EP2300177B1 - Coating compositions for casting moulds and cores for avoiding maculate surfaces - Google Patents
Coating compositions for casting moulds and cores for avoiding maculate surfaces Download PDFInfo
- Publication number
- EP2300177B1 EP2300177B1 EP09753897.9A EP09753897A EP2300177B1 EP 2300177 B1 EP2300177 B1 EP 2300177B1 EP 09753897 A EP09753897 A EP 09753897A EP 2300177 B1 EP2300177 B1 EP 2300177B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- casting
- metal
- coating composition
- binder
- 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.)
- Not-in-force
Links
- 238000005266 casting Methods 0.000 title claims description 105
- 239000008199 coating composition Substances 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 claims description 130
- 239000011230 binding agent Substances 0.000 claims description 108
- 229910052751 metal Inorganic materials 0.000 claims description 62
- 239000002184 metal Substances 0.000 claims description 62
- 239000000654 additive Substances 0.000 claims description 61
- 230000000996 additive effect Effects 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 26
- 150000002739 metals Chemical class 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000005058 metal casting Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 238000004513 sizing Methods 0.000 description 82
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 75
- 239000012778 molding material Substances 0.000 description 75
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 45
- 150000001299 aldehydes Chemical class 0.000 description 31
- 239000003054 catalyst Substances 0.000 description 31
- -1 ferrous metals Chemical class 0.000 description 31
- 238000000034 method Methods 0.000 description 31
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 30
- 239000005011 phenolic resin Substances 0.000 description 30
- 150000002989 phenols Chemical class 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 229920001568 phenolic resin Polymers 0.000 description 28
- 229920001228 polyisocyanate Polymers 0.000 description 25
- 239000005056 polyisocyanate Substances 0.000 description 25
- 239000002253 acid Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 18
- 235000013339 cereals Nutrition 0.000 description 18
- 229910001338 liquidmetal Inorganic materials 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 229920005862 polyol Polymers 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 150000003077 polyols Chemical class 0.000 description 16
- 238000000465 moulding Methods 0.000 description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 14
- 239000004576 sand Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000470 constituent Substances 0.000 description 13
- 239000007849 furan resin Substances 0.000 description 13
- 150000002576 ketones Chemical class 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000011819 refractory material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- 229920003987 resole Polymers 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003139 biocide Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000011253 protective coating Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000003997 cyclic ketones Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910052609 olivine Inorganic materials 0.000 description 3
- 239000010450 olivine Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 230000002028 premature Effects 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- LPCJHUPMQKSPDC-UHFFFAOYSA-N 3,5-diethylphenol Chemical compound CCC1=CC(O)=CC(CC)=C1 LPCJHUPMQKSPDC-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- RCNCKKACINZDOI-UHFFFAOYSA-N 4,5-dimethylbenzene-1,3-diol Chemical compound CC1=CC(O)=CC(O)=C1C RCNCKKACINZDOI-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical class OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005029 sieve analysis Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- DKPQIOQEAATZQU-UHFFFAOYSA-N 1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid;sodium Chemical group [Na].[Na].CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC DKPQIOQEAATZQU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 1
- JJJPNTQYUJPWGQ-UHFFFAOYSA-N 2-(3-Phenylpropyl)pyridine Chemical compound C=1C=CC=NC=1CCCC1=CC=CC=C1 JJJPNTQYUJPWGQ-UHFFFAOYSA-N 0.000 description 1
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 description 1
- AJRRUHVEWQXOLO-UHFFFAOYSA-N 2-(fluoroamino)acetic acid Chemical compound OC(=O)CNF AJRRUHVEWQXOLO-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 1
- ZAISDHPZTZIFQF-UHFFFAOYSA-N 2h-1,4-thiazine Chemical compound C1SC=CN=C1 ZAISDHPZTZIFQF-UHFFFAOYSA-N 0.000 description 1
- HRUHVKFKXJGKBQ-UHFFFAOYSA-N 3,5-dibutylphenol Chemical compound CCCCC1=CC(O)=CC(CCCC)=C1 HRUHVKFKXJGKBQ-UHFFFAOYSA-N 0.000 description 1
- PEZSSBYAUDZEMO-UHFFFAOYSA-N 3,5-dicyclohexylphenol Chemical compound C=1C(O)=CC(C2CCCCC2)=CC=1C1CCCCC1 PEZSSBYAUDZEMO-UHFFFAOYSA-N 0.000 description 1
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CHQPRDVSUIJJNP-NSCUHMNNSA-N 4-[(e)-but-2-enyl]phenol Chemical compound C\C=C\CC1=CC=C(O)C=C1 CHQPRDVSUIJJNP-NSCUHMNNSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- MSFGJICDOLGZQK-UHFFFAOYSA-N 5-ethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1 MSFGJICDOLGZQK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229920006309 Invista Polymers 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009750 centrifugal casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 101150038956 cup-4 gene Proteins 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003628 erosive effect Effects 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000036573 scar formation Effects 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical class NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/10—Cores; Manufacture or installation of cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/18—Finishing
Definitions
- the invention relates to a size, which is particularly suitable for large-scale casting, a method for producing a casting and a mold with a mold coating.
- the lost forms usually consist of a mineral, refractory, granular molding material, often with different added to other additives, for example to achieve good casting surfaces, which is solidified with the aid of a binder.
- a refractory granular molding material usually washed, classified quartz sand is used.
- quartz sand is used.
- chromite, zirconium and olivine sand are also used.
- moldings based on chamotte, magnesite, silimanite or corundum are also used.
- the binders with which the molding materials are solidified may be inorganic or organic in nature.
- Smaller lost molds are predominantly made of molded materials, which are solidified by bentonite as a binder, while for larger molds usually organic polymers are used as binders.
- the production of the molds usually proceeds in such a way that the molding material is first mixed with the binder, so that the grains of the molding material are coated with a thin film of the binder. This molding material mixture is then introduced into a corresponding mold and optionally compressed in order to achieve a sufficient stability of the casting mold. Subsequently, the mold is cured, for example by heating it or by adding a catalyst which effects a curing reaction. If the casting mold has reached at least a certain initial strength, then it may optionally be removed from the mold and, for complete curing, for example, be transferred to an oven in order to be heated there for a predetermined time to a certain temperature.
- Permanent molds are used to make a variety of castings. You must therefore survive undamaged the casting process and the associated loads. Depending on the field of application, cast iron, unalloyed and alloyed steels, as well as copper, aluminum, graphite, sintered metals and ceramics, have been used as material for permanent molds Proven materials. Permanent molding processes include the mold, pressure, spin and continuous casting processes.
- sizing usually consists of an inorganic refractory and a binder, which are dissolved or slurried in a suitable solvent, for example water or alcohol.
- the surface of the casting mold can be modified and matched to the properties of the metal to be processed.
- the size can be used to improve the appearance of the casting by creating a smooth surface because the size compensates for irregularities caused by the size of the grains of the molding material.
- the size may metallurgically influence the casting by, for example, selectively transferring additives to the casting at the surface of the casting via the size which enhance the surface properties of the casting.
- the sizings form a layer which chemically isolates the casting mold from the liquid metal during casting. This prevents any adhesion between the casting and the casting mold so that the casting can be easily removed from the casting mold.
- the sizing ensures a thermal separation of mold and casting.
- the sizing can also be used to selectively control the heat transfer between the liquid metal and the casting mold in order, for example, to effect the formation of a specific metal structure by the cooling rate.
- the commonly used sizing agents contain as base materials e.g. Clays, quartz, diatomaceous earth, cristobalite, tridymite, aluminum silicate, zirconium silicate, mica, chamotte or coke or graphite. These base materials cover the surface of the mold and close the pores against penetration of the liquid metal into the mold. Because of their high insulating power, sizing agents containing silica or diatomaceous earth as base materials are often used since these sizings can be produced at low cost and are available in large quantities.
- base materials e.g. Clays, quartz, diatomaceous earth, cristobalite, tridymite, aluminum silicate, zirconium silicate, mica, chamotte or coke or graphite.
- the paste still contains a binder, usually water glass.
- a binder usually water glass.
- These pastes are applied to surfaces of the mold that come in contact with the liquid metallic material, usually steel, during casting.
- the metals contained in the paste should be protected by the heat of the melt liquid metallic material and form an alloy with this locally on the surface of the casting, which then solidifies as a peripheral shell.
- edge shells with a thickness of up to 10 mm can be produced. These edge shells can then have a very high hardness. In order to be able to produce a casting mold, for example an excavator bucket, it would thus no longer be necessary with this method to produce the entire casting from the corresponding alloy.
- the problem with this method is the different shrinkage coefficient of the different materials.
- the cured surface layer does not consistently have the same thickness or irregularities of the surface are observed, such as cracks, chips or depressions.
- the US 1678931 discloses a coating for centrifugal casting molds whose main component is either graphite or an iron-manganese-aluminum alloy.
- the coating forms with the cast metal (steel) an alloy with a reduced melting point. This alloy delays the cooling of the casting metal on the mold surface, so that a uniform distribution and cooling of the casting is achieved.
- the invention therefore an object of the invention to propose measures by which an improvement in the surface of the casting can be achieved during metal casting, so that the extent of surface treatment of the casting can be reduced after the casting.
- the metallic additive contained in the sizing composition contains at least one metal or compound of a metal, the metal being selected from the group comprising manganese and copper.
- the metallic additive may contain a metal, ie the metal in the oxidation state zero, wherein the metal can be used both in pure form or in the form of an alloy with other metals.
- the metallic additive can also be present in the form of an oxidized metal, ie in the form of an oxide or a salt, such as a carbonate, a nitrate or chloride, the oxide being preferred.
- the metal in a reduced form, ie in the oxidation state zero.
- the metallic additive can be contained in the metallic additive more of the metals or compounds of these metals mentioned. However, preferably only one of the metals, in reduced or oxidized form, is contained in the metallic additive.
- Metals or their compounds selected from the group of manganese and copper are used in the metallic additive.
- the metallic additive can only be formed from the stated metals or their compounds. However, it is also possible that, in addition to these metals or their compounds, further metals or compounds are contained in the metallic additive.
- the metal or the metallic compound calculated as metal and based on the weight of the metallic additive, in a proportion of at least 10 wt .-%, preferably in an amount of at least 20 wt .-%, preferably in one Content of at least 30 wt .-%, more preferably in a proportion of at least 40 wt .-%, particularly preferably in a proportion of at least 50 wt .-% in the metallic additive.
- the metallic additive is formed only by at least one of said metals, in particular manganese or copper. However, according to one embodiment, it is sufficient if the metal or its compound in a proportion of less than 90 wt .-%, according to another embodiment in an amount of less than 80 wt .-%, according to yet another embodiment in a Content of less than 70% by weight is contained in the metallic additive.
- the sizing composition may contain, in addition to the metallic additive, further customary for sizing ingredients.
- the metallic additive based on the solids content of the sizing composition, in a proportion of at least 10 wt .-%, preferably at least 15 wt .-%, especially preferably at least 20% by weight is contained in the sizing composition.
- the surface or edge shell should have essentially the same composition as sections of the casting which are spaced from the surface of the casting, ie in its volume are.
- the proportion of the metallic additive in the sizing composition is less than 50% by weight, preferably less than 40% by weight, particularly preferably less than 35% by weight ,
- the metallic additive can only contain at least one of the above-mentioned metals, preferably at least one of the metals manganese or copper.
- the at least one metal in the form of an alloy is contained in the metallic additive.
- the metal is contained in the form of an iron alloy in the metallic additive.
- the proportion of iron in the metallic additive, calculated as elemental iron, is preferably selected in the range from 20 to 80% by weight, preferably from 30 to 70% by weight.
- the alloy may also contain other ingredients.
- the metallic additive contains aluminum as constituent, the proportion of aluminum in the metallic additive, calculated as elemental aluminum, preferably being less than 10% by weight, preferably less than 8% by weight. According to one embodiment, the metallic additive contains aluminum in a proportion of more than 2 wt .-%. According to one embodiment of the size according to the invention, metallic additive comprises a proportion of aluminum in the range from 2 to 8% by weight, preferably 3 to 6% by weight, particularly preferably 3 to 5% by weight.
- the metallic additive can also be used in the form of a silicon alloy according to one embodiment.
- the silicon content of such a silicon alloy is preferably in Range selected from 20 to 80 wt .-%, particularly preferably 50 to 70 wt .-%.
- the metallic additive may also comprise further constituents, in particular metals, the proportion of which is preferably less than 2% by weight, preferably less than 1% by weight.
- These further constituents are preferably selected from the group of cerium, magnesium, chromium, molybdenum.
- the proportions of these alloy constituents are preferably between 0.01 and 2 wt .-%, preferably 0.1 to 1 wt .-% based on the metallic additive.
- the metallic additive may also contain calcium.
- the content of calcium is preferably selected in the range of 0.2 to 2 wt .-%, particularly preferably 0.5 to 1.5 wt .-%.
- the grain size of the metallic additive should preferably not be too low, in particular if the metals, preferably manganese and copper, are contained in elemental form in the metallic additive, since then there is an increased risk that the metallic additive reacts with other components of the sizing composition and is oxidized, for example.
- the grain size should preferably not be too large, since otherwise the metallic additive can sink, for example, in the sizing composition and thus an inhomogeneous application of the metallic additive takes place on the surface of a casting mold.
- the metallic additive preferably has an average particle size (D 50 ) of less than 0.5 mm, preferably less than 0.4 mm, particularly preferably less than 0.3 mm.
- the average particle size (D 50 ) can be determined, for example, by sieve analysis or by laser granulometry.
- the metallic additive contained in the size according to the invention usually has a relatively high density and therefore decreases rapidly in the size. Although this decrease can be slowed down by adding an actuating agent. However, by decreasing the grain size, the decrease of the seeding agent can be further reduced so that the seeding agent remains homogeneously suspended in the sizing. As a further advantage, when using a spray device for applying the size, the nozzle of the spray device clogs less easily when using a metallic fine grain additive.
- the inoculant has an average grain size of less than 0.3 mm.
- the specific surface area of the metallic additive increases and thus also the reactivity with the liquid contained in the size, for example water.
- the mean grain size is greater than 50 microns, more preferably selected greater than 80 microns.
- the metallic additive is used with a grain size in the range of 20 to 1000 microns, more preferably from 80 to 300 microns.
- the sizing composition according to the invention is preferably provided in the form of a paste or a suspension.
- the sizing composition contains a carrier liquid.
- This carrier liquid is suitably selected so that it can be completely evaporated at the conditions customary in metal casting.
- the carrier liquid should therefore preferably at normal pressure have a boiling point of less than about 130 ° C, preferably less than 110 ° C.
- the carrier liquid can be proportionately or completely formed by water.
- the sizing composition contains a solvent which is formed at least in a proportion of an organic solvent.
- the oxidation of the metallic additive is suppressed by a high proportion of the organic solvent, for example an alcohol, on the carrier liquid.
- the organic solvent for example an alcohol
- an organic solvent is present in the sizing composition, its proportion of the carrier liquid is preferably selected to be greater than 20% by weight, preferably greater than 30% by weight, particularly preferably greater than 40% by weight.
- the carrier liquid may be completely formed by the organic solvent.
- the proportion of the organic solvent in the carrier liquid can also be chosen to be smaller.
- the proportion of the organic solvent in the carrier liquid is less than 90% by weight, according to a further embodiment less than 80% by weight and according to a further embodiment less than 70% by weight.
- Suitable solvents include, for example, aliphatic, cycloaliphatic or aromatic hydrocarbons preferably comprising 5 to 15 carbons, esters of aliphatic carboxylic acids wherein the carboxylic acids preferably contain 2 to 20 carbon atoms and the alcohol component of the ester preferably comprises 1 to 4 carbon atoms.
- Further preferred organic solvents are, for example, ketones having preferably 4 to 20 carbon atoms.
- ethers are suitable as solvents, it also being possible to use polyglycols here.
- the solvent is at least partly formed by at least one alcohol, which preferably comprises 1 to 10 carbon atoms.
- alcohols are ethanol, n-propanol, isopropanol and butanol.
- an alcohol is used as a constituent of the carrier liquid, its fraction, based on the weight of the carrier liquid, is preferably greater than 50% by weight, preferably greater than 60% by weight.
- the size composition according to the invention may contain further constituents customary for sizes.
- the sizing composition according to the invention comprises at least one pulverulent refractory material.
- This refractory material serves to close the pores in a mold against the penetration of the liquid metal.
- the refractory thermal insulation between the mold and liquid metal is achieved by the refractory thermal insulation between the mold and liquid metal.
- refractory material conventional refractory materials can be used in metal casting.
- Suitable refractory materials are quartz, aluminum oxide, zirconium oxide, aluminum silicates such as pyropyllite, kyanite, andalusite or chamotte, zirconium, ciconsilicates, olivine, talc, mica, graphite, coke, feldspar, diatomite, kaolins, calcined kaolins, kaolinite, metakaolinite, iron oxide , Bauxite.
- the refractory material is provided in powder form.
- the grain size is chosen so that a stable structure is produced in the coating and that the sizing can preferably be distributed without problem on the wall of the casting mold with a spray device.
- the refractory material has an average particle size in the range from 0.1 to 500 ⁇ m, particularly preferably in the range from 1 to 200 ⁇ m.
- a refractory material are in particular Materials suitable which have a melting point which is at least 200 ° C above the temperature of the liquid metal and which do not react with the metal.
- the fraction of the refractory material, based on the solids content of the sizing composition is preferably greater than 10% by weight, preferably greater than 20% by weight, more preferably greater than 30% by weight. According to one embodiment, the fraction of the refractory material is chosen to be less than 80% by weight, according to a further embodiment less than 70% by weight and according to a further embodiment less than 60% by weight.
- the size according to the invention may comprise at least one setting agent.
- the adjusting agent causes an increase in the viscosity of the size, so that the solid components of the size in the suspension do not fall or only to a small extent.
- organic and inorganic materials or mixtures of these materials can be used.
- Suitable inorganic adjusting agents are, for example, strong swellable clays.
- the viscosity of the size is preferably selected in the range of 1000 to 3000 mPas, particularly preferably 1200 to 2000 mPas.
- the metallic additive can then be distributed approximately homogeneously in the sizing and therefore evenly applied to a wall of a casting mold. As a result, the amount of metallic additive which is applied to the surface of the casting mold can be controlled very precisely.
- both two-layer silicates and three-layer silicates can be used, such as eg attapulgite, serpentine, kaolins, smectites, such as saponite, montmorillonite, beidellite and nontronite, vermiculite, illite, hectorite and mica.
- Hectorite also imparts thixotropic properties to the sizing, thereby facilitating the formation of the protective layer on the mold, since the sizing no longer flows after application.
- the amount of clay is preferably chosen to be as low as possible.
- the amount of the highly swellable layered silicate is preferably selected in the range of 0.01 to 5.0 wt%, more preferably in the range of 0.1 to 1.0 wt%, based on the solid content of the size.
- organic thickeners are selected as adjusting agents, since they can be dried to such an extent after application of the protective coating that they hardly give off any more water on contact with the liquid metal.
- Suitable organic solvents are, for example, swellable polymers, such as carboxymethyl, methyl, ethyl, hydroxyethyl and hydroxypropylcellulose, mucilages, polyvinyl alcohols, polyvinylpyrrolidone, pectin, gelatin, agar agar and polypeptides, alginates.
- the size according to the invention comprises as further constituent at least one binder.
- the binder allows a better fixation of the size or of the protective coating produced from the size on the wall of the mold.
- the binder increases the mechanical stability of the protective coating so that less erosion is observed under the action of the liquid metal.
- the binder cures irreversibly, so that an abrasion-resistant coating is obtained.
- binders which are in contact do not back up with humidity. All binders which are used in sizing can be contained per se. In this case, both inorganic and organic binders can be used. Clays, for example clays, in particular bentonite, can be used as binders.
- curable binders are used.
- curing can be achieved by free-radical formers which decompose upon irradiation with high energy radiation, for example, ultraviolet radiation to form free radicals.
- exemplary binders are starch, dextrin, peptides, polyvinyl alcohol, polyvinyl acetate copolymers, polyacrylic acid, polystyrene and / or polyvinyl acetate-polyacrylate dispersions.
- binder systems which can be used in aqueous, alcoholic or aqueous-alcoholic systems and which do not soften after curing under the action of atmospheric moisture.
- the binder used is an alkyd resin, which is preferably selected to be soluble in both water and lower alcohols, preferably having from 2 to 4 carbon atoms, such as ethanol, n-propanol and isopropanol.
- the coating composition according to the invention contains silica sol as binder.
- the silica sol is preferably prepared by neutralizing water glass.
- the resulting amorphous silica preferably has a specific surface area in the range from 10 to 1000 m 2 / g, particularly preferably in the range from 30 to 300 m 2 / g.
- the proportion of the binder is preferably selected in the range of 0.1 to 20 wt .-%, particularly preferably 0.5 to 5 wt .-%, based on the solids weight of the sizing composition.
- the size contains a proportion of graphite.
- the proportion of graphite is preferably selected in the range of 1 to 30 wt .-%, particularly preferably 5 to 15 wt .-%, based on the weight of the size.
