WO2023234396A1 - 黒色ジルコニア複合焼結体及びその製造方法 - Google Patents

黒色ジルコニア複合焼結体及びその製造方法 Download PDF

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Publication number
WO2023234396A1
WO2023234396A1 PCT/JP2023/020507 JP2023020507W WO2023234396A1 WO 2023234396 A1 WO2023234396 A1 WO 2023234396A1 JP 2023020507 W JP2023020507 W JP 2023020507W WO 2023234396 A1 WO2023234396 A1 WO 2023234396A1
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Prior art keywords
sintered body
mol
composite sintered
stabilizer
zirconia composite
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PCT/JP2023/020507
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English (en)
French (fr)
Japanese (ja)
Inventor
承央 伊藤
貴広 丹羽
新一郎 加藤
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.)
Kuraray Noritake Dental Inc
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Kuraray Noritake Dental Inc
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Priority to CN202380044116.2A priority Critical patent/CN119301091A/zh
Priority to JP2024524946A priority patent/JP7606051B2/ja
Priority to KR1020247041466A priority patent/KR20250010665A/ko
Priority to US18/870,049 priority patent/US20250326694A1/en
Priority to EP23816153.3A priority patent/EP4534504A1/en
Publication of WO2023234396A1 publication Critical patent/WO2023234396A1/ja
Anticipated expiration legal-status Critical
Priority to JP2024217148A priority patent/JP2025038052A/ja
Ceased legal-status Critical Current

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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/664—Reductive annealing
    • 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
    • C04B2235/786—Micrometer sized grains, 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
    • C04B2235/70—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 black zirconia composite sintered body and a method for manufacturing the same. More specifically, the present invention relates to a black zirconia composite sintered body that has excellent strength and excellent workability in the form of a sintered body, and a method for manufacturing the same.
  • Radio waves used for communication are shifting to higher frequency bands.
  • Metal is mainly used for the back plate of 5G-compatible smartphones, but since metal is inappropriate for transmitters and receivers of radio waves in high frequency bands, plastic, glass, and ceramics are used.
  • zirconia is a material that is difficult to process in the form of a sintered body. Therefore, if a zirconia sintered body is used as a partial material for a smartphone, the processing cost becomes high due to the difficulty of processing the sintered body.
  • black is an essential color for smartphone housings, so black free-cutting ceramics have been developed that contain zirconia but do not use it as a main component (for example, Patent Document 1). .
  • black zirconia sintered bodies have also been developed from the viewpoint of excellent design, although they are significantly inferior in workability (for example, Patent Documents 2 and 3).
  • Patent Document 4 workable zirconia sintered bodies with improved workability have also been developed, although they are not black and are used in the dental field (for example, Patent Document 4).
  • Patent Document 4 79.8 to 92 mol% of ZrO 2 and 4.5 to 10.2 mol% of Y 2 O 3 , and 3.5 to 7.5 mol% of Nb 2 O 5 or 5.5 ⁇ 10.0 mol% of Ta 2 O 5 , and a TiO 2 nanopowder whose mass ratio to the zirconia composite powder is more than 0 mass % and 2.5 mass % or less.
  • Processable zirconia which is a sintered body formed, and a method for manufacturing the same are disclosed.
  • Patent Document 1 zirconia is used as a black pigment by reduction firing. However, when the content of zirconia increases, the free machinability decreases, so the blending ratio of zirconia was low.
  • Patent Document 2 proposes a zirconia sintered body with a deep black color. Further, Patent Document 3 also proposes a black zirconia sintered body that deals with the problem that the color tone changes due to sintering when obtaining the zirconia sintered body.
  • the zirconia sintered body disclosed in Patent Document 4 can be machined even in a sintered state. However, it cannot be said that it has excellent workability, and the processing time to cut out the workpiece is long, and there is still room for improvement in workability.It is not black, but has excellent translucency, so the color tone is completely different. Met. Furthermore, although the zirconia sintered body disclosed in Patent Document 4 can be machined, the number of workpieces obtained by continuous machining using one machining tool is small, and the wear of the machining tool is low. Because of this, there is a problem in that the frequency of changing machining tools increases, the time required to change tools increases, and productivity and economic efficiency decrease.
  • zirconia sintered bodies are only processable, and zirconia sintered bodies have a unique problem due to the sintered state of zirconia that is extremely difficult to process. Therefore, it is still difficult to provide a zirconia sintered body that has excellent workability in the form of a sintered body, and a zirconia sintered body that has excellent workability in the form of a sintered body and exhibits a black color has not been obtained.
  • An object of the present invention is to provide a zirconia composite sintered body that has excellent machinability in the state of a sintered body and exhibits a black color.
  • the present inventors have developed a stabilizer capable of suppressing the phase transition of ZrO 2 , HfO 2 , and zirconia, and Nb 2 O 5 and/or Ta 2 .
  • a capping element or ion in a black zirconia composite sintered body containing O 5 in a predetermined ratio we conducted further research and completed the present invention. It's arrived.
  • the present invention includes the following inventions.
  • [1] Contains ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb 2 O 5 and/or Ta 2 O 5 ,
  • the total content of ZrO 2 and HfO 2 is 78 to 97.5 mol%
  • the content of the stabilizer is 1 to 12 mol%
  • the total content of Nb 2 O 5 and Ta 2 O 5 is 1 to 9 mol%
  • a black zirconia composite sintered body further containing elements or ions derived from a capping agent.
  • the content of elements or ions derived from the capping agent is more than 0 mol% and 5 mol% with respect to the total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 and Ta 2 O 5
  • the chroma C* calculated from a* and b* measured on a white background in the L*a*b* color system using a sample with a diameter of 15 mm and a thickness of 1.2 mm is 10 or less.
  • the value measured using a sample with a diameter of 15 mm and a thickness of 1.2 mm on a white background in the L*a*b* color system is L* ⁇ 60,
  • the element or ion derived from the capping agent is at least one element selected from the group consisting of Cu, Ag, Li, Na, K, Rb, Cs, Fr, At, I, Br, Cl, and F. or ions thereof, the black zirconia composite sintered body according to any one of [1] to [4].
  • the content of the zirconia reinforcing agent is based on the total of 100% by mass of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 and Ta 2 O 5
  • [11] Contains ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb 2 O 5 and/or Ta 2 O 5 , In a total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 , The total content of ZrO 2 and HfO 2 is 78 to 97.5 mol%, The content of the stabilizer is 1 to 12 mol%, The total content of Nb 2 O 5 and Ta 2 O 5 is 1 to 9 mol%, A step of producing a molded body using the raw material composition further containing a capping agent; sintering the molded body, The method for producing a black zirconia composite sintered body according to any one of [1] to [1
  • the step of sintering the molded body includes a step of reduction firing.
  • the capping agent contained in the raw material composition is a compound that can become a monovalent ion, Further comprising a step of wet-mixing each raw material of the raw material composition in a solvent containing water to obtain a raw material composition.
  • the stabilizer includes a stabilizer that is not solidly dissolved in ZrO 2 and HfO 2 A method for producing a sintered body.
  • the present invention it is possible to provide a zirconia composite sintered body that has excellent machinability in the state of a sintered body and exhibits a black color. Further, according to the present invention, the sintered body can be machined, the machining time is short, and the wear and tear of the machining tool can be suppressed. A large number of processed bodies can be machined by continuous processing (hereinafter also simply referred to as "continuous processing"), and a black zirconia composite sintered body with excellent productivity and economic efficiency can be provided. Furthermore, according to the present invention, it is possible to provide a black zirconia composite sintered body that has excellent strength and design. Further, according to the present invention, pressure firing in the method for producing a black zirconia composite sintered body is not necessary.
