CN1329581A - 低热膨胀高强度堇青石结构体的制造 - Google Patents

低热膨胀高强度堇青石结构体的制造 Download PDF

Info

Publication number
CN1329581A
CN1329581A CN99813431A CN99813431A CN1329581A CN 1329581 A CN1329581 A CN 1329581A CN 99813431 A CN99813431 A CN 99813431A CN 99813431 A CN99813431 A CN 99813431A CN 1329581 A CN1329581 A CN 1329581A
Authority
CN
China
Prior art keywords
weight
ceramic
component
phase
mgo
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.)
Granted
Application number
CN99813431A
Other languages
English (en)
Other versions
CN1107660C (zh
Inventor
D·M·比尔
M·J·穆尔塔盖
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.)
Corning Inc
Original Assignee
Corning Inc
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 Corning Inc filed Critical Corning Inc
Publication of CN1329581A publication Critical patent/CN1329581A/zh
Application granted granted Critical
Publication of CN1107660C publication Critical patent/CN1107660C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C04B33/00—Clay-wares
    • C04B33/32—Burning methods
    • 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
    • C04B35/634—Polymers
    • 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
    • C04B35/16—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 silicates other than clay
    • C04B35/18—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 silicates other than clay rich in aluminium oxide
    • C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
    • 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
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C04B35/6365—Cellulose or derivatives 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00129—Extrudable mixtures
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/32—Expansion-inhibited materials
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
    • 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
    • C04B2235/34—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
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
    • 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
    • C04B2235/34—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
    • C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
    • 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
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5292—Flakes, platelets or plates
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—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
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24149—Honeycomb-like

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

本发明涉及烧结陶瓷制品,它包含65－95重量%堇青石和5－35重量%选自富铝红柱石、铝酸镁尖晶石和假蓝宝石的次相的结晶相聚集体,该结晶相聚集体的总分析组成基本上由32－51%SiO2、35－49%Al2O3和7－16%MgO组成。另外,陶瓷制品的有效强度大于约3000,在25－1000℃温度范围内的CTE小于15.0×10－7/℃,且压Hg方法测得的总侵入孔隙度至少为20%。本发明还涉及一种制造具有上述堇青石和次相混合结晶相的烧结陶瓷制品的方法。