- the size composition according to the invention may also contain further components customary for sizing, for example wetting agents, defoamers, pigments, dyes or biocides.
- the proportion of these further constituents in the ready-to-use coating composition is preferably chosen to be less than 1% by weight.
- Suitable wetting agents are, for example, anionic and nonanionic surfactants of medium and high polarity, which have an HSB value of at least 7.
- An example of such a wetting agent is disodium dioctyl sulfosuccinate.
- the wetting agent is preferably used in an amount of 0.01 to 1 wt .-%, preferably 0.05 to 0.3 wt .-%, based on the ready-to-use sizing composition.
- Defoamers or antifoam agents may be used to prevent foaming in the preparation of the sizing composition or in applying it. Foaming on application of the sizing composition can result in uneven layer thickness and holes in the coating.
- defoamers for example, silicone or mineral oil can be used.
- the defoamer is in an amount of 0.01 to 1 wt .-%, preferably from 0.05 to 0.3 Wt .-%, based on the ready-to-use sizing composition.
- any commonly used pigments and dyes may be used. These are added in order to achieve a different contrast, for example between different layers, or to bring about a greater separation effect of the size of the casting.
- pigments are red and yellow iron oxide and graphite.
- dyes are commercially available dyes such as the Luconyl ® color range of BASF AG, Ludwigshafen, Germany.
- the dyes and pigments are preferably contained in an amount of 0.01 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, based on the solids content of the sizing composition.
- the sizing composition contains a biocide to prevent bacterial attack, thereby avoiding a negative impact on the rheology and binding power of the binding agents.
- the carrier liquid contained in the sizing composition is formed essentially from water, that is to say the sizing composition according to the invention is provided in the form of a so-called water sizing.
- suitable biocides are formaldehyde, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-iosthiazolin-3-one (CIT) and 1,2-benzisothiazolin-3-one (BIT).
- MIT, BIT or a mixture thereof are used.
- the biocides are usually used in an amount of from 10 to 1000 ppm, preferably from 50 to 500 ppm, based on the weight of the ready-to-use sizing composition.
- the solids content of the ready-to-use sizing composition is preferably selected in the range from 10 to 60% by weight, preferably from 20 to 50% by weight.
- the sizing composition according to the invention can be prepared by conventional methods.
- a sizing composition according to the present invention can be prepared by initially charging water and breaking up a clay acting as a sizing agent using a high shear stirrer. Subsequently, the refractory components, pigments and dyes and the metallic additive are stirred until a homogeneous mixture is formed. Finally, wetting agents, antifoams, biocides and binders are added.
- the sizing composition according to the invention can be prepared and sold as ready-to-use sizing.
- the size according to the invention can also be prepared and sold in concentrated form. In this case, to provide a ready-to-use size, the amount of carrier liquid necessary to adjust the desired viscosity and density of the size is added.
- the sizing composition according to the invention can also be provided and sold in the form of a kit, wherein, for example, the solid components and the solvent component are present side by side in separate containers.
- the solid components can be provided as a powdery solid mixture in a separate container.
- liquid components to be used such as, for example, binders, wetting agents, wetting agents / defoamers, pigments, dyes and biocides
- the solvent component can either comprise the optionally additionally used components, for example in a common container, or it can be present in a separate container separately from further optional components.
- An inventive Sizing in the ready-to-use state preferably comprises a solids content of from 20 to 80% by weight, preferably from 30 to 70% by weight, based on the ready-to-use sizing composition.
- a sizing composition according to the invention whose solvent component initially consists only of water.
- a volatile alcohol or alcohol mixture preferably ethanol, propanol, isopropanol and mixtures thereof, in preferably amounts of from 40 to 200% by weight, based on the water size
- a ready-to-use alcohol sizing agent can be prepared from this water sizing.
- the solids content of such an alcohol sizing is preferably from 20 to 60 wt .-%, preferably 30 to 40 wt .-%.
- sizing compositions according to the invention used for coating molds and cores in foundry technology have a viscosity of 11 to 25 s, more preferably 12 to 15 s (determined in accordance with DIN 53211, outlet cup 4 mm, Ford cup).
- Preferred densities of a ready-to-use sizing composition are in the range of 0 to 120 ° Be, more preferably 30 to 50 ° Be (determined by the Baume buoyancy method, DIN 12791).
- the sizing compositions according to the invention are suitable for coating casting molds.
- the term "mold” includes all types of bodies necessary to make a casting, such as cores, molds and molds.
- the use according to the invention of the sizing compositions also includes a partial coating of molds.
- a further subject of the invention therefore relates to a method for producing a casting mold, wherein at least one mold cavity provided in the casting mold is coated with the size composition according to the invention.
- a basic mold is produced in a manner known per se from a molding material mixture.
- a refractory molding material is mixed with a binder and then molded into a basic shape or a portion of a basic shape.
- the basic shape essentially corresponds in shape to the casting mold or a part of the casting mold. However, it does not yet have a coating with a size.
- refractory molding material As a refractory molding material, all refractory materials that are customary for the production of moldings for the foundry industry can be used per se. Examples of suitable refractory molding materials are quartz sand, zircon sand, olivine sand, aluminum silicate sand and chrome ore sand or mixtures thereof. Preferably, quartz sand is used.
- the refractory molding material should have a have sufficient particle size, so that the molded body produced from the molding mixture has a sufficiently high porosity to allow escape of volatile compounds during the casting process. Preferably, at least 70 wt .-%, particularly preferably at least 80 wt .-% of the refractory molding material has a particle size ⁇ 290 microns.
- the average particle size of the refractory molding material should preferably be between 100 and 350 ⁇ m.
- the particle size can be determined, for example, by sieve analysis.
- the refractory molding material should be in free-flowing form, so that a binder or a liquid catalyst can be applied well, for example in a mixer to the grains of the refractory molding material.
- regenerated used sands may be used as the refractory molding material. From the used sand larger aggregates are removed and the used sand is separated into individual grains. After a mechanical or thermal treatment, the old sands are dedusted and can then be reused. Before reuse, the acid balance of the regenerated used sand is preferably tested. In particular, during a thermal regeneration by-products contained in the sand, such as carbonates, can be converted into the corresponding oxides, which then react alkaline. If binders are used which are cured by catalysis by an acid, in this case the acid added as a catalyst can be neutralized by the alkaline components of the regenerated used sand. Likewise, for example, in a mechanical regeneration of a used sand, acid remain in the used sand, which must be considered in the preparation of the binder, otherwise, for example, the processing time of the molding material mixture can be shortened.
- the refractory molding material should be dry.
- the refractory molding material contains less than 1 wt .-% water.
- the refractory molding material should not be too warm.
- the refractory molding material should have a temperature in the range of 20 to 35 ° C. Possibly. the refractory molding material can be cooled or heated.
- binders all binders can be used per se, as are customary for the production of casting molds for metal casting. Both inorganic and organic binders can be used.
- inorganic binder for example, water glass can be used, which can be cured thermally or by introducing carbon dioxide.
- organic binders are polyurethane no-bake and cold-box binders, binders based on furan resins or phenolic resins, or also epoxy-acrylate binders.
- Polyurethanes based on polyurethanes are generally composed of two components, a first component containing a phenolic resin and a second component containing a polyisocyanate. These two components are mixed with the refractory molding material and the molding mixture is brought into a mold by ramming, blowing, shooting or other method, compacted and then cured. Depending on the method in which the catalyst is introduced into the molding material mixture, a distinction is made between the "polyurethane no-bake process" and the "polyurethane cold-box process".
- a liquid catalyst generally a liquid tertiary amine
- phenolic resin, polyisocyanate and curing catalyst with the refractory Molded material mixed.
- curing catalyst is added to one of the components.
- the ready-made molding material mixture must have a sufficiently long processing time, so that the molding material mixture can be plastically deformed for a sufficient time and processed into a molding.
- the polymerization must be correspondingly slow so that not already in the storage tanks or supply lines hardening of the molding material mixture.
- the curing should not be too slow to achieve a sufficiently high throughput in the production of molds.
- the processing time can be influenced for example by adding retarders, which slow down the curing of the molding material mixture.
- a suitable retarder is, for example, phosphorus oxychloride.
- the molding material mixture is first brought into a mold without catalyst.
- a gaseous tertiary amine is then passed, which may optionally be mixed with an inert carrier gas.
- the binder binds very quickly, so that a high throughput in the production of molds is achieved.
- the binder systems based on polyurethanes contain a polyol component and a polyisocyanate component, in which case known components can be used.
- the polyisocyanate component of the binder system may comprise an aliphatic, cycloaliphatic or aromatic isocyanate.
- the polyisocyanate preferably contains at least 2 isocyanate groups, preferably 2 to 5 isocyanate groups per molecule.
- mixtures of isocyanates can consist of mixtures of monomers, oligomers and polymers and are therefore referred to below as polyisocyanates.
- the polyisocyanate component per se can be any polyisocyanate which is customary in polyurethane binders for molding mixtures for the foundry industry.
- Suitable polyisocyanates include aliphatic polyisocyanates, e.g. Hexamethylene diisocyanate, alicyclic polyisocyanates, e.g. 4,4'-dicyclohexylmethane diisocyanate, and dimethyl derivatives thereof.
- aromatic polyisocyanates examples include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and methyl derivatives thereof, diphenylmethane-4,4'-diisocyanate and polymethylene-polyphenyl-polyisocyanate.
- aromatic polyisocyanates more preferably polymethylene-polyphenyl polyisocyanate, e.g. commercially available mixtures of diphenylmethane-4,4'-diisocyanate, its isomers and higher homologs.
- the polyisocyanates can be used both in substance and dissolved in an inert or reactive solvent.
- a reactive solvent is understood to mean a solvent which has a reactive group, so that it is incorporated into the framework of the binder when the binder is set.
- the polyisocyanates are preferably used in dilute form in order to be able to coat the grains of the refractory molding material better with a thin film of the binder because of the lower viscosity of the solution.
- the polyisocyanates or their solutions in organic solvents are used in sufficient concentration to effect the curing of the polyol component, usually in a range of from 10 to 500 weight percent, based on the weight of the polyol component. From 20 to 300% by weight, based on the same base, are preferably used.
- Liquid polyisocyanates can be used in undiluted form while solid or viscous polyisocyanates are dissolved in organic solvents. Up to 80 wt .-%, preferably up to 60 wt .-%, particularly preferably up to 40 wt .-% of the isocyanate component may consist of solvents.
- the polyisocyanate is used in an amount such that the number of isocyanate groups is 80 to 120%, based on the number of free hydroxyl groups of the polyol component.
- polyol component all polyols used in polyurethane binders can be used per se.
- the polyol component contains at least 2 hydroxyl groups, which can react with the isocyanate groups of the polyisocyanate component in order to achieve cross-linking of the binder during curing, and thereby better strength of the cured molding.
- the polyols used are preferably phenolic resins which are obtained by condensation of phenols with aldehydes, preferably formaldehyde, in the liquid phase at temperatures up to about 180 ° C. in the presence of catalytic amounts of metal.
- aldehydes preferably formaldehyde
- the processes for the preparation of such phenolic resins are known per se.
- the polyol component is preferably used liquid or dissolved in organic solvents in order to allow a homogeneous distribution of the binder on the refractory molding material.
- the polyol component is preferably used in anhydrous form, because the reaction of the isocyanate component with Water is an undesirable side reaction.
- Non-aqueous or anhydrous in this context means a water content of the polyol component of preferably less than 5 wt .-%, preferably less than 2 wt .-%, mean.
- phenolic resin is meant the reaction product of phenol, phenol derivatives, bisphenols, and higher phenol condensation products with an aldehyde.
- the composition of the phenolic resin depends on the specific starting materials selected, the ratio of the starting materials and the reaction conditions. For example, play the type of catalyst, the time and the reaction temperature, as well as the presence of solvents and other substances.
- the phenolic resin is typically present as a mixture of various compounds and can contain addition products, condensation products and unreacted starting compounds, such as phenols, bisphenol and / or aldehyde, in very different ratios.
- addition product is meant reaction products in which an organic component substitutes at least one hydrogen on a previously unsubstituted phenol or condensation product.
- condensation product is meant reaction products having two or more phenolic rings.
- Novolacs are soluble, meltable, non-self-curing, and shelf-stable oligomers having a molecular weight in the range of about 500 to 5,000 g / mole. They fall in the condensation of aldehydes and phenols in a molar ratio of 1:> 1 in the presence of acidic catalysts. Novolacs are phenol resins free of methylol groups in which the phenyl nuclei are linked via methylene bridges. They may be cured at elevated temperature with crosslinking after addition of curing agents, such as formaldehyde donating agents, preferably hexamethylenetetramine.
- curing agents such as formaldehyde donating agents, preferably hexamethylenetetramine.
- Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and can be obtained by reaction of aldehydes and phenols in a molar ratio of 1: ⁇ 1, if appropriate in the presence of a catalyst, for example a basic catalyst. They have a molecular weight M w of ⁇ 10,000 g / mol.
- phenolic resins particularly suitable as polyol component are known as "o-o” or “high-ortho” novolaks or benzyl ether resins. These are obtainable by condensation of phenols with aldehydes in weakly acidic medium using suitable catalysts.
- Suitable catalysts for the preparation of benzylic ether resins are salts of divalent ions of metals such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Preferably, zinc acetate is used. The amount used is not critical. Typical amounts of metal catalyst are 0.02 to 0.3 wt .-%, preferably 0.02 to 0.15 wt .-%, based on the total amount of phenol and aldehyde.
- phenolic resins For the preparation of phenolic resins, all conventionally used phenols are suitable. In addition to unsubstituted phenols, substituted phenols or mixtures thereof can be used. The phenolic compounds are unsubstituted either in both ortho positions or in an ortho and in the para position to allow polymerization. The remaining ring carbon atoms may be substituted.
- the choice of Substituent is not particularly limited as far as the substituent does not adversely affect the polymerization of the phenol or aldehyde. Examples of substituted phenols are alkyl-substituted phenols, alkoxy-substituted phenols and aryloxy-substituted phenols.
- the abovementioned substituents have, for example, 1 to 26, preferably 1 to 15, carbon atoms.
- suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylene, 3,4-xylene, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3,5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, 3,5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol and p-phenoxyphenol.
- phenol itself.
- higher condensed phenols such as bisphenol A, are suitable.
- polyhydric phenols having more than one phenolic hydroxyl group are also suitable.
- Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups.
- suitable polyhydric phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, fluoroglycine, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcinol or 5-ethylresorcinol.
- Mixtures of various mono- and polyhydric and / or substituted and / or condensed phenolic components can also be used for the preparation of the polyol component.
- phenols of general formula I for the preparation of the phenolic resin component, wherein A, B and C independently of one another from a hydrogen atom, a branched or unbranched alkyl radical, which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms, an aryl or alkylaryl radical, such as, for example, bisphenyls.
- a branched or unbranched alkyl radical which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms,
- Suitable aldehydes for the production of the phenolic resin component are aldehydes of the formula: R-CHO, wherein R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
- R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
- Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde. It is particularly preferred to use formaldehyde, either in its aqueous form, as para-formaldehyde or trioxane.
- an at least equivalent number of moles of aldehyde based on the number of moles of the phenol component, should be used.
- the molar ratio is preferably Aldehyde to phenol 1: 1.0 to 2.5: 1, more preferably 1.1: 1 to 2.2: 1, particularly preferably 1.2: 1 to 2.0: 1.
- the production of the phenolic resin component takes place by methods known to the person skilled in the art.
- the phenol and the aldehyde are reacted under substantially anhydrous conditions in the presence of a divalent metal ion at temperatures of preferably less than 130 ° C.
- the resulting water is distilled off.
- a suitable entraining agent may be added, for example toluene or xylene, or the distillation is carried out at reduced pressure.
- the phenol component is reacted with an aldehyde, preferably benzyl ether resins.
- the reaction with a primary or secondary aliphatic alcohol to an alkoxy-modified phenolic resin in the one-stage or two-stage process is also possible.
- the phenol, aldehyde and alcohol are reacted in the presence of a suitable catalyst.
- an unmodified resin is first prepared, which is subsequently reacted with an alcohol.
- the alcohol component is preferably used in a molar ratio of alcohol: phenol of less than 0.25 so that less than 25% of the hydroxymethyl groups are etherified.
- Suitable alcohols are primary and secondary aliphatic alcohols having one hydroxy group and 1 to 10 carbon atoms. Suitable primary and secondary alcohols are, for example, methanol, ethanol, propanol, n-butanol and n-hexanol. Particularly preferred are methanol and n-butanol.
- the phenolic resin is preferably selected so that crosslinking with the polyisocyanate component is possible.
- phenolic resins comprising molecules having at least two hydroxyl groups in the molecule are particularly suitable.
- the phenolic resin component or the isocyanate component of the binder system is preferably used as a solution in an organic solvent or a combination of organic solvents. Solvents may be required to keep the components of the binder in a sufficiently low viscosity state. This is u.a. required to obtain a uniform crosslinking of the refractory molding material and its flowability.
- solvents for the polyisocyanate or the polyol component of the binder system based on polyurethanes all solvents which are conventionally used in such binder systems for foundry technology can be used per se.
- Suitable solvents are, for example, oxygen-rich, polar, organic solvents.
- Particularly suitable are dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters or cyclic carbonates.
- Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used.
- Dicarboxylic acid esters have the formula R a OOC-R b -COOR 3 , wherein the radicals R a are each independently an alkyl group having 1 to 12, preferably 1 to 6 carbon atoms and R b is an alkylene group, ie a divalent alkyl group, with 1 to 12, preferably 1 to 6 carbon atoms. R b may also include one or more carbon-carbon double bonds. Examples are dimethyl esters of carboxylic acids having 4 to 10 carbon atoms, which are available, for example, under the name "dibasic ester" (DBE) from Invista International S.à.rl, Geneva, CH.
- DBE dibasic ester
- Glycol ether esters are compounds of the formula R c -OR d -OOCR e , where R c is an alkyl group having 1 to 4 carbon atoms, R d is an ethylene group, a propylene group or an oligomeric ethylene oxide or propylene oxide and R e is an alkyl group having 1 to 3 carbon atoms.
- Preference is given to glycol ether acetates, for example butylglycol acetate.
- Glycol diesters accordingly have the general formula R e COO-R d OOCR e , where R d and R e are as defined above and the radicals R e are each independently selected.
- Preferred are glycol diacetates such as propylene glycol diacetate.
- Glycol diethers can be characterized by the formula R c -OR d -OR c , where R c and R d are as defined above and the radicals R c are each independently selected.
- a suitable glycol diether is, for example, dipropylene glycol dimethyl ether. Cyclic ketones, cyclic esters and cyclic carbonates of 4 to 5 carbon atoms are also suitable.
- a suitable cyclic carbonate is, for example, propylene carbonate.
- the alkyl and alkylene groups may each be branched or unbranched.
- the proportion of the solvent in the binder system is preferably not chosen too high, since the solvent evaporates during the production and application of the molded article produced from the molding compound and thus, for example, can lead to unpleasant odors or leads to smoke during the casting.
- the proportion of the solvent in the binder system is less than 50 wt .-%, more preferably less than 40 wt .-%, more preferably less than 35 wt .-%, selected.
- the binder is first mixed with the refractory molding material as described above to form a molding material mixture.
- a suitable catalyst can also already be added to the molding material mixture.
- liquid amines are preferably added to the molding material mixture. These amines preferably have a pK b value of 4 to 11.
- Suitable catalysts are 4-alkylpyridines wherein the alkyl group comprises 1 to 4 carbon atoms, isoquinoline, arylpyridines such as phenylpyridine, pyridine, acryline, 2-methoxypyridine, pyridazine, 3-chloropyridine, quinoline, n-methylimidazole, 4,4'-dipyridine , Phenylpropylpyridine, 1-methylbenzimidazole, 1,4-thiazine, N, N-dimethylbenzylamine, triethylamine, tribenzylamine, N, N-dimethyl-1,3-propanediamine, N, N-dimethylethanolamine and triethanolamine.
- arylpyridines such as phenylpyridine, pyridine, acryline, 2-methoxypyridine, pyridazine, 3-chloropyridine, quinoline, n-methylimidazole, 4,4'-dipyridine , Phen
- the catalyst may optionally be diluted with an inert solvent, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or a fatty acid ester.
- an inert solvent for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or a fatty acid ester.
- the amount of catalyst added is selected in the range of 0.1 to 15% by weight, based on the weight of the polyol component.
- the molding material mixture is then introduced by conventional means into a mold and compacted there.
- the molding material mixture is then cured to a shaped body.
- the shaped body should preferably retain its outer shape.
- a gaseous catalyst is passed through the molded molding material mixture.
- catalyst the usual catalysts in the field of cold-box process can be used.
- amines as catalysts, in particular preferably dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, triethylamine and trimethylamine in their gaseous form or as aerosol.
- a furan resin or a phenolic resin is used as the binder, wherein the molding material mixture is cured according to the "furan no-bake" method with catalysis by a strong acid.
- Furan and phenolic resins show very good disintegration properties during casting. Under the action of heat of the liquid metal, the furan or phenolic resin decomposes and the strength of the mold is lost. After casting, therefore, cores, possibly after prior shaking of the casting, pour out very well from cavities.
