JP2011051846A - Method for manufacturing ceramic sintered compact - Google Patents

Method for manufacturing ceramic sintered compact Download PDF

Info

Publication number
JP2011051846A
JP2011051846A JP2009203003A JP2009203003A JP2011051846A JP 2011051846 A JP2011051846 A JP 2011051846A JP 2009203003 A JP2009203003 A JP 2009203003A JP 2009203003 A JP2009203003 A JP 2009203003A JP 2011051846 A JP2011051846 A JP 2011051846A
Authority
JP
Japan
Prior art keywords
aluminum
source powder
firing
powder
magnesium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
JP2009203003A
Other languages
Japanese (ja)
Inventor
Makio Kimura
真喜男 木村
Keiichiro Suzuki
敬一郎 鈴木
Masayuki Narumi
雅之 鳴海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to JP2009203003A priority Critical patent/JP2011051846A/en
Priority to PCT/JP2010/064930 priority patent/WO2011027783A1/en
Publication of JP2011051846A publication Critical patent/JP2011051846A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/12—Travelling or movable supports or containers for the charge
    • 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
    • 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
    • C04B35/478—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
    • 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
    • C04B35/622—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
    • 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
    • C04B35/622—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
    • C04B35/638—Removal thereof
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • C04B2235/3249—Zirconates or hafnates, e.g. zircon containing also titanium oxide or titanates, e.g. lead zirconate titanate (PZT)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/34—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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/34—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
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/34—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
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/386—Boron nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3865—Aluminium nitrides
    • C04B2235/3869—Aluminium oxynitrides, e.g. AlON, sialon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3886—Refractory metal nitrides, e.g. vanadium nitride, tungsten nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/401—Alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/441—Alkoxides, e.g. methoxide, tert-butoxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/446—Sulfides, tellurides or selenides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6584—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage below that of air
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9615—Linear firing shrinkage
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9623—Ceramic setters properties

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Charging Or Discharging (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of manufacturing a sintered compact showing large shrinkage at firing (firing shrinkage), without destroying the shape such as a honeycomb shape of a molded product. <P>SOLUTION: The method for manufacturing the ceramic sintered compact is a method comprising a step of firing the molded product, provided that a linear shrinkage of dimension of a fired product to dimension of the molded product (linear shrinkage (%)=((dimension of molded product)-(dimension of fired product))/(dimension of molded product)×100) is ≥1%. At firing, the molded product is placed on spherical particles spread on a mat. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、セラミックス焼成体の製造方法に関する。   The present invention relates to a method for producing a ceramic fired body.

セラミックスは、その構成する元素によって種々のものが知られている。中でも、チタン酸アルミニウム系セラミックスは、構成元素としてチタンおよびアルミニウムを含み、Ｘ線回折スペクトルにおいて、チタン酸アルミニウムの結晶パターンを有するセラミックスであって、耐熱性、低熱膨張性に優れたセラミックスとして知られている。チタン酸アルミニウム系セラミックスは、従来からルツボのような焼結用の冶具などとして用いられてきたが、近年では、ディーゼルエンジンなどの内燃機関から排出される排ガスに含まれる微細なカーボン粒子を捕集するためのセラミックスフィルターを構成する材料として、産業上の利用価値が高まっている。   Various ceramics are known depending on the constituent elements. Among these, 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 are excellent in heat resistance and low thermal expansion. ing. Aluminum titanate-based ceramics have been used as a sintering tool such as a crucible, but in recent years, fine carbon particles contained in exhaust gas discharged from internal combustion engines such as diesel engines are collected. As a material constituting a ceramic filter for industrial use, industrial utility value is increasing.

チタン酸アルミニウム系セラミックスの製造方法としては、チタニアなどのチタニウム源化合物の粉末（以下において、チタニウム源粉末ということがある）およびアルミナなどのアルミニウム源化合物の粉末（以下において、アルミニウム源粉末ということがある）を含む原料混合物を焼成する方法が知られている（特許文献１）。   As a method for producing an aluminum titanate-based ceramic, a powder of a titanium source compound such as titania (hereinafter sometimes referred to as a titanium source powder) and a powder of an aluminum source compound such as alumina (hereinafter referred to as an aluminum source powder). There is known a method of firing a raw material mixture containing (A).

しかし、チタン酸アルミニウムは、これをアルミニウム源粉末およびチタニウム源粉末を含む原料粉末または該原料粉末の成形体を焼成することにより調製する場合、焼成時に大きく収縮する、すなわち、焼成収縮率が高いという課題を有していた。焼成収縮率が高いと、焼成時に割れが発生しやすくなる。   However, when aluminum titanate is prepared by firing a raw material powder containing an aluminum source powder and a titanium source powder or a molded body of the raw material powder, the aluminum titanate is greatly shrunk at the time of firing, that is, the firing shrinkage rate is high. Had problems. If the firing shrinkage rate is high, cracks are likely to occur during firing.

かかる課題を解決すべく、特許文献２には、特定の粒径分布特性を示すチタニア粉末、およびアルミナ粉末を含有する原料混合物をハニカム形状に成形し、該成形体を焼成することによりチタン酸アルミニウム質セラミックハニカム構造体を製造する方法が開示されている。   In order to solve such a problem, Patent Document 2 discloses aluminum titanate by forming a raw material mixture containing a titania powder exhibiting specific particle size distribution characteristics and an alumina powder into a honeycomb shape and firing the formed body. A method of manufacturing a quality ceramic honeycomb structure is disclosed.

また、一般にセラミックス焼成体の製造においては、上記のように焼成時に発生する割れを防止するための種々の方法が検討されている（たとえば、特許文献３など）。   In general, in the production of a ceramic fired body, various methods for preventing cracks occurring during firing as described above have been studied (for example, Patent Document 3).

国際公開第０５／１０５７０４号パンフレットWO05 / 105704 pamphlet 国際公開第０８／０７８７４７号パンフレットWO08 / 0778747 Pamphlet 特開平７−２０８８７３号公報JP-A-7-208873

一方、チタン酸アルミニウム系セラミックスからなる焼成体を、たとえば上記セラミックスフィルターに適用する場合、フィルター性能（排ガス処理能力、高すす堆積能力、圧力損失等）向上の観点から、これを構成するチタン酸アルミニウム系焼成体には、多孔性に優れる（大きい細孔径および開気孔率を有する）ことが要求される。また、チタン酸アルミニウム系セラミックスからなる多孔質セラミックス成形体を、上記セラミックスフィルター、特には、ディーゼルエンジンの排ガスフィルター（ディーゼル微粒子フィルター；Ｄｉｅｓｅｌ Ｐａｒｔｉｃｕｌａｔｅ Ｆｉｌｔｅｒ、以下ＤＰＦとも称する）に適用する場合、該成形体には、適切に制御された細孔特性を有することが求められる。   On the other hand, when a fired body made of an aluminum titanate-based ceramic is applied to, for example, the above ceramic filter, the aluminum titanate constituting this from the viewpoint of improving filter performance (exhaust gas treatment capacity, high soot deposition capacity, pressure loss, etc.) The fired body is required to be excellent in porosity (having a large pore diameter and open porosity). Further, when a porous ceramic molded body made of an aluminum titanate ceramic is applied to the ceramic filter, particularly an exhaust gas filter (diesel particulate filter; hereinafter also referred to as DPF) of a diesel engine, the molded body. Is required to have appropriately controlled pore characteristics.

このようなフィルターは、図１の模式図に示すようなセラミックスハニカム構造体１０を含む。図１に示すセラミックスハニカム構造体１０は、複数の流路３を形成する隔壁２と外周壁１とからなるハニカム形状を有し、複数の流路３は互い違いに封止部５ａにより封止されている。図１のＩＩ−ＩＩに沿った断面図を図２に示す。上記セラミックスハニカム構造体１０は、上流側が封止部５ａにより封止された流路４と下流側が封止部５ｂにより封止された流路３とが交互に配置された構造を有する。図１および図２に示すように、セラミックスハニカム構造体の全体にわたりハニカム形状が正確に形成されていることで、フィルター性能がより高いものとなる。   Such a filter includes a ceramic honeycomb structure 10 as shown in the schematic diagram of FIG. A ceramic honeycomb structure 10 shown in FIG. 1 has a honeycomb shape composed of partition walls 2 and outer peripheral walls 1 forming a plurality of flow paths 3, and the plurality of flow paths 3 are alternately sealed by sealing portions 5a. ing. A cross-sectional view along II-II in FIG. 1 is shown in FIG. The ceramic honeycomb structure 10 has a structure in which the flow path 4 whose upstream side is sealed by the sealing portion 5a and the flow path 3 whose downstream side is sealed by the sealing portion 5b are alternately arranged. As shown in FIGS. 1 and 2, the honeycomb shape is accurately formed over the entire ceramic honeycomb structure, so that the filter performance is higher.

上記課題に鑑み、本発明の目的は、ハニカム状などの成形体形状を損なわず、焼成時の線収縮率（焼成収縮率）が大きい焼成体を製造しうる方法を提供することにある。   In view of the above problems, an object of the present invention is to provide a method capable of producing a fired body having a large linear shrinkage rate (firing shrinkage rate) at the time of firing without impairing the shape of a formed body such as a honeycomb shape.

本発明は、セラミックス焼成体の製造方法に関し、成形体を焼成する工程を含むセラミックス焼成体の製造方法であって、成形体の寸法に対する焼成体の寸法の線収縮率（線収縮率（％）＝（成形体の寸法−焼成体の寸法）／（成形体の寸法）×１００）が１％以上であり、成形体を、敷物上に敷いた球状粒子上に配置した状態で焼成することを特徴とする。   The present invention relates to a method for producing a ceramic fired body, which is a method for producing a ceramic fired body including a step of firing a formed body, wherein the linear shrinkage rate (linear shrinkage rate (%)) of the size of the fired body with respect to the size of the formed body. = (Dimension of the molded body−dimension of the fired body) / (dimension of the molded body) × 100) is 1% or more, and the molded body is fired in a state of being arranged on the spherical particles laid on the rug. Features.

上記球状粒子の直径が０．０３ｍｍ以上３ｍｍ以下であることが好ましい。また、上記球状粒子の真球度が０．６以上１．０以下であることが好ましい。   The spherical particles preferably have a diameter of 0.03 mm to 3 mm. The sphericity of the spherical particles is preferably 0.6 or more and 1.0 or less.

上記球状粒子は、安定化酸化ジルコニウム、酸化アルミニウム、窒化アルミニウム、酸化マグネシウム、アルミノケイ酸塩化合物、二酸化ケイ素、炭化ケイ素、チタン酸アルミニウム、チタン酸アルミニウムマグネシウム、チタン酸マグネシウム、窒化チタニウムからなる群より選択される１つの化合物または２つ以上の混合物であることが好ましい。   The spherical particles are selected from the group consisting of stabilized zirconium oxide, aluminum oxide, aluminum nitride, magnesium oxide, aluminosilicate compound, silicon dioxide, silicon carbide, aluminum titanate, aluminum magnesium titanate, magnesium titanate, titanium nitride One compound or a mixture of two or more is preferred.

上記成形体は、球状粒子上に配置される面の断面積が７８５０ｍｍ2以上であり、高さが５０ｍｍ以上、重量が５００ｇ以上の場合に、本発明の方法により焼成体を製造することができる。 The molded body can be produced by the method of the present invention when the cross-sectional area of the surface disposed on the spherical particles is 7850 mm 2 or more, the height is 50 mm or more, and the weight is 500 g or more. .

本発明の製造方法は、上記成形体を構成する原料中に有機物を質量比で１０％以上含む場合に好適である。   The manufacturing method of this invention is suitable when the organic substance is contained in the raw material which comprises the said molded object 10% or more by mass ratio.

上記成形体の形状としては、たとえばハニカム形状とすることができる。
本発明の製造方法には、上記成形体は、アルミニウム源粉末およびチタニウム源粉末を含み、成形体は焼成によりチタン酸アルミニウム組成物を形成する態様が含まれる。 The shape of the molded body can be, for example, a honeycomb shape.
The production method of the present invention includes an embodiment in which the molded body includes an aluminum source powder and a titanium source powder, and the molded body forms an aluminum titanate composition by firing.

また、本発明の製造方法には、上記成形体は、アルミニウム源粉末、チタニウム源粉末、およびマグネシウム源粉末を含み、成形体は焼成によりチタン酸アルミニウムマグネシウム組成物を形成する態様が含まれる。   The production method of the present invention includes an embodiment in which the molded body includes an aluminum source powder, a titanium source powder, and a magnesium source powder, and the molded body forms an aluminum magnesium titanate composition by firing.