Description

低热膨胀高强度堇青石结构体的制造
本申请要求Beall等人1998年11月20日提交的题目为“低热膨胀高强度堇青石结构的制造”的美国临时申请No.60/109,408的优先权。
                        发明背景
1.发明领域
本发明涉及用作催化剂载体的堇青石陶瓷体，尤其是用作纯化汽车废气的催化剂载体用的高强度、低热膨胀、多孔性堇青石体，以及制造该堇青石体的方法。
2.相关技术讨论
利用烃燃料(如烃气体、汽油或柴油)的内燃系统释放出的废气会严重污染大气。这些废气中的众多污染物中有烃和含氧化合物，而后者包括氮氧化物(NOx)和一氧化碳(CO)。许多年来，汽车工业一直设法减少汽车发动机系统的气体释放量，在1970年代中期有了装备有催化转化器的第一批汽车。
堇青石基材，通常是其蜂窝体形式，长期起来一直适合作为基材来支承汽车上催化转化器的催化活性组分，其部分原因是因为堇青石陶瓷具有良好的耐热冲击性。耐热冲击性与热膨胀系数成反比。就是说，低热膨胀的蜂窝体具有良好的耐热冲击性，并能经受使用时所遇到的很大的温度波动。
从含有氧化镁、氧化铝和氧化硅的矿物原料混合物(如粘土和滑石)制造堇青石(2MgO·2Al2O3·5SiO2)陶瓷是众所周知的。这些方法在美国专利2,684,919中有所描述。美国专利No.3,885,977中公开了从粘土/滑石批料制造耐热冲击性堇青石蜂窝陶瓷的方法，该方法是挤压该批料，然后烧结挤压物，从而提供沿至少一个轴膨胀系数非常低的陶瓷。
为了优化堇青石基材的性质，加强其作为催化剂载体的实用性，生产商作了不断的研究。特别是，生产商不断地努力试图优化堇青石基材的耐热冲击性和强度。下列专利各自涉及耐热冲击性或热膨胀系数(CTE)和/或强度有所改善的陶瓷蜂窝的生产。
美国专利53144,643(Beall等人)公开了具有12-16重量％的MgO、35-41％Al2O3和43-53％SiO2的堇青石体的制造。另外，该堇青石体包含至少90重量％的堇青石，在25℃-1000℃内，其热膨胀系数低于大约9×10-7/℃。该方法涉及选择特定的原料以便形成所需堇青石体。具体地说，这些原料的选择不应包括粘土和滑石，应包括粒径分别不大于15和8微米的产生MgO的组分和产生Al2O3的组分。将原料混合在一起，随后干燥，在足以形成上述堇青石体的温度下烧结一定时间。由于其CTE较低，且在这些CTE值下可能产生微裂纹的程度，该文公开的堇青石体强度较小。
美国专利No.5,332,703(Hickman)公开了一种基本上由堇青石组成的陶瓷产品，及其制备方法。具体地说，该陶瓷体由至少90重量％的堇青石组成，其MOR至少为3500psi，总孔隙度不超过大约20％(体积)，在大约室温至800℃下CTE不超过大约4.8×10-7/℃。生产上述陶瓷制品的方法涉及采用包含矿物组分和化学组分这两种组分的组合物。该批料的矿物组分包含粘土和滑石，而化学组分基本上由镁、铝和硅的氧化物、氢氧化物或含水氧化物组成。混合该组合批料，成形，干燥，随后烧结，形成陶瓷体。尽管Hickman的专利显示出所需的低CTE和较高强度的组合，但它是以减少孔隙度为代价来实现这些目的的。这种孔隙度的牺牲却是不能让人接受的，因为在制造蜂窝陶瓷载体基材中，大孔隙度是很重要的，特别是在适当施加大表面积修补基面涂层时尤其需要有大的孔隙度。
虽然这些陶瓷在性能上表现出比用常规方法制得的挤压的堇青石陶瓷有所改善，但是仍要求对这些产品作进一步改进，尤其是在强度方面，而孔隙度有不得减少，且热膨胀不得有不适当的增加。由于现在的发展趋势是生产壁薄的、蜂窝密度较高的、催化转化效率增加的、使用时背压较低的堇青石蜂窝催化剂载体，强度已经在堇青石蜂窝基材的生产中变成越来越重要的考虑因素。换句话说，为了补偿由于上述发展趋势引起的蜂窝基材体强度的减少，需要有增加蜂窝基材本身材料强度的办法。
因此，本发明主要目的是提供改进的堇青石陶瓷，及其制备方法，这种陶瓷能表现出较高的强度和固有的低热膨胀和大的总孔隙度。
                        发明概述
本发明的目的是解决现有技术中的上述问题，提供烧结的陶瓷基材，以及制备所述陶瓷基材的方法，所述陶瓷基材具有包含堇青石的主结晶相和增强的次结晶相。
惊奇地发现，在烧结陶瓷中若形成了组成有意偏离化学计量比的堇青石，该陶瓷会表现出在给定孔隙度下强度有所增加以及热膨胀系数低的新组合。这些性能是通过产生细分散的增强次结晶相来获得的，这些次结晶相(assemblage)包含富铝红柱石和/或假蓝宝石和/或铝酸镁尖晶石。
具体地说，本发明的烧结陶瓷制品中有一种结晶相聚集体，它包含65-95％堇青石主相和5-35％选自富铝红柱石、铝酸镁尖晶石和假蓝宝石的次相，其全分析组成基本上由大约32-51％SiO2、35-49％Al2O3、7-16％MgO(以重量计)组成。另外，陶瓷制品的有效强度大于大约3000，CTE小于大约15×10-7/℃(在25℃-1000℃的范围内)，总侵入孔隙度(intrusion porosity)用压Hg法测得至少为20％。
本发明还涉及制造烧结的陶瓷制品的方法，该陶瓷制品具有结晶堇青石相和次相的混合物，该方法包括制备含有产生SiO2、产生Al2O3和产生MgO的组分的可塑化原料混合物，在该混合物中加入有机粘合剂物系，加以混合，形成可挤压的混合物，随后将该混合物挤压制成具有所需形状的基材。干燥此生坯，在一定温度下烧结一定时间，该烧结温度和时间足以形成强度高、CTE低和总孔隙度大的独特组合的烧结混合结晶相结构。
                        附图简述
图1是SiO2-Al2O3-MgO物系的三元相图，该图显示了本发明所用的组成区域。
                        发明详述
本发明涉及一种陶瓷制品，该制品强度高、耐热冲击性高和孔隙度大，并且表现为是两种结晶相的组合，包含堇青石主结晶相和次要结晶相。另外，本发明涉及一种制造这些制品的方法，该方法采用了原料的优化组合(类型和用量)，该组合得以形成含MgO、Al2O3和SiO2的陶瓷体，该陶瓷体是堇青石相和次结晶相的结晶相组合。
已经发现，通过原料的组成仔细控制三元系组分SiO2、Al2O3和MgO之间的氧化物关系，就可落在偏离于堇青石化学计量比的组成区域内。本发明的具有狭窄规定组成、具有次结晶相的烧结陶瓷制品在该三元区域内。具体地说，经X-射线衍射测定，本发明陶瓷制品的烧结结晶相包含65-95重量％堇青石以及5-35重量％的次相的烧结结晶相，其中次相选自富铝红柱石、铝酸镁尖晶石和假蓝宝石。较佳的，该制品包含至少约70重量％的堇青石。选择原料的类型和各自的相对用量，形成总分析组成基本上由32-51重量％SiO2、35-49重量％Al2O3、7-16重量％MgO组成的混合相陶瓷制品。图1中用1-2-3-4表示的区域代表这一偏离化学计量比的组成范围。
另已发现，为了实现本发明陶瓷制品热膨胀低、强度高和孔隙度大的组合，必须采用特定原料(即具有一定粒径和形态的原料)的优化组合以及特定的烧结规程才能实现所需性能。换句话说，尽管某些原料组合在一起后会落在上述组成范围内，并产生适当混合的主相/次相陶瓷体，但是该陶瓷体的性能可能不在所需数值范围内。换句话说，假定它们对最终的热膨胀、孔隙度和强度性质有影响，仅仅通过组成选择来控制烧结体的最终化学计量比是不够的，而且还需要选择好原料类型以及制造陶瓷体所用的烧结程序。