- furfuryl alcohol as an essential component.
- Furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol is generally not pure furfuryl alcohol used but added to the furfuryl alcohol further compounds which are polymerized into the resin. Examples of such compounds are aldehydes, such as formaldehyde or furfural, ketones, such as acetone, phenols, urea or polyols, such as sugar alcohols or ethylene glycol.
- the resins may be added with other components that affect the properties of the resin, such as its elasticity. Melamine can be added, for example, to
- Furan no-bake binders are most often prepared by first producing furfuryl-containing precondensates from, for example, urea, formaldehyde, and furfuryl alcohol under acidic conditions. The reaction conditions are chosen so that only a slight polymerization of furfuryl alcohol occurs. These precondensates are then diluted with furfuryl alcohol.
- Resoles can also be used to prepare furan no-bake binders. Resoles are prepared by polymerization of mixtures of phenol and formaldehyde. These resoles are then diluted with furfuryl alcohol.
- the second component of the furan no-bake binder forms an acid.
- This acid neutralizes alkaline components, which are contained in the refractory molding material and catalyzed on the other hand, the crosslinking of the reactive furan resin.
- acids mostly aromatic sulfonic acids and in some special cases also phosphoric acid or sulfuric acid are used.
- Phosphoric acid is used in concentrated form, i. used at concentrations greater than 75%. However, it is only suitable for the catalytic curing of furan resins with a relatively high proportion of urea. The nitrogen content of such resins is more than 2.0% by weight).
- Sulfuric acid can be added as a relatively strong acid starter for the curing of furan resins to weaker acids. During casting, however, a smell typical of sulfur compounds develops. There is also the danger that the casting material absorbs sulfur and influences its properties.
- aromatic sulfonic acids are used as catalysts. Because of their good availability and their high acidity especially toluene sulfonic acid, xylylene sulfonic acid and benzenesulfonic acid are used.
- Phenolic resins as the second large group of acid-catalyzed curable no-bake binders contain resoles as reactive resin components, ie phenolic resins which have been prepared with an excess of formaldehyde. Phenol resins show a significantly lower reactivity compared to furan resins and require strong sulfonic acids as catalysts. Phenolic resins show a relatively high viscosity, which increases with prolonged storage of the resin. Especially at temperatures below 20 ° C, the viscosity increases sharply, so that the sand must be heated in order to apply the binder evenly on the surface of the grains of sand can.
- the molding material mixture should be processed as soon as possible, so as not to impair the quality of the molding compound by premature Curing to accept, which can lead to a deterioration in the strength of the molds produced from the molding material mixture.
- the flowability of the molding material mixture is usually poor. In the production of the mold, the molding material mixture must therefore be carefully compacted in order to achieve a high strength of the mold can.
- the preparation and processing of the molding material mixture should be carried out at temperatures in the range of 15 to 35 ° C. If the temperature is too low, the molding material mixture is difficult to process because of the high viscosity of the phenol no-bake resin. At temperatures of more than 35 ° C, the processing time is shortened by premature curing of the binder.
- molding mixtures based on phenol no-bake binders can also be worked up again, in which case mechanical or thermal or combined mechanical / thermal processes can also be used.
- An acid is then applied to the free-flowing refractory to obtain an acid-coated refractory molding material.
- the acid is applied by conventional methods on the refractory molding material, for example by the acid is sprayed onto the refractory molding material.
- the amount of acid is preferably selected in the range of 5 to 45 wt .-%, particularly preferably in the range of 20 to 30 wt .-%, based on the weight of the binder and calculated as the pure acid, ie without taking into account any used solvent. If the acid is not already in liquid form and has a sufficiently low viscosity to be distributed in the form of a thin film on the grains of the refractory molding material, the acid is dissolved in a suitable solvent.
- Exemplary solvents are water or alcohols or mixtures of water and alcohol. Especially when using however, the solution is prepared as concentrated as possible in order to minimize the amount of water entrained into the binder or the molding material mixture. For uniform distribution of the acid on the grains, the mixture of refractory molding material and acid is well homogenized.
- An acid-curable binder is then applied to the acid-coated refractory molding material.
- the amount of the binder is preferably selected in the range of 0.25 to 5 wt .-%, particularly preferably in the range of 1 to 3 wt .-%, based on the refractory molding material and calculated as the resin component.
- the acid-curable binder it is possible to use, as such, all acid-curable binders, especially those acid-curable binders which are already customary for the production of molding compounds for the foundry industry.
- the binder may also contain other customary components, for example solvents for adjusting the viscosity or extenders which replace part of the crosslinkable resin.
- the binder is applied to the acid-coated refractory molding material and distributed by moving the mixture on the grains of the refractory molding material in the form of a thin film.
- the amounts of binder and acid are chosen so that on the one hand sufficient strength of the casting mold and on the other hand a sufficient processing time of the molding material mixture is achieved.
- a processing time in the range of 5 to 45 minutes is suitable.
- the coated with the binder refractory molding material is then formed by conventional methods to a shaped body.
- the molding material mixture can be introduced into a suitable mold and be condensed there.
- the resulting molded body is then allowed to cure.
- furan no-bake binder all furan resins can be used per se, as they are already used in furan no-bake binder systems.
- the furan resins used in technical furan no-bake binders are usually precondensates or mixtures of furfuryl alcohol with other monomers or precondensates.
- the precondensates contained in furan no-bake binders are prepared in a manner known per se.
- furfuryl alcohol is used in combination with urea and / or formaldehyde or urea / formaldehyde precondensates.
- Formaldehyde can be used both in monomeric form, for example in the form of a formalin solution, as well as in the form of its polymers, such as trioxane or paraformaldehyde.
- formaldehyde other aldehydes or ketones can be used.
- Suitable aldehydes are, for example, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, crotonaldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde, glyoxal and mixtures of these aldehydes.
- Formaldehyde is preferred, this being preferably used in the form of paraformaldehyde.
- ketones As ketone component, all ketones can be used which have a sufficiently high reactivity. Exemplary ketones are methyl ethyl ketone, methyl propyl ketone and acetone, with acetone being preferred.
- the said aldehydes and ketones can be used as a single compound but also in admixture with each other.
- the molar ratio of aldehyde, in particular formaldehyde, or ketone to furfuryl alcohol can be selected within wide ranges.
- 0.4 to 4 moles of furfuryl alcohol, preferably 0.5 to 2 moles of furfuryl alcohol, may be used per mole of aldehyde.
- furfuryl alcohol, formaldehyde and urea can be heated to boiling, for example, after the pH has been adjusted to more than 4.5, water being continuously distilled off from the reaction mixture.
- the reaction time can be several hours, for example 2 hours. Under these reaction conditions occurs almost no polymerization of furfuryl alcohol. However, the furfuryl alcohol is condensed into a resin together with the formaldehyde and the urea.
- furfuryl alcohol, formaldehyde and urea are reacted at a pH of well below 4.5, for example at a pH of 2.0, in the heat, wherein the water formed in the condensation are distilled off under reduced pressure can.
- the reaction product has a relatively high viscosity and is diluted with furfuryl alcohol to produce the binder until the desired viscosity is achieved.
- phenol can be reacted under alkaline conditions, first with formaldehyde to a resole resin.
- This resol can then be reacted or mixed with furfuryl alcohol or a furan group-containing resin.
- furan group-containing resins can be obtained, for example, by the methods described above.
- higher phenols for example resorcinol, cresols or also bisphenol A.
- the proportion of phenol or higher phenols in the binder is preferably in the range of up to 45% by weight, preferably up to 20% by weight, especially preferably chosen up to 10 wt .-%.
- the proportion of phenol or higher phenols can be greater than 2 wt .-%, according to a further embodiment greater than 4 wt .-% can be selected.
- condensates of aldehydes and ketones which are then mixed with furfuryl alcohol to produce the binder.
- Such condensates can be prepared by reacting aldehydes and ketones under alkaline conditions.
- the aldehyde used is preferably formaldehyde, in particular in the form of paraformaldehyde.
- the ketone used is preferably acetone.
- the relative molar ratio of aldehyde to ketone is preferably selected in the range of 7: 1 to 1: 1, preferably 1.2: 1 to 3.0: 1.
- the condensation is preferably carried out under alkaline conditions at pH values in the range of 8 to 11.5, preferably 9 to 11.
- a suitable base is, for example, sodium carbonate.
- an improvement in the strength of the casting mold is achieved by a high proportion of furfuryl alcohol.
- the proportion of furfuryl alcohol in the binder in the range of 30 to 95 wt .-%, preferably 50 to 90 wt .-%, particularly preferably 60 to 85 wt .-% is selected.
- the proportion of urea and / or formaldehyde on the binder is preferably in the range of 2 to 70 wt .-%, preferably 5 to 45 wt .-%, particularly preferably 15 to 30 wt .-% selected.
- the proportions include both the unbound portions of these compounds contained in the binder and those bound in the resin.
- the proportion of these extenders in the binder is therefore preferably less than 25% by weight, preferably less than 15% by weight and more preferably less than 10% by weight. In order to achieve a cost saving without having to put an excessive influence on the strength of the mold, the proportion of extenders is chosen according to an embodiment greater than 5 wt .-%.
- the furan no-bake binders may further contain water.
- the proportion of water is preferably chosen as low as possible.
- the proportion of water in the binder is preferably less than 20% by weight, preferably less than 15% by weight. From an economic point of view, an amount of water of more than 5% by weight in the binder can be tolerated.
- Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and by reaction of aldehydes and phenols in a molar ratio of 1: ⁇ 1, if appropriate in the presence of a catalyst, for example a basic Catalyst, are available. They have a molecular weight M w of ⁇ 10,000 g / mol.
- phenolic resins For the preparation of the phenolic resins, all conventionally used phenols are suitable, with phenol being particularly preferred.
- the aldehyde component used is preferably formaldehyde, in particular in the form of paraformaldehyde.
- Alternative phenols and aldehydes have already been explained in connection with the polyurethane binders. The corresponding passages are referred to.
- the binders may contain other customary additives, for example silanes as adhesion promoters.
- Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as ⁇ -hydroxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) trimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane.
- silane is added to the binder in a proportion of 0.1 to 3% by weight, preferably 0.1 to 1% by weight.
- the binders may also contain other conventional components, such as activators or plasticizers.
- the molding material mixture in addition to the refractory molding material, the binder and optionally the catalyst may contain other conventional ingredients.
- exemplary further constituents are iron oxide, ground flax fibers, wood flour granules, ground coal or clay.
- the molding material mixture is then shaped by conventional methods into a basic shape or a part of a basic shape and optionally cured. If appropriate, the basic shape can then be completely or partially assembled and the mold cavity provided in its basic form can be coated in its entirety or in sections with the sizing composition described above. For this purpose, conventional methods can be used.
- the sizing composition can be applied, for example, by dipping, flooding, brushing or by spraying.
- the mold When immersed as an application method, the mold, in the mold cavity of which optionally a base coat has been applied, is immersed for about 2 seconds to 2 minutes in a container filled with a ready-to-use sizing composition according to the invention. The mold is then removed from the sizing composition and excess sizing composition drained from the mold. The time taken to drain the excess sizing composition after dipping depends on the flow behavior of the sizing composition used.
- the sizing composition is filled in a dilute state in a pressure vessel.
- the sizing can be pressed into a spray gun via the overpressure to be set, where it is sprayed with the aid of separately adjustable atomizing air.
- the conditions are preferably chosen so that the pressure for size composition and atomizing air is adjusted to the gun such that the sprayed size composition still wet on the mold or the core, but gives a uniform application.
- the carrier liquid contained in the size is then evaporated so that a dry sizing layer is obtained.
- all conventional drying methods may be used, such as air drying, dehumidified air drying, microwave or infrared radiation drying, convection oven drying, and similar methods.
- the coated casting mold is dried at 100 to 250 ° C, preferably at 120 to 180 ° C, in a convection oven.
- the size composition according to the invention is preferably dried by burning off the alcohol or alcohol mixture.
- the coated casting mold is additionally heated by the heat of combustion.
- the coated casting mold is dried in the air without further treatment.
- the sizing layer can then be further cured, for example by irradiation with UV radiation, if a corresponding curable binder is included in the sizing composition.
- the size can be applied in the form of a single layer or in the form of several layers arranged one above the other.
- the individual layers may be the same or different in their composition.
- a base coat can be made from a commercially available size which does not contain a metallic additive according to the invention.
- a primer coating for example, water-based or alcohol-based sizing can be used.
- the layer which later comes in contact with the liquid metal is always made from the size of the invention.
- each individual layer can be completely or partially dried after application.
- the coating prepared from the sizing composition preferably has a dry film thickness of at least 0.1 mm, preferably at least 0.2 mm, more preferably at least 0.45 mm, most preferably at least 0.55 mm. According to one embodiment, the thickness of the coating is chosen to be less than 1.5 mm.
- the dry layer thickness here is the layer thickness of the dried coating, which was obtained by drying the sizing composition by substantially complete removal of the solvent component and optionally subsequent curing.
- the dry layer thickness of the base coat and the top coat are preferably determined by measurement with the wet film thickness comb.
- the casting mold can then be completely assembled.
- Another object of the invention relates to the use of the casting mold described above for the production of a casting.
- a casting mold is first provided.
- This may be a lost mold made as described above from a refractory material, such as quartz sand, and a binder, or even a permanent mold commonly used to make pipes, bearings or sleeves, the mold cavity having the shape described above Sizing composition was lined.
- the mold has a protective coating on at least the surfaces which contact the liquid metal, which isolates the liquid metal from the mold and which can positively influence the surface finish of the casting.
- liquid metal is introduced, preferably iron or an iron alloy.
- the liquid metal is then allowed to solidify into a casting and then the casting is separated from the casting mold.
- Another object of the invention relates to a mold having a mold coating which has been prepared from the size described above.
- a mold advantageously has an insulation between the liquid metal and the casting mold, whereby the thermal load of the casting mold is reduced during the casting process and thereby increases the durability of the casting mold.
- the mold coating has a metallic additive which can positively influence the surface properties of the casting, in particular suppressing the formation of a scarred surface on the casting.
- Molds having a topcoat made from the sizing composition of the present invention are used, inter alia, to make wind force scars, grinding bowls, engines and engine components, machine beds and turbines, general machine components or dies.
- the core size used in the examples below has the composition given in Table 1.
- Table 1 ⁇ / u> Composition of the sizing component Wt .-% Zirconium silicate 75 ⁇ m 50,00 Manganese (325 mesh) 20.00 clay mineral 03,00 resins 02,00 Rheological additives 00.50 ethanol 14,50 isopropanol 10.00
- the cast molding stock was prepared as follows: isopropanol is charged and the clay is digested for at least 15 minutes using a high shear stirrer. Subsequently, the refractory components, pigments, manganese and dyes are stirred for at least 15 minutes until a homogeneous mixture is formed. Finally, ethanol, rheological additives and binders are stirred in.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
Description
Die Erfindung betrifft eine Schlichte, welche insbesondere für den Großguss geeignet ist, ein Verfahren zur Herstellung eines Gussstücks sowie eine Gießform mit einem Formüberzug.The invention relates to a size, which is particularly suitable for large-scale casting, a method for producing a casting and a mold with a mold coating.
Die meisten Erzeugnisse der Eisen- und Stahlindustrie sowie der Nichteisenmetallindustrie durchlaufen zur ersten Formgebung Gießprozesse. Dabei werden die Schmelzflüssigwerkstoffe, Eisenmetalle bzw. Nichteisenmetalle, in geometrisch bestimmte Gegenstände mit bestimmten Werkstückeigenschaften überführt. Für die Formgebung der Gussstücke müssen zunächst zum Teil sehr komplizierte Gießformen zur Aufnahme der Schmelze hergestellt werden. Die Gießformen werden unterteilt in verlorene Formen, die nach jedem Guss zerstört werden, sowie Dauerformen, mit denen jeweils eine große Anzahl von Gussstücken hergestellt werden kann.Most products of the iron and steel industry and the non-ferrous metal industry undergo casting processes for the first shaping. The molten materials, ferrous metals or non-ferrous metals, are converted into geometrically determined objects with specific workpiece properties. To shape the castings, very complicated casting molds for receiving the melt must first be produced. The casting molds are divided into lost molds that are destroyed after each casting, and permanent molds, with each of which a large number of castings can be produced.
Die verlorenen Formen bestehen meist aus einem mineralischen, feuerfesten, körnigen Formstoff, der oft noch mit verschiedenen weiteren Zusätzen versetzt wird, z.B. zur Erzielung guter Gussoberflächen, der mit Hilfe eines Bindemittels verfestigt wird. Als feuerfester, körniger Formstoff wird meist gewaschener, klassierter Quarzsand verwendet. Für bestimmte Anwendungen, bei denen besondere Anforderungen erfüllt werden müssen, wird auch Chromit-, Zirkon- und Olivinsand eingesetzt. Daneben werden noch Formstoffe auf Schamotte-, sowie Magnesit-, Silimanit- oder Korundbasis benutzt. Die Bindemittel, mit welchen die Formstoffe verfestigt werden, können anorganischer oder organischer Natur sein. Kleinere verlorene Formen werden überwiegend aus Formstoffen hergestellt, welche durch Bentonit als Bindemittel verfestigt werden, während für größere Formen meist organische Polymere als Bindemittel verwendet werden. Die Herstellung der Gießformen verläuft meist in der Weise, dass der Formstoff zunächst mit dem Bindemittel vermengt wird, sodass die Körner des Formstoffs mit einem dünnen Film des Bindemittels überzogen sind. Diese Formstoffmischung wird dann in eine entsprechende Form eingebracht und ggf. verdichtet, um eine ausreichende Standfestigkeit der Gießform zu erreichen. Anschließend wird die Gießform ausgehärtet, beispielsweise indem sie erwärmt wird oder indem ein Katalysator zugegeben wird, der eine Aushärtungsreaktion bewirkt. Hat die Gießform zumindest eine gewisse Anfangsfestigkeit erreicht, so kann sie ggf. aus der Form entnommen werden und zur vollständigen Aushärtung beispielsweise in einen Ofen überführt werden, um dort für eine vorbestimmte Zeit auf eine bestimmte Temperatur erhitzt zu werden.The lost forms usually consist of a mineral, refractory, granular molding material, often with different added to other additives, for example to achieve good casting surfaces, which is solidified with the aid of a binder. As a refractory, granular molding material usually washed, classified quartz sand is used. For certain applications where special requirements have to be met, chromite, zirconium and olivine sand are also used. In addition, moldings based on chamotte, magnesite, silimanite or corundum are also used. The binders with which the molding materials are solidified may be inorganic or organic in nature. Smaller lost molds are predominantly made of molded materials, which are solidified by bentonite as a binder, while for larger molds usually organic polymers are used as binders. The production of the molds usually proceeds in such a way that the molding material is first mixed with the binder, so that the grains of the molding material are coated with a thin film of the binder. This molding material mixture is then introduced into a corresponding mold and optionally compressed in order to achieve a sufficient stability of the casting mold. Subsequently, the mold is cured, for example by heating it or by adding a catalyst which effects a curing reaction. If the casting mold has reached at least a certain initial strength, then it may optionally be removed from the mold and, for complete curing, for example, be transferred to an oven in order to be heated there for a predetermined time to a certain temperature.
Dauerformen werden für die Herstellung einer Vielzahl von Gusstücken verwendet. Sie müssen daher den Gießvorgang und die damit verbundenen Belastungen unbeschädigt überstehen. Als Werkstoff für Dauerformen haben sich je nach Anwendungsbereich besonders Gusseisen sowie unlegierte und legierte Stähle, aber auch Kupfer, Aluminium, Graphit, Sintermetalle und keramische Materialien bewährt. Zu den Dauerformverfahren zählen das Kokillen-, Druck-, Schleuder- und Stranggießverfahren.Permanent molds are used to make a variety of castings. You must therefore survive undamaged the casting process and the associated loads. Depending on the field of application, cast iron, unalloyed and alloyed steels, as well as copper, aluminum, graphite, sintered metals and ceramics, have been used as material for permanent molds Proven materials. Permanent molding processes include the mold, pressure, spin and continuous casting processes.
Gießformen sind während des Gießvorgangs sehr hohen thermischen und mechanischen Belastungen ausgesetzt. An der Kontaktfläche zwischen flüssigem Metall und Gießform können daher Fehler entstehen, beispielsweise indem die Gießform reißt oder indem flüssiges Metall in das Gefüge der Gießform eindringt. Meist werden daher diejenigen Flächen der Gießform, die mit dem flüssigen Metall in Berührung gelangen, mit einer schützenden Beschichtung versehen, die auch als Schlichte bezeichnet wird. Eine solche Schlichte besteht meist aus einem anorganischen feuerfesten Stoff und einem Bindemittel, die in einem geeigneten Lösungsmittel, beispielsweise Wasser oder Alkohol, gelöst oder aufgeschlämmt sind.Molds are exposed during the casting process very high thermal and mechanical loads. At the contact surface between the liquid metal and the mold can therefore cause errors, for example by the mold breaks or by liquid metal penetrates into the structure of the mold. In most cases, therefore, those surfaces of the mold, which come into contact with the liquid metal, provided with a protective coating, which is also referred to as sizing. Such a sizing usually consists of an inorganic refractory and a binder, which are dissolved or slurried in a suitable solvent, for example water or alcohol.
