WO2012008447A1 - Corps moulé cru, et procédé de fabrication de corps cuit en titanate d'aluminium - Google Patents

Corps moulé cru, et procédé de fabrication de corps cuit en titanate d'aluminium Download PDF

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WO2012008447A1
WO2012008447A1 PCT/JP2011/065882 JP2011065882W WO2012008447A1 WO 2012008447 A1 WO2012008447 A1 WO 2012008447A1 JP 2011065882 W JP2011065882 W JP 2011065882W WO 2012008447 A1 WO2012008447 A1 WO 2012008447A1
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source powder
aluminum
molded body
green molded
source
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Japanese (ja)
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康輔 魚江
朝 吉野
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住友化学株式会社
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    • 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
    • C04B35/478—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 aluminium titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B01D39/2093—Ceramic foam
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron

Definitions

  • the present invention relates to a green molded body and a method for producing an aluminum titanate fired body.
  • Aluminum titanate ceramics are known as ceramics that contain titanium and aluminum as constituent elements and have a crystal pattern of aluminum titanate in the X-ray diffraction spectrum, and have excellent heat resistance.
  • Aluminum titanate ceramics have been conventionally used as a sintering jig such as a crucible, but in recent years, fine carbon particles contained in exhaust gas discharged from an internal combustion engine such as a diesel engine are collected.
  • a material constituting a ceramic filter industrial utility value is increasing.
  • Patent Document 1 As a method for producing aluminum titanate ceramics, a method is known in which a raw material mixture containing an aluminum source powder and a titanium source powder is formed and fired (Patent Document 1).
  • the raw material mixture further contains organic additives such as an organic binder and pore former, and the green additive of this raw material mixture is heated to 150 to 900 ° C. in an oxygen-containing atmosphere to remove the organic additives.
  • a method of firing at 1300 ° C. or higher is also known (paragraphs 0031 to 0032 of Patent Document 1).
  • the strength (shape retention) of the green molded body is not sufficient, and the green molded body may not be able to maintain its shape when it is put into a firing furnace. As a result, the dimensional accuracy of the obtained aluminum titanate fired body was not sufficient.
  • An object of the present invention is to provide a green molded body capable of maintaining its shape and a method for producing an aluminum titanate fired body using the green molded body.
  • the inorganic compound source powder includes an aluminum source powder and a titanium source powder,
  • the green molded object whose viscosity in 20 degreeC of a plasticizer is 1000 mPa * s or more.
  • the inorganic compound source powder includes an aluminum source powder and a titanium source powder, The manufacturing method of the aluminum titanate sintered body whose viscosity in 20 degreeC of a plasticizer is 1000 mPa * s or more.
  • the amount of the plasticizer is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the green molded body.
  • the inorganic compound source powder preferably further contains a silicon source powder.
  • the inorganic compound source powder preferably further contains a magnesium source powder.
  • the molar ratio of the aluminum source powder in terms of Al 2 O 3 and the titanium source powder in terms of TiO 2 in the raw material mixture is preferably 35:65 to 45:55.
  • the green molded body preferably has a honeycomb shape.
  • the green molded object of this invention is excellent in shape retention property by including the plasticizer whose viscosity in 20 degreeC is 1000 mPa * s or more. Further, according to the method for producing an aluminum titanate fired body of the present invention, a green molded body having excellent shape retention can be obtained by using a plasticizer having a viscosity at 20 ° C. of 1000 mPa ⁇ s or more as a raw material. An aluminum titanate fired body with high dimensional accuracy can be produced efficiently.
  • FIG. 1A and FIG. 1B are schematic diagrams showing how to investigate shape retention in the embodiment.
  • the green molded body of the present invention includes an inorganic compound source powder, an organic binder, and a plasticizer.
  • the inorganic compound source powder includes an aluminum source powder and a titanium source powder.
  • the inorganic compound source powder can further include a magnesium source powder and / or a silicon source powder.
  • the aluminum source is a compound that becomes an aluminum component constituting the aluminum titanate fired body.
  • the aluminum source include alumina (aluminum oxide).
  • the crystal type of alumina include ⁇ -type, ⁇ -type, ⁇ -type, and ⁇ -type, and may be indefinite (amorphous). Of these, ⁇ -type alumina is preferably used.
