WO2015093549A1 - 白色ジルコニア焼結体及びその製造方法並びにその用途 - Google Patents

白色ジルコニア焼結体及びその製造方法並びにその用途 Download PDF

Info

Publication number
WO2015093549A1
WO2015093549A1 PCT/JP2014/083469 JP2014083469W WO2015093549A1 WO 2015093549 A1 WO2015093549 A1 WO 2015093549A1 JP 2014083469 W JP2014083469 W JP 2014083469W WO 2015093549 A1 WO2015093549 A1 WO 2015093549A1
Authority
WO
WIPO (PCT)
Prior art keywords
sintered body
zirconia sintered
white
silica
white zirconia
Prior art date
Application number
PCT/JP2014/083469
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
勲 山下
絋平 今井
山内　正一
津久間　孝次
Original Assignee
東ソー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Publication of WO2015093549A1 publication Critical patent/WO2015093549A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C04B35/6455—Hot isostatic pressing
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/9646—Optical properties
    • C04B2235/9661—Colour

Definitions

  • the present invention relates to a white zirconia sintered body whose color tone does not change depending on the thickness of a base material and a method for producing the same.
  • zirconia sintered bodies are widely used in industrial products such as grinding media and bearings. Furthermore, in recent years, various colored zirconia sintered bodies have been developed. The colored zirconia sintered body is widely used for decorative purposes and jewelry.
  • a pure zirconia sintered body is a sintered body having a translucent milky white color tone.
  • an inorganic compound having high thermal stability is used as a pigment.
  • a transition metal oxide (Patent Document 1) or a rare earth oxide (Patent Document 2) is added as a pigment, and coloring by light absorption derived from the pigment is used.
  • a method for coloring a zirconia sintered body has been reported.
  • Patent Document 3 a white zirconia sintered body to which alumina has been added (Patent Document 3) has been reported as a zirconia sintered body having optical transparency and a high-grade white color. Further, a zirconia sintered body to which 2 to 25 wt% of silica containing cristobalite is added is disclosed (Patent Document 4).
  • glass materials such as tempered glass and crystallized glass are used for exterior members (hereinafter also simply referred to as “exterior members”) for portable electronic devices and the like.
  • these glass materials are difficult to color. Therefore, the use of a zirconia sintered body that can be easily colored with a pigment as an exterior member as an alternative to a glass material has been studied.
  • the member used for the exterior member is preferably as light as possible. Therefore, when the zirconia sintered body is used as an exterior member, it is necessary to reduce the thickness.
  • a zirconia sintered body exhibiting a dark color tone such as a zirconia sintered body using a black pigment or the like, is colored using light absorption. Therefore, even if the sintered body is thin, the color tone is stable.
  • the white zirconia sintered body light is transmitted through the sintered body by reducing the thickness of the sintered body.
  • the color of the base member is transparent, the color of the zirconia sintered body and the color of the base member overlap, and the color tone changes from the base material zirconia sintered body, Furthermore, there is a problem that the color tone of the base material is different from the color tone of the exterior member in which the base material and the base are combined.
  • quartz glass used as an exterior member has been studied to reduce the transmittance by introducing pores into the glass.
  • a method has been reported in which bubbles are generated in quartz glass by a foaming agent, thereby reducing the transmittance of quartz glass (Patent Document 5).
  • Patent Document 5 a method has been reported in which bubbles are generated in quartz glass by a foaming agent, thereby reducing the transmittance of quartz glass.
  • the strength of the quartz glass is lowered and further, water is contained in the open pores generated in the quartz glass. Therefore, the transmittance reduction method using a foaming agent cannot be applied to quartz glass used as an exterior member application requiring high strength.
  • the present invention relates to a white zirconia sintered body that is suitable for exterior members such as portable electronic devices and has a high design and high density and does not transmit light.
  • a conventional white zirconia sintered body has optical transparency. For this reason, when the sintered body is thin, the color change such as the transparency of the base and the color tone after the change have been problems.
  • a conventional zirconia sintered body is used for an exterior member of an electronic device or the like that tends to be downsized, in order to stabilize the color tone of the exterior member, the zirconia sintered body should be thickened until the base is not transparent. Was necessary.
  • An object of the present invention is to provide a white zirconia sintered body that does not transmit light as a thin member, has a stable color tone, and is excellent in design. Furthermore, it aims at providing the manufacturing method of the said zirconia sintered compact, and its use.
  • the light transmittance of the white zirconia sintered body can be controlled by light scattering by the inclusions.
  • the zirconia sintered body containing silica is non-uniform in the structure of the silica particles in the sintered body. It was found that a white zirconia sintered body that does not transmit light can be obtained by increasing the property.
  • the gist of the present invention is as follows.
  • [1] A zirconia sintered body and silica having a cristobalite crystal structure of 1 to 20 wt%, a relative density of 97% or more, and a total light transmittance (1 mm thickness) of D65 light of 2%
  • a white zirconia sintered body characterized by the following.
  • [2] The white zirconia sintered body according to the above [1], wherein the total light transmittance (1 mm thickness) of D65 light is 0.5% or less.
