4 mol% or more and 1.8 mol% or less, it is contained in the crystal phase of the zirconia sintered body. It is easy to set the monoclinic phase ratio to 0.2% or more and 5% or less.
  • the stabilizer when the stabilizer is only Yb 2 O 3 , if the Yb 2 O 3 is contained in the range of 1.4 mol% or more and 1.8 mol% or less, it is contained in the crystal phase of the zirconia sintered body. It is easy to set the monoclinic phase ratio to 0.2% or more and 5% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is increased. It is easy to make it 0.2% or more and 5% or less.
  • one or more selected from the group consisting of Fe, V, Mn, Co, Zn, Cu, and Ti may be contained.
  • coloring can be preferably performed.
  • the surface monoclinic phase ratio after exposure to water heat conditions at 134 ° C. for 75 hours is 31% or less.
  • the resistance to hydrothermal deterioration is excellent when the surface monoclinic phase ratio is 31% or less after being exposed to hydrothermal conditions at 134 ° C. for 75 hours.
  • the method for producing a zirconia sintered body according to the present invention is as follows. Step X of molding the zirconia powder to obtain a molded body, and After the step X, it is characterized by having a step Y of sintering the molded product under the conditions of 1200 ° C. or higher and 1350 ° C. or lower and 1 hour or longer and 5 hours or shorter.
  • the zirconia powder contains CaO , Y2O3 , Er2O3 , or Yb2O3 as a stabilizer in a specific amount.
  • the zirconia powder is sintered in the range of 1200 ° C. or higher and 1350 ° C. or lower, and the uniclinic crystal phase contained in the crystal phase of the zirconia sintered body obtained is obtained.
  • the crystallization ratio can be controlled within the range of 0.2% or more and 5% or less. This is also clear from the examples.
  • a zirconia powder capable of easily obtaining a zirconia sintered body having high strength and high toughness. Further, it is possible to provide a zirconia sintered body having high strength and high toughness. Further, it is possible to provide a method for producing the zirconia sintered body.
  • zirconia zirconium oxide
  • hafnium an impurity metal compound including hafnium.
  • the expressions "contains” and “contains” include the concepts of “contains”, “contains”, “substantially consists” and “consists only”.
  • the zirconia powder according to this embodiment is Contains stabilizers
  • the stabilizer is CaO , Y2O3 , Er2O3 , or Yb2O3 .
  • the stabilizer is Y 2 O 3
  • the content of the Y 2 O 3 in the entire zirconia powder is 1.4 mol% or more and less than 2.0 mol%.
  • the stabilizer is Er 2 O 3
  • the content of Er 2 O 3 in the entire zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the stabilizer is Yb 2 O 3
  • the content of Yb 2 O 3 in the entire zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the content of the CaO in the entire zirconia powder is 3.5 mol% or more and 4.5 mol% or less.
  • the peak top diameter of the pore volume distribution is 20 nm or more and 120 nm or less, and the pore volume is 0.2 ml / g or more and less than 0.5 ml / g.
  • the pore distribution width is 30 nm or more and 170 nm or less.
  • the zirconia powder contains primary particles containing zirconia as a main component. All or part of the primary particles aggregate to form secondary particles. That is, the zirconia powder contains primary particles that are not aggregated and secondary particles in which the primary particles are aggregated. However, in the zirconia powder, the amount of primary particles that do not become secondary particles and exist in the state of non-aggregating primary particles is extremely small, for example, the entire primary particles (aggregating with non-aggregating primary particles). It is less than 1% by mass of the total of the primary particles that have become secondary particles. That is, the zirconia powder may contain a very small amount of non-aggregated primary particles, but most of them are composed of secondary particles.
  • the primary particles containing zirconia as a main component mean primary particles containing 70% by mass or more of zirconia.
  • the content of zirconia contained in the primary particles is preferably 74% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more.
  • the zirconia powder according to this embodiment contains zirconia as a main component. Specifically, as described above, the zirconia powder contains secondary particles in which primary particles are aggregated and a very small amount of non-aggregated primary particles.
  • the zirconia powder contains a stabilizer.
  • the stabilizer is contained in the primary particles in the form of solid solution or the like.
  • the stabilizer is CaO , Y2O3 , Er2O3 , or Yb2O3 .
  • the stabilizer varies depending on the application , but CaO , Y2O3, and Yb2O3 are more preferable from the viewpoint of cost, coloring, and the like. Further, the stabilizer is preferably CaO from the viewpoint of resistance to water heat deterioration.
  • the content of the Y 2 O 3 in the entire zirconia powder is 1.4 mol% or more and less than 2.0 mol%.
  • the content of Y2 O 3 is preferably 1.45 mol% or more , more preferably 1.5 mol% or more, still more preferably 1.55 mol% or more, particularly preferably 1.57 mol% or more, and particularly preferably 1. It is 6.6 mol% or more.
  • the content of Y 2 O 3 is preferably 1.9 mol% or less, more preferably less than 1.8 mol%, still more preferably 1.75 mol% or less, particularly preferably 1.7 mol% or less, and particularly preferably 1. It is .65 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is 0. . Easy to set to 2% or more and 5% or less.
  • the content of Er 2 O 3 in the entire zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the content of Er 2 O 3 is preferably 1.45 mol% or more, more preferably 1.5 mol% or more, still more preferably 1.55 mol% or more, particularly preferably 1.57 mol% or more, and particularly preferably 1. It is 6.6 mol% or more.
  • the content of Er 2 O 3 is preferably 1.9 mol% or less, more preferably less than 1.8 mol%, still more preferably 1.75 mol% or less, particularly preferably 1.7 mol% or less, and particularly preferably 1. It is .65 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is 0. . Easy to set to 2% or more and 5% or less.
  • the content of Yb 2 O 3 in the entire zirconia powder is 1.4 mol% or more and 1.8 mol% or less.
  • the content of Yb 2 O 3 is preferably 1.45 mol% or more, more preferably 1.5 mol% or more, still more preferably mol% or more, particularly preferably 1.53 mol% or more, and particularly preferably 1.57 mol. % Or more.
  • the content of Yb 2 O 3 is preferably 1.75 mol% or less, more preferably 1.7 mol% or less, still more preferably 1.65 mol% or less, and particularly preferably 1.63 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is 0. . Easy to set to 2% or more and 5% or less.
  • the content of CaO in the entire zirconia powder is 3.5 mol% or more and 4.5 mol% or less.
  • the CaO content is preferably 3.6 mol% or more, more preferably 3.7 mol% or more, still more preferably 3.8 mol% or more, particularly preferably 3.9 mol% or more, and particularly preferably 3.95 mol%. That is all.
  • the CaO content is preferably 4.4 mol% or less, more preferably 4.3 mol% or less, still more preferably 4.2 mol% or less, particularly preferably 4.1 mol% or less, and particularly preferably 4.05 mol%. It is as follows.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body obtained by sintering the zirconia powder is 0.2%. It is easy to make it 5% or less.
  • Peak top diameter of primary particle gap The zirconia powder has a peak top diameter of 20 nm or more and 120 nm or less in the range of 10 nm or more and 200 nm or less in the pore distribution based on the mercury intrusion method.
  • the peak top diameter is preferably 25 nm or more, more preferably 30 nm, still more preferably 32 nm, and particularly preferably 35 nm or more.
  • the peak top diameter is preferably 70 nm or less, more preferably 60 nm or less, still more preferably 57 nm or less, and particularly preferably 54 nm or less.
  • the peak top diameter of the pore volume distribution is 20 nm or more and 120 nm or less” in the present specification refers to the pore distribution. It means that all peak top diameters in the range of 10 nm or more and 200 nm or less are within the range of 20 nm or more and 120 nm or less.