  • the aluminum source may be a compound that becomes alumina by firing alone in air.
  • Examples of such a compound include an aluminum salt, aluminum alkoxide, aluminum hydroxide, metal aluminum and the like.
  • the aluminum salt may be an inorganic salt with an inorganic acid or an organic salt with an organic acid.
  • the inorganic aluminum salt include aluminum nitrates such as aluminum nitrate and ammonium aluminum nitrate; and aluminum carbonates such as ammonium aluminum carbonate.
  • the aluminum organic salt include aluminum oxalate, aluminum acetate, aluminum stearate, aluminum lactate, and aluminum laurate.
  • aluminum alkoxide examples include aluminum isopropoxide, aluminum ethoxide, aluminum sec-butoxide, aluminum tert-butoxide, and the like.
  • Examples of the aluminum hydroxide crystal type include a gibbsite type, a bayerite type, a norosotrandite type, a boehmite type, and a pseudo-boehmite type, and may be amorphous (amorphous).
  • Examples of amorphous aluminum hydroxide include an aluminum hydrolyzate obtained by hydrolyzing an aqueous solution of a water-soluble aluminum compound such as an aluminum salt or an aluminum alkoxide.
  • an aluminum source only 1 type may be used and 2 or more types may be used together.
  • the aluminum source alumina is preferably used, and ⁇ -type alumina is more preferable.
  • the aluminum source may contain trace components derived from the raw materials or inevitably contained in the production process.
  • the particle size of the aluminum source powder is not particularly limited, but the particle size corresponding to a volume-based cumulative percentage of 50% (which may be referred to as D50 or average particle size) measured by a laser diffraction method is in the range of 20 to 60 ⁇ m. Preferably there is. From the viewpoint of reducing shrinkage during firing, it is more preferable to use an aluminum source powder having a D50 in the range of 30 to 60 ⁇ m.
  • titanium source powder The titanium source is a compound that becomes a titanium component constituting the aluminum titanate fired body, and examples of such a compound include titanium oxide.
  • examples of titanium oxide include titanium (IV) oxide, titanium (III) oxide, and titanium (II) oxide.
  • titanium (IV) oxide is preferably used.
  • Examples of the crystal type of titanium oxide (IV) include anatase type, rutile type, brookite type, and the like, and may be amorphous (amorphous). More preferably, it is anatase type or rutile type titanium (IV) oxide.
  • the titanium source may be a compound that becomes titania (titanium oxide) by firing alone in air.
  • examples of such compounds include titanium salts, titanium alkoxides, titanium hydroxide, titanium nitride, titanium sulfide, and titanium metal.
  • titanium salt examples include titanium trichloride, titanium tetrachloride, and titanium (IV) sulfate.
  • titanium alkoxide examples include titanium (IV) ethoxide, titanium (IV) methoxide, titanium (IV) tert-butoxide, titanium (IV) n-butoxide, titanium (IV) isobutoxide, and titanium (IV) n-propoxy.
  • titanium sulfide examples include titanium sulfide (IV) and titanium sulfide (VI).
  • titanium source only 1 type may be used and 2 or more types may be used together.
  • titanium oxide is preferably used as the titanium source, and more preferably titanium (IV) oxide.
  • the titanium source may contain a trace component derived from the raw material or inevitably contained in the production process.
  • the particle size of the titanium source powder is not particularly limited, but a particle size corresponding to a volume-based cumulative percentage of 50% (D50 or an average particle size) measured by a laser diffraction method is in the range of 0.1 to 25 ⁇ m. In order to sufficiently reduce the shrinkage ratio during firing, it is more preferable to use a titanium source powder having a D50 in the range of 0.5 to 20 ⁇ m.
  • the titanium source powder may show a bimodal particle size distribution. When using a titanium source powder showing such a bimodal particle size distribution, the particle size distribution measured by the laser diffraction method is used.
  • the particle diameter of the peak having the larger particle diameter is preferably in the range of 20 to 50 ⁇ m.
  • the mode diameter of the titanium source powder measured by the laser diffraction method is not particularly limited, but a titanium source powder in the range of 0.3 to 60 ⁇ m can be used.
