CN1576262A - 氮化硅质过滤器的制造方法 - Google Patents
氮化硅质过滤器的制造方法 Download PDFInfo
- Publication number
- CN1576262A CN1576262A CN200410069982.6A CN200410069982A CN1576262A CN 1576262 A CN1576262 A CN 1576262A CN 200410069982 A CN200410069982 A CN 200410069982A CN 1576262 A CN1576262 A CN 1576262A
- Authority
- CN
- China
- Prior art keywords
- silicon nitride
- pore
- manufacture method
- particle
- mentioned
- 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
Links
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 54
- -1 inorganic acid salt Chemical class 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 86
- 238000000034 method Methods 0.000 claims description 56
- 239000002923 metal particle Substances 0.000 claims description 52
- 238000000465 moulding Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 239000011800 void material Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 14
- 238000007669 thermal treatment Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011224 oxide ceramic Substances 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 239000011856 silicon-based particle Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005121 nitriding Methods 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004320 controlled atmosphere Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/14—Colouring matters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/573—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
-
- 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
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
- C04B38/0032—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors one of the precursor materials being a monolithic element having approximately the same dimensions as the final article, e.g. a paper sheet which after carbonisation will react with silicon to form a porous silicon carbide porous body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical 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
- 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
- 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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- 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
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- 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
- C04B2235/443—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
- C04B2235/46—Gases other than oxygen used as reactant, e.g. nitrogen used to make a nitride 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
- C04B2235/02—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
- C04B2235/5463—Particle size distributions
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6021—Extrusion moulding
-
- 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
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Filtering Materials (AREA)
- Ceramic Products (AREA)
Abstract
本发明提供一种以金属硅粒子作为起始原料,最适于高强度除尘和脱尘的氮化硅质过滤器的制造方法。它是通过在氮中对含有60-95质量%的金属硅粒子和5-40质量%的气孔形成材料的成形体进行热处理以制得实质上金属硅被氮化的氮化硅,原料的金属硅粒子是粒径为5-100μm的粒子占全部金属硅粒子中的70质量%以上并且平均粒径为10- 75μm的粒子。更加适合的是,在上述成形体中包含含有选自Mg、Ca、Fe及Cu中的1种以上的金属元素的无机酸盐、有机酸盐以及氢氧化物中的1种或1种以上。
Description
技术领域
本发明涉及适合于除去高温废气中所含的粉尘等的氮化硅质过滤器。
背景技术
氮化硅具有优异的耐热性、耐腐蚀性、耐药品性、机械强度等特性,人们期待其制成在高温及腐蚀性环境下进行集尘、脱尘用的过滤器以及除去柴油发动机排出的微粒(以下称为微粒子)用的过滤器(以下称为DPF)。若将起始原料区分的话,上述氮化硅质过滤器的制造方法可被分为以氮化硅粒子为起始原料的制造方法(参考日本特许公开公报平6-256069号(第1-6页)、日本特许公开公报平7-187845号(第1-5页)和日本特许公开公报平8-59364号(第1-7页))和以金属硅粒子为起始原料的制造方法(参考日本特许公开公报昭52-121613号(第1-5页)、国际公开第01/47833号小册子(第3-9页)和日本特许公开公报2002-284585号(第1-5页))。以金属硅粒子为起始原料,通过直接氮化形成氮化硅的制造方法,和以氮化硅粒子作为起始原料的制造方法相比,以其原料费用便宜,所以在制造成本方面具有优异的特性。
以金属硅为起始原料的制造方法的以往技术中,有人提出对采用了微细的金属硅粉末的成形体进行氮化处理而制得氮化硅多孔体的方法(参考日本特许公开公报昭52-121613号(第1-5页))。但是,要制得气孔率高的多孔体,必须对成形体密度低的金属硅成形体进行氮化处理,此时,在表面和内部生成微细的氮化硅纤维,可能成为平均细孔直径小的多孔体。
为了解决上述问题,人们提出如下的制造方法:在氮中对包含40-90%的平均粒径为1-200μm的金属硅粒子和10-60%的气孔形成材料的成形体进行热处理,以制得平均细孔直径为5-40μm的氮化硅多孔体的方法(参考国际公开第01/47833号小册子(第3-9页))。但是,人们要求利用该方法制成DPF使用时,压力损失(以下称为压损)更小、微粒子的收集效率更高的方法。
人们又提出如下的方法:在调配以金属硅为主要成分的成形体,使所得的以金属硅为主要成分的成形体氮化之前,通过控制气氛气来除去金属硅的表面氧化物,其后,引入氮气而使金属硅氮化以制得氮化硅多孔体的方法(参考日本特许公开公报2002-284585号(第1-5页))。但是,利用该方法,不仅很难得到气孔率和细孔径都足够大的氮化硅多孔体,而且因为要在金属硅的氮化处理前控制气氛气,不能使用适于大量生产的连续焙烧炉等,从生产率角度看,存在问题。
本发明的目的在于提供一种以金属硅粒子作为起始原料,机械特性良好的、低压损的、特别是微粒子的收集效率高的可作为DPF的氮化硅质过滤器的制造方法。