さらに、本発明の製造方法には、上記成形体は、アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末、およびケイ素源粉末を含み、成形体は焼成によりチタン酸アルミニウムマグネシウム組成物を形成する態様が含まれる。   Furthermore, in the production method of the present invention, the molded body includes an aluminum source powder, a titanium source powder, a magnesium source powder, and a silicon source powder, and the molded body forms an aluminum magnesium titanate composition by firing. included.

本発明の製造方法によれば、焼成による割れがない状態で、成形体からの収縮率が大きい焼成体を製造することができる。   According to the production method of the present invention, it is possible to produce a fired body having a large shrinkage rate from the formed body without cracking due to firing.

セラミックスハニカム構造体の一例を示す模式図である。It is a schematic diagram which shows an example of a ceramic honeycomb structure. 図１のＩＩ−ＩＩに沿った断面図である。It is sectional drawing along II-II of FIG. 焼成工程における成形体の配置の一例を示す模式図である。It is a schematic diagram which shows an example of arrangement | positioning of the molded object in a baking process. 脱脂工程における成形体の配置の一例を示す模式図である。It is a schematic diagram which shows an example of arrangement | positioning of the molded object in a degreasing process.

以下、本発明についてさらに詳細に説明する。なお、以下の実施の形態の説明では、図面を用いて説明しているが、本願の図面において同一の参照符号を付したものは、同一部分または相当部分を示している。また、本発明は図面に示される形態に限定されるものではない。   Hereinafter, the present invention will be described in more detail. In the following description of the embodiments, the description is made with reference to the drawings. In the drawings of the present application, the same reference numerals denote the same or corresponding parts. Further, the present invention is not limited to the form shown in the drawings.

＜セラミックス焼成体の製造方法＞
本発明におけるセラミックス焼成体は、成形体を焼成する工程（以下において焼成工程ということがある）を含むセラミックス焼成体の製造方法により製造される。本発明の製造方法には、後述のように、焼成工程の前に施される脱脂工程などの他の工程を含んでもよい。本発明において成形体とは、未焼成のセラミックス成形体をいい、成形後の乾燥工程や脱脂工程の後においても成形体に含まれる。 <Method for manufacturing ceramic fired body>
The ceramic fired body in the present invention is produced by a method for producing a ceramic fired body including a step of firing a formed body (hereinafter sometimes referred to as a firing step). As described later, the production method of the present invention may include other steps such as a degreasing step performed before the firing step. In the present invention, the molded body refers to an unfired ceramic molded body, and is included in the molded body even after a drying step and a degreasing step after molding.

図３は上記焼成工程における成形体の配置の一例を示す模式図である。本発明のセラミックス焼成体の製造方法は、図３に示すように、成形体２０を、敷物８上に敷いた球状粒子７上に配置した状態で焼成することを特徴とする。球状粒子７と成形体２０との間には図３に示すように台座６ａを配置してもよい。上記球状粒子７は、敷物８の表面全体を覆うように配置すればよく、少なくとも成形体２０の底面全体の面積と同じかそれよりも大きい領域に配置する。   FIG. 3 is a schematic view showing an example of the arrangement of the molded bodies in the firing step. As shown in FIG. 3, the method for producing a ceramic fired body according to the present invention is characterized in that the shaped body 20 is fired in a state of being arranged on spherical particles 7 laid on a rug 8. A pedestal 6a may be disposed between the spherical particles 7 and the molded body 20 as shown in FIG. The spherical particles 7 may be disposed so as to cover the entire surface of the rug 8, and are disposed in a region at least equal to or larger than the area of the entire bottom surface of the molded body 20.

敷物８は、図３に示すようにスペーサー９上に配置することが好ましい。スペーサーを用いることで、成形体全体に効率よく熱を伝播させることができる。また、焼成工程において上記台座６ａを用いた場合であっても、球状粒子の存在により、成形体が収縮することで発生する底面との摩擦力を緩和する効果は奏される。上記敷物の形状は特に限定されず、このような焼成において用いられる公知のムライト製の敷物などを用いることができる。   The rug 8 is preferably disposed on the spacer 9 as shown in FIG. By using the spacer, heat can be efficiently propagated throughout the molded body. In addition, even when the pedestal 6a is used in the firing step, the presence of the spherical particles has an effect of reducing the frictional force with the bottom surface that is generated when the molded body contracts. The shape of the rug is not particularly limited, and a known mullite rug used in such firing can be used.

＜球状粒子＞
本発明において、上記球状粒子は成形体を焼成する際の収縮で発生する応力による成形体または焼成体に発生する割れを防止するために用いる。本発明者らは、球状粒子を配置することにより、成形体の底面に係る摩擦が軽減され、その結果、焼成の際与えられる応力を緩和することができ、従来の方法では焼成体に発生していた割れを防止できることを見出した。球状粒子は、上記のように敷物上に配置されるものであり、成形体と直接接するように配置してもよいし、台座を介して配置してもよい。 <Spherical particles>
In the present invention, the spherical particles are used for preventing cracks generated in the molded body or fired body due to stress generated by shrinkage when the molded body is fired. By arranging the spherical particles, the present inventors can reduce the friction related to the bottom surface of the molded body, and as a result, can relieve the stress applied during firing, which occurs in the fired body in the conventional method. It was found that it was possible to prevent cracking. The spherical particles are disposed on the rug as described above, and may be disposed so as to be in direct contact with the molded body or may be disposed via a pedestal.

上記球状粒子は、その上に積載する成形体の形状（大きさ、質量）にもよるが、直径が０．０３ｍｍ以上３ｍｍ以下であることが好ましい。球状粒子の直径は０．１ｍｍ以上０．５ｍｍ以下であることがより好ましい。球状粒子がこのような直径を満たす場合は、成形体の焼成時に成形体の底面に係る摩擦力が低減され、焼成の際与えられる応力をより軽減することができ、焼成体全体にわたり割れの発生を防ぐことができる。このような効果は、特にハニカム形状を有する成形体を焼成する際に顕著である。   The spherical particles preferably have a diameter of 0.03 mm or more and 3 mm or less, although it depends on the shape (size, mass) of the molded product loaded thereon. The diameter of the spherical particles is more preferably from 0.1 mm to 0.5 mm. When the spherical particles satisfy such a diameter, the frictional force applied to the bottom surface of the molded body is reduced during the firing of the molded body, the stress applied during the firing can be further reduced, and cracks occur throughout the fired body. Can be prevented. Such an effect is particularly remarkable when a formed body having a honeycomb shape is fired.

上記球状粒子は、直径が±０．１ｍｍ程度の誤差範囲にあるものを配置することが望ましい。このように同程度の直径を有する球状粒子を配置することによって、成形体を球状粒子上に安定に積載することができ、また、応力の緩和が均一となるので、焼成体の割れの発生をより確実に行なうことができる。本発明において、上記球状粒子の直径は、顕微鏡観察により決定される値である。   It is desirable to arrange the spherical particles having a diameter within an error range of about ± 0.1 mm. By arranging the spherical particles having the same diameter in this way, the molded body can be stably loaded on the spherical particles, and the stress can be uniformly relaxed. This can be done more reliably. In the present invention, the diameter of the spherical particles is a value determined by microscopic observation.

上記球状粒子は、それぞれの粒子の真球度が０．６以上１．０以下であることが望ましい。球状粒子の真球度が上記範囲を満たす場合は、成形体を球状粒子上に安定に積載することができ、また、焼成時の成形体から球状粒子に係る応力を緩和することができる。本発明における真球度は、顕微鏡観察写真の画像解析により決定される球状粒子の周長から、真球度＝（球状粒子の投影面積と同じ面積を持つ円の周長）／（測定された球状粒子の周長）により決定される値をいう。   The spherical particles desirably have a sphericity of 0.6 to 1.0. When the sphericity of the spherical particles satisfies the above range, the compact can be stably loaded on the spherical particles, and the stress related to the spherical particles can be relaxed from the compact during firing. The sphericity in the present invention was measured from the circumference of spherical particles determined by image analysis of microscopic observation photographs, and the degree of sphericity = (circle circumference having the same area as the projected area of spherical particles) / (measured) It is a value determined by the circumference of the spherical particles.

上記球状粒子は、敷物表面上に単層で配置するかまたは２層以上の積層状態として配置してもよいが、球状粒子の直径が上記のように±０．１ｍｍ程度の誤差範囲にある球状粒子を単層で敷物表面に敷き詰めるように配置した場合に、すなわち、球状粒子による層の厚みが好ましくは０．１ｍｍ以上０．５ｍｍ以下の場合に、特にハニカム形状を有する焼成体の割れの発生を完全に阻止することができる。上記のように球状粒子を単層で配置した場合は、積層状態とした場合に比べて、特にハニカム形状を有する成形体の底面に対する摩擦係数を軽減することができ、この摩擦係数の低減が焼成の際に与えられる応力の緩和効果をもたらすことがわった。   The spherical particles may be arranged in a single layer on the surface of the rug or may be arranged in a laminated state of two or more layers, but the spherical particles have a spherical particle diameter within an error range of about ± 0.1 mm as described above. When the particles are arranged so as to be spread on the surface of the rug as a single layer, that is, when the layer thickness of the spherical particles is preferably 0.1 mm or more and 0.5 mm or less, particularly the occurrence of cracks in the fired body having a honeycomb shape Can be completely prevented. When spherical particles are arranged in a single layer as described above, the coefficient of friction with respect to the bottom surface of the formed body having a honeycomb shape can be reduced, compared with the case where a laminated state is formed. It was found that the effect of relieving the stress applied during the process was brought about.

本発明における上記球状粒子は、安定化酸化ジルコニウム、酸化アルミニウム、窒化アルミニウム、酸化マグネシウム、アルミノケイ酸塩化合物、二酸化ケイ素、炭化ケイ素、チタン酸アルミニウム、チタン酸アルミニウムマグネシウム、チタン酸マグネシウム、窒化チタニウムからなる群より選択される１つの化合物または２以上の混合物を用いることができる。このような化合物の球状粒子は、上記直径および真球度を満たすものを調整し易い。上記のように混合物を用いても、球状粒子の直径が同程度であれば本発明の効果は奏される。   The spherical particles in the present invention are composed of stabilized zirconium oxide, aluminum oxide, aluminum nitride, magnesium oxide, aluminosilicate compound, silicon dioxide, silicon carbide, aluminum titanate, aluminum magnesium titanate, magnesium titanate, titanium nitride. One compound selected from the group or a mixture of two or more can be used. The spherical particles of such a compound can be easily adjusted to satisfy the above diameter and sphericity. Even when the mixture is used as described above, the effect of the present invention is exhibited as long as the spherical particles have the same diameter.

＜原料粉末＞
本発明における焼成体は、たとえば、アルミニウム源粉末およびチタニウム源粉末などの原料粉末を含む原料混合物の成形体を焼成することにより製造することができる。上記原料混合物にはマグネシウム源粉末やケイ素源粉末を含んでもよい。原料粉末にアルミニウム源粉末およびチタニウム源粉末を含む場合は、焼成によりチタン酸アルミニウム組成物が形成される。原料粉末にアルミニウム源粉末、チタニウム源粉末およびマグネシウム源粉末を含む場合、またはさらにケイ素源粉末を含む場合は、焼成によりチタン酸アルミニウムマグネシウム組成物が形成される。本発明において、少なくともアルミニウム源粉末およびチタニウム源粉末を原料粉末に含む原料混合物を焼成することにより形成される組成物をチタン酸アルミニウム系焼成体という。このような原料混合物を用いて得られるチタン酸アルミニウム系焼成体は、チタン酸アルミニウム系結晶からなる焼成体である。 <Raw material powder>
The fired body in the present invention can be produced, for example, by firing a molded body of a raw material mixture containing raw material powders such as an aluminum source powder and a titanium source powder. The raw material mixture may contain a magnesium source powder and a silicon source powder. When the raw material powder includes an aluminum source powder and a titanium source powder, an aluminum titanate composition is formed by firing. When the raw material powder includes an aluminum source powder, a titanium source powder, and a magnesium source powder, or further includes a silicon source powder, an aluminum magnesium titanate composition is formed by firing. In the present invention, a composition formed by firing a raw material mixture containing at least an aluminum source powder and a titanium source powder in a raw material powder is referred to as an aluminum titanate-based fired body. The aluminum titanate-based fired body obtained using such a raw material mixture is a fired body made of an aluminum titanate-based crystal.