Durch diese Beschichtungen kann also die Oberfläche der Gießform modifiziert und auf die Eigenschaften des zu verarbeitenden Metalls abgestimmt werden. So kann durch die Schlichte das Aussehen des Gussstücks verbessert werden, indem eine glatte Oberfläche erzeugt wird, da durch die Schlichte Unregelmäßigkeiten ausgeglichen werden, die durch die Größe der Körner des Formstoffs verursacht werden. Weiter kann die Schlichte das Gussstück metallurgisch beeinflussen, indem beispielsweise über die Schlichte selektiv an der Oberfläche des Gusstücks Zusätze in das Gusstück übertragen werden, welche die Oberflächeneigenschaften des Gusstücks verbessern. Ferner bilden die Schlichten eine Schicht, welche die Gießform beim Gießen vom flüssigen Metall chemisch isoliert. Dadurch wird jegliche Haftung zwischen Gussstück und Gießform verhindert, sodass sich das Gussstück ohne Schwierigkeiten aus der Gießform entfernen lässt. Darüber hinaus gewährleistet die Schlichte eine thermische Trennung von Gießform und Gussstück. Dies ist insbesondere bei Dauerformen von Bedeutung. Wird diese Funktion nicht erfüllt, erfährt z.B. eine Metallform im Laufe der aufeinander folgenden Gießvorgänge solch hohe thermische Belastungen, dass sie vorzeitig zerstört wird. Die Schlichte kann aber auch dazu genutzt werden, die Wärmeübertragung zwischen flüssigem Metall und Gießform gezielt zu steuern, um beispielsweise durch die Abkühlungsrate die Ausbildung eines bestimmten Metallgefüges zu bewirken.By means of these coatings, therefore, the surface of the casting mold can be modified and matched to the properties of the metal to be processed. Thus, the size can be used to improve the appearance of the casting by creating a smooth surface because the size compensates for irregularities caused by the size of the grains of the molding material. Further, the size may metallurgically influence the casting by, for example, selectively transferring additives to the casting at the surface of the casting via the size which enhance the surface properties of the casting. Further, the sizings form a layer which chemically isolates the casting mold from the liquid metal during casting. This prevents any adhesion between the casting and the casting mold so that the casting can be easily removed from the casting mold. In addition, the sizing ensures a thermal separation of mold and casting. This is particularly important in permanent forms of importance. If this function is not fulfilled, learns eg a metal form in the course of successive casting operations such high thermal loads that it is destroyed prematurely. However, the sizing can also be used to selectively control the heat transfer between the liquid metal and the casting mold in order, for example, to effect the formation of a specific metal structure by the cooling rate.
Die üblicherweise verwendeten Schlichten enthalten als Grundstoffe z.B. Tone, Quarz, Kieselgur, Cristobalit, Tridymit, Aluminiumsilicat, Zirkonsilicat, Glimmer, Schamotte oder auch Koks bzw. Graphit. Diese Grundstoffe bedecken die Oberfläche der Gießform und verschließen die Poren gegen ein Eindringen des flüssigen Metalls in die Gießform. Wegen ihres großen Isoliervermögens werden häufig Schlichten verwendet, welche Siliziumdioxid oder Kieselgur als Grundstoffe enthalten, da diese Schlichten mit geringem Kostenaufwand hergestellt werden können und in großen Mengen verfügbar sind.The commonly used sizing agents contain as base materials e.g. Clays, quartz, diatomaceous earth, cristobalite, tridymite, aluminum silicate, zirconium silicate, mica, chamotte or coke or graphite. These base materials cover the surface of the mold and close the pores against penetration of the liquid metal into the mold. Because of their high insulating power, sizing agents containing silica or diatomaceous earth as base materials are often used since these sizings can be produced at low cost and are available in large quantities.
Man hat bereits versucht, über eine Schlichteschicht gezielt Legierungsbestandteile in die Oberfläche eines Gussstücks einzubringen, um beispielsweise die Härte der Oberfläche zu verbessern. So beschreiben
Beim Eisen- und Stahlguss bilden sich gelegentlich an der Oberfläche des Gussstücks Fehler aus, wie eine narbige, raue oder vererzte Oberfläche, Abplatzungen, Grübchen, Löcher oder Pinholes oder es bilden sich weiße oder schwarze Beläge aus. Die Ursachen für diese Fehler sind noch nicht vollständig verstanden. Man versucht sie zu bekämpfen, indem man beispielsweise die Gießparameter verändert, das Bindemittelsystem der Gießform modifiziert oder auch verschiedene Additive zur Schlichte gibt. Der Erfolg dieser Maßnahmen ist jedoch meist unbefriedigend. Zwar verschwindet der Fehler zunächst. Er tritt nach einiger Zeit jedoch wieder auf, wobei Zeitpunkt, Intensität und Ausmaß des Fehlers jedoch nicht vorhergesagt werden kann.In iron and steel casting, occasionally defects develop on the surface of the casting, such as a scarred, rough or mineralized surface, chipping, pits, holes or pinholes, or white or black deposits are formed. The causes of these errors are not fully understood. One tries to combat them by, for example, changing the casting parameters, modifying the binder system of the casting mold or also adding various additives to the size. However, the success of these measures is usually unsatisfactory. Although the error disappears first. However, it does reoccur after some time but the timing, intensity and extent of the error can not be predicted.
Die
Treten die oben beschriebenen Fehler auf, ist eine aufwändige Nachbearbeitung der Oberfläche des Gussstücks erforderlich, um die gewünschten Oberflächeneigenschaften zu erreichen. Dies erfordert zusätzliche Arbeitsschritte und damit ein Absinken der Produktivität bzw. ein Ansteigen der Kosten. Treten die Fehler an Flächen des Gussstücks auf, die schlecht oder überhaupt nicht zugänglich sind, kann dies auch zu einem Verlust des Gussstücks führen.If the errors described above occur, elaborate reworking of the surface of the casting is required to achieve the desired surface properties. This requires additional work steps and thus a drop in productivity or an increase in costs. If the defects occur on surfaces of the casting which are poorly or not at all accessible, this can also lead to a loss of the casting.
Der Erfindung lag daher die Aufgabe zugrunde, Maßnahmen vorzuschlagen, durch welche beim Metallguss eine Verbesserung der Oberfläche des Gussstücks erreicht werden kann, sodass das Ausmaß der Oberflächenbearbeitung des Gussstücks nach dem Abguss verringert werden kann.The invention therefore an object of the invention to propose measures by which an improvement in the surface of the casting can be achieved during metal casting, so that the extent of surface treatment of the casting can be reduced after the casting.
Diese Aufgabe wird mit einer Schlichtezusammensetzung mit den Merkmalen des Patentanspruchs 1 gelöst. Vorteilhafte Weiterbildungen der erfindungsgemäßen Schlichtezusammensetzung sind Gegenstand der abhängigen Ansprüche.This object is achieved with a sizing composition having the features of patent claim 1. Advantageous developments of the size composition of the invention are the subject of the dependent claims.
Überraschend wurde gefunden, dass bei Zugabe eines bestimmten metallischen Additivs zu einer Schlichtezusammensetzung die Qualität der Oberfläche des Gussstücks nachhaltig verbessert werden kann, und beispielsweise eine Narbenbildung auf der Oberfläche des Gussstücks weitgehend bis vollständig unterdrückt wird. Dabei wird nicht beobachtet, dass größere Mengen des metallischen Additivs bzw. seiner Komponenten in das Gussstück übertreten. Es treten daher auch keine Schwierigkeiten durch unterschiedliche Ausdehnungs- bzw. Schrumpfungskoeffizienten zwischen Gussstück und Randschale auf.Surprisingly, it has been found that the addition of a specific metallic additive to a size composition can sustainably improve the quality of the surface of the casting, and, for example, scar formation on the surface of the casting is largely or completely suppressed. It is not observed that larger amounts of the metallic additive or its components pass into the casting. There are therefore no difficulties due to different expansion or shrinkage coefficients between the casting and the peripheral shell.
Das in der Schlichtezusammensetzung enthaltene metallische Additiv enthält erfindungsgemäß zumindest ein Metall oder eine Verbindung eines Metalls, wobei das Metall ausgewählt ist aus der Gruppe umfassend Mangan und Kupfer.According to the invention, the metallic additive contained in the sizing composition contains at least one metal or compound of a metal, the metal being selected from the group comprising manganese and copper.
Das metallische Additiv kann ein Metall enthalten, also das Metall in der oxidationsstufe Null, wobei das Metall sowohl in reiner Form eingesetzt werden kann oder auch in Form einer Legierung mit anderen Metallen. Das metallische Additiv kann aber auch in Form eines oxidierten Metalls vorliegen, also in Form eines Oxids oder eines Salzes, wie eines Carbonates, eines Nitrats oder Chlorids, wobei das Oxid bevorzugt ist.The metallic additive may contain a metal, ie the metal in the oxidation state zero, wherein the metal can be used both in pure form or in the form of an alloy with other metals. However, the metallic additive can also be present in the form of an oxidized metal, ie in the form of an oxide or a salt, such as a carbonate, a nitrate or chloride, the oxide being preferred.
An sich ist bevorzugt, das Metall in reduzierter Form, also in der Oxidationsstufe Null einzusetzen.As such, it is preferred to use the metal in a reduced form, ie in the oxidation state zero.
Es können mehrere der genannten Metalle bzw. Verbindungen dieser Metalle im metallischen Additiv enthalten sein. Bevorzugt ist jedoch nur eines der Metalle, in reduzierter oder oxidierter Form, im metallischen Additiv enthalten.It can be contained in the metallic additive more of the metals or compounds of these metals mentioned. However, preferably only one of the metals, in reduced or oxidized form, is contained in the metallic additive.
Es werden im metallischen Additiv Metalle bzw. deren Verbindungen verwendet, die aus der Gruppe von Mangan und Kupfer ausgewählt sind.Metals or their compounds selected from the group of manganese and copper are used in the metallic additive.
Das metallische Additiv kann lediglich aus den genannten Metallen bzw. deren Verbindungen gebildet sein. Es ist aber auch möglich, dass neben diesen Metallen bzw. deren Verbindungen noch weitere Metalle bzw. Verbindungen im metallischen Additiv enthalten sind.The metallic additive can only be formed from the stated metals or their compounds. However, it is also possible that, in addition to these metals or their compounds, further metals or compounds are contained in the metallic additive.
Gemäß einer bevorzugten Ausführungsform ist das Metall oder die metallische Verbindung, berechnet als Metall und bezogen auf das Gewicht des metallischen Additivs, in einem Anteil von zumindest 10 Gew.-%, vorzugsweise in einem Anteil von zumindest 20 Gew.-%, bevorzugt in einem Anteil von zumindest 30 Gew.-%, besonders bevorzugt in einem Anteil von zumindest 40 Gew.-%, insbesondere bevorzugt in einem Anteil von zumindest 50 Gew.-% in dem metallischen Additiv enthalten.According to a preferred embodiment, the metal or the metallic compound, calculated as metal and based on the weight of the metallic additive, in a proportion of at least 10 wt .-%, preferably in an amount of at least 20 wt .-%, preferably in one Content of at least 30 wt .-%, more preferably in a proportion of at least 40 wt .-%, particularly preferably in a proportion of at least 50 wt .-% in the metallic additive.
Gemäß einer Ausführungsform wird das metallische Additiv nur von zumindest einem der genannten Metalle, insbesondere Mangan oder Kupfer, gebildet. Es ist aber gemäß einer Ausführungsform ausreichend, wenn das Metall bzw. seine Verbindung in einem Anteil von weniger als 90 Gew.-%, gemäß einer weiteren Ausführungsform in einem Anteil von weniger als 80 Gew.-%, gemäß noch einer weiteren Ausführungsform in einem Anteil von weniger als 70 Gew-% in dem metallischen Additiv enthalten ist.According to one embodiment, the metallic additive is formed only by at least one of said metals, in particular manganese or copper. However, according to one embodiment, it is sufficient if the metal or its compound in a proportion of less than 90 wt .-%, according to another embodiment in an amount of less than 80 wt .-%, according to yet another embodiment in a Content of less than 70% by weight is contained in the metallic additive.
Die Schlichtezusammensetzung kann neben dem metallischen Additiv noch weitere für Schlichten übliche Bestandteile enthalten. Um einen nachhaltigen Einfluss auf die Oberfläche des Gussstücks zu erzielen ist gemäß einer bevorzugten Ausführungsform vorgesehen, dass das metallische Additiv, bezogen auf den Feststoffanteil der Schlichtezusammensetzung, in einem Anteil von zumindest 10 Gew.-%, bevorzugt zumindest 15 Gew.-%, besonders bevorzugt zumindest 20 Gew.-% in der Schlichtezusammensetzung enthalten ist.The sizing composition may contain, in addition to the metallic additive, further customary for sizing ingredients. In order to achieve a lasting influence on the surface of the casting, it is provided according to a preferred embodiment that the metallic additive, based on the solids content of the sizing composition, in a proportion of at least 10 wt .-%, preferably at least 15 wt .-%, especially preferably at least 20% by weight is contained in the sizing composition.
Wie bereits erläutert, soll mit der Schlichte nicht bevorzugt eine Legierung einer Oberflächenschicht eines Gussstücks erreicht werden sondern die Oberfläche bzw. eine Randschale soll im Wesentlichen die gleiche Zusammensetzung aufweisen, wie Abschnitte des Gussstücks, die beabstandet zur Oberfläche des Gussstücks, d.h. in dessen Volumen angeordnet sind.As already explained, it is not preferable for the size to achieve an alloy of a surface layer of a casting, but the surface or edge shell should have essentially the same composition as sections of the casting which are spaced from the surface of the casting, ie in its volume are.
Es ist daher vorgesehen, dass der Anteil des metallischen Additivs an der Schlichtezusammensetzung, bezogen auf den Feststoffgehalt der Schlichtezusammensetzung, geringer als 50 Gew.-%, vorzugsweise geringer als 40 Gew.-%, besonders bevorzugt geringer als 35 Gew.-% gewählt ist.It is therefore envisaged that the proportion of the metallic additive in the sizing composition, based on the solids content of the sizing composition, is less than 50% by weight, preferably less than 40% by weight, particularly preferably less than 35% by weight ,
Wie bereits erläutert, kann das metallische Additiv lediglich zumindest eines der oben erwähnten Metalle enthalten, bevorzugt zumindest eines der Metalle Mangan oder Kupfer. Es ist jedoch gemäß einer Ausführungsform auch möglich, dass das zumindest eine Metall in Form einer Legierung in dem metallischen Additiv enthalten ist. Gemäß einer Ausführungsform ist das Metall in Form einer Eisenlegierung in dem metallischen Additiv enthalten. Der Anteil des Eisens an dem metallischen Additiv, berechnet als elementares Eisen, wird bevorzugt im Bereich von 20 bis 80 Gew.-%, vorzugsweise 30 bis 70 Gew.-% gewählt.As already explained, the metallic additive can only contain at least one of the above-mentioned metals, preferably at least one of the metals manganese or copper. However, according to one embodiment, it is also possible that the at least one metal in the form of an alloy is contained in the metallic additive. According to one embodiment, the metal is contained in the form of an iron alloy in the metallic additive. The proportion of iron in the metallic additive, calculated as elemental iron, is preferably selected in the range from 20 to 80% by weight, preferably from 30 to 70% by weight.
Neben dem Metall und dem Eisen kann die Legierung auch noch weitere Bestandteile enthalten.In addition to the metal and the iron, the alloy may also contain other ingredients.
Gemäß einer weiteren Ausführungsform enthält das metallische Additiv Aluminium als Bestandteil, wobei der Anteil des Aluminiums am metallischen Additiv, berechnet als elementares Aluminium, vorzugsweise geringer als 10 Gew.-%, bevorzugt geringer als 8 Gew.-% gewählt wird. Gemäß einer Ausführungsform enthält des metallische Additiv Aluminium in einem Anteil von mehr als 2 Gew.-%. Gemäß einer Ausführungsform der erfindungsgemäßen Schlichte umfasst metallische Additiv einen Anteil an Aluminium im Bereich von 2 bis 8 Gew.-%, vorzugsweise 3 bis 6 Gew.-%, insbesondere bevorzugt 3 bis 5 Gew.-%.According to a further embodiment, the metallic additive contains aluminum as constituent, the proportion of aluminum in the metallic additive, calculated as elemental aluminum, preferably being less than 10% by weight, preferably less than 8% by weight. According to one embodiment, the metallic additive contains aluminum in a proportion of more than 2 wt .-%. According to one embodiment of the size according to the invention, metallic additive comprises a proportion of aluminum in the range from 2 to 8% by weight, preferably 3 to 6% by weight, particularly preferably 3 to 5% by weight.
Das metallische Additiv kann gemäß einer Ausführungsform auch in Form einer Siliziumlegierung verwendet werden. Der Siliciumanteil einer solchen Siliciumlegierung wird dabei bevorzugt im Bereich von 20 bis 80 Gew.-%, insbesondere bevorzugt 50 bis 70 Gew.-% gewählt.The metallic additive can also be used in the form of a silicon alloy according to one embodiment. The silicon content of such a silicon alloy is preferably in Range selected from 20 to 80 wt .-%, particularly preferably 50 to 70 wt .-%.
Das metallische Additiv kann noch weitere Bestandteile umfassen, insbesondere Metalle, wobei deren Anteil vorzugsweise geringer als 2 Gew.-%, bevorzugt geringer als 1 Gew.-% gewählt wird.The metallic additive may also comprise further constituents, in particular metals, the proportion of which is preferably less than 2% by weight, preferably less than 1% by weight.
Diese weiteren Bestandteile sind bevorzugt ausgewählt aus der Gruppe von Cer, Magnesium, Chrom, Molybdän.These further constituents are preferably selected from the group of cerium, magnesium, chromium, molybdenum.
Die Anteile dieser Legierungsbestandteile betragen bevorzugt zwischen 0,01 und 2 Gew.-%, bevorzugt 0,1 bis 1 Gew.-% bezogen auf das metallische Additiv. Als weiteren Legierungsbestandteil kann das metallische Additiv auch Calcium enthalten. Der Gehalt an Calcium wird dabei bevorzugt im Bereich von 0,2 bis 2 Gew.-%, insbesondere bevorzugt 0,5 bis 1,5 Gew.-% gewählt.The proportions of these alloy constituents are preferably between 0.01 and 2 wt .-%, preferably 0.1 to 1 wt .-% based on the metallic additive. As a further alloying constituent, the metallic additive may also contain calcium. The content of calcium is preferably selected in the range of 0.2 to 2 wt .-%, particularly preferably 0.5 to 1.5 wt .-%.
Die Korngröße des metallischen Additivs sollte bevorzugt nicht zu gering gewählt sein, insbesondere wenn die Metalle, bevorzugt Mangan und Kupfer, in elementarer Form in dem metallischen Additiv enthalten sind, da dann eine erhöhte Gefahr besteht, dass das metallische Additiv mit weiteren Komponenten der Schlichtezusammensetzung reagiert und beispielsweise oxidiert wird. Andererseits sollte die Korngröße bevorzugt nicht zu groß gewählt werden, da sonst das metallische Additiv beispielsweise in der Schlichtezusammensetzung absinken kann und damit ein inhomogener Auftrag des metallischen Additivs auf die Fläche einer Gießform erfolgt.The grain size of the metallic additive should preferably not be too low, in particular if the metals, preferably manganese and copper, are contained in elemental form in the metallic additive, since then there is an increased risk that the metallic additive reacts with other components of the sizing composition and is oxidized, for example. On the other hand, the grain size should preferably not be too large, since otherwise the metallic additive can sink, for example, in the sizing composition and thus an inhomogeneous application of the metallic additive takes place on the surface of a casting mold.