  • a mixing step of mixing zirconia powder and silica powder having an average particle size of 1 ⁇ m or less to obtain a mixed powder, a forming step of forming the mixed powder to obtain a formed body, and a sintering step of sintering the formed body The method for producing a white zirconia sintered body according to any one of the above [1] to [7]. [9] The method for producing a white zirconia sintered body according to the above [8], wherein in the sintering step, sintering is performed at 1400 ° C. or higher under no pressure. [10] After the sintering step is performed under pressureless sintering at 1400 ° C.
  • the primary sintered body is subjected to a pressure of 50 MPa or more using a non-reducing container,
  • a member comprising the white zirconia sintered body according to any one of [1] to [7].
  • the member according to [11] which is used for an exterior of an electronic device, a decorative article, or a dental material.
  • the white zirconia sintered body of the present invention does not transmit light even as a thin member, has a stable color tone, has excellent design properties, and has high strength, such as a thin member such as a portable exterior member, a decorative article, and a dental It is excellent as a material.
  • FIG. 1 The XRD pattern of the white zirconia sintered compact of Example 3 and Example 9.
  • FIG. The XRD pattern of the white zirconia sintered compact of Examples 14, 16, and 18. 3 is an SEM image of the white zirconia sintered body of Example 1.
  • FIG. 20 is an SEM image of a white zirconia sintered body of Example 18.
  • FIG. 2 is an SEM image of a thermally etched product of the white zirconia sintered body of Example 1.
  • FIG. 4 is a TEM image of the white zirconia sintered body of Example 1.
  • the zirconia sintered body of the present invention contains silica, 1 to 20 wt (wt)% of the silica has a cristobalite crystal structure, and the relative density of the sintered body is 97% or more.
  • the total light transmittance (1 mm thickness) is 2% or less. Therefore, the color tone of the zirconia sintered body of the present invention does not change regardless of the thickness of the sintered body.
  • the refractive index n of zirconia is 2.2, while the refractive index n of silica is 1.4.
  • the white zirconia sintered body of the present invention contains silica and zirconia having a large difference in refractive index, the white zirconia sintered body has strong light scattering, and light transmission of zirconia is suppressed. Thereby, the white zirconia sintered body of the present invention becomes a zirconia sintered body having no color tone change (hereinafter, also simply referred to as “color tone change”) due to a change in the thickness of the sintered body.
  • the white zirconia sintered body of the present invention contains silica containing 1 to 20 wt% of cristobalite crystal structure (hereinafter also simply referred to as “cristobalite”).
  • the zirconia sintered body of the present invention has not only a change in color tone but also a sufficient mechanical strength as an exterior member. That is, the silica contained in the white zirconia sintered body of the present invention comprises at least one of amorphous or crystalline silica and cristobalite. At least one of amorphous or crystalline silica is silica other than cristobalite.
  • silica other than cristobalite examples include at least one silica selected from the group consisting of tridymite, quartz, stishovite, cosite, and amorphous, and at least one of quartz and amorphous. Any silica or especially quartz may be used.
  • the silica contained in the white zirconia sintered body of the present invention preferably contains cristobalite and quartz from the viewpoint of high thermal stability and easy structure having nonuniformity due to phase transition.
  • Silica having cristobalite (hereinafter also referred to as “cristobalite-type silica”) undergoes a volume change at about 200 ° C. due to an ⁇ (low temperature phase) - ⁇ (high temperature phase) phase transition. Due to this volume change, microcracks or the like are generated in the silica particles contained in the white zirconia sintered body. Such non-uniformities such as microcracks are introduced into the silica particles in the sintered body, and the light scattering effect by the silica particles can be improved.
  • the white zirconia sintered body of the present invention is not a zirconia sintered body containing silica containing cristobalite only on the surface of the sintered body, but contains at least silica containing cristobalite inside the sintered body. Therefore, the white zirconia sintered body of the present invention can confirm silica containing cristobalite not only on the surface of the sintered body but also on the polished surface of the sintered body and the cross section of the sintered body.
  • the content of silica in the white zirconia sintered body of the present invention is 5 to 30 wt%, more preferably 5 to 20 wt%, more preferably 5 to 15 wt% from the viewpoint of combining light transmission and strength. preferable.
  • the content of silica in the present invention is the weight ratio of silica to the total weight of the white zirconia sintered body of the present invention.
  • the silica content can be determined by composition analysis.
  • the cristobalite contained in the silica in the white zirconia sintered body of the present invention is 1 to 20 wt%, preferably 1 to 15 wt%.
  • the content of cristobalite is less than 1 wt%, the effect of light scattering is reduced, and the color tone change is increased.
  • the content of cristobalite is 1.5 wt% or more, and further 1.9 wt% or more, the color tone change is further suppressed.
  • the content of cristobalite exceeds 20 wt%, the volume expansion due to the phase transition of silica becomes too large, and defects such as cracks occur in the sintered body itself. A sintered body containing such defects is easily broken.
  • the content of cristobalite is 15 wt% or less, and further 13.5 wt% or less, the sintered body is more difficult to break.