本発明において用いられる原料混合物に含有されるアルミニウム源粉末は、チタン酸アルミニウム系焼成体を構成するアルミニウム成分となる化合物の粉末である。アルミニウム源粉末としては、たとえば、アルミナ（酸化アルミニウム）の粉末が挙げられる。アルミナの結晶型としては、α型、γ型、δ型、θ型、などが挙げられ、不定形（アモルファス）であってもよい。なかでも、α型のアルミナが好ましく用いられる。   The aluminum source powder contained in the raw material mixture used in the present invention is a powder of a compound that becomes an aluminum component constituting the aluminum titanate-based fired body. Examples of the aluminum source powder include alumina (aluminum oxide) powder. Examples of the crystal type of alumina include α-type, γ-type, δ-type, and θ-type, and may be amorphous (amorphous). Of these, α-type alumina is preferably used.

上記アルミニウム源粉末は、単独で空気中で焼成することによりアルミナに導かれる化合物の粉末であってもよい。かかる化合物としては、たとえばアルミニウム塩、アルミニウムアルコキシド、水酸化アルミニウム、金属アルミニウムなどが挙げられる。   The aluminum source powder may be a powder of a compound led to alumina by firing alone in air. Examples of such a compound include an aluminum salt, aluminum alkoxide, aluminum hydroxide, and metal aluminum.

アルミニウム塩は、無機酸との無機塩であってもよいし、有機酸との有機塩であってもよい。アルミニウム無機塩として具体的には、たとえば、硝酸アルミニウム、硝酸アンモニウムアルミニウムなどのアルミニウム硝酸塩；炭酸アンモニウムアルミニウムなどのアルミニウム炭酸塩などが挙げられる。アルミニウム有機塩としては、たとえば、蓚酸アルミニウム、酢酸アルミニウム、ステアリン酸アルミニウム、乳酸アルミニウム、ラウリン酸アルミニウムなどが挙げられる。   The aluminum salt may be an inorganic salt with an inorganic acid or an organic salt with an organic acid. Specific examples of aluminum inorganic salts include aluminum nitrates such as aluminum nitrate and ammonium aluminum nitrate; and aluminum carbonates such as ammonium aluminum carbonate. Examples of the aluminum organic salt include aluminum oxalate, aluminum acetate, aluminum stearate, aluminum lactate, and aluminum laurate.

また、アルミニウムアルコキシドとして具体的には、たとえば、アルミニウムイソプロポキシド、アルミニウムエトキシド、アルミニウムｓｅｃ−ブトキシド、アルミニウムｔｅｒｔ−ブトキシドなどが挙げられる。   Specific examples of the aluminum alkoxide include aluminum isopropoxide, aluminum ethoxide, aluminum sec-butoxide, aluminum tert-butoxide, and the like.

水酸化アルミニウムとしては、種々の結晶型のものを用いることができ、具体的な結晶型としては、たとえば、ギブサイト型、バイヤライト型、ノロソトランダイト型、ベーマイト型、擬ベーマイト型などが挙げられ、不定形（アモルファス）であってもよい。アモルファスの水酸化アルミニウムとしては、たとえば、アルミニウム塩、アルミニウムアルコキシドなどのような水溶性アルミニウム化合物の水溶液を加水分解して得られるアルミニウム加水分解物も挙げられる。   As aluminum hydroxide, various crystal types can be used, and specific crystal types include, for example, gibbsite type, bayerite type, norosotrandite type, boehmite type, and pseudoboehmite type. It may be indefinite (amorphous). Examples of the 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.

本発明において、アルミニウム源粉末としては、１種のみが用いられてもよいし、２種以上が併用されてもよい。   In this invention, only 1 type may be used as an aluminum source powder, and 2 or more types may be used together.

上記のなかでも、アルミニウム源粉末としては、アルミナ粉末が好ましく用いられ、より好ましくは、α型のアルミナ粉末である。なお、アルミニウム源粉末は、その原料由来あるいは製造工程において不可避的に含まれる微量成分を含有し得る。   Among the above, alumina powder is preferably used as the aluminum source powder, and α-type alumina powder is more preferable. The aluminum source powder can contain trace components derived from the raw materials or inevitably contained in the production process.

上記アルミニウム源粉末としては、市販品をそのまま用いることもできるし、あるいは、市販品のアルミニウム源粉末に対して、たとえば次のような処理を施して所望の粒径分布を満たすアルミニウム源粉末を用いてもよい。
（ａ）市販品のアルミニウム源粉末を、篩い分け等により分級する。
（ｂ）市販品のアルミニウム源粉末を、造粒機等を用いて造粒する。 As the aluminum source powder, a commercially available product can be used as it is, or an aluminum source powder satisfying a desired particle size distribution by applying the following treatment to the commercially available aluminum source powder, for example. May be.
(A) A commercially available aluminum source powder is classified by sieving or the like.
(B) A commercially available aluminum source powder is granulated using a granulator or the like.

ここで、本発明においては、使用するアルミニウム源粉末の、レーザ回折法により測定される体積基準の累積百分率５０％相当粒子径（Ｄ５０）は、２０μｍ以上、６０μｍ以下の範囲内であることが好ましい。アルミニウム源粉末のＤ５０がこの範囲を満たす粉末を用いる場合は、優れた多孔性を示すチタン酸アルミニウム系焼成体が得られる。アルミニウム源粉末のＤ５０は、より好ましくは３０μｍ以上、６０μｍ以下である。   Here, in the present invention, the volume-based cumulative percentage 50% equivalent particle diameter (D50) of the aluminum source powder to be used as measured by a laser diffraction method is preferably in the range of 20 μm or more and 60 μm or less. . When a powder satisfying this range of D50 of the aluminum source powder is used, an aluminum titanate-based fired body exhibiting excellent porosity is obtained. The D50 of the aluminum source powder is more preferably 30 μm or more and 60 μm or less.

上記原料混合物に含有されるチタニウム源粉末は、チタン酸アルミニウム系焼成体を構成するチタン成分となる化合物の粉末であり、かかる化合物としては、たとえば酸化チタンの粉末が挙げられる。酸化チタンとしては、たとえば、酸化チタン(ＩＶ)、酸化チタン(ＩＩＩ)、酸化チタン(ＩＩ)などが挙げられ、酸化チタン(ＩＶ)が好ましく用いられる。酸化チタン(ＩＶ)の結晶型としては、アナターゼ型、ルチル型、ブルッカイト型などが挙げられ、不定形（アモルファス）であってもよい。より好ましくは、アナターゼ型、ルチル型の酸化チタン(ＩＶ)である。   The titanium source powder contained in the raw material mixture is a powder of a compound that becomes a titanium component constituting the aluminum titanate-based fired body. Examples of such a compound include titanium oxide powder. Examples of titanium oxide include titanium (IV) oxide, titanium (III) oxide, and titanium (II) oxide, and titanium (IV) oxide is preferably used. Examples of the crystal form of titanium (IV) oxide include anatase type, rutile type, brookite type and the like, and may be indefinite (amorphous). More preferred is anatase type or rutile type titanium (IV) oxide.

本発明で用いられるチタニウム源粉末は、単独で空気中で焼成することによりチタニア（酸化チタン）に導かれる化合物の粉末であってもよい。かかる化合物としては、たとえば、チタニウム塩、チタニウムアルコキシド、水酸化チタニウム、窒化チタン、硫化チタン、金属チタンなどが挙げられる。   The titanium source powder used in the present invention may be a powder of a compound that is led to 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.

チタニウム塩として具体的には、三塩化チタン、四塩化チタン、硫化チタン(ＩＶ)、硫化チタン(ＶＩ)、硫酸チタン(ＩＶ)などが挙げられる。チタニウムアルコキシドとして具体的には、チタン(ＩＶ)エトキシド、チタン(ＩＶ)メトキシド、チタン(ＩＶ)ｔ−ブトキシド、チタン(ＩＶ)イソブトキシド、チタン(ＩＶ)ｎ−プロポキシド、チタン(ＩＶ)テトライソプロポキシド、および、これらのキレート化物などが挙げられる。   Specific examples of the titanium salt include titanium trichloride, titanium tetrachloride, titanium (IV) sulfide, titanium sulfide (VI), and titanium sulfate (IV). Specific examples of the titanium alkoxide include titanium (IV) ethoxide, titanium (IV) methoxide, titanium (IV) t-butoxide, titanium (IV) isobutoxide, titanium (IV) n-propoxide, titanium (IV) tetraiso Examples thereof include propoxide and chelates thereof.

本発明において、チタニウム源粉末としては、１種のみが用いられてもよいし、２種以上が併用されてもよい。   In the present invention, as the titanium source powder, only one kind may be used, or two or more kinds may be used in combination.

上記のなかでも、チタニウム源粉末としては、酸化チタン粉末が好ましく用いられ、より好ましくは、酸化チタン(ＩＶ)粉末である。なお、チタニウム源粉末は、その原料由来あるいは製造工程において不可避的に含まれる微量成分を含有し得る。   Among the above, as the titanium source powder, a titanium oxide powder is preferably used, and more preferably a titanium (IV) oxide powder. The titanium source powder may contain a trace component derived from the raw material or inevitably contained in the production process.

チタニウム源粉末の粒径は、特に限定されないが、通常、レーザ回折法により測定される、体積基準の累積百分率５０％相当粒子径（Ｄ５０）が０．１〜２５μｍの範囲内であるものが用いられ、十分に低い焼成収縮率の達成のためには、Ｄ５０が１〜２０μｍの範囲内であるチタニウム源粉末を用いることが好ましい。なお、チタニウム源粉末は、バイモーダルな粒径分布を示すことがあるが、このようなバイモーダルな粒径分布を示すチタニウム源粉末を用いる場合においては、レーザ回折法により測定される、粒径が大きい方のピークを形成する粒子の粒径は、好ましくは２０〜５０μｍの範囲内である。   The particle size of the titanium source powder is not particularly limited, but a titanium source powder having a volume-based cumulative percentage 50% equivalent particle diameter (D50) in the range of 0.1 to 25 μm, usually measured by a laser diffraction method, is used. In order to achieve a sufficiently low firing shrinkage ratio, it is preferable to use a titanium source powder having a D50 in the range of 1 to 20 μm. The titanium source powder may exhibit a bimodal particle size distribution. When using a titanium source powder exhibiting such a bimodal particle size distribution, the particle size measured by a laser diffraction method is used. The particle diameter of the particles forming the larger peak is preferably in the range of 20 to 50 μm.

また、レーザ回折法により測定されるチタニウム源粉末のモード径は、特に限定されないが、０．１〜６０μｍの範囲内であるものを用いることができる。   Further, the mode diameter of the titanium source powder measured by the laser diffraction method is not particularly limited, but a mode diameter in the range of 0.1 to 60 μm can be used.

本発明においては、上記原料混合物中におけるＡｌ2Ｏ3（アルミナ）換算でのアルミニウム源粉末とＴｉＯ2（チタニア）換算でのチタニウム源粉末とのモル比は、３５：６５〜４５：５５の範囲内とすることが好ましく、より好ましくは４０：６０〜４５：５５の範囲内である。このような範囲内で、チタニウム源粉末をアルミニウム源粉末に対して過剰に用いることにより、原料混合物の成形体の焼成収縮率をより効果的に低減させることが可能となる。 In the present invention, 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 raw material mixture is in the range of 35:65 to 45:55. It is preferable to be within, and more preferably within the range of 40:60 to 45:55. Within such a range, by using the titanium source powder excessively relative to the aluminum source powder, it becomes possible to more effectively reduce the firing shrinkage rate of the molded body of the raw material mixture.

また、上記原料混合物は、マグネシウム源粉末を含有していてもよい。原料混合物がマグネシウム源粉末を含む場合、得られるチタン酸アルミニウム系焼成体は、チタン酸アルミニウムマグネシウム結晶からなる焼成体である。マグネシウム源粉末としては、マグネシア（酸化マグネシウム）の粉末のほか、単独で空気中で焼成することによりマグネシアに導かれる化合物の粉末が挙げられる。後者の例としては、たとえば、マグネシウム塩、マグネシウムアルコキシド、水酸化マグネシウム、窒化マグネシウム、金属マグネシウムなどが挙げられる。   Moreover, the said raw material mixture may contain the magnesium source powder. When the raw material mixture includes a magnesium source powder, the obtained aluminum titanate-based fired body is a fired body made of aluminum magnesium titanate crystals. Examples of the magnesium source powder include magnesia (magnesium oxide) powder and a powder of a compound that is led to magnesia by firing alone in air. Examples of the latter include magnesium salt, magnesium alkoxide, magnesium hydroxide, magnesium nitride, metal magnesium and the like.