  • the zirconia powder has a pore distribution width of 30 nm or more and 170 nm or less in the range of 10 nm or more and 200 nm or less in the pore distribution based on the mercury intrusion method.
  • the pore distribution width is preferably 40 nm or more, more preferably 46 nm or more, still more preferably 50 nm or more, and particularly preferably 55 nm or more.
  • the pore distribution width is preferably 105 nm or less, more preferably 95 nm or less, still more preferably 90 nm or less, particularly preferably 85 nm or less, and particularly preferably 80 nm or less.
  • the pore distribution width refers to the width of the peak at which the log differential pore volume (for example, see FIG. 2) is 0.1 ml / g or more.
  • the pore distribution width is 30 nm or more and 170 nm or less” in the present specification means that the horizontal axis is the pore diameter and the vertical axis is the vertical axis.
  • the zirconia powder has a pore volume of 0.2 ml / g or more and less than 0.5 ml / g in the range of 10 nm or more and 200 nm or less in the pore distribution based on the mercury intrusion method.
  • the total pore capacity is preferably 0.22 cm 3 / g or more, more preferably 0.25 cm 3 / g or more, still more preferably 0.3 cm 3 / g or more, and particularly preferably 0.35 cm 3 / g or more. Particularly preferably, it is 0.4 cm 3 / g or more.
  • the total pore capacity is preferably 0.48 cm 3 / g or less, more preferably 0.46 cm 3 / g or less, and particularly preferably 0.44 cm 3 / g or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is 0.2% or more and 5% or less.
  • the present inventor presumes that low-temperature sintering is possible by controlling the physical characteristics of the powder (pore volume / pore distribution width). That is, under the sintering conditions at a high temperature exceeding 1350 ° C., when the stabilizer is reduced in order to obtain high toughness, the phase transition from the square crystal phase to the monoclinic crystal phase at the time of temperature reduction for sintering is performed.
  • the peak top diameter, the pore volume, and the pore distribution width are controlled within the numerical range, the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is 0.2% or more 5 It is clear from the comparison of Examples and Comparative Examples that it is easy to make it less than%.
  • the peak top diameter, the pore distribution width, and the pore volume refer to values obtained by the method described in Examples.
  • the zirconia powder tends to have a monoclinic phase ratio of 0.2% or more and 5% or less in the crystal phase of the zirconia sintered body, it is extremely unlikely that cracks will occur in the obtained zirconia sintered body. Microcracks can be easily formed, and the effect of improving toughness can be obtained by the microcrack strengthening mechanism.
  • the zirconia powder does not need to be a mixture of the two powders, and sintering by HIP is not essential. From the above, according to the zirconia powder, it is possible to easily obtain a highly tough zirconia sintered body.
  • the particle size D 50 of the zirconia powder is preferably 0.1 ⁇ m or more and 0.7 ⁇ m or less.
  • the particle size D 50 is preferably 0.12 ⁇ m or more, more preferably 0.14 ⁇ m or more, still more preferably 0.16 ⁇ m or more, and particularly preferably 0.2 ⁇ m or more.
  • the particle size D 50 is preferably 0.62 ⁇ m or less, more preferably 0.55 ⁇ m or less, still more preferably 0.48 ⁇ m or less, particularly preferably 0.4 ⁇ m or less, particularly preferably 0.3 ⁇ m or less, and particularly preferably. Is less than 0.3 ⁇ m.
  • the particle diameter D 50 refers to a value obtained by the method described in Examples.
  • the particle diameter D 50 may include not only secondary particles but also non-aggregated primary particles when measured, but the amount of non-aggregated primary particles that can be contained in the zirconia powder is very small. It is a very small amount. Therefore, the particle diameter D 50 may be regarded as representing the particle diameter D 50 of the secondary particles, that is, the average particle diameter of the secondary particles. When the particle size D 50 is 0.1 ⁇ m or more and 0.7 ⁇ m or less, the sinterability is excellent.
  • the specific surface area of the zirconia powder is preferably 10 m 2 / g or more and 50 m 2 / g or less.
  • the specific surface area is preferably 20 m 2 / g or more, more preferably 22 m 2 / g or more, further preferably 24 m 2 / g or more, particularly preferably 26 m 2 / g or more, and particularly preferably 28 m 2 / g or more. Is.
  • the specific surface area is preferably 40 m 2 / g or less, more preferably 38 m 2 / g or less, still more preferably 36 m 2 / g or less, particularly preferably 34 m 2 / g or less, and particularly preferably 32 m 2 / g or less. ..
  • the specific surface area refers to a value obtained by the method described in Examples. When the specific surface area is 10 m 2 / g or more and 50 m 2 / g or less, the sinterability is excellent.
  • the zirconia powder may contain an additive.
  • additive refers to an additive added to zirconia particles as a mixture.
  • the additive include sintering aids, colorants and the like.
  • the additive include those that function only as a sintering aid, those that function only as a colorant, and those that function as a sintering aid and also function as a colorant.
  • the sintering aid and the colorant will be described.
  • the zirconia powder may contain 0.005% by mass or more and 2% by mass or less of one or more selected from the group consisting of alumina and metal oxides having a tanman temperature of 1200 ° C. or less.
  • the metal oxide having a Tanman temperature of 1200 ° C. or lower include oxides of iron, germanium, cobalt, chromium and zinc.
  • the content of one or more selected from the group consisting of alumina and metal oxides having a tanman temperature of 1200 ° C. or lower is more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, and particularly preferably. Is 0.05% by mass or more, particularly preferably 0.07% by mass or more.
  • the content of one or more selected from the group consisting of alumina and metal oxides having a tanman temperature of 1200 ° C. or lower is more preferably 1.5% by mass or less, still more preferably 1.2% by mass or less, and particularly preferably. Is 0.5% by mass or less, particularly preferably 0.25% by mass or less.
  • at least one selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or lower is contained within the above numerical range, it functions as a sintering aid and is excellent in low-temperature sinterability. Further, since the zirconia powder contains alumina, it is easy to suppress a decrease in toughness of the zirconia sintered body.
  • the form of alumina is not particularly limited, but alumina powder is preferable from the viewpoint of handleability (when mixed and dispersed in zirconia particles) at the time of preparation of zirconia powder and reduction of residual impurities.
  • the average particle size of the primary particles of alumina is not particularly limited, but is, for example, 0.02 to 0.4 ⁇ m, preferably 0.05 to 0.3 ⁇ m, and more preferably 0.07. It is ⁇ 0.2 ⁇ m.
  • the zirconia powder may contain a sintering aid, but may be configured not to contain a sintering aid.
  • the zirconia powder may contain less than 0.005% by mass of one or more selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or lower.
  • the content of one or more selected from the group consisting of alumina and metal oxides having a tanman temperature of 1200 ° C. or lower is less than 0.005% by mass, it means that the sintering aid is not contained.
  • the zirconia powder may contain sinterable ceramics, a thermosetting resin, or the like for the purpose of improving properties such as strength, in addition to alumina and metal oxides having a tanman temperature of 1200 ° C. or lower.
  • the zirconia powder may contain one or more selected from the group consisting of Fe, V, Er, Mn, Co, Tb, Zn, Cu and Ti.
  • a zirconia sintered body obtained by sintering the zirconia powder can be obtained. It can be preferably colored.
  • the form of the coloring element is not particularly limited, and can be added in the form of an oxide, chloride, or the like.