如前所述，已经发现，利用原料混合物中的某些产生氧化硅、氧化镁和氧化铝的组分，本文描述的这种混合物能得到烧结的陶瓷制品，该陶瓷制品的特点是包含堇青石结晶相和增强次要相的组合，该增强次要相选自富铝红柱石、假蓝宝石和铝酸镁，它在给定孔隙度条件下具有较高的强度和低的热膨胀性。具体地说，本发明的陶瓷体的特征是CTE低，即在25-1000℃下CTE低于大约15×10-7/℃，最佳的是在25℃-1000℃下CTE不超过大约10×10-7/℃。本发明制品的其它特征是孔隙度较高，即经压Hg孔隙度测定法测得，总孔隙度大于大约20％。孔隙度的上限由一些实际因素决定。然而，压Hg孔隙度测定法测得的总孔隙度通常在大约25％-40％之间。
另外，本发明制品的有效强度至少大于3000(该值是主要为堇青石结晶相(即大于90重量％)的现有技术标准的市售陶瓷体的数值)。有效强度(ES)用方程式ES＝MOR＋403(MPS-2.3)＋(TP－31)定义，其中MOR是断裂模量，MPS是中值孔径，TP是压Hg孔隙度测定法测得的总孔隙度。该有效强度是一个强度量度，它将孔隙度和中值孔径对强度的影响归一化，因此能用来对中值孔径和孔隙度不同的陶瓷体的强度进行可比的比较。
本发明提供了一种用来制造上述陶瓷制品的可塑化的原料混合物，该混合物包含产生SiO2的组分，产生Al2O3的组分和产生MgO的组分。必须根据经验来确定哪种产生Al2O3、产生SiO2和产生MgO的原料组分的组合不仅在上述狭窄的偏离化学计量比的组成范围内，而且还使陶瓷体具有必需的低CTE、高强度和大总孔隙度的性质。
原料混合物中可使用粘土作为SiO2和/或Al2O3的来源，但是原料混合物不必由粘土组成。本发明能用的具体的粘土包括生的和经锻烧的、叠状的和脱层的高岭土。较佳的粘土类型是粒径细小、BET表面积在7-15m2/g之间的脱层高岭土。用具有尽可能多定向结构的脱层粘土有助于使所得陶瓷制品的CTE较低。
产生Al2O3的组分可以直接就是氧化铝或在锻烧后形成氧化铝的材料。另外，可接受的产生氧化铝的组分包括矾土、氢氧化铝、含水氧化铝(aluminum oxyhydrate)以及它们的组合。特别佳的产生Al2O3的组分包括高活性氧化铝，其平均粒径小于8微米，较佳的是其平均粒径大约为1微米或更小。该细粒径氧化铝的作用和脱层高岭土一样，是帮助获得CTE较低的陶瓷制品。
产生MgO的组分可以是简单地包含经锻烧的氧化镁、氢氧化镁、碳酸镁、硝酸镁以及它们的组合。在一个较佳的实施方案中，MgO原料是经锻烧或未经锻烧的粗滑石，其平均粒径在大约1-15微米之间，表面积在大约1m2/g-15m2/g之间，更佳的是表面积在3m2/g-8m2/g之间；未经锻烧的滑石是较佳的原料。另外，滑石宜为片状的，换句话说，滑石应当是片状颗粒形态，即颗粒两个尺寸长而一个尺寸短，或是说片状体的长度和宽度比其厚度大得多。较佳的是，滑石具有的形态指数在0.65-0.85之间。形态指数首先在美国专利No.5,141,686中有所描述，它是滑石片状程度的量度。测定形态指数的一种典型的程序是将样品置于夹子中，使片状滑石的取向在样品夹平面内最大。然后测定该取向的滑石的x-射线衍射图。形态指数M通过下列方程式由XRD峰强度半定量地计算，它表达滑石的片状特征程度：
M＝Ix(Ix＋2Iy)-1
其中Ix是(004)峰的强度，Iy是(020)反射的强度。应注意，选自过于片状的滑石可能会使陶瓷制品有较低CTE，但却有不希望的强度。换言之，应选择具有一定片状程度(即形态指数在大约0.65-0.85之间)的滑石，它能降低陶瓷制品的CTE，且陶瓷制品的强度不致减少得太多。
通过从包含脱层高岭土(平均粒径约为1.5微米)、滑石(形态指数为0.75，BET表面积约为5-8m2/g)和细的活性氧化铝(平均粒径约为0.5微米)的原料混合物，能制备性质优良的多相烧结陶瓷制品。
将能构成塑化混合物的上述原料在混合步骤中充分混合，使这些原料在蚁后的热处理时能反应完全。为了获得可成形的混合物，此时加入粘合剂物系。用于本发明的较佳的粘合剂物系包含选自甲基纤维素、甲基纤维素衍生物及其组合物的纤维素醚粘合剂组分、表面活性剂组分(较佳的是硬脂酸或硬脂酸纳)以及溶剂(包含水)。假定100重量份无机原料混合物，用于本发明的优秀的粘合剂物系包含：大约0.2-2重量份硬脂酸纳、大约2.5-6.0重量份甲基纤维素或羟丙基甲基纤维素粘合剂以及大约8-30重量份水。
使粘合剂物系的各个组分与一定量无机粉末材料(如产生SiO2、Al2O3、MgO的组分)以合适的已知方式混合，制得陶瓷材料和粘合剂物系充分混合的能通过例如挤压成形为陶瓷体的混合物。例如，粘合剂物系的所有组分可以预先彼此混合，然后再将该混合物加入陶瓷粉末材料中。在这种情况下，全部粘合剂物系可以一次加入，也可以相隔适当的时间分批依次加入。或者，粘合剂物系的各单组分可以依次加入陶瓷材料中，也可以将粘合剂物系的两种或多种组分预先制得的混合物依次加入陶瓷粉末材料中。另外，粘合剂物系可以先和一部分陶瓷粉末材料混合。在这种情况下，其余部分的陶瓷粉末再随后加入所得的混合物中。无论是哪种情况，粘合剂物系必须与预定部分的陶瓷粉末材料均匀混合。粘合剂物系和陶瓷粉末材料的均匀混合可用已知的捏和方法来实现。
然后用任何已知的常规陶瓷成形方法，如挤压、注模、粉浆浇注、离心浇注、压注、干压等方，将上述所得的粘稠均匀的可挤压的批料混合物成形为生坯。对于适合用作催化剂载体的薄壁蜂窝基材的制备，通过模头进行挤压是较佳的。
然后用任何常规的方法，如热空气干燥或高频干燥，将制得的陶瓷生坯干燥大约5-20分钟，然后进行烧结。
如上所述，不仅通过利用适量的原料来获得烧结体的合适的SiO2、Al2O3和MgO化学计量比很关键，而且在生产中也有必要用导致所需低热膨胀和大孔隙度和高强度性质的烧结规程。如上所述，在选用了原料后，用于每种原料混合物的实际的烧结规程必须根据经验来确定。换句话说，产生上述所需性质的实际烧结方案将因所用原料的类型和用量而异。
一旦确定了合适的烧结方案，就在预定的温度下对干燥的生坯烧结一定时间，烧结的温度和时间应足以获得具有所需低CTE、高强度系数的烧制的陶瓷体，该陶瓷体含有堇青石作为其主要相，并含有选自富铝红柱石、假蓝宝石和铝酸镁尖晶石的次相。尽管烧结条件要根据经验来确定，并因批料以及所需的“烧结陶瓷”性质而异，但一些较佳的烧结条件如下：
以大约5℃-25℃/小时(较佳为大约18℃/小时)的加热速度，将生坯加热至大约600-650℃的第一温度，随后以大约10-50℃/小时(较佳的大约25℃/小时)的加热速度，从第一温度升高至大约1300℃-1450℃之间的第二温度，在第三温度下保温大约6-16小时(较佳的约10小时)，然后以每小时大约100℃-200℃的冷却速度将烧结体冷却至室温。
虽然在此不希望拘泥于理论的解释，但可认为本发明的混合结晶相陶瓷制品具有高强度与低热膨胀系数的独特组合是由两个一般现象引起的：结晶相聚集体构成中的变化以及微裂纹的变化。这两个一般现象是由于引入了富铝红柱石、假蓝宝石或尖晶石的次结晶相而产生的。关于结晶相聚集体变化的这一点，可以理论上认为是次相的引入可能提供了复合的/增强效果，该效果是由次相为混合相陶瓷制品显微结构产生增强作用而引起的。或者，次相的引入可能为原有的堇青石结晶结构提供一种补充的或替换的作用。关于第二种现象，富铝红柱石、假蓝宝石和尖晶石相均表现出与堇青石结晶相相比程度较低的和/或可能不同类型的微裂纹，因此混合相陶瓷制品中出现了使强度增大的微裂纹变化。尽管微裂纹的程度减小和/或类型变化会增加陶瓷制品的强度，但都只是稍稍增加了陶瓷体的CTE，而由于这两种现象组合引起的强度增加幅度远远大于CTE的增加，CTE仍然保持在可接受的低水平，小于大约15×10-7/℃。因此，本发明陶瓷体的明显优点是能提高这些堇青石体的强度而孔隙度不会减少到有害的程度，这与现有技术堇青石体提高强度通常所用的方式相反。