マグネシウム塩として具体的には、塩化マグネシウム、過塩素酸マグネシウム、リン酸マグネシウム、ピロリン酸マグネシウム、蓚酸マグネシウム、硝酸マグネシウム、炭酸マグネシウム、酢酸マグネシウム、硫酸マグネシウム、クエン酸マグネシウム、乳酸マグネシウム、ステアリン酸マグネシウム、サリチル酸マグネシウム、ミリスチン酸マグネシウム、グルコン酸マグネシウム、ジメタクリル酸マグネシウム、安息香酸マグネシウムなどが挙げられる。   Specific examples of 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, magnesium stearate, Examples include magnesium salicylate, magnesium myristate, magnesium gluconate, magnesium dimethacrylate, and magnesium benzoate.

マグネシウムアルコキシドとして具体的には、マグネシウムメトキシド、マグネシウムエトキシドなどが挙げられる。なお、マグネシウム源粉末は、その原料由来あるいは製造工程において不可避的に含まれる微量成分を含有し得る。   Specific examples of the magnesium alkoxide include magnesium methoxide and magnesium ethoxide. The magnesium source powder may contain a trace component derived from the raw material or unavoidably contained in the production process.

マグネシウム源粉末として、マグネシウム源とアルミニウム源とを兼ねた化合物の粉末を用いることもできる。このような化合物としては、たとえば、マグネシアスピネル（ＭｇＡｌ2Ｏ4）が挙げられる。なお、マグネシウム源粉末として、マグネシウム源とアルミニウム源とを兼ねた化合物の粉末を用いる場合、アルミニウム源粉末のＡｌ2Ｏ3（アルミナ）換算量、および、マグネシウム源とアルミニウム源とを兼ねた化合物粉末に含まれるＡｌ成分のＡｌ2Ｏ3（アルミナ）換算量の合計量と、チタニウム源粉末のＴｉＯ2（チタニア）換算量とのモル比が、原料混合物中において上記範囲内となるように調整される。 As the magnesium source powder, a powder of a compound serving as both a magnesium source and an aluminum source can be used. An example of such a compound is magnesia spinel (MgAl 2 O 4 ). As the magnesium source powder, the case of using a powder of a compound serving both as a magnesium source and an aluminum source, Al 2 O 3 (alumina) in terms of the aluminum source powder, and a compound serving both as a magnesium source and aluminum source powder The molar ratio of the total amount of Al 2 O 3 (alumina) equivalent of the Al component contained in the TiO 2 (titania) equivalent of the titanium source powder is adjusted to be within the above range in the raw material mixture. The

本発明において、マグネシウム源粉末としては、１種のみが用いられてもよいし、２種以上が併用されてもよい。   In this invention, only 1 type may be used as a magnesium source powder, and 2 or more types may be used together.

マグネシウム源粉末の粒径は、特に限定されないが、通常、レーザ回折法により測定される、体積基準の累積百分率５０％相当粒子径（Ｄ５０）が０．５〜３０μｍの範囲内であるものが用いられ、原料混合物成形体の焼成収縮率低減の観点からは、Ｄ５０が３〜２０μｍの範囲内であるマグネシウム源粉末を用いることが好ましい。   The particle size of the magnesium source powder is not particularly limited, but those having a volume-based cumulative particle size equivalent to 50% of the volume-based cumulative percentage (D50) in the range of 0.5 to 30 μm are usually used. From the viewpoint of reducing the firing shrinkage rate of the raw material mixture compact, it is preferable to use a magnesium source powder having a D50 in the range of 3 to 20 μm.

原料混合物中におけるＭｇＯ（マグネシア）換算でのマグネシウム源粉末の含有量は、Ａｌ2Ｏ3（アルミナ）換算でのアルミニウム源粉末とＴｉＯ2（チタニア）換算でのチタニウム源粉末との合計量に対して、モル比で、０．０３〜０．１５とすることが好ましく、より好ましくは０．０３〜０．１２である。マグネシウム源粉末の含有量をこの範囲内に調整することにより、耐熱性がより向上された、大きい細孔径および開気孔率を有するチタン酸アルミニウム系焼成体を比較的容易に得ることができる。 The content of magnesium source powder in terms of MgO (magnesia) in the raw material mixture is based on the total amount of aluminum source powder in terms of Al 2 O 3 (alumina) and titanium source powder in terms of TiO 2 (titania). The molar ratio is preferably 0.03 to 0.15, and more preferably 0.03 to 0.12. By adjusting the content of the magnesium source powder within this range, an aluminum titanate-based fired body having a large pore diameter and an open porosity with improved heat resistance can be obtained relatively easily.

また、上記原料混合物は、ケイ素源粉末をさらに含有していてもよい。ケイ素源粉末は、シリコン成分となってチタン酸アルミニウム系焼成体に含まれる化合物の粉末であり、ケイ素源粉末の併用により、耐熱性がより向上されたチタン酸アルミニウム系焼成体を得ることが可能となる。ケイ素源粉末としては、たとえば、二酸化ケイ素、一酸化ケイ素などの酸化ケイ素（シリカ）の粉末が挙げられる。   The raw material mixture may further contain a silicon source powder. The silicon source powder is a powder of a compound contained in the aluminum titanate-based fired body as a silicon component, and by using the silicon source powder in combination, it is possible to obtain an aluminum titanate-based fired body with improved heat resistance. It becomes. Examples of the silicon source powder include powders of silicon oxide (silica) such as silicon dioxide and silicon monoxide.

また、ケイ素源粉末は、単独で空気中で焼成することによりシリカに導かれる化合物の粉末であってもよい。かかる化合物としては、たとえば、ケイ酸、炭化ケイ素、窒化ケイ素、硫化ケイ素、四塩化ケイ素、酢酸ケイ素、ケイ酸ナトリウム、オルトケイ酸ナトリウム、長石、ガラスフリットなどが挙げられる。なかでも、長石、ガラスフリットなどが好ましく用いられ、工業的に入手が容易であり、組成が安定している点で、ガラスフリットなどがより好ましく用いられる。なお、ガラスフリットとは、ガラスを粉砕して得られるフレークまたは粉末状のガラスをいう。ケイ素源粉末として、長石とガラスフリットとの混合物からなる粉末を用いることも好ましい。   The silicon source powder may be a powder of a compound led to 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. Among them, 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. It is also preferable to use a powder made of a mixture of feldspar and glass frit as the silicon source powder.

ガラスフリットを用いる場合、得られるチタン酸アルミニウム系焼成体の耐熱分解性をより向上させるという観点から、屈伏点が７００℃以上のものを用いることが好ましい。本発明において、ガラスフリットの屈伏点は、熱機械分析装置（ＴＭＡ：Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｉｓｉｓ）を用いて、低温からガラスフリットの膨張を測定し、膨張が止まり、次に収縮が始まる温度（℃）と定義される。   When glass frit is used, it is preferable to use one having a yield point of 700 ° C. or higher from the viewpoint of further improving the heat decomposition resistance of the obtained aluminum titanate-based fired body. In the present invention, the yield point of the glass frit is determined by measuring the expansion of the glass frit from a low temperature using a thermomechanical analyzer (TMA), and the temperature (° C.) at which the expansion stops and then the contraction starts. Defined.

上記ガラスフリットを構成するガラスには、ケイ酸（ＳｉＯ2）を主成分（全成分中５０質量％以上）とする一般的なケイ酸ガラスを用いることができる。ガラスフリットを構成するガラスは、その他の含有成分として、一般的なケイ酸ガラスと同様、アルミナ（Ａｌ2Ｏ3）、酸化ナトリウム（Ｎａ2Ｏ）、酸化カリウム（Ｋ2Ｏ）、酸化カルシウム（ＣａＯ）、マグネシア（ＭｇＯ）等を含んでいてもよい。また、ガラスフリットを構成するガラスは、ガラス自体の耐熱水性を向上させるために、ＺｒＯ2を含有していてもよい。 As the glass constituting the glass frit, a general silicate glass containing silicate (SiO 2 ) as a main component (50 mass% or more in all components) can be used. The glass constituting the glass frit is composed of other components such as 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.

本発明において、ケイ素源粉末としては、１種のみが用いられてもよいし、２種以上が併用されてもよい。   In the present invention, as the silicon source powder, only one type may be used, or two or more types may be used in combination.

ケイ素源粉末の粒径は、特に限定されないが、通常、レーザ回折法により測定される、体積基準の累積百分率５０％相当粒子径（Ｄ５０）が０．５〜３０μｍの範囲内であるものが用いられ、原料混合物の成形体の充填率をより向上させ、機械的強度のより高い焼成体を得るためには、Ｄ５０が１〜２０μｍの範囲内であるケイ素源粉末を用いることが好ましい。   The particle size of the silicon source powder is not particularly limited, but a particle having a volume-based cumulative percentage 50% equivalent particle size (D50) of 0.5 to 30 μm, usually measured by a laser diffraction method, is used. In order to further improve the filling rate of the molded body of the raw material mixture and obtain a fired body with higher mechanical strength, it is preferable to use a silicon source powder having a D50 in the range of 1 to 20 μm.

原料混合物がケイ素源粉末を含む場合、原料混合物中におけるケイ素源粉末の含有量は、Ａｌ2Ｏ3（アルミナ）換算でのアルミニウム源粉末とＴｉＯ2（チタニア）換算でのチタニウム源粉末との合計量１００質量部に対して、ＳｉＯ2（シリカ）換算で、通常０．１質量部〜１０質量部であり、好ましくは５質量部以下である。なお、ケイ素源粉末は、その原料由来あるいは製造工程において不可避的に含まれる微量成分を含有し得る。 When the raw material mixture includes a silicon source powder, the content of the silicon source powder in the raw material mixture is the sum of the aluminum source powder in terms of Al 2 O 3 (alumina) and the titanium source powder in terms of TiO 2 (titania). relative to the amount 100 parts by mass, in SiO 2 (silica) terms is usually 0.1 part by weight to 10 parts by weight, preferably not more than 5 parts by weight. The silicon source powder may contain trace components that are derived from the raw materials or inevitably contained in the production process.

なお、本発明では、上記マグネシアスピネル（ＭｇＡｌ2Ｏ4）などの複合酸化物のように、チタニウム、アルミニウム、ケイ素およびマグネシウムのうち、２つ以上の金属元素を成分とする化合物を原料粉末として用いることができる。この場合、そのような化合物は、それぞれの金属源化合物を混合した原料混合物と同じであると考えることができ、このような考えに基づき、原料混合物中におけるアルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末およびケイ素源粉末の含有量が上記範囲内に調整される。 In the present invention, as a raw material powder, a compound containing two or more metal elements among titanium, aluminum, silicon and magnesium as a composite oxide such as magnesia spinel (MgAl 2 O 4 ) is used. be able to. In this case, such a compound can be considered to be the same as the raw material mixture in which the respective metal source compounds are mixed. Based on such an idea, the aluminum source powder, titanium source powder, magnesium source in the raw material mixture are considered. Content of powder and silicon source powder is adjusted in the said range.

また、原料混合物にはチタン酸アルミニウムやチタン酸アルミニウムマグネシウム自体が含まれていてもよく、たとえば、原料混合物の構成成分としてチタン酸アルミニウムマグネシウムを使用する場合、該チタン酸アルミニウムマグネシウムは、チタニウム源、アルミニウム源およびマグネシウム源を兼ね備えた原料に相当する。   Further, the raw material mixture may contain aluminum titanate or aluminum magnesium titanate itself. For example, when aluminum magnesium titanate is used as a constituent of the raw material mixture, the aluminum magnesium titanate contains a titanium source, It corresponds to a raw material having both an aluminum source and a magnesium source.

本発明における原料粉末は、上記のようなチタン酸アルミニウム系のセラミックスを形成する粉末に限られず、焼成工程を経て形成される従来公知のセラミックス源粉末を含むものとすることができ、たとえば、チタン酸バリウム粉末、チタン酸ジルコニウム酸亜鉛粉末、シリカ粉末、炭化ケイ素粉末、窒化ケイ素粉末、酸窒化アルミニウム（ＡｌＯＮ）粉末、サイアロン（ＳｉＡｌＯＮ）粉末、酸化イットリウム粉末、ＹＡＧ（イットリウム・アルミニウム・ガーネット）粉末、窒素ホウ素粉末などの原料粉末をセラミックス源粉末の全重量に対して５０重量％以上含む場合も本発明の範囲に含まれる。   The raw material powder in the present invention is not limited to the powder forming the aluminum titanate-based ceramic as described above, and may include a conventionally known ceramic source powder formed through a firing step, for example, barium titanate. Powder, zinc zirconate titanate powder, silica powder, silicon carbide powder, silicon nitride powder, aluminum oxynitride (AlON) powder, sialon (SiAlON) powder, yttrium oxide powder, YAG (yttrium aluminum garnet) powder, nitrogen boron The case where the raw material powder such as powder is contained in an amount of 50% by weight or more based on the total weight of the ceramic source powder is also included in the scope of the present invention.