  • FIG. 1 is a schematic diagram showing the estimated structure of the black zirconia composite sintered body of the present invention.
  • FIG. 2 is a schematic diagram showing the presumed mechanism of action of the elements or ions derived from the capping agent of the present invention.
  • the black zirconia composite sintered body of the present invention contains ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia (hereinafter also simply referred to as "stabilizer"), Nb 2 O 5 and/or or Ta 2 O 5 ,
  • stabilizer capable of suppressing the phase transition of zirconia
  • the total content of ZrO 2 and HfO 2 is 78 to 97.5 mol%
  • the content of the stabilizer is 1 to 12 mol%
  • the total content of Nb 2 O 5 and Ta 2 O 5 is 1 to 9 mol%
  • it contains elements or ions derived from the capping agent.
  • the black zirconia composite sintered body of the present invention means one in which ZrO 2 particles (powder) are completely sintered (sintered state).
  • the upper and lower limits of the numerical ranges can be combined as appropriate.
  • machining includes cutting and grinding.
  • the machining may be either wet processing or dry processing, and is not particularly limited.
  • an element or ion derived from a capping agent is a component of a zirconia-based composite oxide in a black zirconia composite sintered body composed of a zirconia-based composite oxide.
  • An element or ion that caps the ends of bonds and weakens the strength of crystal interfaces (hereinafter also referred to as “grain boundaries”) (hereinafter also referred to as “grain boundary strength").
  • the capping agent can cap part of grain boundaries.
  • Capping refers to the fact that a target element or ion (capping element or ion) binds to a bond of a zirconia-based composite oxide instead of the metal element and is present at a grain boundary. It is presumed that due to the presence of capping elements or ions in the form of +1-valent cations or -1-valent anions at grain boundaries, the capped cations or anions electrostatically repel each other, weakening the grain boundary strength. .
  • the content of each component in the black zirconia composite sintered body can be calculated from the amount of raw materials charged.
  • the content of each component of ZrO 2 , HfO 2 , stabilizer, Nb 2 O 5 and Ta 2 O 5 in the black zirconia composite sintered body is determined by, for example, inductively coupled plasma (ICP) light emission. It can also be measured by spectroscopic analysis, fluorescent X-ray analysis, etc.
  • the content rate (mol%) of elements or ions derived from the capping agent is the external addition rate with respect to the total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 .
  • the content of elements or ions derived from the capping agent in the black zirconia composite sintered body can be calculated by converting the amount (mass) of the raw material at the time of addition into mol%.
  • the content rate (mass %) of the zirconia reinforcing agent is the external addition rate with respect to the total of 100 mass % of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 . Therefore, the content of the zirconia reinforcing agent in the black zirconia composite sintered body can be calculated from the amount (mass) of the raw material to be added.
  • the black zirconia composite sintered body of the present invention has suitable strength and high machinability, so the reason why it can be machined in the sintered body state is not clear, but it is speculated as follows. .
  • a capping element is added to the grain boundaries.
  • the capping elements or ions act in the form of +1-valent cations or -1-valent anions to reduce the grain boundary strength and facilitate the separation of grains from each other, making it easier to scrape and machining.
  • the black zirconia composite sintered body of the present invention includes zirconia particles 1 containing ZrO 2 , HfO 2 , a stabilizer capable of suppressing phase transition of zirconia, and Nb 2 O 5 and/or Ta 2 O 5 ; A peeling component 2 containing a capping element or ion, and optionally ZrO 2 , HfO 2 , Nb 2 O 5 and/or Ta 2 O 5 , and a metal element derived from a zirconia reinforcing agent (for example, Ti, etc.) It is presumed that the structure includes an adhesive component 3 containing the following.
  • FIG. 1 shows a schematic diagram of a structure estimated in a zirconia composite sintered body according to an embodiment containing a zirconia reinforcing agent. Even when the adhesive component 3 related to the zirconia composite sintered body containing the zirconia reinforcing agent is present, the strength can be increased without suppressing the effect of reducing the grain boundary strength obtained by the peeling component 2.
  • the capping element or ion becomes a +1-valent cation or a -1-valent anion at the grain boundary of the black zirconia composite sintered body, and combines with the bond possessed by the zirconia-based composite oxide. Due to this bond, cations or anions electrostatically repel each other, and while maintaining the strength properties of the particles constituting the black zirconia composite sintered body, the grain boundary strength can be weakened, which leads to improved machinability. It acts on For example, as shown in FIG. 2(a), a +1-valent cation is attached to the other oxygen atom bonded to a metal element (for example, Zr, Hf, Y, Nb, or Ta) contained in a zirconia-based composite oxide.
  • a metal element for example, Zr, Hf, Y, Nb, or Ta
  • M + represents a +1-valent cation.
  • ⁇ 1-valent anions bond with OH 2+ bonded to metal elements (for example, Zr, Hf, Y, Nb, or Ta) contained in the zirconia-based composite oxide. A possible form is to do so.
  • ⁇ 1-valent anions are contained in the zirconia-based composite oxide and are bonded to other metal elements (for example, Zr, Hf, Y, Nb, Alternatively, a form in which it binds to a cation derived from Ta) is considered.
  • X ⁇ represents a ⁇ 1-valent anion.
  • interactions between charged sites and adsorption sites at grain boundaries are schematically shown in (a) to (c).
  • Nb 2 O 5 and/or Ta 2 O 5 act to coarsen the microstructure and reduce hardness in the black zirconia composite sintered body, so Nb 2 O 5 and / or Ta 2 O 5 work together to improve machinability. Therefore, the capping element or ion and Nb 2 O 5 and/or Ta 2 O 5 work together to provide suitable strength and excellent free machinability. In addition to shortening the processing time, it is possible to suppress the wear and tear of the processing tool, and increase the number of workpieces obtained by continuous processing using one processing tool. It is assumed that problems specific to processing can also be solved.
  • the capping element or ion acts as a free machinability imparting agent as described above, and does not significantly impair the strength.
  • the content of capping elements or ions contained in the black zirconia composite sintered body of the present invention is preferably more than 0 mol% and 5 mol% or less, which has excellent machinability and can be continuously processed with one processing tool. From the viewpoint of increasing the number of processed bodies that can be produced, it is more preferably 0.05 mol% or more and 3 mol% or less, even more preferably 0.06 mol% or more and 2.5 mol% or less, and 0.07 mol% or more 1 It is particularly preferably .0 mol% or less, and most preferably 0.08 mol% or more and 0.34 mol% or less.
  • the capping element or ion contained in the black zirconia composite sintered body of the present invention is a Group 17 element or ion
  • the workpiece has excellent machinability and can be processed continuously with one processing tool. From the viewpoint of increasing the number of particles, it is more preferably 0.2 mol% or more and 5 mol% or less, even more preferably 0.3 mol% or more and 4 mol% or less, and 0.4 mol% or more and 3.5 mol% or less. It is particularly preferable that the content is 0.5 mol% or more and 3.0 mol% or less.
  • the capping element or ion can be a +1-valent cation or a -1-valent anion and exist at the grain boundary, from the point of view of appropriate interaction between the charged site and the adsorption site at the grain boundary. is important.
  • Capping elements or ions include elements that belong to periods 2 to 7 of the periodic table and have a lower first ionization energy than Group 18 elements of the same period, or their ions, elements with high electron affinity or their ions, and nitrate ions. , hypochlorite ion, chlorite ion, chlorate ion, perchlorate ion, bromate ion, permanganate ion, metaborate ion, and cyanide ion are preferred.
  • the element or ion thereof derived from the capping agent belongs to periods 2 to 7 of the periodic table, and has a first ionization energy smaller than that of a Group 18 element of the same period. and/or a black zirconia composite sintered body of an element with high electron affinity or its ions.