发明内容
本发明提供一种氮化硅质过滤器的制造方法,其特征在于,通过在氮中对含有60-95质量%的金属硅粒子和5-40质量%的气孔形成材料的成形体进行热处理以制得实质上金属硅被氮化的氮化硅,原料的金属硅粒子是粒径为5-100μm的粒子占全部金属硅粒子中的70质量%以上并且平均粒径为10-75μm的粒子。
通过本制造方法,能够容易制造具有平均细孔直径和气孔率都大并且细孔径大的粒子的比例高的细孔特性的氮化硅质过滤器。并且通过本制造方法所制得的氮化硅质过滤器具有高强度,耐热性、耐腐蚀性及耐药品性都良好,所以特别适用于要求强度、耐热性、耐腐蚀性、耐久性等的DPF。
具体实施方式
在本发明的氮化硅质过滤器的制造方法(以下称为本制造方法)中,使用了包含60-95质量%的金属硅粒子和5-40质量%的气孔形成材料的成形体,其中的金属硅粒子是粒子直径(以下简称为粒径)为5-100μm的粒子占全部金属硅粒子中的70质量%以上并且平均粒径为10-75μm的粒子。
用于本制造方法的金属硅粒子的平均粒径为10-75μm。若金属硅粒子的平均粒径未满10μm的话,所得过滤器的平均细孔直径(以下将细孔直径称为细孔径)在5μm以下,不理想。若金属硅粒子的平均粒径超过75μm的话,所得的氮化硅质过滤器的平均细孔径变大,氮化不一定充分,不理想。金属硅粒子的平均粒径较好在15-65μm,金属硅粒子的平均粒径更好在20-60μm。
用于本制造方法的金属硅粒子不仅平均粒径为10-75μm,而且粒径为5-100μm的范围的金属硅粒子占全体金属硅粒子中的70质量%以上。若粒径为5-100μm的范围的金属硅粒子占全体金属硅粒子中的70质量%以上的话,所得的氮化硅质过滤器的细孔径在5μm以下的细孔变少,压损减少,并且能够高效率收集凝集粒径在10μm以上的微粒子等。粒径为5-100μm的范围的金属硅粒子最好占全体金属硅粒子的85质量%以上,在上述范围的金属硅粒子更好占全体金属硅粒子的95质量%以上。
在本制造方法中,粒径在10-90μm的范围内的金属硅粒子在75质量%以上较好。粒径在20-80μm的范围内的金属硅粒子在75质量%以上更好。粒径在20-80μm的范围内的金属硅粒子在95质量%以上特好。这样具有特定范围的粒度分布的金属硅粒子可通过适当使用气流分级或筛子分级等的分级手段得到。金属硅粒子的纯度可根据目的、用途进行适当选择。
本制造方法的金属硅粒子的含量是上述成形体的60-95质量%。若上述成形体中的金属硅粒子的含量未满60质量%的话,所得的氮化硅质过滤器的气孔率过大,机械强度不够,可能不耐实用。另外,上述成形体中的金属硅粒子的含量超过95质量%的话,氮化硅质过滤器的气孔率过小,可能不能实现作为过滤器的功能。
对于作为本制造方法中的气孔形成材料,无特别限制,只要能够形成气孔的材料即可,若是氧化物陶瓷的中空粒子(以下简称为中空粒子)及/或飞散型气孔形成材料的话,较少的添加量,便可形成所需的气孔,所以较为理想。气孔形成材料的含量是上述成形体中的5-40质量%。若上述成形体中的气孔形成材料的含量未满5质量%的话,氮化硅质过滤器的气孔率过小,可能不能实现作为过滤器的功能。另一方面,若上述成形体中的气孔形成材料的含量超过40质量%时,氮化硅质过滤器的气孔率过大,机械强度不够,可能不耐实用。
作为上述中空粒子,只要是在热处理时可形成气孔,并且对于热处理过程中所生成的氮化硅粒子具有烧结助剂的功能的粒子的话,无论使用晶体质,还是使用非晶质都是适合的。中空粒子若是以选自Al、Si、Ca、Sr、Ba及Mg中的1种以上的金属的氧化物为主要成分的粒子的话,因烧结助剂的效果大,所以较为理想。中空粒子只要是中空的话,相当于外皮的部分可以是致密质的,也可以是多孔质的。中空粒子是外形为球状的粒子时,因容易得到,所以较为理想。即使是球状粒子以外的粒子只要是中空即可。
作为飞散型气孔形成材料,只要是热处理时发生分解等、飞散而形成气孔的材料,有机物、无机物均适合使用。飞散型气孔形成材料为有机高分子粒子,特别是热分解性的高分子粒子的话,在热处理过程中发生分解和飞散,在烧结体内不剩下残留物,不损害所得的氮化硅质过滤器的特性,所以较为理想。只要是热分解而具有烧失的功能的材料,都适合使用。例如,可用丙烯酸树脂、聚乙酸乙烯酯树脂、有机硅树脂等。
上述中空粒子和上述有机高分子粒子的平均粒径为10-100μm时,所得的氮化硅质过滤器的气孔率大且可确保强度,所以较为理想。若上述中空粒子等的平均粒径未满10μm时,气孔形成低下;另一方面,上述中空粒子等的平均粒径超过100μm时,所得的氮化硅质过滤器的强度不够,因此不理想。
在本制造方法的上述成形体中若包含含有选自Mg、Ca、Fe及Cu中1种以上的金属元素的无机酸盐及/或有机酸盐时,可促进金属硅粒子的氮化,因此较为理想。作为无机酸盐,无特别限制,可用硝酸盐、盐酸盐和硫酸盐等。另一方面,作为有机酸盐,可用乙酸盐、草酸盐等的羧酸盐等。尤其是水溶性的盐,因能以溶液形式添加在成形体中,和以氧化物等的盐以外的物质进行添加的情况相比,可以少的添加量得到促进氮化的效果,所以较为理想。上述元素的添加量越少,通常越不阻碍氮化硅质过滤器的特性,所以较为理想。在上述盐中,较好用硝酸铁等的硝酸盐或羧酸盐等。
