WO2024117194A1 - 粉末 - Google Patents

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Publication number
WO2024117194A1
WO2024117194A1 PCT/JP2023/042776 JP2023042776W WO2024117194A1 WO 2024117194 A1 WO2024117194 A1 WO 2024117194A1 JP 2023042776 W JP2023042776 W JP 2023042776W WO 2024117194 A1 WO2024117194 A1 WO 2024117194A1
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WIPO (PCT)
Prior art keywords
less
powder
zirconia
mass
alumina
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/042776
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
長谷川雄祐
細井浩平
永山仁士
土屋聡
吹上拓
川村謙太
伊藤晶子
菅原陵
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.)
Tosoh Corp
Original Assignee
Tosoh Corp
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 Tosoh Corp filed Critical Tosoh Corp
Priority to JP2023574369A priority Critical patent/JPWO2024117194A1/ja
Priority to CN202380081402.6A priority patent/CN120265579A/zh
Priority to EP23897840.7A priority patent/EP4628450A4/en
Priority to US19/133,333 priority patent/US20260070848A1/en
Priority to KR1020257021198A priority patent/KR20250114087A/ko
Publication of WO2024117194A1 publication Critical patent/WO2024117194A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
    • 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

  • This disclosure relates to a powder that serves as a precursor for a black zirconia sintered body, and a method for producing a sintered body using the same.
  • Zirconia sintered compacts are widely used in decorative parts, exterior parts, semiconductor parts, structural parts, etc.
  • Zirconia sintered compacts which are black in color, have a glossy appearance and can create a luxurious feel, so they are used as highly decorative components. When used in components, they are required to be durable in addition to being decorative. For this reason, zirconia sintered compacts that contain yttrium as a stabilizing element and have improved fracture toughness by reducing the content of yttrium, so-called high-toughness zirconia sintered compacts, are being investigated.
  • Patent Document 1 discloses the use of Fe, Ti, Co, and Cr as coloring elements.
  • Patent Document 2 discloses the use of cheaper manganese as a coloring element, a zirconia powder containing 1.6 mol% yttria, 0.25 mass% alumina, and 0.05 mass% MnO2 as stabilizers, and a sintered body obtained from the powder.
  • the sintered body of Patent Document 1 requires multiple elements as coloring elements, which means that the manufacturing costs tend to be high.
  • the sintered body of Patent Document 2 has a light color tone and is not a black sintered body.
  • the objective of the present disclosure is to provide at least one of a powder that produces a zirconia sintered body that contains manganese as the primary coloring element, is black in color, and has high fracture toughness, and that has little variation in color tone due to fluctuations in sintering temperature, and a method for producing the powder.
  • the present inventors have investigated a high-toughness zirconia sintered body that contains manganese as the main coloring element and is black in color. As a result, they have confirmed that in the high-toughness zirconia sintered body, if the content of the coloring element is increased, defects such as cracks occur during sintering, and the sintered body itself cannot be obtained. Furthermore, even if a sintered body is obtained, it has been confirmed that the color tone of the sintered body containing manganese as the main coloring element varies from production lot to production lot. They have focused on the fact that this variation is influenced by the actual sintering temperature, rather than the set temperature of the sintering furnace, such as temperature unevenness in the sintering furnace.
  • the present inventors have discovered that even in a high-toughness zirconia sintered body that contains alumina that functions as a coloring element that presents white, and that contains manganese as the main coloring element and is black in color, the variation in color tone due to fluctuations in the sintering temperature is reduced by controlling the content of the alumina and manganese compound to a specific relationship.
  • a powder containing zirconia containing yttrium as a stabilizing element, a manganese compound, and alumina The content of the stabilizing element calculated as an oxide is 1.3 mol % or more and less than 2.0 mol % with respect to the total amount of zirconia and the stabilizing element calculated as an oxide, The content of the alumina is 0.2 mass% or more and 1.5 mass% or less with respect to the total amount of the powder, The content of the manganese compound is 0.1 mass% or more and 0.6 mass% or less with respect to the total amount of the powder.
  • [8] A powder according to any one of [1] to [7], having a median diameter of 0.1 ⁇ m or more and 1.0 ⁇ m or less.
  • the present disclosure provides at least one of a powder that produces a zirconia sintered body that contains manganese as the primary coloring element, is black in color, and has high fracture toughness, and that has little variation in color tone due to fluctuations in sintering temperature, and a method for producing the powder.
  • the present disclosure will be described below with reference to an example of an embodiment.
  • This disclosure includes any combination of the configurations and parameters disclosed herein, and also includes any combination of the upper and lower limits of the values disclosed herein.
  • the main terms used in this embodiment are as follows.
  • “Monoclinic fraction” and “tetragonal fraction” are the proportions of monoclinic zirconia and tetragonal zirconia in the zirconia crystal phase, respectively.
  • “monoclinic intensity ratio” is the ratio of the area intensity of the XRD peak corresponding to the (11-1) plane of monoclinic zirconia to the area intensity of the XRD peak corresponding to the (111) plane of monoclinic zirconia in the zirconia crystal phase.
  • the powder X-ray diffraction (hereinafter also referred to as "XRD") pattern of the powder is used, while for sintered bodies, the XRD pattern of the surface of the sintered body after mirror polishing is used, and the monoclinic fraction can be calculated from the following formula (1), the tetragonal fraction from the following formula (2), and the monoclinic intensity ratio from the following formula (3).
  • XRD powder X-ray diffraction
  • f m is the monoclinic fraction (%)
  • f t is the tetragonal fraction (%)
  • M (11-1)/(111) is the monoclinic intensity ratio
  • I m (111) and I m (11-1) are the area intensities of the XRD peaks corresponding to the (111) and (11-1) planes of monoclinic zirconia, respectively
  • I t (111) is the area intensity of the XRD peak corresponding to the (111) plane of tetragonal zirconia
  • I c (111) is the area intensity of the XRD peak corresponding to the (111) plane of cubic zirconia. Therefore, the monoclinic fraction and the tetragonal fraction are each calculated as area intensity ratios (%).
  • the XRD peaks corresponding to the respective crystal planes of zirconia are measured as peaks having peak tops at the following 2 ⁇ .
  • XRD peak corresponding to the (111) plane of monoclinic zirconia: 2 ⁇ 31 ⁇ 0.5°
  • XRD peak corresponding to the (11-1) plane of monoclinic zirconia: 2 ⁇ 28 ⁇ 0.5°
  • the area intensity of the XRD peak of each crystal plane can be determined by calculating the area intensity of each diffraction peak (XRD peak) using the calculation program "Smartlab-Studio2 (Rigaku)".
  • the sintered body used for XRD measurement should be a sintered body after surface polishing.
  • This is a sintered body whose surface after sintering is ground using a surface grinder, and then the measurement surface is mirror-polished in the following order: automatic polishing with an abrasive cloth and paper, automatic polishing with diamond slurry with an average particle size of 3 ⁇ m, and automatic polishing with colloidal silica of 0.03 ⁇ m.
  • the "crystallite diameter of monoclinic zirconia” (hereinafter also referred to as “ Dm ”) is a value calculated from the XRD pattern of a powder using the following formula (4)
  • the "crystallite diameter of tetragonal zirconia” (hereinafter also referred to as “ Dt ”) is a value calculated from the XRD pattern of a powder using the following formula (5).
  • Dm is the crystallite diameter (nm) of monoclinic zirconia
  • Dt is the crystallite diameter (nm) of tetragonal zirconia
  • ⁇ is the wavelength (0.15418 nm) of the light source used in the XRD measurement
  • ⁇ is the half-width (rad)
  • ⁇ m is the Bragg angle (rad) of the reflection corresponding to the (11-1) plane of monoclinic zirconia in the XRD measurement
  • ⁇ t is the Bragg angle (rad) of the reflection corresponding to the (111) plane of tetragonal zirconia in the XRD measurement.
  • the "BET specific surface area” is a value determined by the BET multipoint method in accordance with JIS R 1626-1996, using nitrogen (N 2 ) as the adsorbent.
  • the “median diameter” (hereinafter also referred to as "D50”) is the particle diameter that corresponds to a volume fraction of 50% on the cumulative volume particle size distribution curve obtained by volume particle size distribution measurement using the laser diffraction method.
  • the "particle size distribution curve” is a curve that shows the particle size distribution of a powder obtained by measuring the volumetric particle size distribution using the laser diffraction method.
  • the "fracture toughness value” is a fracture toughness value (MPa ⁇ m 0.5 ) measured by a method conforming to the SEPB method specified in JIS R 1607.