  • the content of cristobalite is 1 to 15 wt%, and further 1 to 13 0.5 wt%, preferably 1 to 11 wt%, more preferably 1.5 to 15 wt%, and even more preferably 1.5 to 13.5 wt%, and 1.9 to 13.3 wt%, It is preferably 1.9 to 10.6 wt%, and more preferably 1.9 to 9.2 wt%.
  • the content of cristobalite can be determined by powder X-ray diffraction (hereinafter referred to as “XRD”) measurement. That is, it can be determined from the cristobalite phase fraction obtained from the following equation from the XRD peak area of zirconia and the XRD peak area of cristobalite in the XRD pattern of the white zirconia sintered body of the present invention.
  • XRD powder X-ray diffraction
  • Is (101) is the XRD peak area of the (101) plane of cristobalite
  • I c (111) is the XRD peak area of the cubic (111) plane of zirconia
  • IT (111) is the zirconia This is the XRD peak area of the tetragonal (111) plane.
  • the content of silica having these crystal structures is obtained. Can do.
  • the white zirconia sintered body of the present invention contains silica particles containing at least either crystalline or amorphous silica and cristobalite.
  • the average crystal grain size of the silica particles contained in the white zirconia sintered body of the present invention is preferably 0.1 to 1 ⁇ m, more preferably 0.3 to 0.7 ⁇ m. preferable.
  • the number of silica particles hereinafter also referred to as “silica phase” in the white zirconia sintered body can be increased. Increasing the number of silica particles enables more sufficient light scattering.
  • the color tone of the white zirconia sintered body of the present invention exhibits a clearer white.
  • the shape of the silica particles contained in the white zirconia sintered body of the present invention is not particularly limited, and may be an indefinite shape. It becomes easier to scatter light because the particle shape is indefinite. Further, the silica particles preferably have different shapes. That is, the shape of the silica particles contained in the white zirconia sintered body of the present invention is preferably at least two of a spherical shape, a polyhedral shape, and an indefinite shape. As the shape of the silica particles becomes non-uniform, the light transmission of the white zirconia sintered body of the present invention is more easily suppressed.
  • the zirconia sintered body of the present invention is preferably made of zirconia containing yttria, that is, the zirconia in the white zirconia sintered body is preferably yttria-containing zirconia.
  • yttria as a stabilizer
  • the white zirconia sintered body of the present invention has sufficiently high strength as an exterior member.
  • the zirconia in the white zirconia sintered body of the present invention may contain a stabilizer other than yttria. Examples of the stabilizer other than yttria include at least one selected from the group of calcia, magnesia, and ceria.
  • the zirconia sintered body in the white zirconia sintered body of the present invention is preferably an yttria-containing zirconia sintered body, that is, the zirconia is yttria-containing zirconia.
  • the yttria concentration (also referred to as yttria content) of zirconia contained in the white zirconia sintered body of the present invention is 2 to 4 mol% with respect to zirconia, that is, the yttria concentration of zirconia in the white zirconia sintered body is It is preferably 2 to 4 mol%. Thereby, the white zirconia sintered body of the present invention has excellent strength.
  • the yttria concentration is preferably 2.5 to 3.5 mol%, more preferably 2.8 to 3.2 mol%, and more preferably 3 mol%.
  • the white zirconia sintered body of the present invention has a relative density of 97% or more.
  • the relative density is 97% or more, the white zirconia sintered body of the present invention has sufficient strength as an exterior member.
  • the relative density of the white zirconia sintered body of the present invention is preferably 98% or more, more preferably 99% or more.
  • the three-point bending strength of the white zirconia sintered body of the present invention is 500 MPa or more, preferably 900 MPa or more, and more preferably 1200 MPa or more.
  • the white zirconia sintered body of the present invention has the high relative density as described above, but does not have the light transmittance of the conventional zirconia sintered body and zirconia sintered body. Therefore, the white zirconia sintered body of the present invention has a total light transmittance (hereinafter referred to as “total light transmittance of D65 light (1 mm thickness)” when the thickness of the sintered body is 1 mm and D65 is used as a light source. , “Total light transmittance (1 mm thickness)” or simply “total light transmittance”) is 2% or less. If the total light transmittance is 2% or less, the change in color tone is small.
  • the total light transmittance As the total light transmittance decreases, the color tone does not change depending on the thickness of the sintered body, that is, the color tone becomes stable.
  • the total light transmittance is preferably 1.5% or less, more preferably 1% or less, still more preferably 0.5% or less, and even more preferably 0.1% or less. If the total light transmittance is 0% or more, further more than 0%, or even 0.005% or more, the color tone hardly changes. Therefore, the white zirconia sintered body of the present invention has a total light transmittance of 0% or more and 2% or less, more than 0% and 2% or less, further 0.005% or more and 2% or less, and further 0.000. 005% to 1.5%, further 0.005% to 1%, further 0.005% to 0.5%, and further 0.005% to 0.1% are preferable. .
  • L * is a lightness index
  • a * and b * are chromaticness indices.
  • L * 90 to 96
  • a * ⁇ 0.4 to
  • b * 0.3 to 1.5
  • the method for producing a zirconia sintered body of the present invention includes a mixing step of mixing a zirconia powder and a silica powder having an average particle size of 1 ⁇ m or less to obtain a mixed powder, a forming step of forming the mixed powder to obtain a formed body, and the A molding step of sintering the molded body.