  • the molar ratio of the aluminum source powder in terms of Al 2 O 3 (alumina) and the titanium source powder in terms of TiO 2 (titania) in the green molded body is preferably 35:65 to 45:55, and more It is preferably 40:60 to 45:55. Within such a range, it becomes possible to reduce the shrinkage rate during firing by using the titanium source excessively relative to the aluminum source.
  • the green molded body may contain a magnesium source powder.
  • the obtained aluminum titanate fired body is a fired body containing aluminum magnesium titanate crystals.
  • magnesia manganesium oxide
  • a compound that becomes magnesia by firing alone in air can be used.
  • examples of the latter include magnesium salt, magnesium alkoxide, magnesium hydroxide, magnesium nitride, metal magnesium and the like.
  • magnesium salts include magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium sulfate, magnesium citrate, magnesium lactate, and magnesium stearate.
  • magnesium salts include magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium sulfate, magnesium citrate, magnesium lactate, and magnesium stearate.
  • magnesium salts include magnesium chloride, magnesium perchlorate, magnesium phosphate, magnesium pyrophosphate, magnesium oxalate, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium sulfate, magnesium citrate, magnesium lactate, and magnesium stearate.
  • magnesium alkoxide examples include magnesium methoxide and magnesium ethoxide.
  • a magnesium source can contain the trace component contained unavoidable in the raw material origin or manufacturing process.
  • a compound serving both as a magnesium source and an aluminum source can also be used.
  • An example of such a compound is magnesia spinel (MgAl 2 O 4 ).
  • MgAl 2 O 4 magnesia spinel
  • As magnesium source when using a compound serving both as a magnesium source and an aluminum source, Al 2 O 3 (alumina) equivalent amount of the aluminum source, and, Al component contained in the compound serving both as a magnesium source and an aluminum source.
  • the molar ratio of the total amount of Al 2 O 3 (alumina) converted to the TiO 2 (titania) converted amount of the titanium source is adjusted to be within the above range in the raw material mixture.
  • magnesium source only 1 type may be used and 2 or more types may be used together.
  • the particle size of the magnesium source powder is not particularly limited, but the particle size corresponding to a volume-based cumulative percentage of 50% (D50 or an average particle size) measured by a laser diffraction method is in the range of 0.5 to 30 ⁇ m. It is preferable to use a magnesium source having a D50 of 3 to 20 ⁇ m from the viewpoint of reducing shrinkage during firing.
  • the content of the magnesium source in terms of MgO (magnesia) in the green molded body is set to 1 as the total amount of the aluminum source in terms of Al 2 O 3 (alumina) and the titanium source in terms of TiO 2 (titania).
  • the molar ratio is preferably 0.03 to 0.15, more preferably 0.03 to 0.12.
  • the green molded body may further contain a silicon source powder.
  • the silicon source is a compound that becomes a silicon component and is contained in the aluminum titanate fired body. By using the silicon source in combination, it is possible to obtain an aluminum titanate fired body with improved heat resistance.
  • Examples of the silicon source include silicon oxide (silica) such as silicon dioxide and silicon monoxide.
  • the silicon source may be a compound that becomes silica by firing alone in air.
  • examples of such compounds include silicic acid, silicon carbide, silicon nitride, silicon sulfide, silicon tetrachloride, silicon acetate, sodium silicate, sodium orthosilicate, feldspar, glass frit and the like.
  • feldspar, glass frit and the like are preferably used, and glass frit and the like are more preferably used in terms of industrial availability and stable composition.
  • Glass frit means flakes or powdery glass obtained by pulverizing glass.
  • As the silicon source a powder containing a mixture of feldspar and glass frit can also be used.
  • the silicon source is glass frit
  • the yield point of a glass frit is defined as the temperature (° C.) at which the expansion stops and the shrinkage starts when the glass frit is heated from a low temperature, measured using a thermomechanical analyzer (TMA: Thermo Mechanical Analysis).
  • a general silicate glass containing silicate [SiO 2 ] as a main component (0% by weight or more in all components) can be used.
  • the glass constituting the glass frit includes, as other components, alumina [Al 2 O 3 ], sodium oxide [Na 2 O], potassium oxide [K 2 O], calcium oxide [ CaO], magnesia [MgO] and the like may be included.