  • the fracture toughness value is measured using a columnar sintered body sample with a support distance of 16 mm, width of 4 mm, and thickness of 3 mm, and the average value of 10 measurements may be taken as the fracture toughness value of the sintered body.
  • JIS R 1607 specifies two types of fracture toughness measurement, the IF method and the SEPB method.
  • the IF method tends to measure larger values than the SEPB method.
  • the IF method is a simple measurement method, the measured values vary greatly from measurement to measurement.
  • the absolute values of the fracture toughness value in this embodiment and the fracture toughness value measured by the IF method cannot be compared.
  • the absolute values of the fracture toughness value measured by a method other than the SEPB method and the fracture toughness value measured by the SEPB method cannot be compared.
  • Bending strength refers to the three-point bending strength value determined by a three-point bending test in accordance with JIS R 1601. Bending strength is measured using a columnar sintered body sample with a support distance of 30 mm, width 4 mm, and thickness 3 mm, and the bending strength of the sintered body is determined by the average value of 10 measurements.
  • “Relative density” is the ratio (%) of the measured density to the true density.
  • the measured density of a green body is the ratio (g/cm 3 ) of the mass measured by mass measurement to the volume determined from dimensional measurements.
  • the measured density of a sintered body is the ratio (g/cm 3 ) of the mass measured by mass measurement to the volume measured by Archimedes' method.
  • the true density is the density (g/cm 3 ) calculated from the following formulas (6) to (9).
  • ⁇ 0 is the true density
  • ⁇ Z is the true density of zirconia
  • a and C are constants
  • X is the molar ratio (mol %) of yttrium converted into oxide to the total of zirconia ( ZrO2 ) and yttrium converted into oxide ( Y2O3 )
  • YA and YM are the mass ratios (mass %) of alumina converted into Al2O3 and manganese converted into Mn3O4 to the total of zirconia , yttrium , alumina, and manganese of the molded body or sintered body converted into ZrO2 , Y2O3 , Al2O3 , and Mn3O4 , respectively.
  • ⁇ 0 100/[( YA/ 3.987) + (YM/4.860) + ( YN1 / MN1 ) ... + ( YNn / MNn ) + (100- YA - YM - YN1 ...- YNn ) / ⁇ Z ] (9')
  • Y N1 , ..., Y Nn are mass percentages (mass%) of each toning colorant, calculated as an oxide, relative to the total amount of powder (described later), M N1 , ..., M Nn are the amounts of substance (g/mol) of each toning colorant, calculated as an oxide, and n is an integer.
  • Color tone refers to a color tone quantified in the L * a * b * color system using a method conforming to JIS Z 8781-5 corresponding to ISO 11664-4, and corresponds to the L * a*b * coordinates of one point specified by lightness L * , hue a * and b * .
  • Color tone variation refers to the variation in the lightness L * value in the L * a * b * color system.
  • the color tone variation and color tone may be measured under the following conditions using a general spectrophotometer (e.g., CM-700d, manufactured by Konica Minolta).
  • Light source F2 light source Viewing angle: 10°
  • Measurement method SCI Background: Black background Measurement sample: (sample thickness) 1.3 ⁇ 0.1mm
  • the powder of this embodiment is a powder mainly composed of zirconia (a powder whose main component is zirconia, a so-called zirconia powder), and is not limited to a powder composed only of zirconia, but is a powder containing components other than zirconia, in particular, a powder containing at least zirconia containing yttrium as a stabilizing element, a manganese compound, and alumina.
  • the powder of this embodiment is essentially a powder containing zirconia containing yttrium as a stabilizing element, a manganese compound, and alumina, and may be a powder consisting of zirconia containing yttrium, including a manganese compound and alumina.
  • Zirconia containing yttrium as a stabilizing element is zirconia stabilized with yttrium, i.e., yttrium-stabilized zirconia.
  • Yttrium is contained in zirconia as a stabilizing element. This stabilizes the crystalline phase of zirconia.
  • the yttrium content of the powder may be any content that partially stabilizes zirconia.
  • the amount of yttrium in the powder of this embodiment is preferably 1.3 mol% or more and less than 2.0 mol%.
  • it may be 1.3 mol% or more, 1.4 mol% or more, 1.5 mol% or more, or 1.6 mol% or more, and less than 2.0 mol%, 1.9 mol% or less, 1.8 mol% or less, 1.7 mol% or less, or 1.6 mol% or less.
  • the amount of yttrium is, for example, 1.3 mol% or more and less than 2.0 mol%, 1.3 mol% or more and 1.9 mol% or less, 1.3 mol% or more and 1.8 mol% or less, 1.3 mol% or more and 1.7 mol% or less, 1.3 mol% or more and 1.6 mol% or less, 1.4 mol% or more and less than 2.0 mol%, 1.4 mol% or more and 1.9 mol% or less, 1.4 mol% or more and 1.8 mol% or less, 1.4 mol% or more and 1.7 mol% or less, or 1.4 mol% or less.
  • Yttrium is preferably dissolved in zirconia, and the powder of this embodiment preferably does not contain undissolved yttrium. In this embodiment, if no XRD peaks derived from yttrium compounds are detected in the XRD pattern, it can be considered that the powder does not contain undissolved yttrium (i.e., all of the yttrium is dissolved in zirconia).
  • the powder of this embodiment preferably does not contain any stabilizing elements other than yttrium, but may contain other stabilizing elements as long as the effect of the powder of this embodiment is not impaired.
  • other stabilizing elements include at least one of calcium (Ca) and magnesium (Mg).
  • the main crystal phases of zirconia are known to be monoclinic zirconia, tetragonal zirconia, and cubic zirconia, and the crystal phase of zirconia in this embodiment may be considered to be composed of at least one of these three crystal phases.
  • the zirconia in the powder of this embodiment preferably contains monoclinic zirconia, more preferably contains monoclinic zirconia and at least one of tetragonal zirconia and cubic zirconia, and even more preferably contains monoclinic zirconia and tetragonal zirconia.
  • the crystal phase is composed of monoclinic zirconia and tetragonal zirconia.
  • the monoclinic ratio is preferably more than 70%, more preferably 80% or more, and even more preferably 85% or more.
  • the monoclinic ratio may be 100% or less, and when the zirconia contains at least one of tetragonal zirconia and cubic zirconia, the monoclinic ratio is less than 100%, and may be 99% or less, or 90% or less.
  • the monoclinic ratio may be, for example, more than 70% and 100%, 80% or more and 100% or less, or 85% or more and 95% or less, or may be 90% or more and 100% or less, 95% or more and less than 100%, or 95% or more and 99% or less.
  • the tetragonal ratio is 30% or less, less than 30%, less than 20%, or 15% or less, and may also be 10% or less, or 7% or less. If the zirconia does not contain tetragonal zirconia, the tetragonal ratio is 0%, but the tetragonal ratio may be 0% or more, more than 0%, or 10% or more. For example, the tetragonal ratio may be 0% or more and less than 15%, 0% or more and less than 20%, 0% or more and less than 30%, more than 0% but less than 15%, more than 0% but less than 20%, 10% or more and less than 30%, or 10% or more and less than 15%.
  • the zirconia crystal phase in the powder of this embodiment preferably consists of monoclinic zirconia and tetragonal zirconia, in which case the sum of the monoclinic rate and the tetragonal rate is 100%.
  • the zirconia crystalline phase can be confirmed by the XRD peaks corresponding to the XRD peaks of zirconia in the crystalline phase confirmed by the XRD pattern of the powder of this embodiment.
  • the crystallite size (D m ) of monoclinic zirconia is preferably more than 23 nm, 30 nm or more, 31 nm or more, 32 nm or more, or 34 nm or more, and more preferably 80 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, or 35 nm or less, and more preferably more than 23 nm and 80 nm or less, 30 nm or more and 60 nm or less, 30 nm or more and 50 nm or less, 31 nm or more and 50 nm or less, 31 nm or more and 45 nm or less, 32 nm or more and 45 nm or less, or 34 nm or more and 40 nm or less.
  • D m may decrease when the monoclinic crystal ratio becomes equal to or less than a certain level
  • D m may be more than 23 nm, 31 nm or more, or 32 nm or more, and more preferably 40 nm or less, or 35 nm or less.
  • Dm may be more than 23 nm and not more than 40 nm, 31 nm or more and not more than 35 nm, or 32 nm or more and not more than 35 nm. Examples of the material having such Dm and having a monoclinic crystal ratio of more than 70% and not more than 95% can be given.