  • the zirconia powder used in the production method of the present invention is not particularly limited as long as it contains a predetermined amount of yttria.
  • the amount of yttria contained in the zirconia powder is 2.5 to 3.5 mol%, more preferably 2.8 to 3.2 mol%, and more preferably 3 mol%.
  • the zirconia powder is preferably a yttria solid solution zirconia powder containing the above amount of yttria.
  • An example of such zirconia powder is TZ-3YS (manufactured by Tosoh Corporation).
  • any silica powder can be used as long as the average particle diameter is 1 ⁇ m or less.
  • the silica powder is preferably at least one silica powder selected from the group of cristobalite, tridymite, quartz, stishovite, cosite, and amorphous, and more preferably at least one selected from the group of cristobalite, quartz, and amorphous.
  • Silica powder is preferred, and amorphous silica is more preferred.
  • An example of silica powder that can be used industrially is 1-FX (manufactured by Tatsumori).
  • pulverization methods such as a ball mill, a bead mill, and a jet mill, and made the average particle diameter 1 micrometer or less can also be utilized.
  • the average particle diameter of the silica powder is a value measured as a median value (D50) in volume distribution measurement.
  • zirconia powder and silica powder are mixed to obtain a mixed powder.
  • powder of components other than zirconia and silica can also be mixed with mixed powder. Examples of other components include zircon.
  • the method is not particularly limited as long as both are uniformly dispersed. Since mixing can be performed more uniformly, the mixing method is, for example, at least one of a wet ball mill and a wet stirring mill, but in any case, wet mixing is preferable.
  • a compact is obtained from the mixed powder. If a molded body having an arbitrary shape is obtained, a general method can be used as the molding method. Examples of the molding method include any one selected from the group of press molding, injection molding, sheet molding, extrusion molding, and cast molding. An example of a simple molding method is press molding.
  • the molded body is fired to obtain the white zirconia sintered body of the present invention.
  • a molded body obtained by molding the above-mentioned mixed powder of zirconia powder and silica powder is preferably fired at 1400 ° C. or higher, and more preferably sintered at 1400-1600 ° C.
  • cristobalite type silica is precipitated in the silica particles.
  • the white zirconia sintered body is a sintered body that exhibits a stable white color with suppressed light transmission and no change in color tone depending on the thickness of the sintered body.
  • the firing step is preferably performed at 1400 ° C. or higher under no pressure.
  • silica powder even when using silica powder containing various polymorphic phases such as at least two or more selected from the group of amorphous, cristobalite, tridymite, stishovite, cosite, and quartz, By sintering at 1400 ° C. or higher, more preferably 1450 ° C. or higher, more preferably 1500 ° C. or higher, the cristobalite phase can be precipitated on the silica in the obtained white zirconia sintered body.
  • the firing atmosphere in the firing step may be any of an oxidizing atmosphere, a reducing atmosphere, and an inert atmosphere.
  • As the oxidizing atmosphere baking can be performed in an air atmosphere, which is convenient and preferable.
  • Sintering under no pressure includes sintering at 1400 ° C. or higher in the air for 1 to 10 hours. Note that “under no pressure” is a pressure that does not result in a pressurized state, more preferably atmospheric pressure. More preferable non-pressurized firing includes firing in the air at atmospheric pressure.
  • a sintered body is sintered under no pressure, and then subjected to a hot isostatic pressing (hereinafter referred to as “HIP”) treatment.
  • HIP hot isostatic pressing
  • a sintered body (hereinafter also referred to as “primary sintered body”) obtained by sintering without pressure (hereinafter also referred to as “primary sintered body”) is subjected to HIP treatment and HIP. Get a treatment.
  • HIP treatment silica is treated at high temperature and high pressure. Thereby, the further nonuniformity is introduce
  • the HIP treatment temperature (hereinafter also referred to as “HIP temperature”) may be 1400 ° C. or lower, for example, 1250 ° C. or higher, further 1300 ° C. or higher. preferable.
  • the HIP temperature may be 1400 ° C. or higher, and the HIP temperature is preferably 1400 to 1600 ° C., more preferably 1450 to 1550 ° C. from the viewpoint of introducing non-uniformity and strength.
  • the HIP treatment pressure (hereinafter also referred to as “HIP pressure”) is preferably 50 MPa or more, and more preferably 100 to 200 MPa. By setting the HIP pressure to 50 MPa or more, cracks and the like are more likely to occur in the silica particles, so that non-uniformity in the silica phase is more easily introduced.
  • the HIP processing time (hereinafter also referred to as “HIP time”) is preferably at least one hour. If the HIP process is at least 1 hour, non-uniformity can be introduced even during the HIP process. Since the HIP treatment does not need to be more than necessary, the HIP time is preferably 10 hours or less, more preferably 5 hours or less.
  • the pressure medium for HIP treatment may be a non-oxidizing atmosphere.
  • the pressure medium may be an inert gas, and can be exemplified by at least one of nitrogen gas and argon gas.
  • the pressure medium is preferably argon gas.
  • the container used in the HIP treatment is preferably an alumina container or other non-reducing container.
  • a sample to be processed is accommodated in a carbon container.
  • a reducing container such as a carbon container
  • the sample to be treated is likely to be colored by the reduction with carbon.
  • silica may react with carbon and volatilize.
  • the semi-sealed non-reducing container refers to a state where a container made of a non-reducing material such as alumina is not sealed.
