EP2448884A1 - Verfahren zur herstellung zementierter und gehäuteter nadelförmiger mullitwabenstrukturen - Google Patents
Verfahren zur herstellung zementierter und gehäuteter nadelförmiger mullitwabenstrukturenInfo
- Publication number
- EP2448884A1 EP2448884A1 EP10731872A EP10731872A EP2448884A1 EP 2448884 A1 EP2448884 A1 EP 2448884A1 EP 10731872 A EP10731872 A EP 10731872A EP 10731872 A EP10731872 A EP 10731872A EP 2448884 A1 EP2448884 A1 EP 2448884A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- honeycomb
- cement composition
- cement
- fired
- mullite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 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 title claims abstract description 95
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims description 37
- 239000004568 cement Substances 0.000 claims abstract description 159
- 239000000203 mixture Substances 0.000 claims abstract description 111
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011737 fluorine Substances 0.000 claims abstract description 53
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 53
- 239000011256 inorganic filler Substances 0.000 claims abstract description 47
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000919 ceramic Substances 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010304 firing Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000008119 colloidal silica Substances 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims description 55
- 239000012530 fluid Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910004014 SiF4 Inorganic materials 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical group F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 241000264877 Hippospongia communis Species 0.000 abstract description 130
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 26
- 239000012784 inorganic fiber Substances 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 14
- 230000035939 shock Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 230000002093 peripheral effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- -1 strontium aluminum silicates Chemical class 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000003361 porogen Substances 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003105 Methocel™ A15 LV Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 101100004392 Arabidopsis thaliana BHLH147 gene Proteins 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AQBOUNVXZQRXNP-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.N.N.Cl[Pd]Cl AQBOUNVXZQRXNP-UHFFFAOYSA-L 0.000 description 1
- UXFOSWFWQAUFFZ-UHFFFAOYSA-L barium(2+);diformate Chemical compound [Ba+2].[O-]C=O.[O-]C=O UXFOSWFWQAUFFZ-UHFFFAOYSA-L 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000004814 ceramic processing Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/508—Aluminous cements
-
- 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
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
-
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Definitions
- the present invention relates to a process for producing acicular mullite honeycomb structures having an inorganic cement layer or an inorganic skin.
- Acicular mullite honeycomb structures are often used as filters in high temperature applications. These honeycombs are often used as particulate filters to remove soot particles or droplets from diesel engine exhaust. Filters of these types are frequently exposed to large, rapid changes in temperature. The temperature changes can occur during the normal operation of the vehicle, but they are especially pronounced when the filter is thermally regenerated to burn out the captured soot. These large, rapid temperature changes are sometimes referred to as "thermal shock" events.
- the honeycomb is made up of multiple smaller honeycombs which are cemented together.
- Another approach focuses on the peripheral "skin" of the honeycomb.
- the periphery of the part is often subjected to the highest thermally-induced stresses, especially during rapid temperature increases.
- cracking often initiates at the skin, from which the cracks can propagate throughout the structure and destroy the part.
- This skin can be removed and replaced with another ceramic material that is more compliant than the original acicular mullite skin of the honeycomb.
- the cement and skins are made by applying and firing a cement composition that contains a colloidal silica or alumina, filler particles and a carrier fluid.
- USP 7,083,842 describes a ceramic honeycomb structure in which the original peripheral region of the structure is removed and replaced with an inorganic coating that is fired to form a replacement skin.
- the coating composition includes an inorganic binder, ceramic fibers of up to 100 microns in length, and particles having a diameter of from 0.5 to 100 microns.
- USP 5,914,187 describes a cement that includes an inorganic binder such as a glassy silica phase, as well as both ceramic fibers and other inorganic powders or whiskers. The powders or whiskers are used to increase the thermal conductivity of the cement.
- USP 7,112,233 describes a similar cement, which in this case is formulated to have a specific thermal conductivity.
- the cement described in USP 7,112,233 includes silica-alumina fibers which are at least 1 mm in length. According to USP 7,112,233, shorter fibers do not permit an "elastic" structure to be formed.
- the needed thermal conductivity is provided by including silicon carbide, silicon nitride or boron nitride particles in the cement formulation.
- this invention is a process comprising the steps of (a) forming a ceramic honeycomb containing multiple axially-extending cells defined by intersecting walls, (b) applying to at least one surface of the ceramic honeycomb a cement composition that contains both aluminum and silicon atoms and includes (1) at least one inorganic filler, (2) a colloidal silica, colloidal alumina or mixture thereof which forms a binding phase upon firing, and (3) a carrier fluid and then (c) firing the honeycomb and cement composition at a temperature of at least 1000 0 C in the presence of a fluorine source.
- the resulting ceramic honeycomb structure often has greater thermal shock resistance, compared to when those steps are performed sequentially.
- the invention is not limited to any theory, it is believed that mullite forms in the cement composition when it is fired in the presence of the fluorine source. Some mullite can form when the cement is fired, even in the absence of the fluorine source. However, it has been found that mullite forms faster and to a greater extent in the cement composition when a fluorine source is present.
- the higher mullite content of the fired cement in some cases can more closely match the coefficient of thermal expansion (CTE) of the fired cement to that of the underlying honeycomb, especially in preferred cases in which the honeycomb is acicular mullite. This closer match in CTE is believed to account for the greater shock resistance of the honeycomb structure.
- CTE coefficient of thermal expansion
- the cement composition can function as a cement which adheres the honeycomb to another part of the final structure.
- the honeycomb may be composed of two or more smaller honeycombs, which are cemented together using the cement composition to produce a larger honeycomb.
