DE69420377T2 - Verfahren zur Herstellung von Formen aus feuerfestem Material und Bindemittel dafür - Google Patents
Verfahren zur Herstellung von Formen aus feuerfestem Material und Bindemittel dafürInfo
- Publication number
- DE69420377T2 DE69420377T2 DE69420377T DE69420377T DE69420377T2 DE 69420377 T2 DE69420377 T2 DE 69420377T2 DE 69420377 T DE69420377 T DE 69420377T DE 69420377 T DE69420377 T DE 69420377T DE 69420377 T2 DE69420377 T2 DE 69420377T2
- Authority
- DE
- Germany
- Prior art keywords
- binder
- group
- matrix
- metal
- mold
- 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.)
- Expired - Lifetime
Links
- 239000011230 binding agent Substances 0.000 title claims description 131
- 238000000034 method Methods 0.000 title claims description 50
- 230000008569 process Effects 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000011819 refractory material Substances 0.000 title description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002184 metal Substances 0.000 claims description 61
- 239000011159 matrix material Substances 0.000 claims description 54
- 150000004703 alkoxides Chemical class 0.000 claims description 39
- -1 alkyl silicates Chemical class 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 25
- 239000004576 sand Substances 0.000 claims description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims description 22
- 229910052681 coesite Inorganic materials 0.000 claims description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims description 20
- 229910052682 stishovite Inorganic materials 0.000 claims description 20
- 229910052905 tridymite Inorganic materials 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000005160 aryl oxy alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 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 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 238000005266 casting Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 238000000465 moulding Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 7
- 238000010112 shell-mould casting Methods 0.000 description 7
- 238000005495 investment casting Methods 0.000 description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000004512 die casting Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910001208 Crucible steel Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 101100311330 Schizosaccharomyces pombe (strain 972 / ATCC 24843) uap56 gene Proteins 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 101150018444 sub2 gene Proteins 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- YTJUXOIAXOQWBV-UHFFFAOYSA-N butoxy(trimethyl)silane Chemical compound CCCCO[Si](C)(C)C YTJUXOIAXOQWBV-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- UFWOWQYGXPYINE-UHFFFAOYSA-N diethyl(diphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](CC)(CC)OC1=CC=CC=C1 UFWOWQYGXPYINE-UHFFFAOYSA-N 0.000 description 1
- ZWPNXHXXRLYCHZ-UHFFFAOYSA-N diethyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(CC)OC(C)C ZWPNXHXXRLYCHZ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- KHAYZVWNEUMMDR-UHFFFAOYSA-N dimethyl dipropan-2-yl silicate Chemical compound CC(C)O[Si](OC)(OC)OC(C)C KHAYZVWNEUMMDR-UHFFFAOYSA-N 0.000 description 1
