WO2003062611A1 - Structure en nid d'abeilles contenant si et son procede de fabrication - Google Patents
Structure en nid d'abeilles contenant si et son procede de fabrication Download PDFInfo
- Publication number
- WO2003062611A1 WO2003062611A1 PCT/JP2003/000621 JP0300621W WO03062611A1 WO 2003062611 A1 WO2003062611 A1 WO 2003062611A1 JP 0300621 W JP0300621 W JP 0300621W WO 03062611 A1 WO03062611 A1 WO 03062611A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- honeycomb structure
- phase
- firing step
- firing
- manufacturing
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000010304 firing Methods 0.000 claims abstract description 36
- 238000005192 partition Methods 0.000 claims abstract description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 61
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 33
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 230000007423 decrease Effects 0.000 claims description 10
- 230000000149 penetrating effect Effects 0.000 claims description 9
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021343 molybdenum disilicide Inorganic materials 0.000 claims description 4
- 230000035939 shock Effects 0.000 abstract description 9
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 229910052582 BN Inorganic materials 0.000 description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- GSPPDMIMNFYKRI-UHFFFAOYSA-N boron tin Chemical compound [B].[Sn] GSPPDMIMNFYKRI-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
- B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
-
- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- 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
- C04B35/10—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 aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
-
- 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
- C04B35/185—Mullite 3Al2O3-2SiO2
-
- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
- C04B35/488—Composites
-
- 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
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
-
- 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
-
- 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
- C04B35/581—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 aluminium nitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- 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
- B01D—SEPARATION
- B01D2279/00—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses
- B01D2279/30—Filters adapted for separating dispersed particles from gases or vapours specially modified for specific uses for treatment of exhaust gases from IC Engines
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3821—Boron carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/386—Boron nitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
-
- 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
- C04B2235/50—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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/668—Pressureless 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
-
- 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
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/761—Unit-cell parameters, e.g. lattice constants
-
- 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
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to a Si-containing honeycomb structure and a method for manufacturing the same.
- the present invention relates to a honeycomb structure used for collecting particulates in exhaust gas of an internal combustion engine, a boiler or the like, a catalyst carrier, and the like, and a method for manufacturing the same, and particularly to a honeycomb structure excellent in heat conduction characteristics. And its manufacturing method.
- Honeycomb structures are used as filters for collecting particulates in exhaust gas from internal combustion engines, boilers, etc., particularly diesel particulates, and as catalyst carriers for exhaust gas purification.
- a honeycomb structure used for the purpose of a filter or the like generally has a large number of flow holes 3 penetrating in the X-axis direction partitioned by partition walls 2 as shown in FIGS. 2 (a) and 2 (b). Adjacent flow holes 3 are plugged at one end opposite to each other so that the end faces have a checkered pattern.
- the fluid to be treated flows through the flow hole 3 where one end face 42 is not plugged, that is, the flow hole whose end is plugged on the other end face 44.
- the partition wall 2 serves as a filter, and soot (soot) discharged from the diesel engine, for example, is captured by the partition wall and deposited on the partition wall.
- soot soot discharged from the diesel engine
- DPF filter
- a thermal shock-resistant rotary heat storage is applied by applying a ceramic bonding material that has substantially the same mineral composition as the matrix segment after firing and a difference in thermal expansion coefficient of 0.1% or less at 800 ° C
- An expression has been proposed.
- SAE paper 860 008 of 1996 discloses a ceramic honeycomb structure in which cordierite honeycomb segments are also joined by cordierite cement.
- Japanese Patent Application Laid-Open No. 8-282246 discloses a ceramic honeycomb in which a honeycomb ceramic member is bonded with an elastic sealing material comprising at least three-dimensionally intermingled inorganic fibers, an inorganic binder, an organic binder and inorganic particles. A structure is disclosed.
- Japanese Patent Publication No. Hei 8-137706 proposes the use of Si-SiC-based materials for DPF, and this material has heat resistance, thermal shock resistance, and oxidation resistance. It is disclosed that the material has excellent properties. However, there is no indication of the thermal conductivity problem of this material. Disclosure of the invention
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a honeycomb structure having excellent thermal shock resistance by improving the thermal conductivity of the honeycomb structure. It is in.