- the cement composition may perform such a cementing function.
- the cement composition of the invention may also serve to cement a honeycomb to some other structure.
- the cement composition may instead, or in addition, be used to produce a peripheral skin for the honeycomb structure.
- this invention is a process comprising the steps of (a) forming a ceramic honeycomb containing multiple axially-extending cells defined by intersecting walls, wherein at least a portion of the ceramic honeycomb is an acicular mullite that contains at least 0.5 weight percent residual fluorine, based on the weight of the acicular mullite in the honeycomb (b) applying to at least one surface of the ceramic honeycomb a cement composition that contains both aluminum and silicon atoms and includes (1) at least one inorganic filler, (2) a colloidal silica, colloidal alumina or mixture thereof which forms a binding phase upon being fired, and (3) a carrier fluid, and then (c) exposing the honeycomb and cement composition to a temperature of at least 1200 0 C.
- An additional advantage of this embodiment of this invention is that two normally distinct steps in the manufacture of a ceramic honeycomb structure can be combined into one operation.
- Honeycomb structures made in accordance with the invention are useful in a variety of filtration, heat exchange and catalytic applications. Because those honeycomb structures tend to have good thermal shock resistance, they are particularly useful in applications in which the structure is exposed to rapid and large changes in temperature.
- Figure 1 is graph showing the coefficient of thermal expansion of an acicular mullite honeycomb, a cement (Example 1) formed in accordance with this invention, and of a comparative cement (Comparative Sample A) that is not formed in the presence of a fluorine source.
- Figure 2 is a graph showing the coefficient of thermal expansion of an acicular mullite honeycomb, a cement (Example 2) formed in accordance with this invention, and of a comparative cement (Comparative Sample B) that is not formed in the presence of a fluorine source.
- the ceramic honeycomb is characterized in having multiple cells that extend axially throughout the length of the honeycomb body.
- the cells are defined by multiple intersecting walls.
- the walls and the intersection points define the number of cells, as well as their cross-sectional shape and dimensions.
- a typical honeycomb for many filtration or catalysis applications will contain from 25 to 1000 cells/square inch (about 4 to 150 cells/square centimeter) of cross-sectional area (i.e., transverse to the longitudinal extension).
- Wall thicknesses are typically from 0.05 to 10 mm, preferably from 0.2 to 1 mm, although larger or smaller wall thicknesses might be used.
- the ceramic honeycomb may be monolithic (i.e., formed in a single piece), or may be an assembly of smaller honeycombs which are manufactured separately and then assembled together, usually using a ceramic cement.
- the ceramic cement in such an assembly is in some embodiments a fired cement composition as described herein.
- the walls of the honeycomb preferably are porous, and a fluid can pass through the pores from one cell to one or more adjacent cells.
- the ceramic making up the honeycomb generally has a porosity of about 30% to 85%.
- the porous ceramic has a porosity of at least about 40%, more preferably at least about 45%, even more preferably at least about 50%, and most preferably at least about 55% to preferably at most about 80%, more preferably at most about 75%, and most preferably at most about 70%. Porosities are determined by water immersion methods.
- the ceramic honeycomb may be made from an inorganic material such as alumina, zirconia, silicon carbide, silicon nitride, aluminum nitride, silicon oxynitride, silicon carbonitride, mullite, cordierite, beta spodumene, aluminum titanate, strontium aluminum silicates, lithium aluminum silicates.
- at least a portion of the ceramic honeycomb is an acicular mullite that contains at least 0.5 weight percent residual fluorine. If the ceramic honeycomb is monolithic, then the entire honeycomb preferably is such an acicular mullite.
- the ceramic honeycomb is a cemented assembly of smaller honeycombs
- at least one of the smaller honeycombs preferably is such an acicular mullite. It is preferred that all of the smaller honeycombs are acicular mullite containing at least 0.5 weight percent residual fluorine.
- Acicular mullite honeycomb structures can be prepared by forming a clay from a mullite precursor, shaping the clay into the honeycomb configuration (typically by extrusion) and then mullitizing the clay. Mullitization is performed by exposing the clay to a fluorine-containing compound under conditions that the mullite precursors react with the fluorine-containing compound to form a fluorotopaz which then decomposes to form acicular mullite needles. Suitable methods for preparing acicular mullite honeycombs are described, for example, in WO 92/11219, WO 03/082773 and WO 04/096729.
- the crystals are comprised mainly of a crystalline mullite, although it is possible for small quantities of other crystalline and/or glassy phases to be present.
- the crystals may contain up to about 2 volume percent of a crystalline silica phase such as cristobalite, as described in WO 03/082773, or up to about 10 volume percent of a glassy oxide phase that may contain silicon and/or aluminum as well as one or more metals contributed by a sintering aid and/or other compounds as may be present.
- the acicular mullite crystals are bonded together at points of contact to form a porous mass having essentially the same overall geometry and dimensions as the clay honeycomb.
- the aspect ratio of the mullite crystals is typically at least 5, preferably at least 10, more preferably at least 20.
- the crystals may have a mean grain diameter of from 5 to 50 microns.
- Acicular mullite bodies prepared as described above tend to contain some residual fluorine.
- the amount of fluorine may constitute from 0.5 to about 3 weight percent of the weight of the acicular mullite. More typically, the fluorine constitutes from about 0.8 to 2 weight percent of the acicular mullite.
- this residual fluorine is removed by heating the honeycomb to a temperature of at least 1200 0 C, preferably at least 1400 0 C, preferably in air or the presence of oxygen. In this invention, however, it is preferred that at least a portion of this residual fluorine remains in the acicular mullite honeycomb until the cement composition is applied, as described more fully below.