  • Preferred examples include Cu, Ag, Li, Na, K, Rb, Cs, and Fr.
  • Group 17 elements are preferable because ⁇ 1-valent anions are more easily obtained and they have better machinability.
  • the Group 17 elements At, I, Br, Cl, and F are preferable.
  • the first ionization energy is the energy required to remove one electron from a neutral atom and ionize it.
  • the first ionization energy can be the same as the first ionization energy described in "Schreiber-Atkins Inorganic Chemistry (Part 1) 4th Edition Part I Fundamentals 1. Atomic Structure.”
  • the first ionization energy can also be determined by photoelectron yield spectroscopy (PYS).
  • Electron affinity is the energy released when an electron is introduced into a neutral atom. Electron affinity can be measured by the difference in energy gap from the ionization potential. Ionization potential is defined as the energy difference between the highest energy occupied orbital of a compound's molecules and the vacuum level, and its value is measured using ultraviolet photoelectron spectroscopy.
  • Ionization potential is defined as the energy difference between the highest energy occupied orbital of a compound's molecules and the vacuum level, and its value is measured using ultraviolet photoelectron spectroscopy.
  • For the first ionization energy and electron affinity use the data stored in the NIST Chemistry WebBook (https://webbook.nist.gov/chemistry/) (select Ionization Energy or Electron Affinity from Ion energetics properties). You may. For the first ionization energy and electron affinity, it is sufficient to compare the ease with which the elements become +1-valent cations or -1-valent anions with other comparative elements; therefore, the measurement methods described above can be used as appropriate. Available
  • the capping element examples include Cu, Ag, Li, Na, K, Rb, Cs, Fr, At, I, Br, Cl, and F, which can further improve machinability.
  • Cu, Ag, Li, Na, K, Rb, Cs, Fr, I, Br, Cl, and F are preferred.
  • the element derived from the capping agent is at least one selected from the group consisting of Cu, Ag, Li, Na, K, Rb, Cs, Fr, At, I, Br, Cl, and F.
  • ion of said element is at least one +1 valent cation selected from the group consisting of Cu, Ag, Li, Na, K, Rb, Cs, Fr, I, Br, Cl, and F; or -Black zirconia composite sintered body, which is a monovalent anion, is mentioned.
  • the elements or ions from the capping agent are at least selected from the group consisting of Ag, Li, Na, K, Rb, Cs, Fr, At, I, Br, Cl, and F.
  • a black zirconia composite sintered body containing one element or its ions can be mentioned.
  • the capping elements or ions may be used alone or in combination of two or more.
  • the total content of ZrO 2 and HfO 2 is 78% in total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 . ⁇ 97.5 mol%, and from the viewpoint of superior strength, it is preferably 79 mol% or more and 96 mol% or less, more preferably 80 mol% or more and 94 mol% or less, and even more preferably 81 mol% or more and 93 mol% or less. preferable.
  • Nb 2 O 5 and Ta 2 O 5 act to coarsen the microstructure and reduce hardness, and are integrated with the capping element or ions.
  • the sintered body has excellent machinability.
  • stabilizers that can suppress the phase transition of zirconia include calcium oxide (CaO), magnesium oxide (MgO), yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ), and scandium oxide (Sc 2 O).
  • lanthanum oxide La 2 O 3
  • erbium oxide Er 2 O 3
  • Pr 2 O 3 praseodymium oxide
  • Sm 2 O 3 samarium oxide
  • Eu 2 O 3 europium oxide
  • Oxides such as thulium oxide (Tm 2 O 3 ), gallium oxide (Ga 2 O 3 ), indium oxide (In 2 O 3 ), and ytterbium oxide (Yb 2 O 3 ) are listed, and the effects of the present invention are Y 2 O 3 (yttria) and/or CeO 2 are preferable because they are more excellent, especially aesthetically pleasing.
  • the stabilizers may be used alone or in combination of two or more.
  • the capping element or ion and Nb 2 O 5 and/or Ta 2 O 5 act together, the effect of the stabilizer is not impaired; is not particularly limited, and the effects of the present invention can be achieved.
  • the content of the stabilizer capable of suppressing the phase transition of zirconia is the sum of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5
  • ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 In terms of 100 mol%, it is 1 to 12 mol%, and from the viewpoint of easily obtaining sufficient machinability, it is preferably 2 mol% or more and 10 mol% or less, and from the viewpoint of superior strength, it is 3 mol% or more and 8 mol% or less. is more preferable, and even more preferably 3.5 mol% or more and 7.5 mol% or less.
  • the stabilizer capable of suppressing the phase transition of zirconia contains Y 2 O 3 and/or CeO 2 , and the total content of Y 2 O 3 and CeO 2 is 2 mol% or more.
  • a black zirconia composite sintered body having a content of 10 mol % or less is mentioned.
  • the stabilizer capable of suppressing the phase transition of zirconia contains Y2O3 , and the content of Y2O3 is 2 mol% or more and 10 mol % or less, black zirconia. Examples include composite sintered bodies.
  • the content of Y 2 O 3 and CeO 2 can be changed as appropriate within the range described in this specification.
  • the total content of CeO 2 may be 2.5 mol% or more and 10 mol% or less, or 3 mol% or more and 9 mol% or less.
  • the total content of Nb 2 O 5 and Ta 2 O 5 is 100 mol in total of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 %, it is 1 to 9 mol%, preferably 1.5 mol% or more and 8.5 mol% or less, and acts integrally with the capping element or ion and has better machinability.2. It is more preferably 5 mol% or more and 8 mol% or less, and even more preferably 3 mol% or more and 7 mol% or less.
  • the total content of Nb 2 O 5 and Ta 2 O 5 is less than 1 mol %, sufficient machinability is difficult to obtain.
  • the total content of Nb 2 O 5 and Ta 2 O 5 exceeds 9 mol %, the obtained black zirconia composite sintered body will have chips, etc., making it difficult to obtain sufficient physical properties.
  • Nb 2 O 5 and Ta 2 O 5 act to coarsen the microstructure and reduce hardness, and work together with the capping element or ions to provide excellent free machinability.
  • the sintered density can be maximized by interaction with other components added to the black zirconia composite sintered body (e.g., TiO 2 , Al 2 O 3 ) and the application of HIP, resulting in better design. It is easy to obtain a black zirconia composite sintered body having properties.
  • the content of each component of ZrO 2 , HfO 2 , stabilizer, Nb 2 O 5 and Ta 2 O 5 mentioned above is the total of ZrO 2 , HfO 2 , stabilizer, Nb 2 O 5 and Ta 2 O 5 The proportion is based on 100 mol%, and the total of ZrO 2 , HfO 2 , stabilizer, Nb 2 O 5 and Ta 2 O 5 does not exceed 100 mol %.
  • the content of each component of ZrO 2 , HfO 2 , stabilizer, and Nb 2 O 5 is equal to or smaller than that of ZrO 2 , HfO 2 , stabilizer, and Nb 2 O 5 based on a total of 100 mol %.
  • the ratio of A/B is 0.9 from the viewpoint of machinability. It is preferably 3 or less, more preferably 0.95 or more and 2 or less, increasing the effect of the capping element or ion and Nb 2 O 5 and/or Ta 2 O 5 acting together, 1 or more because it can provide better free-cutting properties, suppress wear of machining tools, and increase the number of workpieces obtained by continuous machining using one machining tool. More preferably, it is 1.6 or less.