  • the crystallite diameter ( Dt ) of the tetragonal zirconia is 30 nm or more, 35 nm or more, or 37 nm or more, and is preferably 85 nm or less to 50 nm or less, 40 nm or less, or 38 nm or less, and examples of such diameters include 30 nm or more to 85 nm or less, 35 nm or more to 40 nm or less, or 37 nm or more to 40 nm or less. Unlike Dm , Dt is less affected by the monoclinic ratio.
  • the ratio of Dm to Dt (hereinafter also referred to as "Dm/Dt") [nm/nm] can be 0.7 to 1.2, 0.8 to 1.0, or 0.8 to 0.9.
  • Dm/Dt the ratio of Dm to Dt [nm/nm]
  • the monoclinic crystal ratio is a certain level or less, there is no correlation between the monoclinic crystal ratio and Dm/Dt, and Dt is larger than Dm.
  • Dm/Dt tends to increase with an increase in the monoclinic crystal ratio. Therefore, for example, when the monoclinic crystal ratio is more than 70% and less than 95%, Dm/Dt is 0.8 to 0.9.
  • Dm/Dt is more than 95% and less than 100%, Dm/Dt is more than 0.9 and less than 1.2, and Dt may be smaller than Dm.
  • the BET specific surface area of the powder of this embodiment is preferably 25 m 2 /g or less, less than 20 m 2 /g, 18 m 2 /g or less, or 17 m 2 /g or less, and is preferably 6 m 2 /g or more, 8 m 2 /g or more, 10 m 2 /g or more, 12 m 2 /g or more, more than 13 m 2 /g, 15 m 2 /g or more, or 16 m 2 /g or more.
  • the BET specific surface area is 6 m 2 /g or more, sintering can easily proceed from a relatively low temperature.
  • the BET specific surface area may be, for example, 6 m 2 /g or more and less than 20 m 2 /g, 8 m 2 /g or more and 18 m 2 /g or less, 10 m 2 /g or more and 17 m 2 /g or less, 12 m 2 /g or more and 17 m 2 /g or less, more than 13 m 2 /g and 17 m 2 /g or less, or 15 m 2 /g or more and 17 m 2 /g or less, or alternatively, it may be 6 m 2 /g or more and 17 m 2 /g or less, 8 m 2 /g or more and 15 m 2 /g or less, or 8 m 2 /g or more and 13 m 2 /g or less.
  • the powder of this embodiment preferably contains zirconia with a monoclinic ratio of more than 70%, a Dm of more than 23 nm and not more than 80 nm, and a BET specific surface area of 25 m2 /g or less, and more preferably contains zirconia with a monoclinic ratio of 85% or more and not more than 95%, a Dm of 30 nm or more and not more than 50 nm, and a BET specific surface area of more than 13 m2 /g and not more than 18 m2 /g.
  • the powder of this embodiment contains a manganese compound as a coloring element (hereinafter also referred to as "black colorant") that exhibits black color.
  • the manganese compound is preferably a manganese compound powder.
  • the manganese compound may be any compound containing manganese (Mn), and is preferably a manganese oxide, such as one or more selected from the group consisting of manganese oxide (MnO), manganese dioxide (MnO 2 ), manganese dioxide (Mn 2 O 3 ), and manganese tetraoxide (Mn 3 O 4 ).
  • Preferred manganese compounds include one or more selected from the group consisting of manganese oxide, manganese dioxide, and manganese tetraoxide, and further manganese tetraoxide.
  • the content of the manganese compound in the powder of this embodiment (hereinafter also referred to as "manganese amount”) is preferably 0.1 mass% or more and 0.6 mass% or less as a mass ratio of the manganese compound converted to Mn 3 O 4 relative to the total amount of the powder. If the manganese content is less than 0.1% by mass, the color tone of the sintered body varies depending on the sintering temperature, particularly the lightness L * .
  • the manganese content is, for example, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more, and 0.6% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, or 0.2% by mass or less.
  • the amount of manganese may be, for example, 0.1% by mass or more and 0.2% by mass or less, 0.1% by mass or more and 0.3% by mass or less, 0.1% by mass or more and 0.4% by mass or less, 0.1% by mass or more and 0.5% by mass or less, 0.1% by mass or more and 0.6% by mass or less, 0.2% by mass or more and 0.3% by mass or less, 0.2% by mass or more and 0.4% by mass or less, 0.2% by mass or more and 0.5% by mass or less, 0.2% by mass or more and 0.6% by mass or less, 0.3% by mass or more and 0.4% by mass or less, 0.3% by mass or more and 0.5% by mass or less, 0.3% by mass or more and 0.6% by mass or less, 0.4% by mass or more and 0.5% by mass or less, 0.4% by mass or more and 0.5% by mass or less, 0.4% by mass or more and 0.5% by mass or less, 0.4% by mass or more and 0.5% by mass or less, 0.4% by mass or more and 0.5% by mass or less, 0.4% by mass
  • the powder of this embodiment may contain only manganese compounds as black colorants.
  • black colorants other than manganese compounds may be contained in addition to the manganese compounds. This allows fine adjustment of the color tone.
  • black colorants other than manganese oxides include compounds of elements such as one or more selected from the group consisting of cobalt (Co), chromium (Cr), iron (Fe), titanium (Ti), nickel (Ni) and vanadium (V), and at least one of cobalt and iron.
  • the content of these elements is preferably less than the amount of manganese, and the mass ratio of the color-changing colorant converted into an oxide relative to the total amount of powder is 0 mass% or more or more than 0 mass%, and 0.3 mass% or less or 0.2 mass% or less, and examples of these include 0 mass% or more and 0.3 mass% or less, more than 0 mass% and 0.3 mass% or less, or more than 0 mass% and 0.2 mass% or less.
  • the "total amount of powder” refers to the total amount of rare earth elements and metal elements contained in the powder in oxide form.
  • the oxide forms of each element are as follows: cobalt (Co) is CO3O4 , chromium (Cr) is Cr2O3 , iron (Fe) is Fe2O3 , titanium (Ti) is TiO2 , nickel ( Ni ) is NiO, vanadium ( V ) is V2O5 , and aluminum (Al) is Al2O3 .
  • the powder of this embodiment contains alumina (Al 2 O 3 ).
  • the alumina is preferably at least one of alumina sol and powder, and more preferably alumina powder. It is believed that the coexistence of a manganese compound and alumina in a content range described below makes it difficult for the color tone of the sintered body to vary even if the sintering temperature varies.
  • the alumina content of the powder of this embodiment (hereinafter also referred to as "alumina amount”) is 0.2 mass% or more and 1.5 mass% or less as the mass ratio of aluminum converted to Al2O3 to the total amount of the powder. If the alumina amount is less than 0.2 mass% or if no alumina is included, the variation in color tone due to the fluctuation of the sintering temperature, particularly the variation in lightness L * , becomes large.
  • the alumina amount is 0.2 mass% or more, 0.25 mass% or more, 0.5 mass% or more, 0.75 mass% or more, 1.0 mass% or more, or 1.2 mass% or more, and 1.5 mass% or less, 1.25 mass% or less, 1.0 mass% or less, 0.75 mass% or less, or 0.5 mass% or less.
  • the amount of alumina is, for example, 0.2 mass% or more and 1.5 mass% or less, 0.2 mass% or more and 1.25 mass% or less, 0.2 mass% or more and 1.0 mass% or less, 0.2 mass% or more and 0.75 mass% or less, 0.2 mass% or more and 0.5 mass% or less, 0.25 mass% or more and 1.5 mass% or less, 0.25 mass% or more and 1.25 mass% or less, 0.25 mass% or more and 1.0 mass% or less, 0.25 mass% or more and 0.75 mass% or less, 0.25 mass% or more and 0.5 mass% or less,
  • Examples of the content include 0.5% by mass or more and 1.5% by mass or less, 0.5% by mass or more and 1.25% by mass or less, 0.5% by mass or more and 1.0% by mass or less, 0.5% by mass or more and 0.75% by mass or less, 0.75% by mass or more and 1.5% by mass or less, 0.75% by mass or more and 1.25% by mass or less, 0.75% by mass or more and 1.
  • yttrium-containing zirconia in which the amount of yttrium is less than 2 mol%, by limiting the amount of manganese compound and alumina to a specific range, a sintered body can be obtained without defects even when a certain amount or more of coloring elements are contained, and the variation in color tone of the sintered body due to the fluctuation of the sintering temperature during sintering is thought to be suppressed.
  • the reasons for this is that in a sintered body of zirconia exhibiting a black color, the visible color tone is more influenced by the lightness L * than by the hue a * and b * .