如上所述，本文所述的原料混合物的主要用途是用来制备作为催化剂载体的高强度堇青石蜂窝基材。尽管本发明特别适合制造薄壁型蜂窝体，但是所要求保护的混合物也可用来制备壁较厚的结构。混合物还可用来制造其它高强度的堇青石结构等，如过滤器等。
                        实施例
为了进一步说明本发明的发明原理，下面将描述几个根据本发明制成的陶瓷体的例子。然而，应理解给予这些实施例只是为了说明的目的，本发明并不局限于这些例子，还可对本发明作出各种不脱离本发明精神的变化和改变。
                       实施例1-11
表I中列出用来制备具有堇青石作为主要结晶相的陶瓷体的无机粉末批料混合物：以重量百分数表示。脱层高岭土平均粒径约为1.5微米，所用的氧化铝是细的活性氧化铝，其平均粒径约为0.8微米。至于滑石原料，滑石1的BET表面积约为5-8m2/g，其形态指数为0.7，而滑石2具有较高的片状程度，其形态指数为0.95。
将表I所示组成的各标号的无机混合物的组分干混在一起，制得各组合物1-11。然后在各无机干混物中加入表I所示用量的有机粘合剂物系，然后进一步混合，制成塑化的陶瓷批料混合物。这13种不同的塑化陶瓷批料混合物的每一种包含不同用量的粘合剂物系组分，详细情况见表I；其范围以总共100份无机物计为30.15-33.15重量份。
将每种经塑化的混合物在适合形成1/4英寸棒的条件下通过挤压机进行挤压。对13种批料组合物的每一种挤压生成的生陶瓷棒进行充分干燥，除去可能存在的水或液体相，然后对其加热进行烧结，该烧结规程足以除去蜂窝基材中的有机粘合剂物系并将蜂窝基材烧结起来。具体地说，在1300-1450℃之间对生基材进行烧结，保温大约10小时；即该烧结条件适合制成具有堇青石作为其主相、并具有富铝红柱石、假蓝宝石或铝酸镁尖晶石次相的陶瓷体。
表I报道了用标准X-射线衍射方法测得的陶瓷体中相的类型和数量，以及分析出的氧化物百分数(以三元相三个角顶的无水氧化物的重量百分数表示)。另外，表I还列出了从表中所示的批料制得的陶瓷的一些性质。这些陶瓷体的性质包括：陶瓷棒的断裂强度模量(MOR)(用psi表示)，在室温(25℃)-1000℃温度范围内的平均热膨胀系数(CTE)(单位是×10-7℃)，压Hg孔隙度测定法测得的孔隙度(用体积百分数表示)，以及如上所述计算出的有效强度。
                                                表I
   1*    2*    3*     4     5     6     7     8     9*     10     11
    无机物滑石1滑石2 40.86- -39.5 30.5- 39.5- 36.51- 37.8- 39.54- 42.29- 40.78- 44.08- 46.5-
 经锻烧的粘土  32.6  31.85  33.2  31.85  31.79     -  29.2  25.86  26.48    -     -
    生粘土  12.82  12.7  13.28  12.7  12.74     -  11.89  10.53  15.37    -     -
   粗氧化铝    -    -    -    -    -     -    -    -  15.35    -     -
  细α-氧化铝  13.72  16.05  23.02  16.05  18.96   37.9  17.36  19.31    -  37.11   37.8
    氧化硅    -    -    -    -    -   24.3   2.0   2.0   2.03  18.82   15.8
 有机粘合剂物系Methocel 2.9 2.9 2.9 2.9 2.9 4.0 3.5 3.5 2.9 4.0 4.0
    硬脂酸  0.75  0.75  0.75  0.75  0.75   1.0   0.5   0.5   0.75   1.0   1.0
    水  29.0  26.5  28.0  28.5  28.0   26.0   21.5   20.0   29.5   26.0   26.0
    油   6.0   6.0
  氧化物百分数SiO2 51.4 49.9 44.9 49.9 47.9 49.1 50.2 49.4 51.4 47.8 46.3
    Al2O3  35.0  37.0  45.0  37.0  40.0   38.6  36.7  36.6  35.0  37.9   38.6
    MgO  13.6  13.1  10.1  13.1  12.1   12.3  13.1  14.0  13.6  14.4   15.2
    性质CTE×10-7/℃ 4.2 3.7 16.8 5.3 10 6.5 5.7 8.0 6.2 6.7 8.6
    MOR(psi)   3400   3100  6600  4000   4900   3700   4600   4900   2500   3400    3900
    孔隙度   26.8   28.0  26.1  28.2   27.2   29.3   26.9   27.4   35.0   32.0    37.0
 有效强度指数   2945   2815  5915  3523   4301   3469   4029   4390   2986   3276    4162
    次相：类型数量(重量％) 富铝红柱石2.0％ 富铝红柱石7.5％ 富铝红柱石35.4％ 富铝红柱石6.3％ 富铝红柱石15.8％ 富铝红柱石/假蓝宝石6％/2％ 富铝红柱石6.0％ 尖晶石8.2％ 富铝红柱石2.0％ 假蓝宝石8.3％ 尖晶石16.3％
*对比例
由表1可见，与标准的堇青石组合物实施例1和9相比，本发明的样品具有与其相似的孔隙度和CTE，但是本发明的陶瓷体表现出强度增加；即，它们表现出较高的有效强度。表中用于比较的组合物1和9代表标准的堇青石组合物，它们是在本发明组成(用氧化物百分数表示)范围外的组合物。具体地说，本发明实施例4-8和对比例1相比，结果显示发明例表现出相似的孔隙度(26.9％至29.3％对26.8％)和CTE(均小于10×10-7/℃)，但MOR较高(3700psi-4900psi对3400psi)。另外，将本发明实施例10和11和对比例9相比，结果显示本发明实施例10和11表现出相似的孔隙度(32.0％和37.0％对35.0％)和CTE(均小于8.6×10-7/℃)，但是MOR较高(3400psi和3900psi对2500psi)。简言之，标准的堇青石陶瓷体各自表现出有效强度指数分别低于3000、2945和2815，而本发明所有实施例均超出了该数值。
对比例2证实了这样的一个原理，即，不仅需要控制各原料量来获得合适的偏离化学计量的烧结体组成，而且所用原料类型的具体组合必须能确保获得所需性能。具体地说，对比例2含有与发明例4相同的批料组成，只是选用了不同的滑石原料，结果表明，采用扁平程度极高(形态指数为0.95所表明的)的滑石原料，而不使用补偿用该滑石所导致的较低强度的原料，会使陶瓷体的性能在本发明范围外。具体地说，尽管对比例2的CTE较低(3.7×10-7/℃)，但是其强度低于所需值(3100psi)，且有效强度低于3000(具体数值为2815)。
对比例3表示组成(用重量百分数表示)在本发明范围外的组合物。所得陶瓷体的富铝红柱石百分数太高(35.4％)，它产生的陶瓷体尽管表现出强度足够高(6600psi)，有效强度为5915，但是这是以热膨胀系数作为代价的，16.0×10-7/℃是太高了。