＜原料混合物＞
本発明においては、上記アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末、ケイ素源粉末などの原料粉末を含む原料混合物を成形して成形体を得た後、当該成形体を焼成することにより、チタン酸アルミニウム系などのセラミックス焼成体を得る。成形してから焼成を行なうことにより、原料混合物を直接焼成する場合と比較して、焼成中の収縮を抑えることができることから、得られるセラミックス焼成体の割れを効果的に抑制でき、また、焼成により生成した多孔質性のチタン酸アルミニウム結晶などの細孔形状が維持されたチタン酸アルミニウム系などのセラミックス焼成体を得ることができる。成形体の形状は特に制限されないが、たとえば、ハニカム形状、棒状、チューブ状、板状、るつぼ形状等を挙げることができる。特に成形体および該成形体を焼成して得られる焼成体をハニカム形状とする場合に、本発明の製造方法による効果が顕著である。すなわち、本発明の製造方法によればハニカム形状における割れを阻止することができる。なお、ハニカム形状は図１に示すような正方形の格子状に限られず、菱型や六角の格子状などの形状も含む。 <Raw material mixture>
In the present invention, after forming a raw material mixture containing raw material powders such as the aluminum source powder, titanium source powder, magnesium source powder, and silicon source powder to obtain a molded body, the molded body is fired to obtain titanium. A ceramic fired body such as aluminum oxide is obtained. Compared to the case where the raw material mixture is directly fired by forming and firing, the shrinkage during firing can be suppressed, so that cracking of the obtained ceramic fired body can be effectively suppressed, and firing It is possible to obtain an aluminum titanate-based ceramic fired body such as a porous aluminum titanate crystal produced by the above-described method, in which the pore shape is maintained. The shape of the formed body is not particularly limited, and examples thereof include a honeycomb shape, a rod shape, a tube shape, a plate shape, and a crucible shape. In particular, when the formed body and the fired body obtained by firing the formed body are formed into a honeycomb shape, the effect of the manufacturing method of the present invention is remarkable. That is, according to the manufacturing method of the present invention, cracks in the honeycomb shape can be prevented. The honeycomb shape is not limited to a square lattice shape as shown in FIG. 1, and includes a shape such as a diamond shape or a hexagonal lattice shape.

上記成形体が、球状粒子上に配置される面の断面積が７８５０ｍｍ2以上であり、高さが５０ｍｍ以上、重量が５００ｇ以上であるような、フィルターとして比較的サイズの大きい場合であっても、本発明のセラミックス焼成体の製造方法によれば、焼成体の全体に割れの発生しない良好なフィルター性能を有する焼成体を製造することができる。このような焼成体においては、高さが高くなるにつれて割れなどの制御をすることが難しいことが知られているが、本発明の製造方法によれば、たとえば上記断面積を有し、５０ｍｍ以上２５０ｍｍ以下の高さの成形体であっても、割れのない焼成体を得ることができる。 Even if the molded body has a relatively large size as a filter, the cross-sectional area of the surface disposed on the spherical particles is 7850 mm 2 or more, the height is 50 mm or more, and the weight is 500 g or more. According to the method for producing a ceramic fired body of the present invention, it is possible to produce a fired body having good filter performance that does not cause cracks in the entire fired body. In such a fired body, it is known that it is difficult to control cracks and the like as the height increases. However, according to the manufacturing method of the present invention, for example, the cross-sectional area is 50 mm or more. Even if it is a molded object with a height of 250 mm or less, a fired body without cracks can be obtained.

原料混合物の成形に用いる成形機としては、一軸プレス、押出成形機、打錠機、造粒機などが挙げられる。押出し成形を行なう際には、原料混合物に、たとえば、造孔剤、バインダ、潤滑剤および可塑剤、分散剤、ならびに溶媒などの添加剤（有機物）を添加して成形することができる。このような有機物は焼成時に消失し、焼成体には実質的に存在しないものである。有機物の配合量が原料粉末１００質量部に対して１０質量部以上、すなわち原料粉末の合計質量の１０質量％以上含まれる場合は、焼成時の収縮が大きくなるが、本発明の製造方法によれば、焼成する工程において成形体の下方に球状粒子を敷いて焼成するので、上記収縮による応力を緩和し、焼成体の割れを防ぐことができる。なお、上記原料粉末とは、焼成する工程において焼成体を形成するアルミニウム源粉末、チタニウム源粉末などの各元素源粉末の混合物をいう。   Examples of the molding machine used for molding the raw material mixture include a uniaxial press, an extrusion molding machine, a tableting machine, and a granulator. When performing extrusion molding, for example, additives (organic substances) such as a pore-forming agent, a binder, a lubricant and a plasticizer, a dispersant, and a solvent can be added to the raw material mixture. Such organic matter disappears upon firing and is substantially absent from the fired body. When the blending amount of the organic substance is 10 parts by mass or more with respect to 100 parts by mass of the raw material powder, that is, 10% by mass or more of the total mass of the raw material powder, the shrinkage during firing increases. For example, since the spherical particles are laid and fired under the molded body in the firing step, the stress due to the shrinkage can be relieved and cracking of the fired body can be prevented. The raw material powder refers to a mixture of element source powders such as an aluminum source powder and a titanium source powder that form a fired body in the firing step.

上記造孔剤としては、グラファイト等の炭素材；ポリエチレン、ポリプロピレン、ポリメタクリル酸メチル等の樹脂類；コーンスターチなどのでんぷん類、ナッツ殻、クルミ殻、コーンなどの植物系材料；氷；およびドライアイス等などが挙げられる。造孔剤の添加量は、アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末およびケイ素源粉末などの原料粉末の合計量１００質量部に対して、通常、０〜４０質量部であり、好ましくは０〜２５質量部である。   Examples of the pore former include carbon materials such as graphite; resins such as polyethylene, polypropylene and polymethyl methacrylate; starches such as corn starch; plant materials such as nut shells, walnut shells and corn; ice; and dry ice Etc. The amount of pore-forming agent added is usually 0 to 40 parts by mass, preferably 0 with respect to 100 parts by mass of the total amount of raw material powders such as aluminum source powder, titanium source powder, magnesium source powder and silicon source powder. ˜25 parts by mass.

上記バインダとしては、メチルセルロース、カルボキシルメチルセルロース、ナトリウムカルボキシルメチルセルロースなどのセルロース類；ポリビニルアルコールなどのアルコール類；リグニンスルホン酸塩などの塩；パラフィンワックス、マイクロクリスタリンワックス等のワックス；ＥＶＡ、ポリエチレン、ポリスチレン、液晶ポリマー、エンジニアリングプラスチックなどの熱可塑性樹脂などが挙げられる。バインダの添加量は、上記原料粉末の合計量１００質量部に対して、通常、２０質量部以下であり、好ましくは１５質量部以下である。   Examples of the binder include celluloses such as methyl cellulose, carboxymethyl cellulose, and sodium carboxymethyl cellulose; alcohols such as polyvinyl alcohol; salts such as lignin sulfonate; waxes such as paraffin wax and microcrystalline wax; EVA, polyethylene, polystyrene, liquid crystal Examples thereof include thermoplastic resins such as polymers and engineering plastics. The addition amount of the binder is usually 20 parts by mass or less, preferably 15 parts by mass or less, with respect to 100 parts by mass of the total amount of the raw material powder.

上記潤滑剤および可塑剤としては、グリセリンなどのアルコール類；カプリル酸、ラウリン酸、パルミチン酸、アラギン酸、オレイン酸、ステアリン酸などの高級脂肪酸；ステアリン酸Ａｌなどのステアリン酸金属塩などが挙げられる。潤滑剤および可塑剤の添加量は、上記原料粉末の合計量１００質量部に対して、通常、０〜１０質量部であり、好ましくは１〜５質量部である。   Examples of the lubricant and plasticizer include alcohols such as glycerin; 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 Al stearate. . The addition amount of the lubricant and the plasticizer is usually 0 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the raw material powder.

上記分散剤としては、たとえば、硝酸、塩酸、硫酸などの無機酸；シュウ酸、クエン酸、酢酸、リンゴ酸、乳酸などの有機酸；メタノール、エタノール、プロパノールなどのアルコール類；ポリカルボン酸アンモニウム、ポリオキシアルキレンアルキルエーテルなどの界面活性剤などが挙げられる。分散剤の添加量は、上記原料粉末の合計量１００質量部に対して、通常、０〜２０質量部であり、好ましくは２〜８質量部である。   Examples of the dispersant 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 polyoxyalkylene alkyl ethers may be mentioned. The addition amount of the dispersing agent is usually 0 to 20 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the total amount of the raw material powder.

また、上記溶媒としては、たとえば、メタノール、エタノール、ブタノール、プロパノールなどのアルコール類；プロピレングリコール、ポリプロピレングリコール、エチレングリコールなどのグリコール類；および水などを用いることができる。なかでも、水が好ましく、不純物が少ない点で、より好ましくはイオン交換水が用いられる。溶媒の使用量は、上記原料粉末の合計量１００質量部に対して、通常、１０質量部〜１００質量部、好ましくは２０質量部〜８０質量部である。   Examples of the solvent include alcohols such as methanol, ethanol, butanol, and propanol; glycols such as propylene glycol, polypropylene glycol, and ethylene glycol; and water. Of these, water is preferable, and ion-exchanged water is more preferably used from the viewpoint of few impurities. The usage-amount of a solvent is 10 mass parts-100 mass parts normally with respect to 100 mass parts of total amounts of the said raw material powder, Preferably it is 20 mass parts-80 mass parts.

成形に供される原料混合物は、上記アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末、ケイ素源粉末などの原料粉末、および上記の各種添加剤をミキサーなどにより混合（混練）することにより得ることができる。   The raw material mixture used for molding can be obtained by mixing (kneading) the above raw material powders such as the aluminum source powder, titanium source powder, magnesium source powder, silicon source powder, and the above-mentioned various additives with a mixer or the like. it can.

チタン酸アルミニウム系焼成体の製造における焼成温度は、通常、１３００℃以上、好ましくは１４００℃以上である。また、焼成温度は、通常、１６５０℃以下、好ましくは１５５０℃以下である。焼成温度までの昇温速度は特に限定されるものではないが、通常、１℃／時間〜５００℃／時間である。また、昇温は一定の昇温速度を所望の焼成温度まで維持してもよく、たとえば、段階的に昇温速度を変化させてもよい。たとえば、ケイ素源粉末を用いる場合には、焼成工程の前に、１１００〜１３００℃の温度範囲で３時間以上保持する工程を設けることが好ましい。これにより、ケイ素源粉末の融解、拡散を促進させることができる。原料混合物がバインダ等の添加燃焼性有機物を含む場合、焼成工程には、これを除去するための仮焼（脱脂）工程が含まれる。脱脂は、典型的には、焼成温度に至るまでの昇温段階（たとえば、１５０〜７００℃の温度範囲）になされる。脱脂工程おいては、昇温速度を極力おさえることが好ましい。   The firing temperature in the production of the aluminum titanate-based fired body is usually 1300 ° C. or higher, preferably 1400 ° C. or higher. The firing temperature is usually 1650 ° C. or lower, preferably 1550 ° C. or lower. The rate of temperature increase up to the firing temperature is not particularly limited, but is usually 1 ° C./hour to 500 ° C./hour. Further, the temperature increase may be maintained at a constant temperature increase rate up to a desired firing temperature. For example, the temperature increase rate may be changed stepwise. For example, when using a silicon source powder, it is preferable to provide the process hold | maintained for 3 hours or more in the temperature range of 1100-1300 degreeC before a baking process. Thereby, melting and diffusion of the silicon source powder can be promoted. When the raw material mixture contains an additive combustible organic substance such as a binder, the firing step includes a calcination (degreasing) step for removing the mixture. Degreasing is typically performed in a temperature rising stage (for example, a temperature range of 150 to 700 ° C.) up to the firing temperature. In the degreasing step, it is preferable to suppress the temperature rising rate as much as possible.