  • the mass ratio of alumina converted into Al 2 O 3 to manganese compound converted into Mn 3 O 4 in the powder of this embodiment (hereinafter also referred to as the "Al/Mn ratio") is preferably 0.1 or more, 0.4 or more, or 0.7 or more, and 5.0 or less, 3.0 or less, 2.5 or less, or 1.5 or less.
  • the Al/Mn ratio of the powder of this embodiment is, for example, 0.1 or more and 5.0 or less, 0.4 or more and 3.0 or less, or 0.4 or more and 1.5 or less.
  • the powder of this embodiment may contain a binder to improve fluidity.
  • the powder of this embodiment may be considered as a powder composition containing the powder and a binder.
  • the binder contained in the powder composition may be any known binder used in ceramic compositions, such as a thermoplastic resin.
  • Preferred binders include one or more of the group consisting of acrylic resin, polystyrene, and polyalkyl carbonate, as well as acrylic resin (e.g., one or more selected from the group consisting of AS-1100, AS-1800, and AS-2000, all manufactured by Toa Gosei Co., Ltd.).
  • the powder composition may contain additives such as wax.
  • additives such as wax.
  • the inclusion of these ingredients provides additional benefits such as improved releasability from the mold (die).
  • ingredients such as wax include one or more selected from the group consisting of polyethylene, polypropylene, polyacrylonitrile, acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, polyacetal resin, petroleum wax, synthetic wax, vegetable wax, stearic acid, phthalate ester plasticizer, and adipic acid ester.
  • the content of the powder in the powder composition can be found from the mass ratio of the powder composition after removing the binder, etc. to the mass of the powder composition.
  • the method for removing the binder, etc. is arbitrary, but examples include heat treatment in the air at 200°C to 500°C.
  • the powder of this embodiment preferably does not contain impurities. However, it may contain unavoidable impurities such as hafnia (HfO 2 ) of zirconia. In calculating values derived from the composition such as content and density, hafnia may be considered as zirconia.
  • the composition may be determined as follows. Total amount of powder: Al2O3 + Mn3O4 + Y2O3 + ZrO2 [g] Alumina content: ⁇ Al2O3 /( Al2O3 + Mn3O4 + Y2O3 + ZrO2 ) ⁇ 100 [mass %] Manganese content: ⁇ Mn3O4 /( Al2O3 + Mn3O4 + Y2O3 + ZrO2 ) ⁇ 100 [mass %] Amount of zirconia (yttrium-containing zirconia): ⁇ ( Y2O3 + ZrO2 ) / ( Al2O3 + Mn3O4 + Y2O3 + ZrO2 ) ⁇ 100 [mass %] Amount of stabilizing element (amount of yttrium)
  • the powder of this embodiment has a median diameter (D50) of 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.3 ⁇ m or more, or 0.4 ⁇ m or more, and may be 1.0 ⁇ m or less, 0.7 ⁇ m or less, 0.55 ⁇ m or less, 0.5 ⁇ m or less, or 0.45 ⁇ m or less.
  • D50 median diameter
  • D50 may be, for example, 0.1 ⁇ m or more and 1.0 ⁇ m or less, 0.1 ⁇ m or more and 0.7 ⁇ m or less, 0.2 ⁇ m or more and 0.55 ⁇ m or less, 0.2 ⁇ m or more and 0.5 ⁇ m or less, 0.2 ⁇ m or more and 0.45 ⁇ m or less, 0.3 ⁇ m or more and 0.45 ⁇ m or less, 0.4 ⁇ m or more and 0.55 ⁇ m or less, or 0.4 ⁇ m or more and 0.5 ⁇ m or less.
  • the powder of this embodiment can be exemplified by a distribution curve of volumetric particle size that is a multimodal distribution, preferably a bimodal distribution, and more preferably a distribution curve of volumetric particle size that has peaks at least at particle sizes of 0.05 ⁇ m to 0.2 ⁇ m and at particle sizes of more than 0.2 ⁇ m to 0.5 ⁇ m, and further preferably a distribution having peaks (extreme values) at particle sizes of 0.05 ⁇ m to 0.2 ⁇ m and at particle sizes of 0.3 ⁇ m to 0.5 ⁇ m.
  • the powder of this embodiment preferably has high moldability, and when the powder is uniaxially press molded at a pressure of 70 ⁇ 5 MPa and then treated with cold isostatic pressing (hereinafter also referred to as "CIP") at a pressure of 196 ⁇ 5 MPa to form a molded body, the relative density of the molded body (hereinafter also referred to as "molded body density”) is preferably 49% or more and 56% or less, or 50% or more and 54% or less.
  • the powder of this embodiment is preferably small in color variation of the sintered body obtained by sintering it.
  • 3 ⁇ 0.3 g of the powder of this embodiment is filled into a mold having a diameter of 25 mm, and 5 molded bodies (compressed powder bodies) are produced by repeatedly performing uniaxial pressing at a pressure of 70 ⁇ 5 MPa and CIP treatment at a pressure of 196 ⁇ 5 MPa.
  • the powder is sintered in an air atmosphere at a heating rate of 100°C/hour for a holding time at the sintering temperature of 2 hours, and one molded body is sintered at normal pressure at each of 1200°C, 1250°C, 1300°C, 1350°C, and 1400°C.
  • the difference between the maximum and minimum values of the lightness L * among the five sintered bodies obtained is preferably 1.4 or less, 1.0 or less, 0.8 or less, or 0.5 or less.
  • the L * variation is preferably small, and can be 0 or more, more than 0, or 0.2 or more, for example, 0 or more and 1.4 or less, more than 0 and 0.8 or less, or 0.2 or more and 0.5 or less.
  • the difference between the maximum and minimum values of chroma C * (hereinafter also referred to as "C * variation") is preferably 0.40 or less, 0.35 or less, or 0.33 or less.
  • C * variation In a jet-black zirconia sintered body, the effect of C * variation on the visible color tone is smaller than that of L * variation.
  • the C* variation is small, and examples of the C * variation include 0 or more, 0.15 or more, or 0.25 or more, and examples of the C* variation include 0 or more and 0.40 or less, 0.15 or more and 0.35 or less, or 0.25 or more and 0.33 or less.
  • the powder of this embodiment can be used as a precursor for calcined or sintered zirconia bodies, and is suitable as a raw powder for structural materials such as pulverizer components, precision machine parts, and optical connector parts, biomaterials such as dental materials, decorative materials, and exterior materials such as electronic equipment exterior parts.
  • a preferred manufacturing method includes a manufacturing method of a powder in which an yttrium-containing zirconia powder containing 1.3 mol% or more and less than 2.0 mol% of yttrium calculated as Y2O3 relative to the total amount of zirconia and yttrium calculated as Y2O3 , an alumina source, and a manganese compound source are mixed, and the alumina content is 0.2 mass% or more and 1.5 mass% or less relative to the total amount of the powder, and the manganese compound content is 0.1 mass% or more and 0.6 mass% or less relative to the total amount of the powder.
  • the yttrium-containing zirconia powder, alumina source, and manganese compound source used in the above process may be the same as the yttrium-containing zirconia, manganese compound, and alumina contained in the powder of this embodiment, respectively.
  • yttrium-containing zirconia powder containing 1.3 mol % or more and less than 2.0 mol % of yttrium calculated as Y 2 O 3 relative to the total amount of zirconia and yttrium calculated as Y 2 O 3 is provided.
  • the BET specific surface area of the yttrium-containing zirconia powder is preferably 6 m 2 /g or more, 8 m 2 /g or more, or 10 m 2 /g or more, and 25 m 2 /g or less, less than 20 m 2 /g, 18 m 2 /g or less, 17 m 2 /g or less, or 15 m 2 /g or less.
  • the range of the BET specific surface area of the yttrium-containing zirconia powder can be 6 m 2 /g or more and 25 m 2 /g or less, 8 m 2 /g or more and 18 m 2 /g or less, 10 m 2 /g or more and 17 m 2 /g or less, 12 m 2 /g or more and 17 m 2 /g or less, or more than 13 m 2 /g and 17 m 2 /g or less, or 6 m 2 /g or more and 18 m 2 /g or less, 6 m 2 /g or more and 15 m 2 /g or less, or 6 m 2 /g or more and 13 m 2 /g or less.
  • the BET specific surface area of the yttrium-containing zirconia powder is affected by the heat treatment temperature (calcination temperature) during its production, and the higher the heat treatment temperature, the smaller the BET specific surface area tends to be.