Claims (20)

1.一种陶瓷制品，它含有65-95重量％堇青石和5-35重量％次相的烧结相组成，该次相选自富铝红柱石、铝酸镁尖晶石和假蓝宝石，它的总分析组成基本上由32-51重量％SiO2、35-49重量％Al2O3和7-16重量％MgO组成，它的总孔隙度不低于20体积％，在25-1000℃温度范围内的热膨胀系数不大于15.0×10-7/℃。
2.根据权利要求1所述的陶瓷制品，其中制品表现出有效强度大于至少3000。
3.根据权利要求1所述的陶瓷制品，其中制品包含至少70重量％的堇青石，次相是富铝红柱石。
4.根据权利要求1所述的陶瓷制品，它表现出在25℃至1000℃的温度范围内的热膨胀系数不超过10×10-7/℃。
5.根据权利要求1所述的陶瓷制品，其中陶瓷制品包含挤压的蜂窝结构体。
6.根据权利要求1所述的陶瓷制品，其中制品表现出孔隙度大于25％。
7.一种含堇青石主相和次相的陶瓷体的制造方法，该方法包括下列步骤：
选择原料以便能形成可塑化的无机原料混合物，该混合物的总分析组成基本上由32-51重量％SiO2、35-49重量％Al2O3和7-16重量％MgO组成，该混合物包含产生SiO2的组分、产生Al2O3的组分和产生MgO的组分；
在无机混合物中加入水和有机粘合剂物系，对该混合物进行捏和，然后挤压形成生坯，
干燥生坯，随后在1150-1450℃的温度下对该生坯进行烧结一定时间，得到烧结相组成为65-95重量％堇青石和5-35重量％选自富铝红柱石、铝酸镁尖晶石和假蓝宝石的次相的烧结陶瓷体，它的总孔隙度不低于20体积％，在25℃至1000℃范围内的热膨胀系数不大于15×10-7/℃。
8.根据权利要求7所述的方法，其中原料混合物包含平均粒径为1.5微米、且BET表面积在7-15m2/g之间的脱层高岭土。
9.根据权利要求7所述的方法，其中产生Al2O3的组分选自氧化铝、矾土、氢氧化铝、含水氧化铝以及它们的混合物。
10.根据权利要求7所述的方法，其中产生Al2O3的组分包含平均粒径为直径小于9微米的高活性氧化铝。
11.根据权利要求7所述的方法，其中产生Al2O3的组分包含平均粒径为1微米或更小的高活性氧化铝。
12.根据权利要求7所述的方法，其中产生MgO的组分选自经锻烧的氧化镁、氢氧化镁、碳酸镁、硝酸镁以及它们的组合物。
13.根据权利要求7所述的方法，其中产生MgO的组分包含平均粒径在1-15微米之间，表面积在1m2/g-15m2/g之间的经锻烧或未经锻烧的滑石。
14.根据权利要求13所述的方法，其中产生MgO的组分包含表面积在3m2/g-8m2/g之间的经锻烧的滑石。
15.根据权利要求7所述的方法，其中产生MgO的组分包含形态指数在0.65-0.85之间的经锻烧的片状滑石。
16.根据权利要求7所述的方法，其中产生MgO的组分包含形态指数为0.75的经锻烧的片状滑石。
17.根据权利要求7所述的方法，其中烧结的陶瓷体表现出有效强度大于3000。
18.根据权利要求7所述的方法，其中生坯是个整个的蜂窝体。
19.根据权利要求7所述的方法，其中有机粘合剂物系包含选自甲基纤维素、甲基纤维素衍生物及其混合物的纤维素醚粘合剂组分、选自硬脂酸、十二烷基硫酸铵、月桂酸、油酸、棕榈酸及其混合物的表面活性剂组分和包含水的溶剂。
20.根据权利要求7所述的方法，其中对于100重量份无机原料混合物采用0.2-2重量份表面活性剂组分、2.5-5重量份纤维素醚粘合剂组分和8-25重量份水。
CN99813431A 1998-11-20 1999-11-10 低热膨胀高强度堇青石结构体的制造 Expired - Lifetime CN1107660C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10940898P 1998-11-20 1998-11-20
US60/109,408 1998-11-20