- the present invention relates to a honeycomb structure having a large number of axially penetrating through holes partitioned by partition walls, and having a lattice constant at room temperature of 0.5430 to 0.543.
- Honeycomb structure characterized by containing Si phase controlled to 11 nm (First aspect).
- the content of boron in the Si phase is preferably equal to or less than 0.02% by mass.
- the honeycomb structure further includes refractory particles serving as an aggregate, and it is more preferable that the refractory particles be SiC. Further, it is preferable that the honeycomb structure is a porous body.
- a second aspect of the present invention is a method for manufacturing a honeycomb structure including a firing step of firing a precursor of an 82-cam structure having a large number of flow holes penetrating in an axial direction, which is partitioned by a partition wall.
- a second aspect of the present invention is to provide a method for manufacturing a honeycomb structure, wherein a precursor contains a Si phase, and a firing step is performed using a kiln material containing no boron-containing compound (second aspect). .
- the present invention relates to a method for manufacturing a honeycomb structure including a firing step of firing a precursor of an 82-cam structure having a large number of flow holes penetrating in the axial direction, which is partitioned by a partition wall.
- a honeycomb structure characterized in that the reduction rate of the Si content in the Si phase after the firing step with respect to the Si content in the Si phase before the process is suppressed to 10% by mass or less. It provides a way (third aspect).
- the firing step is performed using a kiln material containing no carbonaceous material.
- the kiln material comprises one or more components selected from alumina, silicon carbide, oxide-bonded silicon carbide, silicon nitride-bonded silicon carbide, and molybdenum disilicide. It is preferably made of a material as a main component.
- FIG. 1 is a schematic perspective view showing one embodiment of a honeycomb structure.
- FIG. 2A is a schematic perspective view showing another form of the honeycomb structure
- FIG. 2B is a schematic enlarged plan view showing a portion b in FIG. 2A.
- FIG. 3 is a schematic perspective view showing another embodiment of the 82 cam structure.
- a section means a section perpendicular to the longitudinal direction (X-axis direction) of the flow hole unless otherwise specified.
- the honeycomb structure according to the first aspect of the present invention is, for example, a honeycomb structure 1 having a large number of flow holes 3 penetrating in the X-axis direction, partitioned by a partition wall 2 as shown in FIG.
- An important feature of the first aspect is that the honeycomb structure contains a Si phase whose lattice constant at room temperature is controlled to 0.5430 to 0.5431 nm. is there.
- a honeycomb structure made of Si-SiC-based material exhibits excellent properties such as heat resistance, thermal shock resistance, and oxidation resistance, as well as corrosion resistance to acids and alkalis, but has a pure thermal conductivity. It was much lower than the value calculated from pure metallic silicon and silicon carbide.
- the lattice constant of the Si phase in a conventional material containing a Si phase for example, a Si-SiC-based material, was lower than the literature value of pure metallic silicon.
- an extremely high thermal conductivity can be obtained by controlling this lattice constant to 0.54302 to 0.54311 nm.
- the Si phase means a phase mainly composed of Si, for example, a phase of metallic silicon.
- the content of boron (B) in the Si phase is preferably set to 0.02% by mass or less.
- a honeycomb structure made of a material containing a Si phase for example, a Si-SiC-based material, is formed by molding a raw material containing metallic silicon and silicon carbide into a formed body having a honeycomb structure at a predetermined temperature. It was prepared by firing, but it was found that the Si phase in the obtained honeycomb structure contained boron.
- the honeycomb structure according to the first aspect of the present invention preferably contains refractory particles in addition to the Si phase, and preferably contains Si or a Si-refractory particle composite material as a main component.
- the main component means that it constitutes 50% by mass or more of the honeycomb structure.