在本制造方法中,可以代替无机酸盐,而合用含有选自Mg、Ca、Fe及Cu中的1种以上的金属元素的氢氧化物,或者无机酸盐或者有机酸盐。例如,在用水进行混炼制成挤压成形用坯土的过程中,因硝酸镁之类的容易溶解于水中的无机酸盐和水进行反应而形成氢氧化物,所以也可用氢氧化镁。即,在成形体中包含含有选自Mg、Ca、Fe及Cu中的1种以上的金属元素的无机酸盐有机酸盐及氢氧化物中的1种或1种以上时,能促进金属硅粒子的氮化,所以较为理想。
本制造方法的上述无机酸盐及/或有机酸盐的添加量,相对于金属硅粒子100质量份,按金属元素计较好为0.1-3质量份。若上述添加量未满0.1质量份时,可能不能得到添加的效果。另一方面,若上述添加量超过3质量份时,可能阻碍氮化硅质过滤器的耐热性等特性,上述添加量更好为0.5-2质量份。
在本制造方法中,为了代替无机酸盐,而合用含有选自Mg、Ca、Fe及Cu中的1种以上的金属元素的氢氧化物,或者无机酸盐或者有机酸盐时的添加量较好为:相对于金属硅粒子100质量份,以金属元素计,添加0.1-3质量份。上述添加量更好为0.5-2质量份。
对于本制造方法的气孔形成材料和金属硅粒子的混合,可使用球磨机或混合机等的通常的混合手段,作为制得含有气孔形成材料和金属硅粒子的成形体的方法,可适当采用压制成形、挤压成形、浇铸成形等的通常的陶瓷成形法。在成形时,还可以添加有机粘合剂。作为这样的有机粘合剂,可用聚乙烯醇或其改性物、淀粉或其改性物、羧基甲基纤维素、羟基甲基纤维素、聚乙烯基吡咯烷酮、丙烯酸树脂或丙烯酸类共聚物、乙酸乙烯酯树脂或乙酸乙烯酯类共聚物等的有机物。
热处理上述成形体的条件为:在氮气氛下进行2阶段的热处理,较好分成适合于金属硅粒子的氮化的第1阶段及适合于生成的氮化物氮化硅粒子的烧结的第2阶段。
作为第1阶段的热处理条件,较好在氮气氛下于1200-1400℃保持4-12小时。若温度未满1200℃时,金属硅粒子不发生氮化,另一方面,温度超过1400℃时,在金属硅的熔点(1410℃)附近,金属硅粒子熔解,不能保持烧结体的形状,所以不理想。温度保持时间未满4小时的话,金属硅粒子的氮化变得不充分,不理想,若温度保持时间超过12小时的话,氮化反应几乎不能进一步进行,运转费用上升,所以不理想。
作为第2阶段的热处理条件,较好是在氮气氛下,于1500-1800℃保持1-12小时。若温度未满1500℃时,氮化硅粒子的烧结不能进行,不理想。超过1800℃时,氮化硅粒子分解,也不理想。若温度保持时间未满1小时的话,粒子间的结合不能充分进行,所以不理想。另一方面,若超过12小时的话,特别在高温下氮化硅容易分解,不理想。第1阶段的热处理和第2阶段的热处理,可以在中途一段时间中使温度下降,或者不下降温度连续进行。
热处理时的升温速度可根据成形体的大小和形状等进行适当选择,若50-600℃/h的话,从氮化率和气孔径的角度出发,较为理想。在升温过程中,在第1阶段及第2阶段所规定的温度范围内时,其经过时间是分别加上第1阶段及第2阶段的保持时间的。这里的氮气氛气是指实质上只含有氮不含有氧的气氛气,也可以含有其它的惰性气体,氮分压较好在50kPa以上。
本制造方法所得的氮化硅质过滤器的气孔率较好为45-80%。气孔率是经阿基米德法测得的。气孔率未满45%的话,压损增大,作为过滤器不好,气孔率超过80%时,强度低,所以作为过滤器不理想。
本制造方法所得的氮化硅质过滤器的经汞压入法测得的平均细孔径较好为5-40μm。平均细孔径未满5μm时,过滤器使用时的压损变大,不理想。平均细孔径超过40μm时,微粒子那样的废气微粒子的捕捉除去很难进行,所以不理想。
将本制造方法制得的氮化硅质过滤器的平均细孔径设为d0时,细孔径为0.5d0-1.5d0的细孔的细孔容积之和在全体细孔容积之和的50体积%以上,全部细孔中,用于过滤器的细孔的比例增高,所以不会降低捕集效率并能形成低压损。其结果是由于压损降低,不会白白增大气孔率而使过滤器的机械强度降低,因能形成同时具有低压损和高捕集效率的氮化硅质过滤器,所以较为理想。
(实施例)
以下列举实施例(例1、例2、例4-例6)和比较例(例3),所得的多孔体经如下所述的评价法进行评价。
(评价方法)
气孔率:经阿基米德法算出。
平均细孔径:利用水银孔度计(ユアサアイオニクス株式会社制造的AUTOSCAN-33)测定。
结晶相:利用X射线衍射装置(リガク公司制造,商品名:ガイガ一フレツクスRAD-IIA)鉴定。
室温强度:从制成蜂窝状的薄膜上切取由纵横为7×7的小室构成的、长度为12mm的试验片,与挤压方向平行以施加速度为0.5mm/分钟施加负荷,进行测定来作为压缩强度。
(例1)
