WO2024203828A1 - 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 - Google Patents

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 Download PDF

Info

Publication number
WO2024203828A1
WO2024203828A1 PCT/JP2024/011255 JP2024011255W WO2024203828A1 WO 2024203828 A1 WO2024203828 A1 WO 2024203828A1 JP 2024011255 W JP2024011255 W JP 2024011255W WO 2024203828 A1 WO2024203828 A1 WO 2024203828A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
less
zirconia
mol
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/JP2024/011255
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
裕貴 小松
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
Application filed by Daiichi Kigenso Kagaku Kogyo Co Ltd filed Critical Daiichi Kigenso Kagaku Kogyo Co Ltd
Priority to EP24779946.3A priority Critical patent/EP4563548A1/en
Priority to CN202480004005.3A priority patent/CN119894847A/zh
Priority to JP2025510706A priority patent/JPWO2024203828A1/ja
Publication of WO2024203828A1 publication Critical patent/WO2024203828A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • A61K6/844—Noble metals
    • 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
    • C04B35/01—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
    • 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
    • C04B35/4885—Composites with aluminium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A61C13/083—Porcelain or ceramic teeth
    • 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
    • C01P2002/60—Compounds characterised by their crystallite size
    • 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
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides 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
    • C04B2235/3289—Noble metal oxides
    • C04B2235/3291—Silver 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
    • 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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/408—Noble metals
    • 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
    • C04B2235/70—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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, 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
    • C04B2235/70—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
    • 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
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts

Definitions

  • the present invention relates to a silver-containing zirconia sintered body, a silver-containing stabilized zirconia powder, a method for producing the silver-containing stabilized zirconia powder, and a method for producing a silver-containing zirconia sintered body.
  • a common method for imparting antibacterial properties to zirconia ceramics is to coat the ceramic surface with an antibacterial substance.
  • Antibacterial substances used include silver, which has a wide antibacterial spectrum, and titanium oxide, which functions as a photocatalyst.
  • Non-Patent Documents 1 and 2 disclose that coating prosthetic devices with silver nanoparticles provides antibacterial properties.
  • ceramic knives have traditionally been sold with antibacterial properties imparted by baking a titanium oxide coating onto the surface.
  • Silver is said to have a broader antibacterial spectrum and stronger antibacterial effect than copper and zinc, which also have antibacterial effects.
  • the sinterability and resistance to hydrothermal deterioration are not reduced.
  • the present invention has been made in consideration of the above-mentioned problems, and an object of the present invention is to provide a silver-containing zirconia sintered body that is excellent in mechanical properties, sinterability, and resistance to hydrothermal degradation. It is also an object of the present invention to provide a silver-containing stabilized zirconia powder that can be sintered to obtain the silver-containing zirconia sintered body. It is also an object of the present invention to provide a method for producing the silver-containing stabilized zirconia powder. It is also an object of the present invention to provide a method for producing the silver-containing zirconia sintered body.
  • the inventors conducted extensive research into silver-containing zirconia sintered bodies to address the above-mentioned issues. As a result, they discovered that by adopting the following configuration, it is possible to provide a silver-containing zirconia sintered body that is excellent in mechanical properties, sinterability, and resistance to hydrothermal degradation, and thus completed the present invention.
  • the present invention provides the following.
  • Silver particles, Stabilized zirconia containing zirconia and a stabilizer The average particle size of the silver particles is 0.5 ⁇ m or less, The average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less, A silver-containing zirconia sintered body having a relative sintered density of 98% or more.
  • the silver particles are not coated on the surface of the sintered body, but are contained in the silver-containing zirconia sintered body itself. Therefore, even if the surface of the silver-containing zirconia sintered body wears down, the silver particles are exposed from the inside, and the antibacterial effect can be maintained.
  • the manufacturing method described below it is possible to atomize the silver particles in the silver-containing zirconia sintered body.
  • the average particle size of the silver particles can be made 0.5 ⁇ m or less.
  • the silver particles are fine, it is possible to suppress the segregation of the silver particles in the silver-containing zirconia sintered body. As a result, sintering at a low temperature is possible. In addition, the deterioration of mechanical properties is suppressed.
  • the dispersibility of the silver particles in the silver-containing zirconia sintered body it is possible to densify it (it is possible to increase the relative sintered density), and the deterioration of the mechanical properties of the silver-containing zirconia sintered body is suppressed.
  • the relative sintered density 98% or more, the deterioration of the mechanical properties of the silver-containing zirconia sintered body is suppressed.
  • the relative sintered density can also be improved by increasing the sintering temperature (e.g., above 1500°C).
  • increasing the sintering temperature increases the crystal grain size of zirconia, resulting in a decrease in hydrothermal degradation resistance.
  • the sintering temperature is set relatively low so that the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less, thereby suppressing the decrease in hydrothermal degradation resistance.
  • the average particle size of the silver particles As described above, according to the configuration of [1], by setting the average particle size of the silver particles to 0.5 ⁇ m or less, the decrease in sinterability is suppressed, and densification is possible (relative sintered density is 98% or more), and the decrease in mechanical properties is suppressed. In addition, since the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less, the decrease in hydrothermal degradation resistance is suppressed.
  • the present invention provides the following: [2] The silver-containing zirconia sintered body according to [1], wherein the average crystal grain size of the stabilized zirconia is 0.25 ⁇ m or less.
  • the sintering temperature can be said to be lower.
  • the present invention provides the following: [3] The silver-containing zirconia sintered body according to [1] or [2], containing silver particles in an amount of 0.025% by mass or more and 20% by mass or more, calculated as Ag 2 O, when the total amount of zirconia and the stabilizer is 100% by mass.
  • the content of the silver particles is 0.025% by mass or more, the antibacterial properties are excellent. Furthermore, when the content of the silver particles is 20% by mass or less, the mechanical properties and sinterability are excellent.
  • the present invention provides the following: [4] The silver-containing zirconia sintered body according to any one of [1] to [3], having a three-point bending strength of 600 MPa or more.
  • the three-point bending strength is 600 MPa or more, it can be said to have higher strength.
  • the present invention provides the following: [5] The silver-containing zirconia sintered body according to any one of [1] to [4], having a toughness value of 5 MPa m 0.5 or more as measured by an IF method.
  • the toughness value is 5 MPa ⁇ m 0.5 or more, it can be said that the toughness is higher.
  • the present invention provides the following: [6] The silver-containing zirconia sintered body according to any one of [1] to [5], having a monoclinic ratio of 10% or less after hydrothermal treatment at 134 ° C., 0.3 MPa, and 15 hours.
  • the monoclinic ratio after hydrothermal treatment at 134°C, 0.3 MPa for 15 hours is 10% or less, it can be said to have better resistance to hydrothermal degradation.
  • the present invention provides the following: [7] The silver-containing zirconia sintered body according to any one of the above [1] to [6], wherein the stabilizer is one or more selected from the group consisting of Y 2 O 3 , CeO 2 , Er 2 O 3 , and CaO.
  • the stabilizer is at least one selected from the group consisting of Y 2 O 3 , CeO 2 , Er 2 O 3 , and CaO, the low-temperature sintering property and the mechanical strength are superior.
  • the present invention provides the following: [8] The silver-containing zirconia sintered body according to any one of [1] to [7], wherein the content of the stabilizer is 15 mol% or less when the zirconia and the stabilizer are taken as the whole.
  • the content of the stabilizer is 15 mol% or less, the mechanical strength is superior.
  • the present invention provides the following: [9] A stabilized zirconia containing zirconia and a stabilizer; A silver-containing stabilized zirconia powder having an average particle size of 0.5 ⁇ m or less, characterized by containing silver and/or silver oxide.
  • the silver oxide particles become silver particles when thermally decomposed.
  • the silver-containing stabilized zirconia powder of [9] contains stabilized zirconia and silver and/or silver oxide having an average particle size of 0.5 ⁇ m or less, and therefore, by sintering the silver-containing stabilized zirconia powder, a sintered body containing silver (silver particles) having an average particle size of 0.5 ⁇ m or less can be obtained.
  • the silver-containing stabilized zirconia powder contains only silver oxide having an average particle diameter of 0.5 ⁇ m or less
  • the silver-containing stabilized zirconia powder contains both silver and silver oxide having an average particle diameter of 0.5 ⁇ m or less
  • the silver-containing stabilized zirconia powder contains only silver having an average particle diameter of 0.5 ⁇ m or less
  • the silver oxide particles become silver particles when thermally decomposed, and therefore, by sintering the silver-containing stabilized zirconia powder, a sintered body containing silver (silver particles) having an average particle diameter of 0.5 ⁇ m or less can be obtained.
  • the average particle size of silver and/or silver oxide is reduced to 0.5 ⁇ m or less and is highly dispersed in the powder of stabilized zirconia.
  • the crystal grain size of stabilized zirconia in the zirconia sintered body obtained by sintering can be easily controlled to 0.35 ⁇ m or less, and desired hydrothermal degradation properties and mechanical properties can be obtained.
  • the present invention provides the following: [10] The silver-containing stabilized zirconia powder according to [9], wherein the peak top diameter of the pore volume distribution is 30 nm or more and 100 nm or less, the pore volume is 0.25 ml/g or more and 0.46 ml/g or less, and the pore distribution width is 40 nm or more and 120 nm or less in the range of 10 nm or more and 0.5 ⁇ m or less in a pore distribution based on mercury intrusion porosimetry.
  • the crystal grain size of the stabilized zirconia in the zirconia sintered body obtained by sintering can be easily controlled to 0.25 ⁇ m or less, and the desired hydrothermal degradation properties and mechanical properties can be obtained.
  • the present invention provides the following: [11] A method for producing a silver-containing stabilized zirconia powder, comprising the step of mixing stabilized zirconia containing zirconia and a stabilizer with silver oxide having an average particle size of 0.5 ⁇ m or less.
  • Silver is difficult to atomize by grinding because of its excellent ductility and malleability, whereas silver oxide can be atomized by grinding due to its nature.
  • silver oxide finely granulated to an average particle size of 0.5 ⁇ m or less is mixed with stabilized zirconia to obtain a zirconia powder containing stabilized zirconia and silver oxide having an average particle size of 0.5 ⁇ m or less.
  • the silver oxide particles can be converted into silver particles by heating and pyrolyzing them. Therefore, by sintering the silver-containing stabilized zirconia powder obtained by the manufacturing method of [10], a sintered body containing silver (silver particles) having an average particle size of 0.5 ⁇ m or less can be obtained.
  • the present invention provides the following: [12] A step X of molding the silver-containing stabilized zirconia powder according to the above [9] or [10] to obtain a molded body; A method for producing a silver-containing zirconia sintered body, comprising, after the step X, a step Y of sintering the molded body under conditions of 1250° C. or more and 1500° C. or less and 1 hour or more and 5 hours or less.
  • the silver-containing stabilized zirconia powder described in [9] or [10] is used, so that a sintered body with high sintering density can be obtained under low-temperature sintering conditions of 1250°C or higher and 1500°C or lower.
  • the sintering is performed at a low temperature, the obtained sintered body has excellent resistance to hydrothermal degradation.
  • the present invention can provide a silver-containing zirconia sintered body that is excellent in mechanical properties, sinterability, and resistance to hydrothermal degradation. It can also provide a silver-containing stabilized zirconia powder that can be sintered to obtain the silver-containing zirconia sintered body. It can also provide a method for producing the silver-containing stabilized zirconia powder. It can also provide a method for producing the silver-containing zirconia sintered body.
  • FIG. 2 is a schematic diagram for explaining a method for producing a silver-containing stabilized zirconia powder according to the present embodiment.
  • FIG. 2 is a schematic diagram for explaining an indentation length and a crack length.
  • zirconia zirconium oxide
  • hafnia the expressions "contain” and “include” include the concepts of “contain”, “include”, “consist essentially of” and “consist only of”.
  • silver-containing zirconia sintered body An example of the silver-containing zirconia sintered body according to the present embodiment will be described below. However, the silver-containing zirconia sintered body of the present invention is not limited to the following example.
  • the silver-containing zirconia sintered body according to this embodiment is Silver particles,
  • the stabilized zirconia includes zirconia and a stabilizer. Contains silver particles, zirconia, and a stabilizer;
  • the average particle size of the silver particles is 0.5 ⁇ m or less,
  • the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less,
  • the relative sintered density is 98% or more.
  • the silver-containing zirconia sintered body contains silver particles.