- SWLVAJXQIOKFSJ-UHFFFAOYSA-N dimethyl(diphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](C)(C)OC1=CC=CC=C1 SWLVAJXQIOKFSJ-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- BPXCAJONOPIXJI-UHFFFAOYSA-N dimethyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(C)OC(C)C BPXCAJONOPIXJI-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ITAHRPSKCCPKOK-UHFFFAOYSA-N ethyl trimethyl silicate Chemical compound CCO[Si](OC)(OC)OC ITAHRPSKCCPKOK-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- HGWSCXYVBZYYDK-UHFFFAOYSA-N ethyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(CC)OC1=CC=CC=C1 HGWSCXYVBZYYDK-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- CQKJKOOGNRRFGH-UHFFFAOYSA-N methyl tripropan-2-yl silicate Chemical compound CC(C)O[Si](OC)(OC(C)C)OC(C)C CQKJKOOGNRRFGH-UHFFFAOYSA-N 0.000 description 1
- DRXHEPWCWBIQFJ-UHFFFAOYSA-N methyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C)OC1=CC=CC=C1 DRXHEPWCWBIQFJ-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- HXHRHZNQGGIWMZ-UHFFFAOYSA-N methyl-tris(2-methylphenoxy)silane Chemical compound CC1=CC=CC=C1O[Si](C)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C HXHRHZNQGGIWMZ-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- TWMWZRUDJDOLDG-UHFFFAOYSA-N tetrakis(2-methylphenyl) silicate Chemical compound CC1=CC=CC=C1O[Si](OC=1C(=CC=CC=1)C)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C TWMWZRUDJDOLDG-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- HSDAZXVGQVMFAY-UHFFFAOYSA-N tributyl methyl silicate Chemical compound CCCCO[Si](OC)(OCCCC)OCCCC HSDAZXVGQVMFAY-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- QYBKVVRRGQSGDC-UHFFFAOYSA-N triethyl methyl silicate Chemical compound CCO[Si](OC)(OCC)OCC QYBKVVRRGQSGDC-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- UCUKUIPXDKEYLX-UHFFFAOYSA-N triethyl(propan-2-yloxy)silane Chemical compound CC[Si](CC)(CC)OC(C)C UCUKUIPXDKEYLX-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- NNLPAMPVXAPWKG-UHFFFAOYSA-N trimethyl(1-methylethoxy)silane Chemical compound CC(C)O[Si](C)(C)C NNLPAMPVXAPWKG-UHFFFAOYSA-N 0.000 description 1
- PHPGKIATZDCVHL-UHFFFAOYSA-N trimethyl(propoxy)silane Chemical compound CCCO[Si](C)(C)C PHPGKIATZDCVHL-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/205—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of organic silicon or metal compounds, other organometallic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/6325—Organic additives based on organo-metallic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35414893 | 1993-12-28 | ||
| JP06183048A JP3139918B2 (ja) | 1993-12-28 | 1994-07-13 | 耐火物成形品の製造方法および耐火物成形品用バインダ |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE69420377D1 DE69420377D1 (de) | 1999-10-07 |
| DE69420377T2 true DE69420377T2 (de) | 2000-03-02 |
Family
ID=26501623
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE69420377T Expired - Lifetime DE69420377T2 (de) | 1993-12-28 | 1994-12-23 | Verfahren zur Herstellung von Formen aus feuerfestem Material und Bindemittel dafür |
| DE0661246T Pending DE661246T1 (de) | 1993-12-28 | 1994-12-23 | Verfahren zur Herstellung von Formen aus feuerfestem Material und Bindemittel dafür. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE0661246T Pending DE661246T1 (de) | 1993-12-28 | 1994-12-23 | Verfahren zur Herstellung von Formen aus feuerfestem Material und Bindemittel dafür. |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5569320A (cg-RX-API-DMAC7.html) |