- the honeycomb structure is S i — S
- the honeycomb structure of the first aspect of the present invention is preferably a porous body because it can be suitably used for a filter, a catalyst carrier, and the like. If the porosity is too large, the strength is insufficient, and if it is too small, the pressure loss is undesirably large, especially when used as a filter.
- the range of the porosity is preferably 30 to 90% by volume.
- the Si phase is a form in which the refractory particles are bonded to each other as a binder.
- the honeycomb structure is mainly composed of Si-SiC-based composite material
- SiZ Si + SiC
- the binder is insufficient. Adhesion of the adjacent SiC particles by the Si phase becomes insufficient, which not only reduces the thermal conductivity, but also makes it difficult to obtain strength enough to maintain a thin-walled structure such as a honeycomb structure.
- the Si content is preferably 5 to 50% by mass. And more preferably 10 to 40% by mass.
- the thickness of the partition wall there is no particular limitation on the thickness of the partition wall.
- the partition wall if the partition wall is too thick, the pressure loss when the fluid to be treated permeates the porous partition wall becomes too large. If the thickness is too thin, the strength is insufficient, which is not preferable.
- the thickness of the partition walls preferably ranges from 30 to 200 m, more preferably from 40 to 1000 m, most preferably from 50 to 500 m.
- the cell density the number of flow holes per unit cross-sectional area
- the cell density is too low, the strength as a filter and the effective GSA (geometric surface area) are insufficient, and the cell density is too high When the fluid to be treated flows, the pressure loss increases.
- the cell density is preferably from 6 to 2000 cells / square inch (0.9311 cells Z cm 2 ), and more preferably from 50 to 1000 cells Z square inch (7.8- It is in the range of 15.5 cells Z cm 2 ), most preferably 100-400 cells Z square inch (15.5-62.0 cells Z cm 2 ).
- the cross-sectional shape (cell shape) of the flow hole is not particularly limited, but is preferably any one of a triangular shape, a square shape, a hexagonal shape, and a corrugated shape from the viewpoint of manufacturing.
- the cross-sectional shape of the honeycomb structure For example, in addition to the circular shape shown in FIG. It can be irregularly shaped.
- the opening of a predetermined flow hole 3 is formed at one end face 42. It is preferable to be sealed, and the opening of the remaining predetermined flow hole 3 be sealed to the other end face 4. In particular, it is preferable that all the flow holes are sealed at any one of the end faces, and the adjacent flow holes 3 are opposite to each other so that the end faces 42 and 44 have a checkered pattern. It is preferable that one end on the side is sealed.
- the fluid to be treated flowing from one end face 42 passes through the partition wall 2 and flows out from the other end face 44, and when the fluid to be treated passes through the partition wall 2, it becomes porous.
- the partition wall 2 serves as a filter, and can remove an object.
- the material used for the sealing one or more materials selected from among the preferable main components of the honeycomb structure can be suitably used.
- the honeycomb structure 1 is divided into a plurality of segments 12 which are joined to each other. This is preferable because the properties can be further improved.
- the size of the segments is not limited, but if each segment is too large, the effect of improving the thermal shock resistance is reduced, and if it is too small, the production and joining of each segment becomes complicated, which is not preferable.
- the shape of each segment For example, as shown in Fig. 3 (b), when the cross-sectional shape is a square shape, that is, when the honeycomb segments 12
- the shape of the honeycomb segment on the outer peripheral side can be appropriately selected according to the shape of the honeycomb structure of the above.
- the honeycomb structure according to the first aspect of the present invention is used as a catalyst carrier for purifying exhaust gas of a heat engine such as an internal combustion engine or a combustion device such as a boiler, or reforming a liquid fuel or a gaseous fuel
- a catalyst for example, a metal having catalytic ability.
- metals having catalytic ability include Pt, Pd, and Rh. It is preferable that at least one of these metals is supported on the honeycomb structure.
- the main feature of the second aspect of the present invention resides in that a honeycomb structure precursor containing a Si phase is fired using a kiln material not containing a boron-containing compound such as BN.
- a honeycomb structure precursor containing a Si phase is fired using a kiln material not containing a boron-containing compound such as BN.