  • the average particle size of the silver particles is 0.5 ⁇ m or less. Because the average particle size of the silver particles is 0.5 ⁇ m or less, segregation of the silver particles within the silver-containing zirconia sintered body can be suppressed. As a result, a decrease in sinterability is suppressed. Also, a decrease in mechanical properties is suppressed. In other words, by improving the dispersibility of the silver particles in the silver-containing zirconia sintered body, densification is possible (the relative sintered density can be increased), and a decrease in the mechanical properties of the silver-containing zirconia sintered body is suppressed.
  • the average particle size of the silver particles is preferably 0.4 ⁇ m or less.
  • the average particle size of the silver particles is preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 0.4 ⁇ m or less.
  • the average particle size of the silver particles is measured by the method described in the Examples.
  • the content of the silver particles is preferably within a range of 0.025% by mass or more and 20% by mass or less in terms of Ag 2 O, when the total of the zirconia and the stabilizer is taken as 100% by mass.
  • the content of the silver particles is 0.025% by mass or more, the antibacterial properties are excellent.
  • the content of the silver particles is 20% by mass or less, the mechanical properties and sinterability are more excellent.
  • the content of the silver particles, calculated as Ag 2 O is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more, when the total of zirconia and the stabilizer is 100% by mass.
  • the content of the silver particles, calculated as Ag 2 O is more preferably 16% by mass or less, further preferably 12% by mass or less, and particularly preferably 10% by mass or less, when the total of zirconia and the stabilizer is 100% by mass.
  • the content of the silver particles, calculated as Ag 2 O, is more preferably 0.05% by mass or more and 16% by mass or less, even more preferably 0.1% by mass or more and 12% by mass or less, and particularly preferably 0.5% by mass or more and 10% by mass or less, when the total of zirconia and the stabilizer is 100% by mass.
  • the silver-containing zirconia sintered body contains stabilized zirconia that contains zirconia and a stabilizer.
  • the total content of zirconia and the stabilizer in the silver-containing zirconia sintered body is preferably 70% by mass or more, more preferably 80% by mass or more, when the entire silver-containing zirconia sintered body is taken as 100% by mass.
  • the total content of zirconia and the stabilizer can be 99.9% by mass or less, 99% by mass or less, etc., when the entire silver-containing zirconia sintered body is taken as 100% by mass.
  • the total content of zirconia and the stabilizer in the silver-containing zirconia sintered body is more preferably 70% by mass or more and 99.9% by mass or less, and even more preferably 80% by mass or more and 99.9% by mass or less, when the entire silver-containing zirconia sintered body is taken as 100% by mass.
  • the stabilizer is preferably one or more oxides selected from alkaline earth metals and rare earth elements.
  • the alkaline earth metals are Ca, Sr, Ba, and Ra.
  • the rare earth elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the stabilizer is preferably one or more selected from the group consisting of Y2O3 , CeO2 , Er2O3 , and CaO. When the stabilizer is one or more selected from the group consisting of Y2O3 , CeO2 , Er2O3 , and CaO , the low-temperature sintering property and mechanical strength are more excellent.
  • the content of the stabilizer is preferably 15 mol% or less when the zirconia and stabilizer are taken as the whole. When the content of the stabilizer is 15 mol% or less, the mechanical strength is superior.
  • the content of the stabilizer is preferably 1.4 mol % or more, more preferably 1.5 mol % or more, and even more preferably 1.6 mol % or more.
  • the content of the stabilizer is preferably 14 mol % or less, more preferably 13 mol % or less, and even more preferably 12.5 mol % or less.
  • the content of the stabilizer is more preferably from 1.4 mol % to 14 mol %, further preferably from 1.5 mol % to 13 mol %, and particularly preferably from 1.6 mol % to 12.5 mol %.
  • the content of Y 2 O 3 is preferably 1.4 mol% or more and 7.5 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content of Y 2 O 3 is more preferably 1.5 mol% or more, and even more preferably 1.6 mol% or more.
  • the content of Y 2 O 3 is more preferably 6.5 mol% or less, even more preferably 6 mol%, particularly preferably 5.6 mol% or less, especially preferably 5 mol% or less, and especially preferably 4.5 mol% or less.
  • the content of Y 2 O 3 in the total of zirconia and the stabilizer is more preferably 1.5 mol % or more and 6.5 mol % or less, and further preferably 1.6 mol % or more and 6 mol % or less.
  • the content of CeO 2 is preferably 10 mol% or more and 15 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content of CeO 2 is more preferably 11 mol% or more, and even more preferably 11.5 mol% or more.
  • the content of CeO 2 is more preferably 14 mol% or less, even more preferably 13 mol% or less, particularly preferably 12.5 mol% or less, especially preferably 14 mol% or less, and especially preferably 12 mol% or less.
  • the silver-containing zirconia sintered body has better mechanical strength.
  • the content of CeO 2 is preferably 10 mol% or more and 14 mol% or less.
  • the content of CeO2 in the total of zirconia and the stabilizer is more preferably 11 mol% or more and 14 mol% or less, even more preferably 11.5 mol% or more and 13 mol% or less, and particularly preferably 11.5 mol% or more and 12.5 mol% or less.
  • the content of the stabilizer is preferably 1.4 mol% or more and 7.5 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content is more preferably 1.5 mol% or more, and even more preferably 1.6 mol % or more.
  • the content is more preferably 6.5 mol% or less, even more preferably 6 mol%, particularly preferably 5.6 mol % or less, especially preferably 5 mol % or less, and especially preferably 4.5 mol% or less.
  • the silver-containing zirconia sintered body has superior mechanical strength.
  • the content of the stabilizer in the total amount of zirconia and the stabilizer is more preferably 1.5 mol % or more and 6.5 mol % or less, and even more preferably 1.6 mol % or more and 6 mol % or less.
  • the content of CaO is preferably 3.5 mol% or more and 15 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content of CaO is more preferably 3.8 mol% or more, and even more preferably 4.0 mol% or more.
  • the content of CaO is more preferably 12.0 mol% or less, and even more preferably 9.0 mol% or less.
  • the content of CaO in the total of zirconia and the stabilizer is more preferably 3.8 mol % or more and 12 mol % or less, and even more preferably 4 mol % or more and 9 mol % or less.
  • the total amount of the stabilizer is 2.5 mol% or more and 6.5 mol % or less in terms of oxide when zirconia and the stabilizer are taken as the whole, and the ratio of [amount of CaO (mol%)]/[total amount of stabilizer (mol%)] is 50% or more and 98% or less.
  • the ratio of the amount of CaO (mol %) to the total amount of stabilizers (mol %) is more preferably 55% or more, and further preferably 60% or more.
  • the ratio of the amount of CaO (mol %) to the total amount of stabilizers (mol %) is more preferably 90% or less, and further preferably 80% or less.
  • the ratio of the amount of CaO (mol %) to the total amount of stabilizers (mol %) is more preferably 55% or more and 90% or less, and further preferably 60% or more and 80% or less.
  • the total amount of the stabilizer is preferably 2.5 mol% or more and 6.5 mol% or less in terms of oxide, when the zirconia and the stabilizer are taken as a whole.
  • the total amount of the stabilizer is 2.5 mol% or more in terms of oxide, the monoclinic phase ratio in the obtained zirconia sintered body can be reduced, and the occurrence of cracks in the zirconia sintered body obtained by sintering the zirconia powder can be prevented.
  • the total amount of the stabilizer when the total amount of the stabilizer is 6.5 mol% or less in terms of oxide, the cubic phase ratio with low mechanical properties (strength, toughness) can be reduced, and the tetragonal phase ratio with high mechanical properties can be increased.
  • the total amount of the stabilizer is preferably 2.7 mol % or more, more preferably 2.9 mol % or more, and even more preferably 3.0 mol % or more, calculated as oxide.
  • the total amount of the stabilizer is preferably 6.0 mol % or less, more preferably 5.5 mol % or less, further preferably 5.0 mol % or less, and particularly preferably 4.5 mol % or less, calculated as oxide.
  • the total amount of the stabilizer is preferably 2.7 mol % or more and 6.0 mol % or less, more preferably 2.9 mol % or more and 5.5 mol % or less, further preferably 3.0 mol % or more and 5.0 mol % or less, and particularly preferably 3.0 mol % or more and 4.5 mol % or less, calculated as oxide.
  • the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less. Since the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less, it has excellent resistance to hydrothermal degradation. Note that if the sintering temperature is increased, the crystal grain size of the stabilized zirconia will increase, but since the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less, the sintering temperature can be said to be low.
  • the average crystal grain size of the stabilized zirconia is preferably 0.3 ⁇ m or less, more preferably 0.25 ⁇ m or less, and further preferably 0.2 ⁇ m or less.
  • the average crystal grain size of the stabilized zirconia is preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less, more preferably 0.05 ⁇ m or more and 0.25 ⁇ m or less.
  • the average crystal grain size of the stabilized zirconia is measured by the method described in the Examples.
  • the silver-containing zirconia sintered body may contain 25% by mass or less of Al 2 O 3 (alumina) when the total amount of zirconia and the stabilizer is 100% by mass.
  • alumina Al 2 O 3
  • the alumina acts as a sintering aid when the zirconia powder is sintered to obtain the silver-containing zirconia sintered body.
  • the content of Al 2 O 3 is more preferably 10 mass % or less, and further preferably 1 mass % or less, from the viewpoint of allowing the Al 2 O 3 to suitably function as a sintering aid.
  • the content of Al 2 O 3 is more preferably 0.1 mass % or more, and further preferably 0.25 mass % or more, from the viewpoint of allowing the Al 2 O 3 to suitably function as a sintering aid.
  • the content of Al 2 O 3 is more preferably 0.1 mass % or more and 10 mass % or less, and further preferably 0.25 mass % or more and 1 mass % or less.
  • the silver-containing zirconia sintered body may contain, in addition to alumina, sinterable ceramics, thermosetting resins, etc., in order to improve properties such as strength.
  • the silver-containing zirconia sintered body may contain one or more elements selected from the group consisting of Fe, V, Mn, Co, Zn, Cu, and Ti.
  • the silver-containing zirconia sintered body contains one or more elements selected from the group consisting of Fe, V, Mn, Co, Zn, Cu, and Ti, it can be suitably colored.
  • the monoclinic fraction contained in the crystal phase of the silver-containing zirconia sintered body is preferably 0% or more and 10% or less.
  • the monoclinic fraction is preferably 0%, but is preferably 0.1% or more, 0.5% or more, etc.
  • the monoclinic fraction is more preferably 5% or less, and even more preferably 1% or less.
  • the monoclinic fraction is more preferably 0% or more and 10% or less, and further preferably 0% or more and 1% or less. When the monoclinic fraction is from 0% to 10%, the mechanical properties (flexural strength, fracture toughness) are more excellent.
  • the monoclinic fraction can be controlled by, for example, the average particle size of the silver particles, the content of the silver particles, the content and ratio of the stabilizer, the sintering temperature, and the like.
  • the method for determining the monoclinic fraction is the method described in the Examples.
  • the silver-containing zirconia sintered body preferably has a monoclinic fraction of 80% or less after hydrothermal treatment at 134° C. and 0.3 MPa (absolute pressure 0.3 MPa) for 15 hours. If the monoclinic fraction after the hydrothermal treatment is 80% or less, it can be said that the resistance to hydrothermal deterioration is more excellent.
  • the monoclinic fraction after the hydrothermal treatment can be controlled, for example, by the average particle size of the silver particles, the content of the silver particles, the content and content ratio of the stabilizer, the sintering temperature, etc.
  • the monoclinic fraction after the hydrothermal treatment is more preferably 50% or less, and further preferably 10% or less.
  • the monoclinic fraction after the hydrothermal treatment is more preferably 0% or more and 50% or less, and further preferably 0% or more and 10% or less.
  • the silver-containing zirconia sintered body preferably has a three-point bending strength of 600 MPa or more.
  • the three-point bending strength is more preferably 700 MPa or more, and further preferably 800 MPa or more.
  • the three-point bending strength is more preferably 700 MPa or more and 1500 MPa or less, and further preferably 800 MPa or more and 1500 MPa or less.
  • the three-point bending strength is 600 MPa or more, it can be said to have higher strength.
  • the three-point bending strength is determined according to the method described in the examples.