  • Specific examples of the colorant containing the coloring element include Fe 2 O 3 , V 2 O 5 , Er 2 O 3 , MnO 2 , CoO, Tb 4 O 7 , ZnO, CuO, and TIO 2 . Can be mentioned.
  • the colorant is preferably added as a mixture to the zirconia powder.
  • the content of the colorant is preferably 0.005% by mass or more and 1% by mass or less, preferably 0.05% by mass, when the whole zirconia powder is 100% by mass. More preferably 0.5% by mass or less.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • V 2 O 5 When V 2 O 5 is contained as the colorant, it is preferably 0.005% by mass or more and 0.5% by mass or less, and 0.01% by mass or more and 0.1% by mass, when the whole zirconia powder is 100% by mass. The following is more preferable.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 10% by mass or less, preferably 0.1% by mass, when the whole zirconia powder is 100% by mass. More preferably, it is 5% by mass or less.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • MnO 2 is contained as the colorant, it is preferably 0.005% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 1.1% by mass or less, when the whole zirconia powder is 100% by mass. ..
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 2% by mass or less, preferably 0.01% by mass or more, when the whole zirconia powder is 100% by mass. More preferably, it is 5% by mass or less.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 5% by mass or less, preferably 0.1% by mass, when the whole zirconia powder is 100% by mass. More preferably, it is 3% by mass or less.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 1% by mass or less, and 0.1% by mass or more and 0. More preferably, it is 5% by mass or less.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 1% by mass or less, and 0.05% by mass or more and 0. 6% by mass or less is more preferable.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 2% by mass or less, preferably 0.01% by mass or more 1 when the whole zirconia powder is 100% by mass. More preferably, it is 0.1% by mass or more, and further preferably 0.3% by mass or less.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the zirconia powder preferably has a relative molding density of 45 to 50% when molded at a molding pressure of 2 t / cm 2 .
  • the relative molding density is a value calculated by the following formula.
  • Relative molding density (%) (molding density / theoretical sintering density) x 100 ... (4)
  • the theoretical sintering density (assumed to be ⁇ 0 ) is a value calculated by the formula (2-1) described in the section "Method for measuring the relative sintering density of the zirconia sintered body" below.
  • the upper limit of the relative molding density is preferably 45.5% or more, more preferably 46% or more.
  • the lower limit is preferably 49.5% or less, more preferably 49% or less, further preferably 48.5% or less, and particularly preferably 48% or less.
  • the zirconia powder according to this embodiment has been described above.
  • the method for producing zirconia powder according to this embodiment is Step 1, in which the zirconium salt solution and the sulfate chloride solution are separately heated to 95 ° C. or higher and 100 ° C. or lower.
  • a reaction containing basic zirconium sulfate as a mixed solution by contacting the heated zirconium salt solution and the heated sulfate chloride solution so that the concentration of the mixed solution does not change from the start to the end of the contact.
  • Step 3 the basic zirconium sulfate-containing reaction solution obtained in Step 2 is aged at 95 ° C. or higher for 3 hours or longer.
  • Step 4 in which a stabilizer is added to the reaction solution containing basic zirconium sulfate after aging obtained in Step 3.
  • Step 5 to obtain a zirconium-containing hydroxide by adding an alkali to the basic zirconium sulfate-containing reaction solution obtained in step 4.
  • Step 6 to obtain zirconia powder by heat-treating the zirconium-containing hydroxide obtained in step 5.
  • the SO 4-2- / ZrO 2 weight ratio in the mixed solution is maintained in the range of 0.3 to 0.8 and the temperature of the mixed solution is maintained at 95 ° C. or higher from the start to the end of the contact. do.
  • each step will be described in detail.
  • step 1 the zirconium salt solution and the sulfate chloride solution, which are the starting materials, are separately heated to 95 ° C. or higher and 100 ° C. or lower.
  • the zirconium salt used to prepare the zirconium salt solution may be any one that supplies zirconium ions, and for example, zirconium oxynitrite, zirconium oxychloride, zirconium nitrate, or the like can be used. These can be used in one type or two or more types. Among these, zirconium oxychloride is preferable because it has high productivity on an industrial scale.
  • the solvent used to prepare the zirconium salt solution may be selected according to the type of the zirconium salt and the like. Usually, water (pure water, ion-exchanged water, the same applies hereinafter) is preferable.
  • the concentration of the zirconium salt solution is not particularly limited, but is generally preferably 5 to 250 g, more preferably 20 to 150 g, in terms of zirconium oxide (ZrO 2 ) with respect to 1000 g of the solvent. ..
  • the sulfate chloride agent may be any agent that reacts with zirconium ions to generate sulfate (that is, a reagent that causes sulfate chloride), and is, for example, sodium sulfate, potassium sulfate, ammonium sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, or di. Examples thereof include potassium sulfate, sodium disulfate, and sulfur trioxide.
  • the sulfate chloride agent may be in any form such as powder or solution, but a solution (particularly an aqueous solution) is preferable.
  • the solvent the same solvent as that used for preparing the zirconium salt solution can be used.
  • the acid concentration of the zirconium salt solution is preferably 0.1 to 2.0 N.
  • the acid concentration can be adjusted by using, for example, hydrochloric acid, nitric acid, sodium hydroxide or the like.
  • the concentration of the sulfate chloride agent (the sulfate chloride agent solution) is not particularly limited, but it is generally preferable that the concentration of the sulfate chloride agent is 5 to 250 g, particularly 20 to 150 g with respect to 1000 g of the solvent.
  • the material of the container for preparing the zirconium salt solution and the sulfate chloride solution is not particularly limited as long as it has a capacity to sufficiently stir the zirconium salt solution and the sulfate chloride solution, respectively. However, it is preferable to have equipment capable of appropriately heating so that the temperature of each solution does not fall below 95 ° C.
  • the heating temperature of the zirconium salt solution and the sulfate chloride solution may be 95 ° C. or higher and 100 ° C. or lower, preferably 97 ° C. or higher.
  • step 2 is carried out while the temperatures of the zirconium salt solution and the sulfate chloride solution are lower than 95 ° C., the zirconium salt solution and the sulfate chloride solution do not sufficiently react and the yield decreases.
  • Step 2 the heated zirconium salt solution and the heated sulfuric acid chloride solution are brought into contact with each other so that the concentration of the mixed solution does not change from the start to the end of the contact, so that the mixed solution is basic. Obtain a zirconium sulfate-containing reaction solution.
  • the SO 4-2- / ZrO 2 weight ratio in the mixed solution is maintained in the range of 0.3 to 0.8, and the temperature of the mixed solution is maintained at 95 ° C. or higher.
  • FIG. 1 is a schematic diagram for explaining a method for producing a zirconia powder according to the present embodiment.
  • the container 10 is connected to an upper end (left side in FIG. 1) of the T-shaped tube 20 via a valve 12.
  • the container 30 is connected to the upper other end (right side in FIG. 1) of the T-shaped tube 20 via a valve 32.
  • a zirconium solution heated to 95 ° C. or higher and 100 ° C. or lower is stored in the container 10.
  • a sulfuric acid chloride solution heated to 95 ° C. or higher and 100 ° C. or lower is stored in the container 30.