- the acicular mullite in the honeycomb should contain at least 0.5 weight percent fluorine.
- the cement composition is applied to one surface of the ceramic honeycomb.
- the cement composition may perform a cementing function, adhering the ceramic honeycomb to another honeycomb or to some other structure.
- the cement composition may instead, or in addition, serve as a peripheral skin for the honeycomb structure.
- the cement composition contains both silicon and aluminum atoms. Its constituent components include (1) inorganic filler particles, (2) a colloidal silica, colloidal alumina or mixture thereof which forms a binding phase upon firing, and (3) a carrier fluid.
- the inorganic filler particles are materials which do not form a binding phase when the cement composition is fired, and thus are distinguished from the colloidal silica and/or colloidal alumina component of the composition.
- the inorganic filler particles instead retain their particulate nature throughout the firing process, although they may become bound by the binding phase to other particles or to the inorganic fibers.
- Other components may be present in the cement composition, as described more fully below. Colloidal silica and colloidal aluminum are of course sources of silicon and aluminum atoms, respectively.
- the cement composition must contain some additional source of aluminum atoms.
- This source is typically the inorganic filler particles, which may contain silicon atoms in addition to the necessary aluminum atoms.
- the cement composition must contain some additional source, of silicon atoms, which again typically will be the inorganic filler particles.
- the inorganic filler may contain aluminum atoms in addition to the needed silicon atoms.
- the inorganic filler particles contain aluminum atoms, silicon atoms or both aluminum and silicon atoms.
- the preferred inorganic filler particles are therefore aluminate, silicate or aluminosilicate materials.
- the filler particles may be amorphous, partially crystalline or fully crystalline.
- the inorganic filler particles may contain a crystalline phase that is surrounded by glass.
- the inorganic filler particles may also contain other elements such as rare earths, zirconium, iron, boron and alkaline earths.
- silicon- and/or aluminum -containing materials that can be used as the inorganic filler particles are alumina, borosilicate glass, quartz, e-glass, s-glass, silicon carbide, silicon nitride, mullite, cordierite, alumina silicates, alumina-zirconia-silicates, wollastonite, basalt and aluminum titanate. If no silicon or aluminum atoms are needed in the inorganic filler particles, other materials such as boron nitride or carbon nitride particles can be used.
- aluminosilicate material that can be at least partially converted to mullite as the inorganic filler particles.
- the inorganic filler particles are in the form of fibers that have a diameter of from 100 nanometers to 20 microns and an aspect ratio (longest dimension divided by shortest dimension) of at least 10, preferably at least 20.
- a preferred fiber diameter is from 0.5 to 10 microns.
- a more preferred fiber diameter is from 3 to 10 microns.
- the number average length of the inorganic fibers may range from 100 microns to 130 millimeters or more.
- the number average length is preferably at least 100 microns and more preferably at least 200 microns.
- the number average length is preferably no greater than 10 millimeters.
- the number average length may be no greater than 5 millimeters or no greater than 2 millimeters.
- Longer fibers, such as those having lengths of 10 mm or more often tend to form bundles during processing. These bundles cause difficulties in applying the skin and also lead to inconsistencies in the skin composition. Therefore, longer fibers preferably are used somewhat sparingly if at all.
- the fibers have a length of less than 1 mm.
- the fibers have a bimodal or multimodal length distribution, in which one portion of the fibers are shorter fibers having a number average length of from 100 to 1000 microns, and at least one other portion of the fibers are longer fibers having a number average length of at least 1 millimeter, preferably from 1 to 100 millimeters, more preferably from 2 to 100 millimeters and even more preferably from 5 to 30 millimeters.
- the longer fibers preferably constitute from 1 to 50, more preferably from 3 to 30 and even more preferably from 5 to 25 percent of the total weight of the inorganic fibers.
- Mixed length fibers provide certain advantages.
- the presence of a minor proportion of longer fibers tends to increase the viscosity of the cement composition, at a given fiber content in the composition.
- the viscosity of the cement composition should be somewhat high, so it can be applied and shaped readily without sagging or flowing off of the honeycomb before it can dry.
- the presence of a minor proportion of longer fibers can allow a good working viscosity to be achieved without unduly increasing the fiber content. If the fiber content becomes too high, there may not be enough colloidal silica and/or colloidal alumina in the composition to adequately bind the fibers to each other or to the underlying honeycomb.
- the strength of the fired cement composition tends to decrease with increasing fiber length, because the number of fibers decreases as their length increases, and fewer fibers means fewer points of intersection where they can be bound together.
- the strength of the fired cement composition is often comparable to that of a cement that contains an equivalent proportion of only short fibers.
- a mixture of shorter fibers and a minor proportion of longer fibers can provide significant processing benefits with little or no corresponding disadvantages.
- useful organic fibers include mullite fibers, such as are available from Unifrax; alumina-zirconium-silicate fibers, such as are available from Unifrax; alumina fibers containing up to 10% by weight silica, such as are available from Saffil; ⁇ -alumina and ⁇ -alumina + mullite fibers such as Nextel 312 or Nextel 610 fibers from 3M; ⁇ -alumina + mullite + amorphous SiCh fibers such as Nextel 440 fibers from 3M; ⁇ - alumina + amorphous Si ⁇ 2 fibers such as Nextel 550 fibers from 3M; quartz fibers such as are available from Saint Gobain; e-glass or s-glass fibers; borosilicate fibers such as are available from Mo-SiC Corporation; basalt fibers such as are available from Albarrie, wollastonite fibers such as are available from Fibertec, and the like.