- the kiln material means a material constituting a surface in contact with a space in a kiln in which a precursor is placed, and the material constituting these surfaces must substantially contain boron.
- the material constituting the surface of the material placed in the firing kiln space such as a shell for arranging the precursors and a heater, is substantially e. It does not contain nitrogen. If this surface does not contain a boron-containing compound, the amount of boron entering the Si phase can be suppressed, and the effects of the present invention can be achieved.
- the main feature of the third aspect of the present invention is that in the firing step, the Si content in the Si phase after the firing step is 100% by mass relative to the Si content in the Si phase before the firing step.
- the reduction rate is controlled to 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less.
- the thermal conductivity decreases due to the effect of reducing the conduction path when Si evaporates. Therefore, by suppressing the volatilization of Si by the above-described configuration, it is possible to secure a Si amount substantially as blended, and it is possible to suppress a decrease in thermal conductivity.
- a kiln material not containing a carbonaceous material In order to suppress a decrease in the Si content, it is preferable to perform the firing step using a kiln material not containing a carbonaceous material.
- carbonaceous materials have conventionally been used as kiln materials.However, in the firing process at a high temperature of 100 ° C. or more, the carbonaceous materials of The volatilization of Si from the fired product occurred at an accelerated rate due to the reaction of reacting with the more volatile Si and causing silicification. Therefore, when the volatilization of Si from the fired product does not occur at an accelerated rate, the volatilization of Si can be suppressed by using a kiln material containing no carbon material.
- the kiln material means a material constituting a surface that comes into contact with the space inside the firing kiln where the precursor is placed.
- the carbonaceous material means a material mainly composed of C—C bonds, such as graphite, and a material mainly composed of a bond of carbon and another element, for example, silicon carbide is a carbonaceous material. Is not included.
- preferred kiln materials are selected from alumina, silicon carbide, oxide-bonded silicon carbide, silicon nitride-bonded silicon carbide, and molybdenum disilicide from the viewpoint of heat resistance and the like. It is a material containing one or more components as main components. Specifically, materials such as alumina fiber, silicon carbide, oxide-bonded silicon carbide, and silicon nitride-bonded silicon carbide are preferable for the kiln inner wall or sealer, and materials such as silicon carbide and molybdenum disilicide are preferable for the heater. .
- oxide-bonded silicon carbide refers to charcoal This is a material obtained by sintering silicon oxide particles with an oxide such as clay as a binder.
- a method for forming a precursor of a honeycomb structure containing a Si phase is not particularly limited, and for example, the precursor can be formed by the following method.
- the raw material powder for example, metal silicon and silicon carbide powder are used, a binder such as methylcellulose and hydroxypropoxylmethylcellulose is added thereto, and further a surfactant and water are added to produce a plastic clay.
- a honeycomb-structured body having a large number of axially penetrating flow holes partitioned by partition walls is obtained.
- the obtained molded body is dried, for example, with a microwave and / or hot air, and then heated and degreased, for example, in an N 2 atmosphere to obtain a precursor containing a Si phase.
- Such a precursor is fired at a predetermined firing temperature, for example, 140 to 180 ° C. in an inert atmosphere, for example, in an argon atmosphere, using the above-described kiln, to obtain a honeycomb.
- a predetermined firing temperature for example, 140 to 180 ° C.
- an inert atmosphere for example, in an argon atmosphere
- argon atmosphere using the above-described kiln
- the structure can be manufactured. If the firing temperature is too low, the Si phase will melt and it will be difficult to bond the refractory particles. If the temperature is too high, it will be difficult to prevent the volatilization of Si by the third aspect.
- a catalyst may be supported on the honeycomb structure.
- This method may be a method commonly performed by those skilled in the art.
- the catalyst can be supported by flash-coating a catalyst slurry, followed by drying and calcining. This step may be performed at any time after the formation of the molded body.
- the flow holes may be plugged, for example, by masking the flow holes that are not plugged, applying the raw material in the form of a slurry, applying the raw material to the opening end surface of the honeycomb segment, drying and firing. Can be performed.