  • the zirconium solution and the sulfate chloride solution are brought into contact with each other by opening the valve 12 and the valve 32.
  • the mixed solution (reaction solution containing basic zirconium sulfate) obtained by contacting the mixture immediately flows into the aging container 40 from below the T-shaped tube 20.
  • the concentration of the reaction solution concentration of the reaction solution in the T-shaped tube 20
  • the change in the concentration of SO 4-2 / ZrO 2 from the start to the end of contact is suppressed, so that a uniform reactant can be obtained.
  • the SO 4-2- / ZrO 2 weight ratio in the mixed solution in step 2 is preferably in the range of 0.3 to 0.8, more preferably 0.4 to 0.7, still more preferably 0.45 to 0. It is .65.
  • step 2 in order to maintain the temperature of the mixed solution at 95 ° C. or higher, it is preferable to install a heater in a pipe (for example, a T-shaped tube 20) for supplying each solution.
  • a pipe for example, a T-shaped tube 20
  • a T-shaped tube having an upper end (left side in FIG. 1) having a tube diameter L1 of 10 mm, an upper multi-end (right side in FIG. 1) having a tube diameter L2 of 10 mm, and a lower tube diameter L3 of 15 mm.
  • the time (contact time) is preferably 30 seconds to 300 seconds, more preferably 60 seconds to 200 seconds, and further preferably 90 seconds to 150 seconds.
  • step 3 the basic zirconium sulfate-containing reaction solution obtained in step 2 is aged at 95 ° C. or higher for 3 hours or longer.
  • step 3 for example, the reaction solution containing basic zirconium sulfate that has flowed into the aging container 40 is aged at 95 ° C. or higher for 3 hours or longer while being stirred by the stirrer 42.
  • the upper limit of the aging time is not particularly limited, but is, for example, 7 hours or less.
  • the temperature (aging temperature) of the mixed solution (reaction solution containing basic zirconium sulfate) in step 3 is preferably 95 ° C. or higher, more preferably 97 ° C. or higher and 100 ° C. or lower.
  • the mixed solution contains basic zirconium sulfate as a main component and is a basic zirconium sulfate slurry.
  • step 4 a stabilizer is added to the reaction solution containing basic zirconium sulfate after aging obtained in step 3.
  • step 5 an alkali is added to the basic zirconium sulfate-containing reaction solution obtained in step 4 to carry out a neutralization reaction.
  • Neutralization produces zirconium-containing hydroxides.
  • the alkali is not limited, and examples thereof include caustic soda, sodium carbonate, ammonia, hydrazine ammonium hydrogencarbonate and the like.
  • the concentration of alkali is not particularly limited, but it is diluted with water and usually 5 to 30% is used.
  • the slurry is filtered to obtain a zirconium-containing hydroxide. It is preferable to remove impurities from this zirconium-containing hydroxide by washing it with pure water or the like, if necessary. After washing with water, it can be dried or the like if necessary.
  • step 6 the zirconium-containing hydroxide obtained in step 5 is heat-treated (baked) to oxidize the zirconium-containing hydroxide to obtain a zirconia powder.
  • the heat treatment temperature (calcination temperature) and the heat treatment time (calcination time) of the zirconium-containing hydroxide are not particularly limited, but are usually carried out at about 600 to 1050 ° C. for 1 hour to 10 hours.
  • the firing temperature is more preferably 650 ° C. or higher and 1000 ° C. or lower, and further preferably 700 ° C. or higher and 950 ° C. or lower.
  • the firing temperature is more preferably 2 hours to 6 hours, still more preferably 2 hours to 4 hours.
  • the specific surface area of the obtained zirconia powder can be in a suitable range. Further, by setting the heat treatment temperature to 600 ° C. or higher and 1050 ° C. or lower, the pore distribution of the obtained zirconia powder can be set in a suitable range.
  • the heat treatment atmosphere is not particularly limited, but may be usually in the atmosphere or in an oxidizing atmosphere.
  • the obtained zirconia powder may be pulverized into a slurry, if necessary.
  • a binder may be added in order to improve the moldability.
  • the binder and the zirconia powder may be uniformly mixed in a kneader.
  • the binder an organic binder is preferable. Since the organic binder can be easily removed from the molded body in an oxidizing atmosphere heating furnace and a degreased body can be obtained, impurities are less likely to remain in the sintered body in the end.
  • Examples of the organic binder include those that are soluble in alcohol, and those that are soluble in a mixed solution of two or more selected from the group consisting of alcohol, water, aliphatic ketones and aromatic hydrocarbons.
  • Examples of the organic binder include at least one selected from the group consisting of polyethylene glycol, glycol fatty acid ester, glycerin fatty acid ester, polyvinyl butyral, polyvinyl methyl ether, polyvinyl ethyl ether and vinyl propionate.
  • the organic binder may further contain one or more thermoplastic resins that are insoluble in alcohol or the mixture. After the addition of the organic binder, a known method is applied to perform treatments such as drying and pulverization to obtain the desired zirconia powder.
  • the particle size D 50 of the zirconia powder can be controlled.
  • pulverization can be performed according to the state of the zirconia powder obtained in step 5, and the particle size D 50 of the zirconia powder can be controlled within the range of 0.1 ⁇ m or more and 0.7 ⁇ m or less.
  • the zirconia powder containing the sintering aid, the colorant, or the like can be obtained by adding and mixing after the step 6.
  • a sintering aid, a colorant, or the like it is preferable to disperse the mixture in pure water or the like to form a slurry and perform wet mixing.
  • a sintering aid, a colorant, or the like may be added when the step 7 is performed.
  • the zirconia powder according to this embodiment has been described above.
  • the method for producing a zirconia sintered body according to the present embodiment is as follows. Step X of molding the zirconia powder to obtain a molded body, and After the step X, there is a step Y of sintering the molded body under the conditions of 1200 ° C. or higher and 1350 ° C. or lower and 1 hour or longer and 5 hours or lower.
  • zirconia powder is prepared.
  • zirconia powder those described in the section of [zirconia powder] can be used.
  • the zirconia powder is molded to obtain a molded body (step X).
  • a commercially available mold molding machine or a cold isotropic pressure pressurization method (CIP) can be adopted.
  • the zirconia powder may be temporarily molded by a mold molding machine and then main-molded by press molding.
  • Press molding may usually be in the range of 0.1 t to 3 t / cm 2 . It is preferably 0.5t to 2.5t / cm 2 , more preferably 0.8t to 2.2t / cm 2 , and even more preferably 1t to 2t / cm 2 .
  • the molded product is sintered at 1200 ° C. or higher and 1350 ° C. or lower under the conditions of 1 hour or longer and 5 hours or lower (step Y).
  • the monoclinic phase ratio contained in the crystal phase of the obtained zirconia sintered body is determined by containing a relatively small amount of stabilizer and setting the sintering temperature to a low temperature of 1200 to 1350 ° C. It can be controlled within the range of 0.2% or more and 5% or less. Sintering at a high temperature exceeding 1350 ° C. may increase the monoclinic phase ratio (more than 5%). As a result, the obtained sintered body can be made into a sintered body having high strength and high toughness.
  • the sintering temperature is more preferably 1200 ° C. or higher and 1300 ° C. or lower, and 1200 ° C. or higher and 1250 ° C. or lower.
  • the holding time at the time of sintering is also not particularly limited, but is preferably about 1 to 5 hours, more preferably 1 to 3 hours, for example.
  • the sintering atmosphere can be in the atmosphere or in an oxidizing atmosphere. Sintering may be performed under normal pressure, and no particular pressurization is required.