  • a preferred embodiment of the present invention includes ZrO2 , HfO2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb2O5 and/or Ta2O5 ,
  • ZrO2 , HfO2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb2O5 and/or Ta2O5 In a total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 , The total content of ZrO 2 and HfO 2 is 78 to 97.5 mol%, The content of the stabilizer is 1 to 12 mol%, The total content of Nb 2 O 5 and Ta 2 O 5 is 1 to 9 mol%, Further containing a capping element or ion, The stabilizer contains Y 2 O 3 and/or CeO 2 , The content of the capping element or ion is more than 0 mol% and 3 mol% or less with respect to
  • a stabilizer capable of suppressing the phase transition of zirconia, Nb 2 O 5 and/or Ta 2 O 5 , and a capping element or ion, , and a black zirconia composite sintered body further containing a zirconia reinforcing agent is a capping agent in a black zirconia composite sintered body containing ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb 2 O 5 and/or Ta 2 O 5 It can act integrally with elements or ions to improve the strength of the sintered body.
  • the total content of ZrO 2 and HfO 2 , the type and content of the stabilizer, the total content of Nb 2 O 5 and Ta 2 O 5 can be changed as appropriate.
  • the content of the zirconia reinforcing agent is determined by combining ZrO 2 , HfO 2 , and a stabilizer capable of suppressing the phase transition of zirconia in order to suppress the influence on black color.
  • Nb 2 O 5 and Ta 2 O 5 are preferably more than 0 mass % and 5.0 mass % or less with respect to the total of 100 mass %, and when combined with the capping element or ion, they act together.
  • the content is preferably 0.01% by mass or more and 4.5% by mass or less, and preferably 0.5% by mass or more and 4.0% by mass or less. More preferred.
  • zirconia reinforcing agent examples include TiO 2 and Al 2 O 3 .
  • the zirconia reinforcing agents may be used alone or in combination of two or more.
  • a preferred embodiment includes a black zirconia composite sintered body in which the zirconia reinforcing agent includes TiO 2 and the content of TiO 2 is 0.6 to 3.7% by mass.
  • a preferred embodiment includes ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb 2 O 5 and/or Ta 2 O 5 ,
  • ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb 2 O 5 and/or Ta 2 O 5 In a total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 , The total content of ZrO 2 and HfO 2 is 78 to 97.5 mol%, The content of the stabilizer is 1 to 12 mol%, The total content of Nb 2 O 5 and Ta 2 O 5 is 1 to 9 mol%, Further containing a capping element or ion, The stabilizer contains Y 2 O 3 and/or CeO 2 , The zirconia reinforcing agent contains TiO 2 and the content of TiO 2 is 0.6 to 3.7% by mass, The content of
  • the average crystal grain size of the black zirconia composite sintered body of the present invention is preferably 0.5 to 5.0 ⁇ m, and from the viewpoint of better machinability and strength, it is preferably 0.5 to 4.5 ⁇ m.
  • the thickness is more preferably 1.0 to 4.0 ⁇ m.
  • the method for measuring the average crystal grain size is as described in the Examples below. The average crystal grain size is measured by adjusting the number of particles so that the number of particles included in one field of view of the SEM photographic image is about 50 or 100. I can do it.
  • the density of the black zirconia composite sintered body is preferably 5.5 g/cm 3 or more, and preferably 5.7 g/cm 3 or more , since the higher the density, the smaller the internal voids and the higher the strength. More preferably, it is 5.9 g/cm 3 or more. It is particularly preferable that the black zirconia composite sintered body contains substantially no voids.
  • the density of the composite sintered body can be calculated by (mass of the composite sintered body)/(volume of the composite sintered body).
  • Another embodiment of the present invention includes ZrO2 , HfO2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb2O5 and/or Ta2O5 ,
  • ZrO2 , HfO2 , a stabilizer capable of suppressing the phase transition of zirconia, and Nb2O5 and/or Ta2O5 In a total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 , The total content of ZrO 2 and HfO 2 is 78 to 97.5 mol%, The content of the stabilizer is 1 to 12 mol%, The total content of Nb 2 O 5 and Ta 2 O 5 is 1 to 9 mol%,
  • a method for producing a black zirconia composite sintered body includes a step of sintering the molded body.
  • the raw material composition used for manufacturing the black zirconia composite sintered body includes ZrO 2 , HfO 2 , a stabilizer capable of suppressing the phase transition of zirconia, Nb 2 O 5 and/or Ta 2 O 5 , and capping. including agents.
  • the raw material composition of the black zirconia composite sintered body may be in a dry state, or may be in a state containing a liquid or a state contained in a liquid.
  • the raw material composition may be in the form of, for example, powder, granules, granules, paste, slurry, or the like.
  • the raw material composition contains a capping agent so that the obtained black zirconia composite sintered body contains a capping element or ion.
  • the capping agent is not particularly limited as long as it is a compound that can become a monovalent ion (+1-valent cation or -1-valent anion) in a solvent containing water, for example, water containing elements or ions derived from the capping agent. Examples include oxides, salts, halides (fluorides, chlorides, bromides, iodides), cyanides, and the like.
  • the capping agents may be used alone or in combination of two or more.
  • hydroxides containing capping elements or ions include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and francium hydroxide.
  • salts containing capping elements or ions include carbonates, hydrogen carbonates, nitrates, hypochlorites, chlorites, chlorates, perchlorates, bromates, permanganates, Includes metaborates, sulfide salts, and cyanide salts.
  • Examples of carbonates containing capping elements or ions include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, francium carbonate, cesium carbonate, and the like.
  • Examples of the hydrogen carbonate containing a capping element or ion include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, francium hydrogen carbonate, cesium hydrogen carbonate, and the like.
  • nitrates containing capping elements or ions include calcium nitrate, strontium nitrate, iron (II) nitrate, iron (III) nitrate, cobalt (II) nitrate, magnesium nitrate, gallium nitrate, yttrium (III) nitrate, and lanthanum nitrate.
  • III praseodymium nitrate, neodymium (III) nitrate, manganese (II) nitrate, europium nitrate, copper (II) nitrate, thorium nitrate, aluminum nitrate, nickel (II) nitrate, chromium (III) nitrate, titanium (IV) nitrate ), zirconium nitrate, zirconium (IV) oxynitrate hydrate (ZrO(NO 3 ) 2.xH 2 O), cerium (III) nitrate, tin nitrate, bismuth (III) nitrate, scandium (III) nitrate, indium nitrate (III), hafnium (IV) nitrate, and the like.
  • hypochlorite containing a capping element or ion examples include sodium hypochlorite, calcium hypochlorite, and the like.
  • chlorites containing capping elements or ions include sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, magnesium chlorite, barium chlorite, copper chlorite ( II), copper (III) chlorite, silver chlorite, nickel chlorite, and the like.
  • chlorates containing capping elements or ions include calcium chlorate, barium chlorate, cobalt chlorate, nickel chlorate, magnesium chlorate, zinc chlorate, copper chlorate, and the like.
  • perchlorates containing capping elements or ions include iron (III) perchlorate, barium perchlorate, calcium perchlorate, cobalt perchlorate, nickel perchlorate, magnesium perchlorate, and perchlorate. Examples include beryllium acid, aluminum perchlorate, and cerium perchlorate.
  • the bromate containing a capping element or ion include neodymium bromate, lanthanum bromate, praseodymium bromate, and the like.
  • permanganate containing a capping element or ion include calcium permanganate (VII), potassium permanganate (VII), and sodium permanganate (VII).
  • metaborate containing a capping element or ion examples include sodium metaborate, barium metaborate, and the like.
  • sulfide salt containing a capping element or ion examples include copper (I) sulfide.
  • cyanide salts containing capping elements or ions include barium cyanide, sodium cyanide, potassium cyanide, calcium cyanide, and the like.
  • fluorides containing capping elements or ions include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, and fluoride.