  • a crucible-shaped container made of a non-reducing material is sealed, and the container is covered with a non-reducing material.
  • a sintering method in which the primary sintered body is subjected to HIP treatment using a non-reducing container, pressure is applied.
  • HIP pressure is preferably 50 MPa or more, more preferably 50 to 150 MPa
  • temperature is preferably 1400 to 1600 ° C., more preferably 1450 to 1500 ° C. it can.
  • the white zirconia sintered body of the present invention does not have light transmittance. Therefore, even if the sintered body is thin, it is possible to provide a stable color tone without being affected by the color tone of the member used as the base of the sintered body. Thereby, the white zirconia sintered compact of this invention can be used conveniently as exterior members, such as a portable electronic device. Furthermore, the white zirconia sintered body of the present invention can be suitably used as a decorative product such as a watch or a jewelry, and a dental material.
  • the density (measured density) of the zirconia sintered body was determined by measuring the weight in water by the Archimedes method. Zirconia (manufactured by Tosoh Corporation, TZ-3YS), silica, and the true density of alumina, as respectively 6.0956g / cm 3, 2.3g / cm 3, and 3.99 g / cm 3, the measured density to the true density The relative density was calculated as a value. In addition, the theoretical density of cristobalite type
  • the surface roughness Ra is a value obtained by extracting a reference length from the roughness curve in the direction of the average line, and summing and averaging the absolute values of deviations from the average line of the extracted portion to the measurement curve. Arithmetic mean height.
  • the total light transmittance of the measurement sample was measured by a method according to JIS K7105 “Testing method for optical properties of plastic”.
  • the light source was D65 light.
  • SEM scanning electron microscope
  • the measurement sample was subjected to surface grinding, and then mirror polished using diamond abrasive grains (average particle diameters: 9 ⁇ m, 6 ⁇ m, and 1 ⁇ m). Gold was deposited on the measurement sample after mirror polishing, and this was observed.
  • a sample obtained by thermally etching the zirconia sintered body sample was also subjected to SEM observation in the same manner, and the average crystal grain size of the zirconia crystal particles was obtained.
  • an apparatus manufactured by JEOL Ltd. JEM-2000FX
  • TEM Transmission electron microscope
  • the D65 light beam is applied to a measurement sample with a black plate on the back surface, the light transmitted through the measurement sample is reflected by the black plate, the light transmitted through the measurement sample is measured again, and the lightness index L *, chromaty The Knes index a * and b * were determined.
  • D65 light ray was used for the measurement and the viewing angle was set to 2 degrees.
  • the bending strength was measured by a three-point bending test based on JIS R1601 “Fine ceramic bending strength test method”. Ten samples were measured for one sample, and the average value of the three three-point bending strengths was taken as the bending strength of the measuring sample.
  • X (Im (111) + Im (11-1)) / (Im (111) + Im (11-1) + It (111) + Ic (111)) (1)
  • X is a monoclinic crystal ratio
  • Im, It, and Ic are monoclinic, tetragonal, and cubic powder X-ray diffraction peaks of zirconia, respectively.
  • the parentheses in Im, It and Ic in the formula (1) indicate the reflection index.
  • Examples 1 to 3 (Preparation of raw material powder) A mixed powder of zirconia powder and silica powder was prepared as a raw material powder. First, 10 wt% silica powder was added to 3 mol% yttria stabilized zirconia powder. As the 3 mol% yttria-stabilized zirconia powder, one produced by a hydrolysis method (trade name: TZ-3YS, manufactured by Tosoh Corporation, average particle size 0.3 ⁇ m, surface area 7 m 2 / g) was used.
  • a hydrolysis method trade name: TZ-3YS, manufactured by Tosoh Corporation, average particle size 0.3 ⁇ m, surface area 7 m 2 / g
  • the silica powder includes high-purity silica powder synthesized by a melting method (amorphous silica, trade name: 1-FX, manufactured by Tatsumori Co., Ltd., average particle size 0.38 ⁇ m, surface area 30 m 2 / g, purity 99% or more. )It was used. These powders were mixed in a ball mill for 72 hours using 10 mm diameter balls made of zirconia in an ethanol solvent, and dried to obtain raw material powders.
  • a melting method amorphous silica, trade name: 1-FX, manufactured by Tatsumori Co., Ltd., average particle size 0.38 ⁇ m, surface area 30 m 2 / g, purity 99% or more.
  • the raw material powder is molded at a pressure of 50 MPa by a die press and then further CIP-molded at a pressure of 200 MPa using a cold isostatic press (hereinafter referred to as “CIP”) apparatus, and a cylindrical shape having a diameter of 20 mm and a thickness of 2 mm.
  • CIP cold isostatic press
  • a molded body was obtained.
  • the obtained cylindrical molded body was accommodated in an alumina container and fired (primary sintering) to obtain a zirconia sintered body (primary sintered body).
  • the sintering conditions for the primary sintering were, in air, a temperature increase rate of 100 ° C./hour, and a sintering temperature of 1400 ° C. (Examples 1 and 2) and 1500 ° C. (Example 3).
  • the sintering time was 2 hours.
  • HIP processing body A zirconia sintered body (primary sintered body) obtained by sintering in air was subjected to HIP treatment to obtain a HIP-treated body.
  • the obtained processed body was the white zirconia sintered body of this example.
  • the HIP treatment conditions were a temperature of 1450 ° C. (Example 3) and 1500 ° C. (Examples 1 and 2).
  • the HIP pressure was 150 MPa, and the holding time for the HIP treatment was 1 hour. Note that argon gas having a purity of 99.9% was used as the pressure medium, and the sample was processed using a semi-sealed container made of alumina.