  • a sintered body having high strength and high toughness can be obtained even by sintering at a low temperature of 1200 ° C to 1350 ° C. Therefore, various known molding methods such as press molding, injection molding, casting molding, and sheet molding can be widely used. Moreover, since the zirconia powder of the present embodiment is easy to mass-produce, it has excellent cost competitiveness and can be suitably used for various purposes.
  • zirconia sintered body Asinafter, an example of the zirconia sintered body according to the present embodiment will be described. However, the zirconia sintered body of the present invention is not limited to the following examples.
  • the zirconia sintered body according to this embodiment is The monoclinic phase ratio contained in the crystal phase is 0.2% or more and 5% or less.
  • the crack length generated in the sintered body is 1 ⁇ m or more and 90 ⁇ m or less when the load is 50 kgf.
  • the 3-point bending strength is 80 kg / mm 2 or more and 150 kg / mm 2 or more.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is 0.2% or more and 5% or less.
  • the monoclinic phase ratio is preferably 0.3% or more, more preferably 0.4% or more, still more preferably 0.5% or more, particularly preferably 0.6% or more, and particularly preferably 0.7. % Or more.
  • the monoclinic phase ratio is preferably 4% or less, more preferably 3.5% or less, still more preferably 3% or less, particularly preferably 2.5% or less, and particularly preferably 2% or less. Since the monoclinic phase ratio is 0.2% or more and 5% or less, it is possible to develop a microcrack strengthening mechanism.
  • the monoclinic phase ratio can be controlled, for example, by the content of the stabilizer and the sintering temperature. The method for determining the monoclinic phase ratio is as described in Examples.
  • the zirconia sintered body has a crack length of 1 ⁇ m or more and 90 ⁇ m or less when the load is 50 kgf in the toughness measurement by the IF method.
  • the crack length is preferably 3 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 12 ⁇ m or more, particularly preferably 15 ⁇ m or more, and particularly preferably 20 ⁇ m or more.
  • the crack length is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 55 ⁇ m or less, particularly preferably 50 ⁇ m or less, and particularly preferably 40 ⁇ m or less.
  • the crack length can be controlled by the monoclinic phase ratio. Since the crack length is 1 ⁇ m or more and 90 ⁇ m or less, the toughness is excellent. The method for determining the crack length is as described in the examples.
  • the toughness value of the zirconia sintered body is preferably 10 MPa ⁇ m 0.5 or more and 40 MPa ⁇ m 0.5 or less when the weight is 50 kgf in the toughness measurement by the IF method.
  • the toughness value is preferably 13 MPa ⁇ m 0.5 or more, more preferably 15 MPa ⁇ m 0.5 or more, further preferably 17 MPa ⁇ m 0.5 or more, particularly preferably 20 MPa ⁇ m 0.5 or more, particularly. It is preferably 25 MPa ⁇ m 0.5 or more.
  • the toughness value is preferably MPa ⁇ m 0.5 or less, more preferably 36 MPa ⁇ m 0.5 or less, further preferably 33 MPa ⁇ m 0.5 or less, particularly preferably 30 MPa ⁇ m 0.5 or less, particularly. It is preferably 28 MPa ⁇ m 0.5 or less.
  • the toughness value can be controlled by the monoclinic phase ratio. The method for obtaining the toughness value is as described in Examples.
  • the zirconia sintered body has a three-point bending strength of 80 kg / mm 2 or more and 150 kg / mm 2 or less.
  • the three-point bending strength is preferably 90 kg / mm 2 or more, more preferably 95 kg / mm 2 or more, still more preferably 100 kg / mm 2 or more, and particularly preferably 110 kg / mm 2 or more.
  • the three-point bending strength is preferably 140 kg / mm 2 or less, more preferably 135 kg / mm 2 or less, further preferably 130 kg / mm 2 or less, particularly preferably 125 kg / mm 2 or less, and particularly preferably 120 kg / mm 2 . It is as follows.
  • the strength is excellent.
  • the three-point bending strength can be controlled by, for example, the monoclinic phase ratio.
  • the three-point bending strength can be controlled by, for example, the relative sintering density. Specifically, by increasing the relative sintering density, high strength (80 kg / mm 2 or more) can be obtained.
  • the method for determining the three-point bending strength is as described in the examples.
  • the relative sintering density of the zirconia sintered body is preferably 98.5% or more, more preferably 99.0% or more, further preferably 99.1% or more, and 99.2. % Or more is particularly preferable, 99.3% or more is particularly preferable, 99.4% or more is particularly preferable, and 99.5% or more is particularly preferable.
  • the zirconia sintered body has higher strength.
  • the relative sintering density refers to the relative sintering density represented by the following formula (1).
  • Relative sintering density (%) (sintering density / theoretical sintering density) x 100 ... (1)
  • the theoretical sintering density (assumed to be ⁇ 0 ) is a value calculated by the following equation (2-1).
  • ⁇ 0 100 / [(Y / 3.987) + (100-Y) / ⁇ z] ... (2-1)
  • ⁇ z is a value calculated by the following equation (2-2).
  • ⁇ z [124.25 (100-X) + [Molecular weight of stabilizer] ⁇ X] / [150.5 (100 + X) A 2C ] ... (2-2)
  • molecular weight of the stabilizer 225.81 is used when the stabilizer is Y2O3 , 382.52 when the stabilizer is Er2O3 , and 394.11 when the stabilizer is Yb2O3.
  • X and Y are the stabilizer concentration (mol%) and the alumina concentration (% by weight), respectively.
  • a and C are values calculated by the following equations (2-3) and (2-4), respectively.
  • A 0.5080 + 0.06980X / (100 + X) ...
  • the theoretical sintering density varies depending on the composition of the powder.
  • the theoretical sintering density of zirconia containing itria is 6.117 g / cm 3 when the itria content is 2 mol%, 6.098 g / cm 3 when the itria content is 3 mol%, and 6.051 g when the itria content is 5.5 mol%.
  • ⁇ z is a value calculated by the following formula (3).
  • ⁇ z -0.0400 (molar concentration of CaO) +6.1700 ...
  • the theoretical colorant densities are Fe 2 O 3 at 5.24 g / cm 3 , ZnO at 5.61 g / cm 3 , MnO 2 at 5.03 g / cm 3 , CoO at 6.10 g / cm 3 , and TIO 2 at 4. It is assumed that .23 g / cm 3 , Tb 4 O 7 is 7.80 g / cm 3 , and CuO is 6.31 g / cm 3 .
  • the sintering density is measured by the Archimedes method.
  • the surface of the zirconia sintered body is preferably 32% or less after being exposed to hydrothermal conditions at 134 ° C. for 75 hours.
  • the monoclinic phase ratio is preferably 31.5% or less, more preferably 30% or less, still more preferably 25% or less, particularly preferably 23% or less, and particularly preferably 20% or less.
  • the surface monoclinic phase ratio can be achieved, for example, by using certain stabilizers (eg, CaO).
  • the monoclinic phase ratio is 32% or less, it can be said that the resistance to water heat deterioration is excellent.
  • the method for measuring the monoclinic phase ratio is as described in Examples.
  • the zirconia sintered body contains a stabilizer, and the stabilizer is one or more selected from the group consisting of CaO , Y2O3 , Er2O3 , and Yb2O3. preferable.
  • the stabilizer varies depending on the application , but CaO , Y2O3, and Yb2O3 are more preferable from the viewpoint of cost, coloring, and the like. Further, the stabilizer is preferably CaO from the viewpoint of resistance to water heat deterioration.
  • the content of the Y 2 O 3 in the entire zirconia powder is preferably 1.4 mol% or more and less than 2.0 mol%.
  • the content of Y2 O 3 is preferably 1.45 mol% or more , more preferably 1.5 mol% or more, still more preferably 1.55 mol% or more, particularly preferably 1.57 mol% or more, and particularly preferably 1. It is 6.6 mol% or more.
  • the content of Y 2 O 3 is preferably 1.9 mol% or less, more preferably less than 1.8 mol%, still more preferably 1.75 mol% or less, particularly preferably 1.7 mol% or less, and particularly preferably 1. It is .65 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is likely to be 0.2% or more and 5% or less. ..
  • the content of Er 2 O 3 in the entire zirconia powder is preferably 1.4 mol% or more and 1.8 mol% or less.
  • the content of Er 2 O 3 is preferably 1.45 mol% or more, more preferably 1.5 mol% or more, still more preferably 1.55 mol% or more, particularly preferably 1.57 mol% or more, and particularly preferably 1. It is 6.6 mol% or more.