Das metallische Additiv weist vorzugsweise eine mittlere Korngröße (D50) von weniger als 0,5 mm bevorzugt weniger als 0,4 mm, besonders bevorzugt weniger als 0,3 mm auf. Die mittlere Korngröße (D50) lässt sich beispielsweise durch Siebanalyse oder durch Lasergranulometrie ermitteln. Das in der erfindungsgemäßen Schlichte enthaltene metallische Additiv weist gewöhnlich eine relativ hohe Dichte auf und sinkt daher in der Schlichte rasch ab. Dieses Absinken kann zwar durch Zugabe eines Stellmittels abgebremst werden. Durch eine Verkleinerung der Korngröße kann jedoch das Absinken des Impfmittels weiter verringert werden, so dass das Impfmittel homogen in der Schlichte suspendiert verbleibt. Als weiterer Vorteil verstopft bei Verwendung einer Sprühvorrichtung zum Aufbringen der Schlichte die Düse der Sprühvorrichtung bei Verwendung eines metallischen Additivs mit feiner Körnung weniger leicht. Insbesondere bevorzugt weist das Impfmittel eine mittlere Korngröße von weniger 0,3 mm auf. Mit abnehmender Körnung nimmt jedoch die spezifische Oberfläche des metallischen Additivs zu und damit auch die Reaktivität mit der in der Schlichte enthaltenen Flüssigkeit, beispielsweise Wasser. Bei einer Reaktion des metallischen Additivs mit beispielsweise Wasser wird eine Gasbildung beobachtet, was zu einer Schaumbildung führt. Die Schlichte lässt sich dann nicht mehr zuverlässig pumpen bzw. versprühen. Vorzugsweise wird daher die mittlere Korngröße größer als 50 µm, insbesondere bevorzugt größer als 80 µm gewählt. Besonders bevorzugt wird das metallische Additiv mit einer Körnung im Bereich von 20 bis 1000 µm, weiter bevorzugt von 80 bis 300 µm verwendet.The metallic additive preferably has an average particle size (D 50 ) of less than 0.5 mm, preferably less than 0.4 mm, particularly preferably less than 0.3 mm. The average particle size (D 50 ) can be determined, for example, by sieve analysis or by laser granulometry. The metallic additive contained in the size according to the invention usually has a relatively high density and therefore decreases rapidly in the size. Although this decrease can be slowed down by adding an actuating agent. However, by decreasing the grain size, the decrease of the seeding agent can be further reduced so that the seeding agent remains homogeneously suspended in the sizing. As a further advantage, when using a spray device for applying the size, the nozzle of the spray device clogs less easily when using a metallic fine grain additive. Most preferably, the inoculant has an average grain size of less than 0.3 mm. With decreasing grain size, however, the specific surface area of the metallic additive increases and thus also the reactivity with the liquid contained in the size, for example water. In a reaction of the metallic additive with, for example, water, gas formation is observed, resulting in foaming. The size can then no longer reliably pump or spray. Preferably, therefore, the mean grain size is greater than 50 microns, more preferably selected greater than 80 microns. Particularly preferably, the metallic additive is used with a grain size in the range of 20 to 1000 microns, more preferably from 80 to 300 microns.
Die erfindungsgemäße Schlichtezusammensetzung wird bevorzugt in Form einer Paste oder einer Suspension bereitgestellt. Bei dieser Ausführungsform enthält die Schlichtezusammensetzung eine Trägerflüssigkeit. Diese Trägerflüssigkeit wird geeignet so ausgewählt, dass sie bei den im Metallguss üblichen Bedingungen vollständig verdampft werden kann. Die Trägerflüssigkeit sollte daher bevorzugt bei Normaldruck einen Siedepunkt von weniger als etwa 130°C, vorzugsweise weniger als 110°C aufweisen.The sizing composition according to the invention is preferably provided in the form of a paste or a suspension. In this embodiment, the sizing composition contains a carrier liquid. This carrier liquid is suitably selected so that it can be completely evaporated at the conditions customary in metal casting. The carrier liquid should therefore preferably at normal pressure have a boiling point of less than about 130 ° C, preferably less than 110 ° C.
Die Trägerflüssigkeit kann anteilig oder vollständig von Wasser gebildet sein. Insbesondere wenn das metallisch Additiv jedoch in Form elementarer Metalle bzw. einer Legierung elementarer Metalle vorliegt, wird jedoch gelegentlich eine Oxidation des metallischen Additivs beobachtet. Gemäß einer bevorzugten Ausführungsform enthält die Schlichtezusammensetzung daher ein Lösungsmittel, welches zumindest zu einem Anteil von einem organischen Lösungsmittel gebildet wird.The carrier liquid can be proportionately or completely formed by water. In particular, if the metallic additive but in the form of elemental metals or an alloy elementary Metals present, however, occasionally an oxidation of the metallic additive is observed. Therefore, according to a preferred embodiment, the sizing composition contains a solvent which is formed at least in a proportion of an organic solvent.
Die Oxidation des metallischen Additivs wird durch einen hohen Anteil des organischen Lösungsmittels, beispielsweise eines Alkohols, an der Trägerflüssigkeit zurückgedrängt. Als weiterer Vorteil lässt sich die Schlichte nach dem Auftrag sehr leicht trocknen, indem das Lösungsmittel abgebrannt wird.The oxidation of the metallic additive is suppressed by a high proportion of the organic solvent, for example an alcohol, on the carrier liquid. As a further advantage, the size can be dried very easily after application by the solvent is burned off.
Sofern ein organisches Lösungsmittel in der Schlichtezusammensetzung enthalten ist, so wird dessen Anteil an der Trägerflüssigkeit vorzugsweise größer als 20 Gew.-%, bevorzugt größer als 30 Gew.-%, besonders bevorzugt größer als 40 Gew.-% gewählt.If an organic solvent is present in the sizing composition, its proportion of the carrier liquid is preferably selected to be greater than 20% by weight, preferably greater than 30% by weight, particularly preferably greater than 40% by weight.
Die Trägerflüssigkeit kann vollständig von dem organischen Lösungsmittel gebildet sein. Gemäß einer Ausführungsform kann der Anteil des organischen Lösungsmittels an der Trägerflüssigkeit jedoch auch kleiner gewählt werden. Gemäß einer Ausführungsform beträgt der Anteil des organischen Lösungsmittels an der Trägerflüssigkeit weniger als 90 Gew.-%, gemäß einer weiteren Ausführungsform weniger als 80 Gew.-% und gemäß einer weiteren Ausführungsform weniger als 70 Gew.-%.The carrier liquid may be completely formed by the organic solvent. However, according to one embodiment, the proportion of the organic solvent in the carrier liquid can also be chosen to be smaller. According to one embodiment, the proportion of the organic solvent in the carrier liquid is less than 90% by weight, according to a further embodiment less than 80% by weight and according to a further embodiment less than 70% by weight.
Geeignete Lösungsmittel sind beispielsweise aliphatische, cycloaliphatische oder aromatische Kohlenwasserstoffe, die bevorzugt 5 bis 15 Kohlenstoffe umfassen, Ester aliphatischer Carbonsäuren, wobei die Carbonsäuren bevorzugt 2 bis 20 Kohlenstoffatome und die Alkoholkomponente des Esters bevorzugt 1 bis 4 Kohlenstoffatome umfasst. Weitere bevorzugt organische Lösungsmittel sind beispielsweise Ketone mit vorzugsweise 4 bis 20 Kohlenstoffatomen. Weiter sind Ether als Lösungsmittel geeignet, wobei hier auch Polyglykole verwendet werden können.Suitable solvents include, for example, aliphatic, cycloaliphatic or aromatic hydrocarbons preferably comprising 5 to 15 carbons, esters of aliphatic carboxylic acids wherein the carboxylic acids preferably contain 2 to 20 carbon atoms and the alcohol component of the ester preferably comprises 1 to 4 carbon atoms. Further preferred organic solvents are, for example, ketones having preferably 4 to 20 carbon atoms. Further, ethers are suitable as solvents, it also being possible to use polyglycols here.
Gemäß einer bevorzugten Ausführungsform ist das Lösungsmittel zumindest anteilig von zumindest einem Alkohol gebildet, der vorzugsweise 1 bis 10 Kohlenstoffatome umfasst. Beispielhafte Alkohole sind Ethanol, n-Propanol, Isopropanol und Butanol.According to a preferred embodiment, the solvent is at least partly formed by at least one alcohol, which preferably comprises 1 to 10 carbon atoms. Exemplary alcohols are ethanol, n-propanol, isopropanol and butanol.
Sofern ein Alkohol als Bestandteil der Trägerflüssigkeit verwendet wird, wird dessen Anteil, bezogen auf das Gewicht der Trägerflüssigkeit, vorzugsweise größer als 50 Gew.-%, bevorzugt größer als 60 Gew.-% gewählt.If an alcohol is used as a constituent of the carrier liquid, its fraction, based on the weight of the carrier liquid, is preferably greater than 50% by weight, preferably greater than 60% by weight.
Neben den bereits genannten Bestandteilen kann die erfindungsgemäße Schlichtezusammensetzung weitere für Schlichten übliche Bestandteile enthalten.In addition to the constituents already mentioned, the size composition according to the invention may contain further constituents customary for sizes.
So umfasst die erfindungsgemäße Schlichtezusammensetzung gemäß einer bevorzugten Ausführungsform zumindest einen pulverförmiger Feuerfeststoff. Dieser Feuerfeststoff dient dazu, die Poren in einer Gießform gegen das Eindringen des flüssigen Metalls zu verschließen. Weiter wird durch den Feuerfeststoff eine thermische Isolierung zwischen Gießform und flüssigem Metall erreicht. Als Feuerfeststoff können im Metallguss übliche Feuerfeststoffe verwendet werden. Beispiele für geeignete Feuerfeststoffe sind Quarz, Aluminiumoxid, Zirkonoxid, Aluminiumsilicate, wie Pyropyllit, Kyanit, Andalusit oder Schamotte, Zirkonsande, Zikonsilikate, Olivin, Talk, Glimmer, Grafit, Koks, Feldspat, Diatomit, Kaoline, kalzinierte Kaoline, Kaolinit, Metakaolinit, Eisenoxid, Bauxit.Thus, according to a preferred embodiment, the sizing composition according to the invention comprises at least one pulverulent refractory material. This refractory material serves to close the pores in a mold against the penetration of the liquid metal. Next is achieved by the refractory thermal insulation between the mold and liquid metal. As refractory material, conventional refractory materials can be used in metal casting. Examples of suitable refractory materials are quartz, aluminum oxide, zirconium oxide, aluminum silicates such as pyropyllite, kyanite, andalusite or chamotte, zirconium, ciconsilicates, olivine, talc, mica, graphite, coke, feldspar, diatomite, kaolins, calcined kaolins, kaolinite, metakaolinite, iron oxide , Bauxite.
Der Feuerfeststoff wird in Pulverform bereitgestellt. Die Korngröße wird dabei so gewählt, dass in der Beschichtung ein stabiles Gefüge entsteht und dass sich die Schlichte vorzugsweise mit einer Sprühvorrichtung problemlos auf der Wand der Gießform verteilen lässt. Geeignet weist der Feuerfeststoff eine mittlere Korngröße im Bereich von 0,1 bis 500 µm, insbesondere bevorzugt im Bereich von 1 bis 200 µm auf. Als Feuerfeststoff sind insbesondere Materialien geeignet, welche einen Schmelzpunkt aufweisen, der zumindest 200°C oberhalb der Temperatur des flüssigen Metalls liegt und die keine Reaktion mit dem Metall eingehen.The refractory material is provided in powder form. The grain size is chosen so that a stable structure is produced in the coating and that the sizing can preferably be distributed without problem on the wall of the casting mold with a spray device. Suitably, the refractory material has an average particle size in the range from 0.1 to 500 μm, particularly preferably in the range from 1 to 200 μm. As a refractory material are in particular Materials suitable which have a melting point which is at least 200 ° C above the temperature of the liquid metal and which do not react with the metal.
Der Anteil des Feuerfeststoffs, bezogen auf den Feststoffanteil der Schlichtezusammensetzung, wird vorzugsweise größer als 10 Gew.-%, bevorzugt größer als 20 Gew.-%, besonders bevorzugt größer als 30 Gew.-% gewählt. Gemäß einer Ausführungsform wird der Anteil des Feuerfeststoffs geringer als 80 Gew.-%, gemäß einer weiteren Ausführungsform geringer als 70 Gew.-% und gemäß einer weiteren Ausführungsform geringer als 60 Gew.-% gewählt.The fraction of the refractory material, based on the solids content of the sizing composition, is preferably greater than 10% by weight, preferably greater than 20% by weight, more preferably greater than 30% by weight. According to one embodiment, the fraction of the refractory material is chosen to be less than 80% by weight, according to a further embodiment less than 70% by weight and according to a further embodiment less than 60% by weight.
Die erfindungsgemäße Schlichte kann gemäß einer Ausführungsform mindestens ein Stellmittel umfassen. Das Stellmittel bewirkt eine Erhöhung der Viskosität der Schlichte, so dass die festen Bestandteile der Schlichte in der Suspension nicht bzw. nur in geringem Ausmaß absinken. Zur Erhöhung der Viskosität können sowohl organische als auch anorganische Materialien oder Gemische dieser Materialien eingesetzt werden. Geeignete anorganische Stellmittel sind beispielsweise starke quellfähige Tone.According to one embodiment, the size according to the invention may comprise at least one setting agent. The adjusting agent causes an increase in the viscosity of the size, so that the solid components of the size in the suspension do not fall or only to a small extent. To increase the viscosity, both organic and inorganic materials or mixtures of these materials can be used. Suitable inorganic adjusting agents are, for example, strong swellable clays.
Um ein Absinken der festen Bestandteile der Schlichte zu verhindern und gleichzeitig einen gleichmäßigen Auftrag auf der Gießform erreichen zu können, wird die Viskosität der Schlichte vorzugsweise im Bereich von 1000 bis 3000 mPas, insbesondere bevorzugt 1200 bis 2000 mPas gewählt.In order to prevent a sinking of the solid constituents of the size and at the same time to achieve a uniform application on the casting mold, the viscosity of the size is preferably selected in the range of 1000 to 3000 mPas, particularly preferably 1200 to 2000 mPas.
Das metallische Additiv kann dann annähernd homogen in der Schlichte verteilt und daher auch gleichmäßig auf eine Wand einer Gießform aufgebracht werden. Dadurch lässt sich die Menge an metallischem Additiv, welches auf der Oberfläche der Gießform aufgebracht wird, sehr genau steuern.The metallic additive can then be distributed approximately homogeneously in the sizing and therefore evenly applied to a wall of a casting mold. As a result, the amount of metallic additive which is applied to the surface of the casting mold can be controlled very precisely.
Als hochquellfähiges Schichtsilikat können sowohl Zwei-Schicht-Silikate als auch Drei-Schicht-Silikate verwendet werden, wie z.B. Attapulgit, Serpentine, Kaoline, Smektite, wie Saponit, Montmorillonit, Beidellit und Nontronit, Vermiculit, Illit, Hectorit und Glimmer. Hectorit verleiht der Schlichte auch thixotrope Eigenschaften, wodurch die Ausbildung der Schutzschicht auf der Gießform erleichtert wird, da die Schlichte nach dem Aufbringen nicht mehr fließt. Da Schichtsilicate in den Zwischenschichten Wasser enthalten, welches beim Aufbringen der Schlichte auf die heiße Gießform, welche eine Temperatur im Bereich von etwa 250 bis 350°C aufweist, nicht verdampft, wird die Menge des Tons vorzugsweise möglichst gering gewählt. Die Menge des hochquellfähigen Schichtsilicats wird bevorzugt im Bereich von 0,01 bis 5,0 Gew.-%, insbesondere bevorzugt im Bereich von 0,1 bis 1,0 Gew.-% ausgewählt, bezogen auf Feststoffgehalt der Schlichte.As a highly swellable layered silicate, both two-layer silicates and three-layer silicates can be used, such as eg attapulgite, serpentine, kaolins, smectites, such as saponite, montmorillonite, beidellite and nontronite, vermiculite, illite, hectorite and mica. Hectorite also imparts thixotropic properties to the sizing, thereby facilitating the formation of the protective layer on the mold, since the sizing no longer flows after application. Since phyllosilicates contain water in the interlayers, which does not evaporate on application of the size to the hot mold, which has a temperature in the range from about 250 to 350 ° C., the amount of clay is preferably chosen to be as low as possible. The amount of the highly swellable layered silicate is preferably selected in the range of 0.01 to 5.0 wt%, more preferably in the range of 0.1 to 1.0 wt%, based on the solid content of the size.
Vorzugsweise werden als Stellmittel organische Verdickungsmittel ausgewählt, da diese nach dem Aufbringen der Schutzbeschichtung soweit getrocknet werden können, dass sie beim Kontakt mit dem flüssigen Metall kaum noch Wasser abgeben. Als organische Stellmittel kommen beispielsweise quellfähige Polymere in Frage, wie Carboxymethyl-, Methyl-, Ethyl-, Hydroxyethyl- und Hydroxyproylcellulose, Pflanzenschleime, Polyvinylalkohole, Polyvinylpyrrolidon, Pektin, Gelatine, Agar Agar und Polypeptiden, Alginaten.Preferably, organic thickeners are selected as adjusting agents, since they can be dried to such an extent after application of the protective coating that they hardly give off any more water on contact with the liquid metal. Suitable organic solvents are, for example, swellable polymers, such as carboxymethyl, methyl, ethyl, hydroxyethyl and hydroxypropylcellulose, mucilages, polyvinyl alcohols, polyvinylpyrrolidone, pectin, gelatin, agar agar and polypeptides, alginates.
Gemäß einer bevorzugten Ausführungsform umfasst die erfindungsgemäße Schlichte als weiteren Bestandteil zumindest ein Bindemittel. Das Bindemittel ermöglicht eine bessere Fixierung der Schlichte bzw. des aus der Schlichte hergestellten Schutzüberzugs auf der Wand der Gießform. Außerdem wird durch das Bindemittel die mechanische Stabilität der Schutzbeschichtung erhöht, so dass eine geringere Erosion unter der Einwirkung des flüssigen Metalls beobachtet wird. Vorzugsweise härtet das Bindemittel irreversibel aus, sodass eine abriebfeste Beschichtung erhalten wird. Insbesondere bevorzugt sind Bindemittel, die bei Kontakt mit Luftfeuchtigkeit nicht rückerweichen. Es können an sich alle Bindemittel enthalten sein, die in Schlichten verwendet werden. Dabei können sowohl anorganische als auch organische Bindemittel verwendet werden. Als Bindemittel können beispielsweise Tone werden, insbesondere Bentonit.According to a preferred embodiment, the size according to the invention comprises as further constituent at least one binder. The binder allows a better fixation of the size or of the protective coating produced from the size on the wall of the mold. In addition, the binder increases the mechanical stability of the protective coating so that less erosion is observed under the action of the liquid metal. Preferably, the binder cures irreversibly, so that an abrasion-resistant coating is obtained. Particular preference is given to binders which are in contact do not back up with humidity. All binders which are used in sizing can be contained per se. In this case, both inorganic and organic binders can be used. Clays, for example clays, in particular bentonite, can be used as binders.
Bevorzugt werden härtbare Bindemittel verwendet. Zum Beispiel kann bei Acrylatsystemen eine Härtung durch Radikalbildner erreicht werden, die bei Bestrahlung mit hochenergetischer Strahlung, beispielsweise ultraviolette Strahlung unter Bildung von Radikalen zerfallen.Preferably, curable binders are used. For example, in acrylate systems, curing can be achieved by free-radical formers which decompose upon irradiation with high energy radiation, for example, ultraviolet radiation to form free radicals.
Andere beispielhafte Bindemittel sind Stärke, Dextrin, Peptide, Polyvinylalkohol, Polyvinylacetatcopolymere, Polyacrylsäure, Polystyrol- und/oder Polyvinylacetat-Polyacylatdispersionen. Allgemein werden bevorzugt Bindemittelsysteme verwendet, die sich in wässrigen, alkoholischen oder wässrig-alkoholischen Systemen einsetzen lassen und die nach dem Aushärten unter Einwirkung von Luftfeuchtigkeit nicht rückerweichen.Other exemplary binders are starch, dextrin, peptides, polyvinyl alcohol, polyvinyl acetate copolymers, polyacrylic acid, polystyrene and / or polyvinyl acetate-polyacrylate dispersions. In general, preference is given to using binder systems which can be used in aqueous, alcoholic or aqueous-alcoholic systems and which do not soften after curing under the action of atmospheric moisture.
Gemäß einer bevorzugten Ausführungsform wird als Bindemittel ein Alkydharz verwendet, wobei dieses vorzugsweise so ausgewählt wird, dass es sowohl in Wasser als auch in niedrigen Alkoholen, die bevorzugt 2 bis 4 Kohlenstoffatome aufweisen, wie Ethanol, n-Propanol und Isopropanol, löslich ist.In a preferred embodiment, the binder used is an alkyd resin, which is preferably selected to be soluble in both water and lower alcohols, preferably having from 2 to 4 carbon atoms, such as ethanol, n-propanol and isopropanol.
Gemäß einer weiteren Ausführungsform enthält die erfindungsgemäße Beschichtungsmasse Kieselsol als Bindemittel. Das Kieselsol wird bevorzugt durch Neutralisieren von Wasserglas hergestellt. Die erhaltene amorphe Kieselsäure weist dabei bevorzugt eine spezifische Oberfläche im Bereich von 10 bis 1000 m2/g, insbesondere bevorzugt im Bereich von 30 bis 300 m2/g auf.According to a further embodiment, the coating composition according to the invention contains silica sol as binder. The silica sol is preferably prepared by neutralizing water glass. The resulting amorphous silica preferably has a specific surface area in the range from 10 to 1000 m 2 / g, particularly preferably in the range from 30 to 300 m 2 / g.
Der Anteile des Bindemittels wird bevorzugt im Bereich von 0,1 bis 20 Gew.-%, besonders bevorzugt 0,5 bis 5 Gew.-%, bezogen auf das Feststoffgewicht der Schlichtezusammensetzung gewählt.The proportion of the binder is preferably selected in the range of 0.1 to 20 wt .-%, particularly preferably 0.5 to 5 wt .-%, based on the solids weight of the sizing composition.