- mullite fibers such as are available from
- the cement composition may contain low aspect ratio inorganic filler particles in addition to or instead of the inorganic fibers described above.
- Low aspect ratio refers to an aspect ratio of less than 10. These inorganic filler particles are different from and do not include the colloidal silica and/or colloidal alumina component of the cement composition. The low aspect ratio inorganic filler particles do not form a binding phase when the cement composition is fired. The low aspect ratio inorganic filler particles instead retain their particulate nature throughout the firing process, although they may become bound by the glassy binding phase to other particles or to the inorganic fibers.
- a mixtue of inorganic fibers and low aspect ratio inorganic filler particles may be present.
- these low aspect ratio inorganic filler particles can be classified into two types.
- the first type is particles that have the same CTE or very nearly the same CTE as the inorganic fiber (i.e., differing by no more than 1 ppm/°C in the temperature range of from 100 to 600 0 C), after the firing step is completed.
- the comparison is performed on the basis of the fired skin composition to account for changes in CTE that may occur to the fibers and/or other particles during the firing step, due to, for example, changes in crystallinity and/or composition that may occur.
- Particles of this type generally have the same or nearly the same chemical composition as the inorganic fiber.
- a common source of this type of particle is so-called "shot" material, which is a by-product of the fiber manufacturing process and is included in many commercial grades of inorganic fibers.
- this type of particle may be supplied from other sources as well.
- This first type of inorganic filler particle may constitute from 0 to as much as 60% of the total weight of the inorganic filler.
- this type of inorganic filler particle constitutes no more than 50%, more preferably no more than 25% and still more preferably no more than 10% to the total weight of the inorganic fillers.
- the second type of inorganic filler particles have a CTE which is significantly different (i.e., different by more than 1 ppm/°C, preferably by at least 2 ppm/°C in the temperature range from 100 to 600 0 C) than that of the inorganic fibers, after the firing step is completed.
- Inorganic filler particles of this type if present at all, constitute no more than 5% by weight of the solids of the cement composition.
- the "solids" are constituted by the inorganic materials in the cement composition that remain in the skin after the firing step is completed, including fillers and inorganic binding phase.
- the cement composition may contain no inorganic filler particles of the second type at all, or may contain only very small proportions thereof, such as, for example, from 0 to 3% or from 0 to 2% or from 0 to 1% of the solids of the cementcomposition.
- this second type of inorganic filler particles are alumina, silicon carbide, silicon nitride, mullite, cordierite and aluminum titanate.
- the inorganic filler contains only the inorganic fiber, "shot” material from the inorganic fiber, and optionally the second type of inorganic filler particle, which may be present in an amount from 0 to 5% by weight of the solids of the cement composition, but essentially no (less than 5 weight percent, preferably no more than 1%) other organic filler particles of the first type.
- the inorganic fibers constitute at least 50, at least 75 or at least 90% of the total weight of the inorganic filler, and that the "shot" material constitutes no more than 50, no more than 25 or no more than 10% of the total weight of the inorganic filler.
- An especially inorganic filler of this type includes only inorganic fiber and "shot" material.
- the inorganic filler contains only the inorganic fiber and from 0-5 weight percent of the second type of inorganic filler, but no "shot" material or other inorganic filler of the first type.
- the inorganic filler particles in the aggregate may constitute from about 30 to 90% by weight of the solids in the cement. A preferred amount is from 50 to 85% by weight of the solids and a more preferred amount is from 60 to 80% by weight of the solids.
- the "solids" in the composition are those inorganic materials that remain after the firing step is completed. In most cases, the solids will be made up of the inorganic filler particles and the colloidal silica and/or colloidal alumina. Carrier fluids and organic materials generally are lost from the cement during the firing step(s). The "solids" therefore do not include any amounts of those materials.
- the colloidal silica and/or colloidal alumina may constitute from 10 to 70%, preferably from 15 to 50% and more preferably from 20 to 40% of the weight of the solids portion of the cement composition.
- the cement composition also includes a carrier liquid.
- the mixture of carrier fluid and colloidal silica and/or alumina particles forms a paste or viscous fluid in which the inorganic fibers are dispersed.
- the fluid or semi-fluid nature of the cement composition permits it to be applied easily and to adhere well to the underlying honeycomb until the firing step is completed.
- the carrier liquid may be, for example, water, or an organic liquid. Suitable organic liquids include alcohols, glycols, ketones, ethers, aldehydes, esters, carboxylic acids, carboxylic acid chlorides, amides, amines, nitriles, nitro compounds, sulfides, sulfoxides, sulfones and the like.
- Hydrocarbons including aliphatic, unsaturated aliphatic (including alkenes and alkynes) and/or aromatic hydrocarbons, are useful carriers.
- Organometallic compounds are also useful carriers.
- the carrier fluid is an alcohol, water or combination thereof. When an alcohol is used it is preferably methanol, propanol, ethanol or combinations thereof. Water is the most preferred carrier fluid.
- the cement composition contains enough of the carrier fluid to wet the colloidal silica and/or alumina and produce a paste or viscous fluid, in which the inorganic filler particles are dispersed.
- a useful Brookfield viscosity as measured at 25°C using a #6 spindle at 5 rpm, is typically at least about 5, 10, 25, 50, 75 or even 100 Pa-s.
- the cement composition may exhibit shear-thinning behavior, such that its viscosity becomes lower at higher shear.
- the total amount of carrier fluid in the cement composition (including any carrier fluid that may be brought in with the colloidal silica and/or colloidal alumina) is generally from about 25% by weight to at most about 90% by weight of the entire composition.