  • the silver-containing zirconia sintered body preferably has a toughness value measured by an IF method of 5 MPa ⁇ m 0.5 or more.
  • the toughness value is more preferably 6 MPa ⁇ m 0.5 or more, and further preferably 10 MPa ⁇ m 0.5 or more.
  • the toughness value is more preferably 6 MPa ⁇ m 0.5 or more and 20 MPa ⁇ m 0.5 or less, and further preferably 10 MPa ⁇ m 0.5 or more and 20 MPa ⁇ m 0.5 or less.
  • the toughness value is 5 MPa ⁇ m 0.5 or more, it can be said that the toughness is higher.
  • the toughness value is determined by the method described in the Examples.
  • the relative sintered density of the silver-containing zirconia sintered body is preferably 98% or more, more preferably 98.5% or more.
  • the relative sintered density is 98% or more, the silver-containing zirconia sintered body can be said to be sufficiently sintered.
  • the relative sintered density is 98% or more, the silver-containing zirconia sintered body can be said to have a higher strength.
  • the relative sintered density is represented by the following formula (1).
  • Relative sintered density (%) (sintered density / theoretical sintered density) ⁇ 100 (1)
  • the theoretical sintered density ( ⁇ 0 ) is a value calculated by the following formula (2-1).
  • ⁇ 0 (100+Y+Z)/[(100/ ⁇ z)+(Y/3.987)+(Z/10.49)]...(2-1)
  • Y is the alumina concentration (wt %)
  • Z is the silver concentration (wt %).
  • the silver concentration (wt %) is calculated from formula (2-2).
  • ⁇ z is a value calculated by the following formula (2-3).
  • ⁇ z [124.25(100 ⁇ X)+[molecular weight of stabilizer] ⁇ X]/150[150.5(100+X)A 2 C] (2-3)
  • the molecular weight of the stabilizer is 225.81 when the stabilizer is Y2O3 , 382.52 when the stabilizer is Er2O3 , and 394.11 when the stabilizer is Yb2O3 .
  • X is the stabilizer concentration (mol %)
  • a and C are values calculated by the following formulas (2-4) and (2-5), respectively.
  • the theoretical sintered density varies depending on the composition of the powder.
  • ⁇ z is a value calculated by the following formula (3).
  • ⁇ z -0.0402 (molar concentration of Sc2O3 ) + 6.1294 ... (3)
  • ⁇ z is a value calculated by the following formula (3-1).
  • ⁇ z -0.0400 (molar concentration of CaO) + 6.1700 ... (3-1)
  • Z is the colorant concentration (wt %) and V is the colorant theoretical density (g/cm 3 ).
  • the theoretical density of the colorants is 5.24 g/ cm3 for Fe2O3 , 5.61 g/ cm3 for ZnO, 5.03 g/ cm3 for MnO2 , 6.10 g/ cm3 for CoO, 5.22 g/ cm3 for Cr2O3 , 4.23 g/ cm3 for TiO2 , 7.80 g/ cm3 for Tb4O7 , 6.31 g/ cm3 for CuO , and 3.36 g / cm3 for V2O5 .
  • the sintered density is measured by the Archimedes method.
  • the silver-containing zirconia sintered body according to this embodiment can be obtained, for example, by the method for producing a silver-containing zirconia sintered body described below.
  • the silver-containing zirconia sintered body according to the present embodiment can be used as an industrial part, an aesthetic part, a dental material, etc. More specifically, it can be used for jewelry, watch parts, watch dials, artificial teeth, molding parts, wear-resistant parts, chemical-resistant parts, etc.
  • a blade is made from the silver-containing zirconia sintered body, the deterioration of the antibacterial effect caused by wear and sharpening during use can be suppressed.
  • the resistance to hydrothermal degradation is improved by low-temperature sintering, the blade can exhibit stable mechanical properties even under conditions that cause hydrothermal degradation, such as in a dishwasher.
  • the silver-containing stabilized zirconia powder according to this embodiment is A stabilized zirconia containing zirconia and a stabilizer; It contains silver and/or silver oxide having an average particle size of 0.5 ⁇ m or less.
  • the silver-containing stabilized zirconia powder contains primary particles of stabilized zirconia containing zirconia as a main component. All or a part of the primary particles are aggregated to form secondary particles. That is, the silver-containing stabilized zirconia powder contains primary particles of stabilized zirconia that are not aggregated, and secondary particles formed by aggregation of the primary particles. However, in the silver-containing stabilized zirconia powder, the amount of primary particles that do not become secondary particles and exist in the form of non-aggregated primary particles is very small, for example, less than 1 mass % of the total primary particles (the total of non-aggregated primary particles and primary particles that have aggregated to become secondary particles).
  • the silver-containing stabilized zirconia powder may contain a very small amount of non-aggregated primary particles, but the majority is composed of secondary particles.
  • zirconia as the main component means that the primary particles contain 70 mass% or more of zirconia when the primary particles are taken as 100 mass%. That is, in this specification, primary particles containing zirconia as the main component refer to primary particles containing 70 mass% or more of zirconia.
  • the content of zirconia contained in the primary particles is preferably 74 mass% or more, more preferably 80 mass% or more, and even more preferably 85 mass% or more.
  • the silver-containing stabilized zirconia powder according to this embodiment contains silver and/or silver oxide having an average particle size of 0.5 ⁇ m or less.
  • the silver oxide particles become silver particles when thermally decomposed.
  • the silver-containing stabilized zirconia powder contains stabilized zirconia and silver and/or silver oxide having an average particle size of 0.5 ⁇ m or less, and therefore, by sintering the silver-containing stabilized zirconia powder, a sintered body containing silver (silver particles) having an average particle size of 0.5 ⁇ m or less can be obtained.
  • the silver-containing stabilized zirconia powder contains only silver oxide having an average particle diameter of 0.5 ⁇ m or less
  • the silver-containing stabilized zirconia powder contains both silver and silver oxide having an average particle diameter of 0.5 ⁇ m or less
  • the silver-containing stabilized zirconia powder contains only silver having an average particle diameter of 0.5 ⁇ m or less
  • the silver oxide particles become silver particles when thermally decomposed, and therefore, by sintering the silver-containing stabilized zirconia powder, a sintered body containing silver (silver particles) having an average particle diameter of 0.5 ⁇ m or less can be obtained.
  • the average particle size of silver and/or silver oxide refers to the overall average particle size of silver and silver oxide, without distinguishing between silver and silver oxide.
  • the method for measuring the average particle size of silver and/or silver oxide is as described in the Examples.
  • the average particle size of the silver and/or silver oxide is preferably 0.4 ⁇ m or less, more preferably 0.3 ⁇ m or less.
  • the average particle size of the silver and/or silver oxide is preferably 0.01 ⁇ m or more and 0.4 ⁇ m or less, and more preferably 0.01 ⁇ m or more and 0.3 ⁇ m or less.
  • the content of the silver and/or silver oxide is preferably within a range of 0.025% by mass or more and 20% by mass or less in terms of Ag 2 O, when the total of the zirconia and the stabilizer is taken as 100% by mass.
  • the content of the silver and/or silver oxide is 0.025% by mass or more, the antibacterial properties are excellent.
  • the content of the silver and/or silver oxide is 20% by mass or less, the sinterability is more excellent.
  • the content of the silver and/or silver oxide is 20% by mass or less, the mechanical properties of the obtained sintered body are more excellent.
  • the content of the silver and/or silver oxide is more preferably 0.05 mass% or more, further preferably 0.1 mass% or more, and particularly preferably 0.5 mass% or more, calculated as Ag2O , when the total of zirconia and the stabilizer is 100 mass%.
  • the content of the silver and/or silver oxide is more preferably 16 mass% or less, further preferably 12 mass% or less, and particularly preferably 10 mass% or less, calculated as Ag 2 O, when the total of zirconia and the stabilizer is 100 mass%.
  • the content of the silver and/or silver oxide is more preferably 0.05% by mass or more and 16% by mass or less, further preferably 0.1% by mass or more and 12% by mass or less, and particularly preferably 0.5% by mass or more and 10% by mass or less, calculated as Ag 2 O, when the total of zirconia and the stabilizer is 100% by mass.
  • the silver-containing stabilized zirconia powder contains stabilized zirconia that includes zirconia and a stabilizer.
  • the stabilized zirconia contains a stabilizer.
  • the stabilizer is contained in the primary particles in the form of a solid solution or the like. Because the stabilizer is contained, the silver-containing stabilized zirconia powder can be suitably sintered at low temperatures.
  • the stabilizer is preferably one or more oxides selected from alkaline earth metals and rare earth elements.
  • the alkaline earth metals are Ca, Sr, Ba, and Ra.
  • the rare earth elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the stabilizer is preferably one or more selected from the group consisting of Y2O3 , CeO2 , Er2O3 , and CaO .
  • the stabilizer is one or more selected from the group consisting of Y2O3 , CeO2 , Er2O3 , and CaO , the low-temperature sintering property is excellent, and the mechanical strength of the obtained sintered body is also excellent.
  • the content of the stabilizer is preferably 15 mol% or less when the zirconia and stabilizer are taken as the whole. If the content of the stabilizer is 15 mol% or less, the mechanical strength of the obtained sintered body is superior.
  • the content of the stabilizer is preferably 1.4 mol % or more, more preferably 1.5 mol % or more, and even more preferably 1.6 mol % or more.
  • the content of the stabilizer is preferably 14 mol % or less, more preferably 13 mol % or less, and even more preferably 12.5 mol % or less.
  • the content of the stabilizer is more preferably from 1.4 mol % to 14 mol %, further preferably from 1.5 mol % to 13 mol %, and particularly preferably from 1.6 mol % to 12.5 mol %.
  • the content of Y 2 O 3 is preferably 1.4 mol% or more and 7.5 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content of Y 2 O 3 is more preferably 1.5 mol% or more, and even more preferably 1.6 mol% or more.
  • the content of Y 2 O 3 is more preferably 6.5 mol% or less, even more preferably 6 mol%, particularly preferably 5.6 mol% or less, especially preferably 5 mol% or less, and especially preferably 4.5 mol% or less.
  • the zirconia sintered body obtained by sintering the silver-containing stabilized zirconia powder has better mechanical strength.
  • the content of Y 2 O 3 in the total of zirconia and the stabilizer is more preferably 1.5 mol % or more and 6.5 mol % or less, and further preferably 1.6 mol % or more and 6 mol % or less.
  • the content of CeO 2 is preferably 10 mol% or more and 15 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content of CeO 2 is more preferably 11 mol% or more, and even more preferably 11.5 mol% or more.
  • the content of CeO 2 is more preferably 14 mol% or less, even more preferably 13 mol% or less, particularly preferably 12.5 mol% or less, and especially preferably 12 mol% or less.
  • the zirconia sintered body obtained by sintering the silver-containing stabilized zirconia powder has better mechanical strength.
  • the content of CeO 2 is preferably 10 mol% or more and 14 mol% or less.
  • the content of CeO2 in the total of zirconia and the stabilizer is more preferably 11 mol% or more and 14 mol% or less, even more preferably 11.5 mol% or more and 13 mol% or less, and particularly preferably 11.5 mol% or more and 12.5 mol% or less.
  • the content of the stabilizer is preferably 1.4 mol% or more and 7.5 mol% or less when the zirconia and the stabilizer are taken as a whole.
  • the content is more preferably 1.5 mol% or more, and even more preferably 1.6 mol % or more.
  • the content is more preferably 6.5 mol% or less, even more preferably 6 mol%, particularly preferably 5.6 mol % or less, especially preferably 5 mol % or less, and especially preferably 4.5 mol% or less.
  • the zirconia sintered body obtained by sintering the silver-containing stabilized zirconia powder has superior mechanical strength.
  • the content of the stabilizer in the total amount of zirconia and the stabilizer is more preferably 1.5 mol % or more and 6.5 mol % or less, and even more preferably 1.6 mol % or more and 6 mol % or less.
  • the content of CaO is preferably 3.5 mol% or more and 15 mol% or less when the zirconia and the stabilizer are taken as the whole.
  • the content of CaO is more preferably 3.8 mol% or more, and even more preferably 4.0 mol% or more.
  • the content of CaO is more preferably 12.0 mol% or less, and even more preferably 9.0 mol% or less.
  • the zirconia sintered body obtained by sintering the silver-containing stabilized zirconia powder has better mechanical strength.
  • the content of CaO in the total of zirconia and the stabilizer is more preferably 3.8 mol % or more and 12 mol % or less, and even more preferably 4 mol % or more and 9 mol % or less.
  • the total amount of the stabilizer is 2.5 mol% or more and 6.5 mol % or less in terms of oxide when zirconia and the stabilizer are taken as the whole, and the ratio of [CaO amount (mol%)]/[total amount of stabilizer (mol%)] is 50% or more and 98% or less.