Gemäß einer weiteren bevorzugten Ausführungsform enthält die Schlichte einen Anteil an Graphit. Dies unterstützt die Ausbildung von Lamellenkohlenstoff an der Grenzfläche zwischen Gussstück und Gießform. Der Anteil des Graphits wird vorzugsweise im Bereich von 1 bis 30 Gew.-%, insbesondere bevorzugt 5 bis 15 Gew.-%, bezogen auf das Gewicht der Schlichte, gewählt.According to a further preferred embodiment, the size contains a proportion of graphite. This supports the formation of lamellar carbon at the interface between casting and mold. The proportion of graphite is preferably selected in the range of 1 to 30 wt .-%, particularly preferably 5 to 15 wt .-%, based on the weight of the size.
Die erfindungsgemäße Schlichtezusammensetzung kann gegebenenfalls auch noch weitere, für Schlichten übliche Komponenten enthalten, wie beispielsweise Netzmittel, Entschäumer, Pigmente, Farbstoffe oder Biozide. Der Anteil dieser weiteren Bestandteile an der gebrauchsfertigen Beschichtungsmasse wird bevorzugt geringer als 1 Gew.-% gewählt.If appropriate, the size composition according to the invention may also contain further components customary for sizing, for example wetting agents, defoamers, pigments, dyes or biocides. The proportion of these further constituents in the ready-to-use coating composition is preferably chosen to be less than 1% by weight.
Als Netzmittel können beispielsweise anionische und nichtanionische Tenside mittlerer und hoher Polarität verwendet werden, welche einen HSB-Wert von mindestens 7 aufweisen. Ein Beispiel für ein derartiges Netzmittel ist Dinatrium-dioctylsulfosuccinat. Das Netzmittel wird vorzugsweise in einer Menge von 0,01 bis 1 Gew.-%, bevorzugt 0,05 bis 0,3 Gew.-%, bezogen auf die gebrauchsfertige Schlichtezusammensetzung eingesetzt.Suitable wetting agents are, for example, anionic and nonanionic surfactants of medium and high polarity, which have an HSB value of at least 7. An example of such a wetting agent is disodium dioctyl sulfosuccinate. The wetting agent is preferably used in an amount of 0.01 to 1 wt .-%, preferably 0.05 to 0.3 wt .-%, based on the ready-to-use sizing composition.
Entschäumer oder Antischaummittel können verwendet werden, um bei der Herstellung der Schlichtezusammensetzung oder beim Auftragen derselben eine Schaumbildung zu verhindern. Schaumbildung beim Auftragen der Schlichtezusammensetzung kann zu einer ungleichmäßigen Schichtdicke und zu Löchern in der Beschichtung führen. Als Entschäumer können beispielsweise Silikon- oder Mineralöl verwendet werden. Vorzugsweise ist der Entschäumer in einer Menge von 0,01 bis 1 Gew.-%, bevorzugt von 0,05 bis 0,3 Gew.-% enthalten, bezogen auf die gebrauchsfertige Schlichtezusammensetzung.Defoamers or antifoam agents may be used to prevent foaming in the preparation of the sizing composition or in applying it. Foaming on application of the sizing composition can result in uneven layer thickness and holes in the coating. As defoamers, for example, silicone or mineral oil can be used. Preferably, the defoamer is in an amount of 0.01 to 1 wt .-%, preferably from 0.05 to 0.3 Wt .-%, based on the ready-to-use sizing composition.
In der erfindungsgemäßen Schlichtezusammensetzung können gegebenenfalls üblicherweise verwendete Pigmente und Farbstoffe verwendet werden. Diese werden zugesetzt, um einen anderen Kontrast, z.B. zwischen verschiedenen Schichten zu erreichen, beziehungsweise einen stärkeren Trenneffekt der Schlichte vom Guss zu bewirken. Beispiele für Pigmente sind rotes und gelbes Eisenoxid sowie Graphit. Beispiele für Farbstoffe sind handelsübliche Farbstoffe wie die Luconyl® Farbreihe der BASF AG, Ludwigshafen, DE. Die Farbstoffe und Pigmente sind vorzugsweise in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise von 0,1 bis 5 Gew.-% enthalten, bezogen auf den Feststoffgehalt der Schlichtezusammensetzung.In the sizing composition of the present invention, any commonly used pigments and dyes may be used. These are added in order to achieve a different contrast, for example between different layers, or to bring about a greater separation effect of the size of the casting. Examples of pigments are red and yellow iron oxide and graphite. Examples of dyes are commercially available dyes such as the Luconyl ® color range of BASF AG, Ludwigshafen, Germany. The dyes and pigments are preferably contained in an amount of 0.01 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, based on the solids content of the sizing composition.
Gemäß einer weiteren Ausführungsform enthält die Schlichtezusammensetzung ein Biozid, um einen bakteriellen Befall zu verhindern und damit einen negativen Einfluss auf die Rheologie und die Bindekraft der Bindungsmittel zu vermeiden. Dies ist insbesondere bevorzugt, wenn die in der Schlichtezusammensetzung enthaltene Trägerflüssigkeit im Wesentlichen aus Wasser gebildet wird, also die erfindungsgemäße Schlichtezusammensetzung in Form einer sogenannten Wasserschlichte bereitgestellt wird. Beispiele für geeignete Biozide sind Formaldehyd, 2-Methyl-4-isothiazolin-3-on (MIT), 5-Chlor-2-methyl-4-iosthiazolin-3-on (CIT) und 1,2-Benzisothiazolin-3-on (BIT). Vorzugsweise werden MIT, BIT oder ein Gemisch davon eingesetzt. Die Biozide werden üblicherweise in einer Menge von 10 bis 1000 ppm, vorzugsweise von 50 bis 500 ppm verwendet, bezogen auf das Gewicht der gebrauchsfertigen Schlichtezusammensetzung.In another embodiment, the sizing composition contains a biocide to prevent bacterial attack, thereby avoiding a negative impact on the rheology and binding power of the binding agents. This is particularly preferred if the carrier liquid contained in the sizing composition is formed essentially from water, that is to say the sizing composition according to the invention is provided in the form of a so-called water sizing. Examples of suitable biocides are formaldehyde, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-iosthiazolin-3-one (CIT) and 1,2-benzisothiazolin-3-one (BIT). Preferably, MIT, BIT or a mixture thereof are used. The biocides are usually used in an amount of from 10 to 1000 ppm, preferably from 50 to 500 ppm, based on the weight of the ready-to-use sizing composition.
Der Feststoffgehalt der gebrauchsfertigen Schlichtezusammensetzung wird vorzugsweise im Bereich von 10 bis 60 Gew.-%, bevorzugt 20 bis 50 Gew.-% gewählt.The solids content of the ready-to-use sizing composition is preferably selected in the range from 10 to 60% by weight, preferably from 20 to 50% by weight.
Die erfindungsgemäßen Schlichtezusammensetzung kann nach üblichen Verfahren hergestellt werden. Beispielsweise kann eine erfindungsgemäße Schlichtezusammensetzung hergestellt werden, indem Wasser vorgelegt und hierin ein als Stellmittel wirkender Ton unter Verwendung eines hochscherenden Rührers aufgeschlossen wird. Anschließend werden die Feuerfestkomponenten, Pigmente und Farbstoffe sowie das metallische Additiv eingerührt, bis eine homogene Mischung entsteht. Zum Schluss werden Netz-, Antischaummittel, Biozide und Bindemittel eingerührt.The sizing composition according to the invention can be prepared by conventional methods. For example, a sizing composition according to the present invention can be prepared by initially charging water and breaking up a clay acting as a sizing agent using a high shear stirrer. Subsequently, the refractory components, pigments and dyes and the metallic additive are stirred until a homogeneous mixture is formed. Finally, wetting agents, antifoams, biocides and binders are added.
Die erfindungsgemäße Schlichtezusammensetzung kann als gebrauchsfertig formulierte Schlichte hergestellt und vertrieben werden. Die erfindungsgemäße Schlichte kann aber auch in konzentrierter Form hergestellt und vertrieben werden. Im diesem Fall wird zur Bereitstellung einer gebrauchsfertigen Schlichte die Menge der Trägerflüssigkeit zugegeben, die nötig ist, um die gewünschte Viskosität und Dichte der Schlichte einzustellen. Darüber hinaus kann die erfindungsgemäße Schlichtezusammensetzung auch in Form eines Kits bereitgestellt und vertrieben werden, wobei z.B. die Feststoffkomponenten und die Lösungsmittelkomponente nebeneinander in getrennten Behältnissen vorliegen. Die Feststoffkomponenten können als pulverförmiges Feststoffgemisch in einem separaten Behältnis bereitgestellt werden. Gegebenenfalls zu verwendende weitere flüssige Komponenten, wie z.B. Bindemittel, Netzmittel, Netzer/Entschäumer, Pigmente, Farbstoffe und Biozide, können in diesem Kit wiederum in einem getrennten Behältnis vorliegen. Die Lösungsmittelkomponente kann entweder die gegebenenfalls zusätzlich zu verwendenden Komponenten umfassen, z.B. in einem gemeinsamen Behältnis, oder sie kann getrennt von weiteren optionalen Bestandteilen in einem separaten Behältnis vorhanden sein. Zur Herstellung einer gebrauchsfertigen Schlichte werden die geeigneten Mengen der Feststoffkomponente, der optionalen weiteren Komponenten und der Lösungsmittelkomponente miteinander vermengt. Eine erfindungsgemäße Schlichte umfasst im gebrauchsfertigen Zustand vorzugsweise einen Feststoffgehalt von 20 bis 80 Gew.-%, vorzugsweise 30 bis 70 Gew.-%, bezogen auf die gebrauchsfertige Schlichtezusammensetzung. Es ist ferner auch möglich, eine erfindungsgemäße Schlichtezusammensetzung bereitzustellen, deren Lösungsmittelkomponente zunächst nur aus Wasser besteht. Durch Zugabe beispielsweise eines flüchtigen Alkohols oder Alkoholgemischs, vorzugsweise Ethanol, Propanol, Isopropanol und Gemische davon, in vorzugsweise Mengen von 40 bis 200 Gew.-% bezogen auf die Wasserschlichte kann aus dieser Wasserschlichte eine gebrauchsfertige Alkoholschlichte bereitgestellt werden. Der Feststoffgehalt einer solchen Alkoholschlichte beträgt dabei vorzugsweise 20 bis 60 Gew.-%, bevorzugt 30 bis 40 Gew.-%.The sizing composition according to the invention can be prepared and sold as ready-to-use sizing. However, the size according to the invention can also be prepared and sold in concentrated form. In this case, to provide a ready-to-use size, the amount of carrier liquid necessary to adjust the desired viscosity and density of the size is added. In addition, the sizing composition according to the invention can also be provided and sold in the form of a kit, wherein, for example, the solid components and the solvent component are present side by side in separate containers. The solid components can be provided as a powdery solid mixture in a separate container. Optionally, further liquid components to be used, such as, for example, binders, wetting agents, wetting agents / defoamers, pigments, dyes and biocides, can again be present in a separate container in this kit. The solvent component can either comprise the optionally additionally used components, for example in a common container, or it can be present in a separate container separately from further optional components. To prepare a ready-to-use size, the appropriate amounts of the solid component, the optional further components and the solvent component are mixed together. An inventive Sizing in the ready-to-use state preferably comprises a solids content of from 20 to 80% by weight, preferably from 30 to 70% by weight, based on the ready-to-use sizing composition. It is also possible to provide a sizing composition according to the invention whose solvent component initially consists only of water. By adding, for example, a volatile alcohol or alcohol mixture, preferably ethanol, propanol, isopropanol and mixtures thereof, in preferably amounts of from 40 to 200% by weight, based on the water size, a ready-to-use alcohol sizing agent can be prepared from this water sizing. The solids content of such an alcohol sizing is preferably from 20 to 60 wt .-%, preferably 30 to 40 wt .-%.
Je nach gewünschter Verwendung der Schlichtezusammensetzung, z.B. als Grundbeschichtung oder als Deckbeschichtung, und gewünschter Schichtdicke der aus der Schlichtezusammensetzung hergestellten Beschichtung können weitere charakteristische Parameter der Schlichtezusammensetzung eingestellt werden. So weisen erfindungsgemäße Schlichtezusammensetzungen, die zur Beschichtung von Formen und Kernen in der Gießereitechnik verwendet werden, in einer bevorzugten Ausführungsform eine Viskosität von 11 bis 25 s, stärker bevorzugt 12 bis 15 s auf (bestimmt nach DIN 53211; Auslaufbecher 4mm, Ford-Cup). Bevorzugte Dichten einer gebrauchsfertige Schlichtezusammensetzung liegen im Bereich von 0 bis 120°Bé, stärker bevorzugt von 30 bis 50°Bé (bestimmt nach der Baume-Auftriebsmethode; DIN 12791).Depending on the desired use of the sizing composition, e.g. as a basecoat or as a topcoat, and desired layer thickness of the coating made from the sizing composition, other characteristic parameters of the sizing composition may be adjusted. Thus, in one preferred embodiment, sizing compositions according to the invention used for coating molds and cores in foundry technology have a viscosity of 11 to 25 s, more preferably 12 to 15 s (determined in accordance with DIN 53211, outlet cup 4 mm, Ford cup). , Preferred densities of a ready-to-use sizing composition are in the range of 0 to 120 ° Be, more preferably 30 to 50 ° Be (determined by the Baume buoyancy method, DIN 12791).
Die erfindungsgemäßen Schlichtezusammensetzungen eignen sich zum Beschichten von Gießformen. Der hier verwendete Ausdruck "Gießform" umfasst alle Arten von Körpern, welche zur Herstellung eines Gussstücks notwendig sind, wie etwa Kerne, Formen und Kokillen. Die erfindungsgemäße Verwendung der Schlichtezusammensetzungen umfasst auch ein teilweises Beschichten von Gießformen.The sizing compositions according to the invention are suitable for coating casting molds. As used herein, the term "mold" includes all types of bodies necessary to make a casting, such as cores, molds and molds. The use according to the invention of the sizing compositions also includes a partial coating of molds.
Ein weiterer Gegenstand der Erfindung betrifft daher ein Verfahren zur Herstellung einer Gießform, wobei zumindest ein in der Gießform vorgesehener Formhohlraum mit der erfindungsgemäßen Schlichtezusammensetzung beschichtet wird.A further subject of the invention therefore relates to a method for producing a casting mold, wherein at least one mold cavity provided in the casting mold is coated with the size composition according to the invention.
Dabei wird:
- eine Formstoffmischung bereitgestellt, welche zumindest einen feuerfesten Formstoff und ein Bindemittel enthält,
- die Formstoffmischung zu einer Grundform geformt, welche einen Formhohlraum umfasst; und
- zumindest die Flächen des Formhohlraums der Grundform mit einer Schlichtezusammensetzung beschichtet, wie sie oben beschrieben wurde.
- a molding material mixture containing at least one refractory molding material and a binder,
- molding the molding material mixture into a basic shape comprising a mold cavity; and
- at least the surfaces of the mold cavity of the basic mold coated with a sizing composition, as described above.
Zunächst wird in an sich bekannter Weise aus einer Formstoffmischung eine Grundform hergestellt. Zur Herstellung der Formstoffmischung wird ein feuerfester Formstoff mit einem Bindemittel vermischt und dann zu einer Grundform oder zu einem Teilstück einer Grundform geformt. Die Grundform entspricht in ihrer Form im Wesentlichen der Gießform bzw. einem Teil der Gießform. Sie weist jedoch noch keine Beschichtung mit einer Schlichte auf.First, a basic mold is produced in a manner known per se from a molding material mixture. To produce the molding material mixture, a refractory molding material is mixed with a binder and then molded into a basic shape or a portion of a basic shape. The basic shape essentially corresponds in shape to the casting mold or a part of the casting mold. However, it does not yet have a coating with a size.
Als feuerfester Formstoff können an sich alle feuerfesten Stoffe verwendet werden, die für die Herstellung von Formkörpern für die Gießereiindustrie üblich sind. Beispiele geeigneter feuerfester Formstoffe sind Quarzsand, Zirkonsand, Olivinsand, Aluminiumsilikatsand und Chromerzsand bzw. deren Gemische. Bevorzugt wird Quarzsand verwendet. Der feuerfeste Formstoff sollte eine ausreichende Partikelgröße aufweisen, so dass der aus der Formstoffmischung hergestellte Formkörper eine ausreichend hohe Porosität aufweist, um ein Entweichen flüchtiger Verbindungen während des Gießvorgangs zu ermöglichen. Bevorzugt weisen mindestens 70 Gew.-%, insbesondere bevorzugt mindestens 80 Gew.-% des feuerfesten Formstoffs eine Partikelgröße ≤ 290 µm auf. Die durchschnittliche Partikelgröße des feuerfesten Formstoffs soll vorzugsweise zwischen 100 und 350 µm betragen. Die Partikelgröße lässt sich beispielsweise durch Siebanalyse ermitteln. Der feuerfeste Formstoff soll in rieselfähiger Form vorliegen, sodass sich ein Bindemittel oder ein flüssiger Katalysator beispielsweise in einem Mischer gut auf die Körner des feuerfesten Formstoffs auftragen lässt.As a refractory molding material, all refractory materials that are customary for the production of moldings for the foundry industry can be used per se. Examples of suitable refractory molding materials are quartz sand, zircon sand, olivine sand, aluminum silicate sand and chrome ore sand or mixtures thereof. Preferably, quartz sand is used. The refractory molding material should have a have sufficient particle size, so that the molded body produced from the molding mixture has a sufficiently high porosity to allow escape of volatile compounds during the casting process. Preferably, at least 70 wt .-%, particularly preferably at least 80 wt .-% of the refractory molding material has a particle size ≤ 290 microns. The average particle size of the refractory molding material should preferably be between 100 and 350 μm. The particle size can be determined, for example, by sieve analysis. The refractory molding material should be in free-flowing form, so that a binder or a liquid catalyst can be applied well, for example in a mixer to the grains of the refractory molding material.
Gemäß einer Ausführungsform können als feuerfester Formstoff regenerierte Altsande verwendet werden. Aus dem Altsand werden größere Aggregate entfernt und der Altsand ggf. kornvereinzelt. Nach einer mechanischen bzw. thermischen Behandlung werden die Altsande entstaubt und können dann wiederverwendet werden. Vor der erneuten Verwendung wird bevorzugt die Säurebilanz des regenerierten Altsandes geprüft. Insbesondere während einer thermischen Regenerierung können im Sand enthaltene Nebenprodukte, wie Carbonate, in die entsprechenden Oxide umgewandelt werden, die dann alkalisch reagieren. Werden Bindemittel verwendet, die unter Katalyse durch eine Säure ausgehärtet werden, kann in diesem Fall die als Katalysator zugesetzte Säure durch die alkalischen Komponenten des regenerierten Altsandes neutralisiert werden. Ebenso kann, beispielsweise bei einer mechanischen Regenerierung eines Altsandes, Säure im Altsand verbleiben, welche bei der Herstellung des Bindemittels berücksichtigt werden muss, da sonst beispielsweise die Verarbeitungszeit der Formstoffmischung verkürzt werden kann.According to one embodiment, regenerated used sands may be used as the refractory molding material. From the used sand larger aggregates are removed and the used sand is separated into individual grains. After a mechanical or thermal treatment, the old sands are dedusted and can then be reused. Before reuse, the acid balance of the regenerated used sand is preferably tested. In particular, during a thermal regeneration by-products contained in the sand, such as carbonates, can be converted into the corresponding oxides, which then react alkaline. If binders are used which are cured by catalysis by an acid, in this case the acid added as a catalyst can be neutralized by the alkaline components of the regenerated used sand. Likewise, for example, in a mechanical regeneration of a used sand, acid remain in the used sand, which must be considered in the preparation of the binder, otherwise, for example, the processing time of the molding material mixture can be shortened.
Der feuerfeste Formstoff sollte trocken sein. Vorzugsweise enthält der feuerfeste Formstoff weniger als 1 Gew.-% Wasser. Um eine vorzeitige Aushärtung des Bindemittels durch die Einwirkung von Wärme zu verhindern, sollte der feuerfeste Formstoff nicht zu warm sein. Bevorzugt sollte der feuerfeste Formstoff eine Temperatur im Bereich von 20 bis 35 °C aufweisen. Ggf. kann der feuerfeste Formstoff gekühlt bzw. erwärmt werden.The refractory molding material should be dry. Preferably, the refractory molding material contains less than 1 wt .-% water. To prevent premature curing of the binder by the action of heat, the refractory molding material should not be too warm. Preferably, the refractory molding material should have a temperature in the range of 20 to 35 ° C. Possibly. the refractory molding material can be cooled or heated.
Als Bindemittel können an sich alle Bindemittel verwendet werden, wie sie für die Herstellung von Gießformen für den Metallguss üblich sind. Es können sowohl anorganische als auch organische Bindemittel verwendet werden. Als anorganisches Bindemittel kann beispielsweise Wasserglas verwendet werden, welches thermisch oder durch Einleiten von Kohlendioxid ausgehärtet werden kann. Beispielhafte organische Bindemittel sind Polyurethan-No-Bake- und Cold-Box-Bindmittel, Bindemittel auf der Basis von Furanharzen oder Phenolharzen, oder auch Epoxy-Acrylatbindemittel.As binders, all binders can be used per se, as are customary for the production of casting molds for metal casting. Both inorganic and organic binders can be used. As the inorganic binder, for example, water glass can be used, which can be cured thermally or by introducing carbon dioxide. Exemplary organic binders are polyurethane no-bake and cold-box binders, binders based on furan resins or phenolic resins, or also epoxy-acrylate binders.