  • the content of Er 2 O 3 is preferably 1.9 mol% or less, more preferably less than 1.8 mol%, still more preferably 1.75 mol% or less, particularly preferably 1.7 mol% or less, and particularly preferably 1. It is .65 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is likely to be 0.2% or more and 5% or less. ..
  • the content of Yb 2 O 3 in the whole zirconia powder is preferably 1.4 mol% or more and 1.8 mol% or less.
  • the content of Yb 2 O 3 is preferably 1.75 mol% or less, more preferably 1.7 mol% or less, still more preferably 1.65 mol% or less, and particularly preferably 1.63 mol% or less.
  • the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is likely to be 0.2% or more and 5% or less. ..
  • the content of the CaO with respect to the entire zirconia powder is preferably 3.5 mol% or more and 4.5 mol% or less.
  • the CaO content is preferably 3.6 mol% or more, more preferably 3.7 mol% or more, still more preferably 3.8 mol% or more, particularly preferably 3.9 mol% or more, and particularly preferably 3.95 mol%. That is all.
  • the CaO content is preferably 4.4 mol% or less, more preferably 4.3 mol% or less, still more preferably 4.2 mol% or less, particularly preferably 4.1 mol% or less, and particularly preferably 4.05 mol%. It is as follows. When the CaO is contained in the range of 3.5 mol% or more and 4.5 mol% or less, the monoclinic phase ratio contained in the crystal phase of the zirconia sintered body is likely to be 0.2% or more and 5% or less.
  • the zirconia sintered body may contain 0.005% by mass or more and 2% by mass or less of one or more selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or less.
  • the metal oxide having a Tanman temperature of 1200 ° C. or lower include oxides of iron, germanium, cobalt, chromium and zinc.
  • the content of one or more selected from the group consisting of alumina and metal oxides having a tanman temperature of 1200 ° C. or lower is more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, and particularly preferably. Is 0.05% by mass or more, particularly preferably 0.07% by mass or more.
  • the content of one or more selected from the group consisting of alumina and metal oxides having a tanman temperature of 1200 ° C. or lower is more preferably 1.5% by mass or less, still more preferably 1.2% by mass or less, and particularly preferably. Is 0.5% by mass or less, particularly preferably 0.25% by mass or less.
  • at least one selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or lower is contained within the above numerical range, it functions as a sintering aid and is excellent in low-temperature sinterability. Further, since the zirconia sintered body contains alumina, it is easy to suppress a decrease in the toughness of the zirconia sintered body.
  • the zirconia sintered body may contain alumina or a metal oxide having a tanman temperature of 1200 ° C. or lower, but may be configured not to contain it. Specifically, the zirconia sintered body may contain less than 0.005% by mass of one or more selected from the group consisting of alumina and a metal oxide having a tanman temperature of 1200 ° C. or lower. ..
  • the zirconia sintered body may contain sinterable ceramics, thermosetting resin, etc. for the purpose of improving properties such as strength, in addition to alumina and metal oxides having a tanman temperature of 1200 ° C. or lower.
  • the zirconia sintered body may contain one or more selected from the group consisting of Fe, V, Mn, Co, Zn, Cu and Ti. If one or more selected from the group consisting of Fe, V, Mn, Co, Zn, Cu and Ti is contained, coloring can be preferably performed.
  • the form of the element is not particularly limited, and it can be added in the form of an oxide, chloride, or the like.
  • Specific examples of the oxide containing the element include Fe 2 O 3 , V 2 O 5 , MnO 2 , CoO, ZnO, CuO, and TiO 2 .
  • the content of the Fe 2 O 3 is preferably 0.005% by mass or more and 1% by mass or less, preferably 0.05% by mass or more, when the whole zirconia powder is 100% by mass. More preferably, it is 0.5% by mass or less.
  • the content of Fe 2 O 3 is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the V 2 O 5 is preferably 0.005% by mass or more and 0.5% by mass or less, preferably 0.01% by mass, when the whole zirconia powder is 100% by mass. % Or more and 0.1% by mass or less is more preferable.
  • the content of V 2 O 5 is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the MnO 2 is preferably 0.005% by mass or more and 2% by mass or less, and 0.1% by mass or more and 1.1% by mass, when the whole zirconia powder is 100% by mass. % Or less is more preferable.
  • the content of MnO 2 is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the CoO is preferably 0.005% by mass or more and 2% by mass or less, and 0.01% by mass or more and 1.5% by mass or less, when the whole zirconia powder is 100% by mass. Is more preferable.
  • the CoO content is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the ZnO is preferably 0.005% by mass or more and 1% by mass or less, and 0.1% by mass or more and 0.5% by mass or less, when the whole zirconia powder is 100% by mass. Is more preferable.
  • the ZnO content is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the colorant is preferably 0.005% by mass or more and 1% by mass or less, and 0.05% by mass or more and 0. 6% by mass or less is more preferable, and 0.1% by mass or more and 0.3% by mass or less is further preferable.
  • the content of the colorant is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the content of the TiO 2 is preferably 0.005% by mass or more and 2% by mass or less, and 0.01% by mass or more and 1% by mass or less, when the whole zirconia powder is 100% by mass. Is more preferable.
  • the content of TiO 2 is 0.005% by mass or more, the intended coloring can be easily obtained. That is, the color tone can be easily adjusted.
  • the zirconia sintered body according to the present embodiment can be obtained by normal pressure sintering using the above-mentioned zirconia powder. Specifically, for example, it can be obtained by the method for producing the zirconia sintered body.
  • the zirconia sintered body according to this embodiment can be used as an industrial part, an aesthetic part, and a dental material. More specifically, it can be used for jewelry, watch parts, watch faces, artificial teeth, molding processing members, wear resistant members, chemical resistant members and the like.
  • the zirconia powder and the zirconia sintered body in Examples and Comparative Examples contain 1.3 to 2.5% by mass of hafnium oxide as an unavoidable impurity with respect to zirconium oxide (calculated by the following formula (X)). )are doing. ⁇ Equation (X)> ([Mass of hafnium oxide] / ([Mass of zirconium oxide] + [Mass of hafnium oxide])) ⁇ 100 (%)
  • Example 1 Preparation of zirconia powder
  • 213 g of a 25 mass% sodium sulfate aqueous solution and 450 g of a zirconium oxychloride aqueous solution (acid concentration: 1N) having 16 mass% in terms of ZrO 2 were separately heated to 95 ° C. (step 1).
  • the heated aqueous solutions were brought into contact with each other over 2 minutes so that the SO 4-2- / ZrO 2 mass ratio of the mixed solution was 0.50 (step 2).
  • the obtained basic zirconium sulfate-containing reaction solution was held at 95 ° C. for 4 hours and aged to obtain basic zirconium sulfate (step 3).
  • a 10 % by mass yttrium chloride aqueous solution in terms of Y2O3 was added so that Y2O3 was 1.5 mol% , and the mixture was uniformly mixed ( . Step 4).
  • a 25% by mass sodium hydroxide aqueous solution was added to the obtained mixed solution and neutralized until the pH reached 13 or higher to generate a hydroxide precipitate (step 5).
  • the obtained hydroxide precipitate was filtered, thoroughly washed with water, and the obtained hydroxide was dried at 105 ° C. for 24 hours. The dried hydroxide was heat-treated in the air at 860 ° C.
  • step 6 an unground zirconia-based powder (yttria-stabilized zirconia-based powder) (step 6).
  • Alumina powder having an average particle diameter of 0.1 ⁇ m of primary particles was added to the obtained unground yttria-stabilized zirconia powder in an amount of 0.25% by mass based on the yttria-stabilized zirconia powder, and a wet type using water as a dispersion medium was added. It was pulverized and mixed in a ball mill for 40 hours. Zirconia beads ⁇ 5 mm were used for pulverization. The zirconia slurry obtained after pulverization was dried at 110 ° C. to obtain the zirconia powder according to Example 1. Specifically, the above operation was performed by an apparatus as described with reference to FIG.