  • the obtained HIP-treated body (white zirconia sintered body of this example) was white.
  • the relative density of each white zirconia sintered body was 99% or more.
  • Table 1 shows the total light transmittance of the obtained white zirconia sintered body.
  • the total light transmittance of any white zirconia sintered body was 0.5% or less.
  • white zirconia sintered bodies having extremely low transmittance were obtained.
  • Table 1 also shows the color tone when a black plate is used as the back plate. It turned out that the white zirconia sintered compact of an Example shows high brightness L * (90 or more), even if the back is black. This confirmed that the white zirconia sintered body of the example did not transmit the base color.
  • Example 4 A HIP-treated body was obtained by the same method as in Example 1 except that the amount of silica added was 20 wt%.
  • the obtained processed body was the white zirconia sintered body of this example.
  • the atmospheric sintering temperature was 1400 ° C.
  • the HIP temperature in the HIP treatment was 1500 ° C.
  • Table 1 shows the total light transmittance of the obtained white zirconia sintered body.
  • the relative density of the white zirconia sintered body was 99% or more, and the total light transmittance was 0.01%.
  • Table 1 also shows the color tone when a black plate is used as the back plate. It was found that the obtained white zirconia sintered body showed high brightness L * (90 or more) even when the back was black.
  • Examples 5 to 7 5 wt% silica was added, the atmospheric sintering temperature was 1400 ° C. (Example 5) and 1500 ° C. (Examples 6 and 7), and the HIP temperature was 1400 ° C. (Example 5) and 1500 ° C. (
  • a white zirconia sintered body was produced under the same conditions as in Example 1 except that Examples 6 and 7) were used. The results are shown in Table 1. In any of the examples, a white zirconia sintered body having a relative density of 99% or more, a total light transmittance of 2% or less, and a lightness L * of 90 or more was obtained.
  • Examples 8 to 13 A white zirconia sintered body to which 10 wt% silica was added was prepared in the same manner as in Example 1. That is, the atmospheric sintering temperature was set to 1500 ° C. (Examples 8 and 9) or 1400 ° C. (Examples 10 to 13), and the HIP temperature was set to 1300 ° C. (Examples 8 and 10 to 12) or 1400 ° C. A HIP-treated body was obtained in the same manner as in Example 1 except that Example 9 and 13) were used. The obtained processed body was the white zirconia sintered body of these examples. The obtained results are summarized in Table 1. In these examples, a white zirconia sintered body having a relative density of 99% or more, a total light transmittance of 2% or less, and a lightness L * of 90 or more was obtained.
  • Examples 14 to 18 A 10 wt% silica-added zirconia powder was produced in the same manner as in Example 1. The powder was molded to obtain a molded body. The obtained molded body was sintered at a temperature of 1400 ° C. (Examples 14 and 15), 1450 ° C. (Example 16), or 1500 ° C. (Examples 17 and 19). Sintering was performed in the atmosphere, the holding temperature was 2 hours, and the heating rate was 100 ° C./h. The obtained sintered body was used as the white zirconia sintered body of these examples. The results are shown in Table 1. In each example, a white zirconia sintered body having a relative density of 99% or more, a total light transmittance of 2% or less, and a lightness L * of 90 or more was obtained.
  • Example 19 A 20 wt% silica-added zirconia powder was produced in the same manner as in Example 1. The powder was molded to obtain a molded body. The obtained molded body was sintered at 1500 ° C. in the atmosphere. The holding temperature for sintering was 2 hours, and the heating rate was 100 ° C./h. The obtained sintered body was used as the white zirconia sintered body of this example. The results are shown in Table 1. As shown in Table 1, the relative density of the white zirconia sintered body of the present invention was 99% or more, the total light transmittance was 2% or less, and the lightness L * was 90 or more.
  • Example 21 (Observation of Silica Crystal Particles)
  • SEM observation was performed on the white zirconia sintered body obtained in Example 1 and Example 18.
  • the average crystal grain size of the silica crystal particles contained in the white zirconia sintered body was 1 ⁇ m or less.
  • the SEM photograph of Example 1 and 18 is shown in FIG.3 and FIG.4, respectively. 3 and 4, the white portion is zirconia crystal particles and the black portion is silica particles.
  • the shape of the silica particles in the white zirconia sintered body of Example 1 and FIG. 18 was mainly an indeterminate shape and was a polyhedral or indeterminate crystal particle.
  • Example 22 Measurement of average crystal grain size of crystal grains.
  • the white zirconia sintered body obtained in Example 1 was subjected to thermal etching at 1400 ° C. for 1 hour, and after the thermal etching, The SEM observation of the joint was performed. An SEM observation diagram is shown in FIG.
  • the average crystal grain size of the zirconia crystal particles of the white zirconia sintered body determined by the planimetric method was 0.5 ⁇ m.
  • Example 23 (observation of silica dispersibility)
  • the white zirconia sintered body obtained in Example 1 was observed with a TEM.
  • the obtained TEM observation figure is shown in FIG.
  • contrast shades derived from the heterogeneous interface were observed.
  • a peak attributed to ⁇ -quartz was observed in addition to ⁇ -cristobalite in the silica particles. This confirmed that the silica particles contained cristobalite and quartz.
  • Examples 24-26 A HIP-treated body was obtained in the same manner as in Example 1 except that the amount of silica added was 5 wt% (Example 24), 10 wt% (Example 25), and 20 wt% (Example 26).
  • the obtained processed body was the white zirconia sintered body of this example.