Publications (2)

Publication Number Publication Date
CN1329581A true CN1329581A (zh) 2002-01-02
CN1107660C CN1107660C (zh) 2003-05-07

Family

ID=22327497

Family Applications (1)

Application Number Title Priority Date Filing Date
CN99813431A Expired - Lifetime CN1107660C (zh) 1998-11-20 1999-11-10 低热膨胀高强度堇青石结构体的制造

Country Status (6)

Country Link
US (1) US6319870B1 (zh)
EP (1) EP1133457B1 (zh)
JP (1) JP2002530262A (zh)
KR (1) KR20010078396A (zh)
CN (1) CN1107660C (zh)
WO (1) WO2000030995A1 (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101808957A (zh) * 2007-08-31 2010-08-18 康宁股份有限公司 将生坯体烧制成多孔陶瓷制品的方法
CN101205136B (zh) * 2006-12-18 2010-08-25 北京中德汇高技术有限公司 一种可在常温下微波加热的远红外陶瓷小球及其制造方法
CN102320841A (zh) * 2011-06-14 2012-01-18 武汉理工大学 一种利用红柱石制备蜂窝陶瓷铸造过滤片的方法
CN104892021A (zh) * 2015-05-18 2015-09-09 新化县恒睿电子陶瓷科技有限公司 一种电子烟净化器用开气孔陶瓷材料及其制备方法
CN107434410A (zh) * 2017-08-28 2017-12-05 中国兵器工业第五二研究所烟台分所 一种堇青石陶瓷粉体的制备方法
CN108752011A (zh) * 2018-05-30 2018-11-06 安徽理工大学 一种以无水氯化镁为熔盐基低温合成堇青石粉体的方法
CN109608227A (zh) * 2019-01-29 2019-04-12 重庆奥福精细陶瓷有限公司 低膨胀高强度薄壁高孔密度蜂窝陶瓷载体
CN112608627A (zh) * 2020-12-03 2021-04-06 山东奥福环保科技股份有限公司 一种低热膨胀蜂窝陶瓷体外周涂层材料及其制备方法
CN114981229A (zh) * 2020-01-27 2022-08-30 贺利氏科纳米北美有限责任公司 用于半导体应用的高纯度堇青石材料