  • Examples 2 to 19, Comparative Examples 1 to 7 Except for changing the amount of yttrium chloride aqueous solution added so that the amount of Y 2 O 3 added is the amount shown in Table 1, and changing the amount of alumina powder added to the amount shown in Table 1. Obtained the zirconia powders according to Examples 2 to 19 and Comparative Examples 1 to 7 in the same manner as in Example 1.
  • Example 20 to Example 21 Instead of adding the aqueous solution of yttrium chloride, 10% by mass of an aqueous solution of erbium chloride in terms of Er 2 O 3 was added so that Er 2 O 3 was 1.6 mol%, and the same procedure as in Example 1 was carried out.
  • the zirconia powder according to Example 20 to Example 21 was obtained.
  • Example 22 The zirconia powder according to Example 22 was obtained in the same manner as in Example 1 except that calcium carbonate (CaCO 3 ) was added so as to be 3.8 mol% in terms of CaO instead of adding the yttrium chloride aqueous solution.
  • CaCO 3 calcium carbonate
  • Examples 23 to 25 The zirconia powders according to Examples 23 to 25 were obtained in the same manner as in Example 22 except that the amount of calcium carbonate added was changed so that the amount of CaO added was the amount shown in Table 1.
  • Example 26 Instead of adding the yttrium chloride aqueous solution, the same procedure as in Example 1 was carried out except that a 10% by mass ytterbium chloride aqueous solution in terms of Yb 2 O 3 was added so that Yb 2 O 3 was 1.6 mol%. The zirconia powder according to Example 26 was obtained.
  • Example 27 Examples except that the addition amount of the yttrium chloride aqueous solution was changed so that the addition amount of Y 2 O 3 was the amount shown in Table 1, and 0.25% by mass of Fe 2 O 3 was added.
  • the zirconia powder according to Example 27 was obtained in the same manner as in 1.
  • Example 28 Same as Example 1 except that the addition amount of the yttrium chloride aqueous solution was changed so that the addition amount of Y2O3 was the amount shown in Table 1 , and 0.05% by mass of ZnO was added. The zirconia powder according to Example 28 was obtained.
  • Example 29 Except that the addition amount of the yttrium chloride aqueous solution was changed so that the addition amount of Y 2 O 3 was the amount shown in Table 1, and 0.05% by mass of MnO 2 was added, the same as in Example 1. Similarly, the zirconia powder according to Example 29 was obtained.
  • Example 30 Same as Example 1 except that the amount of yttrium chloride aqueous solution added was changed so that the amount of Y 2 O 3 added was the amount shown in Table 1, and 0.05% by mass of CoO was added. The zirconia powder according to Example 30 was obtained.
  • Example 31 Except that the addition amount of the yttrium chloride aqueous solution was changed so that the addition amount of Y 2 O 3 was the amount shown in Table 1, and 0.1% by mass of TiO 2 was added, the same as in Example 1. Similarly, the zirconia powder according to Example 31 was obtained.
  • Example 32 Examples except that the addition amount of the yttrium chloride aqueous solution was changed so that the addition amount of Y 2 O 3 was the amount shown in Table 1, and 0.1% by mass of Tb 4 O 7 was added.
  • the zirconia powder according to Example 32 was obtained in the same manner as in 1.
  • Example 33 Same as Example 1 except that the amount of yttrium chloride aqueous solution added was changed so that the amount of Y 2 O 3 added was the amount shown in Table 1, and 0.3% by mass of CuO was added. The zirconia powder according to Example 33 was obtained.
  • Example 34 The amount of yttrium chloride aqueous solution added was changed so that the amount of Y 2 O 3 added was the amount shown in Table 1, and the amount of MnO 2 powder added instead of alumina powder was changed to 1.0% by mass.
  • the zirconia powder according to Example 34 was obtained in the same manner as in Example 1 except that it was changed.
  • the peak top diameter, pore volume, and pore distribution width in the range of 10 nm or more and 200 nm or less were determined.
  • the results are shown in Table 2.
  • the pore distribution width refers to the width of the peak at which the log differential pore volume is 0.1 ml / g or more.
  • FIGS. 2 and 3 show the pore distribution of the zirconia powder of Example 2 and Example 7, and FIG. 3 shows the pore distribution of the zirconia powder of Comparative Example 7.
  • composition measurement The composition (oxide equivalent) of the zirconia powders of Examples and Comparative Examples was analyzed using ICP-AES ("ULTIMA-2" manufactured by HORIBA). The results are shown in Table 1.
  • Monoclinic phase ratio (%) (Im (111) + Im (11-1)) / (Im (111) + Im (11-1) + It (101) + Ic (111)) ⁇ 100
  • Im (111) is the diffraction intensity of (111) in the monoclinic phase
  • Im (11-1) is the diffraction intensity of (11-1) in the monoclinic phase
  • It (101) is the diffraction intensity of (101) in the tetragonal phase
  • Ic (111) is the diffraction intensity of (111) in the cubic phase.
  • the cubic phase may be distorted depending on the amount of stabilizer added and the manufacturing method, and the peak position may shift.
  • the peak between (004) and (220) of the tetragonal phase is cubic. It was calculated as the peak of the phase. The results are shown in Table 3.
  • Hv Vickers hardness [GPa] a: Half of the average indentation length on the X and Y axes [ ⁇ m] c: Half of the average crack length on the X and Y axes [ ⁇ m] E: Young's modulus [GPa]
  • the X-axis indentation length and the Y-axis indentation length when determining d are as shown in FIG.
  • Relative sintering density (sintering density / theoretical sintering density) x 100 ... (1)
  • the theoretical sintering density (assumed to be ⁇ 0 ) is a value calculated by the following equation (2-1).
  • ⁇ 0 100 / [(Y / 3.987) + (100-Y) / ⁇ z] ... (2-1)
  • ⁇ z is a value calculated by the following equation (2-2).
  • ⁇ z [124.25 (100-X) + [Molecular weight of stabilizer] ⁇ X] / [150.5 (100 + X) A 2C ] ... (2-2)
  • molecular weight of the stabilizer 225.81 is used when the stabilizer is Y2O3 , 382.52 when the stabilizer is Er2O3 , and 394.11 when the stabilizer is Yb2O3.
  • X and Y are the stabilizer concentration (mol%) and the alumina concentration (% by weight), respectively.
  • a and C are values calculated by the following equations (2-3) and (2-4), respectively.
  • A 0.5080 + 0.06980X / (100 + X) ...
  • the theoretical sintering density varies depending on the composition of the powder.
  • the theoretical sintering density of zirconia containing itria is 6.117 g / cm 3 when the itria content is 2 mol%, 6.098 g / cm 3 when the itria content is 3 mol%, and 6.051 g when the itria content is 5.5 mol%.
  • ⁇ z is a value calculated by the following formula (3).
  • ⁇ z -0.0400 (molar concentration of CaO) +6.1700 ...
  • the theoretical colorant densities are Fe 2 O 3 at 5.24 g / cm 3 , ZnO at 5.61 g / cm 3 , MnO 2 at 5.03 g / cm 3 , CoO at 6.10 g / cm 3 , and TIO 2 at 4. .23 g / cm 3 , Tb 4 O 7 was 7.80 g / cm 3 , and CuO was 6.31 g / cm 3 .
  • the sintering density was measured by the Archimedes method.
  • Relative molding density (molding density / theoretical sintering density) x 100 ... (4)
  • the theoretical sintering density (assumed to be ⁇ 0 ) is a value calculated by the above equation (2-1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
PCT/JP2021/036911 2020-10-09 2021-10-06 ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法 Ceased WO2022075346A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022523220A JP7195481B2 (ja) 2020-10-09 2021-10-06 ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
EP21877645.8A EP4039648B1 (en) 2020-10-09 2021-10-06 Zirconia powder, zirconia sintered body, and method for producing zirconia sintered body
CN202180006966.4A CN114787085B (zh) 2020-10-09 2021-10-06 氧化锆粉末、氧化锆烧结体以及氧化锆烧结体的制造方法
US17/755,491 US12612338B2 (en) 2020-10-09 2021-10-06 Zirconia powder, zirconia sintered body, and method for producing zirconia sintered body