准备如下混合粉末:将粒径5-100μm的粒子占全部金属硅粒子的97质量%且平均粒径为30μm的金属硅粒子70质量%和作为气孔形成材料的平均粒径为45μm的球状二氧化硅-氧化铝类玻璃质中空粒子30质量%混合而成。在该混合粉末中,添加硝酸镁以使相对于金属硅100质量份,为1质量份,作为成形体用粉末。在100质量份的上述成形体用粉末中添加甲基纤维素20质量份,56质量份的离子交换水,作为挤压成形原料。
利用真空挤压机将上述挤压成形原料挤压成形为蜂窝状的成形体后,于100℃进行干燥。在氮气氛中,以升温速度为2℃/分将干燥后的蜂窝状成形体升温至1350℃后,保持4小时进行第1阶段的热处理,再以升温速度为4℃/分升温至1700℃,保持4小时,制得多孔质的氮化硅质的蜂窝状烧结体。对所得的多孔体进行X射线衍射测定的结果是:氮化硅的衍射峰被鉴定出,而金属硅的衍射峰没有被鉴定出。所得的多孔体的细孔特性为:气孔率为60%,平均细孔径为12μm,细孔径为6-18μm的细孔的细孔容积之和是全部细孔容积之和的79体积%。所得的多孔体的室温强度为15MPa。
(例2)
除了相对于100质量份的金属硅,添加3质量份的平均粒径为3μm的氢氧化镁粉末来代替硝酸镁以外,和例1一样进行。对所得的多孔体进行X射线衍射测定的结果为:鉴定出氮化硅的衍射峰,没有鉴定出金属硅的衍射峰。所得的多孔体的细孔特性为:气孔率为70%,平均细孔径为8μm,细孔径为4-12μm的细孔的细孔容积之和是全部细孔容积之和的76体积%。所得的多孔体的室温强度为4MPa。
(例3)
除了使用粒径5-100μm的粒子占全部金属硅粒子的40质量%并且平均粒径为4μm的金属硅粒子来代替例1的金属硅粒子以外,和例1一样,对所得的多孔体进行X射线衍射测定,其结果为:鉴定出氮化硅的衍射峰,没有鉴定出金属硅的衍射峰。所得的多孔体的细孔特性为:气孔率为55%,平均细孔径为7μm,细孔径为3.5-10.5μm的细孔的细孔容积之和是全部细孔容积之和的30体积%。所得的多孔体的室温强度为40MPa。
(例4)
准备如下混合粉末:将粒径45-75μm的粒子占全部金属硅粒子的99质量%且平均粒径为55μm的金属硅粒子70质量%和作为气孔形成材料的平均粒径为30μm的球状二氧化硅-氧化铝类玻璃质中空粒子20质量%混合而成。在该混合粉末中,添加硝酸铁以使相对于金属硅100质量份,为2质量份,作为成形体用粉末。在100质量份的上述成形体用粉末中添加甲基纤维素15质量份,50质量份的离子交换水,作为挤压成形原料。
利用真空挤压机将上述挤压成形原料挤压成形为蜂窝状的成形体后,于100℃进行干燥。在氮气氛中,以升温速度为2℃/分将干燥后的蜂窝状成形体升温至1350℃后,保持10小时进行第1阶段的热处理,再以升温速度为4℃/分升温至1700℃,保持4小时,制得多孔质的氮化硅质的蜂窝状烧结体。对所得的多孔体进行X射线衍射测定的结果是:氮化硅的衍射峰被鉴定出,而金属硅的衍射峰没有被鉴定出。所得的多孔体的细孔特性为:气孔率为63%,平均细孔径为25μm,细孔径为12.5-37.5μm的细孔的细孔容积之和是全部细孔容积之和的72体积%。所得的多孔体的室温强度为8MPa。
(例5)
除了不添加例4的硝酸铁以外,和例4一样制备。通过X射线对所得的多孔体进行相同的鉴定,其结果为:确认除了氮化硅以外,还残留有硅。所得的多孔体的气孔率为67%,平均细孔径为30μm,细孔径为15-45μm的细孔的细孔容积之和是全部细孔容积之和的67体积%。所得的多孔体的室温强度为4MPa。
(例6)
除了使用平均粒径为10μm的丙烯酸树脂作为例4的气孔形成材料以外,和例4一样制备。对所得的多孔体进行X射线衍射测定,虽然鉴定出氮化硅的衍射峰,但没有发现硅的衍射峰。所得的多孔体的气孔率为64%,平均细孔径为20μm,细孔径为10-30μm的细孔的细孔容积之和是全部细孔容积之和的85体积%。所得的多孔体的室温强度为10MPa。
产业上应用的可能性
本发明是氮化硅质过滤器的制造方法,其特征在于,以具有特定粒度分布的金属硅作为起始原料,并将其氮化而形成氮化硅,所以该方法适用作为机械特性好、特别是低压损并且微粒子的捕集效率高的、可适合于DPF的过滤器的制造方法。
Claims (10)
1.氮化硅质过滤器的制造方法,其特征在于,通过在氮中对含有60-95质量%的金属硅粒子和5-40质量%的气孔形成材料的成形体进行热处理以制得实质上金属硅被氮化的氮化硅,原料的金属硅粒子是粒径为5-100μm的粒子占全部金属硅粒子中的70质量%以上并且平均粒径为10-75μm的粒子。
2.根据权利要求1所述的氮化硅质过滤器的制造方法,其特征在于,在上述成形体中包含含有选自Mg、Ca、Fe及Cu中的1种以上的金属元素的无机酸盐有机酸盐及氢氧化物中的1种或1种以上。
3.根据权利要求2所述的氮化硅质过滤器的制造方法,其特征在于,上述盐是水溶性的。
4.根据权利要求2或3所述的氮化硅质过滤器的制造方法,其特征在于,上述无机酸盐为硝酸盐、盐酸盐或硫酸盐。
5.根据权利要求2或3所述的氮化硅质过滤器的制造方法,其特征在于,上述有机酸盐为羧酸盐。