- the material of the plugging material to be used is not particularly limited, but it is preferable to use a raw material having the same material as the raw material used for forming the precursor.
- a molded article having a honeycomb structure having a square of 35 mm on a side and a length of 152 mm was obtained. This is plugged with a material similar to the material used for manufacturing the honeycomb structure at one end where the adjacent flow holes are opposite to each other so that the end surface has a checkered pattern, and dried. After that, the precursor was degreased at about 400 ° C to obtain the precursor. The honeycomb structure was fired at 450 ° C. for 2 hours to obtain a honeycomb structure. The lattice constant of metallic silicon, which is the Si phase, in the obtained honeycomb structure was calculated from the diffraction profile obtained by X-ray diffraction using the WPPD method.
- the boron content in the Si phase was calculated by the ICP method after extracting only metallic silicon by the solution treatment.
- the Si content after calcination was measured by the fluorescent X-ray method after preparing a calibration curve Furthermore, the rate of change before and after firing was determined by calculation, and the rate of decrease in the Si content in the Si phase was determined.
- the thermal conductivity was measured by a laser flash method.
- the porosity of each of the obtained honeycomb structures was within the range of 44 to 46% as measured by the Archimedes method.
- Heater material Lattice constant of Si phase Thermal conductivity of Si phase in Si phase Heater material Furnace inner wall material Lnm] Boron content Si content reduction rate [W / m]
- Example 1 Alumina Alumina SiC 0.54309 0.01 1 35
- Example 3 SiC Alumina SiC 0.54305 0.01 1 31
- Example 6 Boron Nitride Alumina SiC 0.54293 0.04 1 24
- Example 7 Alumina Alumina Carbon 0.54308 0.008 12 25
- Example 8 Alumina Carbon Carbon 0.54308 0.009 15 25
- Example 9 Power Carbon Carbon 0.54308 0.01 20 24
- the samples fired using the kiln materials of Examples 7 to 9 had the same composition as the samples fired using the kiln materials of Comparative Examples 1 or 2, but had the same composition as the samples fired with the Si phase.
- the lattice constant was within the range of the first side surface, and the thermal conductivity was higher than those of the samples of Comparative Examples 1 and 2, which were out of the range of the first side surface.
- the thermal conductivity was higher than those of the samples of Comparative Examples 1 and 2. .
- the lattice constant and the Si content reduction rate were within the ranges of the first and third aspects, respectively, of the present invention, and the thermal conductivity was very high, 3 O WZmK or more. It shows a high value and is particularly preferable as a honeycomb structure used for a DPF substrate.
- the thermal conductivity is low.
- the honeycomb structure had a very high rate and was resistant to thermal shock.
- an 82 cam structure having a high thermal conductivity was able to be manufactured by the second or third aspect of the present invention.