  • the atmospheric sintering temperature was 1400 ° C.
  • the HIP temperature was 1500 ° C.
  • a three-point bending test was performed on the obtained white zirconia sintered body. The results are shown in Table 2.
  • Example 27 A white zirconia sintered body was produced in the same manner as in Example 1.
  • the atmospheric sintering temperature was 1400 ° C., and the HIP sintering temperature was 1500 ° C.
  • the obtained white zirconia sintered body was subjected to double-side grinding and then double-side polished to obtain a zirconia plate having a thickness of about 1 mm.
  • the density of the obtained zirconia plate was 5.230 g / cm 3 and the relative density was 99.4%.
  • Each surface of the obtained zirconia plate and glass fiber reinforced plastic (trade name: epoxy / glass cloth laminate molded product SL-EC, manufactured by Nitto Shinko Co., Ltd.) was washed with acetone.
  • an epoxy-based thermosetting resin (trade name: XN1245SR, manufactured by Nagase ChemteX Corporation) is uniformly applied to the adhesive surface, and the load is uniformly applied to the upper and lower surfaces of the composite plate.
  • a composite plate was obtained by bonding under conditions of 30 minutes.
  • the obtained composite plate was cut to a size of 32 mm ⁇ 25 mm.
  • the composite plate having a thickness of about 0.8 mm was finally obtained by grinding and polishing the zirconia plate side of the cut composite plate. Grinding and polishing were carried out under conditions that produce as little residual stress as possible. There was no peeling of the adhesive or chipping of the zirconia plate due to processing, and the composite plate had high workability.
  • 2.0 g / cm 3 was used as the reinforced plastic density.
  • the thickness of the produced composite plate was 0.750 mm.
  • the thickness of each layer of the composite plate was 0.221 mm for the zirconia plate, 18 ⁇ m for the adhesive layer, and 0.511 mm for fiber reinforced plastics.
  • the thickness of the zirconia plate / fiber reinforced plastics was 0.43.
  • the composite plate had an apparent density of 2.9 g / cm 3 and a Vickers hardness of 1200.
  • L *, a *, and b * were 92.0, ⁇ 0.33, and 0.04, and the lightness L * was 90 or more.
  • a steel ball drop test was performed in 5 cm increments. The test result was 25 cm, and it was found that the composite plate did not crack even when a hard sphere was dropped from 25 cm and exhibited high impact resistance. Further, a steel ball drop test was performed in which a healthy portion of the tested test piece was aimed at and dropped once from a steel ball drop height of 30 cm. There was no crack and the impact resistance was higher than that evaluated in 5 cm increments. It is considered that a high value was exhibited because there was no interface peeling of the adhesive layer due to repeated impact tests.
  • Comparative Example 1 Using only zirconia powder (TZ-3YS, manufactured by Tosoh Corporation) as a raw material powder not containing silica, a molded body was obtained in the same manner as in Example 1. The obtained molded body was sintered in the atmosphere at an atmospheric sintering temperature of 1500 ° C. for 2 hours to obtain a primary sintered body. The obtained primary sintered body was subjected to HIP treatment at an HIP sintering temperature of 1500 ° C., an HIP treatment time of 1 hour, and an HIP treatment pressure of 150 MPa to produce a sintered body of this comparative example. The results are shown in Table 3. The obtained sintered body showed translucency, and the lightness L * was less than 90.
  • TZ-3YS zirconia powder
  • Comparative Example 2 Using only zirconia powder (TZ-3YS, manufactured by Tosoh Corporation) as a raw material powder not containing silica, a molded body was obtained in the same manner as in Example 1. The obtained molded body was sintered in the atmosphere at an atmospheric sintering temperature of 1500 ° C. for 2 hours to obtain a sintered body. The results are shown in Table 3. The obtained sintered body showed translucency, and the lightness L * was less than 90.
  • TZ-3YS zirconia powder
  • Comparative Example 3 Zirconia (TZ-3YS, manufactured by Tosoh Corporation) to which 5 wt% of amorphous silica was added was sintered at 1350 ° C. for 2 hours to obtain a sintered body. As a result of XRD measurement, no peaks due to cristobalite and other silica polymorphs were observed. The results are shown in Table 3. The silica particles of the sintered body were composed only of amorphous silica and did not contain cristobalite type silica. The sintered body had a total light transmittance of over 2% and a lightness L * of less than 90.
  • Comparative Example 4 A zirconia sintered body was produced in the same manner as in Example 1 except that 50 wt% silica was added.
  • the atmospheric sintering temperature was 1400 ° C.
  • the HIP temperature was 1500 ° C.
  • the relative density of the obtained sintered body was 99.5%.
  • the sintered body was a sintered body having cracks in zirconia crystal particles in addition to the microcracks in the silica particles.
  • the cristobalite phase fraction was 32 wt%.
  • the white zirconia sintered body of the present invention does not transmit light as a thin member, has a stable color tone, is excellent in design, and has high strength. Therefore, it is suitable for exterior members of electronic devices and the like that tend to be miniaturized, and can also be used as ornaments such as watches and jewelry, and also as dental materials. It should be noted that the specification, claims, drawings and Japanese Patent Application No. 2013-262188 filed on December 19, 2013 and Japanese Patent Application No. 2014-10000972 filed on May 14, 2014 The entire contents of the abstract are hereby incorporated by reference as the disclosure of the specification of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Adornments (AREA)
PCT/JP2014/083469 2013-12-19 2014-12-17 白色ジルコニア焼結体及びその製造方法並びにその用途 WO2015093549A1 (ja)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2013262188 2013-12-19
JP2013-262188 2013-12-19
JP2014-100972 2014-05-14
JP2014100972 2014-05-14