  • the glass constituting the glass frit may contain ZrO 2 in order to improve the hot water resistance of the glass itself.
  • the molar ratio of the Al 2 O 3 (alumina) equivalent amount of the aluminum source and the total amount of alumina in the glass frit and the TiO 2 (titania) equivalent amount of the titanium source is: It adjusts so that it may become in the said range in a raw material mixture.
  • silicon source only 1 type may be used and 2 or more types may be used together.
  • the particle size of the silicon source is not particularly limited, but the particle size corresponding to a volume-based cumulative percentage of 50% (which may be referred to as D50 or average particle size) measured by a laser diffraction method is in the range of 0.5 to 30 ⁇ m.
  • the green molded body comprising a silicon source
  • the amount is preferably 0.1 to 10 parts by weight, more preferably 5 parts by weight or less, in terms of SiO 2 (silica) with respect to parts by weight.
  • the content of the silicon source in the green molded body is more preferably 2 wt% or more and 5 wt% or less in the inorganic compound source contained in the green molded body.
  • the silicon source may contain trace components that are derived from the raw materials or inevitably contained in the production process.
  • a compound containing two or more metal elements among titanium, aluminum, silicon, and magnesium can be used as a raw material.
  • a compound containing two or more metal elements among titanium, aluminum, silicon, and magnesium can be used as a raw material.
  • such a compound can be considered to be the same as a mixture of the respective metal source compounds, and based on such an idea, an aluminum source, a titanium source, a magnesium source and silicon in the green molded body The amount of source is adjusted within the above range.
  • the green molded body can contain aluminum titanate or aluminum magnesium titanate.
  • the aluminum magnesium titanate when aluminum magnesium titanate is used as a component of the green molded body, the aluminum magnesium titanate contains a titanium source, an aluminum source, and magnesium. It corresponds to the raw material which has a source.
  • the green molded body contains a plasticizer.
  • This plasticizer is usually a liquid and has a viscosity at 20 ° C. of 1000 mPa ⁇ s or more, preferably 2000 mPa ⁇ s or more, and preferably 4000 mPa ⁇ s or less. If it exceeds 4000 mPa ⁇ s, it may be difficult to measure.
  • plasticizers examples include polyoxyalkylene alkyl ethers.
  • Commercially available products include, for example, “UNILUB 50MB-72” (polyoxyethylene polyoxypropylene butyl ether, viscosity at 20 ° C. of 1020 mPa ⁇ s) manufactured by NOF Corporation, “UNILUB 50MB-168” (poly Oxyethylene polyoxypropylene butyl ether and a viscosity at 20 ° C. of 2880 mPa ⁇ s).
  • the amount of the plasticizer is preferably 0.1 to 20 parts by weight with respect to the total amount of the aluminum source, the titanium source, the magnesium source and the silicon source, that is, 100 parts by weight of the inorganic compound source powder.
  • the amount is more preferably 1 to 10 parts by weight, still more preferably 0.1 to 6 parts by weight.
  • the green molded body contains an organic binder.
  • This organic binder is preferably water-soluble.
  • the viscosity of a 2% by weight aqueous solution of the organic binder is preferably 5000 mPa ⁇ s or more, and more preferably 10,000 mPa ⁇ s or more.
  • the viscosity is a viscosity when the aqueous solution is 20 ° C.
  • the organic binder examples include celluloses such as methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose; alcohols such as polyvinyl alcohol; salts such as lignin sulfonate.
  • the amount of the organic binder is preferably 20 parts by weight or less, more preferably 15 parts by weight with respect to 100 parts by weight of the total amount of the aluminum source, the titanium source, the magnesium source and the silicon source, that is, the inorganic compound source powder. Or less, more preferably 6 parts by weight.
  • an organic binder is 0.1 weight part or more, More preferably, it is 3 weight part or more.
  • the green molded body can contain other additives.
  • Other additives are, for example, pore formers, lubricants, dispersants, and solvents.
  • the pore-forming agent examples include carbon materials such as graphite; resins such as polyethylene, polypropylene, and polymethyl methacrylate; plant materials such as starch, nut shells, walnut shells, and corn; ice; and dry ice.