6.根据权利要求1-5中任一项所述的氮化硅质过滤器的制造方法,其特征在于,作为上述气孔形成材料,使用金属氧化物陶瓷中空粒子及/或飞散型气孔形成材料。
7.根据权利要求1-6中任一项所述的氮化硅质过滤器的制造方法,其特征在于,上述过滤器的气孔率为45-80%。
8.根据权利要求1-7中任一项所述的氮化硅质过滤器的制造方法,其特征在于,利用上述过滤器的汞压入法所测得的平均细孔直径为5-40μm。
9.根据权利要求1-8中任一项所述的氮化硅质过滤器的制造方法,其特征在于,设上述过滤器的平均细孔直径为d0时,细孔直径为0.5d0-1.5d0的细孔的细孔容积之和在全体细孔容积之和的50体积%以上。
10.根据权利要求1-9中任一项所述的氮化硅质过滤器的制造方法,其特征在于,上述热处理条件为:在温度1200-1400℃的氮气氛中保持成形体4-12小时,进行第1阶段的热处理后,再在温度为1500-1800℃的范围内保持1-12小时,进行第2阶段的热处理。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003276170 | 2003-07-17 | ||
JP2003276170 | 2003-07-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1576262A true CN1576262A (zh) | 2005-02-09 |
CN100339338C CN100339338C (zh) | 2007-09-26 |
Family
ID=33475574
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2004100699826A Expired - Fee Related CN100339338C (zh) | 2003-07-17 | 2004-07-16 | 氮化硅质过滤器的制造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US7368076B2 (zh) |
EP (1) | EP1498400A3 (zh) |
CN (1) | CN100339338C (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105503200A (zh) * | 2016-01-12 | 2016-04-20 | 中钢集团洛阳耐火材料研究院有限公司 | 一种氮化硅纤维过滤材料的制备方法 |
CN105645998A (zh) * | 2016-01-12 | 2016-06-08 | 中钢集团洛阳耐火材料研究院有限公司 | 一种低热导率氮化硅隔热材料的制备方法 |
CN105801122A (zh) * | 2016-03-01 | 2016-07-27 | 中钢集团洛阳耐火材料研究院有限公司 | 一种梯度孔结构碳化硅基多孔陶瓷的制备方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3698143B2 (ja) * | 2003-01-21 | 2005-09-21 | 住友電気工業株式会社 | フィルタ用多孔質Si3N4とその製造方法 |
CN100339338C (zh) | 2003-07-17 | 2007-09-26 | 旭硝子株式会社 | 氮化硅质过滤器的制造方法 |
CN100343198C (zh) * | 2003-07-29 | 2007-10-17 | 旭硝子株式会社 | 氮化硅质蜂窝式过滤器及其制造方法 |
JP2006102631A (ja) * | 2004-10-05 | 2006-04-20 | Asahi Glass Co Ltd | 窒化ケイ素質フィルタの製造法 |
JP2006160533A (ja) * | 2004-12-02 | 2006-06-22 | Asahi Glass Co Ltd | 窒化ケイ素質ハニカムフィルタの製造法 |
EP2067589B1 (en) * | 2006-09-28 | 2012-04-11 | Hitachi Metals, Ltd. | Method and apparatus for manufacturing ceramic honeycomb structure |
US20110111205A1 (en) * | 2009-11-09 | 2011-05-12 | Korea Institute Of Machinery & Materials | METHOD OF MANUFACTURING POROUS SINTERED REACTION-BONDED SILICON NITRIDE CERAMICS FROM GRANULAR Si MIXTURE POWDER AND POROUS SINTERED REACTION-BONDED SILICON NITRIDE CERAMICS MANUFACTURED THEREBY |