  • Strontium chloride barium fluoride, scandium(III) fluoride, yttrium(III) fluoride, lanthanum(III) fluoride, cerium(III) fluoride, neodymium(III) fluoride, titanium(III) fluoride, fluoride Titanium(IV) fluoride, zirconium(IV) fluoride, hafnium(IV) fluoride, tantalum(V) fluoride, manganese(II) fluoride, manganese(III) fluoride, iron(II) fluoride, fluoride Iron(III), copper(II) fluoride, zinc(II) fluoride, aluminum fluoride, chromium(III) fluoride, bismuth(III) fluoride, indium(III) fluoride, tin(II) fluoride etc.
  • chlorides containing capping elements or ions include zirconium oxychloride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, Scandium (III) chloride, yttrium (III) chloride, lanthanum (III) chloride, cerium (III) chloride, praseodymium chloride, neodymium (III) chloride, samarium chloride, europium chloride, titanium (III) chloride, titanium (IV) chloride , zirconium(IV) chloride, hafnium(IV) chloride, tantalum(V) chloride, manganese chloride, iron(II) chloride, iron(III) chloride, cobalt(II) chloride, nickel(II) chloride, copper(I) chloride ), copper(II) chloride, zinc(II)
  • bromides containing capping elements or ions include lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, beryllium bromide, magnesium bromide, calcium bromide, and bromide.
  • iodides containing capping elements or ions include lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, beryllium iodide, calcium iodide, magnesium iodide, and iodide.
  • Strontium chloride barium iodide, scandium (III) iodide, yttrium (III) iodide, lanthanum (III) iodide, cerium (III) iodide, neodymium (III) iodide, titanium (IV) iodide, iodine Zirconium(IV) chloride, hafnium(IV) iodide, tantalum(V) iodide, manganese(II) iodide, iron(II) iodide, iron(III) iodide, cobalt(II) iodide, iodide Nickel (II), copper (I) iodide, zinc (II) iodide, aluminum iodide, chromium (III) iodide, vanadium (II) iodide, bismuth (III) iodide, indium (III
  • zirconia powder As for ZrO 2 and HfO 2 , commercially available zirconia powder can be used. Commercially available products include, for example, zirconia powder (trade name "Zpex (registered trademark)" (Y 2 O 3 content: 3 mol %), “Zpex (registered trademark) 4" (Y 2 O 3 content: 4 mol %).
  • the commercially available zirconia powder also contains HfO2 .
  • a commercially available product one that also contains Y 2 O 3 can also be used.
  • the raw material composition of the present invention includes zirconia in which Y 2 O 3 is uniformly dispersed as a solid solution, such as the commercially available TZ series (a part of the product name includes "TZ"). Powders can also be used.
  • zirconia powder there are no particular restrictions on the method for producing zirconia powder, and for example, known methods such as a breakdown process in which coarse particles are pulverized and pulverized, and a building-up process in which zirconia powder is synthesized from atoms or ions through a nucleation and growth process may be employed. I can do it.
  • the type of zirconia powder in the raw material composition is not particularly limited, and if the zirconia powder contains ZrO 2 and HfO 2 and does not contain a stabilizer, or the content of the stabilizer is increased as necessary. If necessary, stabilizer particles can be added separately.
  • the stabilizer particles are not particularly limited as long as the content of the stabilizer contained in the black zirconia composite sintered body can be adjusted to the above-mentioned predetermined range.
  • a commercially available product may be used, or a commercially available powder may be pulverized using a known pulverizing and mixing device (such as a ball mill) before use.
  • the stabilizer may be either a stabilizer that does not form a solid solution in ZrO 2 and HfO 2 or a stabilizer that forms a solid solution in ZrO 2 and HfO 2 .
  • a stabilizer preferably Y 2 O 3
  • a method for producing a black zirconia composite sintered body containing a stabilizer that is not solidly dissolved in ZrO 2 and HfO 2 is mentioned. It can be confirmed, for example, by an X-ray diffraction (XRD) pattern that the zirconia contains a stabilizer that is not solidly dissolved.
  • a peak derived from the stabilizer is confirmed in the XRD pattern of the raw material composition or the molded body, there is a stabilizer that is not solidly dissolved in ZrO 2 and HfO 2 in the raw material composition or the molded body. That means you are doing it.
  • the entire amount of the stabilizer is dissolved in ZrO 2 and HfO 2 , basically no peak derived from the stabilizer is observed in the XRD pattern.
  • the stabilizer may not be solidly dissolved in ZrO 2 and HfO 2 . could be.
  • the stabilizer includes a stabilizer that is not solidly dissolved in ZrO 2 and HfO 2 will be described below using yttria as an example.
  • the abundance f y of yttria that is not dissolved in ZrO 2 and HfO 2 is determined by the following formula (1).
  • f y I 29 /(I 28 +I 29 +I 30 ) ⁇ 100
  • the peak of the other stabilizer is substituted for I29 , and the calculation is also applied to the calculation of the undissolved abundance rate of the stabilizer other than yttria. be able to.
  • f y when the content of yttria in the raw material composition or molded article of the present invention is 3 mol% or more and 8 mol% or less, the following is true.
  • f y when the content of yttria is 3 mol% or more and less than 4.5 mol%, f y can be 15% or less.
  • f y When the content of yttria is 4.5 mol% or more and less than 5.8 mol%, f y can be 20% or less.
  • f y when the content of yttria is 5.8 mol% or more and 8 mol% or less, f y can be 25% or less.
  • f y is preferably 2% or more, more preferably 3% or more, and even more preferably 4% or more. , 5% or more is particularly preferred.
  • f y is preferably 3% or more, more preferably 4% or more, and even more preferably 5% or more. , more preferably 6% or more, and particularly preferably 7% or more.
  • f y is preferably 4% or more, more preferably 5% or more, even more preferably 6% or more, and 7 % or more is even more preferable, and particularly preferably 8% or more.
  • the term "stabilizer dissolved in solid solution” means, for example, that elements (atoms) contained in the stabilizer are dissolved in ZrO 2 and HfO 2 as solid solution.
  • the Nb 2 O 5 and/or Ta 2 O 5 added to the raw material composition of the present invention is such that the content of Nb 2 O 5 and/or Ta 2 O 5 contained in the black zirconia composite sintered body is within the above-mentioned predetermined range. It is not particularly limited as long as it can be adjusted within the range.
  • Nb 2 O 5 and/or Ta 2 O 5 are not particularly limited, and for example, a commercially available product may be used, and a commercially available powder may be pulverized with a known pulverizing and mixing device (such as a ball mill) before use. Good too.
  • each raw material of the raw material composition ZrO 2 , HfO 2 , a stabilizer, Nb 2 O 5 and/or Ta 2 O 5 , and a capping agent (e.g. , a compound that can become a monovalent ion in a water-containing solvent) and, if necessary, a zirconia reinforcing agent) are wet-mixed in a water-containing solvent to obtain a raw material composition.
  • a capping agent e.g. , a compound that can become a monovalent ion in a water-containing solvent
  • a zirconia reinforcing agent e.g. , a compound that can become a monovalent ion in a water-containing solvent
  • each raw material is wet-pulverized and mixed in a known pulverization-mixing device (such as a ball mill) to form a slurry, and then the slurry is mixed.
  • a known pulverization-mixing device such as a ball mill
  • the slurry is mixed.
  • additives such as a binder, plasticizer, dispersant, emulsifier, antifoaming agent, pH adjuster, and lubricant may be further included.
  • the additives may be used alone or in combination of two or more.
  • the binder is prepared by adding a primary powder consisting of a mixture of ZrO 2 , HfO 2 , Y 2 O 3 , Nb 2 O 5 and/or Ta 2 O 5 , and a capping agent to water to form a slurry. , may be added later to the pulverized slurry.