- the honeycomb structure of the present invention is particularly preferably used for a DPF, the effect of the present invention is to suppress an excessive rise in temperature by improving the thermal conductivity and to make the temperature distribution in the structure uniform. Yes, its use is not limited to DPF
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Geometry (AREA)
- Physics & Mathematics (AREA)
- Filtering Materials (AREA)
- Ceramic Products (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
- Catalysts (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03701853A EP1469172B1 (en) | 2002-01-25 | 2003-01-24 | HONEYCOMB STRUCTURE CONTAINING Si AND METHOD FOR MANUFACTURE THEREOF |
PL364164A PL207122B1 (pl) | 2002-01-25 | 2003-01-24 | Struktura komórkowa plastra pszczelego oraz sposób wytwarzania struktury komórkowej plastra pszczelego |
KR10-2003-7013958A KR100516537B1 (ko) | 2002-01-25 | 2003-01-24 | Si함유 하니콤 구조체 및 그 제조 방법 |
US10/474,309 US7029511B2 (en) | 2002-01-25 | 2003-01-24 | Si-containing honeycomb structure and process for production thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002017366A JP3927038B2 (ja) | 2001-12-21 | 2002-01-25 | Si含有ハニカム構造体及びその製造方法 |
JP2002-017366 | 2002-01-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003062611A1 true WO2003062611A1 (fr) | 2003-07-31 |
Family
ID=27606166
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/000621 WO2003062611A1 (fr) | 2002-01-25 | 2003-01-24 | Structure en nid d'abeilles contenant si et son procede de fabrication |
Country Status (6)
Country | Link |
---|---|
US (1) | US7029511B2 (ja) |
EP (1) | EP1469172B1 (ja) |
JP (1) | JP3927038B2 (ja) |
KR (1) | KR100516537B1 (ja) |
PL (1) | PL207122B1 (ja) |
WO (1) | WO2003062611A1 (ja) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6961595B2 (en) * | 2002-08-08 | 2005-11-01 | Flarion Technologies, Inc. | Methods and apparatus for operating mobile nodes in multiple states |
US7363039B2 (en) | 2002-08-08 | 2008-04-22 | Qualcomm Incorporated | Method of creating and utilizing diversity in multiple carrier communication system |
US8190163B2 (en) * | 2002-08-08 | 2012-05-29 | Qualcomm Incorporated | Methods and apparatus of enhanced coding in multi-user communication systems |
US8593932B2 (en) * | 2003-05-16 | 2013-11-26 | Qualcomm Incorporated | Efficient signal transmission methods and apparatus using a shared transmission resource |
US7925291B2 (en) * | 2003-08-13 | 2011-04-12 | Qualcomm Incorporated | User specific downlink power control channel Q-bit |
WO2005044425A1 (ja) * | 2003-11-07 | 2005-05-19 | Ibiden Co., Ltd. | 排気ガス浄化用ハニカムフィルタおよびその製造方法 |
JPWO2005064128A1 (ja) * | 2003-12-25 | 2007-07-19 | イビデン株式会社 | 排気ガス浄化装置および排気ガス浄化装置の再生方法 |
JP2005254751A (ja) * | 2004-03-15 | 2005-09-22 | Ngk Insulators Ltd | セラミックスハニカム構造体の製造方法 |
DE102004016690A1 (de) * | 2004-04-05 | 2005-10-27 | Arvin Technologies, Inc., Troy | Vorrichtung zum Reinigen von Fahrzeugabgasen, insbesondere Dieselrußfilter, und Fahrzeug mit entsprechender Vorrichtung |
CN1906141B (zh) * | 2004-12-27 | 2010-11-03 | 揖斐电株式会社 | 蜂窝状结构体和密封材料层 |
KR100692942B1 (ko) * | 2005-02-01 | 2007-03-12 | 이비덴 가부시키가이샤 | 허니컴 구조체 |
FR2893861B1 (fr) * | 2005-11-30 | 2008-01-04 | Saint Gobain Ct Recherches | Structure de filtration d'un gaz a base de sic de porosite de surface de paroi controlee |