脱脂工程は、たとえば図４に示すように、形成体３０をスペーサー１１上に積載した台座６上に配置して行なう。スペーサー１１により設けられた空間から成形体３０の中央部分に熱風を送り込み、成形体全体の燃焼効率を向上させることが好ましい。上記台座６は、生台座６ｂと焼成台座６ｃとを積層して用いてもよい。生台座６ｂは、通常、成形体３０と同様の材質とする。焼成台座６ｃは、特に限定されることなく、たとえば成形体を別途の工程で焼成したものを用いることができる。   For example, as shown in FIG. 4, the degreasing step is performed by placing the formed body 30 on the pedestal 6 loaded on the spacer 11. It is preferable to send hot air from the space provided by the spacer 11 to the central portion of the molded body 30 to improve the combustion efficiency of the entire molded body. The pedestal 6 may be formed by stacking a raw pedestal 6b and a firing pedestal 6c. The raw pedestal 6 b is usually made of the same material as the molded body 30. The firing pedestal 6c is not particularly limited, and for example, a fired product of a molded body can be used in a separate process.

焼成は通常、大気中で行なわれるが、用いる原料粉末、すなわちアルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末、ケイ素源粉末などの原料粉末や、造孔剤、バインダ、潤滑剤および可塑剤の種類や使用量比によっては、窒素ガス、アルゴンガスなどの不活性ガス中で焼成してもよいし、一酸化炭素ガス、水素ガスなどのような還元性ガス中で焼成してもよい。また、水蒸気分圧を高くまたは低くした雰囲気中で焼成を行なってもよい。   Firing is usually performed in the atmosphere, but the raw material powder used, that is, the raw material powder such as aluminum source powder, titanium source powder, magnesium source powder, silicon source powder, and the kind of pore former, binder, lubricant and plasticizer Depending on the usage ratio, it may be fired in an inert gas such as nitrogen gas or argon gas, or may be fired in a reducing gas such as carbon monoxide gas or hydrogen gas. Further, firing may be performed in an atmosphere in which the water vapor partial pressure is increased or decreased.

焼成は、通常、管状電気炉、箱型電気炉、トンネル炉、遠赤外線炉、マイクロ波加熱炉、シャフト炉、反射炉、ロータリー炉、ローラーハース炉などの通常の焼成炉を用いて行なわれる。焼成は回分式で行なってもよいし、連続式で行なってもよい。また、静置式で行なってもよいし、流動式で行なってもよい。   Firing is usually performed using a conventional 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, a rotary furnace, or a roller hearth furnace. Firing may be performed batchwise or continuously. Moreover, you may carry out by a stationary type and may carry out by a fluid type.

焼成に要する時間は、原料混合物の成形体がチタン酸アルミニウム系結晶などの結晶に遷移するのに十分な時間であればよく、原料混合物の量、焼成炉の形式、焼成温度、焼成雰囲気などにより異なるが、通常は１０分〜２４時間である。   The time required for firing is sufficient as long as the molded body of the raw material mixture transitions to a crystal such as an aluminum titanate-based crystal, and depends on the amount of the raw material mixture, the type of firing furnace, the firing temperature, the firing atmosphere, etc. Usually, it is 10 minutes to 24 hours.

以上のようにして、目的の焼成体を得ることができる。このようなチタン酸アルミニウム系焼成体などの焼成体は、成形直後の成形体の形状をほぼ維持した形状を有する。得られたチタン酸アルミニウム系焼成体は、研削加工等により、所望の形状に加工することもできる。   As described above, a desired fired body can be obtained. Such a fired body such as an aluminum titanate-based fired body has a shape that substantially maintains the shape of the molded body immediately after molding. The obtained aluminum titanate-based fired body can be processed into a desired shape by grinding or the like.

本発明により得られる焼成体は、たとえば、ルツボ、セッター、コウ鉢、炉材などの焼成炉用冶具；ディーゼルエンジン、ガソリンエンジンなどの内燃機関の排気ガス浄化に用いられる排ガスフィルターや、触媒担体、ビールなどの飲食物の濾過に用いる濾過フィルター、石油精製時に生じるガス成分、たとえば一酸化炭素、二酸化炭素、窒素、酸素などを選択的に透過させるための選択透過フィルターなどのセラミックスフィルター；基板、コンデンサーなどの電子部品などに好適に適用することができる。なかでも、セラミックスフィルターなどとして用いる場合、本発明における焼成体は高い細孔容積および開気孔率を有することから、良好なフィルター性能を長期にわたって維持することができる。   The fired body obtained by the present invention includes, for example, a firing furnace jig such as a crucible, a setter, a mortar, and a furnace material; an exhaust gas filter used for exhaust gas purification of an internal combustion engine such as a diesel engine and a gasoline engine, a catalyst carrier, Filters used for filtering food and drink such as beer, ceramic filters such as selective permeation filters for selectively permeating gas components generated during petroleum refining, such as carbon monoxide, carbon dioxide, nitrogen, oxygen; substrates, capacitors It can be suitably applied to electronic parts such as. Especially, when using as a ceramics filter etc., since the sintered body in this invention has a high pore volume and open porosity, it can maintain favorable filter performance over a long period of time.

上記焼成体がチタン酸アルミニウム系焼成体の場合、Ｘ線回折スペクトルにおいて、チタン酸アルミニウムまたはチタン酸アルミニウムマグネシウムの結晶パターンのほか、アルミナ、チタニアなどの結晶パターンを含んでいてもよい。なお、上記チタン酸アルミニウム系焼成体は、チタン酸アルミニウムマグネシウム結晶からなる場合、組成式：Ａｌ2(1−ｘ)ＭｇxＴｉ(1＋x)Ｏ5で表すことができ、ｘの値は０．０３以上であり、好ましくは０．０３以上０．１５以下、より好ましくは０．０３以上０．１２以下である。また、上記チタン酸アルミニウム系焼成体は、原料由来あるいは製造工程において不可避的に含まれる微量成分を含有し得る。 When the fired body is an aluminum titanate-based fired body, the X-ray diffraction spectrum may include a crystal pattern of alumina, titania, or the like in addition to the crystal pattern of aluminum titanate or aluminum magnesium titanate. When the aluminum titanate-based fired body is made of aluminum magnesium titanate crystal, it can be represented 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 0.03 or more and 0.15 or less, more preferably 0.03 or more and 0.12 or less. In addition, the aluminum titanate-based fired body may contain a trace component derived from the raw material or inevitably contained in the manufacturing process.

＜セラミックス焼成体＞
本発明の製造方法により得られるセラミックス焼成体は、主にチタン酸アルミニウム系結晶からなる多孔性のセラミックスとすることができる。「主にチタン酸アルミニウム系結晶からなる」とは、多孔性のセラミックス（多孔質セラミックス）を構成する主結晶相がチタン酸アルミニウム系結晶相であることを意味し、チタン酸アルミニウム系結晶相は、たとえば、チタン酸アルミニウム結晶相、チタン酸アルミニウムマグネシウム結晶相などであってよい。 <Ceramic fired body>
The ceramic fired body obtained by the production method of the present invention can be a porous ceramic mainly composed of an aluminum titanate crystal. “Mainly composed of an aluminum titanate crystal” means that the main crystal phase constituting the porous ceramic (porous ceramic) is an aluminum titanate crystal phase. For example, it may be an aluminum titanate crystal phase, an aluminum magnesium titanate crystal phase, or the like.

上記多孔質セラミックスは、チタン酸アルミニウム系結晶相以外の相（結晶相）を含んでいてもよい。このようなチタン酸アルミニウム系結晶相以外の相（結晶相）としては、多孔質セラミックスの作製に用いる原料由来の相などを挙げることができる。原料由来の相とは、より具体的には、多孔質セラミックスを上記した本発明のセラミックス焼成体の製造方法に従い製造する場合における、チタン酸アルミニウム系結晶相を形成することなく残存したアルミニウム源粉末、チタニウム源粉末および／またはマグネシウム源粉末由来の相などである。また、上記原料混合物がケイ素源粉末を含む場合、多孔質セラミックスは、ＳｉＯ2成分を含むガラス相等のケイ素源粉末由来の相を含む。 The porous ceramics may contain a phase (crystal phase) other than the aluminum titanate crystal phase. Examples of such a phase (crystal phase) other than the aluminum titanate-based crystal phase include a phase derived from a raw material used for producing porous ceramics. More specifically, the raw material-derived phase refers to an aluminum source powder that remains without forming an aluminum titanate-based crystal phase when a porous ceramic is produced according to the method for producing a ceramic fired body of the present invention described above. , A phase derived from a titanium source powder and / or a magnesium source powder. Further, when the raw material mixture containing a silicon source powder, porous ceramic includes phase from the silicon source powder of glass phase or the like including a SiO 2 component.

また、本発明におけるセラミックス焼成体は、主に炭化ケイ素系結晶からなる多孔質セラミックスとすることができる。このような焼成体は、公知の原料粉末の調整により所望の結晶相を含むものとすることができる。   Moreover, the ceramic fired body in the present invention can be a porous ceramic mainly composed of a silicon carbide crystal. Such a fired body can contain a desired crystal phase by adjusting a known raw material powder.

本発明におけるセラミックス焼成体の形状は、特に制限されず、ハニカム形状、棒状、チューブ状、板状（シート状）、るつぼ形状等であってよい。なかでも、本発明の多孔質セラミックス成形体をＤＰＦなどのセラミックスフィルターとして用いる場合には、ハニカム形状とすることが好ましい。このような形状は、通常、成形体の形状により決定されることになる。   The shape of the ceramic fired body in the present invention is not particularly limited, and may be a honeycomb shape, a rod shape, a tube shape, a plate shape (sheet shape), a crucible shape, or the like. In particular, when the porous ceramic formed body of the present invention is used as a ceramic filter such as DPF, it is preferably a honeycomb shape. Such a shape is usually determined by the shape of the molded body.

本発明におけるセラミックス焼成体は、ガラス相を含んでいてもよい。ガラス相とは、ＳｉＯ2が主要成分である非晶質相を指す。この場合、ガラス相の含有率は、５質量％以下であることが好ましく、また、２質量％以上であることが好ましい。ガラス相を５質量％以下含むことにより、ＤＰＦなどのセラミックスフィルターに要求される細孔特性を充足するセラミックス焼成体が得られやすくなる。 The ceramic fired body in the present invention may contain a glass phase. The glass phase refers to an amorphous phase in which SiO 2 is a main component. In this case, the glass phase content is preferably 5% by mass or less, and more preferably 2% by mass or more. By including 5% by mass or less of the glass phase, it becomes easy to obtain a ceramic fired body that satisfies the pore characteristics required for a ceramic filter such as DPF.

上記のような細孔特性を備える、主にチタン酸アルミニウム系結晶からなる多孔性のセラミックス焼成体の製造には、上記本発明の製造方法を好適に用いることができる。すなわち、アルミニウム源粉末、チタニウム源粉末、ならびに任意で使用されるマグネシウム源粉末およびケイ素源粉末を含む原料混合物を成形して成形体を得た後、当該成形体を球状粒子を敷いた状態で焼成することにより本発明の多孔性のセラミックス焼成体を得ることができる。   The production method of the present invention can be suitably used for the production of a porous ceramic fired body mainly composed of an aluminum titanate-based crystal having the above pore characteristics. That is, an aluminum source powder, a titanium source powder, and a raw material mixture containing optional magnesium source powder and silicon source powder are molded to obtain a molded body, and then the molded body is fired in a state where spherical particles are spread. By doing so, the porous ceramic fired body of the present invention can be obtained.

ここで、主にチタン酸アルミニウム系結晶からなる多孔性のセラミックス焼成体に上記のような細孔特性を付与するためには、原料混合物にケイ素源粉末を含むことが好ましい。ケイ素源粉末としては前述したものを用いることができるが、なかでもガラスフリット、長石、またはこれらの混合物を用いることが好ましい。また、多孔性のセラミックス焼成体に上記のような細孔特性を付与するためには、ケイ素源粉末の含有量を、原料混合物中に含まれる無機成分中、２質量％以上５質量％以下とすることがより好ましい。原料混合物中に含まれる無機成分とは、多孔質セラミックス成形体を構成する元素を含む成分であり、典型的には、アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末およびケイ素源粉末である。ただし、原料混合物に含まれる添加剤（造孔剤、バインダ、潤滑剤、可塑剤、分散剤等）が無機成分を含む場合、それらも含まれる。   Here, in order to impart the above pore characteristics to a porous ceramic fired body mainly composed of aluminum titanate-based crystals, it is preferable that the raw material mixture contains a silicon source powder. As the silicon source powder, those described above can be used, and among them, glass frit, feldspar, or a mixture thereof is preferably used. Further, in order to impart the above pore characteristics to the porous ceramic fired body, the content of the silicon source powder is 2% by mass or more and 5% by mass or less in the inorganic component contained in the raw material mixture. More preferably. The inorganic component contained in the raw material mixture is a component containing an element constituting the porous ceramic molded body, and is typically an aluminum source powder, a titanium source powder, a magnesium source powder, and a silicon source powder. However, when the additive (pore forming agent, binder, lubricant, plasticizer, dispersant, etc.) contained in the raw material mixture contains an inorganic component, these are also included.