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020170949 2020-10-09
JP2020-170949 2020-10-09

Publications (1)

Publication Number Publication Date
WO2022075346A1 true WO2022075346A1 (ja) 2022-04-14

Family

ID=81125996

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/036911 Ceased WO2022075346A1 (ja) 2020-10-09 2021-10-06 ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法

Country Status (5)

Country Link
US (1) US12612338B2 (https=)
EP (1) EP4039648B1 (https=)
JP (1) JP7195481B2 (https=)
CN (1) CN114787085B (https=)
WO (1) WO2022075346A1 (https=)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070689A1 (ja) * 2022-09-30 2024-04-04 東レ株式会社 セラミックス球形体およびセラミックス球形体の製造方法
RU2820108C1 (ru) * 2023-10-31 2024-05-29 Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" Способ получения слабоагрегированного дисперсного порошка диоксида циркония
WO2024117194A1 (ja) 2022-11-30 2024-06-06 東ソー株式会社 粉末
WO2025070294A1 (ja) * 2023-09-29 2025-04-03 第一稀元素化学工業株式会社 ジルコニア焼結体、ジルコニア焼結体の製造方法、及び、ジルコニア粉末
WO2025197742A1 (ja) * 2024-03-22 2025-09-25 東レ株式会社 ベアリングボールおよびベアリングボールの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7195482B2 (ja) * 2020-10-09 2022-12-23 第一稀元素化学工業株式会社 ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570224A (ja) 1991-02-25 1993-03-23 Sumitomo Cement Co Ltd ジルコニア焼結体の製造方法及びジルコニア焼結体
JP2005097094A (ja) * 2003-08-22 2005-04-14 Matsushita Electric Works Ltd ジルコニア−アルミナ複合セラミック材料
WO2015145787A1 (ja) * 2014-03-28 2015-10-01 第一稀元素化学工業株式会社 ジルコニア系多孔質体及びその製造方法
WO2020196650A1 (ja) * 2019-03-25 2020-10-01 第一稀元素化学工業株式会社 ジルコニア粉末、ジルコニア粉末の製造方法、ジルコニア焼結体の製造方法、及び、ジルコニア焼結体

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986005174A1 (fr) 1985-03-07 1986-09-12 Nippon Soda Co., Ltd. Zircone frittee et procede de production
JPH0667785B2 (ja) 1985-07-15 1994-08-31 東レ株式会社 ジルコニア焼結体
AU2004203889B2 (en) 2003-08-22 2006-02-23 Panasonic Healthcare Holdings Co., Ltd. ZrO2-Al2O3 composite ceramic material
JP5356639B2 (ja) 2005-03-04 2013-12-04 東ソー株式会社 ジルコニア微粉末及びその製造方法
JP5356665B2 (ja) 2007-08-27 2013-12-04 東ソー株式会社 ジルコニア焼結体
EP2674408B1 (en) * 2008-04-09 2017-06-07 Tosoh Corporation Translucent zirconia sintered body and use of the same
JP5407614B2 (ja) 2009-07-14 2014-02-05 東ソー株式会社 黄色ジルコニア焼結体
US10231807B2 (en) * 2013-05-10 2019-03-19 Kuraray Noritake Dental Inc. Zirconia sintered body, zirconia composition, zirconia pre-sintered body and preparing method thereof, and dental prosthesis
CN105164084B (zh) * 2013-05-10 2017-05-03 可乐丽则武齿科株式会社 氧化锆烧结体、氧化锆组合物和氧化锆煅烧体、以及牙科用修复物
JP6221663B2 (ja) 2013-11-13 2017-11-01 東ソー株式会社 ジルコニア粉末
PT107543A (pt) 2014-03-27 2015-09-28 Innovnano Materiais Avançados Sa Material cerâmico sinterizado, composicão em pó para a sua obtenção, processo de fabrico e respectivas peças cerâmicas
CN104445395A (zh) * 2014-12-01 2015-03-25 淄博华创精细陶瓷有限公司 制备稳定氧化锆原料的方法
JP6231470B2 (ja) * 2014-12-04 2017-11-15 株式会社ノリタケカンパニーリミテド ジルコニア原料粉末およびその製造方法
US10273191B2 (en) * 2015-01-15 2019-04-30 Tosoh Corporation Translucent zirconia sintered body, method for manufacturing same, and use thereof
DK3345870T3 (da) * 2016-03-30 2020-05-25 Daiichi Kigenso Kagaku Kogyo Fint zirconiumdioxidpulver og fremgangsmåde til fremstilling deraf
JP7198667B2 (ja) * 2016-09-20 2023-01-04 クラレノリタケデンタル株式会社 ジルコニア組成物、仮焼体及び焼結体、並びにそれらの製造方法
JP6885021B2 (ja) 2016-11-14 2021-06-09 東ソー株式会社 オレンジ色ジルコニア焼結体及びその製造方法
CN107244914B (zh) * 2017-05-10 2019-10-18 杭州而然科技有限公司 一种彩色氧化锆陶瓷

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570224A (ja) 1991-02-25 1993-03-23 Sumitomo Cement Co Ltd ジルコニア焼結体の製造方法及びジルコニア焼結体
JP2005097094A (ja) * 2003-08-22 2005-04-14 Matsushita Electric Works Ltd ジルコニア−アルミナ複合セラミック材料
WO2015145787A1 (ja) * 2014-03-28 2015-10-01 第一稀元素化学工業株式会社 ジルコニア系多孔質体及びその製造方法
WO2020196650A1 (ja) * 2019-03-25 2020-10-01 第一稀元素化学工業株式会社 ジルコニア粉末、ジルコニア粉末の製造方法、ジルコニア焼結体の製造方法、及び、ジルコニア焼結体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4039648A4

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070689A1 (ja) * 2022-09-30 2024-04-04 東レ株式会社 セラミックス球形体およびセラミックス球形体の製造方法
WO2024117194A1 (ja) 2022-11-30 2024-06-06 東ソー株式会社 粉末
KR20250114087A (ko) 2022-11-30 2025-07-28 도소 가부시키가이샤 분말
EP4628450A1 (en) 2022-11-30 2025-10-08 Tosoh Corporation Powder
EP4628450A4 (en) * 2022-11-30 2026-04-08 Tosoh Corp POWDER
WO2025070294A1 (ja) * 2023-09-29 2025-04-03 第一稀元素化学工業株式会社 ジルコニア焼結体、ジルコニア焼結体の製造方法、及び、ジルコニア粉末
RU2820108C1 (ru) * 2023-10-31 2024-05-29 Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" Способ получения слабоагрегированного дисперсного порошка диоксида циркония
WO2025197742A1 (ja) * 2024-03-22 2025-09-25 東レ株式会社 ベアリングボールおよびベアリングボールの製造方法

Also Published As

Publication number Publication date
CN114787085B (zh) 2024-03-15
EP4039648A4 (en) 2023-11-15
JP7195481B2 (ja) 2022-12-23
CN114787085A (zh) 2022-07-22
US20220380261A1 (en) 2022-12-01
JPWO2022075346A1 (https=) 2022-04-14
EP4039648A1 (en) 2022-08-10
EP4039648B1 (en) 2026-04-01
US12612338B2 (en) 2026-04-28

Similar Documents

Publication Publication Date Title
JP7195481B2 (ja) ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
KR101822542B1 (ko) 색상을 갖는 소결된 지르코늄 산화물
US12286379B2 (en) Zirconia powder, method for producing zirconia powder, method for producing zirconia sintered body, and zirconia sintered body
JPWO2006080473A1 (ja) 複合セラミックス及びその製法
CN119894846A (zh) 氧化锆组合物及其制造方法
Vasanthavel et al. Stabilization of at-ZrO 2 polymorph in a glassy SiO 2 matrix at elevated temperatures accomplished by ceria additions
JP7756794B2 (ja) ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
US20250042819A1 (en) Zirconia sintered body, zirconia powder, and method for producing zirconia sintered body
CN118265683A (zh) 烧结氧化锆珠粒
JP7195482B2 (ja) ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
JP6405699B2 (ja) ジルコニア焼結体及びその製造方法
JPWO2003076336A1 (ja) セリウム系複合酸化物、その焼結体及び製造法
JP7631611B1 (ja) ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
JP2026071480A (ja) ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
WO2025070294A1 (ja) ジルコニア焼結体、ジルコニア焼結体の製造方法、及び、ジルコニア粉末
WO2024203828A1 (ja) 銀含有ジルコニア焼結体、銀含有安定化ジルコニア粉末、銀含有安定化ジルコニア粉末の製造方法、及び、銀含有ジルコニア焼結体の製造方法
Smyrnova-Zamkova et al. Physico-chemical properties of fine-grained powder in Al2O3-ZrO2-Y2O3-CeO2 system produced by combined method
US20260070848A1 (en) Powder
JP2025118961A (ja) 粉末及びその製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2022523220

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2021877645

Country of ref document: EP

Effective date: 20220503

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

Ref document number: 21877645

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWG Wipo information: grant in national office

Ref document number: 2021877645

Country of ref document: EP