  • the amount of pore-forming agent added is preferably 0 to 40 parts by weight, more preferably the total amount of aluminum source, titanium source, magnesium source and silicon source, that is, 100 parts by weight of the inorganic compound source powder. Is 0 to 25 parts by weight.
  • Lubricants include alcohols such as glycerine; higher fatty acids such as caprylic acid, lauric acid, palmitic acid, alginic acid, oleic acid and stearic acid; and stearic acid metal salts such as aluminum stearate.
  • the addition amount of the lubricant is preferably 0 to 10 parts by weight, more preferably 100 parts by weight of the total amount of the aluminum source, titanium source, magnesium source and silicon source, that is, 100 parts by weight of the inorganic compound source powder. 0.1 to 5 parts by weight.
  • the dispersant examples include inorganic acids such as nitric acid, hydrochloric acid and sulfuric acid; organic acids such as oxalic acid, citric acid, acetic acid, malic acid and lactic acid; alcohols such as methanol, ethanol and propanol; ammonium polycarboxylate; Surfactants such as oxyalkylene alkyl ethers are listed.
  • the addition amount of the dispersant is preferably 0 to 20 parts by weight, more preferably the total amount of the aluminum source, the titanium source, the magnesium source and the silicon source, that is, 100 parts by weight of the inorganic compound source powder. 2 to 8 parts by weight.
  • the solvent for example, alcohols such as methanol, ethanol, butanol and propanol; glycols such as propylene glycol, polypropylene glycol and ethylene glycol; and water can be used. Of these, water is preferable, and ion-exchanged water is more preferably used from the viewpoint of few impurities.
  • the amount of the solvent used is preferably 10 to 100 parts by weight, more preferably the total amount of the aluminum source, titanium source, magnesium source and silicon source, that is, 100 parts by weight of the inorganic compound source powder. Is 20 to 80 parts by weight.
  • the shape of the green molded body is not particularly limited, and can take any shape depending on the application, and examples thereof include a rod shape, a tube shape, a plate shape, and a crucible shape.
  • a so-called honeycomb shape that is, a shape having a large number of through holes extending in the same direction and a large number of flow paths formed by the large number of through holes separated by partition walls.
  • a so-called honeycomb shape that is, a shape having a large number of through holes extending in the same direction and a large number of flow paths formed by the large number of through holes separated by partition walls.
  • honeycomb shape that is, a shape having a large number of through holes extending in the same direction and a large number of flow paths formed by the large number of through holes separated by partition walls.
  • a green molded object can be manufactured as follows, for example. First, an inorganic compound source powder, an organic binder, a plasticizer, and additives such as a solvent added as necessary are prepared.
  • the inorganic compound source powder includes an aluminum source powder, a titanium source powder, and a magnesium source powder and a silicon source powder blended as necessary. And these are mixed with a kneader etc. by the above-mentioned ratio, a raw material mixture is obtained, and the green molded object of a desired shape can be obtained by shape
  • molding method is not specifically limited, For example, the method of using a uniaxial press machine, an extrusion molding machine, a tableting machine, a granulator etc. is mentioned.
  • An aluminum titanate fired body can be obtained by calcining (degreasing) and firing the green molded body described above.
  • the obtained aluminum titanate fired body is a fired body containing aluminum titanate crystals.
  • shrinkage during firing can be suppressed, and cracking of the obtained aluminum titanate fired body is effective.
  • cracking of the obtained aluminum titanate fired body is effective.
  • the pore shape of the porous aluminum titanate crystal produced by firing can be maintained.
  • Calcination is a process for removing the organic binder in the green molded body and additives blended as necessary by burning, decomposition, etc., typically until reaching the firing temperature.
  • the temperature rising stage for example, a temperature range of 150 to 900 ° C.
  • the calcination (degreasing) step it is preferable to suppress the temperature increase rate as much as possible.
  • the firing temperature in firing the green molded body is usually 1300 ° C. or higher, preferably 1400 ° C. or higher. Moreover, it is preferable that a calcination temperature is 1650 degrees C or less, More preferably, it is 1550 degrees C or less.