CN114716252B (zh) * | 2022-04-27 | 2023-05-09 | 中国科学院上海硅酸盐研究所 | 一种易烧结高纯氮化硅粉体的制备方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT989744B (it) | 1972-10-02 | 1975-06-10 | Ford Motor Co | Convertitore catalitico a base di nitruro di silicio per il tratta mento dei gas di scarico di motori a combustione interna e procedi mento per la sua produzione |
US3960581A (en) * | 1974-04-29 | 1976-06-01 | The University Of Utah | Process for producing a solid solution of aluminum oxide in silicon nitride |
GB1546928A (en) | 1976-01-06 | 1979-05-31 | Gen Electric | Si3n4 formed by nitridation of sintered silicon compact |
JPH06256069A (ja) | 1993-02-26 | 1994-09-13 | Kikusui Kagaku Kogyo Kk | セラミック多孔体およびその製造方法 |
JP3596910B2 (ja) | 1993-06-14 | 2004-12-02 | 新原 ▲晧▼一 | セラミックス多孔体及びその製造方法 |
JPH0859364A (ja) | 1994-08-11 | 1996-03-05 | Fine Ceramics Center | セラミックス多孔質体の製造方法 |
US5827472A (en) * | 1994-10-19 | 1998-10-27 | Sumitomo Electric Industries, Ltd. | Process for the production of silicon nitride sintered body |
CN1059883C (zh) * | 1995-04-20 | 2000-12-27 | 郑州华宇耐火材料集团公司 | 半石墨化碳氮化硅材料及其生产方法 |
JPH09249457A (ja) * | 1996-01-09 | 1997-09-22 | Sumitomo Electric Ind Ltd | 高強度窒化ケイ素多孔体及びその製造方法 |
WO2001047833A1 (fr) | 1999-12-24 | 2001-07-05 | Asahi Glass Company, Limited | Filtre au nitrure de silicium et procede de fabrication correspondant |
JP2001316188A (ja) * | 2000-04-28 | 2001-11-13 | Asahi Glass Co Ltd | 窒化ケイ素質多孔体およびその製造方法 |
DE60120586T2 (de) | 2000-10-13 | 2007-05-31 | Asahi Glass Co., Ltd. | Verfahren zur Herstellung eines Siliziumnitridfilters |
JP4574044B2 (ja) | 2001-03-26 | 2010-11-04 | 日本碍子株式会社 | 窒化珪素多孔体及びその製造方法 |
JPWO2004050318A1 (ja) | 2002-12-05 | 2006-03-30 | 旭硝子株式会社 | セラミックスハニカム用液剤注入装置およびそれを使用した封止方法 |
CN100339338C (zh) | 2003-07-17 | 2007-09-26 | 旭硝子株式会社 | 氮化硅质过滤器的制造方法 |
CN100343198C (zh) * | 2003-07-29 | 2007-10-17 | 旭硝子株式会社 | 氮化硅质蜂窝式过滤器及其制造方法 |
-
2004
- 2004-07-16 CN CNB2004100699826A patent/CN100339338C/zh not_active Expired - Fee Related
- 2004-07-16 EP EP04016818A patent/EP1498400A3/en not_active Withdrawn