- a preferred amount of carrier fluid is from 40 to 70% by weight of the entire composition.
- the cement may contain other useful components in addition to the inorganic filler particles, colloidal silica and/or colloidal alumina and carrier fluid.
- An organic binder or plasticizer can provide desirable rheological properties to the cement composition, and therefore preferably is present.
- the binder dissolves in the carrier liquid.
- suitable binders and organic plasticizers include cellulose ethers, such as methyl cellulose, ethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, carboxylm ethyl cellulose and the like; polyethylene glycol, fatty acids, fatty acid esters and the like.
- the cement composition also may contain one or more porogens. Porogens are materials specifically added to create voids in the skin after being heated to form the amorphous phase. Typically these are any particulates that decompose, evaporate or in some way volatilize during a heating or firing step to leave a void. Examples include flour, wood flour, carbon particulates (amorphous or graphitic), nut shell flour or combinations thereof.
- Organic materials such as binders, plasticizers and porogens typically constitute, in the aggregate, from 0 to 15%, preferably from 1 to 10% of the total weight of the cement composition.
- the cement composition is applied to at least one surface of the honeycomb.
- the manner of applying the cement composition not critical, and any suitable method by which the composition can be applied at the desired thickness is suitable.
- the cement can be applied manually or through the use of various types of mechanical apparatus.
- the cement composition may be applied under sub-atmospheric pressures to facilitate removal of the carrier fluid during the application process. If the cement is used to assemble multiple parts (such as multiple honeycombs) into a larger assembly, the cement is applied in any convenient manner to a surface of one or more of the parts that are being assembled, and the parts are then joined with the cement interposed between the parts.
- the cement composition is to be used to form a skin on the honeycomb (or an assembly containing the honeycomb), the composition is applied to at least a portion of the periphery of the honeycomb.
- Ceramic honeycombs as manufactured typically have an outer peripheral "skin", which may be simply the exterior cell walls of the peripheral cells of the honeycomb structure. It is generally preferable to remove such a skin before applying a replacement skin in accordance with this invention. At least the exterior walls of the peripheral cells of the honeycomb are removed. More typically, the removal of the "skin" is only part of a more general shaping process, in which outer portions of the ceramic honeycomb are removed to bring its cross-sectional shape and size to necessary specifications.
- This step of removing peripheral portions of the ceramic honeycomb exposes the interior of the axially- extending cells that remain on the periphery of the honeycomb after the removal step is completed.
- the cement composition is then applied to at least a portion of the newly exposed periphery of the honeycomb.
- the periphery of the honeycomb usually is not smooth, and in most cases a certain proportion of the axially-extending cells around the periphery of the honeycomb will be open before the cement composition is applied to form a skin.
- the cement composition typically will be applied in such a manner as to fill those open cells and to form a somewhat smooth exterior surface. Therefore, the thickness of the skin usually will vary. At its thinnest points, the applied skin should be at least 1 mm in thickness, and may be as much as 25 mm thick.
- the cement composition is fired after it is applied to the honeycomb.
- the firing step removes the carrier fluid and any organic materials (including any porogen) from the cement.
- the colloidal silica and/or colloidal alumina form a binding phase during the firing step.
- At least a portion of the firing step is performed at a temperature of at least 1000 0 C in the presence of a fluorine source.
- the temperature may be as high as 1600 0 C, and preferably is up to 1500 0 C.
- the fluorine source may be, for example, SiF4, AIF3, HF, Na ⁇ SiF ⁇ , NaF, NH4F, a fluorinated polymer such a fluorinated polyethylene or polytetrafluoroethene or some mixture of any two or more thereof.
- the fluorine source is residual fluorine contained in an acicular mullite honeycomb or a mixture of that residual fluorine and an additional fluorine source as described in the preceding paragraph.
- the firing temperature preferably is at least 1200 0 C and is more preferably at least 1400°C.
- residual fluorine is released from the acicular mullite honeycomb, possibly in the form of SiF4.
- the released fluorine or SiF4 is believed to contribute to mullite formation in the cement under the firing conditions.
- a significant quantity of mullite tends to form from the silicon- and aluminum -containing components of the cement.
- mullite formation may occur more rapidly when the firing step is performed in accordance with this invention.
- the honeycomb and applied cement composition are heated at a rate of no greater than 20°C/minute, preferably no greater than 10°C/minute and still more preferably no greater than 5°C/minute, from ambient temperature up to at least 1000 ° C (or at least 1200 0 C, when the fluorine source is an acicular mullite honeycomb).
- the gradual heating rate is intended to help prevent thermal shocks and also to provide time for the carrier fluid and any organic materials to be removed.
- the assembly may be held at one or more intermediate temperatures for a period. This may be desirable, for example, to remove the carrier fluid, organic binders and/or porogens in some predetermined sequence, to allow some chemical reaction to take place, or for some other reason.
- the assembly Once the assembly reaches the necessary temperature, it is preferably held at or above that that temperature for a period of from 5 minutes to 10 hours. This allows time for the fluorine source to react with the cement composition to produce mullite, and, in preferred embodiments, allows time for residual fluorine to escape from the acicular mullite honeycomb. In the preferred embodiments, it is preferred to reduce the residual fluorine in the acicular honeycomb to less than 0.5 weight percent, more preferably less than 0.1 weight percent, of the acicular mullite.
- the assembly, with the cement now being fired, is then cooled to ambient temperature, preferably at some gradual cooling rate (such as no greater than 10 or 20°C/minute) to prevent damage from thermal shock.