  • the binder is not particularly limited, and any known binder can be used.
  • the binder include polyvinyl alcohol binder, acrylic binder, wax binder (paraffin wax, etc.), methyl cellulose, carboxymethyl cellulose, polyvinyl butyral, polymethyl methacrylate, ethyl cellulose, polyethylene, polypropylene, ethylene vinyl acetate copolymer, Examples include polystyrene, atactic polypropylene, and methacrylic resin.
  • plasticizer examples include polyethylene glycol, glycerin, propylene glycol, dibutylphthalic acid, and the like.
  • dispersants include ammonium polycarboxylate (triammonium citrate, etc.), ammonium polyacrylate, acrylic copolymer resin, acrylic ester copolymer, polyacrylic acid, bentonite, carboxymethylcellulose, and anionic surfactants. agents (for example, polyoxyethylene alkyl ether phosphates such as polyoxyethylene lauryl ether phosphates), nonionic surfactants, oleic glycerides, amine salt type surfactants, oligosaccharide alcohols, stearic acid, etc. Can be mentioned.
  • ammonium polycarboxylate triammonium citrate, etc.
  • ammonium polyacrylate acrylic copolymer resin
  • acrylic ester copolymer acrylic acid
  • bentonite carboxymethylcellulose
  • anionic surfactants for example, polyoxyethylene alkyl ether phosphates such as polyoxyethylene lauryl ether phosphates
  • nonionic surfactants for example, polyoxyethylene alkyl
  • emulsifiers examples include alkyl ethers, phenyl ethers, sorbitan derivatives, and the like.
  • antifoaming agents examples include alcohol, polyether, silicone, and wax.
  • pH adjuster examples include ammonia, ammonium salts (including ammonium hydroxide such as tetramethylammonium hydroxide), and the like.
  • lubricant examples include polyoxyethylene alkyl ether and wax.
  • the solvent used for wet mixing is not particularly limited as long as it contains water, and an organic solvent, a mixed solvent of water and an organic solvent may be used, or only water may be used.
  • organic solvents include ketone solvents such as acetone and ethyl methyl ketone; ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, glycerin, diglycerin, polyglycerin, propylene glycol, dipropylene glycol, Examples include alcohol solvents such as polypropylene glycol, ethylene glycol, diethylene glycol, polyethylene glycol, polyethylene glycol monomethyl ether, 1,2-pentadiol, 1,2-hexanediol, and 1,2-octanediol.
  • the raw material composition of the black zirconia composite sintered body used in the present invention contains ZrO 2 , Y 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , a capping agent, and, if necessary, as long as the effects of the present invention are achieved. It may also contain other components than the zirconia reinforcing agent. Examples of the other components include colorants (pigments and composite pigments), fluorescent agents, SiO 2 and the like. The other components may be used alone or in combination of two or more.
  • Examples of the composite pigment include (Zr, V)O 2 , Fe(Fe,Cr) 2 O 4 , (Ni, Co, Fe) (Fe, Cr) 2 O 4 .ZrSiO 4 , (Co, Zn) Examples include Al 2 O 4 .
  • the molding method is not particularly limited, and known methods (for example, press molding, etc.) can be used.
  • a specific method of press molding includes, for example, uniaxial press.
  • the press pressure is appropriately set to an optimal value depending on the size of the desired compact, open porosity, biaxial bending strength, and particle size of the raw material powder, and is usually 5 MPa or more and 1000 MPa or less.
  • a cold isostatic pressing (CIP) treatment may be further performed after uniaxial pressing.
  • the term "molded object" means an object that has not reached either a semi-sintered state (calcined state) or a sintered state. That is, a molded body is distinguished from a calcined body and a sintered body in that it is unfired after being molded into a molded body.
  • the sintering temperature (maximum sintering temperature) for obtaining a black zirconia composite sintered body is, for example, preferably 1300°C or higher, more preferably 1350°C or higher, even more preferably 1400°C or higher, even more preferably 1450°C or higher. , 1500°C or higher is particularly preferred.
  • the sintering temperature is, for example, preferably 1680°C or lower, more preferably 1650°C or lower, and even more preferably 1600°C or lower.
  • the sintering temperature is preferably a temperature in the atmosphere.
  • the holding time (mooring time) at the maximum sintering temperature depends on the temperature, but is preferably 30 hours or less, more preferably 20 hours or less, even more preferably 10 hours or less, even more preferably 5 hours or less, and even more preferably 3 hours or less. is particularly preferred, and most preferably 2 hours or less. Furthermore, the holding time can be 25 minutes or less, 20 minutes or less, or 15 minutes or less. Further, the holding time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more. According to the production method of the present invention, a black zirconia composite sintered body having excellent bending strength and machinability can be produced depending on the content of the stabilizer. Furthermore, the sintering time may be shortened as long as the effects of the present invention can be obtained. By shortening the sintering time, production efficiency can be increased and energy costs can be reduced.
  • the temperature increase rate is not particularly limited, but is preferably 0.1°C/min or more, and 0.2°C/min.
  • the heating rate is more preferably at least 0.5° C./min, and even more preferably at least 0.5° C./min.
  • the temperature increase rate is preferably 50°C/min or less, more preferably 30°C/min or less, and even more preferably 20°C/min or less. Productivity improves when the temperature increase rate is equal to or higher than the above lower limit.
  • a common zirconia firing furnace can be used in the step of sintering the molded body.
  • a commercially available product may be used as the zirconia firing furnace.
  • Commercially available products include Noritake Katana (registered trademark) F-1, F-1N, and F-2 (all manufactured by SK Medical Electronics Co., Ltd.).
  • a black zirconia composite sintered body can also be obtained by sintering a molded body to which a black pigment is added.
  • the black pigment include black organic pigments, color-mixing organic pigments, and inorganic pigments.
  • the black organic pigment include carbon black, perylene black, aniline black, and benzofuranone pigments. These may be coated with resin.
  • mixed color organic pigments include those obtained by mixing two or more pigments such as red, blue, green, purple, yellow, magenta and/or cyan to create a pseudo-black color.
  • black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides. metal oxynitrides; metal carbides and the like.
  • metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver
  • metal oxides such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver
  • metal oxides such as titanium composite oxides
  • metal sulfides metal nitrides.
  • metal oxynitrides metal carbides and the like.
  • the total content of titanium does not exceed 5.0% by mass, which is the upper limit of the content of TiO 2 in the zirconia reinforcing agent.
  • a preferred embodiment includes a method for producing a black zirconia composite sintered body, in which the step of sintering the compact includes a step of reduction firing in addition to sintering at the maximum sintering temperature described above.
  • the reduction firing process is not particularly limited as long as it is sintering performed in a reducing atmosphere, but includes, for example, a process of hot isostatic pressing (HIP) in a reducing atmosphere.
  • HIP hot isostatic pressing
  • the sintered body obtained by sintering at the maximum sintering temperature described above will be referred to as a "primary sintered body", and the sintered body after HIP treatment will be referred to as a "HIP-treated sintered body”.
  • the HIP treatment can be performed using a known hot isostatic press (HIP) device.
  • HIP hot isostatic press
  • the temperature of the HIP treatment is not particularly limited, but since a dense black zirconia composite sintered body with high strength can be obtained, the HIP temperature is preferably 1200°C or higher, and preferably 1300°C or higher. More preferably, the temperature is 1400°C or higher. Further, the HIP temperature is preferably 1700°C or lower, more preferably 1650°C or lower, and even more preferably 1600°C or lower.