Bindemittel auf der Basis von Polyurethanen sind im Allgemeinen aus zwei Komponenten aufgebaut, wobei eine erste Komponente ein Phenolharz und eine zweite Komponente ein Polyisocyanat enthält. Diese beiden Komponenten werden mit dem feuerfesten Formstoff gemischt und die Formstoffmischung durch Rammen, Blasen, Schießen oder ein anderes Verfahren in eine Form gebracht, verdichtet und anschließend ausgehärtet. Je nach dem Verfahren, mit welchem der Katalysator in die Formstoffmischung eingebracht wird, unterscheidet man zwischen dem "Polyurethan-No-Bake-Verfahren" und dem "Polyurethan-Cold-Box-Verfahren".Polyurethanes based on polyurethanes are generally composed of two components, a first component containing a phenolic resin and a second component containing a polyisocyanate. These two components are mixed with the refractory molding material and the molding mixture is brought into a mold by ramming, blowing, shooting or other method, compacted and then cured. Depending on the method in which the catalyst is introduced into the molding material mixture, a distinction is made between the "polyurethane no-bake process" and the "polyurethane cold-box process".
Beim No-Bake-Verfahren wird ein flüssiger Katalysator, im Allgemeinen ein flüssiges tertiäres Amin, in die Formstoffmischung eingebracht, ehe diese in eine Form gebracht und ausgehärtet wird. Für die Herstellung der Formstoffmischung werden Phenolharz, Polyisocyanat und Aushärtungskatalysator mit dem feuerfesten Formstoff gemischt. Dabei kann beispielsweise in der Weise vorgegangen werden, dass der feuerfeste Formstoff zunächst mit einer Komponente des Bindemittels umhüllt wird, und dann die andere Komponente zugegeben wird. Der Aushärtungskatalysator wird dabei einer der Komponenten zugegeben. Die fertig zubereitete Formstoffmischung muss eine ausreichend lange Verarbeitungszeit aufweisen, sodass die Formstoffmischung ausreichend lange plastisch verformt und zu einem Formkörper verarbeitet werden kann. Die Polymerisation muss dazu entsprechend langsam verlaufen, sodass nicht bereits in den Vorratsbehältern oder Zuführungsleitungen eine Aushärtung der Formstoffmischung erfolgt. Andererseits darf die Aushärtung nicht zu langsam erfolgen, um einen ausreichend hohen Durchsatz bei der Herstellung von Gießformen zu erreichen. Die Verarbeitungszeit kann beispielsweise durch Zugabe von Verzögerern beeinflusst werden, welche die Aushärtung der Formstoffmischung verlangsamen. Ein geeigneter Verzögerer ist beispielsweise Phosphoroxychlorid.In the no-bake process, a liquid catalyst, generally a liquid tertiary amine, is introduced into the molding material mixture before it is shaped and cured. For the preparation of the molding material mixture are phenolic resin, polyisocyanate and curing catalyst with the refractory Molded material mixed. In this case, for example, proceed in such a way that the refractory molding material is first coated with a component of the binder, and then the other component is added. The curing catalyst is added to one of the components. The ready-made molding material mixture must have a sufficiently long processing time, so that the molding material mixture can be plastically deformed for a sufficient time and processed into a molding. The polymerization must be correspondingly slow so that not already in the storage tanks or supply lines hardening of the molding material mixture. On the other hand, the curing should not be too slow to achieve a sufficiently high throughput in the production of molds. The processing time can be influenced for example by adding retarders, which slow down the curing of the molding material mixture. A suitable retarder is, for example, phosphorus oxychloride.
Beim Cold-Box-Verfahren wird die Formstoffmischung zunächst ohne Katalysator in eine Form gebracht. Durch die Formstoffmischung wird anschließend ein gasförmiges tertiäres Amin geleitet, welches gegebenenfalls mit einem inerten Trägergas versetzt sein kann. Bei Kontakt mit dem gasförmigen Katalysator bindet das Bindemittel sehr schnell ab, so dass ein hoher Durchsatz bei der Herstellung von Gießformen erzielt wird.In the cold-box process, the molding material mixture is first brought into a mold without catalyst. Through the molding material mixture, a gaseous tertiary amine is then passed, which may optionally be mixed with an inert carrier gas. On contact with the gaseous catalyst, the binder binds very quickly, so that a high throughput in the production of molds is achieved.
Die Bindemittelsysteme auf Basis von Polyurethanen enthalten eine Polyolkomponente sowie eine Polyisocyanatkomponente, wobei hier an sich auf bekannte Komponenten zurückgegriffen werden kann.The binder systems based on polyurethanes contain a polyol component and a polyisocyanate component, in which case known components can be used.
Die Polyisocyanatkomponente des Bindemittelsystems kann ein aliphatisches, cycloaliphatisches oder aromatisches Isocyanat umfassen. Das Polyisocyanat enthält vorzugsweise mindestens 2 Isocyanatgruppen, vorzugsweise 2 bis 5 Isocyanatgruppen pro Molekül. Je nach den gewünschten Eigenschaften können auch Mischungen von Isocyanaten eingesetzt werden. Die verwendeten Isocyanate können aus Gemischen von Monomeren, Oligomeren und Polymeren bestehen und werden deshalb im Folgenden als Polyisocyanate bezeichnet.The polyisocyanate component of the binder system may comprise an aliphatic, cycloaliphatic or aromatic isocyanate. The polyisocyanate preferably contains at least 2 isocyanate groups, preferably 2 to 5 isocyanate groups per molecule. Depending on the desired properties, it is also possible to use mixtures of isocyanates. The isocyanates used can consist of mixtures of monomers, oligomers and polymers and are therefore referred to below as polyisocyanates.
Als Polyisocyanatkomponente kann an sich jedes Polyisocyanat eingesetzt werden, das in Polyurethan-Bindemitteln für Formstoffmischungen für die Gießereiindustrie üblich ist. Geeignete Polyisocyanate umfassen aliphatische Polyisocyanate, z.B. Hexamethylendiisocyanat, alicyclische Polyisocyanate, wie z.B. 4,4'-Dicyclohexylmethandiisocyanat, und Dimethylderivate hiervon. Beispiele geeigneter aromatischer Polyisocyanate sind Toluol-2,4-diisocyanat, Toluol-2,6-diisocyanat, 1,5-Naphthalindiisocyanat, Xylylendiisocyanat und Methylderivate hiervon, Diphenylmethan-4,4'-diisocyanat und Polymethylen-Polyphenyl-Polyisocyanat.The polyisocyanate component per se can be any polyisocyanate which is customary in polyurethane binders for molding mixtures for the foundry industry. Suitable polyisocyanates include aliphatic polyisocyanates, e.g. Hexamethylene diisocyanate, alicyclic polyisocyanates, e.g. 4,4'-dicyclohexylmethane diisocyanate, and dimethyl derivatives thereof. Examples of suitable aromatic polyisocyanates are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and methyl derivatives thereof, diphenylmethane-4,4'-diisocyanate and polymethylene-polyphenyl-polyisocyanate.
Obwohl prinzipiell alle herkömmlichen Polyisocyanate mit dem phenolischen Harz unter Bildung einer vernetzten Polymerstruktur reagieren, werden bevorzugt aromatische Polyisocyanate eingesetzt, besonders bevorzugt Polymethylen-Polyphenyl-Polyisocyanat, wie z.B. kommerziell erhältliche Gemische von Diphenylmethan-4,4'-diisocyanat, seinen Isomeren und höheren Homologen.Although, in principle, all conventional polyisocyanates react with the phenolic resin to form a crosslinked polymer structure, it is preferred to use aromatic polyisocyanates, more preferably polymethylene-polyphenyl polyisocyanate, e.g. commercially available mixtures of diphenylmethane-4,4'-diisocyanate, its isomers and higher homologs.
Die Polyisocyanate können sowohl in Substanz als auch gelöst in einem inerten oder reaktiven Lösungsmittel eingesetzt werden. Unter einem reaktiven Lösungsmittel wird dabei ein Lösungsmittel verstanden, welches eine reaktive Gruppe aufweist, so dass es beim Abbinden des Bindemittels in das Gerüst des Bindemittels eingebaut wird. Bevorzugt werden die Polyisocyanate in verdünnter Form eingesetzt, um wegen der niedrigeren Viskosität der Lösung die Körner des feuerfesten Formstoff besser mit einem dünnen Film des Bindemittels umhüllen zu können.The polyisocyanates can be used both in substance and dissolved in an inert or reactive solvent. A reactive solvent is understood to mean a solvent which has a reactive group, so that it is incorporated into the framework of the binder when the binder is set. The polyisocyanates are preferably used in dilute form in order to be able to coat the grains of the refractory molding material better with a thin film of the binder because of the lower viscosity of the solution.
Die Polyisocyanate oder ihre Lösungen in organischen Lösungsmitteln werden in ausreichender Konzentration eingesetzt, um die Aushärtung der Polyolkomponente zu bewerkstelligen, üblicherweise in einem Bereich von 10 bis 500 Gew.-% bezogen auf das Gewicht der Polyolkomponente. Bevorzugt werden 20 bis 300 Gew.-%, bezogen auf die gleiche Basis, eingesetzt. Flüssige Polyisocyanate können in unverdünnter Form eingesetzt werden, während feste oder viskose Polyisocyanate in organischen Lösungsmitteln gelöst werden. Bis zu 80 Gew.-%, vorzugsweise bis zu 60 Gew.-%, besonders bevorzugt bis zu 40 Gew.-% der Isocyanatkomponente können aus Lösungsmitteln bestehen.The polyisocyanates or their solutions in organic solvents are used in sufficient concentration to effect the curing of the polyol component, usually in a range of from 10 to 500 weight percent, based on the weight of the polyol component. From 20 to 300% by weight, based on the same base, are preferably used. Liquid polyisocyanates can be used in undiluted form while solid or viscous polyisocyanates are dissolved in organic solvents. Up to 80 wt .-%, preferably up to 60 wt .-%, particularly preferably up to 40 wt .-% of the isocyanate component may consist of solvents.
Bevorzugt wird das Polyisocyanat in einer Menge eingesetzt, dass die Anzahl der Isocyanatgruppen 80 bis 120 % bezogen auf die Anzahl der freien Hydroxylgruppen der Polyolkomponente beträgt.Preferably, the polyisocyanate is used in an amount such that the number of isocyanate groups is 80 to 120%, based on the number of free hydroxyl groups of the polyol component.
Als Polyolkomponente können an sich alle in Polyurethanbindemitteln verwendeten Polyole eingesetzt werden. Die Polyolkomponente enthält mindestens 2 Hydroxylgruppen, die mit den Isocyanatgruppen der Polyisocyanatkomponente reagieren können, um eine Vernetzung des Bindemittels beim Aushärten erreichen zu können, und dadurch eine bessere Festigkeit des ausgehärteten Formkörpers.As the polyol component, all polyols used in polyurethane binders can be used per se. The polyol component contains at least 2 hydroxyl groups, which can react with the isocyanate groups of the polyisocyanate component in order to achieve cross-linking of the binder during curing, and thereby better strength of the cured molding.
Als Polyole werden vorzugsweise Phenolharze verwendet, die durch Kondensation von Phenolen mit Aldehyden, vorzugsweise Formaldehyd, in flüssiger Phase bei Temperaturen bis zu etwa 180°C in Gegenwart katalytischer Mengen von Metall, erhalten werden. Die Verfahren zur Herstellung derartiger Phenolharze sind an sich bekannt.The polyols used are preferably phenolic resins which are obtained by condensation of phenols with aldehydes, preferably formaldehyde, in the liquid phase at temperatures up to about 180 ° C. in the presence of catalytic amounts of metal. The processes for the preparation of such phenolic resins are known per se.
Die Polyolkomponente wird vorzugsweise flüssig bzw. in organischen Lösungsmitteln gelöst eingesetzt, um eine homogene Verteilung des Bindemittels auf dem feuerfesten Formstoff zu ermöglichen. Die Polyolkomponente wird vorzugsweise in wasserfreier Form eingesetzt, weil die Reaktion der Isocyanatkomponente mit Wasser eine unerwünschte Nebenreaktion ist. Nicht-wässrig oder wasserfrei soll in diesem Zusammenhang einen Wassergehalt der Polyolkomponente von vorzugsweise kleiner als 5 Gew.-%, bevorzugt kleiner als 2 Gew.-%, bedeuten.The polyol component is preferably used liquid or dissolved in organic solvents in order to allow a homogeneous distribution of the binder on the refractory molding material. The polyol component is preferably used in anhydrous form, because the reaction of the isocyanate component with Water is an undesirable side reaction. Non-aqueous or anhydrous in this context means a water content of the polyol component of preferably less than 5 wt .-%, preferably less than 2 wt .-%, mean.
Unter "Phenolharz" wird das Reaktionsprodukt von Phenol, Phenolderivaten, Bisphenolen sowie höherer Phenol-Kondensationsprodukte mit einem Aldehyd verstanden. Die Zusammensetzung des Phenolharzes ist abhängig von den spezifisch ausgewählten Ausgangsstoffen, dem Verhältnis der Ausgangsstoffe und den Reaktionsbedingungen. So spielen z.B. die Art des Katalysators, die Zeit und die Reaktionstemperatur eine wichtige Rolle, ebenso wie die Anwesenheit von Lösungsmitteln und anderen Stoffen.By "phenolic resin" is meant the reaction product of phenol, phenol derivatives, bisphenols, and higher phenol condensation products with an aldehyde. The composition of the phenolic resin depends on the specific starting materials selected, the ratio of the starting materials and the reaction conditions. For example, play the type of catalyst, the time and the reaction temperature, as well as the presence of solvents and other substances.
Das Phenolharz liegt typischerweise als Gemisch verschiedener Verbindungen vor und kann in sehr unterschiedlichen Verhältnissen Additionsprodukte, Kondensationsprodukte und nicht umgesetzte Ausgangsverbindungen, wie Phenole, Bisphenol und/oder Aldehyd enthalten.The phenolic resin is typically present as a mixture of various compounds and can contain addition products, condensation products and unreacted starting compounds, such as phenols, bisphenol and / or aldehyde, in very different ratios.
Als "Additionsprodukt" werden Reaktionsprodukte verstanden, in denen eine organische Komponente wenigstens einen Wasserstoff an einem vorher nicht substituierten Phenol oder einem Kondensationsprodukt substituiert. Unter "Kondensationsprodukt" werden Reaktionsprodukte mit zwei oder mehr Phenolringen verstanden.By "addition product" is meant reaction products in which an organic component substitutes at least one hydrogen on a previously unsubstituted phenol or condensation product. By "condensation product" is meant reaction products having two or more phenolic rings.
Als Kondensationsreaktionen von Phenolen mit Aldehyden resultieren Phenolharze, die in Abhängigkeit von den Mengenverhältnissen der Edukte, den Reaktionsbedingungen und den eingesetzten Katalysatoren in zwei Produktklassen, die Novolake und Resole, eingeteilt werden:The condensation reactions of phenols with aldehydes result in phenolic resins, which are subdivided into two product classes, the novolacs and resoles, depending on the proportions of the reactants, the reaction conditions and the catalysts used:
Novolake sind lösliche, schmelzbare, nicht selbsthärtende und lagerstabile Oligomere mit einem Molekülgewicht im Bereich von ungefähr 500 bis 5.000 g/Mol. Sie fallen bei der Kondensation von Aldehyden und Phenolen im Molverhältnis von 1 : >1 in Gegenwart saurer Katalysatoren an. Novolake sind methylolgruppenfreie Phenolharze, in denen die Phenylkerne über Methylenbrücken verknüpft sind. Sie können nach Zusatz von Härtungsmitteln, wie Formaldehyd spendenden Mitteln, bevorzugt Hexamethylentetramin, bei erhöhter Temperatur unter Vernetzung gehärtet werden.Novolacs are soluble, meltable, non-self-curing, and shelf-stable oligomers having a molecular weight in the range of about 500 to 5,000 g / mole. They fall in the condensation of aldehydes and phenols in a molar ratio of 1:> 1 in the presence of acidic catalysts. Novolacs are phenol resins free of methylol groups in which the phenyl nuclei are linked via methylene bridges. They may be cured at elevated temperature with crosslinking after addition of curing agents, such as formaldehyde donating agents, preferably hexamethylenetetramine.
Resole sind Gemische von Hydroxymethylphenolen, die über Methylen- und Methylenetherbrücken verknüpft sind und durch Reaktion von Aldehyden und Phenolen im Molverhältnis von 1 : <1, gegebenenfalls in Gegenwart eines Katalysators, z.B. eines basischen Katalysators, erhältlich sind. Sie weisen ein Molgewicht Mw von ≤ 10.000 g/mol auf.Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and can be obtained by reaction of aldehydes and phenols in a molar ratio of 1: <1, if appropriate in the presence of a catalyst, for example a basic catalyst. They have a molecular weight M w of ≦ 10,000 g / mol.
Die als Polyolkomponente besonders geeigneten Phenolharze sind unter der Bezeichnung "o-o"' oder "high-ortho"-Novolake bzw. Benzyletherharze bekannt. Diese sind durch Kondensation von Phenolen mit Aldehyden in schwach saurem Medium unter Verwendung geeigneter Katalysatoren erhältlich.The phenolic resins particularly suitable as polyol component are known as "o-o" or "high-ortho" novolaks or benzyl ether resins. These are obtainable by condensation of phenols with aldehydes in weakly acidic medium using suitable catalysts.
Zur Herstellung von Benzyletherharzen geeignete Katalysatoren sind Salze zweiwertiger Ionen von Metallen, wie Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca und Ba. Bevorzugt wird Zinkacetat verwendet. Die eingesetzte Menge ist nicht kritisch. Typische Mengen an Metallkatalysator betragen 0,02 bis 0,3 Gew.-%, bevorzugt 0,02 bis 0,15 Gew.-%, bezogen auf die Gesamtmenge an Phenol und Aldehyd.Suitable catalysts for the preparation of benzylic ether resins are salts of divalent ions of metals such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Preferably, zinc acetate is used. The amount used is not critical. Typical amounts of metal catalyst are 0.02 to 0.3 wt .-%, preferably 0.02 to 0.15 wt .-%, based on the total amount of phenol and aldehyde.
Zur Herstellung der Phenolharze sind alle herkömmlich verwendeten Phenole geeignet. Neben unsubstituierten Phenolen können substituierte Phenole oder Gemische hiervon eingesetzt werden. Die Phenolverbindungen sind entweder in beiden ortho-Positionen oder in einer ortho- und in der para-Position nicht substituiert, um eine Polymerisation zu ermöglichen. Die verbleibenden Ring-Kohlenstoffatome können substituiert sein. Die Wahl des Substituenten ist nicht besonders beschränkt, sofern der Substituent die Polymerisation des Phenols oder des Aldehyds nicht nachteilig beeinflusst. Beispiele substituierter Phenole sind alkylsubstituierte Phenole, alkoxysubstituierte Phenole und aryloxysubstituierte Phenole.For the preparation of phenolic resins, all conventionally used phenols are suitable. In addition to unsubstituted phenols, substituted phenols or mixtures thereof can be used. The phenolic compounds are unsubstituted either in both ortho positions or in an ortho and in the para position to allow polymerization. The remaining ring carbon atoms may be substituted. The choice of Substituent is not particularly limited as far as the substituent does not adversely affect the polymerization of the phenol or aldehyde. Examples of substituted phenols are alkyl-substituted phenols, alkoxy-substituted phenols and aryloxy-substituted phenols.
Die vorstehend genannten Substituenten haben beispielsweise 1 bis 26, bevorzugt 1 bis 15 Kohlenstoffatome. Beispiele geeigneter Phenole sind o-Kresol, m-Kresol, p-Kresol, 3,5-Xylol, 3,4-Xylol, 3,4,5-Trimethylphenol, 3-Ethylphenol, 3,5-Diethylphenol, p-Butylphenol, 3,5-Dibutylphenol, p-Amylphenol, Cyclohexylphenol, p-Octylphenol, p-Nonylphenol, 3,5-Dicyclohexylphenol, p-Crotylphenol, p-Phenylphenol, 3,5-Dimethoxyphenol und p-Phenoxyphenol.The abovementioned substituents have, for example, 1 to 26, preferably 1 to 15, carbon atoms. Examples of suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylene, 3,4-xylene, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3,5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, 3,5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol and p-phenoxyphenol.
Besonders bevorzugt ist Phenol selbst. Auch höher kondensierte Phenole, wie Bisphenol A, sind geeignet. Darüber hinaus eignen sich auch mehrwertige Phenole, die mehr als eine phenolische Hydroxylgruppe aufweisen. Bevorzugte mehrwertige Phenole weisen 2 bis 4 phenolische Hydroxylgruppen auf. Spezielle Beispiele geeigneter mehrwertiger Phenole sind Brenzkatechin, Resorcin, Hydrochinon, Pyrogallol, Fluoroglycin, 2,5-Dimethylresorcin, 4,5-Dimethylresorcin, 5-Methylresorcin oder 5-Ethylresorcin.Particularly preferred is phenol itself. Also higher condensed phenols, such as bisphenol A, are suitable. In addition, polyhydric phenols having more than one phenolic hydroxyl group are also suitable. Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups. Specific examples of suitable polyhydric phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, fluoroglycine, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcinol or 5-ethylresorcinol.