- the mullite content of the fired cement will of course depend somewhat on the amount of silicon atoms, aluminum atoms and fluorine that were available in the starting materials.
- the fired cement may contain as much as 85% by weight mullite. More typically, the fired cement contains from about 45 to 80% mullite, or from 45 to 75% mullite.
- the mullite formation has little effect on the morphology of the fired cement.
- the inorganic filler particles largely maintain their particulate or fibrous nature, and are bound together via a binding phase that is mainly formed from colloidal the silica and/or colloidal alumina component of the cement.
- Mullite may be present in the filler particles or fibers, in the binding phase, or both.
- the fired cement is usually porous.
- the porosity of the fired cement may be from 10 to 90%, and is more typically from 40 to 70%.
- the fired cement typically has a modulus that is significantly lower than that of the honeycomb.
- the modulus of the fired cement may be, for example in the range of 3 to 25% of that of the ceramic material in the honeycomb. It is believed that this lower modulus imparts high crack resistance of the fired cement.
- the modulus of the fired cement can be measured by forming 8 mm X 4 mm X 40 mm test bars from the cement composition, firing the blocks and measuring modulus using the Grindosonic impulse excitation apparatus following ASTM Standard C 1259-98, Standard Test Method for Dynamic Young's Modulus, Shear Modulus, and Poisson's Ratio for Advanced Ceramics by Impulse Excitation of Vibration.
- a honeycomb made in accordance with the invention tends to exhibit excellent thermal shock resistance, whether the cement is used as a skin, to adhere constituent parts of the honeycomb together to form an assembly, or both.
- a suitable method of evaluating thermal shock resistance is described in the following examples. In this method, the structure is subjected to increasingly harsh thermal cycles, and inspected for cracking after each of the cycles.
- a honeycomb produced in accordance with the invention can be used as a particulate filter, especially for removing particulate matter from power plant (mobile or stationary) exhaust gases.
- a specific application of this type is a soot filter for an internal combustion engine, especially a diesel engine.
- Functional materials can be applied to the honeycomb, before or after applying and firing the cement composition, using various methods.
- the functional materials may be organic or inorganic.
- Inorganic functional materials, particularly metals and metal oxides, are of interest as many of these have desirable catalytic properties, function as sorbents or perform some other needed function.
- One method of introducing a metal or metal oxide onto the composite body is by impregnating the honeycomb with a solution of a salt or acid of the metal, and then heating or otherwise removing the solvent and, if necessary calcining or otherwise decomposing the salt or acid to form the desired metal or metal oxide.
- an alumina coating or a coating of another metal oxide is often applied in order to provide a higher surface area upon which a catalytic or sorbent material can be deposited.
- Alumina can be deposited by impregnating the honeycomb with colloidal alumina, followed by drying, typically by passing a gas through the impregnated body. This procedure can be repeated as necessary to deposit a desired amount of alumina.
- Other ceramic coatings such as titania can be applied in an analogous manner.
- Metals such as barium, platinum, palladium, silver, gold and the like can be deposited on the composite body by impregnating the honeycomb (the internal walls of which are preferably coated with alumina or other metal oxide) with a soluble salt of the metal, such as, for example, platinum nitrate, gold chloride, rhodium nitrate, tetraamine palladium nitrate, barium formate, followed by drying and preferably calcination.
- Catalytic converters for power plant exhaust streams, especially for vehicles, can be prepared from the skinned honeycomb in that manner.
- Suitable methods for depositing various inorganic materials onto a honeycomb structure are described, for example, in US 205/0113249 and WO2001045828. These processes are generally in relation to the skinned honeycomb of this invention.
- alumina and platinum, alumina and barium or alumina, barium and platinum can be deposited onto the honeycomb in one or more steps to from a filter that is simultaneously capable of removing particulates such as soot, NOx compounds, carbon monoxide and hydrocarbons from a power plant exhaust, such as from vehicle engines.
- a cement composition is prepared by mixing 42.0 wt% of ball milled aluminum silicate fiber (HP-95-SAB-T60, available from Thermal Ceramics Inc., Augusta, GA), 13.5 wt% of colloidal alumina (AL20SD, available from Nyacol Nano Technologies, Inc., Ashland, MA), 40.5 wt% of water, 2 wt% methyl cellulose (METHOCEL A15LV, available from The Dow Chemical Co. Midland, MI), and 2 wt% polyethylene glycol 400 (available from Alfa Aesar, Ward Hill, MA) to obtain a uniform mixture.
- a cement composition is prepared by mixing 42.0 wt% of ball milled aluminum silicate fiber (HP-95-SAB-T60, available from Thermal Ceramics Inc., Augusta, GA), 13.5 wt% of colloidal alumina (AL20SD, available from Nyacol Nano Technologies, Inc., Ashland, MA), 40.5 wt% of water, 2 wt% methyl cellulose (METHOC
- a portion of the cement composition is applied onto as-mullitized acicular mullite honeycomb segments, which are joined together using the mixture as a cement to form a larger honeycomb assembly.
- the as-mullitized acicular mullite honeycombs contain 1- 1.4% by weight residual fluorine.
- Another portion of the cement composition is applied onto the periphery an as- mullitized acicular mullite honeycomb to form a skin coating.
- a third portion of the cement composition is formed into blocks for material property measurements.
- honeycomb assembly, coated honeycombs and cement blocks are fired together by heating them tol400°C at a rate of 2°C/minute, holding at 1400 0 C for 6 hours and then cooling slowly to room temperature. Residual fluorine is removed from the acicular mullite honeycombs during this firing step, and a binding phase is simultaneously formed.