  • the ratio of the amount of CaO (mol %) to the total amount of stabilizers (mol %) is more preferably 55% or more, and further preferably 60% or more.
  • the ratio of the amount of CaO (mol %) to the total amount of stabilizers (mol %) is more preferably 90% or less, and further preferably 80% or less.
  • the ratio of the amount of CaO (mol %) to the total amount of stabilizers (mol %) is more preferably 55% or more and 90% or less, and further preferably 60% or more and 80% or less.
  • the total amount of the stabilizer is preferably 2.5 mol% or more and 6.5 mol% or less in terms of oxide, when the zirconia and the stabilizer are taken as a whole.
  • the total amount of the stabilizer is 2.5 mol% or more in terms of oxide, the monoclinic phase ratio in the obtained zirconia sintered body can be reduced, and the occurrence of cracks in the zirconia sintered body obtained by sintering the zirconia powder can be prevented.
  • the total amount of the stabilizer when the total amount of the stabilizer is 6.5 mol% or less in terms of oxide, the cubic phase ratio with low mechanical properties (strength, toughness) can be reduced, and the tetragonal phase ratio with high mechanical properties can be increased.
  • the total amount of the stabilizer is preferably 2.7 mol % or more, more preferably 2.9 mol % or more, and even more preferably 3.0 mol % or more, calculated as oxide.
  • the total amount of the stabilizer is preferably 6.0 mol % or less, more preferably 5.5 mol % or less, further preferably 5.0 mol % or less, and particularly preferably 4.5 mol % or less, calculated as oxide.
  • the total amount of the stabilizer is preferably 2.7 mol % or more and 6.0 mol % or less, more preferably 2.9 mol % or more and 5.5 mol % or less, further preferably 3.0 mol % or more and 5.0 mol % or less, and particularly preferably 3.0 mol % or more and 4.5 mol % or less, calculated as oxide.
  • the silver-containing zirconia powder may contain 25% by mass or less of Al 2 O 3 (alumina) when the total amount of zirconia and the stabilizer is 100% by mass.
  • alumina Al 2 O 3
  • the alumina acts as a sintering aid when the zirconia powder is sintered to obtain a silver-containing zirconia sintered body.
  • the content of Al 2 O 3 is more preferably 10 mass % or less, and further preferably 1 mass % or less, from the viewpoint of allowing the Al 2 O 3 to suitably function as a sintering aid.
  • the content of Al 2 O 3 is more preferably 0.1 mass % or less, and further preferably 0.25 mass % or less, from the viewpoint of allowing the Al 2 O 3 to suitably function as a sintering aid.
  • the content of Al 2 O 3 is more preferably 0.1 mass % or more and 10 mass % or less, and further preferably 0.25 mass % or more and 1 mass % or less.
  • the alumina in the silver-containing stabilized zirconia powder is in the form of a powder
  • the average particle size of the primary particles of the 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 to 0.2 ⁇ m.
  • the silver-containing stabilized zirconia powder can be sintered at a low temperature when it has the following pore volume distribution. Therefore, even if it does not contain a sintering aid, low-temperature sintering is possible.
  • the silver-containing stabilized zirconia powder may contain, in addition to alumina, sinterable ceramics, thermosetting resins, etc., in order to improve properties such as strength.
  • the silver-containing stabilized zirconia powder may contain one or more elements selected from the group consisting of Fe, V, Mn, Co, Cr, Tb, Zn, Cu, and Ti.
  • the silver-containing stabilized zirconia powder contains one or more elements selected from the group consisting of Fe, V, Mn, Co, Cr, Tb, Zn, Cu, and Ti as a coloring element
  • the zirconia sintered body obtained by sintering the silver-containing stabilized zirconia powder can be suitably colored.
  • the silver-containing stabilized zirconia powder preferably has a peak top diameter of pore volume distribution of 20 nm to 200 nm in the range of 10 nm to 0.5 ⁇ m in the pore distribution based on mercury intrusion porosimetry.
  • the peak top diameter is preferably 25 nm or more, more preferably 30 nm or more, even more preferably 32 nm or more, and particularly preferably 35 nm or more.
  • the peak top diameter is preferably 150 nm or less, more preferably 120 nm or less, even more preferably 100 nm or less, and particularly preferably 85 nm or less.
  • the peak top diameter is preferably 25 nm or more and 150 nm or less, and more preferably 30 nm or more and 120 nm or less.
  • the phrase "the peak top diameter of the pore volume distribution is 20 nm or more and 200 nm or less" in this specification means that all peak top diameters in the range of 10 nm or more and 0.5 ⁇ m or less of the pore distribution are within the range of 20 nm or more and 200 nm or less.
  • the silver-containing stabilized zirconia powder preferably has a pore distribution width of 40 nm to 200 nm in the range of 10 nm to 0.5 ⁇ m in the pore distribution based on the mercury intrusion method.
  • the pore distribution width is preferably 43 nm or more, more preferably 46 nm or more, even more preferably 50 nm or more, and particularly preferably 55 nm or more.
  • the pore distribution width is preferably 150 nm or less, more preferably 120 nm or less, even more preferably 110 nm or less, particularly preferably 100 nm or less, and especially preferably 80 nm or less.
  • the pore distribution width is preferably 43 nm or more and 150 nm or less, and more preferably 46 nm or more and 120 nm or less.
  • 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.
  • the term "pore distribution width is 40 nm or more and 200 nm or less" in this specification means that in a graph showing pore distribution with pore diameter on the horizontal axis and log differential pore volume on the vertical axis, the point where the pore diameter first crosses the log differential pore volume of 0.1 mL/g (the point where the pore diameter crosses while ascending) as viewed from the smaller pore diameter side, the point where the pore diameter crosses the log differential pore volume of 0.1 mL/g again (the point where the pore diameter crosses while descending) is taken as the minimum diameter, and the difference between the maximum diameter and the minimum diameter is 40 nm or more and 200 nm or less.
  • the silver-containing stabilized zirconia powder preferably 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 0.5 ⁇ m or less in the pore distribution based on mercury intrusion porosimetry.
  • the pore volume is preferably 0.22 ml/g or more, more preferably 0.25 ml/g or more, even more preferably 0.3 ml/g or more, particularly preferably 0.35 ml/g or more, and especially preferably 0.4 ml/g or more.
  • the pore volume is preferably 0.48 ml/g or less, more preferably 0.46 ml/g or less, and particularly preferably 0.44 ml/g or less.
  • the pore volume is preferably 0.22 ml/g or more and 0.48 ml/g or less, and more preferably 0.25 ml/g or more and 0.46 ml/g or less.
  • the “range of 10 nm or more and 0.5 ⁇ m or less in the pore size distribution based on mercury intrusion porosimetry” is the range in which pores can exist as gaps between primary particles of the silver-containing stabilized zirconia powder.
  • the peak top diameter of the pore volume distribution is 20 nm or more and 200 nm or less and the pore distribution width is 40 nm or more and 200 nm or less in the range of 10 nm or more and 0.5 ⁇ m or less in the pore distribution based on mercury intrusion porosimetry
  • the size of each pore is small and uniform (the distribution is sharp). Therefore, the primary particles constituting the secondary particles are uniformly and densely aggregated, and no large pores exist.
  • zirconia particles (including primary particles and secondary particles) have the characteristic that they are difficult to sinter if their pore volume is large.
  • zirconia particles in order to sinter at low temperatures, not only must the size of the pores originating from the gaps between primary particles in the secondary particles be small and have a sharp distribution, but the pore volume originating from the gaps between primary particles must also be small at the same time.
  • the pore volume in the range of 10 nm or more and 0.5 ⁇ m or less in the pore distribution based on mercury intrusion porosimetry is 0.2 ml/g or more and less than 0.5 ml/g, the pore volume originating from the gaps between primary particles is small and no large pores are present, making it possible to obtain a sintered body with a high sintered density.
  • the pore size, pore distribution, and pore volume of the gaps between primary particles it is possible to perform sintering at a low temperature and obtain a sintered body with a high sintered density.
  • the particle size D 50 of the silver-containing stabilized zirconia powder is preferably 0.1 ⁇ m or more and 1.5 ⁇ m or less.
  • the particle size D 50 is preferably 0.1 ⁇ m or more, more preferably 0.20 ⁇ m or more, even more preferably 0.25 ⁇ m or more, and particularly preferably 0.30 ⁇ m or more.
  • the particle size D 50 is preferably 1.2 ⁇ m or less, more preferably 1.0 ⁇ m or less, even more preferably 0.8 ⁇ m or less, particularly preferably 0.7 ⁇ m or less, especially preferably 0.6 ⁇ m or less, and especially preferably less than 0.5 ⁇ m.
  • the particle size D50 of the silver-containing stabilized zirconia powder is preferably 0.1 ⁇ m or more and 1.5 ⁇ m or less, and more preferably 0.20 ⁇ m or more and 1.0 ⁇ m or less.
  • the particle diameter D50 refers to a value obtained by the method described in the Examples.
  • the particle diameter D50 may include not only secondary particles but also non-aggregated primary particles when measured, but the amount of non-aggregated primary particles contained in the silver-containing stabilized zirconia powder is very small. Therefore, the particle diameter D50 may be regarded as representing the particle diameter D50 of the secondary particles, i.e., the average particle diameter of the secondary particles.
  • the particle diameter D50 of the silver-containing stabilized zirconia powder is 1.5 ⁇ m or less, the particle diameter of the secondary particles is relatively small, so that the gap between the secondary particles can be made small. As a result, the low-temperature sintering property is excellent. In addition, since the gap between the secondary particles is small, a sintered body with a high sintering density can be obtained.
  • the specific surface area of the silver-containing stabilized zirconia powder is preferably 5 m2 /g or more and 60 m2 /g or less.
  • the specific surface area is preferably 5 m2 /g or more, more preferably 9 m2 /g or more, even more preferably 13 m2 /g or more, and particularly preferably 15 m2 /g or more.
  • the specific surface area is preferably 50 m2 /g or less, more preferably 40 m2 /g or less, even more preferably 35 m2 /g or less, and particularly preferably 30 m2 /g or less.
  • the specific surface area of the silver-containing stabilized zirconia powder is more preferably 9 m 2 /g to 40 m 2 /g, further preferably 13 m 2 /g to 35 m 2 /g, and particularly preferably 15 m 2 /g to 30 m 2 /g.
  • the specific surface area of the silver-containing stabilized zirconia powder is more preferably 9 m 2 /g to 40 m 2 /g, further preferably 13 m 2 /g to 35 m 2 /g, and particularly preferably 15 m 2 /g to 30 m 2 /g.
  • the specific surface area refers to a value obtained by the method described in the Examples.
  • Method of manufacturing silver-containing stabilized zirconia powder An example of a method for producing a silver-containing stabilized zirconia powder will be described below, although the method for producing a silver-containing stabilized zirconia powder is not limited to the following example.
  • the method for producing the silver-containing stabilized zirconia powder according to this embodiment is as follows: The method includes a step of mixing stabilized zirconia containing zirconia and a stabilizer with silver oxide having an average particle size of 0.5 ⁇ m or less.
  • the method for producing the silver-containing stabilized zirconia powder preferably comprises the steps of: Step 1: heating the zirconium salt solution and the sulfating agent solution separately to 95° C. or higher and 100° C. or lower; a step 2 of contacting the heated zirconium salt solution with the heated sulfating agent solution so that the concentration of the mixed solution does not change from the start to the end of the contact, thereby obtaining a basic zirconium sulfate-containing reaction solution as a mixed solution; Step 3: aging the reaction solution containing basic zirconium sulfate obtained in step 2 at 95° C.
  • a step 7 includes mixing the stabilized zirconia obtained in the step 6 with silver oxide having an average particle size of 0.5 ⁇ m or less, In the step 2, from the start to the end of the contact, the SO 4 2 ⁇ /ZrO 2 weight ratio in the mixed liquid is maintained in the range of 0.3 to 0.8, and the temperature of the mixed liquid is maintained at 95° C. or higher.
  • step 1 the zirconium salt solution and the sulfating agent solution, which are starting materials, are each heated separately to a temperature of 95° C. or higher and 100° C. or lower.
  • the zirconium salt used to prepare the zirconium salt solution may be any that supplies zirconium ions, and examples of such zirconium salts include zirconium nitrate, zirconium oxychloride, and zirconium nitrate. These may be used alone or in combination of two or more. Among these, zirconium oxychloride is preferred in terms of its high productivity on an industrial scale.
