WO2023176461A1 - Méthode de production de corps solidifié - Google Patents

Méthode de production de corps solidifié Download PDF

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WO2023176461A1
WO2023176461A1 PCT/JP2023/007655 JP2023007655W WO2023176461A1 WO 2023176461 A1 WO2023176461 A1 WO 2023176461A1 JP 2023007655 W JP2023007655 W JP 2023007655W WO 2023176461 A1 WO2023176461 A1 WO 2023176461A1
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containing compound
solidified body
mixture
compound
compound containing
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PCT/JP2023/007655
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English (en)
Japanese (ja)
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夏希 佐藤
亮介 澤
直樹 栗副
達郎 吉岡
徹 関野
知代 後藤
成訓 趙
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パナソニックＩｐマネジメント株式会社
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Publication of WO2023176461A1 publication Critical patent/WO2023176461A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates

Definitions

  • the present invention relates to a method for producing a solidified body.
  • Perovskite-type composite oxides with a perovskite-type structure have physical properties such as anion conduction such as oxide ion conduction, cation conduction such as lithium ion conduction, proton conduction, electron conduction, ferroelectricity, ferromagnetism, and high-temperature superconductivity. shows.
  • anion conduction such as oxide ion conduction
  • cation conduction such as lithium ion conduction
  • proton conduction proton conduction
  • electron conduction electron conduction
  • ferroelectricity ferroelectricity
  • ferromagnetism ferromagnetism
  • Patent Document 1 discloses a strontium titanate sintered body in which the particles constituting the sintered body have an average particle diameter of 1 to 200 nm and a density of 90% or more of the theoretical density.
  • strontium titanate powder having an average primary particle size of 1 to 60 nm is sintered using a discharge plasma sintering method.
  • strontium titanate powder is sintered at 700 to 1000° C. while pressurizing it to 20 to 400 MPa.
  • Non-Patent Document 1 discloses a room temperature synthesis reaction of perovskite oxide using an acid-base reaction.
  • powder of barium zirconate (BaZrO 3 ) which is a perovskite oxide, can be synthesized by the reaction of barium hydroxide octahydrate and zirconia hydrogel, as shown in the following chemical reaction formula.
  • Non-Patent Document 1 states that barium hydroxide is strongly basic and zirconia hydrogel is an acidic solid that can release protons, so these reactions can be expressed as acid-base reactions between raw materials. .
  • Non-Patent Document 1 further discloses that a sintered body of barium zirconate can be obtained through the following steps. First, a zirconia hydrogel layer necessary for the synthesis reaction is introduced into BaZrO 3 particles, and then the BaZrO 3 particles are bonded by reacting with a hydroxide at 100° C. or lower. The BaZrO 3 gel-modified particle powder thus produced is uniaxially pressed to form pellets. Thereafter, a chemically sintered body of BaZrO 3 is obtained by reacting the pellet with an aqueous barium hydroxide solution.
  • An object of the present invention is to provide a method for producing a solidified body containing a perovskite compound by a simple method.
  • a method for producing a solidified body includes mixing a compound containing one or more types of M(I) and a compound containing one or more types of M(II).
  • the method includes a mixing step for obtaining a mixture, and a reaction step for producing a solidified body by pressurizing the mixture at a temperature of 30° C. or more and 300° C. or less.
  • the solidified body is produced by a reaction between a compound containing M(I) and a compound containing M(II), and the perovskite compounds represented by the composition formula: M(I)M(II) O3 are
  • the porosity is 20% or less.
  • M(I) is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba
  • M(II) is at least one element selected from the group consisting of Ti, Zr, Hf, and Sn. Both the compound containing M(I) and the compound containing M(II) do not have a perovskite structure.
  • FIG. 1(a) is a schematic diagram showing a state in which a mold is filled with a mixture formed by mixing a compound containing M(I) and a compound containing M(II).
  • FIG. 1(b) is a schematic diagram showing a state in which a mixture formed by mixing a compound containing M(I) and a compound containing M(II) is heated and pressurized inside a mold.
  • FIG. 1(c) is a perspective view schematically showing an example of the obtained solidified body.
  • Figure 2 shows the X-ray diffraction pattern of test sample 1 of Example 1, the X-ray diffraction pattern of strontium titanate (SrTiO 3 ) registered in the Inorganic Crystal Structure Database (ICSD), and the raw material strontium hydroxide 8
  • It is a graph showing the X-ray diffraction pattern of hydrate powder (Sr(OH) 2.8H 2 O) and the X-ray diffraction pattern of titanium oxide powder (TiO 2 ).
  • FIG. 3 is a graph showing the X-ray diffraction pattern of Test Sample 2 of Example 2.
  • FIG. 4 is a graph showing the X-ray diffraction patterns of each of Test Sample 1 of Example 1, Test Sample 3 of Example 3, and Test Sample 4 of Example 4.
  • FIG. 5 is a graph showing the X-ray diffraction pattern of test sample 5 of Example 5.
  • FIG. 6 is a scanning electron micrograph showing the results of observing the cross section of test sample 1 of Example 1 at magnifications of 1000x, 3000x, 10000x, 30000x, 50000x, and 100000x.
  • FIG. 7 is a photograph showing a binarized image of the backscattered electron image shown in FIG. 6 with a magnification of 100,000 times.
  • M(I) is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba
  • M(II) is at least one element selected from the group consisting of Ti, Zr, Hf, and Sn. Since the matrix portion of the solidified body has few internal pores and the compound having a perovskite structure is dense, the solidified body has high strength. Moreover, since the solidified body has a compound having a perovskite structure as a main phase, it can exhibit characteristics due to the compound. Note that in this specification, a "compound having a perovskite structure" is also referred to as a "perovskite compound.”
  • the porosity in the cross section of the matrix portion is 20% or less. That is, when observing the cross section of the matrix portion, the average value of the ratio of pores per unit area is 20% or less. When the porosity is 20% or less, the number of pores inside the matrix portion decreases, resulting in a solidified body with high strength. Note that the porosity in the cross section of the matrix portion is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.
  • porosity can be determined as follows. First, the cross section of the solidified body is observed and the matrix portion and pores are determined. Then, the unit area and the area of pores in the unit area are measured, and the ratio of pores per unit area is determined. After determining the ratio of pores per unit area at a plurality of locations, the average value of the ratio of pores per unit area is determined as the porosity. Note that when observing the cross section of the matrix portion, an optical microscope, a scanning electron microscope (SEM), or a transmission electron microscope (TEM) can be used. Further, the unit area and the area of pores within the unit area may be measured by binarizing an image observed with a microscope.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the main phase of the solidified body of this embodiment is a compound having a perovskite structure represented by M(I)M(II)O 3 . Therefore, the solidified body has characteristics unique to the perovskite compound, and can be applied to, for example, a dielectric substrate.
  • the solidified body of this embodiment can be manufactured by the following method.
  • the method for producing a solidified body according to the present embodiment includes a mixing step of mixing a compound containing one or more types of M(I) and a compound containing one or more types of M(II) to obtain a mixture.
  • the production method further includes a reaction step of heating and pressurizing the mixture to cause the compound containing M(I) and the compound containing M(II) to react to produce a solidified body. Note that the compound containing M(I) and the compound containing M(II) are mutually different compounds.
  • a "compound containing M(I)” is also referred to as an "M(I)-containing compound", and a “compound containing M(II)” is also referred to as an "M(II)-containing compound”.
  • an M(I)-containing compound and an M(II)-containing compound are mixed to prepare a mixture.
  • the method of mixing the M(I)-containing compound and the M(II)-containing compound is not particularly limited, and it can be carried out in a dry or wet manner. Further, the powders of the M(I)-containing compound and the M(II)-containing compound may be mixed in air or under an inert atmosphere.
  • a mixture may be prepared by mixing one type of M(I)-containing compound and one type of M(II)-containing compound. Moreover, in the mixing step, a mixture may be prepared by mixing two or more types of M(I)-containing compounds and two or more types of M(II)-containing compounds.
  • Both the M(I)-containing compound and the M(II)-containing compound can be used in powder form.
  • the average particle size of the M(I)-containing compound and the M(II)-containing compound is not particularly limited, but may be 1 ⁇ m to 100 ⁇ m. Further, the average particle diameter of the M(I)-containing compound and the M(II)-containing compound may be 10 nm to 1000 nm. Since the M(I)-containing compound and the M(II)-containing compound are nano-sized particles, it becomes possible to promote the reaction between the M(I)-containing compound and the M(II)-containing compound. Note that the average particle diameter of the M(I)-containing compound and the M(II)-containing compound can be measured by a dynamic light scattering method or a laser diffraction/scattering method.
  • M(I)-containing compound a compound containing at least one element selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba) can be used. Further, as the M(II)-containing compound, a compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf), and tin (Sn) can be used.
  • M(I) is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba. Furthermore, in the M(II)-containing compound, M(II) is at least one element selected from the group consisting of Ti, Zr, Hf, and Sn. However, in the M(I)-containing compound, M(I) may contain 50 mol% or more of Sr. Alternatively, in the M(II)-containing compound, M(II) may contain 50 mol% or more of Ti. In this case, the obtained solidified body can have strontium titanate (SrTiO 3 ) having a perovskite structure as a main phase.
  • M(I) may contain 50 mol% or more of Ba.
  • M(II) may contain 50 mol% or more of Zr.
  • the obtained solidified body can have barium zirconate (BaZrO 3 ) having a perovskite structure as a main phase.
  • the M(I)-containing compound can be at least one selected from the group consisting of M(I)-containing oxides, hydroxides, nitrides, and carbonates.
  • the M(II)-containing compound can be at least one selected from the group consisting of M(II)-containing oxides, hydroxides, nitrides, and carbonates.
  • the M(I)-containing compound is preferably an oxide containing M(I) or a hydroxide containing M(I). Further, the M(II)-containing compound is preferably an oxide containing M(II) or a hydroxide containing M(II).
  • the M(I)-containing compound and the M(II)-containing compound are oxides, water is generated when the M(I)-containing compound and the M(II)-containing compound react in the reaction step described below. This is preferable because it makes it easier to control the press environment.
  • the M(I)-containing compound and/or the M(II)-containing compound is a hydroxide
  • the reactivity is higher than that of an oxide, so that a solidified body of a perovskite compound with high purity can be efficiently prepared. I can do it.
  • the M(I)-containing compound may be a hydrate of an oxide containing M(I) or a hydrate of a hydroxide containing M(I). Further, the M(II)-containing compound may be a hydrate of an oxide containing M(II) or a hydrate of a hydroxide containing M(II).
  • the M(I)-containing compound and/or the M(II)-containing compound is an oxide hydrate or a hydroxide hydrate
  • the M(I)-containing compound and the M(II)-containing compound are combined in the reaction step described below.
  • the generation of water occurs during the reaction with the contained compounds. Since this water acts as a reaction liquid that promotes the reaction between the M(I)-containing compound and the M(II)-containing compound, it is possible to efficiently prepare a solidified body of the perovskite compound with high purity.
  • the M(I)-containing compound can be at least one of magnesium oxide (MgO) and magnesium hydroxide (Mg(OH) 2 ).
  • M(I) is calcium
  • the M(I)-containing compound can be at least one of calcium oxide (CaO) and calcium hydroxide (Ca(OH) 2 ).
  • M(I) is strontium
  • the M(I)-containing compounds include strontium oxide (SrO), strontium hydroxide (Sr(OH) 2 ) and strontium hydroxide octahydrate (Sr(OH) 2.8H It can be at least one selected from the group consisting of 2 O).
  • the M(I)-containing compounds include barium oxide (BaO), barium hydroxide (Ba(OH) 2 ) and barium hydroxide octahydrate (Ba(OH) 2.8H ). It can be at least one selected from the group consisting of 2 O).
  • the M(II)-containing compound is selected from the group consisting of titanium(IV) oxide (TiO 2 ), metatitanic acid (H 2 TiO 3 ) and orthotitanic acid (H 4 TiO 4 ). At least one of them can be selected.
  • M(II) is zirconium
  • the M(II)-containing compound includes zirconium(IV) oxide (ZnO 2 ), zirconium(IV) hydroxide (Zr(OH) 4 ), and zirconium(IV) oxide hydrate. It can be at least one selected from the group consisting of (ZnO 2 .nH 2 O).
  • the M(II)-containing compound includes hafnium(IV) oxide (HfO 2 ), hafnium(IV) hydroxide (Hf(OH) 4 ), and hafnium(IV) oxide hydrate. It can be at least one selected from the group consisting of (HfO 2 .nH 2 O).
  • the M(II) containing compounds include tin(IV) oxide (SnO 2 ), tin(IV) hydroxide (Sn(OH) 4 ) and stannic acid (H 2 SnO 3 ). At least one selected from the group consisting of:
  • the combination of the M(I)-containing compound and the M(II)-containing compound is SrO and H 4 TiO 4
  • the combination of the M(I)-containing compound and the M(II)-containing compound is Ba(OH) 2.8H 2 O and ZrO 2 .nH 2 O can be mentioned.
  • the reaction solution may be mixed with the mixture of the M(I)-containing compound and the M(II)-containing compound.
  • the reaction liquid When the reaction liquid is added to the mixture, the M(I)-containing compound and the M(II)-containing compound are easily dissolved in the reaction liquid in the reaction step. Thereafter, by removing the reaction solution, a solidified body in which perovskite compounds represented by M(I)M(II)O 3 are bonded to each other can be obtained.
  • a mixture of the M(I)-containing compound and the M(II)-containing compound is used. It is preferable to add the reaction solution to.
  • reaction liquid at least one selected from the group consisting of water, acidic aqueous solution, alkaline aqueous solution, alcohol, ketone, and ester can be used.
  • acidic aqueous solution an aqueous solution having a pH of 1 to 3 can be used.
  • alkaline aqueous solution an aqueous solution having a pH of 10 to 14 can be used.
  • acidic aqueous solution it is preferable to use an aqueous solution of an organic acid.
  • alcohol it is preferable to use an alcohol having 1 to 12 carbon atoms.
  • the reaction solution contains at least water.
  • the mixing step when the M(I)-containing compound or the M(II)-containing compound is a hydroxide or a hydrate, the above-mentioned It is possible to avoid mixing the reaction solutions.
  • the reaction step described below when a mixture of such an M(I)-containing compound and an M(II)-containing compound is heated and pressurized, the M(I)-containing compound and/or the M(II)-containing compound are separated. Water is generated. Then, the M(I)-containing compound and the M(II)-containing compound are dissolved in the generated water. Thereafter, by removing water from the mixture, a solidified body in which perovskite compounds represented by M(I)M(II)O 3 are bonded to each other can be obtained.
  • the M(I)-containing compound and/or the M(II)-containing compound is a hydroxide or a hydrate
  • a solidified product can be obtained without using a reaction liquid.
  • the above-mentioned reaction solution was mixed with the mixture of the M(I)-containing compound and the M(II)-containing compound. It's okay.
  • a reaction step is performed in which the mixture is heated and pressurized.
  • a mixture 3 obtained by mixing an M(I)-containing compound 1 and an M(II)-containing compound 2 is filled into a mold 10.
  • the mold 10 includes a cylindrical die 11, a lower punch 12, and an upper punch 13.
  • the lower punch 12 is arranged below the die 11, and the central protrusion 12a is inserted into the die 11 from the lower end thereof.
  • the upper punch 13 is arranged above the die 11, and the central protrusion 13a is inserted into the die 11 from the upper end thereof.
  • the mold 10 is heated as necessary. Thereafter, the lower punch 12 and the upper punch 13 are pressed to uniaxially pressurize the mixture 3 inside the mold 10, thereby bringing the inside of the mold 10 into a high pressure state. At this time, the mixture becomes densified and the M(I)-containing compound and the M(II)-containing compound react with each other, so that a perovskite compound represented by M(I)M(II)O 3 is generated.
  • the M(I)-containing compound and/or the M(II)-containing compound is a hydroxide or a hydrate
  • the M(I)-containing compound and/or the M(II)-containing compound is a hydroxide or a hydrate
  • water is generated from the M(I)-containing compound and/or the M(II)-containing compound.
  • the M(I)-containing compound and the M(II)-containing compound are dissolved in the generated water, and the M(I)-containing compound and the M(II)-containing compound react. Water is then removed from the mixture by reducing the pressure inside the mold 10. Thereby, a solidified body 20 in which perovskite compounds represented by M(I)M(II)O 3 are bonded to each other can be obtained.
  • the heating and pressurizing conditions for the mixture of the M(I)-containing compound and the M(II)-containing compound are not particularly limited as long as the conditions allow the reaction between the M(I)-containing compound and the M(II)-containing compound to proceed. .
  • the temperature when heating the mixture containing the M(I)-containing compound and the M(II)-containing compound is more preferably 80°C or more and 250°C or less, and more preferably 100°C or more and 200°C or less. preferable.
  • the pressure when pressurizing the mixture containing the M(I)-containing compound and the M(II)-containing compound is preferably 10 MPa or more and 500 MPa or less, more preferably 50 MPa or more and 500 MPa or less, and 200 MPa or more and 500 MPa or less. It is more preferable that it is the following.
  • the molded body is taken out from the inside of the mold 10, and as shown in FIG. 1(c), the perovskite compounds represented by M(I)M(II) O3 bond together.
  • a solidified body 20 can be obtained.
  • the M(I)-containing compound and the M(II)-containing compound completely react, and the M(I)-containing compound and the M(II)-containing compound are present in the obtained solidified product.
  • a configuration that does not include this may also be possible.
  • a structure may be adopted in which a portion of the M(I)-containing compound and/or the M(II)-containing compound remains in the obtained solidified body. In this case, the remaining M(I)-containing compound and/or M(II)-containing compound may act as an aggregate to increase the strength of the solidified body.
  • the solidified body of this embodiment can be manufactured by pressurizing a mixture of raw materials while heating it. Therefore, by changing the mold, solidified bodies of various shapes can be obtained.
  • the shape of the solidified body is not particularly limited, it can be, for example, plate-shaped.
  • the thickness t of the solidified body (matrix portion) is not particularly limited, but may be, for example, 50 ⁇ m or more.
  • the thickness t of the solidified body (matrix portion) can be 1 mm or more, and can also be 1 cm or more.
  • the upper limit of the thickness t of the solidified body (matrix portion) is not particularly limited, but may be, for example, 50 cm.
  • the method for producing a solidified product of the present embodiment includes a mixing step of mixing a compound containing one or more types of M(I) and a compound containing one or more types of M(II) to obtain a mixture. , and a reaction step of producing a solidified body by pressurizing the mixture at a temperature of 30° C. or more and 300° C. or less.
  • the solidified body is produced by a reaction between a compound containing M(I) and a compound containing M(II), and the perovskite compounds represented by the composition formula: M(I)M(II) O3 are
  • the porosity is 20% or less.
  • M(I) is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba
  • M(II) is at least one element selected from the group consisting of Ti, Zr, Hf, and Sn. be.
  • Both the compound containing M(I) and the compound containing M(II) do not have a perovskite structure.
  • the manufacturing method of the present embodiment is to obtain a mixture by mixing an M(I)-containing compound and an M(II)-containing compound, and then pressurizing the mixture while heating. )
  • a solidified body consisting of a perovskite compound represented by O3 can be obtained. Therefore, a solidified body containing a perovskite compound can be produced by a simple method.
  • Non-Patent Document 1 a chemically sintered body of BaZrO 3 is formed by reacting BaZrO 3 pellets into which a zirconia hydrogel layer is introduced with an aqueous barium hydroxide solution. Therefore, the manufacturing method of Non-Patent Document 1 has complicated steps and high manufacturing costs.
  • a mixture of an M(I)-containing compound and an M(II)-containing compound is solidified by a simple method of heating and pressurizing at a low temperature of 30°C or higher and 300°C or lower. body can be manufactured.
  • a solidified body formed by bonding perovskite compounds represented by M(I)M(II)O 3 can be obtained through the mixing step and the reaction step. Therefore, in this manufacturing method, as in Non-Patent Document 1, it is necessary to contact the structure obtained by the reaction step with a solution containing an M(I)-containing compound and/or a solution containing an M(II)-containing compound. There isn't.
  • the solidified body of this embodiment has a matrix portion in which particles of a compound having a perovskite structure represented by M(I)M(II) O3 are bonded to each other.
  • M(I) is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba
  • M(II) is at least one element selected from the group consisting of Ti, Zr, Hf, and Sn.
  • the solidified body of this embodiment includes an inorganic material in addition to the matrix portion. Specifically, in the solidified body, the inorganic material is highly dispersed inside the matrix portion.
  • the inorganic material acts as an aggregate, so that the strength of the solidified body can be increased. Furthermore, since the solidified body contains the inorganic material, it is possible to obtain a solidified body that has a function due to the inorganic material.
  • the inorganic material as an aggregate contained in the solidified body is a compound different from the M(I)-containing compound and the M(II)-containing compound that are the raw materials.
  • the inorganic material as aggregate contained in the solidified body is preferably in the form of particles.
  • the inorganic particles serving as the aggregate can be an oxide of at least one metal element selected from the group consisting of alkali metals, alkaline earth metals, transition metals, base metals, and metalloids.
  • alkaline earth metals include beryllium and magnesium in addition to calcium, strontium, barium, and radium.
  • Base metals include aluminum, zinc, gallium, cadmium, indium, tin, mercury, thallium, lead, bismuth and polonium.
  • Metalloids include boron, silicon, germanium, arsenic, antimony and tellurium.
  • inorganic particles as aggregates include alumina ( Al2O3 ), zirconia ( ZrO2 ), mullite ( 3Al2O3.2SiO2 ), zircon ( ZrSiO4 ) , and cordierite (2MgO.2Al) .
  • 2MgO.SiO2 forsterite
  • Y2O3 yttria
  • steatite MgO.SiO2
  • silica quartz glass, SiO2
  • TiO2 titanium oxide
  • Particles made of at least one selected from the group consisting of copper oxide (CuO) and iron oxide (Fe 2 O 3 ) can be used.
  • the solidified body may contain inorganic carbide particles as inorganic particles serving as aggregate. Since inorganic carbide also acts as an aggregate, the strength of the solidified body can be increased by including the inorganic carbide.
  • inorganic carbide particles made of a carbide of at least one metal element selected from the group consisting of alkali metals, alkaline earth metals, transition metals, base metals, and metalloids can be used.
  • particles made of silicon carbide (SiC) can also be used as the inorganic carbide.
  • the average particle diameter of the inorganic particles as aggregate is preferably 5 ⁇ m or less.
  • the average particle diameter of the inorganic particles is more preferably 3 ⁇ m or less, and even more preferably 1 ⁇ m or less.
  • the average particle diameter of the inorganic particles can be measured using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
  • the inorganic material as an aggregate contained in the solidified body is fibrous.
  • the inorganic fibers used as the aggregate metal fibers made of pure metal or alloy can be used.
  • the metals that make up the metal fibers include, for example, gold, silver, copper, platinum, iridium, palladium, ruthenium, rhodium, titanium, aluminum, tantalum, niobium, tungsten, molybdenum, vanadium, magnesium, chromium, iron, cobalt, nickel, and zinc. At least one metal element selected from the group consisting of , tin, and lead can be used.
  • the metal constituting the metal fiber may be a simple substance of these metal elements, or may be an alloy of any combination of the metal elements.
  • the aspect ratio (fiber length/fiber diameter) of the metal fiber is preferably 10 or more, more preferably 100 or more, even more preferably 200 or more, and particularly preferably 500 or more. Further, the fiber diameter of the metal fiber is not particularly limited, but can be 1 ⁇ m to 100 ⁇ m.
  • the inorganic material as the aggregate is preferably a material having a perovskite structure represented by the composition formula: M(I)M(II) O3 .
  • M(I) is at least one element selected from the group consisting of Mg, Ca, Sr, and Ba
  • M(II) is at least one element selected from the group consisting of Ti, Zr, Hf, and Sn.
  • the matrix portion of the solidified body is made of strontium titanate (SrTiO 3 )
  • the inorganic material as the aggregate is also SrTiO 3
  • the matrix portion of the solidified body is made of barium zirconate (BaZrO 3 )
  • the inorganic material as the aggregate is also BaZrO 3 .
  • the porosity in the cross section of the matrix portion is preferably 20% or less, more preferably 15% or less, and preferably 10% or less, as in the first embodiment. More preferably, it is particularly preferably 5% or less.
  • the inorganic material that is the aggregate can be sealed inside the matrix part, the contact rate between oxygen and water vapor from outside the matrix part and the aggregate is reduced. Therefore, it becomes possible to suppress oxidation of the aggregate over a long period of time.
  • the porosity of this embodiment can be determined as follows. First, the cross section of the solidified body is observed to identify the matrix portion, the inorganic material that is the aggregate, and the pores. Then, as in the first embodiment, the unit area and the area of pores in the unit area are measured, and the ratio of pores per unit area is determined. After determining the ratio of pores per unit area at a plurality of locations, the average value of the ratio of pores per unit area is determined as the porosity.
  • the manufacturing method of the present embodiment includes a mixing step of mixing one or more types of M(I)-containing compounds, one or more types of M(II)-containing compounds, and an inorganic material that is an aggregate to obtain a mixture.
  • the production method further includes a reaction step of heating and pressurizing the mixture to cause the compound containing M(I) and the compound containing M(II) to react to produce a solidified body.
  • one or more M(I)-containing compounds, one or more M(II)-containing compounds, and an inorganic material as an aggregate are mixed to prepare a mixture.
  • the method of mixing the M(I)-containing compound, the M(II)-containing compound, and the inorganic material is not particularly limited, and the mixing may be carried out in a dry or wet manner. Further, these powders may be mixed in air or under an inert atmosphere. Note that the same M(I)-containing compound and M(II)-containing compound as in the first embodiment can be used. Further, as in the first embodiment, in the mixing step, a reaction liquid may be mixed with the mixture of the M(I)-containing compound, the M(II)-containing compound, and the inorganic material as necessary. There is no need to mix the liquids.
  • a reaction step is performed in which the mixture of the M(I)-containing compound, the M(II)-containing compound, and the inorganic material obtained in the mixing step is heated and pressurized.
  • the reaction step can be performed in the same manner as in the first embodiment.
  • the M(I)-containing compound and the M(II)-containing compound react with each other while the inorganic material is included, and a perovskite compound is generated.
  • the molded body is removed from the inside of the mold, and the perovskite compounds represented by M(I)M(II) O3 are bonded to each other to obtain a solidified body containing an inorganic material. be able to.
  • test samples solidified bodies according to Examples 1 to 5 were prepared. The following raw materials were used to prepare the test samples of Examples 1 to 5.
  • - Strontium oxide powder (SrO): Kojundo Kagaku Kenkyusho Co., Ltd., purity 98%
  • - Strontium hydroxide octahydrate powder (Sr(OH) 2.8H 2 O): Kojundo Kagaku Kenkyusho Co., Ltd. Made by Kishida Chemical Co., Ltd., purity 2N.
  • Metatitanic acid powder (H 2 TiO 3 ): Made by Kishida Chemical Co., Ltd., purity ⁇ 100%.
  • Orthotitanium. Acid powder (H 4 TiO 4 ): manufactured by Kishida Chemical Co., Ltd., purity 90% (min), barium hydroxide octahydrate powder (Ba(OH) 2.8H 2 O): manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. ), purity 98%, zirconium (IV) oxide hydrate powder (ZrO 2 .nH 2 O): manufactured by Mitsuwa Chemical Co., Ltd., purity ZrO 2 >77%
  • Example 1 Sr(OH) 2.8H 2 O, which is an M(I)-containing compound, and TiO 2, which is an M(II)-containing compound, were weighed in the proportions shown in Table 1 . Next, a mixture was obtained by dry mixing Sr(OH) 2.8H 2 O and TiO 2 using an agate mortar and pestle.
  • Test sample 1 of this example was obtained by heating and pressurizing the mixture at 400 MPa, 180° C., and 30 minutes.
  • a reaction solution for promoting the reaction between the M(I)-containing compound and the M(II)-containing compound was not added to the mixture.
  • Example 2 SrO, which is an M(I)-containing compound, and H 4 TiO 4 , which is an M(II)-containing compound, were weighed in the proportions shown in Table 1. Next, a mixture was obtained by dry mixing SrO and H 4 TiO 4 using an agate mortar and pestle.
  • Test sample 2 of this example was obtained by heating and pressurizing the mixture under conditions of 400 MPa, 180° C., and 30 minutes.
  • a reaction solution for promoting the reaction between the M(I)-containing compound and the M(II)-containing compound was not added to the mixture.
  • Example 3 Sr(OH) 2.8H 2 O, which is an M(I)-containing compound, and H 2 TiO 3 , which is an M(II)-containing compound, were weighed in the proportions shown in Table 1. Next, a mixture was obtained by dry mixing Sr(OH) 2.8H 2 O and H 2 TiO 3 using an agate mortar and pestle.
  • Test sample 3 of this example was obtained by heating and pressurizing the mixture at 400 MPa, 180° C., and 30 minutes.
  • a reaction solution for promoting the reaction between the M(I)-containing compound and the M(II)-containing compound was not added to the mixture.
  • Example 4 Sr(OH) 2.8H 2 O, which is an M(I)-containing compound, and H 4 TiO 4 , which is an M(II)-containing compound, were weighed in the proportions shown in Table 1. Next, a mixture was obtained by dry mixing Sr(OH) 2.8H 2 O and H 4 TiO 4 using an agate mortar and pestle.
  • Test sample 4 of this example was obtained by heating and pressurizing the mixture at 400 MPa, 180° C., and 30 minutes.
  • a reaction solution for promoting the reaction between the M(I)-containing compound and the M(II)-containing compound was not added to the mixture.
  • Example 5 Ba(OH) 2 .8H 2 O, which is an M(I)-containing compound, and ZrO 2 .nH 2 O, which is an M(II)-containing compound, were weighed in the proportions shown in Table 1. Next, a mixture was obtained by dry mixing Ba(OH) 2 ⁇ 8H 2 O and ZrO 2 ⁇ nH 2 O using an agate mortar and pestle.
  • Test sample 5 of this example was obtained by heating and pressurizing the mixture at 400 MPa, 180° C., and 30 minutes.
  • a reaction solution for promoting the reaction between the M(I)-containing compound and the M(II)-containing compound was not added to the mixture.
  • FIG. 2 shows the X-ray diffraction pattern of Test Sample 1 and the X-ray diffraction pattern of strontium titanate (SrTiO 3 ) registered as 186725 in the Inorganic Crystal Structure Database (ICSD).
  • FIG. 2 also shows the X-ray diffraction patterns of strontium hydroxide octahydrate powder (Sr(OH) 2.8H 2 O) and titanium oxide powder (TiO 2 ), which are raw materials.
  • the titanium oxide powder which is a raw material, contains anatase as a main component and a small amount of rutile.
  • Test Sample 1 was a solidified body containing strontium titanate as the main phase, although it slightly contained a different phase of strontium carbonate and titanium oxide.
  • FIG. 3 shows the results of measuring the X-ray diffraction pattern of Test Sample 2 of Example 2 using an X-ray diffraction device. Note that the X-ray diffraction pattern of Test Sample 2 was measured using a powder obtained by pulverizing Test Sample 2. As shown in FIG. 3, in Test Sample 2, a diffraction peak derived from strontium titanate was also observed, and the diffraction peak of strontium titanate was the main one. From this, it was found that Test Sample 2 was also a solidified body containing strontium titanate as a main phase.
  • FIG. 4 shows the results of measuring the X-ray diffraction patterns of Test Sample 3 of Example 3 and Test Sample 4 of Example 4 using an X-ray diffraction device. Note that the X-ray diffraction patterns of Test Samples 3 and 4 were measured using powder obtained by pulverizing Test Samples 3 and 4. Moreover, in FIG. 4, the X-ray diffraction pattern of test sample 1 of Example 1 is also shown. As shown in FIG. 4, in test samples 3 and 4, diffraction peaks derived from strontium titanate were also observed, and the diffraction peak of strontium titanate was the main one. From this, it was found that test samples 3 and 4 were also solidified bodies containing strontium titanate as a main phase.
  • FIG. 5 shows the results of measuring the X-ray diffraction pattern of Test Sample 5 of Example 5 using an X-ray diffraction device. Note that the X-ray diffraction pattern of Test Sample 5 was measured using a powder obtained by pulverizing Test Sample 5. As shown in FIG. 5, in test sample 5, a diffraction peak derived from barium zirconate (BaZrO 3 ) was observed, and the diffraction peak of barium zirconate was the main one. From this, it was found that Test Sample 5 was a solidified body containing barium zirconate as the main phase.
  • barium zirconate BaZrO 3
  • FIG. 7 shows a binarized image of the backscattered electron image shown in FIG. 6 with a magnification of 100,000 times.
  • the black part is the matrix part 21 containing strontium titanate
  • the white part is the pores 22.
  • the area ratio of the pores was calculated from the binarized image, and the average value was taken as the porosity.
  • the area percentages of the pores calculated from the SEM images of six fields of view are 4.3%, 4.6%, 4.4%, 4.5%, 2.8%, and 4.5%, respectively.
  • the average value was 4.2%. Therefore, the porosity of Test Sample 1 was 4.2%.
  • the test sample 1 of Example 1 has a porosity of less than 5%, it can be seen that the matrix portion 21 is dense.

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Abstract

Une méthode de production d'un corps solidifié (20) comprend : une étape de mélange pour mélanger un composé (1) contenant un ou plusieurs types de M(I) avec un composé (2) contenant un ou plusieurs types de M(II) pour obtenir un mélange (3) ; et une étape de réaction pour générer un corps solidifié (20) par mise sous pression du mélange (3) à 30-300°C, inclus. Le corps solidifié (20) est généré par réaction du composé contenant M(I) avec le composé contenant M(II), est obtenu par liaison de composés de pérovskite représentés par la formule de composition : M(I)M(II)O3, et a une porosité inférieure ou égale à 20 %. M(I) est au moins un élément choisi dans le groupe constitué par Mg, Ca, Sr et Ba, et M(II) est au moins un élément choisi dans le groupe constitué par Ti, Zr, Hf et Sn.
PCT/JP2023/007655 2022-03-18 2023-03-01 Méthode de production de corps solidifié WO2023176461A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106257A (ja) * 1997-10-01 1999-04-20 Japan Energy Corp スパッタリング用高純度ＢａｘＳｒ１−ｘＴｉＯ３−ｙターゲット材
CN106587994A (zh) * 2016-12-16 2017-04-26 哈尔滨工程大学 一种钛酸钡铁电陶瓷的低温冷烧结制备方法
US20210101839A1 (en) * 2018-06-20 2021-04-08 Drexel University Ceramic oxide composites reinforced with 2d mx-enes
CN114478029A (zh) * 2022-02-15 2022-05-13 吉林大学 一种制备abo3型钙钛矿陶瓷块体的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106257A (ja) * 1997-10-01 1999-04-20 Japan Energy Corp スパッタリング用高純度ＢａｘＳｒ１−ｘＴｉＯ３−ｙターゲット材
CN106587994A (zh) * 2016-12-16 2017-04-26 哈尔滨工程大学 一种钛酸钡铁电陶瓷的低温冷烧结制备方法
US20210101839A1 (en) * 2018-06-20 2021-04-08 Drexel University Ceramic oxide composites reinforced with 2d mx-enes
CN114478029A (zh) * 2022-02-15 2022-05-13 吉林大学 一种制备abo3型钙钛矿陶瓷块体的方法

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