- 2004-07-16 US US10/892,200 patent/US7368076B2/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105503200A (zh) * | 2016-01-12 | 2016-04-20 | 中钢集团洛阳耐火材料研究院有限公司 | 一种氮化硅纤维过滤材料的制备方法 |
CN105645998A (zh) * | 2016-01-12 | 2016-06-08 | 中钢集团洛阳耐火材料研究院有限公司 | 一种低热导率氮化硅隔热材料的制备方法 |
CN105801122A (zh) * | 2016-03-01 | 2016-07-27 | 中钢集团洛阳耐火材料研究院有限公司 | 一种梯度孔结构碳化硅基多孔陶瓷的制备方法 |
CN105801122B (zh) * | 2016-03-01 | 2019-04-12 | 中钢集团洛阳耐火材料研究院有限公司 | 一种梯度孔结构碳化硅基多孔陶瓷的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20050023735A1 (en) | 2005-02-03 |
EP1498400A3 (en) | 2006-06-07 |
EP1498400A2 (en) | 2005-01-19 |
CN100339338C (zh) | 2007-09-26 |
US7368076B2 (en) | 2008-05-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1028018C (zh) | 高温低热膨胀陶瓷 | |
JP2005521624A (ja) | ムライト体及びムライト体の形成方法 | |
CN1079785C (zh) | 氮化铝烧结体及其制造方法 | |
CN100339338C (zh) | 氮化硅质过滤器的制造方法 | |
JP2012046418A (ja) | 改良された多孔質ムライト体及びそれらの形成方法 | |
JP2012502878A (ja) | 多孔質のムライト含有複合体の作製方法 | |
US20080017573A1 (en) | Diesel particulate filter | |
WO2014058459A1 (en) | Improved porous bodies comprised of mullite and methods of forming them | |
CN1247488C (zh) | 多孔Si3N4及其制备方法 | |
DE60120586T2 (de) | Verfahren zur Herstellung eines Siliziumnitridfilters | |
CN100343198C (zh) | 氮化硅质蜂窝式过滤器及其制造方法 | |
KR101155549B1 (ko) | 다공성 반응소결질화규소의 제조 방법 및 그에 의해 제조된 다공성 반응소결질화규소 | |
EP1674438A1 (en) | Method for producing silicon nitride honeycomb filter | |
US20050023736A1 (en) | Method for producing a silicon nitride honeycomb filter | |
JP2683452B2 (ja) | セラミックス多孔体およびその製造方法 | |
JP2004018361A (ja) | 金属粒子担持複合酸化物焼結構造体およびその製造方法 | |
JP2007131528A (ja) | 非酸化物系多孔質セラミック材の製造方法 | |
JP3605632B2 (ja) | 高強度アルミナ多孔体とその製造方法 | |
JP3707866B2 (ja) | 窒化アルミニウムグリーン体の製造方法 | |
JP2005058999A (ja) | 窒化ケイ素質ハニカムフィルタの製造法 | |
JP2005047796A (ja) | 窒化ケイ素質フィルタの製造法 | |
JP2002121073A (ja) | 窒化ケイ素フィルタの製造法 | |
KR101212638B1 (ko) | 다공성 반응소결질화규소의 제조 방법 및 그에 의해 제조된 다공성 반응소결질화규소 | |
JPH0987040A (ja) | セラミックグリーン体 | |
JP2004123416A (ja) | ケイ素を主体とする非酸化物系多孔質セラミック材の製造方法 |
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 | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070926 |