  • the solvent used to prepare the zirconium salt solution may be selected according to the type of zirconium salt, etc. Usually, water (pure water, ion-exchanged water, the same applies below) is preferred.
  • the concentration of the zirconium salt solution is not particularly limited, but in general, it is preferable that the zirconium salt solution contains 5 to 250 g, and more preferably 20 to 150 g, calculated as zirconium oxide (ZrO 2 ) per 1000 g of solvent.
  • the sulfating agent may be any agent that reacts with zirconium ions to produce sulfates (i.e., a sulfating agent), and examples thereof include sodium sulfate, potassium sulfate, ammonium sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, potassium disulfate, sodium disulfate, and sulfur trioxide.
  • the sulfating agent may be in any form, such as a powder or a solution, but a solution (particularly an aqueous solution) is preferred.
  • the solvent may be the same as that used to prepare the zirconium salt solution.
  • the acid concentration of the zirconium salt solution is preferably 0.1 to 2.0 N.
  • the acid concentration can be adjusted, for example, by using hydrochloric acid, nitric acid, sodium hydroxide, etc.
  • the concentration of the sulfating agent is not particularly limited, but it is generally preferable to use 5 to 250 g, and particularly 20 to 150 g, of sulfating agent per 1000 g of solvent.
  • the materials of the containers for preparing the zirconium salt solution and the sulfating agent solution are not particularly limited as long as they have a capacity capable of sufficiently stirring the zirconium salt solution and the sulfating agent solution, respectively. However, it is preferable that the containers have a device capable of appropriately heating the solutions so that the temperatures of the solutions do not fall below 95° C.
  • the heating temperature of the zirconium salt solution and the sulfating agent solution may be from 95° C. to 100° C., and is preferably at least 97° C. If step 2 is performed while the temperatures of the zirconium salt solution and the sulfating agent solution are less than 95° C., the zirconium salt solution and the sulfating agent do not react sufficiently, resulting in a reduced yield.
  • Step 2 the heated zirconium salt solution and the heated sulfating agent 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, thereby obtaining a basic zirconium sulfate-containing reaction solution as a mixed 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 the method for producing a silver-containing stabilized zirconia powder according to the present embodiment.
  • a container 10 is connected to one end (left side in Fig. 1) above a T-shaped tube 20 via a valve 12.
  • a container 30 is connected to the other end (right side in Fig. 1) above the T-shaped tube 20 via a valve 32.
  • a zirconium solution heated to 95°C or more and 100°C or less is stored in the container 10.
  • a sulfating agent solution heated to 95°C or more and 100°C or less is stored in the container 30.
  • the zirconium solution is contacted with the sulfating agent solution by opening valve 12 and valve 32.
  • the mixed solution (basic zirconium sulfate-containing reaction solution) obtained by the contact immediately flows into the aging vessel 40 from the lower part of the T-shaped tube 20.
  • this method is used to prevent the concentration of the reaction solution (concentration of the reaction solution in the T-shaped tube 20) from changing from the start to the end of the contact between the zirconium solution and the sulfating agent solution.
  • the change in concentration of SO 4 2- /ZrO 2 from the start to the end of the contact is suppressed, so that a uniform reaction product is obtained.
  • the SO 4 2- /ZrO 2 weight ratio in the mixed solution in step 2 is preferably within the range of 0.3 to 0.8, more preferably 0.4 to 0.7, and even more preferably 0.45 to 0.65.
  • step 2 in order to maintain the temperature of the mixed liquid at 95° C. or higher, it is preferable to install heaters in the pipes (e.g., T-shaped pipe 20) supplying each solution.
  • step 2 When a T-shaped tube having a tube diameter L1 of 10 mm at one upper end (left side in FIG. 1), a tube diameter L2 of 10 mm at the other upper end (right side in FIG. 1), and a tube diameter L3 of 15 mm at the lower end is used as the T-shaped tube 20, and 213 g of a 25 mass% aqueous sodium sulfate solution is contacted with 450 g of a 16 mass% aqueous zirconium oxychloride solution calculated as ZrO2, the time (contact time) from the start of contact to the end of contact (until the aqueous zirconium chloride solution in container 10 and the sulfating agent solution in container 30 are exhausted) is preferably 30 seconds to 300 seconds, more preferably 60 seconds to 200 seconds, and even more preferably 90 seconds to 150 seconds.
  • step 3 the basic zirconium sulfate-containing reaction liquid obtained in step 2 is aged at 95° C. or higher for 3 hours or more.
  • step 3 for example, the basic zirconium sulfate-containing reaction liquid flowing into the aging vessel 40 is aged at 95° C. or higher for 3 hours or more while being stirred with 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 liquid (basic zirconium sulfate-containing reaction liquid) in step 3 is preferably 95° C. or higher, more preferably 97° C. or higher and 100° C. or lower. By setting the aging temperature to 95° C.
  • the mixture contains basic zirconium sulfate as a main component and is a basic zirconium sulfate slurry.
  • step 4 a stabilizer is added to the basic zirconium sulfate-containing reaction liquid after aging obtained in step 3.
  • step 5 an alkali is added to the basic zirconium sulfate-containing reaction liquid obtained in step 4 to carry out a neutralization reaction.
  • a zirconium-containing hydroxide is produced by the neutralization.
  • the alkali is not limited, and examples thereof include caustic soda, sodium carbonate, ammonia, hydrazine ammonium hydrogen carbonate, etc.
  • the concentration of the alkali is not particularly limited, but it is usually diluted with water to 5 to 30%.
  • the slurry is filtered to obtain a zirconium-containing hydroxide.
  • the zirconium-containing hydroxide is preferably washed with pure water or the like to remove impurities. After washing with water, drying or the like can be performed as necessary.
  • step 6 the zirconium-containing hydroxide obtained in step 5 is heat-treated (calcined) to oxidize the zirconium-containing hydroxide, thereby obtaining stabilized zirconia.
  • the heat treatment temperature (calcination temperature) and heat treatment time (calcination time) of the zirconium-containing hydroxide are not particularly limited, but are usually performed at about 600 to 1050°C for 1 to 10 hours.
  • the calcination temperature is more preferably 650°C or higher and 1000°C or lower, and even more preferably 700°C or higher and 980°C or lower.
  • the calcination temperature is more preferably 2 to 6 hours, and even more preferably 2 to 4 hours.
  • the specific surface area of the obtained stabilized zirconia can be set in a suitable range (for example, 5 m2 /g or higher and 60 m2 /g or lower).
  • the heat treatment atmosphere is not particularly limited, but is usually performed in air or an oxidizing atmosphere.
  • step 7 the stabilized zirconia obtained in step 6 is mixed with silver oxide having an average particle size of 0.5 ⁇ m or less.
  • the stabilized zirconia powder and the silver oxide may be made into a slurry to homogenize them. This produces a silver-containing stabilized zirconia powder.
  • the silver-containing stabilized zirconia powder obtained may be pulverized to form a slurry, if necessary.
  • a binder may be added to improve moldability.
  • the binder and the silver-containing stabilized zirconia powder may be mixed uniformly in a kneader.
  • the binder is preferably an organic binder, since the organic binder can be easily removed from the molded body in a heating furnace in an oxidizing atmosphere and a degreased body can be obtained, so that impurities are less likely to remain in the final sintered body.
  • the organic binder may be soluble in alcohol or soluble in a mixture of two or more selected from the group consisting of alcohol, water, aliphatic ketones, and aromatic hydrocarbons.
  • the organic binder may be, for example, 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 include one or more thermoplastic resins that are insoluble in alcohol or the mixture. After the organic binder is added, the mixture is dried, pulverized, and otherwise treated by a known method to obtain the desired silver-containing stabilized zirconia powder.
  • the particle size D 50 of the silver-containing stabilized zirconia powder can be controlled by the pulverization in step 8.
  • the particle size D 50 of the silver-containing stabilized zirconia powder can be controlled by pulverization depending on the state of the silver-containing stabilized zirconia powder obtained in step 5.
  • the silver-containing stabilized zirconia powder immediately after step 7 is a silver-containing stabilized zirconia powder containing stabilized zirconia and silver oxide, and usually does not contain silver.
  • the silver oxide is decomposed to become silver.
  • all or a part of the silver oxide is decomposed to become silver.
  • a silver-containing stabilized zirconia powder containing stabilized zirconia and silver oxide having an average particle size of 0.5 ⁇ m or less and not containing silver is obtained;
  • heating is performed to such an extent that part of the silver oxide is decomposed, whereby stabilized zirconia and a silver-containing stabilized zirconia powder containing silver and silver oxide and having an average particle size of 0.5 ⁇ m or less can be obtained.
  • step 7 heating is carried out to such an extent that all of the silver oxide is decomposed, whereby a silver-containing stabilized zirconia powder containing stabilized zirconia and silver having an average particle size of 0.5 ⁇ m or less and containing no silver oxide is obtained.
  • a sintering aid, a colorant, etc. When a sintering aid, a colorant, etc. are added, it is possible to obtain a silver-containing stabilized zirconia powder containing the sintering aid, the colorant, etc. by adding and mixing in the above-mentioned step 7. As a more detailed method of mixing, it is preferable to disperse the ingredients in pure water or the like to form a slurry and wet mix the slurry. When the step 7 is carried out, a sintering aid, a colorant, etc. may be added.
  • the method for producing a zirconia sintered body according to this embodiment is as follows: A step X of molding the silver-containing stabilized zirconia powder to obtain a molded body; After the step X, the method includes a step Y of sintering the molded body under conditions of 1250° C. to 1500° C. and 1 hour to 5 hours.
  • silver-containing stabilized zirconia powder is prepared.
  • the silver-containing stabilized zirconia powder the one described in the section [Silver-containing stabilized zirconia powder] can be used.
  • the silver-containing stabilized zirconia powder is molded to obtain a molded body (step X).
  • a commercially available metal molder or cold isostatic pressing (CIP) can be used.
  • the silver-containing stabilized zirconia powder may be temporarily molded using a metal molder, and then finally molded by press molding.
  • the pressure for press molding is usually in the range of 0.1t to 3t/ cm2 .
  • it is 0.5t to 2.5t/ cm2 , more preferably 0.8t to 2.2t/ cm2 , and even more preferably 1t to 2t/ cm2 .
  • the molded body is sintered under conditions of 1250° C. to 1500° C. and 1 hour to 5 hours (step Y).
  • the sintering temperature can be set to a low temperature of 1250 to 1500°C.
  • the sintering temperature is more preferably 1300°C or higher and 1450°C or lower, and particularly preferably 1350°C or higher and 1400°C or lower.
  • the holding time during sintering is not particularly limited, but is preferably about 1 to 5 hours, and more preferably 1 to 3 hours, for example.
  • the sintering atmosphere can be air or an oxidizing atmosphere. Sintering may be performed under normal pressure, and pressurization is not particularly required.
  • step Y if silver oxide remains in the silver-containing stabilized zirconia powder, all of the silver oxide is thermally decomposed to silver by this sintering step (step Y). Depending on the sintering conditions, some (e.g., a very small amount) of silver oxide may remain.
  • a silver-containing zirconia sintered body that contains silver particles, zirconia, and a stabilizer, in which the average particle size of the silver particles is 0.5 ⁇ m or less, the average crystal grain size of the stabilized zirconia is 0.35 ⁇ m or less, and the relative sintered density is 98% or more.
  • the present invention will be described in detail below using examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.
  • the silver-containing stabilized zirconia powder and the silver-containing zirconia sintered body in the examples and comparative examples contain 1 to 3 mass % of hafnium as an inevitable impurity relative to zirconium (calculated by the following formula (X)).
  • X formula
  • Example 1 213 g of a 25% by mass aqueous solution of sodium sulfate and 450 g of a 16% by mass aqueous solution of zirconium oxychloride (acid concentration: 1 N) calculated as ZrO2 were each heated to 95° C. separately (step 1). Thereafter, the heated aqueous solutions were brought into contact with each other for 2 minutes so that the SO 4 2 ⁇ /ZrO 2 mass ratio of the mixed solution became 0.50 (step 2). Next, the obtained reaction liquid containing basic zirconium sulfate was kept at 95° C. for 4 hours for aging, thereby obtaining basic zirconium sulfate (Step 3).