  • the rate of temperature increase up to the firing temperature is not particularly limited, but is usually 1 ° C./hour to 500 ° C./hour.
  • the green molded body contains the silicon source powder, it is preferable to provide a step of holding at a temperature range of 1100 to 1300 ° C. for 3 hours or more before the firing step. Thereby, melting and diffusion of the silicon source powder can be promoted.
  • Firing is usually carried out in the atmosphere, but depending on the type and usage ratio of the raw material powder used, that is, aluminum source powder, titanium source powder, magnesium source powder and silicon source powder, an inert gas such as nitrogen gas or argon gas.
  • the firing may be performed in a reducing gas such as carbon monoxide gas or hydrogen gas. Further, the firing may be performed in an atmosphere in which the water vapor partial pressure is lowered.
  • Calcination is usually performed using a normal firing furnace such as a tubular electric furnace, a box-type electric furnace, a tunnel furnace, a far-infrared furnace, a microwave heating furnace, a shaft furnace, a reflection furnace, or a roller hearth furnace. Firing may be performed batchwise or continuously.
  • a normal firing furnace such as a tubular electric furnace, a box-type electric furnace, a tunnel furnace, a far-infrared furnace, a microwave heating furnace, a shaft furnace, a reflection furnace, or a roller hearth furnace. Firing may be performed batchwise or continuously.
  • the time required for firing may be sufficient time for the green molded body to transition to the aluminum titanate crystal, and varies depending on the amount of the green molded body, the type of the firing furnace, the firing temperature, the firing atmosphere, etc. Preferably it is ⁇ 24 hours.
  • a desired aluminum titanate fired body can be obtained.
  • Such an aluminum titanate fired body has a shape that substantially maintains the shape of the green molded body immediately after molding.
  • the obtained aluminum titanate fired body can be processed into a desired shape by grinding or the like.
  • the aluminum titanate fired body obtained by the above-described method is used for, for example, firing furnace jigs such as crucibles, setters, mortars, and furnace materials; catalyst carriers; exhaust gas purification of internal combustion engines such as diesel engines and gasoline engines. Ceramic filters such as exhaust gas filters, filtration filters used for filtering food and drink such as beer, selective permeation filters for selectively permeating gas components generated during petroleum refining, such as carbon monoxide, carbon dioxide, nitrogen, oxygen, etc. It can be suitably applied to electronic components such as substrates and capacitors. Among these, when used as a ceramic filter, the aluminum titanate fired body has a high pore volume and an open porosity, so that good filter performance can be maintained over a long period of time.
  • the aluminum titanate fired body may contain a crystal pattern of alumina, titania or the like in addition to the crystal pattern of aluminum titanate or aluminum magnesium titanate.
  • the aluminum titanate fired body contains aluminum magnesium titanate crystals, it can be expressed by a composition formula: Al 2 (1-x) Mg x Ti (1 + x) O 5 , and the value of x is 0.03 or more Preferably, it is 0.03 or more and 0.15 or less, More preferably, it is 0.03 or more and 0.12 or less.
  • the aluminum titanate fired body obtained by the present invention can contain trace components that are derived from the raw materials or are unavoidably included in the production process.
  • (1) Shape retention of green molded body As shown to (a) of FIG. 1, the test piece 10 of the magnitude
  • the vertical displacement X of the lower surface of the portion 10b on the other end side of the test piece 10 60 seconds after removing the support was measured.
  • the vertical displacement X was measured at a position 25 mm away from the end surface 5 b of the pedestal 5 in the horizontal direction.
  • the displacement was measured for a total of three test pieces, and the average value was obtained.
  • Viscosity of plasticizer at 20 ° C. The viscosity of the plasticizer before mixing was measured under the condition of 20 ° C. using a B-type viscometer.
  • Example 1 A green molded body was obtained using the following as the inorganic compound source powder.
  • Mixing composition of the inorganic compound source powder, alumina [Al 2 O 3], titania [TiO 2], magnesia [MgO] and silica in a molar percentage of [SiO 2] terms, [Al 2 O 3] / [TiO 2] / [MgO] / [SiO 2 ] 35.1% / 51.3% / 9.6% / 4.0%.