  • the average particle size (D50) of the yttrium-containing zirconia powder subjected to the mixing process is preferably 0.1 ⁇ m or more and 1.0 ⁇ m or less, more preferably 0.1 ⁇ m or more and 0.7 ⁇ m or less, 0.2 ⁇ m or more and 0.5 ⁇ m or less, 0.2 ⁇ m or more and 0.45 ⁇ m or less, or 0.3 ⁇ m or more and 0.45 ⁇ m or less.
  • the crystallite size of the monoclinic crystals of the yttrium-containing zirconia powder is preferably greater than 23 nm and less than 80 nm, greater than 30 nm and less than 60 nm, greater than 30 nm and less than 50 nm, greater than 31 nm and less than 50 nm, or greater than 32 nm and less than 45 nm.
  • the yttrium-containing zirconia powder may be a powder obtained by any manufacturing method, but is preferably a zirconia powder obtained by one or more methods selected from the group consisting of hydrolysis, hydrothermal synthesis, and coprecipitation, and is preferably a zirconia powder obtained by a hydrolysis method.
  • Particularly preferred zirconia powders include zirconia powders obtained by hydrolysis of a zirconia sol having an average sol particle size of 150 nm or more and 400 nm or less, preferably 180 nm or more and 400 nm or less, and more preferably 185 nm or more and 300 nm or less.
  • the manganese compound source is preferably at least one of manganese oxide and its precursor manganese compound, and examples thereof include one or more selected from the group consisting of manganese oxide, manganese dioxide, manganese trimanganese, manganese tetraoxide, manganese hydroxide, manganese oxyhydroxide, manganese chloride, and manganese acetate, and is preferably one or more selected from the group consisting of manganese oxide, manganese trimanganese, and manganese tetraoxide, with manganese trimanganese tetraoxide being more preferred.
  • the manganese compound source is preferably a manganese compound powder.
  • the content of the manganese compound source can be expressed as the ratio (mass % ) of the manganese compound source converted into Mn3O4 to the total mass of the yttrium-containing zirconia powder, the manganese compound source converted into Mn3O4 , and the alumina source converted into Al2O3 after mixing.
  • the content of the manganese compound source is preferably 0.1 mass % or more and 0.6 mass % or less, 0.2 mass % or more and 0.5 mass % or less, or 0.3 mass % or more and 0.5 mass % or less.
  • the alumina source is at least one of alumina and an aluminum compound that is a precursor thereof, and examples thereof include one or more selected from the group consisting of alumina, aluminum hydroxide, aluminum nitrate, and aluminum chloride.
  • Alumina is preferable, and at least one of alumina sol and alumina powder is more preferable.
  • the alumina source is at least one of an aluminum compound sol and powder, and further an aluminum compound sol is more preferable, and alumina sol is more preferable.
  • Alumina sol has a smaller particle size and a larger specific surface area than alumina powder. Therefore, when the alumina source is alumina sol, the BET specific surface area of the resulting powder tends to increase as the content of the alumina source increases.
  • the content of the alumina source can be expressed as a ratio (mass %) of the alumina source to the total mass of the yttrium-containing zirconia powder after mixing, the manganese compound source converted into Mn 3 O 4 , and the alumina source converted into Al 2 O 3.
  • the content of the alumina source is preferably 0.2 mass % or more and 1.5 mass % or less, 0.2 mass % or more and 1.25 mass % or less, or 0.25 mass % or more and 1.0 mass % or less.
  • the mixing step the yttria-containing zirconia powder, the manganese compound source, and the alumina source are mixed together so as to have a composition similar to that of the desired powder.
  • the mixing method in the mixing step may be at least one of wet mixing and dry mixing, and wet mixing is preferred. Specific examples of wet mixing include one or more selected from the group consisting of ball mills, vibration mills, and continuous media stirring mills, and ball mills are preferred.
  • Examples of mixing conditions using a ball mill include mixing an yttrium-containing zirconia powder, an alumina source, and a manganese compound source with a solvent to form a slurry in which the mass ratio of these powders to the slurry mass is 30% by mass or more and 60% by mass or less, and grinding and mixing the slurry using zirconia balls with a diameter of 1 mm to 15 mm as a grinding medium.
  • Yttrium-containing zirconia with a low yttrium content is prone to cracking and chipping during sintering.
  • the treatment time may be appropriately changed depending on the amount of powder to be pulverized and the pulverization conditions, and the longer the pulverization and mixing time, the greater the tendency for the BET specific surface area to increase until equilibrium is reached, and the smaller the average particle size to decrease until equilibrium is reached.
  • the mixing time may be, for example, from 1 hour to 100 hours, or from 10 hours to 50 hours, or may be from 1 hour to 10 hours, or from 1 hour to 5 hours.
  • the mixed powder may be dried by any method as necessary.
  • the drying conditions include drying in the air at 110° C. or higher and 130° C. or lower.
  • the manufacturing method of the powder of this embodiment may include a step of granulating the powder (hereinafter, also referred to as a "granulation step").
  • Granulation is a process of agglomerating powder particles to form coagulated particles.
  • Granulation can be performed by any method, but an example is spray granulation of a slurry in which the powder and a solvent are mixed.
  • the solvent is at least one of water and alcohol, preferably water.
  • the granulated powder (hereinafter, also referred to as "powder granules”) has an average granule diameter of 30 ⁇ m to 90 ⁇ m, and further 40 ⁇ m to 60 ⁇ m, and a bulk density of 1.00 g/cm 3 to 1.40 g/cm 3 , and further 1.10 g/cm 3 to 1.30 g/cm 3 .
  • a sintered body may be manufactured by a method for manufacturing a sintered body having a step of sintering the powder of this embodiment at atmospheric pressure at a temperature of 1200° C. to 1400° C., a method for manufacturing a sintered body having a sintering step of sintering a molded body containing the powder of this embodiment, or a method for manufacturing a sintered body having a molding step of molding the powder of this embodiment to obtain a molded body and a sintering step of sintering the molded body.
  • a green body is a composition having a certain shape composed of powder particles aggregated by physical force, and in particular, a composition in a state in which the composition has not been subjected to a heat treatment after the shape has been imparted (e.g., after molding). Also, a green body is used interchangeably with a green compact.
  • the main composition of the compact obtained by the molding process i.e., zirconia containing yttrium as a stabilizing element, manganese compound, and alumina, does not change before and after molding, and has the same composition as the powder of this embodiment.
  • the obtained compact is a compact containing zirconia containing yttrium as a stabilizing element, manganese compound, and alumina, in which the content of the stabilizing element calculated as an oxide is 1.3 mol% or more and less than 2.0 mol% with respect to the total amount of zirconia and the stabilizing element calculated as an oxide, the content of the alumina is 0.2 mass% or more and 1.5 mass% or less with respect to the total amount of the compact, and the content of the manganese compound is 0.1 mass% or more and 0.6 mass% or less with respect to the total amount of the compact.
  • the molded body may be calcined as necessary.
  • the calcination may be performed by heat treatment at a temperature lower than the temperature at which densification due to sintering of the powder progresses.
  • a calcination method having a heat treatment step in which the molded body containing the powder of this embodiment is heat-treated in an air atmosphere at 800°C or higher and lower than 1200°C can be mentioned. This results in a calcined body.
  • the calcined body is a composition having a certain shape composed of fused particles, and is in a state in which it has been heat-treated at a temperature lower than the sintering temperature.
  • the main composition of the calcined body obtained by the calcination process i.e., zirconia containing yttrium as a stabilizing element, manganese compound, and alumina, does not change before and after calcination, and has the same composition as the powder and molded body of this embodiment.
  • the calcined body obtained is a molded body containing zirconia containing yttrium as a stabilizing element, manganese compound, and alumina, in which the content of the stabilizing element calculated as an oxide is 1.3 mol% or more and less than 2.0 mol% with respect to the total amount of zirconia and the stabilizing element calculated as an oxide, the content of the alumina is 0.2 mass% or more and 1.5 mass% or less with respect to the total amount of the calcined body, and the content of the manganese compound is 0.1 mass% or more and 0.6 mass% or less with respect to the total amount of the calcined body.
  • the molded body or the like may be sintered.
  • the sintering may be performed by a known method, such as one or more selected from the group consisting of pressure sintering, vacuum sintering, and atmospheric sintering.
  • the sintering is preferably atmospheric sintering.
  • the sintering atmosphere is preferably an oxidizing atmosphere, and more preferably an air atmosphere.
  • a preferred sintering method is atmospheric sintering at a temperature of 1200°C to 1550°C, preferably 1200°C to 1500°C, more preferably 1200°C to 1400°C, in an air atmosphere.