  • step 4 an aqueous solution of yttrium chloride having a concentration of 10 mass % in terms of Y 2 O 3 was added thereto so that the concentration of Y 2 O 3 was 3.2 mol %, and the mixture was mixed uniformly (step 4).
  • a 25% by mass aqueous solution of sodium hydroxide was added to the resulting mixed solution to neutralize it to a pH of 13 or more, thereby forming a hydroxide precipitate (step 5).
  • the above operation was carried out using the apparatus as explained with reference to FIG.
  • the resulting hydroxide precipitate was filtered and thoroughly washed with water, and the resulting hydroxide was heat-treated in air at 1000° C.
  • step 6 unground stabilized zirconia (yttria-stabilized zirconia powder) (step 6).
  • Silver oxide powder manufactured by Mitsuwa Chemical Co., Ltd., product name: silver oxide (I), average particle size: 20 ⁇ m
  • alumina powder having an average primary particle size of 0.1 ⁇ m was added in an amount of 0.5 mass% relative to the stabilized zirconia, and the mixture was ground and mixed for 40 hours in a wet ball mill using water as a dispersion medium (step 7).
  • Zirconia beads ⁇ 5 mm were used for the grinding.
  • the zirconia slurry obtained after grinding was dried at 110° C. to obtain the silver-containing stabilized zirconia powder described in Example 1.
  • Example 2-5 The silver-containing stabilized zirconia powder according to Example 2-5 was obtained in the same manner as in Example 1, except that the amount of silver oxide added was changed as shown in Table 1, no alumina powder was added, and the firing temperature was changed to 850°C.
  • Example 6 A silver-containing stabilized zirconia powder according to Example 6 was obtained in the same manner as in Example 1, except that no alumina powder was added and the firing temperature was changed to 1,150°C.
  • Example 7 A silver-containing stabilized zirconia powder according to Example 7 was obtained in the same manner as in Example 1, except that no alumina powder was added and the firing temperature was changed to 830°C.
  • Example 8 The same powder as the silver-containing stabilized zirconia powder of Example 3 was used as the silver-containing stabilized zirconia powder of Example 8.
  • Example 9-Example 10 Silver-containing stabilized zirconia powders according to Examples 9 and 10 were obtained in the same manner as in Example 1, except that the amount of Y 2 O 3 added was changed as shown in Table 1 and the firing temperature was changed to 850°C.
  • Example 11 A silver-containing stabilized zirconia powder according to Example 11 was obtained in the same manner as in Example 1, except that instead of adding an aqueous solution of yttrium chloride, an aqueous solution of 10 mass% erbium chloride calculated as Er 2 O 3 was added so that the content of Er 2 O 3 was 3.2 mol %, and the firing temperature was changed to 850°C.
  • Example 12 A silver-containing stabilized zirconia powder according to Example 12 was obtained in the same manner as in Example 1 , except that, instead of adding the yttrium chloride aqueous solution, a 12 mass% cerium chloride aqueous solution calculated as CeO2 was added so that CeO2 was 12 mol%, and the amount of alumina powder added was changed to 0.25 mass%.
  • Example 13 The silver-containing stabilized zirconia powder of Example 13 was obtained in the same manner as Example 1 , except that instead of adding an aqueous solution of yttrium chloride having a concentration of 10 mass% in terms of Y2O3 so that Y2O3 was 3.2 mol%, an aqueous solution of yttrium chloride was added so that Y2O3 was 0.9 mol%, and calcium carbonate ( CaCO3 ) was added so that Y2O3 was 2.1 mol% in terms of CaO, no alumina powder was added, and the firing temperature was changed to 950°C.
  • an aqueous solution of yttrium chloride having a concentration of 10 mass% in terms of Y2O3 so that Y2O3 was 3.2 mol% an aqueous solution of yttrium chloride was added so that Y2O3 was 0.9 mol%, and calcium carbonate ( CaCO3 ) was added so that Y2O3 was 2.1
  • Example 14 A silver-containing stabilized zirconia powder according to Example 14 was obtained in the same manner as in Example 1, except that the amount of alumina powder added was changed to 20 mass % and the firing temperature was changed to 850°C.
  • step 4 an aqueous solution of yttrium chloride having a concentration of 10 mass % in terms of Y 2 O 3 was added thereto so that the concentration of Y 2 O 3 was 3.2 mol %, and the mixture was mixed uniformly (step 4).
  • a 25% by mass aqueous solution of sodium hydroxide was added to the resulting mixed solution to neutralize it to a pH of 13 or more, thereby forming a hydroxide precipitate (step 5).
  • the above operation was carried out using the apparatus as explained with reference to FIG.
  • the resulting hydroxide precipitate was filtered and thoroughly washed with water, and the resulting hydroxide was heat-treated in air at 850° C.
  • step 6 (calcination temperature) for 4 hours to obtain unground stabilized zirconia (yttria-stabilized zirconia powder) (step 6).
  • Silver powder (manufactured by Mitsuwa Chemical Co., Ltd., product name: silver (particles), particle size: 2 to 4 ⁇ m) was added to the obtained unpulverized stabilized zirconia in an amount of 1 mass % relative to the stabilized zirconia, and the mixture was pulverized and mixed for 40 hours in a wet ball mill using water as a dispersion medium (step 7).
  • Zirconia beads with a diameter of 5 mm were used for pulverization.
  • the zirconia slurry obtained after pulverization was dried at 110° C. to obtain the silver-containing stabilized zirconia powder according to Example 1.
  • Comparative Example 2 99% silver (powder) (up to 525 mesh) manufactured by Mitsuwa Chemical Co., Ltd. was heat-treated at 400°C for 2 hours. This caused the particle size to become coarse.
  • a silver-containing stabilized zirconia powder according to Comparative Example 2 was obtained in the same manner as in Example 3, except that the obtained silver powder was used.
  • composition measurement of silver-containing stabilized zirconia powder The compositions (in terms of oxides) of the silver-containing stabilized zirconia powders of the examples and comparative examples were analyzed using an ICP-AES ("ULTIMA-2" manufactured by HORIBA). The results are shown in Table 1.
  • the peak top diameter, pore volume, and pore distribution width in the range of 10 nm to 0.5 ⁇ m were determined.
  • the results are shown in Table 1.
  • 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.
  • the silver-containing zirconia sintered body of Comparative Example 3 is a silver-containing zirconia sintered body obtained by sintering the silver-containing stabilized zirconia powder of Comparative Example 2 at a sintering temperature of 1550° C.
  • a sintering temperature of 1550° C. When the silver particles are large, as in the silver-containing stabilized zirconia powder of Comparative Example 2, sintering at 1550° C. is necessary for densification.
  • the silver-containing zirconia sintered body of Comparative Example 3 obtained by sintering the silver-containing stabilized zirconia powder of Comparative Example 2 at a sintering temperature of 1550° C. has deteriorated hydrothermal degradation resistance due to the increased sintering temperature.
  • Relative sintered density (%) (sintered density / theoretical sintered density) ⁇ 100 (1)
  • the theoretical sintered density ( ⁇ 0 ) is a value calculated by the following formula (2-1).
  • ⁇ 0 (100+Y+Z)/[(100/ ⁇ z)+(Y/3.987)+(Z/10.49)]...(2-1)
  • Y is the alumina concentration (wt %)
  • Z is the silver concentration (wt %).
  • the silver concentration (wt %) is calculated from formula (2-2).
  • ⁇ z is a value calculated by the following formula (2-3).
  • ⁇ z [124.25(100 ⁇ X)+[molecular weight of stabilizer] ⁇ X]/150[150.5(100+X)A 2 C] (2-3)
  • the molecular weight of the stabilizer is 225.81 when the stabilizer is Y2O3 , 382.52 when the stabilizer is Er2O3 , and 394.11 when the stabilizer is Yb2O3 .
  • X is the stabilizer concentration (mol %)
  • a and C are values calculated by the following formulas (2-4) and (2-5), respectively.
  • the theoretical sintered density varies depending on the composition of the powder.
  • ⁇ z is a value calculated by the following formula (3).
  • ⁇ z -0.0402 (molar concentration of Sc2O3 ) + 6.1294 ... (3)
  • ⁇ z is a value calculated by the following formula (3-1).
  • ⁇ z -0.0400 (molar concentration of CaO) + 6.1700 ... (3-1)
  • Z is the colorant concentration (wt %) and V is the colorant theoretical density (g/cm 3 ).
  • the theoretical density of the colorants is 5.24 g/ cm3 for Fe2O3 , 5.61 g/ cm3 for ZnO, 5.03 g/ cm3 for MnO2 , 6.10 g/ cm3 for CoO, 5.22 g/ cm3 for Cr2O3 , 4.23 g/ cm3 for TiO2 , 7.80 g/ cm3 for Tb4O7 , 6.31 g/ cm3 for CuO , and 3.36 g / cm3 for V2O5 .
  • the sintered density was measured by the Archimedes method.
  • Relative Molding Density> Relative molded density (%) (molded density / theoretical sintered density) ⁇ 100 (4)
  • the theoretical sintered density ( ⁇ 0 ) is a value calculated by the above formula (2-1).
  • the crystal grain size of the stabilized zirconia in the zirconia sintered bodies of the Examples and Comparative Examples was determined as follows. The results are shown in Table 2. SEM observations of the sintered body samples obtained by scanning electron microscope observation were obtained. The samples for SEM observation were prepared based on JIS R1633. The SEM observations were made so that the number of crystal grains of stabilized zirconia was 150 or more in one field of view. A rectangle of any size was drawn in the SEM observation, and the number of grains present on the sides and diagonals of the rectangle was calculated.
  • a magnification of 30,000 times was used, and a rectangle of 3.497 ⁇ m x 2.375 ⁇ m was drawn. Each side of the rectangle was set to a length of 80% or more of the field of view.
  • X, x1, x2, Y, y1, y2, D, d1, and d2 represent the following.
  • the sintered body samples were pretreated by mirror polishing and then thermal etching.
  • the mirror polishing was carried out by grinding the surface of the sintered body with a surface grinder, and then polishing it with diamond abrasive grains having average grain sizes of 9 ⁇ m, 6 ⁇ m, and 3 ⁇ m in a mirror polishing machine in that order.
  • the mirror polishing was performed by grinding the surface of the sintered body with a surface grinder, and then polishing with diamond abrasive grains having average grain sizes of 9 ⁇ m, 6 ⁇ m, and 3 ⁇ m in order with a mirror polishing device.
  • the results are shown in Table 2. Specifically, the monoclinic fraction of the silver-containing zirconia sintered bodies of the Examples and Comparative Examples was determined according to the following [Identification of Crystal Phase].
  • the silver-containing zirconia sintered body was subjected to an X-ray diffraction spectrum measurement using an X-ray diffractometer (RINT2500, manufactured by Rigaku Corporation) under the following measurement conditions.
  • 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
  • It(220) is the diffraction intensity of (220) in the tetragonal phase
  • It(004) is the diffraction intensity of (004) in the tetragonal phase
  • Ic(004) is the diffraction intensity of (004) in the cubic 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, but in this example, the peak between (004) and (220) of the tetragonal phase was taken as the peak of the cubic phase and calculated.
  • the toughness of the silver-containing zirconia sintered bodies of the Examples and Comparative Examples obtained above was determined as follows.
  • the toughness measurement by the IF method was performed with a load of 30 kgf (294.2 N) in accordance with JIS R1607 (Room temperature fracture toughness test method for fine ceramics).
  • JIS R1607 Room temperature fracture toughness test method for fine ceramics.
  • the toughness value was determined by averaging the toughness values of the five indentations excluding the smallest and largest values.
  • the indentations to be measured were invalid if no cracks extended from the indentation, and indentations with four cracks extending from the tip of the rectangle were used.
  • Hv Vickers hardness [GPa] a: Half the average value of the indentation length on the X and Y axes [ ⁇ m] c: Half 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 calculating d are as shown in FIG.
  • Hv Vickers hardness [GPa]
  • F Test force [N]
  • d average value of X-axis indentation length and Y-axis indentation length [mm]
  • the Young's modulus used was 210 GPa, which is known as the value of common yttria-stabilized zirconia.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Compositions Of Oxide Ceramics (AREA)
PCT/JP2024/011255 2023-03-31 2024-03-22 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 Ceased WO2024203828A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP24779946.3A EP4563548A1 (en) 2023-03-31 2024-03-22 Silver-containing zirconia sintered body, silver-containing stabilized zirconia powder, method for producing silver-containing stabilized zirconia powder, and method for producing silver-containing zirconia sintered body
CN202480004005.3A CN119894847A (zh) 2023-03-31 2024-03-22 含银氧化锆烧结体、含银稳定氧化锆粉末、含银稳定氧化锆粉末的制造方法以及含银氧化锆烧结体的制造方法
JP2025510706A JPWO2024203828A1 (https=) 2023-03-31 2024-03-22