  • the content of the silicon source powder in the total amount of the aluminum source powder, the titanium source powder, the magnesium source powder and the silicon source powder was 4.0% by weight.
  • Aluminum source powder ⁇ -alumina powder having an average particle diameter shown in Table 1 24.6 parts by weight
  • Magnesium source powder 15.7 parts by weight of magnesia spinel powder having an average particle size shown in Table 1 (4) Silicon source powder Glass frit having an average particle size shown in Table 1 (“CK0832” manufactured by Takara Standard) 3.4 parts by weight
  • the green molded body is quickly heated in a microwave dryer, then dried by holding at 100 ° C. for 5 hours, and then calcined (degreasing) to remove the binder in an air atmosphere and fired.
  • a porous sintered body of aluminum magnesium titanate was obtained.
  • the maximum temperature during firing was 1450 ° C., and the holding time at the maximum temperature was 5 hours.
  • Example 2 As a plasticizer, instead of 4.6 parts by weight of polyoxyethylene polyoxypropylene butyl ether (trade name: UNILOVE 50MB-72) having a viscosity of 1020 mPa ⁇ s at 20 ° C., polyoxyethylene having a viscosity of 2880 mPa ⁇ s at 20 ° C. Except for using 4.6 parts by weight of polyoxypropylene butyl ether (trade name: Unilube 50MB-168), the same operation as in Example 1 was performed to obtain a green molded body and a porous sintered body of aluminum magnesium titanate. . The green molded body had a shape retention (displacement X) of 5.0 mm.
  • ⁇ Comparative Example 1> As a plasticizer, instead of 4.6 parts by weight of polyoxyethylene polyoxypropylene butyl ether (trade name: UNILOVE 50MB-72) having a viscosity of 1020 mPa ⁇ s at 20 ° C., polyoxyethylene having a viscosity of 326 mPa ⁇ s at 20 ° C. Except for using 4.6 parts by weight of polyoxypropylene butyl ether (trade name: Unilube 50MB-26), the same operation as in Example 1 was performed to obtain a green molded body and a porous sintered body of aluminum magnesium titanate. . The green molded body had a shape retention (displacement X) of 10.5 mm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Filtering Materials (AREA)

Abstract

L'invention concerne un corps moulé cru qui contient une poudre source de composé inorganique, un liant organique, et un plastifiant. Ladite poudre source de composé inorganique contient une poudre source d'aluminium et une poudre source de titane. La viscosité dudit plastifiant à 20°C, est supérieure ou égale à 1000mPa.s.
PCT/JP2011/065882 2010-07-14 2011-07-12 Corps moulé cru, et procédé de fabrication de corps cuit en titanate d'aluminium WO2012008447A1 (fr)

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EP3990127A4 (fr) * 2019-06-29 2023-07-19 Aquaguidance Technologies, Ltd. Procédé de formation de milieux filtrants poreux

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JP2016108209A (ja) * 2014-12-10 2016-06-20 住友電気工業株式会社 セラミックス成形体の製造方法及びセラミックス焼結体の製造方法

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JPH07197071A (ja) * 1993-12-29 1995-08-01 Mitsubishi Cable Ind Ltd 潤滑剤組成物
JP2007022870A (ja) * 2005-07-19 2007-02-01 Nippon Shokubai Co Ltd セラミックグリーン成形体製造用混合物
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JPH0616870A (ja) * 1990-11-27 1994-01-25 Hoechst Ag 可塑剤および金属およびセラミック粉末材料の射出成 形組成物
JPH07197071A (ja) * 1993-12-29 1995-08-01 Mitsubishi Cable Ind Ltd 潤滑剤組成物
JP2007022870A (ja) * 2005-07-19 2007-02-01 Nippon Shokubai Co Ltd セラミックグリーン成形体製造用混合物
WO2009122538A1 (fr) * 2008-03-31 2009-10-08 イビデン株式会社 Structure en nid d'abeilles
WO2010067859A1 (fr) * 2008-12-11 2010-06-17 住友化学株式会社 Processus de fabrication de produit cuit à base de titanate d’aluminium

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EP3990127A4 (fr) * 2019-06-29 2023-07-19 Aquaguidance Technologies, Ltd. Procédé de formation de milieux filtrants poreux

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