| EP (1) | EP0661246B1 (cg-RX-API-DMAC7.html) |
| JP (1) | JP3139918B2 (cg-RX-API-DMAC7.html) |
| KR (1) | KR0128008B1 (cg-RX-API-DMAC7.html) |
| CN (3) | CN1067358C (cg-RX-API-DMAC7.html) |
| AU (1) | AU685194B2 (cg-RX-API-DMAC7.html) |
| CA (1) | CA2139016C (cg-RX-API-DMAC7.html) |
| DE (2) | DE69420377T2 (cg-RX-API-DMAC7.html) |
| TW (1) | TW270905B (cg-RX-API-DMAC7.html) |
Families Citing this family (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200631B1 (en) * | 1997-10-27 | 2001-03-13 | Praxair Technology, Inc. | Method for producing corrosion resistant refractories |
| US6238595B1 (en) * | 1998-02-17 | 2001-05-29 | Schlumberger Technology Corp. | Target for testing perforating systems |
| CA2663076C (en) * | 1998-11-20 | 2013-11-12 | Rolls-Royce Corporation | Method and apparatus for production of a cast component |
| DE19943789A1 (de) * | 1999-09-13 | 2001-03-15 | Fraunhofer Ges Forschung | Verfahren zur Abscheidung von Zirkonoxid-Schichten unter Verwendung von löslichen Pulvern |
| JP4002200B2 (ja) * | 2002-03-13 | 2007-10-31 | 花王株式会社 | 鋳物製造用抄造部品 |
| JP4471629B2 (ja) * | 2002-11-13 | 2010-06-02 | 花王株式会社 | 鋳物製造用部品の製造方法 |
| US20070151702A1 (en) * | 2003-01-07 | 2007-07-05 | Francois Batllo | Method of improving the removal of investment casting shells |
| KR100901912B1 (ko) * | 2003-09-02 | 2009-06-10 | 신토고교 가부시키가이샤 | 주형의 조형방법 및 금속주조용 코어 |
| KR20050041888A (ko) * | 2003-10-30 | 2005-05-04 | 니폰 파이오니쿠스 가부시키가이샤 | 절연막 성막용 원료 및 그것을 이용한 성막 방법 |
| US20060081350A1 (en) * | 2004-10-14 | 2006-04-20 | Francois Batllo | Method of improving the removal of investment casting shells |
| WO2007063888A1 (ja) * | 2005-11-30 | 2007-06-07 | Kao Corporation | 鋳物製造用部品及びその製造方法 |
| JP5507262B2 (ja) * | 2008-01-22 | 2014-05-28 | Ａｇｃセラミックス株式会社 | 鋳型用骨材粒子 |
| CN101977709B (zh) * | 2008-03-19 | 2013-03-20 | 旭有机材工业株式会社 | 壳型用酚醛树脂组合物、壳型用树脂覆膜砂以及使用其得到的铸型 |
| JP5213059B2 (ja) * | 2008-07-18 | 2013-06-19 | 株式会社キャディック | 鋳型用組成物 |
| JP4975050B2 (ja) * | 2009-02-05 | 2012-07-11 | 株式会社豊田中央研究所 | シリカ構造体の製造方法 |
| EP2462079A4 (en) * | 2009-08-09 | 2015-07-29 | Rolls Royce Corp | CARRIER FOR A BURNED ARTICLE |
| JP5553410B2 (ja) * | 2010-08-03 | 2014-07-16 | 株式会社キャディック | 高温鋳型を用いた鋳造方法 |
| US9227241B2 (en) | 2010-12-08 | 2016-01-05 | Nalco Company | Investment casting shells having an organic component |
| EP2740550B1 (en) | 2011-08-03 | 2016-07-20 | Hitachi Metals, Ltd. | Ceramic core and method for producing same |
| KR101273361B1 (ko) * | 2011-10-17 | 2013-07-04 | 주식회사 성일터빈 | 실리카 전구체를 이용한 주조 주형 및 주조 주형의 제조방법 |
| JP6037756B2 (ja) * | 2012-10-12 | 2016-12-07 | 三菱重工業株式会社 | 鋳型製造方法及び鋳型 |
| JP5347077B1 (ja) | 2013-03-19 | 2013-11-20 | テクノメタル株式会社 | 砂型鋳造方法 |
| CN104338892A (zh) * | 2013-07-31 | 2015-02-11 | 见得行股份有限公司 | 用于添加湿砂模的安定剂 |
| US9968991B2 (en) | 2015-12-17 | 2018-05-15 | General Electric Company | Method and assembly for forming components having internal passages using a lattice structure |
| US10118217B2 (en) | 2015-12-17 | 2018-11-06 | General Electric Company | Method and assembly for forming components having internal passages using a jacketed core |