  • the sintering step is preferably not performed with sintering other than atmospheric sintering, and preferably does not have a pressure sintering step.
  • the sintering time may be appropriately set depending on the amount and size of the molded body or the like to be sintered, the characteristics of the sintering furnace, and the like, and may be performed, for example, for 0.5 hours to 5 hours, or 1 hour to 4 hours.
  • the "atmospheric sintering" in this embodiment is a method of sintering a sintered object (such as a molded body) by heating the object to be sintered at a temperature at which densification by sintering progresses without applying an external force to the object to be sintered during sintering.
  • the sintering conditions in the sintering step include the following conditions.
  • Sintering method normal pressure sintering
  • Sintering temperature 1200°C to 1400°C
  • Sintering time 1 hour to 5 hours
  • Heating rate 80°C/hour to 120°C/hour
  • Sintering atmosphere oxidizing atmosphere, preferably air atmosphere
  • Sintering method normal pressure sintering Sintering temperature: 1200°C, 1250°C, 1300°C, 1350°C, or 1400°C Sintering time: 2 hours Heating rate: 100°C/hour Sintering atmosphere: air
  • the sintered body of this embodiment is a sintered body of yttrium-containing zirconia containing manganese and alumina and having an yttrium content of less than 2 mol%, and further a zirconia sintered body containing manganese and alumina and having an yttrium content of less than 2 mol% as a main phase.
  • the sintered body of this embodiment is a sintered body exhibiting a black color, that is, a so-called black sintered body (black zirconia sintered body).
  • yttrium is dissolved in zirconia, and it is more preferable that it does not contain undissolved yttrium and that all of the yttrium is dissolved in zirconia. In this embodiment, if no XRD peaks for yttrium or its compounds can be confirmed, it can be considered that it does not contain undissolved yttrium.
  • the monoclinic ratio of the sintered body of this embodiment is preferably 0.5% or more, 0.5% or more, 1% or more, 2% or more, 5% or more, or 7% or more, and is preferably 15% or less, 14% or less, 12% or less, 11% or less, or 10% or less. More preferably, it is 0.5% to 15% or 0.8% to 12%. Since there is a tendency for fracture toughness to be high, it is preferable for the monoclinic ratio to be 1% to 15% or 2% to 14% or 5% to 12% or 7% to 11%. On the other hand, since there is a tendency for bending strength to be high, it is preferable for the monoclinic ratio to be 0.5% to 11% or 0.8% to 10%.
  • the surface of the sintered body immediately after sintering is rough and contains many sources of destruction such as unevenness.
  • the mirror surface is a smooth surface, and can be exemplified by a surface with Ra ⁇ 0.04 ⁇ m.
  • the monoclinic ratio is the value on the mirror surface of the sintered body.
  • the sintered body of this embodiment preferably has monoclinic zirconia on its mirror surface that satisfies the above-mentioned monoclinic ratio. It is therefore considered that the sintered body of this embodiment can be a sintered body that has monoclinic zirconia throughout the entire sintered body, or a sintered body that contains tetragonal zirconia that is prone to transformation into monoclinic zirconia.
  • the zirconia contains monoclinic zirconia and at least one of tetragonal zirconia and cubic zirconia, and is preferably made of monoclinic zirconia and tetragonal zirconia.
  • the monoclinic zirconia contained in the sintered body of this embodiment is preferably monoclinic zirconia having an XRD peak corresponding to at least the monoclinic zirconia (111) plane in its XRD pattern.
  • the sintered body tends to exhibit a high fracture toughness value and is less susceptible to hydrothermal deterioration.
  • the intensity of the XRD peak mainly corresponding to the monoclinic zirconia (11-1) plane in the XRD pattern becomes stronger.
  • the monoclinic zirconia contained in the sintered body of this embodiment preferably has an XRD peak corresponding to at least the monoclinic zirconia (111) plane in its XRD pattern.
  • the monoclinic intensity ratio of the sintered body of this embodiment is preferably 0 or more, 0.3 or more, 0.4 or more, 0.5 or more, or 1.0 or more.
  • the monoclinic intensity ratio may be 10 or less, 8 or less, 5 or less, 3 or less, 1.5 or less, 1.2 or less, or 1.0 or less, and may be 0 to 10, 0.5 to 3, or 1.0 to 1.5.
  • the monoclinic intensity ratio is calculated from formula (3).
  • the sintered body of this embodiment does not include a sintered body with an infinite monoclinic intensity ratio.
  • the sintered body of this embodiment has a relative density (hereinafter also referred to as "sintered body density") of, for example, 98% or more, 98.4% or more, or 99% or more, and preferably 98% or more and 100% or less, 98.4% or more and 100% or less, or 99% or more and 100% or less.
  • the sintered body of this embodiment is preferably a sintered body obtained by atmospheric sintering (so-called atmospheric sintered body), and more preferably a sintered body obtained by atmospheric sintering in an air atmosphere. Also, it is preferable that the sintered body is in a state in which no sintering treatment other than atmospheric sintering has been performed, and more preferably, the sintered body is in a state in which no sintering treatment has been performed after atmospheric sintering.
  • sintering treatment other than atmospheric sintering include one or more selected from the group consisting of pressure sintering, vacuum sintering, and microwave sintering.
  • the sintered body of this embodiment has a fracture toughness value (measured by a method conforming to the SEPB method specified in JIS R1607) of 6 MPa ⁇ m 0.5 or more and 12 MPa ⁇ m 0.5 or less, for example, 6.2 MPa ⁇ m 0.5 or more, 7 MPa ⁇ m 0.5 or more, 7.7 MPa ⁇ m 0.5 or more, or 8 MPa ⁇ m 0.5 or more.
  • the fracture toughness value is preferably high, and examples thereof include 12 MPa ⁇ m 0.5 or less, 11.5 MPa ⁇ m 0.5 or less, 10.5 MPa ⁇ m 0.5 or less, 10.0 MPa ⁇ m 0.5 or less, or 9.5 MPa ⁇ m 0.5 or less.
  • These upper and lower limits may be in any combination, for example, 6 MPa ⁇ m 0.5 to 12 MPa ⁇ m 0.5 , 6 MPa ⁇ m 0.5 to 11.5 MPa ⁇ m 0.5 , 6.2 MPa ⁇ m 0.5 to 12 MPa ⁇ m 0.5 , 6.2 MPa ⁇ m 0.5 to 11.5 MPa ⁇ m 0.5 , 7 MPa ⁇ m 0.5 to 12 MPa ⁇ m 0.5 , 7 MPa ⁇ m 0.5 to 11.5 MPa ⁇ m 0.5 , 8 MPa ⁇ m 0.5 to 12 MPa ⁇ m 0.5 , 7.7 MPa ⁇ m 0.5 to 12 MPa ⁇ m 0.5 , or 7.7 MPa ⁇ m 0.5 to 11.5 MPa ⁇ m 0.5 .
  • the sintered body of this embodiment may be made into a sintered body having a thickness of 0.05 mm to 0.3 mm, or even 0.08 mm to 0.25 mm.
  • the sintered body of this embodiment preferably has a bending strength of 900 MPa or more, 1000 MPa or more, 1100 MPa or more, or 1200 MPa or more, and 1550 MPa or less, 1500 MPa or less, 1460 MPa or less, or 1400 MPa or less.
  • bending strength include 900 MPa or more and 1550 MPa or less, 1000 MPa or more and 1500 MPa or less, 1000 MPa or more and 1500 MPa or less, 1100 MPa or more and 1460 MPa or less, or 1200 MPa or more and 1400 MPa or less.
  • the tetragonal zirconia contained in the sintered body of this embodiment is preferably resistant to transformation into monoclinic zirconia by hydrothermal treatment (hereinafter also referred to as "hydrothermal deterioration").
  • the ratio of the tetragonal fraction after immersion in hot water at 134°C for 5 hours to the tetragonal fraction before immersion in hot water at 134°C for 5 hours (hereinafter also referred to as "residual tetragonal fraction" or " ⁇ T%) is preferably 15% or more, 70% or more, or 80% or more.
  • the residual tetragonal fraction in the sintered body of this embodiment is 100% or less, and examples of this include 95% or less, or 90% or less, and examples of this include 15% to 95% and 80% to 90%.
  • the residual tetragonal crystal ratio can be, for example, 15% to 100%, 20% to 100%, 50% to 100%, 65% to 100%, 70% to 95%, or 80% to 95%.
  • the sintered body of this embodiment exhibits a black color.