Publications (1)

Publication Number Publication Date
WO2015093549A1 true WO2015093549A1 (ja) 2015-06-25

Family

ID=53402893

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/083469 WO2015093549A1 (ja) 2013-12-19 2014-12-17 白色ジルコニア焼結体及びその製造方法並びにその用途

Country Status (3)

Country Link
JP (1) JP6464713B2 (zh)
TW (1) TW201524936A (zh)
WO (1) WO2015093549A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020132518A (ja) * 2019-02-15 2020-08-31 東ソー株式会社 ピンク系ジルコニア焼結体及びその製造方法
CN112585103A (zh) * 2018-08-20 2021-03-30 东曹株式会社 氧化锆烧结体及其制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021088501A (ja) * 2019-04-25 2021-06-10 東ソー株式会社 焼結体、粉末及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08295534A (ja) * 1995-02-28 1996-11-12 Shinetsu Quartz Prod Co Ltd クリストバライト結晶相含有シリカガラスおよびその製造方法
JPH11278928A (ja) * 1998-03-31 1999-10-12 Tosoh Corp 複合系セラミックス材料
JP2004143031A (ja) * 2002-05-20 2004-05-20 Tosoh Corp セラミックス及びその製造方法
JP2006342036A (ja) * 2005-06-10 2006-12-21 Tosoh Corp 黒色ジルコニア焼結体、その原料粉末ならびにそれらの製造方法
JP2008050247A (ja) * 2006-07-25 2008-03-06 Tosoh Corp 高強度ジルコニア焼結体および製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3631621B2 (ja) * 1998-08-31 2005-03-23 京セラ株式会社 時計用文字盤
JP2005170719A (ja) * 2003-12-10 2005-06-30 Nippon Denko Kk 明度および白色度が高い酸化ジルコニウム粉末、その焼結体及びその製造方法
WO2009096478A1 (ja) * 2008-01-29 2009-08-06 Kyocera Corporation 白色セラミックス
JP2013155074A (ja) * 2012-01-30 2013-08-15 Sumitomo Electric Ind Ltd 複合酸化物焼結体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08295534A (ja) * 1995-02-28 1996-11-12 Shinetsu Quartz Prod Co Ltd クリストバライト結晶相含有シリカガラスおよびその製造方法
JPH11278928A (ja) * 1998-03-31 1999-10-12 Tosoh Corp 複合系セラミックス材料
JP2004143031A (ja) * 2002-05-20 2004-05-20 Tosoh Corp セラミックス及びその製造方法
JP2006342036A (ja) * 2005-06-10 2006-12-21 Tosoh Corp 黒色ジルコニア焼結体、その原料粉末ならびにそれらの製造方法
JP2008050247A (ja) * 2006-07-25 2008-03-06 Tosoh Corp 高強度ジルコニア焼結体および製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112585103A (zh) * 2018-08-20 2021-03-30 东曹株式会社 氧化锆烧结体及其制造方法
CN112585103B (zh) * 2018-08-20 2023-10-10 东曹株式会社 氧化锆烧结体及其制造方法
JP2020132518A (ja) * 2019-02-15 2020-08-31 東ソー株式会社 ピンク系ジルコニア焼結体及びその製造方法
JP7434993B2 (ja) 2019-02-15 2024-02-21 東ソー株式会社 ピンク系ジルコニア焼結体及びその製造方法

Also Published As

Publication number Publication date
TW201524936A (zh) 2015-07-01
JP2015231934A (ja) 2015-12-24
JP6464713B2 (ja) 2019-02-06

Similar Documents

Publication Publication Date Title
CN107922272B (zh) 红色氧化锆烧结体及其制造方法
EP2610232B1 (en) Zirconia sintered bodies with high total light transmission
WO2012063746A1 (ja) 着色透光性ジルコニア焼結体及びその製造方法並びにその用途
JP5125065B2 (ja) 透明ジルコニア焼結体
WO2010140644A1 (ja) 高強度透明ジルコニア焼結体及びその製造方法、並びにその用途
JP6464713B2 (ja) 白色ジルコニア焼結体及びその製造方法並びにその用途
JP5655512B2 (ja) 着色透光性ジルコニア焼結体及びその製造方法並びにその用途
EP2808313B1 (en) Colored alumina sintered body of high toughness and high translucency, and its production method and its uses
JP5770431B2 (ja) 高強度透明ジルコニア焼結体
JP7434993B2 (ja) ピンク系ジルコニア焼結体及びその製造方法
JP5505063B2 (ja) 高透明ジルコニア焼結体
JP2023016927A (ja) 紫色ジルコニア焼結体及びその製造方法
KR102641166B1 (ko) 지르코니아 소결체 및 이의 제조 방법
JP7432816B2 (ja) ピンク系ジルコニア焼結体及びその製造方法
JP6885021B2 (ja) オレンジ色ジルコニア焼結体及びその製造方法
JP2019182740A (ja) ジルコニア焼結体及びその製造方法
JP7279545B2 (ja) 濃灰色焼結体
JP7432817B2 (ja) ピンク系ジルコニア焼結体及びその製造方法
CN117986004B (zh) 一种尖晶石型高熵透明陶瓷及其制备方法和应用
JP6897088B2 (ja) オレンジ色ジルコニア焼結体及びその製造方法
Parish et al. Transparent ceramics for sensor applications
JP2018002527A (ja) 透光性ジルコニア焼結体及びその製造方法並びにその用途

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: 14872498

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14872498

Country of ref document: EP

Kind code of ref document: A1