  • the HIP pressure is not particularly limited, and since a dense sintered body with high strength can be obtained, HIP The pressure is preferably 100 MPa or higher, more preferably 125 MPa or higher, even more preferably 130 MPa or higher. Further, the upper limit of the HIP pressure is not particularly limited, but may be, for example, 400 MPa or less, 300 MPa or less, or even 200 MPa or less.
  • the heating rate is not particularly limited, and is preferably 0.1°C/min or more, and 0.2°C/min or more. It is more preferable that it is 0.degree. C./min or more, and even more preferably that it is 0.5.degree. C./min or more. Further, the temperature increase rate is preferably 50°C/min or less, more preferably 30°C/min or less, and even more preferably 20°C/min or less. Productivity improves when the temperature increase rate is equal to or higher than the above lower limit.
  • the HIP time is not particularly limited, and a dense black zirconia composite sintered body with high strength can be obtained. Therefore, the time for HIP treatment is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more. Further, the time for the HIP treatment is preferably 10 hours or less, more preferably 6 hours or less, and even more preferably 3 hours or less.
  • the pressure medium is not particularly limited, and from the viewpoint of having a low influence on zirconia, the pressure medium may be At least one kind selected from the group consisting of inert gases (for example, nitrogen, argon, etc.) can be selected.
  • inert gases for example, nitrogen, argon, etc.
  • the carbon used in the reduction and firing step is not particularly limited, and examples thereof include referthermo (common thermal history sensor, which contains a small amount of organic component (organic binder (PVA/PEG type)), and the like.
  • the black zirconia composite sintered body of the present invention is not particularly limited as long as it exhibits the effects of the present invention, and may be a primary sintered body or a HIP-treated sintered body.
  • the black zirconia composite sintered body of the present invention is a sintered body, it has excellent machinability, so it is machined in a mill blank state of a semi-sintered calcined body, and then sintered. There is no need to make it into a sintered body.
  • a method for producing a black zirconia composite sintered body a molded body obtained using the raw material composition is calcined to produce a semi-sintered calcined body, and the unprocessed calcined body is machined. After that, a method of producing a sintered body may be adopted.
  • Another embodiment includes a step of producing a molded body using the raw material composition, a step of calcining the obtained molded body to obtain a zirconia calcined body (calcination step), and a step of producing a zirconia calcined body by calcining the obtained molded body. a step of sintering the fired body; A method for producing a black zirconia composite sintered body is mentioned.
  • the calcination temperature (calcination temperature) in the calcination step is preferably, for example, 800°C or higher, more preferably 900°C or higher, and even more preferably 950°C or higher, in order to ensure block formation. Further, the calcination temperature is preferably, for example, 1200°C or lower, more preferably 1150°C or lower, and even more preferably 1100°C or lower. The calcination temperature is preferably 800°C to 1200°C, for example. At such a calcination temperature, it is considered that solid solution of the stabilizer does not proceed significantly in the calcination step.
  • the zirconia calcined body of the present invention means that the ZrO 2 particles are necked (fixed) to each other, and the ZrO 2 particles (powder) are not completely sintered (semi-sintered state).
  • the density of the zirconia calcined body is preferably 2.7 g/cm 3 or more. Further, the density of the zirconia calcined body is preferably 4.0 g/cm 3 or less, more preferably 3.8 g/cm 3 or less, and even more preferably 3.6 g/cm 3 or less. When the density is within this range, processing can be easily performed.
  • the density of the calcined body can be calculated, for example, as (mass of the calcined body)/(volume of the calcined body).
  • the three-point bending strength of the zirconia calcined body is preferably 15 to 70 MPa, more preferably 18 to 60 MPa, and even more preferably 20 to 50 MPa.
  • the bending strength can be measured using a test piece with a thickness of 5 mm x width of 10 mm x length of 50 mm in accordance with ISO 6872:2015 except for the size of the test piece.
  • the face and C face (the face where the corners of the test piece are chamfered at an angle of 45°) of the test piece are finished in the longitudinal direction with 600-grit sandpaper.
  • the test piece is arranged so that its widest surface faces the vertical direction (loading direction). For bending test measurements, the span is 30 mm and the crosshead speed is 1.0 mm/min.
  • the process of sintering the zirconia calcined body can be performed in the same manner and under the same conditions (temperature, pressure, etc.) as the process of sintering the molded body described above. Therefore, in the embodiment of the manufacturing method using the zirconia calcined body, the "molded body" can also be read as the "calcined body”.
  • the black zirconia composite sintered body of the present invention has excellent strength.
  • the biaxial bending strength of the black zirconia composite sintered body of the present invention is preferably 300 MPa or more, more preferably 350 MPa or more, even more preferably 400 MPa or more, and even more preferably 450 MPa or more. More preferably, it is particularly preferably 500 MPa or more. Since the black zirconia composite sintered body of the present invention has such biaxial bending strength, it is possible to suppress breakage, for example.
  • the biaxial bending strength can be, for example, 1200 MPa or less, and further 1000 MPa or less. Note that the biaxial bending strength of the black zirconia composite sintered body can be measured in accordance with ISO 6872:2015.
  • the black zirconia composite sintered body of the present invention preferably has a desired color tone from the viewpoint of excellent design.
  • the color tone can be evaluated using L*,
  • are the L*a*b* color system (JIS Z 8781-4:2013 Colorimetry - Part 4) for a measurement sample with a diameter of 15 mm and a thickness of 1.2 mm.
  • L*, a*, b* according to CIE 1976 L*a*b* color space), for example, using a spectrophotometer "CM-3610A" manufactured by Konica Minolta, Inc., D65 light source, measurement mode. It can be calculated by measuring under the conditions of SCI, measurement diameter/illumination diameter ⁇ 8 mm/ ⁇ 11 mm.
  • a black zirconia composite sintered body has L* of 60 or less,
  • L* is 50 or less,
  • a value measured on a white background in the L*a*b* color system using a sample with a diameter of 15 mm and a thickness of 1.2 mm since it is easy to obtain better design properties.
  • Examples include a black zirconia composite sintered body in which L* ⁇ 60,
  • the color tone was measured using a sample with a diameter of 15 mm and a thickness of 1.2 mm against a white background in the L*a*b* color system.
  • the saturation C* calculated from * and b* is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • saturation C * ((a * ) 2 +(b * ) 2 ) 1/2 can be calculated from the average value of a* and b * obtained by the method described above.
  • the coefficient of thermal expansion (CTE) of the black zirconia composite sintered body of the present invention is preferably 8 ⁇ 10 ⁇ 6 /°C to 13 ⁇ 10 ⁇ 6 /°C, and preferably 8.5 ⁇ 10 ⁇ 6 /°C to 12 It is more preferably ⁇ 10 -6 /°C, and even more preferably 9 ⁇ 10 -6 /°C to 11 ⁇ 10 -6 /°C. Since the black zirconia composite sintered body of the present invention has a coefficient of thermal expansion (CTE) within the above range, it can be suitably used in combination with a metal material.
  • the coefficient of thermal expansion (CTE) can be measured in accordance with ISO 6872:2015 with an analysis temperature range of 25° C. to 500° C., for example, at a heating rate of 5° C./min.
  • the black zirconia composite sintered body of the present invention is particularly suitable for use in zirconia members that require an irregular or complicated shape and strength.
  • the black zirconia composite sintered body of the present invention can be processed directly from the sintered body. Therefore, for example, it is economical when a desired zirconia member can be obtained in a short time, and there is no need to mechanically fit multiple members in the case of complex-shaped parts that are difficult to manufacture using conventional manufacturing methods. Therefore, it is possible to obtain a zirconia member that maintains high strength.