  • the color tone is expressed by the L * a * b * color system
  • the lightness L * is preferably 40 to 50, 42 to 48, or 44 to 48.
  • the hue a * is preferably -1.5 to 1.5, more preferably -1.0 to 1.5, and even more preferably 0 to 1.0
  • the hue b * is preferably -1.5 to 1.5, more preferably -1.5 to 1.0, and even more preferably -1.0 to 0.5.
  • the variation in color tone due to the change in sintering temperature is preferably 1.4 or less, 1.0 or less, 0.8 or less, or 0.5 or less.
  • the L * variation is preferably small, but may be 0 or more, more than 0, or 0.2 or more, for example, 0 or more and 1.4 or less, more than 0 or 0.8 or less, or 0.2 or more and 0.5 or less.
  • the chroma C * can be calculated by the following formula.
  • C * ⁇ (a * ) 2 + (b * ) 2 ⁇ 0.5
  • the chroma C * is preferably 0 to 1.5, 0 to 1.2, or 0 to 1.0.
  • the chroma variation due to the change in sintering temperature is preferably 0.4 or less, 0.35 or less, or 0.33 or less, when expressed as the difference between the maximum and minimum values of C * (C * variation).
  • the C * variation in the black sintered body has a smaller effect on the visually recognized color tone than the L * variation.
  • the C * variation is preferably small, and can be exemplified as 0 or more or 0.2 or more.
  • the C * variation and L * variation are variations when the sintering temperature difference is ⁇ 200° C., respectively.
  • BET specific surface area Using a general automatic specific surface area measuring device (device name: Tristar 3300II, manufactured by Shimadzu Corporation) and nitrogen as the adsorption gas, the BET specific surface area of the powder sample was measured by a multipoint method based on JIS R 1626-1996. Prior to the measurement, the powder sample was degassed at 250°C for 30 minutes as a pretreatment.
  • the volume particle size distribution curve of the powder sample was obtained using the HRA mode of a Microtrac particle size distribution meter (product name: MT3000EXII, manufactured by Microtrac Bell Co., Ltd.), and the median diameter (D50) was measured from this. Prior to the measurement, the powder sample was suspended in pure water and dispersed for 3 minutes using an ultrasonic homogenizer as a pretreatment. The measurement conditions are shown below.
  • Light source Semiconductor laser (wavelength: 780 nm)
  • Voltage 3mW Refractive index of zirconia: 2.17 Refractive index of solvent (water): 1.33
  • the actual density of the sintered body samples was measured by the Archimedes method. Prior to the measurement, the mass of the dried sintered body was measured, and then the sintered body was placed in water and boiled for 1 hour as a pretreatment. The true density was calculated from the above formulas (6) to (9), and the relative density (%) was calculated from the value of the actual density ( ⁇ ) relative to the true density ( ⁇ 0 ), and was used as the density of the sintered body.
  • the fracture toughness value of the sintered body sample was measured by a method conforming to the SEPB method specified in JIS R1607.
  • the bending strength of the sintered body samples was measured by a three-point bending test in accordance with JIS R1601. The measurement was performed using a columnar sintered body sample with a support distance of 30 mm, a width of 4 mm, and a thickness of 3 mm, and the bending strength was calculated by averaging the measurements ten times.
  • the color tone of the sintered body sample was measured using a spectrophotometer (device name: CM-700d, manufactured by Konica Minolta) under the following conditions.
  • Light source F2 light source Viewing angle: 10°
  • Measurement method SCI Background: Black background Measurement sample: (sample thickness) 1.3 ⁇ 0.1mm
  • the variation in color tone was expressed by the difference between the maximum and minimum values of L * for the sintered bodies at each sintering temperature (L * variation).
  • the variation in chroma was represented by the difference between the maximum and minimum values of C * of the sintered body at each sintering temperature (C * variation).
  • Example 1 A precipitate was obtained by adding yttrium chloride hexahydrate and an aqueous ammonia solution to the aqueous hydrated zirconia sol solution so that the yttrium content was 1.6 mol%.
  • the precipitate obtained was washed with pure water and dried in an air atmosphere, and then calcined in an air atmosphere at a calcination temperature of 1000°C for 2 hours to obtain an yttrium-containing zirconia powder having an yttrium content of 1.6 mol%.
  • the BET specific surface area of the obtained powder was 13.5 m2 /g.
  • the obtained powder was mixed with pure water to form a slurry, and then alumina sol and Mn3O4 powder ( Brownox (registered trademark), manufactured by Tosoh Corporation) were added so that the alumina content was 0.25 mass% and the manganese content was 0.44 mass% in terms of Mn3O4 relative to the total amount (100 mass%) of the yttrium-containing zirconia powder, alumina sol, and Mn3O4 powder to obtain a mixed slurry.
  • alumina sol and Mn3O4 powder Brownox (registered trademark), manufactured by Tosoh Corporation
  • the mixed slurry (powder content: 200 g) was treated in a ball mill using zirconia balls with a diameter of 2 mm, and then dried at 120°C in an air atmosphere to obtain a powder of yttrium-containing zirconia having an alumina content of 0.25 mass% and an manganese content of 0.44 mass%, containing alumina and manganese trioxide, and having an yttrium content of 1.6 mol%. This was the powder of this example.
  • the zirconia crystal phase consisted of monoclinic zirconia and tetragonal zirconia, the monoclinic ratio was 89.3%, and the tetragonal ratio was 10.7%.
  • the monoclinic zirconia crystallite diameter (Dm) of the powder of this example was 32.7 nm
  • the tetragonal zirconia crystallite diameter (Dt) was 37.1 nm
  • Dm/Dt was 0.88 [nm/nm]
  • D50 was 0.44 ⁇ m
  • the BET specific surface area was 15.6 m 2 /g.
  • the particle size distribution of the powder of this example was a bimodal distribution having peaks at particle sizes of 0.15 ⁇ m and 0.45 ⁇ m.
  • 3 g of the powder of this example was filled into a die having a diameter of 25 mm, uniaxially pressed at a pressure of 70 MPa, and then subjected to CIP treatment at a pressure of 196 MPa to obtain a green body (green compact).
  • the obtained green bodies were each sintered under the following conditions to obtain sintered bodies.
  • Sintering method normal pressure sintering Sintering temperature: 1200°C, 1250°C, 1300°C, 1350°C or 1400°C
  • Sintering atmosphere air
  • Example 2 A powder and a sintered body were obtained in the same manner as in Example 1, except that the amount of alumina sol added was 0.5 mass%.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia, with a monoclinic ratio of 86.4% and a tetragonal ratio of 13.6%.
  • the crystallite diameter (Dm) of the monoclinic zirconia of the powder was 33.5 nm
  • the crystallite diameter (Dt) of the tetragonal zirconia was 37.5 nm
  • Dm/Dt was 0.89 [nm/nm]
  • D50 was 0.43 ⁇ m
  • the BET specific surface area was 16.1 m 2 /g.
  • the particle size distribution of the powder in this example was a bimodal distribution with peaks at particle sizes of 0.15 ⁇ m and 0.45 ⁇ m.
  • Example 3 A powder and a sintered body were obtained in the same manner as in Example 1, except that the amount of alumina sol added was 0.75 mass%.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia, with a monoclinic ratio of 87.0% and a tetragonal ratio of 13.0%.
  • the crystallite diameter (Dm) of the monoclinic zirconia of the powder was 31.2 nm
  • the crystallite diameter (Dt) of the tetragonal zirconia was 36.2 nm
  • Dm/Dt was 0.86 [nm/nm]
  • D50 was 0.35 ⁇ m
  • the BET specific surface area was 16.7 m 2 /g.
  • Example 4 A powder and a sintered body were obtained in the same manner as in Example 1, except that the amount of alumina sol added was 1.25 mass%.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia, with a monoclinic ratio of 87.0% and a tetragonal ratio of 13.0%.
  • the crystallite diameter (Dm) of the monoclinic zirconia of the powder was 31.2 nm
  • the crystallite diameter (Dt) of the tetragonal zirconia was 36.2 nm
  • Dm/Dt was 0.86 [nm/nm]
  • D50 was 0.36 ⁇ m
  • the BET specific surface area was 16.9 m 2 /g.
  • Example 5 A powder and a sintered body were obtained in the same manner as in Example 1, except that yttrium chloride hexahydrate was added to the hydrated zirconia sol solution so that the yttrium content was 1.9 mol%, the amount of Mn 3 O 4 powder added was 0.55 mass%, and the amount of alumina sol added was 0.5 mass%.
  • all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia, with a monoclinic ratio of 88.8% and a tetragonal ratio of 11.2%.
  • the crystallite diameter (Dm) of the monoclinic zirconia of the powder was 32.2 nm
  • the crystallite diameter (Dt) of the tetragonal zirconia was 36.8 nm
  • Dm/Dt was 0.88 [nm/nm]
  • D50 was 0.36 ⁇ m
  • the BET specific surface area was 15.8 m 2 /g.
  • Example 6 An yttrium-containing zirconia powder having an yttrium content of 1.6 mol % was obtained in the same manner as in Example 1, except that the calcination temperature was set to 1100° C. The BET specific surface area of the obtained powder was 8.0 m 2 /g.
  • a powder and a sintered body were obtained in the same manner as in Example 1, except that the obtained yttrium-containing zirconia powder was used.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia, with a monoclinic rate of 97.3% and a tetragonal rate of 2.7%.
  • the crystallite size (Dm) of the monoclinic zirconia powder was 37.4 nm, D50 was 0.51 ⁇ m, and the BET specific surface area was 10.5 m 2 /g.
  • Example 7 An yttrium-containing zirconia powder having an yttrium content of 1.6 mol % was obtained in the same manner as in Example 1, except that the calcination temperature was set to 1100° C. The BET specific surface area of the obtained powder was 8.0 m 2 /g.
  • a powder and a sintered body were obtained in the same manner as in Example 1, except that the obtained yttrium-containing zirconia powder was used and alumina sol was added so that the alumina content was 0.55 mass%.
  • all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia, with a monoclinic crystallographic ratio of 96.9% and a tetragonal crystallographic ratio of 3.1%.
  • the crystallite diameter (Dm) of the monoclinic zirconia of the powder was 37.3 nm
  • the crystallite diameter (Dt) of the tetragonal zirconia was 37.5 nm
  • Dm/Dt was 0.99 [nm/nm]
  • D50 was 0.50 ⁇ m
  • the BET specific surface area was 11.2 m 2 /g.
  • Comparative Example 1 A powder and a sintered body were obtained in the same manner as in Example 3, except that the amount of Mn 3 O 4 powder added was 0.66 mass%.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phase was monoclinic zirconia and tetragonal zirconia.
  • the crystallite size (Dm) of the monoclinic zirconia powder was 31.2 nm, D50 was 0.35 ⁇ m, and the BET specific surface area was 16.8 m 2 /g.
  • Comparative Example 2 A powder and a sintered body were obtained in the same manner as in Example 1, except that the amount of Mn 3 O 4 powder added was 0.88 mass%. In the powder of this example, all of the yttrium was dissolved in zirconia, and the crystal phases were monoclinic zirconia and tetragonal zirconia. The BET specific surface area was 16.8 m 2 /g.
  • Comparative Example 3 An yttrium-containing zirconia powder having an yttrium content of 1.6 mol % was obtained in the same manner as in Example 1, except that the calcination temperature was 980° C. The BET specific surface area of the obtained powder was 14.1 m 2 /g.
  • a powder and a sintered body were obtained in the same manner as in Example 1, except that the obtained yttrium-containing zirconia powder was used and alumina sol was not added.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phases were monoclinic zirconia and tetragonal zirconia.
  • the BET specific surface area was 17.7 m 2 /g.
  • Comparative Example 4 An yttrium-containing zirconia powder having an yttrium content of 1.6 mol % was obtained in the same manner as in Example 1, except that the calcination temperature was 980° C. The BET specific surface area of the obtained powder was 14.1 m 2 /g.
  • a powder and a sintered body were obtained in the same manner as in Example 1, except that the obtained yttrium-containing zirconia powder was used and the amount of alumina sol added was 0.05 mass%.
  • the powder of this example all of the yttrium was dissolved in zirconia, and the crystal phases were monoclinic zirconia and tetragonal zirconia.
  • the BET specific surface area was 17.8 m 2 /g.
  • Comparative Example 5 A powder and a sintered body were obtained in the same manner as in Example 1, except that the amount of Mn 3 O 4 powder added was 0.044 mass%. In the powder of this comparative example, all of the yttrium was dissolved in zirconia, and the crystal phases were monoclinic zirconia and tetragonal zirconia. The BET specific surface area was 16.5 m 2 /g.
  • the powders of the examples had an Al/Mn ratio of 0.5 or more and 3 or less, and a BET specific surface area of 10 m2 /g or more and 17 m2 /g or less. It was confirmed from Examples 1 to 4 that the BET specific surface area tends to increase with an increase in the content of alumina sol. Similarly, it was confirmed in Examples 6 and 7 that the BET specific surface area increases with an increase in the content of alumina sol.
  • the sintered bodies of the Examples had small L * variation values and small color variation.
  • the sintered body of Comparative Example 1 which has a Mn 3 O 4 content of 0.66 mass%, had a large L * variation of 1.60
  • the sintered body of Comparative Example 2 which has a Mn 3 O 4 content of 0.88 mass%, ended up cracking.
  • the sintered body of Comparative Example 5 which has a Mn 3 O 4 content of 0.044 mass%, had an L * variation of 9.86, and thus had a very large color variation.
  • the sintered body of Comparative Example 3 which had a Mn3O4 content of 0.44 mass% and did not contain Al2O3 , had an L * variation of 1.41
  • the sintered body of Comparative Example 4 which had a Mn3O4 content of 0.44 mass% and an Al2O3 content of 0.05 mass%, had an L * variation of 1.45, and both had large color tone variations.
  • the monoclinic intensity ratios for Example 1 were 1.08 (sintering temperature 1250°C), 2.13 (sintering temperature 1300°C), and 1.71 (sintering temperature 1350°C), and for Example 2 were 1.20 (sintering temperature 1250°C), 1.14 (sintering temperature 1300°C), and 1.86 (sintering temperature 1350°C).
  • the fracture toughness value of the sintered body obtained by sintering the powder of this example at a low sintering temperature of 1250° C. is 8.5 MPa/ m0.5 or more, and that the sintered body exhibits a high fracture toughness value despite containing a coloring element and exhibiting a black color.
  • the fracture toughness value tends to increase when the sintering temperature is increased, and that even at a sintering temperature of 1300° C., a high-toughness zirconia with a fracture toughness value of 7.5 MPa/m 0.5 or more, or even 9.0 MPa/m 0.5 or more can be obtained.
  • the fracture toughness value is 7.5 MPa/m 0.5 or more, or even 9.0 MPa/m 0.5 or more, and the bending strength is 1000 MPa or more, and it can be seen that a high-toughness zirconia sintered body having both high bending strength and high fracture toughness value can be obtained from the powder of this example.
  • Example 2 Furthermore, the sintered body obtained in Example 1 was immersed in hot water at 134°C for 5 hours, and the remaining tetragonal crystal ratio was determined. The results are shown in Table 6.

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JP2013014473A (ja) * 2011-07-04 2013-01-24 Tosoh Corp ジルコニア混合粉末及び茶色ジルコニア焼結体
JP2016026990A (ja) * 2014-06-26 2016-02-18 京セラ株式会社 カラーセラミックス
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
JP2022034289A (ja) 2020-08-18 2022-03-03 第一稀元素化学工業株式会社 黒色系ジルコニア焼結体、黒色系ジルコニア粉末、及び、黒色系ジルコニア粉末の製造方法
WO2022075346A1 (ja) 2020-10-09 2022-04-14 第一稀元素化学工業株式会社 ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
JP2022162546A (ja) * 2021-04-12 2022-10-24 東ソー株式会社 焼結体

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CN112500159B (zh) * 2020-12-28 2023-05-23 长裕控股集团股份有限公司 高韧性高强度黑色氧化锆陶瓷材料的制备方法

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JPH04114964A (ja) * 1990-09-06 1992-04-15 Nippon Soda Co Ltd 強度の高い黒色系ジルコニア焼結体およびその製造方法
JP2013014473A (ja) * 2011-07-04 2013-01-24 Tosoh Corp ジルコニア混合粉末及び茶色ジルコニア焼結体
JP2016026990A (ja) * 2014-06-26 2016-02-18 京セラ株式会社 カラーセラミックス
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
JP2022034289A (ja) 2020-08-18 2022-03-03 第一稀元素化学工業株式会社 黒色系ジルコニア焼結体、黒色系ジルコニア粉末、及び、黒色系ジルコニア粉末の製造方法
WO2022075346A1 (ja) 2020-10-09 2022-04-14 第一稀元素化学工業株式会社 ジルコニア粉末、ジルコニア焼結体、及び、ジルコニア焼結体の製造方法
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