Families Citing this family (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60126218T2 (de) * 2000-04-07 2007-10-31 Ngk Insulators, Ltd., Nagoya Verfahren zur herstellung von honigwabenförmigen keramiken vom cordierittyp
BR0108502A (pt) * 2000-04-07 2003-03-18 Ngk Insulators Ltd Alvéolo cerâmico de cordierita de expansão térmica baixa e processo de produção do mesmo
AU2001261354A1 (en) * 2000-06-01 2001-12-11 Corning Incorporated Cordierite body
JP4082559B2 (ja) 2001-11-22 2008-04-30 日本碍子株式会社 触媒体及びその製造方法
US6864198B2 (en) * 2003-01-30 2005-03-08 Corning Incorporated Cordierite ceramic body and method
WO2006032008A2 (en) * 2004-09-14 2006-03-23 Carbo Ceramics Inc. Sintered spherical pellets
CN101048352A (zh) 2004-10-29 2007-10-03 日本碍子株式会社 蜂窝结构体的制造方法以及蜂窝结构体
EA011732B1 (ru) 2005-03-01 2009-04-28 Карбо Керамикс Инк. Способы получения спеченных частиц из суспензии содержащего оксид алюминия исходного материала
WO2007043022A2 (fr) * 2005-10-12 2007-04-19 Institut National Interuniversitaire Des Silicates, Sols Et Materiaux (I.N.I.S.Ma.), A.S.B.L. Procede de fabrication d'un materiau ceramique poreux et materiau ainsi obtenu
EA013245B1 (ru) * 2005-10-19 2010-04-30 Карбо Керамикс Инк. Состав для литья и способ его получения
US7858554B2 (en) * 2007-05-24 2010-12-28 Geo2 Technologies, Inc. Cordierite fiber substrate and method for forming the same
US8038759B2 (en) 2005-11-16 2011-10-18 Geoz Technologies, Inc. Fibrous cordierite materials
US7744980B2 (en) * 2005-12-20 2010-06-29 Corning Incorporated Low CTE cordierite honeycomb article and method of manufacturing same
US20070254798A1 (en) * 2006-03-31 2007-11-01 Addiego William P Peroxide containing compounds as pore formers in the manufacture of ceramic articles
EP2024299A2 (en) * 2006-05-31 2009-02-18 Corning Incorporated Crack-resistant ceramic honeycomb articles and methods of manufacturing same
US7828998B2 (en) 2006-07-11 2010-11-09 Carbo Ceramics, Inc. Material having a controlled microstructure, core-shell macrostructure, and method for its fabrication
CN101489950B (zh) * 2006-07-21 2013-05-08 陶氏环球技术有限责任公司 改进的柴油机颗粒过滤器
US7964262B2 (en) 2006-08-29 2011-06-21 Corning Incorporated Layered silicate modified cordierite and method
US8063000B2 (en) 2006-08-30 2011-11-22 Carbo Ceramics Inc. Low bulk density proppant and methods for producing the same
US8298311B2 (en) * 2006-11-15 2012-10-30 Corning Incorporated Filters with controlled submicron porosity
EP2109907B1 (en) 2006-12-13 2010-09-15 NanoCell Systems Inc. Electrode assembly for a solid oxide fuel cell and method for making the same
JP2010522106A (ja) * 2007-03-20 2010-07-01 コーニング インコーポレイテッド セラミック・フィルタのための低収縮率施栓用混合物、栓を施されたハニカム・フィルタおよびその製造方法
EA201000114A1 (ru) 2007-07-06 2010-06-30 Карбо Керамикс Инк. Проппант и способ гидравлического разрыва пласта (варианты)
WO2009017642A1 (en) * 2007-07-31 2009-02-05 Corning Incorporated Compositions for applying to ceramic honeycomb bodies
CN101376103B (zh) * 2007-08-27 2011-07-27 比亚迪股份有限公司 汽车尾气净化催化剂载体的预处理方法及汽车尾气净化催化剂
US20090113863A1 (en) * 2007-11-05 2009-05-07 Yanxia Lu Low Expansion Cement Compositions for Ceramic Monoliths
EP2592059B1 (en) 2007-11-30 2020-09-23 Corning Incorporated Composition for applying to honeycomb bodies
US8530368B2 (en) * 2008-08-19 2013-09-10 Basf Corporation Blended hydrous kaolin clay product
US8129302B2 (en) * 2008-08-19 2012-03-06 Basf Corporation Blended hydrous kaolin clay product
CN102171164B (zh) 2008-08-28 2014-11-12 康宁股份有限公司 蜂窝状基材中的孔径分布控制
US7914718B2 (en) * 2008-08-28 2011-03-29 Corning Incorporated Gas pore former in cellular monoliths
JP2012502878A (ja) * 2008-09-18 2012-02-02 ダウ グローバル テクノロジーズ エルエルシー 多孔質のムライト含有複合体の作製方法
JP5657210B2 (ja) * 2009-01-28 2015-01-21 京セラ株式会社 コージェライト質焼結体からなる半導体製造装置用部材
US8051703B2 (en) * 2009-02-27 2011-11-08 Corning Incorporated Methods for using a fluid stream to test a honeycomb body
WO2010114062A1 (ja) 2009-03-31 2010-10-07 日立金属株式会社 セラミックハニカム構造体及びその製造方法
US9227878B2 (en) 2009-04-30 2016-01-05 Corning Incorporated Selected binders for the extrusion of ultra-thin wall cellular ceramics
US20100301515A1 (en) * 2009-05-29 2010-12-02 Thomas William Brew Honeycomb Extrusion Die Apparatus And Methods
US20100329975A1 (en) * 2009-06-29 2010-12-30 William Peter Addiego Cordierite-Forming Compositions With Hydratable Alumina And Methods Therefor
ES2362533B1 (es) * 2009-12-21 2012-05-17 Consejo Superior De Investigaciones Cientificas (Csic) Material compuesto con coeficiente de expansión térmica controlado con cer�?micas ox�?dicas y su procedimiento de obtención.
JP5526850B2 (ja) * 2010-02-18 2014-06-18 株式会社デンソー ハニカム構造体及びその製造方法
CN102770396B (zh) * 2010-02-25 2015-03-11 康宁股份有限公司 制备低热膨胀陶瓷体的组合物和方法
EP2390307A1 (en) 2010-05-27 2011-11-30 Corning Incorporated Porous ceramic processing using prilled wax and non-ionic surfactant
US8925350B2 (en) 2010-07-23 2015-01-06 King Abdulaziz City For Science And Technology Preparation of sintered cordierite glass-ceramic bodies
JP2013100216A (ja) * 2011-10-14 2013-05-23 Asahi Glass Co Ltd 酸化物セラミックス焼結体およびその製造方法
MX2017015281A (es) 2015-05-29 2018-08-15 Corning Inc Obstrucción de filtro tipo panal y aparato para obstrucción de filtro tipo panal.
DE112016002824A5 (de) * 2015-06-25 2018-03-08 Neue Porzellanfabrik Triptis Gmbh Cordierithaltiger keramischer Werkstoff, ein Verfahren zu dessen Herstellung, sowie seine Verwendung
EP3880342B1 (en) 2018-11-16 2024-06-12 Corning Incorporated Cordierite-containing ceramic bodies, batch composition mixtures, and methods of manufacturing cordierite-containing ceramic bodies
EP4013727A1 (en) 2019-08-13 2022-06-22 Corning Incorporated Cement mixtures for plugging honeycomb bodies and methods of making the same
US11731907B2 (en) * 2020-08-04 2023-08-22 Applied Materials, Inc. Ceramic material with high thermal shock resistance and high erosion resistance
US20230278933A1 (en) 2020-08-25 2023-09-07 Corning Incorporated Cement mixtures for plugging honeycomb bodies and methods of making the same

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885977A (en) 1973-11-05 1975-05-27 Corning Glass Works Anisotropic cordierite monolith
US4033779A (en) * 1976-03-23 1977-07-05 Corning Glass Works Non-equilibrium cordierite-alumina
JPS602270B2 (ja) * 1976-04-08 1985-01-21 日本碍子株式会社 コージエライト系セラミツクハニカムおよびその製法
JPS5382822A (en) * 1976-12-28 1978-07-21 Ngk Insulators Ltd Cordierite ceramics
JPS5919069B2 (ja) 1980-04-02 1984-05-02 日本碍子株式会社 低膨脹セラミックス
US4434117A (en) 1980-04-04 1984-02-28 Nippon Soken, Inc. Method for producing a cordierite body
JPS6117469A (ja) 1984-07-03 1986-01-25 日本碍子株式会社 緻密質コ−ジエライトの製造法
US4772580A (en) 1985-12-27 1988-09-20 Ngk Insulators, Ltd. Catalyst carrier of cordierite honeycomb structure and method of producing the same
US4877670A (en) 1985-12-27 1989-10-31 Ngk Insulators, Ltd. Cordierite honeycomb structural body and method of producing the same
US4869944A (en) 1987-02-12 1989-09-26 Ngk Insulators, Ltd. Cordierite honeycomb-structural body and a method for producing the same
US4745092A (en) 1987-04-27 1988-05-17 The Dow Chemical Company Strengthened cordierite having minor amounts of calcia
US5141686A (en) 1988-11-21 1992-08-25 Corning Incorporated Method for producing cordierite articles
US5270270A (en) 1989-02-25 1993-12-14 Schott Glaswerke Process for producing dense-sintered cordierite bodies
US4950628A (en) 1989-04-19 1990-08-21 Corning Incorporated Material and process to produce low thermal expansion cordierite structures
US5281462A (en) 1989-11-01 1994-01-25 Corning Incorporated Material, structure, filter and catalytic converter
US5114644A (en) 1991-02-13 1992-05-19 Corning Incorporated Fabrication of cordierite bodies
US5114643A (en) * 1991-02-13 1992-05-19 Corning Incorporated Fabrication of cordierite bodies
US5258150A (en) 1991-12-06 1993-11-02 Corning Incorporated Fabrication of low thermal expansion, high porosity cordierite body
US5409870A (en) * 1992-11-20 1995-04-25 Corning Incorporated Modified cordierite precursors
US5332703A (en) 1993-03-04 1994-07-26 Corning Incorporated Batch compositions for cordierite ceramics
CN1210835A (zh) * 1997-07-28 1999-03-17 康宁股份有限公司 烧成时间显著缩短的堇青石物体的制备方法
EP0894776B1 (en) * 1997-07-28 2003-09-10 Corning Incorporated Method of producing fast-fired cordierite bodies
US6113829A (en) * 1997-08-27 2000-09-05 Corning Incorporated Method of forming and shaping plasticized mixtures by low to moderate shear extrusion