| US10099276B2 (en) | 2015-12-17 | 2018-10-16 | General Electric Company | Method and assembly for forming components having an internal passage defined therein |
| US10099283B2 (en) | 2015-12-17 | 2018-10-16 | General Electric Company | Method and assembly for forming components having an internal passage defined therein |
| US10046389B2 (en) | 2015-12-17 | 2018-08-14 | General Electric Company | Method and assembly for forming components having internal passages using a jacketed core |
| US9987677B2 (en) | 2015-12-17 | 2018-06-05 | General Electric Company | Method and assembly for forming components having internal passages using a jacketed core |
| US10137499B2 (en) | 2015-12-17 | 2018-11-27 | General Electric Company | Method and assembly for forming components having an internal passage defined therein |
| US10150158B2 (en) | 2015-12-17 | 2018-12-11 | General Electric Company | Method and assembly for forming components having internal passages using a jacketed core |
| US10099284B2 (en) | 2015-12-17 | 2018-10-16 | General Electric Company | Method and assembly for forming components having a catalyzed internal passage defined therein |
| US9579714B1 (en) | 2015-12-17 | 2017-02-28 | General Electric Company | Method and assembly for forming components having internal passages using a lattice structure |
| US10286450B2 (en) | 2016-04-27 | 2019-05-14 | General Electric Company | Method and assembly for forming components using a jacketed core |
| US10335853B2 (en) | 2016-04-27 | 2019-07-02 | General Electric Company | Method and assembly for forming components using a jacketed core |
| JP6923533B2 (ja) * | 2016-08-31 | 2021-08-18 | 旭有機材株式会社 | 鋳型の製造方法 |
| EP3568245A4 (en) | 2017-01-11 | 2020-09-23 | HA-International LLC | COMPOSITIONS AND PROCESSES FOR HIGH PRESSURE CASTING CORES |
| US10494305B2 (en) | 2017-03-16 | 2019-12-03 | Magneco/Metrel, Inc. | Method of making refractory article resistant to high temperature shock and creep |
| US9994486B1 (en) * | 2017-03-16 | 2018-06-12 | Magneco/Metrel, Inc. | Refractory composition resistant to high temperature shock and creep |
| US10429130B2 (en) * | 2017-03-16 | 2019-10-01 | Magneco/Metrel, Inc. | Refractory kiln car resistant to high temperature shock and creep |
| CN108080576B (zh) * | 2017-12-01 | 2020-11-10 | 东方电气集团东方汽轮机有限公司 | 一种中温蜡熔模精密铸造用陶瓷型芯预处理方法 |
| EP3501690A1 (en) * | 2017-12-20 | 2019-06-26 | Imertech Sas | Method of making particulate refractory material foundry articles, and product made by such method |
| WO2020122312A1 (ko) * | 2018-12-14 | 2020-06-18 | 창원대학교 산학협력단 | 대형 주조품을 위한 고강도 주형 및 중자의 제조방법 |
| RU2713049C1 (ru) * | 2018-12-17 | 2020-02-03 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Способ изготовления керамических плавильных тиглей |
| KR102243038B1 (ko) * | 2020-01-28 | 2021-04-21 | 창원대학교 산학협력단 | 무기바인더를 이용하는 사형 주조용 주형 및 중자의 제조방법과 이를 이용하는 주조품 제조방법 |
| CN115319018B (zh) * | 2022-08-14 | 2024-09-20 | 湖南洛兰新材料有限公司 | 一种钇溶胶及其制备方法 |
| CN117531959B (zh) * | 2023-11-15 | 2024-06-25 | 广东金志利科技股份有限公司 | 一种球墨铸铁铸造成型装置及铸造方法 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0063034A3 (en) * | 1981-04-10 | 1983-04-20 | Zirconal Processes Limited | Rigid coherent gel |