  • the sintered body can be processed as it is, a sintering step is not necessary when dimensional accuracy is required, and uneven firing shrinkage is eliminated, so a zirconia member can be obtained with high precision. Further, machining can be performed using, for example, a commercially available machining device.
  • the black zirconia composite sintered body of the present invention can be used for jewelry (brooches, tie pins, handbag fittings, bracelets, etc.), engine parts and interior parts for mobility devices such as aircraft and automobiles, and display panels.
  • It can also be used as a method for manufacturing exterior members such as mobile phone cases and earphone housings, electrical appliance parts, household goods parts, logo marks for various products, and parts for toys.
  • the present zirconia member and a different material may be fitted together to form a composite member.
  • the present invention includes embodiments in which all or part of the above configurations are combined in various ways within the scope of the technical idea of the present invention as long as the effects of the present invention are achieved.
  • the average particle diameter is the average primary particle diameter, and can be determined by a laser diffraction scattering method. Specifically, it can be measured on a volume basis using a laser diffraction particle size distribution measuring device (SALD-2300, manufactured by Shimadzu Corporation) using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.
  • SALD-2300 laser diffraction particle size distribution measuring device
  • Examples 1 to 17 and Comparative Examples 1 to 4 The measurement samples of each Example and Comparative Example were produced through the steps of producing a granular raw material composition, producing a molded body, and producing a sintered body (fabrication of a primary sintered body, and HIP treatment).
  • raw material composition a granular raw material composition (hereinafter also simply referred to as "raw material composition"), which was used to produce a molded article described below.
  • the average particle diameter is a value measured on a volume basis using a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation) using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.
  • SALD-2300 laser diffraction particle size distribution analyzer
  • TZ-3Y Y 2 O 3 content: 3 mol%)
  • TZ-6Y Y 2 O 3 content: 6 mol%) was mixed at a ratio of 18.7:81.3.
  • the proportions of each component were adjusted so that the proportions were as shown in Table 1.
  • a pellet-shaped molded body and a block-shaped molded body were produced as follows so as to obtain sintered body samples for strength evaluation and workability evaluation.
  • a cylindrical mold with a diameter of 19 mm was used, and the raw material composition was placed in the mold so that the thickness of the black zirconia composite sintered body after sintering was 1.2 mm.
  • the raw material composition was press-molded using a uniaxial press-molding machine at a surface pressure of 200 MPa to produce a pellet-shaped molded body.
  • the raw material composition was placed in a mold with inner dimensions of 19 mm x 18 mm so that the height of the black zirconia composite sintered body after sintering was 14.5 mm.
  • the raw material composition was press-molded using a uniaxial press-molding machine at a surface pressure of 200 MPa to produce a block-shaped molded body.
  • pellet-shaped and block-shaped zirconia sintered bodies were heated to 150 MPa using argon gas as the pressure medium using the HIP device "O 2 -Dr. HIP" of Kobe Steel, Ltd.
  • Samples of pellet-shaped and block-shaped black zirconia composite sintered bodies were obtained by mooring for 2 hours at the HIP temperature listed in Tables 1 and 2 and with or without refer thermometer. Ta.
  • the pellet shape was 15 mm in diameter x 1.2 mm in thickness
  • the block shape was 15.7 mm in width x 16.5 mm in length x 14.5 mm in height.
  • the content of each component in the sintered body in Tables 1 and 2 is a value calculated from the amount of raw materials charged.
  • the content rate (mol%) of the capping element or ion in Tables 1 and 2 is the external addition rate to a total of 100 mol% of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 .
  • the respective contents (mol%) of ZrO 2 , HfO 2 , the stabilizer, Nb 2 O 5 , and Ta 2 O 5 in Tables 1 and 2 are as follows: ZrO 2 , HfO 2 , the stabilizer, Nb This is the content of each component in a total of 100 mol% of 2 O 5 and Ta 2 O 5 .
  • ZrO 2 and HfO 2 are shown as the total content of ZrO 2 and HfO 2 .
  • the contents (mass%) of TiO 2 and Al 2 O 3 in Tables 1 and 2 are the external This is the addition rate.
  • A/B in Tables 1 and 2 represents the ratio of A to B when the content of Y2O3 is Amol% and the total content of Nb2O5 and Ta2O5 is Bmol%. .
  • the crystal grain size obtained with Image-Pro Plus is the length of the line segment connecting the outline lines passing through the center of gravity determined from the outline of the crystal grain, measured every 2 degrees around the center of gravity, and averaged.
  • the average value of the crystal grain sizes of all particles that do not overlap the edges of the image is the average crystal grain size (number based) in the sintered body.
  • particles that do not extend to the edges of the image refer to particles excluding particles whose outlines do not fit within the screen of the SEM photographic image (particles whose outlines are interrupted on the upper, lower, left, and right boundaries).
  • the grain size of all particles that do not extend to the edge of the image was selected in Image-Pro Plus with the option to exclude all borderline particles.
  • the average crystal grain size of the crystal grains in the black zirconia composite sintered body of Example 3 was 2.7 ⁇ m, and the average crystal grain size of the crystal grains in the black zirconia composite sintered body of Example 8 was 2.2 ⁇ m. .
  • the processing program uses the software "inLab (registered trademark) CAM version 20.0.1.203841", Manufacture: IVOCLAR VIVADENT, Material name: IPS e. max CAD, Production Method: Grinding, Block size: C16 were selected, and Step Bur 12 and Cylinder Pointed Bur 12S were used as processing tools.
  • the number of processed pieces shown in Tables 1 and 2 means that the processing of the sample is started using a new set of processing tools under the conditions described in [Workability evaluation of black zirconia composite sintered body] above. This is the number of samples that could be processed into the crown shape of a front tooth without changing the processing tool even once.
  • the maximum number of samples used in the test was 30, and if machining of up to 30 samples could be completed with one machining tool, no additional machining test was performed, and the sample was uniformly determined to be ⁇ 30 or more''.
  • the black zirconia composite sintered body of the present invention has excellent machinability despite being in a sintered body state. Furthermore, it was confirmed that the black zirconia composite sintered body of the present invention had suitable strength. Furthermore, in Examples 1 to 17, it was possible to suppress the wear and tear of the machining tool, and it was possible to increase the number of workpieces that can be continuously machined with one machining tool compared to the conventional technique. On the other hand, in Comparative Example 1 which does not contain Nb 2 O 5 and Ta 2 O 5 , machining could not be performed. In Comparative Example 2, which does not contain a capping element or ion, the processing time was not sufficiently shortened and the number of pieces processed was very small.
  • Comparative Example 3 containing a divalent metal element which is a metal element not included in the capping element, the processing time was not sufficiently shortened.
  • Comparative Example 4 containing a trivalent metal element which is a metal element not included in the capping element, the processing time was not sufficiently shortened.
  • Patent Document 4 it is shown that the strength of TiO2 decreases in proportion to the amount added ( Figure 7 of Patent Document 4), but the black zirconia composite sintered material of the present invention
  • the compact contains Nb 2 O 5 and/or Ta 2 O 5 as a component, by further including a capping element or ion, TiO 2 acts integrally and increases the strength of the black zirconia composite sintered compact. It was confirmed from a comparison between Example 4 and Example 5 that this could be improved.
  • the black zirconia composite sintered body of the present invention has excellent machinability and exhibits a black color with excellent design.

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CN118145991A (zh) * 2024-02-21 2024-06-07 中山大学 一种氧化钇稳定氧化锆粉体的制备方法

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JP7610081B2 (ja) 2022-06-01 2025-01-07 クラレノリタケデンタル株式会社 ジルコニア複合焼結体及びその製造方法
CN118145991A (zh) * 2024-02-21 2024-06-07 中山大学 一种氧化钇稳定氧化锆粉体的制备方法

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