また、多孔性のセラミックス焼成体に上記のような細孔特性を付与するためには、原料混合物は、マグネシウム源粉末を含むことが好ましい。原料混合物中におけるマグネシウム源粉末の好ましい含有量は、上記したとおりである。   In addition, in order to impart the above pore characteristics to the porous ceramic fired body, the raw material mixture preferably contains a magnesium source powder. The preferable content of the magnesium source powder in the raw material mixture is as described above.

なお、本発明の製造方法が適用される成形体およびそれにより得られる焼成体は、成形体の寸法に対する焼成体の寸法の線収縮率（線収縮率（％）＝（成形体の寸法−焼成体の寸法）／（成形体の寸法）×１００）が１％以上である。このような熱による線収縮率の大きい成形体の場合は、従来の製造方法においては割れや亀裂が発生しやすいが、球状粒子を用いる本発明の製造方法を適用する場合は、割れや亀裂のない焼成体を製造することができる。   Note that the molded body to which the production method of the present invention is applied and the fired body obtained thereby have a linear shrinkage ratio (linear shrinkage rate (%) = (molded body dimension−fired) of the size of the fired body relative to the size of the molded body. Body dimension) / (molded body dimension) × 100) is 1% or more. In the case of such a molded article having a large linear shrinkage due to heat, cracks and cracks are likely to occur in the conventional production method, but when applying the production method of the present invention using spherical particles, No fired body can be produced.

なお、上記線収縮率は、焼成前（押し出し成形後脱脂工程前）の成形体と、焼成後の成形体の押し出し断面方向（成形体における押し出し方向とは垂直な方向の断面）の長さ（隔壁ピッチ幅）を、それぞれ２点測定し、それらの値を平均することに得られる焼成前の平均長さ（成形体の寸法）および焼成後の平均長さ（焼成体の寸法）から、上記式に基づき算出する値とする。   The linear shrinkage rate is the length of the molded body before firing (after extrusion molding and before the degreasing step) and the extruded cross-sectional direction of the molded body after firing (cross section in a direction perpendicular to the extrusion direction in the molded body) ( From the average length before firing (dimensions of the molded body) and the average length after firing (dimensions of the fired body) obtained by measuring two points each of the partition wall pitch width) and averaging those values, The value is calculated based on the formula.

本発明のセラミックス焼成体の製造方法により製造される多孔性のセラミックス焼成体は、焼成工程において球状粒子を用いることにより焼成の際に与えられる応力を緩和することができるので、得られる焼成体の全体にわたって割れのない、フィルター性能に優れたものとなる。   Since the porous ceramic fired body produced by the method for producing a ceramic fired body of the present invention can relieve stress applied during firing by using spherical particles in the firing step, The filter performance is excellent with no cracks throughout.

以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

＜線収縮率＞
焼成前（押し出し成形乾燥後）のハニカム形状の成形体と、焼成後の成形体の押し出し断面方向（成形体における押し出し方向とは垂直な方向の断面）の長さ（隔壁ピッチ幅）を、それぞれ２点測定し、それらの値を平均することに得られる焼成前の平均長さ（成形体の寸法）および焼成後の平均長さ（焼成体の寸法）から、下記式に基づき線収縮率を算出した。
線収縮率（％）＝（成形体の寸法−焼成体の寸法）／（成形体の寸法）×１００
（実施例１）
表１に示す組成に沿った原料をミキサーで混合し、成形体の原料混合物の前駆体混合物を得た。 <Linear shrinkage>
The honeycomb-shaped molded body before firing (after extrusion molding drying) and the length (partition wall pitch width) of the extruded cross-sectional direction (cross-section in a direction perpendicular to the extrusion direction in the molded body) of the molded body after firing, From the average length before firing (dimensions of the molded body) and the average length after firing (dimensions of the fired body) obtained by measuring two points and averaging those values, the linear shrinkage rate is calculated based on the following formula: Calculated.
Linear shrinkage ratio (%) = (dimension of molded body−dimension of fired body) / (dimension of molded body) × 100
Example 1
The raw materials along the composition shown in Table 1 were mixed with a mixer to obtain a precursor mixture of the raw material mixture of the molded body.

Figure 2011051846
Figure 2011051846

表１において、ユニルーブ（登録商標）は日油社製のポリオキシアルキレン系化合物である。また、表１における造孔剤、バインダおよび潤滑剤は、いずれも焼成により燃焼する成分（有機物）である。前駆体混合物に含まれる成分のうち上記燃焼する成分以外の成分（すなわち原料粉末）の合計量１００質量部に対して、チタニア換算のチタニウム源粉末の配合量は４９．０質量部、アルミナ換算のアルミニウム源粉末の配合量は４１．８質量部、マグネシア換算のマグネシウム源粉末の配合量は５．２質量部、シリカ換算のケイ素源粉末の配合量は４．０質量部であった。この前駆体混合物１６９．３ｋｇに対し水４５ｋｇを添加し、押出成形機により、１６０ｍｍ径のハニカム形状の成形体を得た。   In Table 1, Unilube (registered trademark) is a polyoxyalkylene compound manufactured by NOF Corporation. In addition, all of the pore-forming agent, binder and lubricant in Table 1 are components (organic substances) combusted by firing. Of the components contained in the precursor mixture, the compounding amount of the titanium source powder in terms of titania is 49.0 parts by mass with respect to 100 parts by mass of the total amount of components other than the above combusting components (ie, raw material powder). The compounding amount of the aluminum source powder was 41.8 parts by mass, the compounding amount of the magnesium source powder in terms of magnesia was 5.2 parts by mass, and the compounding amount of the silicon source powder in terms of silica was 4.0 parts by mass. 45 kg of water was added to 169.3 kg of the precursor mixture, and a honeycomb-shaped formed body having a diameter of 160 mm was obtained by an extruder.

得られた成形体は、１６０ｍｍφ、セル密度３００ＣＰＳＩ（１平方インチあたり３００セル）、セル壁（隔壁）の厚みが０．３ｍｍのハニカム形状であり、高さを５２ｍｍになるように切り出したハニカム形状の成形体である。これを、マイクロ波乾燥機を用いて、成形体の乾燥品を得た。乾燥品の外径はおよそ１５０ｍｍφであった。   The obtained molded body has a honeycomb shape of 160 mmφ, a cell density of 300 CPSI (300 cells per square inch), a cell wall (partition wall) thickness of 0.3 mm and a height of 52 mm. It is a molded article. This was used to obtain a dried product of a molded body using a microwave dryer. The outer diameter of the dried product was approximately 150 mmφ.

＜脱脂工程＞
先ず、成形体に含まれる上記有機物を除去する（脱脂する）ために、ハニカム形状の成形体を表２に示すＯ2濃度のＮ2中で、昇温速度７℃／時間で５００℃まで昇温し、続いて室温まで１００℃／時間で降温した。 <Degreasing process>
First, in order to remove (degrease) the organic matter contained in the formed body, the honeycomb-shaped formed body was heated to 500 ° C. at a temperature increase rate of 7 ° C./hour in N 2 having an O 2 concentration shown in Table 2. Then, the temperature was lowered to room temperature at 100 ° C./hour.

上記高さで切り出したハニカム形状の成形体の脱脂品を図４に示すようにスペーサー１１上に積載した台座６上に配置した。台座６としては、別工程で製造したハニカム形状の焼成体からなる焼成台座６ｃと、上記成形体と同様であって高さが３０ｍｍの未焼成台座（生台座６ｂ）とを重ねて用いた。   The degreased product of the honeycomb-shaped formed body cut out at the above height was placed on the base 6 loaded on the spacer 11 as shown in FIG. As the pedestal 6, a fired pedestal 6 c made of a honeycomb-shaped fired body manufactured in a separate process and an unfired pedestal (raw pedestal 6 b) having the same height as the above-described molded body and having a height of 30 mm were used.

＜焼成工程＞
脱脂工程後、表３に示すように、空気中で９００℃から１５００℃の温度領域での昇温速度が２０℃／時間となるように昇温し、１５００℃で５時間保持することにより、セラミックス焼成体を得た。本実施例１における焼成する工程では、図３に示すように、スペーサー９上に積載したムライト製の敷物８の上に、球状粒子７として０．３ｍｍφ、真球度０．９８のＺｒＯ2ビーズを５０ｇ敷いてほぼ１層（単層）の球状粒子層を形成し、該球状粒子７の上にさらに台座６ａとして上記脱脂工程を経た台座６ｂを配置した。 <Baking process>
After the degreasing step, as shown in Table 3, the temperature was raised so that the temperature rising rate in the temperature range from 900 ° C. to 1500 ° C. was 20 ° C./hour in air, and kept at 1500 ° C. for 5 hours, A ceramic fired body was obtained. In the firing step in Example 1, as shown in FIG. 3, a ZrO 2 bead having a spherical particle size of 0.3 mmφ and a sphericity of 0.98 is formed on a mullite covering 8 loaded on a spacer 9. A spherical particle layer of approximately one layer (single layer) was formed by spreading 50 g of spheres, and a pedestal 6b that had undergone the above degreasing step was further disposed on the spherical particles 7 as a pedestal 6a.

実施例１における上記線収縮率は、９％であった。
球状粒子８上を成形体３０を滑らせたときの摩擦係数は、約１×１０-3Ｎ／ｇ−成形体であった。上記摩擦係数は、敷物８の上に５０ｇの球状粒子を敷き、その上に載せたハニカム形状の成形体が動き始める力［Ｎ］をテンションゲージを用いて測定し、ハニカム形状の成形体重量［ｇ］と動き始める力［Ｎ］との関係から、摩擦係数［Ｎ／ｇ］の値を求めた。 The linear shrinkage rate in Example 1 was 9%.
The coefficient of friction when the compact 30 was slid on the spherical particles 8 was about 1 × 10 −3 N / g-compact. The friction coefficient is determined by measuring the force [N] at which 50 g of spherical particles are laid on the rug 8 and the honeycomb-shaped molded body placed thereon starts to move using a tension gauge, and the weight of the honeycomb-shaped molded body [ The value of the friction coefficient [N / g] was obtained from the relationship between [g] and the starting force [N].

実施例１の昇温および降温の温度条件および昇温および降温速度、脱脂工程および焼成工程における酸素濃度（体積％）を表２および表３に示す。   Tables 2 and 3 show the temperature conditions of temperature increase and temperature decrease, the temperature increase and decrease rate, the oxygen concentration (volume%) in the degreasing step and the firing step of Example 1.

Figure 2011051846
Figure 2011051846

Figure 2011051846
Figure 2011051846

脱脂工程後の成形体および焼成工程後の焼成体においていずれも割れや亀裂は発生していなかった。   Neither cracks nor cracks occurred in the molded body after the degreasing step and the fired body after the firing step.

（比較例１）
球状粒子を敷かない以外は、実施例１と同様に脱脂工程および焼成工程により成形体を焼成して、セラミックス焼成体を製造した。これらの工程の条件および割れや亀裂の状態を表２および表４に示す。 (Comparative Example 1)
A ceramic fired body was manufactured by firing the formed body by the degreasing process and the firing process in the same manner as in Example 1 except that the spherical particles were not spread. Tables 2 and 4 show the conditions of these steps and the states of cracks and cracks.

成形体を敷物上で滑らせたときの摩擦係数は、約７×１０-3Ｎ／ｇ−成形体であった。 The coefficient of friction when the molded body was slid on the rug was about 7 × 10 −3 N / g-molded body.

Figure 2011051846
Figure 2011051846

表３および表４の結果から分かるように、球状粒子を敷いた実施例１の場合は、ハニカム形状の成形体は、焼成後に割れや亀裂がないのに対して、球状粒子を敷かなかった比較例１の場合は、焼成の昇温速度が緩やかであるにもかかわらず、焼成後にハニカム形状のセルの目切れ（割れ）や亀裂が観測された。   As can be seen from the results of Tables 3 and 4, in the case of Example 1 in which spherical particles were laid, the honeycomb-shaped formed body had no cracks or cracks after firing, but a comparison in which spherical particles were not laid. In the case of Example 1, although the firing rate of heating was moderate, breaks (cracks) and cracks of the honeycomb-shaped cells were observed after firing.