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101205136B (zh) * 2006-12-18 2010-08-25 北京中德汇高技术有限公司 一种可在常温下微波加热的远红外陶瓷小球及其制造方法
CN101808957A (zh) * 2007-08-31 2010-08-18 康宁股份有限公司 将生坯体烧制成多孔陶瓷制品的方法
CN101808957B (zh) * 2007-08-31 2013-06-05 康宁股份有限公司 将生坯体烧制成多孔陶瓷制品的方法
CN102320841A (zh) * 2011-06-14 2012-01-18 武汉理工大学 一种利用红柱石制备蜂窝陶瓷铸造过滤片的方法
CN104892021B (zh) * 2015-05-18 2018-05-22 新化县恒睿电子陶瓷科技有限公司 一种电子烟净化器用开气孔陶瓷材料及其制备方法
CN104892021A (zh) * 2015-05-18 2015-09-09 新化县恒睿电子陶瓷科技有限公司 一种电子烟净化器用开气孔陶瓷材料及其制备方法
CN107434410A (zh) * 2017-08-28 2017-12-05 中国兵器工业第五二研究所烟台分所 一种堇青石陶瓷粉体的制备方法
CN107434410B (zh) * 2017-08-28 2020-08-11 中国兵器工业第五二研究所烟台分所 一种堇青石陶瓷粉体的制备方法
CN108752011A (zh) * 2018-05-30 2018-11-06 安徽理工大学 一种以无水氯化镁为熔盐基低温合成堇青石粉体的方法
CN108752011B (zh) * 2018-05-30 2021-05-18 安徽理工大学 一种以无水氯化镁为熔盐基低温合成堇青石粉体的方法
CN109608227A (zh) * 2019-01-29 2019-04-12 重庆奥福精细陶瓷有限公司 低膨胀高强度薄壁高孔密度蜂窝陶瓷载体
CN114981229A (zh) * 2020-01-27 2022-08-30 贺利氏科纳米北美有限责任公司 用于半导体应用的高纯度堇青石材料
CN112608627A (zh) * 2020-12-03 2021-04-06 山东奥福环保科技股份有限公司 一种低热膨胀蜂窝陶瓷体外周涂层材料及其制备方法
CN112608627B (zh) * 2020-12-03 2021-09-17 山东奥福环保科技股份有限公司 一种低热膨胀蜂窝陶瓷体外周涂层材料及其制备方法

Also Published As

Publication number Publication date
US6319870B1 (en) 2001-11-20
EP1133457A4 (en) 2006-04-19
EP1133457A1 (en) 2001-09-19
EP1133457B1 (en) 2016-04-06
KR20010078396A (ko) 2001-08-20
CN1107660C (zh) 2003-05-07
JP2002530262A (ja) 2002-09-17
WO2000030995A1 (en) 2000-06-02

Similar Documents

Publication Publication Date Title
CN1107660C (zh) 低热膨胀高强度堇青石结构体的制造
CN1166584C (zh) 低热膨胀高孔隙率高强度堇青石体及其制造方法
EP1261564B1 (en) Fabrication of ultra-thinwall cordierite structures
CN101374786B (zh) 低热膨胀系数的堇青石蜂窝状制品及其制造方法
CN1189418C (zh) 特低热膨胀堇青石结构体的制造方法
US4435512A (en) Process for producing cordierite ceramic products
JP3416750B2 (ja) コージーライトボディおよびそのボディの製造方法
US8148297B2 (en) Reticular cordierite composition, article and manufacture thereof
CN1242953C (zh) 可塑炼的混合物和可挤压的混合物
US6562284B2 (en) Fabrication of ultra-thinwall cordierite structures
JPH1157496A (ja) コージェライト質セラミックハニカム構造体の製造方法
JPH0717761A (ja) 可塑化可能な混合材およびそれから作られる改良コージエライト基体の製造方法
CN1287546A (zh) 孔径分布窄的低热膨胀性堇青石体及其制造方法
CN1213962C (zh) 孔径分布窄的低热膨胀性堇青石体及其制造方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Assignee: Corelle (Shanghai) Co., Ltd.

Assignor: Corning Incorporated

Contract fulfillment period: 2008.9.25 to 2021.11.29

Contract record no.: 2008990000638

Denomination of invention: Fabrication of low thermal expansion high strength cordierite structures

Granted publication date: 20030507

License type: Exclusive license

Record date: 2008.10.9

LIC Patent licence contract for exploitation submitted for record

Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.9.25 TO 2021.11.29; CHANGE OF CONTRACT

Name of requester: KANGNING( SHANGHAI ) CO., LTD.

Effective date: 20081009

CX01 Expiry of patent term

Granted publication date: 20030507

CX01 Expiry of patent term