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023057562 2023-03-31
JP2023-057562 2023-03-31

Publications (1)

Publication Number Publication Date
WO2024203828A1 true WO2024203828A1 (ja) 2024-10-03

Family

ID=92906251

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/011255 Ceased WO2024203828A1 (ja) 2023-03-31 2024-03-22 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

Country Status (4)

Country Link
EP (1) EP4563548A1 (https=)
JP (1) JPWO2024203828A1 (https=)
CN (1) CN119894847A (https=)
WO (1) WO2024203828A1 (https=)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228320A (ja) * 1998-02-20 1999-08-24 Hokko Chem Ind Co Ltd 抗菌剤及びその製造方法
JP2007063530A (ja) * 2005-08-01 2007-03-15 Saga Prefecture 黄着色用複合微粒子、および黄着色用複合微粒子の製造方法
US20160015483A1 (en) * 2014-04-30 2016-01-21 Osseodyne Surgical Solutions, LLC. Osseointegrative surgical implant
CN105367056A (zh) * 2015-12-15 2016-03-02 东莞信柏结构陶瓷有限公司 氧化锆陶瓷造粒粉的制备方法
WO2020049299A1 (en) * 2018-09-04 2020-03-12 Cambridge Nanoceramix Limited Implant with ceramic coating, method of forming an implant, and method of applying a ceramic coating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228320A (ja) * 1998-02-20 1999-08-24 Hokko Chem Ind Co Ltd 抗菌剤及びその製造方法
JP2007063530A (ja) * 2005-08-01 2007-03-15 Saga Prefecture 黄着色用複合微粒子、および黄着色用複合微粒子の製造方法
US20160015483A1 (en) * 2014-04-30 2016-01-21 Osseodyne Surgical Solutions, LLC. Osseointegrative surgical implant
CN105367056A (zh) * 2015-12-15 2016-03-02 东莞信柏结构陶瓷有限公司 氧化锆陶瓷造粒粉的制备方法
WO2020049299A1 (en) * 2018-09-04 2020-03-12 Cambridge Nanoceramix Limited Implant with ceramic coating, method of forming an implant, and method of applying a ceramic coating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAIJIN XU: "Microorganism adhesion inhibited by silver doped Yttria-stabilized zirconia ceramics", CERAM. INT., vol. 37, 2011, pages 2109 - 2115, XP028238323, DOI: 10.1016/j.ceramint.2011.02.023
YAMADA, R.: "Ag nanoparticle-coated zirconia for antibacterial prosthesis", MATER. SCI. ENG. C, vol. 78, 2017, pages 1054 - 1060, XP085046594, DOI: 10.1016/j.msec.2017.04.149

Also Published As

Publication number Publication date
EP4563548A1 (en) 2025-06-04
JPWO2024203828A1 (https=) 2024-10-03
CN119894847A (zh) 2025-04-25

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
US12286379B2 (en) Zirconia powder, method for producing zirconia powder, method for producing zirconia sintered body, and zirconia sintered body
EP1514856B1 (en) Alumina/zirconia ceramics and method of producing the same
AU2010255358A1 (en) Alumina and zirconia sintered material
JPWO2006080473A1 (ja) 複合セラミックス及びその製法
EP2460782B1 (en) Nanostructured composite material of stabilized zirconia with cerium oxide and doped alumina with zirconia, use, and procedure for obtaining same
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
JP7220309B2 (ja) 安定化ジルコニア焼結体、及び、ジルコニア粉末
JP7734268B2 (ja) ジルコニア焼結体、ジルコニア粉末、及び、ジルコニア焼結体の製造方法
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
JPWO2003076336A1 (ja) セリウム系複合酸化物、その焼結体及び製造法
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
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
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
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

Legal Events

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

Ref document number: 24779946

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2025510706

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2024779946

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2024779946

Country of ref document: EP

Effective date: 20250226

WWE Wipo information: entry into national phase

Ref document number: 202480004005.3

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 202480004005.3

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2024779946

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE