WO2010008020A1 - Matière de dépôt en phase vapeur pour la production de films d'oxyde composite de strontium/calcium - Google Patents

Matière de dépôt en phase vapeur pour la production de films d'oxyde composite de strontium/calcium Download PDF

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Publication number
WO2010008020A1
WO2010008020A1 PCT/JP2009/062809 JP2009062809W WO2010008020A1 WO 2010008020 A1 WO2010008020 A1 WO 2010008020A1 JP 2009062809 W JP2009062809 W JP 2009062809W WO 2010008020 A1 WO2010008020 A1 WO 2010008020A1
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Prior art keywords
strontium
calcium
vapor deposition
deposition material
range
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PCT/JP2009/062809
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English (en)
Japanese (ja)
Inventor
彰 増田
薫 高崎
真人 財田
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宇部マテリアルズ株式会社
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Application filed by 宇部マテリアルズ株式会社 filed Critical 宇部マテリアルズ株式会社
Priority to JP2010520881A priority Critical patent/JP5543348B2/ja
Priority to CN2009801360529A priority patent/CN102159502A/zh
Publication of WO2010008020A1 publication Critical patent/WO2010008020A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/082—Oxides of alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C01F11/04—Oxides or hydroxides by thermal decomposition
    • C01F11/06—Oxides or hydroxides by thermal decomposition of carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/34—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of sprayed or atomised solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the present invention relates to a vapor deposition material that can be advantageously used when producing a strontium / calcium composite oxide film, particularly by an electron beam vapor deposition method, and a method for producing the vapor deposition material.
  • the present invention also relates to a method for producing a strontium / calcium composite oxide film using an electron beam evaporation method.
  • An AC type plasma display panel (hereinafter referred to as AC type PDP) is generally composed of a front plate serving as an image display surface and a back plate disposed so as to face each other across a discharge space filled with a discharge gas.
  • the front plate includes a front glass substrate, a pair of discharge electrodes formed on the front glass substrate, a dielectric layer covering the discharge electrodes, and a dielectric layer protective film formed on the surface of the dielectric layer.
  • the back plate is a back glass substrate, an address electrode formed on the back glass substrate, a partition that covers the back glass substrate and the address electrode and partitions the discharge space, and red and green disposed on the surface of the partition And a phosphor layer formed of a blue phosphor.
  • the following steps (1) to (4) are repeated to increase the number of charged particles in the discharge space.
  • Light is generated.
  • the generated vacuum ultraviolet light excites red, green, and blue phosphors to generate visible light, and an image is formed by a combination of the visible light.
  • An electric field is generated between the discharge electrodes, and charged particles such as ions and electrons existing in the discharge gas are accelerated and collide with the dielectric layer protective film.
  • Secondary electrons are emitted from the dielectric layer protective film by collision of charged particles.
  • the emitted secondary electrons collide with discharge gas atoms that are not ionized to generate discharge gas ions.
  • the generated discharge gas ions collide with the dielectric layer protective film through the process (1).
  • the dielectric layer protective film not only protects the dielectric layer from impact caused by collision of charged particles, but also functions as a secondary electron emission film.
  • the dielectric layer protective film has high impact resistance against charged particles (that is, high sputtering resistance) and a high secondary electron emission coefficient (that is, the effect of reducing the discharge start voltage and the discharge sustain voltage). High).
  • the magnesium oxide film for the dielectric layer protective film is formed by a physical vapor deposition method (PVD method) such as an electron beam evaporation method.
  • PVD method physical vapor deposition method
  • the strontium / calcium composite oxide film has a higher secondary electron emission coefficient than the magnesium oxide film.
  • Non-Patent Document 1 discloses that an AC type PDP using a strontium / calcium composite oxide film as a dielectric layer protective film has a lower discharge voltage than an AC type PDP using a magnesium oxide film as a dielectric layer protective film. It has been reported.
  • Vapor deposition material used to manufacture AC type PDP dielectric layer protective film by physical vapor deposition such as electron beam vapor deposition is difficult to adsorb water vapor or carbon dioxide gas in air and has low reactivity Is preferred. This is because the vapor deposition material altered by the adsorption of water vapor or carbon dioxide gas or reaction with them takes time to release the adsorbed gas in the vacuum chamber of the vapor deposition apparatus and evacuate the vacuum chamber. This is because it is difficult to maintain a constant degree of vacuum in the vacuum chamber.
  • oxides and composite oxides of alkaline earth metals such as magnesium, calcium, strontium, and barium are known to have high adsorptivity to or reactivity with water vapor and carbon dioxide gas.
  • Patent Document 1 discloses a vapor deposition material for an AC type PDP protective film, which is a sintered body having a relative density of 90% or more and made of an alkaline earth metal oxide or composite oxide and having an average particle diameter of 100 ⁇ m or more. It is described that the moisture resistance of the vapor deposition material is improved by subjecting the vapor deposition material to a surface treatment with an organic silicate.
  • Patent Document 2 describes a highly moisture-resistant vapor-deposited material formed of an alkaline earth metal oxide or composite oxide polycrystal, sintered body or single crystal whose surface is covered with a fluoride layer. There is a description of a strontium-calcium composite oxide polycrystal having a surface covered with a fluoride layer.
  • Patent Document 3 discloses a moisture-resistant material formed of a polycrystal, sintered body or single crystal of an alkaline earth metal oxide or composite oxide whose surface is covered with a sulfate layer and / or a sulfide layer.
  • a high vapor deposition material in which there is a description of a strontium / calcium composite oxide polycrystal whose surface is covered with a sulfate layer (sulfide layer).
  • the vapor deposition material described in Patent Document 1 has a large average particle diameter of 100 ⁇ m or more and the specific surface area of the crystal particles is small, so that each crystal particle has low adsorption of water vapor or carbon dioxide gas, Moreover, the reactivity with those gases is also low. However, as the size of the crystal particles increases, the gaps (pores) between the crystal particles usually increase. On the other hand, according to the study by the present inventor, when the average pore size is increased in the polycrystalline body of strontium / calcium composite oxide crystal particles, the mass increase due to contact with water vapor or carbon dioxide gas (that is, water vapor or carbon dioxide gas It has been found that the mass increase due to adsorption or reaction with them increases.
  • the method of coating the surface of the vapor deposition material described in Patent Documents 1 to 3 with a coating material is an effective method in terms of reducing the adsorption of water vapor or carbon dioxide gas or the reactivity with them.
  • a physical vapor deposition method such as an electron beam vapor deposition method using a vapor deposition material coated with a coating material, together with the film material in a vacuum chamber of the vapor deposition apparatus.
  • the coating material is also vaporized, the degree of vacuum in the vacuum chamber becomes unstable, and the uniformity and crystallinity of the resulting film may be reduced.
  • a physical vapor deposition method such as an electron beam vapor deposition method, which is composed of fine crystal particles whose average crystal particle diameter is smaller than 100 ⁇ m.
  • vapor deposition of a polycrystal of strontium / calcium complex oxide crystal particles that does not involve vaporization of impurities other than strontium / calcium complex oxide and has low adsorptivity to water vapor or carbon dioxide gas or low reactivity with them To provide materials.
  • the present inventor includes calcium carbonate particles and strontium carbonate particles in a ratio in which the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2.
  • An average crystal is obtained by a method in which a granule obtained by spray-drying a particle mixture dispersion in which a particle mixture in the range of 0.05 to 2.0 ⁇ m is dispersed in a liquid medium is formed into a pellet and then fired.
  • Sintered small and fine pores with an average pore diameter of 0.01 to 0.50 ⁇ m formed from a polycrystal of fine strontium / calcium complex oxide crystal particles with a particle diameter of 1.0 to 90 ⁇ m It has been found that body pellets can be obtained.
  • the particle mixture dispersion calcium and strontium are included at a molar ratio of 0.2: 0.8 to 0.8: 0.2, and the average particle diameter is 0.05 to Even if a strontium / calcium carbonate double salt particle dispersion liquid in which strontium / calcium carbonate double salt particles in the range of 2.0 ⁇ m are dispersed in a liquid medium is used, polycrystals of fine strontium / calcium composite oxide crystal particles are similarly obtained. It was found that a dense sintered body pellet formed from the body and having a small average pore diameter can be obtained. The sintered body pellet has a mass increase rate of 0.5% by mass or less when left at a temperature of 25 ° C.
  • the film is formed by electron beam evaporation using the sintered pellet, the degree of vacuum in the vacuum chamber of the evaporation system is highly stable, and the film is formed under stable conditions.
  • the present invention was completed by confirming that the obtained strontium / calcium composite oxide film showed high crystallinity.
  • the general formula is represented by Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8), and the average crystal particle diameter is in the range of 1.0 to 90 ⁇ m.
  • the preferable aspect of the vapor deposition material of this invention is as follows. (1) The relative density is 90% or more. (2) For producing a strontium / calcium composite oxide film by an electron beam vapor deposition method, the surface is not provided with a coating made of a material that is vaporized by electron beam irradiation. (3) The mass increase rate is 0.5% by mass or less when left at a temperature of 25 ° C. for 168 hours in an atmosphere with a relative humidity of 47%.
  • the general formula is represented by Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8), and the average crystal grain size is in the range of 1.0 to 90 ⁇ m. 168 in an atmosphere of a relative humidity of 47% at a temperature of 25 ° C. without being provided with a film made of a polycrystal of a strontium / calcium complex oxide crystal particle and made of a material that is vaporized by irradiation with an electron beam on the surface.
  • a vapor deposition material for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method having a mass increase rate of 0.5% by mass or less when left standing for a time.
  • the vapor deposition material of the present invention preferably has a relative density of 90% or more.
  • the vapor deposition material of the present invention is irradiated with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide, and deposit the vaporized strontium / calcium composite oxide on the substrate.
  • the present invention also includes calcium carbonate particles and strontium carbonate particles in a ratio in which the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2.
  • a method for producing a vapor deposition material of the present invention which includes a step of forming a pellet into a pellet and a step of firing the obtained pellet-shaped molded product.
  • the present invention further includes an average particle size in the range of 0.05 to 2.0 ⁇ m, containing calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2.
  • a step of preparing a strontium / calcium carbonate double salt particle dispersion in which the strontium / calcium carbonate double salt particles are dispersed in a liquid medium a step of spray-drying the dispersion to obtain carbonate double salt particle granules
  • There is also a method for producing a vapor deposition material of the present invention including a step of forming a granular body into a pellet and a step of firing the obtained pellet-shaped product.
  • the vapor deposition material of the present invention itself has low adsorptivity of water vapor and carbon dioxide gas or reactivity with them, it is not particularly necessary to cover the surface with a coating material. Therefore, by using the vapor deposition material of the present invention, a highly crystalline strontium / calcium composite oxide film can be produced under stable conditions using a physical vapor deposition method such as an electron beam vapor deposition method. It is known that strontium / calcium composite oxide films with high crystallinity generally have high sputtering resistance, and strontium / calcium composite oxide films have a higher secondary electron emission coefficient than magnesium oxide films. . Therefore, the strontium / calcium composite oxide film produced using the vapor deposition material of the present invention is useful as a dielectric layer protective film of the AC type PDP.
  • a polycrystalline body that can be advantageously used to form a strontium / calcium composite oxide film by physical vapor deposition is obtained by utilizing the method for producing a vapor deposition material of the present invention. Can be manufactured.
  • the vapor deposition material of the present invention comprises a polycrystalline body of strontium / calcium composite oxide crystal particles represented by a general formula Sr 1-x Ca x O.
  • x is a value in the range of 0.2 to 0.8, preferably a value in the range of 0.3 to 0.7.
  • the vapor deposition material of the present invention has an average pore diameter in the range of 0.01 to 0.50 ⁇ m, preferably in the range of 0.01 to 0.30 ⁇ m, particularly preferably in the range of 0.01 to 0.20 ⁇ m.
  • the average pore diameter is a value measured by a mercury intrusion method.
  • the average crystal particle diameter of the strontium / calcium complex oxide crystal particles constituting the vapor deposition material of the present invention is in the range of 1.0 to 90 ⁇ m, preferably in the range of 5.0 to 80 ⁇ m.
  • the shape of the vapor deposition material of the present invention is not particularly limited, but is preferably a disc shape.
  • the disk-shaped vapor deposition material preferably has a diameter in the range of 2.0 to 10 mm, and preferably has a thickness in the range of 1.0 to 5.0 mm. The thinner the thickness, the higher the deposition rate while maintaining the quality of the strontium / calcium composite oxide film (homogeneity of film density, uniformity of crystal orientation, etc.) obtained by the electron beam evaporation method.
  • the aspect ratio (thickness / diameter) of the disk-shaped vapor deposition material is preferably 1.0 or less.
  • the vapor deposition material of the present invention preferably has a relative density of 90% or more, particularly preferably 95% or more.
  • the relative density is a value representing the ratio between the bulk density and the true density as a percentage.
  • the true density of the vapor deposition material is as follows from the true density of calcium oxide, the true density of strontium oxide, and the molar ratio of calcium to strontium in the vapor deposition material when the total molar amount is 1. Calculated using the formula.
  • True density (g / cm 3) 3.350g / cm 3 ( true density of strontium oxide) ⁇ the molar ratio of calcium in the polycrystalline body + 5.009g / cm 3 (true density of calcium oxide) ⁇ polycrystalline body Molar ratio of strontium
  • the vapor deposition material of the present invention has a mass increase rate of 0.5% by mass or less, particularly in a range of 0.01 to 0.5% by mass when left at a temperature of 25 ° C. in an atmosphere of 47% relative humidity for 168 hours.
  • the adsorption property of water vapor and carbon dioxide gas or the reactivity with them is low. For this reason, it is not particularly necessary to coat the surface of the vapor deposition material of the present invention with a coating material.
  • the vapor deposition material of the present invention can be advantageously used to form a strontium / calcium composite oxide film by physical vapor deposition.
  • physical vapor deposition methods that can use the vapor deposition material of the present invention include electron beam vapor deposition, ion plating, and sputtering.
  • the vapor deposition material of the present invention can be advantageously used for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method. That is, the vapor deposition material of the present invention is placed in a vapor deposition chamber of an electron beam vapor deposition apparatus, and the vapor deposition material is irradiated with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide, thereby vaporizing the vaporized strontium / calcium composite oxide.
  • the pressure in the vapor deposition chamber at the time of film production is preferably 6.00 ⁇ 10 ⁇ 2 Pa or less in total pressure.
  • oxygen gas is present in the vapor deposition chamber in an oxygen partial pressure range of 0.10 to 5.99 ⁇ 10 ⁇ 2 Pa, particularly 0.50 to 4.00 ⁇ 10 ⁇ 2 Pa. Is preferred.
  • the vapor deposition material of the present invention contains, for example, calcium carbonate particles and strontium carbonate particles in a ratio such that the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2.
  • the average particle diameter means a value measured by a laser diffraction method when the value is 0.1 ⁇ m or more, and a value measured by a dynamic light scattering method when the value is less than 0.1 ⁇ m. means.
  • the particle mixture dispersion is obtained by adding calcium carbonate particles and strontium carbonate particles into a liquid medium, and using a pulverizer such as a ball mill or a media mill (stirring mill) to obtain calcium carbonate particles and strontium carbonate particles. And pulverizing with mixing.
  • the raw material calcium carbonate particles preferably have an average particle size in the range of 0.05 to 100 ⁇ m, and more preferably in the range of 0.08 to 100 ⁇ m.
  • the calcium carbonate particles preferably have a BET specific surface area in the range of 0.1 to 50 m 2 / g.
  • the calcium carbonate particles preferably have a cubic primary particle shape, and more preferably have a cubic shape with an aspect ratio in the range of 1 to 2.
  • the purity of the calcium carbonate particles is preferably 99% by mass or more.
  • the raw material strontium carbonate particles preferably have an average particle size in the range of 0.05 to 100 ⁇ m, and more preferably in the range of 0.08 to 100 ⁇ m.
  • the strontium carbonate particles preferably have a BET specific surface area in the range of 0.1 to 70 m 2 / g.
  • the primary particles are preferably needle-like or cubic.
  • the purity of the strontium carbonate particles is preferably 99% by mass or more.
  • the time required for pulverizing the average particle size of the particle mixture of calcium carbonate particles and strontium carbonate particles in the mixture dispersion to 2.0 ⁇ m or less is larger when the BET specific surface area is larger. Since it becomes short, it is preferable.
  • liquid medium water, monohydric alcohol and a mixture thereof can be used.
  • monohydric alcohols include ethanol, propanol and butanol.
  • the liquid medium is preferably water.
  • Polycarboxylic acid salt may be added to the particle mixture dispersion.
  • the polycarboxylate acts as a dispersant.
  • the polycarboxylate is preferably an ammonium salt or an alkyl ammonium salt.
  • the addition amount of the polycarboxylate is preferably in the range of 0.5 to 20 parts by mass, particularly preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the solid content in the particle mixture dispersion.
  • the polycarboxylate may be added to the particle mixture dispersion, or may be preliminarily attached to the surface of either or both of the raw material calcium carbonate particles and strontium carbonate particles.
  • a binder having compatibility with the liquid medium it is preferable to add a binder having compatibility with the liquid medium to the particle mixture dispersion.
  • the binder having compatibility with water include polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, and an acrylic copolymer.
  • the addition amount of the binder is preferably in the range of 0.10 to 10 parts by mass with respect to 100 parts by mass of the solid content in the particle mixture dispersion.
  • the binder may be added before mixing and grinding the calcium carbonate particles and strontium carbonate particles, or after mixing and grinding and before spray drying of the particle mixture dispersion.
  • the spray drying of the particle mixture dispersion can be performed using a normal spray dryer.
  • the spray drying temperature is preferably in the range of 150 to 280 ° C.
  • the dried mixed granule obtained by spray drying the particle mixture dispersion is formed into pellets, and the obtained pellets are fired to oxidize calcium carbonate and strontium carbonate while producing strontium
  • the vapor deposition material of the present invention can be obtained by sintering the calcium composite oxide.
  • a normal press molding method can be used for molding the pellet-shaped molded product.
  • the molding pressure is generally in the range of 0.3 to 3 ton / cm 2 .
  • the pellet-shaped molded product is preferably fired at a temperature of 1400 to 1800 ° C.
  • the firing time varies depending on requirements such as the size (particularly thickness) of the molded product and the firing temperature, and cannot be uniformly determined, but is generally 1 to 7 hours.
  • the vapor deposition material of the present invention can also be produced using strontium / calcium carbonate double salt particles as a raw material. That is, the vapor deposition material of the present invention contains calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2 and has an average particle size of 0.05 to 2.
  • a step of preparing a strontium / calcium carbonate double salt particle dispersion in which strontium / calcium carbonate double salt particles in a range of 0.0 ⁇ m are dispersed in a liquid medium, and spray-drying the dispersion to form a carbonate double salt particle granule It can also be produced by a method including a step of obtaining, a step of forming the granular body into a pellet, and a step of firing the obtained pellet-shaped product.
  • the strontium-calcium carbonate double salt particles used as a raw material contain a strontium-calcium aqueous solution containing calcium ions and strontium ions in an amount ranging from 0.2: 0.8 to 0.8: 0.2 in molar ratio Further, it can be synthesized by adding an aqueous ammonia solution to adjust the pH to the range of 7 to 14 and then supplying carbon dioxide gas. It can also be synthesized by supplying carbon dioxide gas to an aqueous solution containing calcium hydroxide and strontium hydroxide in a molar ratio of 0.2: 0.8 to 0.8: 0.2. can do.
  • the temperature of the aqueous solution when synthesizing the strontium / calcium carbonate double salt particles is preferably in the range of 5 to 80 ° C.
  • the strontium / calcium carbonate double salt produced by carbonation of calcium ions and strontium ions is preferably taken out from the aqueous solution, washed and dried, and then used as a material for the vapor deposition material.
  • the strontium / calcium carbonate double salt particle dispersion can be prepared by pulverizing the strontium / calcium carbonate double salt particles synthesized as described above in a liquid medium using a pulverizer such as a ball mill or a media mill. it can.
  • the liquid medium is preferably water.
  • a binder having compatibility with the liquid medium is preferably added to the carbonate double salt particle dispersion before spray drying.
  • the addition amount of the binder is preferably in the range of 0.10 to 10 parts by mass with respect to 100 parts by mass of the strontium / calcium carbonate double salt particles in the dispersion.
  • the step of spraying and drying carbonate double salt particle dispersion to obtain carbonate double salt particle granules the step of forming the granules into pellets, and the step of firing the obtained pellets, This can be the same as when calcium particles and strontium carbonate particles are used.
  • Example 1 (1) Preparation of Particle Mixture Dispersion Calcium carbonate particles (purity: 99.5% by mass, BET specific surface area: 44 m 2 / g, average particle size: 6.9 ⁇ m, primary particle shape: cubic) 101 g, strontium carbonate particles ( Purity: 99.5% by mass, BET specific surface area: 20 m 2 / g, average particle size: 1.2 ⁇ m, primary particle shape: needle shape) 149 g and 583 mL of water were mixed, and calcium carbonate particles and strontium carbonate particles were mixed. A mixed solution was obtained (the molar ratio of calcium to strontium was 0.5: 0.5).
  • This mixed solution was put into a ball mill filled with nylon balls with a core (diameter: 10 mm), and calcium carbonate particles and strontium carbonate particles were mixed and ground for 25 hours to prepare a particle mixture dispersion.
  • the average particle diameter and the BET specific surface area of the particle mixture in the particle mixture dispersion were measured by the following method. The results and the molar ratio of calcium and strontium in the particle mixture dispersion are shown in Table 1.
  • Measurement was performed using a laser diffraction particle size distribution analyzer (Microtrack 9320HRA, manufactured by Nikkiso Co., Ltd.). A sample for measuring the average particle size was prepared by diluting the particle mixture dispersion with 50 g of water with respect to 0.5 g of the solid content in the dispersion, followed by ultrasonic dispersion for 3 minutes.
  • BET specific surface area A part of the particle mixture dispersion is dried at a temperature of 120 ° C., and the BET specific surface area of the obtained dry powder is measured by a BET one-point method using a specific surface area measuring device (Monosorb, Yuasa Ionics Co., Ltd.). did.
  • the sintered pellet was cut in the diameter direction, and the cut surface was mirror polished. Then, the average crystal particle diameter of the strontium / calcium composite oxide crystal particles on the cut surface was measured using a field emission scanning electron microscope. The average crystal particle size was determined by observing 200 crystal particles at an enlargement magnification of 1500 times, measuring the longest diameter (Ferret diameter) of each crystal particle, and averaging this.
  • Average pore diameter 4 ⁇ cumulative pore volume / cumulative specific surface area
  • Mass increase rate The sintered pellets whose mass was measured in advance were allowed to stand for 168 hours in a constant temperature and humidity chamber prepared at a temperature of 25 ° C. and a relative humidity of 47%. The mass increase rate after standing was measured, and the mass increase rate was calculated.
  • the X-ray diffraction pattern of the strontium / calcium composite oxide film was measured using an X-ray diffractometer under the conditions of a tube voltage of 40 kV, a tube current of 200 mA, a scanning angle of 20 to 80 degrees, and a scanning speed of 0.02 degrees / second. The intensity of the diffraction line peak corresponding to the (111) plane was measured.
  • Example 2 In Example 1 (1), a mixed solution of calcium carbonate particles and strontium carbonate particles was charged into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 mm.
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding for 15 minutes, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 3 In Example 1 (1), a mixed solution of calcium carbonate particles and strontium carbonate particles was charged into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 mm.
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding for 60 minutes, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 4 In Example 1 (1), calcium carbonate particles having a purity of 99.5% by mass, a BET specific surface area of 0.22 m 2 / g, an average particle size of 13.8 ⁇ m, and a primary particle shape of cubic calcium carbonate particles. Used, a mixed solution of calcium carbonate particles and strontium carbonate particles is put into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 ⁇ m, and mixed and ground for 45 minutes. Sintered pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared, and the sintered pellets were evaluated.
  • MINIZETA manufactured by Ashizawa Finetech Co., Ltd.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 5 In Example 1 (1), the amount of calcium carbonate particles was 20.02 g, the amount of strontium carbonate particles was 118.10 g (the molar ratio of calcium to strontium was 0.2: 0.8), and the amount of water
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 322 mL, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 6 In Example 1 (1), the amount of calcium carbonate particles was 80.06 g, the amount of strontium carbonate particles was 29.52 g (the molar ratio of calcium to strontium was 0.8: 0.2), and the amount of water
  • a sintered body pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 256 mL, and the sintered body pellet was evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 7 (1) Preparation of strontium / calcium carbonate double salt particle dispersion calcium carbonate particles (purity: purity: 99.5% by mass, BET specific surface area: 44 m 2 / g, average particle size: 6.9 ⁇ m, primary particle shape: cubic ) 101 g and strontium carbonate particles (purity: 99.5% by mass, BET specific surface area: 20 m 2 / g, average particle size: 1.2 ⁇ m, primary particle shape: needle shape) are mixed with 149 g of water and 583 mL of water.
  • strontium-calcium carbonate double salt particles 247 g of the obtained strontium-calcium carbonate double salt particles and 576 mL of water are mixed and put into a ball mill filled with a nylon ball with a core (diameter 10 mm), and the strontium-calcium carbonate double salt particles are mixed for 25 hours. By pulverizing, a strontium / calcium carbonate double salt particle dispersion was prepared.
  • Example 8 In Example 7 (1), the amount of calcium carbonate particles was 80.06 g, the amount of strontium carbonate particles was 29.52 g (the molar ratio of calcium to strontium was 0.8: 0.2), and the amount of water was 256 mL. As described above, sintered pellets were manufactured in the same manner as in Example 7 except that the calcium / strontium aqueous solution was manufactured, and the sintered pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the carbonate double salt particle dispersion, the average particle diameter and BET specific surface area of the carbonate double salt particles, and Table 2 shows the average crystal particle diameter, average pore diameter of the sintered pellet, The relative density and the mass increase rate are shown in Table 3, and the measurement results of the average vapor deposition current value and the peak intensity of the (111) plane are shown.
  • Example 1 calcium carbonate particles having a purity of 99.5% by mass, a BET specific surface area of 0.22 m 2 / g, an average particle size of 13.8 ⁇ m, and a primary particle shape of cubic calcium carbonate particles.
  • a sintered body pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared using a mixed pulverization time of the mixed liquid of calcium carbonate particles and strontium carbonate particles for 24 hours.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 1 the sintered pellet was prepared in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding the mixed solution of calcium carbonate particles and strontium carbonate particles for 5 hours. Manufacture and evaluation of sintered compact pellets were performed. Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 3 In Example 1 (1), the amount of calcium carbonate particles was 10.01 g, the amount of strontium carbonate particles was 142.87 g (the molar ratio of calcium to strontium was 0.1: 0.9), and the amount of water A sintered pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 333 mL, and the sintered pellet was evaluated. Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 1 the amount of calcium carbonate particles was 90.07 g, the amount of strontium carbonate particles was 14.76 g (the molar ratio of calcium to strontium was 0.9: 0.1), and the amount of water
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 245 mL, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • the peak intensity of the (111) plane is a relative value where the peak intensity of the (111) plane of the strontium / calcium composite oxide film obtained in Comparative Example 1 is 1.

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Abstract

L'invention porte sur une matière de dépôt en phase vapeur pour la production de films d'oxyde composite de strontium/calcium, qui consiste en une matière polycristalline composée de grains d'oxyde composite de strontium/calcium représentée par la formule générale Sr1-xCaxO (où x vaut 0,2 à 0,8) et un diamètre moyen de grain de 1,0 à 90 µm et qui a un diamètre moyen de pore de 0,01 à 50 µm. La matière de dépôt en phase vapeur en elle-même a une faible capacité d'adsorption pour la vapeur d'eau ou le dioxyde de carbone gazeux ou a une faible aptitude à réagir avec eux, de telle sorte que la matière de dépôt en phase vapeur n'a pas besoin d'être revêtue en surface, en particulier par un matériau de revêtement.
PCT/JP2009/062809 2008-07-15 2009-07-15 Matière de dépôt en phase vapeur pour la production de films d'oxyde composite de strontium/calcium WO2010008020A1 (fr)

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JP2010520881A JP5543348B2 (ja) 2008-07-15 2009-07-15 ストロンチウム・カルシウム複合酸化物膜製造用の蒸着材
CN2009801360529A CN102159502A (zh) 2008-07-15 2009-07-15 用于制备锶钙复合氧化物膜的蒸镀材料

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JP2011146194A (ja) * 2010-01-13 2011-07-28 Ube Material Industries Ltd ストロンチウムとカルシウムとを含む酸化物膜製造用の蒸着材

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CN103694998B (zh) * 2014-01-08 2018-07-20 中国科学院福建物质结构研究所 一种硫氧化物红色长余辉发光材料及其制备方法
JP7065058B2 (ja) 2019-08-05 2022-05-11 株式会社神鋼環境ソリューション 流動床炉における流動媒体の回収方法

Citations (2)

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Publication number Priority date Publication date Assignee Title
JP2002294432A (ja) * 2001-01-25 2002-10-09 Mitsubishi Materials Corp Ｆｐｄの保護膜用蒸着材及びその製造方法
JP2008091074A (ja) * 2006-09-29 2008-04-17 Tateho Chem Ind Co Ltd 耐湿性に優れたプラズマディスプレイパネル保護膜用蒸着材

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JP3893793B2 (ja) 1999-04-05 2007-03-14 三菱マテリアル株式会社 ＭｇＯ蒸着材及びその製造方法
JP4147988B2 (ja) 2003-03-17 2008-09-10 三菱マテリアル株式会社 Ｆｐｄの保護膜用蒸着材およびその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002294432A (ja) * 2001-01-25 2002-10-09 Mitsubishi Materials Corp Ｆｐｄの保護膜用蒸着材及びその製造方法
JP2008091074A (ja) * 2006-09-29 2008-04-17 Tateho Chem Ind Co Ltd 耐湿性に優れたプラズマディスプレイパネル保護膜用蒸着材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011146194A (ja) * 2010-01-13 2011-07-28 Ube Material Industries Ltd ストロンチウムとカルシウムとを含む酸化物膜製造用の蒸着材

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