- the resulting materials are referred to collectively as Example 1.
- a fourth portion of the cement composition is applied to heat-treated acicular mullite honeycombs that contain less than 0.5% by weight residual fluorine. The acicular mullite honeycombs are then joined together to form a larger honeycomb assembly.
- a fifth portion of the cement composition is applied as a skin over a heat- treated acicular mullite honeycomb.
- a sixth portion of the cement composition is formed into blocks. The honeycomb assembly, skinned honeycomb and blocks are fired together in the same manner as Example 1. The fired materials are referred to collectively as Comparative Sample A.
- X-ray diffraction (XRD) on the cement and skin of Example 1 shows that they contain 69.7% mullite, 16.4% cristobalite and 13.9% aluminum oxide.
- the cement and skin of Comparative Sample A contain only 47.4% mullite, wheres the cristobalite and aluminum oxide phases are larger (being 26.0% and 26.6%, respectively). Therefore, firing in the presence of an acicular mullite having residual fluorine increases mullite formation by about 47%.
- the higher mullite content of the fired cement and skin results in a closer chemical composition match of with the acicular mullite honeycomb, and in a closer match of CTE, as shown in Figure 1.
- the CTE of Example 1 over the temperature range from about 25°C to 800 0 C is indicated by line 1
- that of Comparative Sample A is indicated by line A.
- the thermal expansion of cement and skin fired in presence of an acicular mullite honeycomb containing residual fluorine is closer to that of mullite substrate, compared to when the acicular mullite honeycomb has little residual fluorine, as in Comparative Sample A.
- the closer thermal expansion match with mullite substrate is due to the increase of mullite phase in the cement and skin fired in presence of fluorine and can result in improved thermal shock performance.
- the porosity of the cement and the skin of Example 1 are measured by water intrusion methods and found to be 64%, which is nearly identical to that of Comparative Sample A. Therefore, the co-firing of the cement and skin with the removal of residual fluorine from the acicular mullite honeycomb does not result in changes in the microstructure or porosity of the cement and the skin.
- the elastic modulus of the fired cement composition is measured by Grindosonic method. Cement bars with 8 mm x 4 mm x 40 mm dimensions are cut from fired cement blocks. Cement bars fired in presence of fluorine (Example 1) has an elastic modulus of 4.9 GPa, whereas the elastic modulus of the Comparative Sample A cement bars is nearly the same (4.7 GPa).
- the acicular mullite in the honeycombs has an elastic modulus of 23.6 GPa.
- the fired cement composition is more compliant than the underlying honeycomb and therefore helps relieve the thermomechanical stresses generated in thermal shock situation.
- Example 1 and Comparative Sample A are repeated, this time using a cement composition prepared by mixing 48.8 wt% of ball milled aluminum silicate fiber (PS3400 fiber, available from Unifrax LLC, Niagara Falls, NY), 11.9 wt% of colloidal alumina (AL20SD, available from Nyacol Nano Technologies, Inc, Ashland, MA), 35.9 wt% of water, 1.7 wt% methyl cellulose (METHOCEL A15LV, available from The Dow Chemical Co., Midland, MI), and 1.7 wt% polyethylene glycol 400 (available from Alfa Aesar, Ward Hill, MA).
- this cement composition is used to join and skin acicular mullite honeycombs that contain 1-1.4% residual fluorine, and to form cement blocks.
- Comparative Sample B the honeycombs are previously heat-treated to reduce residual fluorine to below 0.1%. The materials are then fired as described with respect to Example 1 and Comparative Sample A, to form Example 2 and Comparative Sample B, respectively.
- PS3400 fiber available
- Example 2 The cement and skin of Example 2 contain 76.7% mullite, 8.1% cristobalite and 15.3% aluminum oxide by XRD, compared to only 69.2% mullite, 4.9% cristobalite and 25.9% aluminum oxide for Comparative Sample B. This indicates that mullite content in the cement and skin increase by 10.8% when the acicular mullite honeycomb contains residual fluorine when the cement composition is fired.
- the thermal expansion of cement and skin for both Example 2 and Comparative Sample B are shown in Figure 2. In Figure 1, the CTE of Example 2 over the temperature range from about 25°C to 800 0 C is indicated by line 2, whereas that of Comparative Sample B is indicated by line B.
- Example 2 cement and skin The thermal expansion of the Example 2 cement and skin is closer to that of the acicular mullite honeycomb substrate than are the cement and skin of Comparative Sample B.
- the closer thermal expansion match with mullite substrate is due to the increased mullite content of Example 2 and can result in improved thermal shock performance.
- Example 1 and Comparative Sample A are again repeated, this time using a cement composition prepared by mixing 27.5 wt% of ball milled aluminum zirconium silicate fiber (Z-95-SAB-T30, available from Thermal Ceramics Inc., Augusta, GA), 16.9 wt% of colloidal alumina (AL20SD, available from Nyacol Nano Technologies, Inc., Ashland, MA), 50.6 wt% of water, 2.5 wt% methyl cellulose (METHOCEL A15LV, available from The Dow Chemical Co. Midland, MI), and 2.5 wt% polyethylene glycol 400 (available from Alfa Aesar, Ward Hill, MA).
- Z-95-SAB-T30 available from Thermal Ceramics Inc., Augusta, GA
- A20SD available from Nyacol Nano Technologies, Inc., Ashland, MA
- 50.6 wt% of water 2.5 wt% methyl cellulose
- ME 2.5 wt% polyethylene glycol 400
- Alfa Aesar Ward Hill, MA
- Example 3 this cement composition is used to join and skin acicular mullite honeycombs that contain 1-1.4% residual fluorine, and to form cement blocks.