| JPS629739A (ja) * | 1985-07-05 | 1987-01-17 | Nissan Chem Ind Ltd | 精密鋳型作製用結合剤 |
| JPS62173053A (ja) * | 1986-01-27 | 1987-07-29 | M C L:Kk | 中空鋳物の製造方法 |
| JPH0815636B2 (ja) * | 1986-07-29 | 1996-02-21 | 日産化学工業株式会社 | 精密鋳型作製用結合剤 |
| JPS6349343A (ja) * | 1986-08-14 | 1988-03-02 | Nobuyoshi Sasaki | 中子、その製造方法およびインベストメント鋳造用鋳型の製造方法 |
| GB8621714D0 (en) * | 1986-09-09 | 1986-10-15 | Manchem Ltd | Binders for refractories |
| JP2568402B2 (ja) * | 1987-01-08 | 1997-01-08 | リョービ株式会社 | 崩壊性中子の製造方法 |
| US4834165A (en) * | 1987-08-03 | 1989-05-30 | Ryobi Ltd. | Collapsible core and method for producing the collapsible core feasible for high speed high pressure casting |
| US5271768A (en) * | 1988-02-02 | 1993-12-21 | Hitachi Chemical Co., Ltd. | Coating for forming an oxide coating |
| JP2655275B2 (ja) * | 1988-05-20 | 1997-09-17 | 株式会社佐々木信義事務所 | インベストメント鋳造用鋳型の製造方法 |
| DE68923000T2 (de) * | 1988-08-24 | 1995-11-02 | Asahi Glass Co Ltd | Transparente, leitfähige keramische beschichtung formende flüssigkeit zur beschichtung, mit dieser transparenten, leitfähigen keramik beschichtetes basismaterial und herstellung desselben sowie verwendung des mit der transparenten, leitfähigen keramik beschichteten basismaterials. |
| GB9115153D0 (en) * | 1991-07-12 | 1991-08-28 | Patel Bipin C M | Sol-gel composition for producing glassy coatings |
-
1994
- 1994-07-13 JP JP06183048A patent/JP3139918B2/ja not_active Expired - Lifetime
- 1994-12-22 AU AU81694/94A patent/AU685194B2/en not_active Ceased
- 1994-12-23 DE DE69420377T patent/DE69420377T2/de not_active Expired - Lifetime
- 1994-12-23 DE DE0661246T patent/DE661246T1/de active Pending
- 1994-12-23 TW TW083112123A patent/TW270905B/zh not_active IP Right Cessation
- 1994-12-23 EP EP94309748A patent/EP0661246B1/en not_active Expired - Lifetime
- 1994-12-23 CA CA002139016A patent/CA2139016C/en not_active Expired - Fee Related
- 1994-12-27 CN CN94119913A patent/CN1067358C/zh not_active Expired - Fee Related
- 1994-12-27 CN CNB001201417A patent/CN1195708C/zh not_active Expired - Fee Related
- 1994-12-28 KR KR1019940038053A patent/KR0128008B1/ko not_active Expired - Fee Related
- 1994-12-28 US US08/365,111 patent/US5569320A/en not_active Expired - Lifetime
-
1996
- 1996-07-16 US US08/680,635 patent/US5611848A/en not_active Expired - Lifetime
-
2000
- 2000-07-14 CN CN00120142A patent/CN1116943C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR0128008B1 (ko) | 1998-04-02 |
| CN1195708C (zh) | 2005-04-06 |
| CN1067358C (zh) | 2001-06-20 |
| EP0661246B1 (en) | 1999-09-01 |
| DE69420377D1 (de) | 1999-10-07 |
| EP0661246A1 (en) | 1995-07-05 |
| US5611848A (en) | 1997-03-18 |
| CA2139016A1 (en) | 1995-06-29 |
| CA2139016C (en) | 1999-05-04 |
| US5569320A (en) | 1996-10-29 |
| KR950017809A (ko) | 1995-07-20 |
| JP3139918B2 (ja) | 2001-03-05 |
| CN1289739A (zh) | 2001-04-04 |
| CN1289655A (zh) | 2001-04-04 |
| CN1111601A (zh) | 1995-11-15 |
| AU685194B2 (en) | 1998-01-15 |
| CN1116943C (zh) | 2003-08-06 |
| JPH07232967A (ja) | 1995-09-05 |
| AU8169494A (en) | 1995-07-06 |
| DE661246T1 (de) | 1996-02-15 |
| TW270905B (cg-RX-API-DMAC7.html) | 1996-02-21 |
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| 8328 | Change in the person/name/address of the agent |
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