US20070211669A1 (en) * | 2006-03-07 | 2007-09-13 | Bhupesh Manoharlal Umatt | Method and apparatus for searching radio technologies |
CA2674429C (en) * | 2007-01-11 | 2013-10-08 | Qualcomm Incorporated | Using dtx and drx in a wireless communication system |
JP5075606B2 (ja) * | 2007-12-13 | 2012-11-21 | 日本碍子株式会社 | 炭化珪素質多孔体 |
WO2009110978A2 (en) * | 2008-02-29 | 2009-09-11 | Corning Incorporated | Method for porous ceramic honeycomb shrinkage reduction |
JP2010247079A (ja) * | 2009-04-16 | 2010-11-04 | Denso Corp | 排ガス浄化触媒の製造方法 |
JP5465052B2 (ja) * | 2010-03-19 | 2014-04-09 | 日本碍子株式会社 | セラミックス−金属接合体、及びその製造方法 |
JP5749894B2 (ja) * | 2010-03-31 | 2015-07-15 | 日本碍子株式会社 | ハニカム構造体 |
KR20120086184A (ko) * | 2011-01-25 | 2012-08-02 | 한국에너지기술연구원 | 탄화규소 허니컴 및 이의 제조방법 |
WO2013047790A1 (ja) * | 2011-09-30 | 2013-04-04 | 日本碍子株式会社 | ハニカム構造体 |
JP5992857B2 (ja) * | 2013-03-29 | 2016-09-14 | 日本碍子株式会社 | ハニカム構造体 |
JP6111122B2 (ja) * | 2013-03-29 | 2017-04-05 | 日本碍子株式会社 | ハニカム構造体及びその製造方法 |
JP6633014B2 (ja) | 2017-03-17 | 2020-01-22 | 日本碍子株式会社 | 炭化珪素質ハニカム構造体の製造方法 |
JP2019136939A (ja) * | 2018-02-09 | 2019-08-22 | 日本碍子株式会社 | ハニカム成形体又は焼成品の製造方法、受け台、及び受け台の製造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0828246A (ja) | 1994-07-14 | 1996-01-30 | Ibiden Co Ltd | セラミック構造体 |
EP0753490A1 (en) * | 1995-07-12 | 1997-01-15 | Nippondenso Co., Ltd. | Honeycomb structural body and method of manufacturing the same |
US5733352A (en) * | 1995-08-22 | 1998-03-31 | Denki Kagaku Kogyo Kabushiki Kaisha | Honeycomb structure, process for its production, its use and heating apparatus |
WO2000068941A1 (fr) * | 1999-05-11 | 2000-11-16 | Hitachi Maxell, Ltd. | Support d'enregistrement magnetique et son procede de fabrication; enregistreur magnetique |
JP2001010871A (ja) * | 1999-06-25 | 2001-01-16 | Oji Paper Co Ltd | 多孔質炭化ケイ素繊維構造体の製造方法 |
WO2001070373A1 (fr) * | 2000-03-24 | 2001-09-27 | Ngk Insulators, Ltd | Filtre de purification de gaz d'echappement |
WO2001079138A1 (fr) | 2000-04-14 | 2001-10-25 | Ngk Insulators, Ltd. | Structure en nid d'abeille et son procede de production |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5546338A (en) | 1978-09-28 | 1980-04-01 | Ngk Insulators Ltd | Heat and shock resistant, revolving and heat-regenerating type ceramic heat exchanger body and its manufacturing |
US4335783A (en) * | 1980-11-10 | 1982-06-22 | Corning Glass Works | Method for improving thermal shock resistance of honeycombed structures formed from joined cellular segments |
JPS60131862A (ja) * | 1983-12-16 | 1985-07-13 | 三菱マテリアル株式会社 | 高強度炭化けい素基焼結体 |
US5145825A (en) * | 1991-04-08 | 1992-09-08 | Engelhard Corporation | Oxidation catalyst resistant to sulfation |
JPH0813706B2 (ja) * | 1991-07-02 | 1996-02-14 | 工業技術院長 | 炭化珪素/金属珪素複合体及びその製造方法 |
JP4464568B2 (ja) * | 2001-02-02 | 2010-05-19 | 日本碍子株式会社 | ハニカム構造体及びその製造方法 |
JP3997825B2 (ja) * | 2001-06-28 | 2007-10-24 | 株式会社デンソー | セラミックフィルタおよび触媒付セラミックフィルタ |
JP4136380B2 (ja) * | 2001-12-21 | 2008-08-20 | 日本碍子株式会社 | 高熱伝導性含Si材料及びその製造方法 |
-
2002
- 2002-01-25 JP JP2002017366A patent/JP3927038B2/ja not_active Expired - Lifetime
-
2003
- 2003-01-24 WO PCT/JP2003/000621 patent/WO2003062611A1/ja active Application Filing
- 2003-01-24 US US10/474,309 patent/US7029511B2/en not_active Expired - Lifetime