- Comparative Sample C the honeycombs are previously heat-treated to reduce residual fluorine to below 0.5%. The materials are then fired as described with respect to Example 1 and Comparative Sample A to form Example 3 and Comparative Sample C, respectively.
- Example 3 The cement and skin of Example 3 contain 53.0% mullite, 13.7% crystobalite, 24.6% aluminum oxide and 8.6% zirconium oxide by XRD, compared to only 42.0% mullite, 18.0% cristobalite, 32.1% aluminum oxide and 7.9% zirconium oxide for Comparative Sample C. This indicates that mullite content in the cement and skin increase by 26.2% when the acicular mullite honeycomb contains residual fluorine when the cement composition is fired, even when the fibers in the cement composition are doped with zirconium.
- Example 3 cement and skin has an elastic modulus of 3.3 GPa,which is nearly unchanged from that of Comparative Sample C (3.6 GPa). These values are much lower that that of the underlying acicular mullite honeycomb, indicating greater compliance and ability to relieve thermomechanical stresses.
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WO2012135401A1 (en) * | 2011-03-29 | 2012-10-04 | Dow Global Technologies Llc | Method for making porous mullite-tialite composites |
WO2012154357A1 (en) * | 2011-05-12 | 2012-11-15 | Dow Global Technologies Llc | A mullite body and method of forming the mullite body |
CN104703944B (zh) * | 2012-10-08 | 2019-05-21 | 陶氏环球技术有限责任公司 | 改进的包含多铝红柱石的多孔主体和其形成方法 |
US9862650B2 (en) | 2014-03-18 | 2018-01-09 | Corning Incorporated | Skinning of ceramic honeycomb bodies |
US10562816B2 (en) | 2017-06-29 | 2020-02-18 | Ruentex Materials Co., Ltd. | Non-calcined cementitious compositions, non-calcined concrete compositions, non-calcined concrete and preparation methods thereof |
DE102017006168A1 (de) | 2017-06-29 | 2019-01-03 | Ruentex Materials Co., Ltd | Nichtcalcinierte zementöse zusammensetzungen, nichtcalcinierte betonzusammensetzungen, nichtcalcinierter beton und verfahren zu deren herstellung |
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CA2097292A1 (en) | 1990-12-21 | 1992-06-22 | Peter A. Doty | Preparation and use of mullite whisker networks |
EP1382442B1 (de) | 1996-01-12 | 2013-04-24 | Ibiden Co., Ltd. | Abgasreinigungsfilter |
DE60041464D1 (de) | 1999-09-29 | 2009-03-12 | Ibiden Co Ltd | Wabenförmiger Filter und Anordnung von keramischen Filtern |
KR100843992B1 (ko) | 1999-12-23 | 2008-07-07 | 다우 글로벌 테크놀로지스 인크. | 촉매 장치 |
CN1111093C (zh) * | 2000-02-25 | 2003-06-11 | 上海交通大学 | 莫来石质蜂窝陶瓷载体 |
JP2005521624A (ja) * | 2002-03-25 | 2005-07-21 | ダウ グローバル テクノロジーズ インコーポレイティド | ムライト体及びムライト体の形成方法 |
US7528087B2 (en) | 2003-04-24 | 2009-05-05 | Dow Global Technologies, Inc. | Porous mullite bodies and methods of forming them |
AU2003252272A1 (en) * | 2003-07-28 | 2005-02-14 | Ngk Insulators, Ltd. | Honeycomb structure and method of producing the same |
CA2546234A1 (en) | 2003-11-24 | 2005-06-09 | Dow Global Technologies Inc. | Catalyst for a diesel particulate filter |
WO2006025498A1 (ja) | 2004-09-02 | 2006-03-09 | Ibiden Co., Ltd. | ハニカム構造体、その製造方法及び排気浄化装置 |
JP4975619B2 (ja) * | 2005-06-24 | 2012-07-11 | イビデン株式会社 | ハニカム構造体 |
CN101074161B (zh) * | 2007-04-14 | 2010-06-02 | 安徽宁国市先浩高温材料有限公司 | 一种钛酸铝-莫来石质蜂窝陶瓷及其制备方法 |
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2010
- 2010-06-24 CN CN201080029391.XA patent/CN102471173B/zh not_active Expired - Fee Related
- 2010-06-24 EP EP10731872A patent/EP2448884A1/de not_active Withdrawn
- 2010-06-24 BR BRPI1010157A patent/BRPI1010157A2/pt not_active Application Discontinuation
- 2010-06-24 KR KR1020127002366A patent/KR101806575B1/ko active IP Right Grant
- 2010-06-24 JP JP2012518557A patent/JP2012532087A/ja active Pending
- 2010-06-24 CA CA2766653A patent/CA2766653A1/en not_active Abandoned
- 2010-06-24 MX MX2011014009A patent/MX2011014009A/es not_active Application Discontinuation
- 2010-06-24 WO PCT/US2010/039842 patent/WO2011008463A1/en active Application Filing
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KR20120103548A (ko) | 2012-09-19 |
CN102471173B (zh) | 2014-02-19 |
JP2012532087A (ja) | 2012-12-13 |
CN102471173A (zh) | 2012-05-23 |
BRPI1010157A2 (pt) | 2016-03-29 |
KR101806575B1 (ko) | 2017-12-07 |
CA2766653A1 (en) | 2011-01-20 |
WO2011008463A1 (en) | 2011-01-20 |
MX2011014009A (es) | 2012-04-02 |
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