（実施例２）
成形体の形状（サイズ）および脱脂工程における条件を表２および表３に示すように変更した以外は、実施例１と同様の方法によりハニカム形状のセラミックス焼成体を製造した。実施例２における上記線収縮率は、１１％であった。得られたセラミックス焼成体に割れ、亀裂は観測されなかった。 (Example 2)
A honeycomb-shaped ceramic fired body was manufactured in the same manner as in Example 1 except that the shape (size) of the formed body and the conditions in the degreasing process were changed as shown in Tables 2 and 3. The linear shrinkage rate in Example 2 was 11%. Cracks and cracks were not observed in the obtained ceramic fired body.

（実施例３）
成形体の形状（サイズ）および脱脂工程においてスペーサーおよび台座を用いない以外は、実施例２と同様の方法によりハニカム形状のセラミックス焼成体を製造した。実施例３における上記線収縮率は、９％であった。得られたセラミックス焼成体に割れ、亀裂は観測されなかった。本実施例３および上記実施例２の結果から、焼成工程において球状粒子を用いる場合は焼成体の特性が良好となることが示された。 (Example 3)
A honeycomb-shaped ceramic fired body was manufactured in the same manner as in Example 2, except that the shape (size) of the formed body and the spacer and pedestal were not used in the degreasing step. The linear shrinkage rate in Example 3 was 9%. Cracks and cracks were not observed in the obtained ceramic fired body. From the results of Example 3 and Example 2, it was shown that when spherical particles are used in the firing step, the properties of the fired product are improved.

（実施例４）
成形体の形状（サイズ）および球体粒子を表３に示すものに変更した以外は実施例１と同様の方法によりハニカム形状のセラミックス焼成体を製造した。球体粒子の真球度は０．９８であり、実施例４における上記線収縮率は、１１％であった。得られたセラミックス焼成体に割れ、亀裂は観測されなかった。 Example 4
A honeycomb-shaped ceramic fired body was manufactured in the same manner as in Example 1 except that the shape (size) of the compact and the spherical particles were changed to those shown in Table 3. The sphericity of the spherical particles was 0.98, and the linear shrinkage rate in Example 4 was 11%. Cracks and cracks were not observed in the obtained ceramic fired body.

（比較例２）
脱脂工程において生台座を用いない以外は比較例１と同様の方法によりハニカム形状のセラミックス焼成体を製造した。表２および表４の結果に示すように、焼成体には割れおよび亀裂が観測された。また、実施例１と比較例１および比較例２との結果から、脱脂工程の条件に関係なく焼成工程において球状粒子を敷くことにより、焼成体の割れや亀裂の発生を阻止することができることがわかった。 (Comparative Example 2)
A honeycomb-shaped ceramic fired body was manufactured by the same method as in Comparative Example 1 except that the green base was not used in the degreasing step. As shown in the results of Table 2 and Table 4, cracks and cracks were observed in the fired body. Further, from the results of Example 1, Comparative Example 1 and Comparative Example 2, it is possible to prevent the fired body from cracking or cracking by placing the spherical particles in the firing process regardless of the conditions of the degreasing process. all right.

以上のように本発明の実施の形態および実施例について説明を行なったが、上述の各実施の形態および実施例の構成を適宜組み合わせることも当初から予定している。   Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。   It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

１ 外周壁、２ 隔壁、３，４ 流路、５ａ，５ｂ 封止部、６，６ａ 台座、６ｂ 生台座、６ｃ 焼成台座、７ 球状粒子、８ 敷物、９，１１ スペーサー、１０ セラミックスハニカム構造体、２０，３０ 成形体。   DESCRIPTION OF SYMBOLS 1 Outer wall, 2 Partition, 3, 4 Flow path, 5a, 5b Sealing part, 6, 6a Pedestal, 6b Raw base, 6c Firing base, 7 Spherical particle, 8 Rug, 9,11 Spacer, 10 Ceramic honeycomb structure , 20, 30 Molded body.

Claims (10)

成形体を焼成する工程を含むセラミックス焼成体の製造方法であって、
前記成形体の寸法に対する前記焼成体の寸法の線収縮率（線収縮率（％）＝（成形体の寸法−焼成体の寸法）／（成形体の寸法）×１００）が１％以上であり、
成形体を敷物上に敷いた球状粒子上に配置した状態で焼成することを特徴とするセラミックス焼成体の製造方法。 A method for producing a ceramic fired body including a step of firing a formed body,
The linear shrinkage ratio (linear shrinkage rate (%) = (dimension of molded article−dimension of fired article) / (dimension of molded article) × 100) of the dimension of the fired article relative to the dimensions of the molded article is 1% or more. ,
A method for producing a ceramic fired body, comprising firing the molded body placed on spherical particles laid on a rug. 前記球状粒子の直径が０．０３ｍｍ以上３ｍｍ以下である請求項１に記載のセラミックス焼成体の製造方法。   The method for producing a ceramic fired body according to claim 1, wherein the spherical particles have a diameter of 0.03 mm to 3 mm. 前記球状粒子の真球度が０．６以上１．０以下である請求項１または２に記載のセラミックス焼成体の製造方法。   The method for producing a ceramic fired body according to claim 1 or 2, wherein the spherical particles have a sphericity of 0.6 or more and 1.0 or less. 前記球状粒子は、安定化酸化ジルコニウム、酸化アルミニウム、窒化アルミニウム、酸化マグネシウム、アルミノケイ酸塩化合物、二酸化ケイ素、炭化ケイ素、チタン酸アルミニウム、チタン酸アルミニウムマグネシウム、チタン酸マグネシウム、窒化チタニウムからなる群より選択される１つの化合物または２つ以上の混合物である請求項１〜３のいずれかに記載のセラミックス焼成体の製造方法。   The spherical particles are selected from the group consisting of stabilized zirconium oxide, aluminum oxide, aluminum nitride, magnesium oxide, aluminosilicate compound, silicon dioxide, silicon carbide, aluminum titanate, aluminum magnesium titanate, magnesium titanate, titanium nitride. The method for producing a ceramic fired body according to any one of claims 1 to 3, which is one compound or a mixture of two or more. 前記成形体は、前記球状粒子上に配置される面の断面積が７８５０ｍｍ2以上であり、高さが５０ｍｍ以上、重量が５００ｇ以上である請求項１〜４のいずれかに記載のセラミックス焼成体の製造方法。 5. The ceramic fired body according to claim 1, wherein the compact has a cross-sectional area of 7850 mm 2 or more, a height of 50 mm or more, and a weight of 500 g or more. Manufacturing method. 前記成形体は、該成形体を構成する原料中に有機物を質量比で１０％以上含む請求項１〜５のいずれかに記載のセラミックス焼成体の製造方法。   The said molded object is a manufacturing method of the ceramic sintered body in any one of Claims 1-5 which contains 10% or more of organic substances by mass ratio in the raw material which comprises this molded object. 前記成形体はハニカム形状である請求項１〜６のいずれかに記載のセラミックス焼成体の製造方法。   The method for manufacturing a ceramic fired body according to any one of claims 1 to 6, wherein the formed body has a honeycomb shape. 前記成形体は、アルミニウム源粉末およびチタニウム源粉末を含み、焼成によりチタン酸アルミニウム組成物を形成する請求項１〜７のいずれかに記載のセラミックス焼成体の製造方法。   The method of manufacturing a ceramic fired body according to any one of claims 1 to 7, wherein the formed body includes an aluminum source powder and a titanium source powder, and an aluminum titanate composition is formed by firing. 前記成形体は、アルミニウム源粉末、チタニウム源粉末、およびマグネシウム源粉末を含み、焼成によりチタン酸アルミニウムマグネシウム組成物を形成する請求項１〜７のいずれかに記載のセラミックス焼成体の製造方法。   The said molded object is a manufacturing method of the ceramic sintered body in any one of Claims 1-7 which contains an aluminum source powder, a titanium source powder, and a magnesium source powder, and forms an aluminum magnesium titanate composition by baking. 前記成形体は、アルミニウム源粉末、チタニウム源粉末、マグネシウム源粉末、およびケイ素源粉末を含み、焼成によりチタン酸アルミニウムマグネシウム組成物を形成する請求項１〜７のいずれかに記載のセラミックス焼成体の製造方法。   The ceramic body according to any one of claims 1 to 7, wherein the formed body includes an aluminum source powder, a titanium source powder, a magnesium source powder, and a silicon source powder, and forms an aluminum magnesium titanate composition by firing. Production method.
JP2009203003A 2009-09-02 2009-09-02 Method for manufacturing ceramic sintered compact Withdrawn JP2011051846A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2009203003A JP2011051846A (en) 2009-09-02 2009-09-02 Method for manufacturing ceramic sintered compact
PCT/JP2010/064930 WO2011027783A1 (en) 2009-09-02 2010-09-01 Method for producing fired ceramic body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009203003A JP2011051846A (en) 2009-09-02 2009-09-02 Method for manufacturing ceramic sintered compact

Publications (1)

Publication Number Publication Date
JP2011051846A true JP2011051846A (en) 2011-03-17

Family

ID=43649319

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009203003A Withdrawn JP2011051846A (en) 2009-09-02 2009-09-02 Method for manufacturing ceramic sintered compact

Country Status (2)

Country Link
JP (1) JP2011051846A (en)
WO (1) WO2011027783A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011073945A (en) * 2009-10-01 2011-04-14 Sumitomo Chemical Co Ltd Method for producing aluminum titanate ceramic fired object
JP2019042635A (en) * 2017-08-30 2019-03-22 イビデン株式会社 Manufacturing method of honeycomb structure

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5937800B2 (en) * 2011-09-29 2016-06-22 住友化学株式会社 Method for manufacturing honeycomb fired body
JP2018123008A (en) * 2015-06-12 2018-08-09 住友化学株式会社 Manufacturing method of ceramic fired body
CN110108130A (en) * 2019-04-30 2019-08-09 惠达卫浴股份有限公司 A kind of kiln-loading method of sanitary ceramics
CN113372124A (en) * 2021-06-30 2021-09-10 广州市尤特新材料有限公司 Sintering method of target material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3620662B2 (en) * 1994-10-24 2005-02-16 株式会社日本自動車部品総合研究所 Method for firing ceramic honeycomb structure
JP4461414B2 (en) * 2002-07-26 2010-05-12 日立金属株式会社 Method for firing ceramic honeycomb structure
WO2008078747A1 (en) * 2006-12-27 2008-07-03 Hitachi Metals, Ltd. Process for producing aluminum-titanate-based ceramic honeycomb structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011073945A (en) * 2009-10-01 2011-04-14 Sumitomo Chemical Co Ltd Method for producing aluminum titanate ceramic fired object
JP2019042635A (en) * 2017-08-30 2019-03-22 イビデン株式会社 Manufacturing method of honeycomb structure

Also Published As

Publication number Publication date
WO2011027783A1 (en) 2011-03-10

Similar Documents

Publication Publication Date Title
US9272957B2 (en) Process for producing aluminum titanate-based ceramics fired body
JP4844770B2 (en) Method for producing aluminum titanate-based fired body
WO2011037177A1 (en) Method for producing ceramic fired article
WO2010079806A1 (en) Molded porous ceramic article, and method for manufacturing same
JP4965734B1 (en) Method for manufacturing green molded body and honeycomb structure
JP2013039514A (en) Honeycomb structure
WO2011027783A1 (en) Method for producing fired ceramic body
WO2010074231A1 (en) Method for producing aluminum titanate fired body
WO2011111666A1 (en) Green compact and method for producing aluminum titanate sintered body.
JP2011051854A (en) Method of manufacturing aluminum titanate based fired body and ceramic molding
WO2013024744A1 (en) Honeycomb filter
JP2010111547A (en) Method of manufacturing aluminum titanate-based porous fired body
JP2010215482A (en) Method for producing molded porous ceramic article and molded porous ceramic article
JP5528717B2 (en) Method for producing aluminum titanate-based fired body and porous ceramic molded body
JP2011241116A (en) Method for producing aluminum titanate sintered compact and aluminum titanate sintered compact
JP2011245430A (en) Honeycomb structure
JP2010138035A (en) Method for producing aluminum titanate-based sintered body
WO2012176888A1 (en) Aluminum titanate ceramic and molded body
JP5391246B2 (en) Method for producing aluminum titanate-based fired body
JP2012001413A (en) Method for manufacturing green mold and honeycomb fired body
JP2013103188A (en) Honeycomb structure and honeycomb filter

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 20121106