- 2003-01-24 EP EP03701853A patent/EP1469172B1/en not_active Expired - Lifetime
- 2003-01-24 PL PL364164A patent/PL207122B1/pl unknown
- 2003-01-24 KR KR10-2003-7013958A patent/KR100516537B1/ko active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0828246A (ja) | 1994-07-14 | 1996-01-30 | Ibiden Co Ltd | セラミック構造体 |
EP0753490A1 (en) * | 1995-07-12 | 1997-01-15 | Nippondenso Co., Ltd. | Honeycomb structural body and method of manufacturing the same |
US5733352A (en) * | 1995-08-22 | 1998-03-31 | Denki Kagaku Kogyo Kabushiki Kaisha | Honeycomb structure, process for its production, its use and heating apparatus |
WO2000068941A1 (fr) * | 1999-05-11 | 2000-11-16 | Hitachi Maxell, Ltd. | Support d'enregistrement magnetique et son procede de fabrication; enregistreur magnetique |
JP2001010871A (ja) * | 1999-06-25 | 2001-01-16 | Oji Paper Co Ltd | 多孔質炭化ケイ素繊維構造体の製造方法 |
WO2001070373A1 (fr) * | 2000-03-24 | 2001-09-27 | Ngk Insulators, Ltd | Filtre de purification de gaz d'echappement |
WO2001079138A1 (fr) | 2000-04-14 | 2001-10-25 | Ngk Insulators, Ltd. | Structure en nid d'abeille et son procede de production |
EP1277714A1 (en) | 2000-04-14 | 2003-01-22 | Ngk Insulators, Ltd. | Honeycomb structure and method for its manufacture |
Non-Patent Citations (1)
Title |
---|
See also references of EP1469172A4 |
Also Published As
Publication number | Publication date |
---|---|
PL364164A1 (en) | 2004-12-13 |
KR100516537B1 (ko) | 2005-09-22 |
JP3927038B2 (ja) | 2007-06-06 |
EP1469172A4 (en) | 2006-11-08 |
EP1469172B1 (en) | 2011-05-11 |
US7029511B2 (en) | 2006-04-18 |
US20040118095A1 (en) | 2004-06-24 |
JP2003247412A (ja) | 2003-09-05 |
PL207122B1 (pl) | 2010-11-30 |
EP1469172A1 (en) | 2004-10-20 |
KR20030094364A (ko) | 2003-12-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2003062611A1 (fr) | Structure en nid d'abeilles contenant si et son procede de fabrication | |
EP1437168B1 (en) | Honeycomb filter | |
JP4532063B2 (ja) | ハニカム構造体 | |
US7011803B2 (en) | Honeycomb structure and method for its manufacture | |
EP1413345B1 (en) | Honeycomb structural body and method of manufacturing the structural body | |
EP1741686B1 (en) | Honeycomb structure and method for producing same | |
WO2003044338A1 (fr) | Corps structural en nid d'abeilles et procede de fabrication de celui-ci | |
WO2003031023A1 (fr) | Filtre en nid d'abeilles | |
WO2001023069A1 (fr) | Filtre en nid d'abeilles et ensemble de filtres ceramiques | |
JP5469337B2 (ja) | ハニカム構造体 | |
JP2001096116A (ja) | セラミックフィルタ集合体、ハニカムフィルタ | |
JPH08281036A (ja) | ハニカム構造体及びその製造方法 | |
JP2004292197A (ja) | ハニカム構造体の製造方法 | |
EP1482016B1 (en) | Sealing material, method for sealing honeycomb structure and sealed honeycomb structure | |
JP2022128501A (ja) | セラミックス多孔体及びその製造方法、並びに集塵用フィルタ | |
JP7205671B1 (ja) | 炭化珪素質セラミックハニカム構造体及びその製造方法 | |
JP2004203704A (ja) | セラミックス構造体の製造方法 | |
JP5612149B2 (ja) | 窒化ケイ素系多孔体、窒化ケイ素系多孔体の製造方法、ハニカム構造体およびハニカムフィルタ | |
KR20050031065A (ko) | 벌집형 구조체 및 그 제조 방법 | |
KR20090045703A (ko) | 탄화규소 필터용 조성물, 상기를 포함하는 탄화규소 필터및 그의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 10474309 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003701853 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020037013958 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003701853 Country of ref document: EP |