Es können auch Gemische aus verschiedenen ein- und mehrwertigen und/oder substituierten und/oder kondensierten Phenolkomponenten für die Herstellung der Polyolkomponente verwendet werden.Mixtures of various mono- and polyhydric and / or substituted and / or condensed phenolic components can also be used for the preparation of the polyol component.
In einer Ausführungsform werden Phenole der allgemeinen Formel I:
Als Aldehyd zur Herstellung der Phenolharzkomponente eignen sich Aldehyde der Formel:
R-CHO,
wobei R ein Wasserstoffatom oder ein Kohlenstoffatomrest mit vorzugsweise 1 bis 8, besonders bevorzugt 1 bis 3 Kohlenstoffatomen ist. Spezielle Beispiele sind Formaldehyd, Acetaldehyd, Propionaldehyd, Furfurylaldehyd und Benzaldehyd. Besonders bevorzugt wird Formaldehyd eingesetzt, entweder in seiner wässrigen Form, als para-Formaldehyd oder Trioxan.Suitable aldehydes for the production of the phenolic resin component are aldehydes of the formula:
R-CHO,
wherein R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms. Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde. It is particularly preferred to use formaldehyde, either in its aqueous form, as para-formaldehyde or trioxane.
Um die Phenolharze zu erhalten, sollte eine mindestens äquivalente Molzahl an Aldehyd, bezogen auf die Molzahl der Phenolkomponente, eingesetzt werden. Bevorzugt beträgt das Molverhältnis Aldehyd zu Phenol 1 : 1,0 bis 2,5 : 1, besonders bevorzugt 1,1 : 1 bis 2,2 : 1, insbesondere bevorzugt 1,2 : 1 bis 2,0 : 1.In order to obtain the phenolic resins, an at least equivalent number of moles of aldehyde, based on the number of moles of the phenol component, should be used. The molar ratio is preferably Aldehyde to phenol 1: 1.0 to 2.5: 1, more preferably 1.1: 1 to 2.2: 1, particularly preferably 1.2: 1 to 2.0: 1.
Die Herstellung der Phenolharzkomponente erfolgt nach dem Fachmann bekannten Verfahren. Dabei wird das Phenol und der Aldehyd unter im Wesentlichen wasserfreien Bedingungen in Gegenwart eines zweiwertigen Metallions bei Temperaturen von vorzugsweise weniger als 130°C umgesetzt. Das entstehende Wasser wird abdestilliert. Dazu kann der Reaktionsmischung ein geeignetes Schleppmittel zugesetzt werden, beispielsweise Toluol oder Xylol, oder die Destillation wird bei reduziertem Druck durchgeführt.The production of the phenolic resin component takes place by methods known to the person skilled in the art. The phenol and the aldehyde are reacted under substantially anhydrous conditions in the presence of a divalent metal ion at temperatures of preferably less than 130 ° C. The resulting water is distilled off. For this purpose, the reaction mixture, a suitable entraining agent may be added, for example toluene or xylene, or the distillation is carried out at reduced pressure.
Für das Bindemittel der Formstoffmischung wird die Phenolkomponente mit einem Aldehyd, bevorzugt zu Benzyletherharzen, umgesetzt. Die Umsetzung mit einem primären oder sekundären aliphatischen Alkohol zu einem alkoxymodifizierten Phenolharz im Einstufen- oder Zweistufenverfahren (
Das Phenolharz wird bevorzugt so gewählt, dass eine Vernetzung mit der Polyisocyanatkomponente möglich ist. Für den Aufbau eines Netzwerkes sind Phenolharze, die Moleküle mit mindestens zwei Hydroxylgruppen im Molekül umfassen, besonders geeignet. Die Phenolharzkomponente bzw. die Isocyanatkomponente des Bindemittelsystems wird bevorzugt als Lösung in einem organischen Lösungsmittel oder einer Kombination von organischen Lösungsmitteln eingesetzt. Lösungsmittel können erforderlich sein, um die Komponenten des Bindemittels in einem ausreichend niedrigviskosen Zustand zu halten. Dieser ist u.a. erforderlich, um eine gleichmäßige Vernetzung des feuerfesten Formstoffes und dessen Rieselfähigkeit zu erhalten.The phenolic resin is preferably selected so that crosslinking with the polyisocyanate component is possible. For the construction of a network, phenolic resins comprising molecules having at least two hydroxyl groups in the molecule are particularly suitable. The phenolic resin component or the isocyanate component of the binder system is preferably used as a solution in an organic solvent or a combination of organic solvents. Solvents may be required to keep the components of the binder in a sufficiently low viscosity state. This is u.a. required to obtain a uniform crosslinking of the refractory molding material and its flowability.
Als Lösungsmittel für die Polyisocyanat- bzw. die Polyolkomponente des Bindemittelsystems auf Basis von Polyurethanen können an sich alle Lösungsmittel eingesetzt werden, die konventionell in derartigen Bindemittelsystemen für die Gießereitechnik Verwendung finden. Als Lösungsmittel eignen sich beispielsweise sauerstoffreiche, polare, organische Lösungsmittel. Geeignet sind vor allem Dicarbonsäureester, Glykoletherester, Glykoldiester, Glykoldiether, cyclische Ketone, cyclische Ester oder cyclische Carbonate. Bevorzugt werden Dicarbonsäureester, cyclische Ketone und cyclische Carbonate verwendet. Dicarbonsäureester weisen die Formel RaOOC-Rb-COOR3 auf, wobei die Reste Ra jeweils unabhängig voneinander eine Alkylgruppe mit 1 bis 12, bevorzugt 1 bis 6 Kohlenstoffatomen darstellen und Rb eine Alkylengruppe, also eine zweibindige Alkylgruppe, mit 1 bis 12, bevorzugt 1 bis 6 Kohlenstoffatomen ist. Rb kann auch ein oder mehrere Kohlenstoff-Kohlenstoff-Doppelbindungen umfassen. Beispiele sind Dimethylester von Carbonsäuren mit 4 bis 10 Kohlenstoffatomen, die z.B. unter der Bezeichnung "dibasic ester" (DBE) von Invista International S.à.r.l., Genf, CH, erhältlich sind. Glykoletherester sind Verbindungen der Formel Rc-O-Rd-OOCRe, wobei Rc eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, Rd eine Ethylengruppe, eine Propylengruppe oder ein oligomeres Ethylenoxid bzw. Propylenoxid und Re eine Alkylgruppe mit 1 bis 3 Kohlenstoffatomen ist. Bevorzugt sind Glykoletheracetate, z.B. Butylglykolacetat. Glykoldiester weisen entsprechend die allgemeine Formel ReCOO-RdOOCRe auf, wobei Rd und Re wie vorstehend definiert sind und die Reste Re jeweils unabhängig voneinander ausgewählt werden. Bevorzugt sind Glykoldiacetate, wie beispielsweise Propylenglykoldiacetat. Glykoldiether lassen sich durch die Formel Rc-O-Rd-O-Rc charakterisieren, wobei Rc und Rd wie vorstehend definiert sind und die Reste Rc jeweils unabhängig voneinander ausgewählt werden. Ein geeigneter Glykoldiether ist beispielsweise Dipropylenglykoldimethylether. Cyclische Ketone, cyclische Ester und cyclische Carbonate mit 4 bis 5 Kohlenstoffatomen sind ebenfalls geeignet. Ein geeignetes cyclisches Carbonat ist beispielsweise Propylencarbonat. Die Alkyl- und Alkylengruppen können jeweils verzweigt oder unverzweigt sein.As solvents for the polyisocyanate or the polyol component of the binder system based on polyurethanes, all solvents which are conventionally used in such binder systems for foundry technology can be used per se. Suitable solvents are, for example, oxygen-rich, polar, organic solvents. Particularly suitable are dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters or cyclic carbonates. Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used. Dicarboxylic acid esters have the formula R a OOC-R b -COOR 3 , wherein the radicals R a are each independently an alkyl group having 1 to 12, preferably 1 to 6 carbon atoms and R b is an alkylene group, ie a divalent alkyl group, with 1 to 12, preferably 1 to 6 carbon atoms. R b may also include one or more carbon-carbon double bonds. Examples are dimethyl esters of carboxylic acids having 4 to 10 carbon atoms, which are available, for example, under the name "dibasic ester" (DBE) from Invista International S.à.rl, Geneva, CH. Glycol ether esters are compounds of the formula R c -OR d -OOCR e , where R c is an alkyl group having 1 to 4 carbon atoms, R d is an ethylene group, a propylene group or an oligomeric ethylene oxide or propylene oxide and R e is an alkyl group having 1 to 3 carbon atoms. Preference is given to glycol ether acetates, for example butylglycol acetate. Glycol diesters accordingly have the general formula R e COO-R d OOCR e , where R d and R e are as defined above and the radicals R e are each independently selected. Preferred are glycol diacetates such as propylene glycol diacetate. Glycol diethers can be characterized by the formula R c -OR d -OR c , where R c and R d are as defined above and the radicals R c are each independently selected. A suitable glycol diether is, for example, dipropylene glycol dimethyl ether. Cyclic ketones, cyclic esters and cyclic carbonates of 4 to 5 carbon atoms are also suitable. A suitable cyclic carbonate is, for example, propylene carbonate. The alkyl and alkylene groups may each be branched or unbranched.
Der Anteil des Lösungsmittels am Bindemittelsystem wird bevorzugt nicht zu hoch gewählt, da das Lösungsmittel während der Herstellung und Anwendung des aus der Formstoffmischung hergestellten Formkörpers verdampft und damit beispielsweise zu Geruchsbelästigungen führen kann oder beim Abguss zu einer Rauchentwicklung führt. Bevorzugt wird der Anteil des Lösungsmittels am Bindemittelsystem geringer als 50 Gew.-%, besonders bevorzugt kleiner als 40 Gew.-%, insbesondere bevorzugt kleiner als 35 Gew.-%, gewählt.The proportion of the solvent in the binder system is preferably not chosen too high, since the solvent evaporates during the production and application of the molded article produced from the molding compound and thus, for example, can lead to unpleasant odors or leads to smoke during the casting. Preferably, the proportion of the solvent in the binder system is less than 50 wt .-%, more preferably less than 40 wt .-%, more preferably less than 35 wt .-%, selected.
Zur Herstellung des Formkörpers wird zunächst wie oben beschrieben das Bindemittel mit dem feuerfesten Formstoff zu einer Formstoffmischung vermischt. Soll die Herstellung des Formkörpers nach dem PU-No-Bake-Verfahren erfolgen, kann der Formstoffmischung auch bereits ein geeigneter Katalysator zugegeben werden. Bevorzugt werden dazu flüssige Amine zur Formstoffmischung gegeben. Diese Amine weisen bevorzugt einen pKb-Wert von 4 bis 11 auf. Beispiele geeigneter Katalysatoren sind 4-Alkylpyridine, wobei die Alkylgruppe 1 bis 4 Kohlenstoffatome umfasst, Isochinolin, Arylpyridine, wie Phenylpyridin, Pyridin, Acrylin, 2-Methoxypyridin, Pyridazin, 3-Chlorpyridin, Chinolin, n-Methylimidazol, 4,4'-Dipyridin, Phenylpropylpyridin, 1-Methylbenzimidazol, 1,4-Thiazin, N,N-Dimethylbenzylamin, Triethylamin, Tribenzylamin, N,N-Dimethyl-1,3-propandiamin, N,N-Dimethylethanolamin sowie Triethanolamin. Der Katalysator kann gegebenenfalls mit einem inerten Lösungsmittel verdünnt werden, beispielsweise 2,2,4-Trimethyl-1,3-pentandiol-diisobutyrat, oder einem Fettsäureester. Die Menge des zugegebenen Katalysator wird, bezogen auf das Gewicht der Polyolkomponente, im Bereich von 0,1 bis 15 Gew.-% gewählt.To produce the shaped article, the binder is first mixed with the refractory molding material as described above to form a molding material mixture. If the molding is to be produced by the PU-No-Bake process, a suitable catalyst can also already be added to the molding material mixture. For this purpose, liquid amines are preferably added to the molding material mixture. These amines preferably have a pK b value of 4 to 11. Examples of suitable catalysts are 4-alkylpyridines wherein the alkyl group comprises 1 to 4 carbon atoms, isoquinoline, arylpyridines such as phenylpyridine, pyridine, acryline, 2-methoxypyridine, pyridazine, 3-chloropyridine, quinoline, n-methylimidazole, 4,4'-dipyridine , Phenylpropylpyridine, 1-methylbenzimidazole, 1,4-thiazine, N, N-dimethylbenzylamine, triethylamine, tribenzylamine, N, N-dimethyl-1,3-propanediamine, N, N-dimethylethanolamine and triethanolamine. The catalyst may optionally be diluted with an inert solvent, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or a fatty acid ester. The amount of catalyst added is selected in the range of 0.1 to 15% by weight, based on the weight of the polyol component.
Die Formstoffmischung wird dann mit üblichen Mitteln in eine Form eingebracht und dort verdichtet. Die Formstoffmischung wird anschließend zu einem Formkörper ausgehärtet. Bei der Härtung sollte der Formkörper bevorzugt seine äußere Form behalten.The molding material mixture is then introduced by conventional means into a mold and compacted there. The molding material mixture is then cured to a shaped body. When curing, the shaped body should preferably retain its outer shape.
Sofern die Aushärtung nach dem PU-Cold-Box-Verfahren erfolgen soll, wird ein gasförmiger Katalysator durch die geformte Formstoffmischung geleitet. Als Katalysator können die üblichen Katalysatoren auf dem Gebiet des Cold-Box-Verfahrens verwendet werden. Besonders bevorzugt werden Amine als Katalysatoren verwendet, insbesondere bevorzugt Dimethylethylamin, Dimethyl-n-propylamin, Dimethylisopropylamin, Dimethyl-n-butylamin, Triethylamin und Trimethylamin in ihrer gasförmigen Form oder als Aerosol.If the curing is to take place by the PU cold box process, a gaseous catalyst is passed through the molded molding material mixture. As catalyst, the usual catalysts in the field of cold-box process can be used. Particular preference is given to using amines as catalysts, in particular preferably dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, triethylamine and trimethylamine in their gaseous form or as aerosol.
Gemäß einer weiteren bevorzugten Ausführungsform wird als Bindemittel ein Furanharz oder ein Phenolharz eingesetzt, wobei die Formstoffmischung gemäß dem "Furan-No-Bake"-Verfahren unter Katalyse durch eine starke Säure ausgehärtet wird.According to a further preferred embodiment, a furan resin or a phenolic resin is used as the binder, wherein the molding material mixture is cured according to the "furan no-bake" method with catalysis by a strong acid.
Furan- und Phenolharze zeigen beim Guss sehr gute Zerfallseigenschaften. Unter der Hitzeeinwirkung des flüssigen Metalls zersetzt sich das Furan- oder Phenolharz und die Festigkeit der Gießform geht verloren. Nach dem Guss lassen sich daher Kerne, ggf. nach vorherigem Rütteln des Gussstücks, sehr gut aus Hohlräumen ausgießen.Furan and phenolic resins show very good disintegration properties during casting. Under the action of heat of the liquid metal, the furan or phenolic resin decomposes and the strength of the mold is lost. After casting, therefore, cores, possibly after prior shaking of the casting, pour out very well from cavities.
Die als erste Komponente in "Furan-No-Bake-Bindemitteln" enthaltenen reaktiven Furanharze umfassen als wesentliche Komponente Furfurylalkohol. Furfurylalkohol kann unter saurer Katalyse mit sich selbst reagieren und ein Polymer ausbilden. Für die Herstellung von Furan-No-Bake-Bindemitteln wird im Allgemeinen nicht reiner Furfurylalkohol verwendet sondern dem Furfurylalkohol weitere Verbindungen zugesetzt, die in das Harz einpolymerisiert werden. Beispiele für derartige Verbindungen sind Aldehyde, wie Formaldehyd oder Furfural, Ketone, wie Aceton, Phenole, Harnstoff oder auch Polyole, wie Zuckeralkohole oder Ethylenglykol. Den Harzen können noch weitere Komponenten zugegeben werden, welche die Eigenschaften des Harzes beeinflussen, beispielsweise dessen Elastizität. Melamin kann beispielsweise zugesetzt werden, um freies Formaldehyd zu binden.The reactive furan resins contained as the first component in "furan no-bake binders" comprise furfuryl alcohol as an essential component. Furfuryl alcohol can react with itself under acid catalysis and form a polymer. For the production of furan no-bake binders is generally not pure furfuryl alcohol used but added to the furfuryl alcohol further compounds which are polymerized into the resin. Examples of such compounds are aldehydes, such as formaldehyde or furfural, ketones, such as acetone, phenols, urea or polyols, such as sugar alcohols or ethylene glycol. The resins may be added with other components that affect the properties of the resin, such as its elasticity. Melamine can be added, for example, to bind free formaldehyde.
Furan-No-Bake-Bindemittel werden meist in der Weise dargestellt, indem zuerst furfurylhaltige Vorkondensate aus beispielsweise Harnstoff, Formaldehyd und Furfurylalkohol bei sauren Bedingungen erzeugt werden. Die Reaktionsbedingungen werden dabei so gewählt, dass nur eine geringfügige Polymerisation des Furfurylalkohols eintritt. Diese Vorkondensate werden dann mit Furfurylalkohol verdünnt. Zur Herstellung von Furan-No-Bake-Bindemitteln können auch Resole verwendet werden. Resole werden durch Polymerisation von Gemischen aus Phenol und Formaldehyd hergestellt. Diese Resole werden dann mit Furfurylalkohol verdünnt.Furan no-bake binders are most often prepared by first producing furfuryl-containing precondensates from, for example, urea, formaldehyde, and furfuryl alcohol under acidic conditions. The reaction conditions are chosen so that only a slight polymerization of furfuryl alcohol occurs. These precondensates are then diluted with furfuryl alcohol. Resoles can also be used to prepare furan no-bake binders. Resoles are prepared by polymerization of mixtures of phenol and formaldehyde. These resoles are then diluted with furfuryl alcohol.
Die zweite Komponente der Furan-No-Bake-Bindemittel bildet eine Säure. Diese Säure neutralisiert zum Einen alkalische Komponenten, die im feuerfesten Formstoff enthalten sind und katalysiert zum Anderen die Vernetzung des reaktiven Furanharzes.The second component of the furan no-bake binder forms an acid. This acid neutralizes alkaline components, which are contained in the refractory molding material and catalyzed on the other hand, the crosslinking of the reactive furan resin.
Als Säuren werden meist aromatische Sulfonsäuren und in einigen speziellen Fällen auch Phosphorsäure oder Schwefelsäure verwendet. Phosphorsäure wird in konzentrierter Form, d.h. bei Konzentrationen von mehr als 75 % verwendet. Sie eignet sich jedoch nur für die katalytische Aushärtung von Furanharzen mit einem relativ hohen Anteil an Harnstoff. Der Stickstoffgehalt derartiger Harze liegt bei mehr als 2,0 Gew.-%). Schwefelsäure kann als relativ starke Säure als Starter für die Aushärtung der Furanharze schwächeren Säuren zugesetzt werden. Beim Abguss entwickelt sich dann jedoch ein für Schwefelverbindungen typischer Geruch. Außerdem besteht die Gefahr, dass vom Gusswerkstoff Schwefel aufgenommen wird und dessen Eigenschaften beeinflusst. Meist werden aromatische Sulfonsäuren als Katalysatoren eingesetzt. Wegen ihrer guten Verfügbarkeit und ihrer hohen Säurestärke werden vor allem Toluolsulfonsäure, Xylyolsulfonsäure sowie Benzolsulfonsäure verwendet.As acids mostly aromatic sulfonic acids and in some special cases also phosphoric acid or sulfuric acid are used. Phosphoric acid is used in concentrated form, i. used at concentrations greater than 75%. However, it is only suitable for the catalytic curing of furan resins with a relatively high proportion of urea. The nitrogen content of such resins is more than 2.0% by weight). Sulfuric acid can be added as a relatively strong acid starter for the curing of furan resins to weaker acids. During casting, however, a smell typical of sulfur compounds develops. There is also the danger that the casting material absorbs sulfur and influences its properties. Mostly aromatic sulfonic acids are used as catalysts. Because of their good availability and their high acidity especially toluene sulfonic acid, xylylene sulfonic acid and benzenesulfonic acid are used.
Phenolharze als zweite große Gruppe säurekatalysiert aushärtbarer No-Bake-Bindemittel enthalten als reaktive Harzkomponente Resole, also Phenolharze, die mit einem Überschuss an Formaldehyd hergestellt wurden. Phenolharze zeigen im Vergleich zu Furanharzen eine deutlich geringere Reaktivität und erfordern als Katalysatoren starke Sulfonsäuren. Phenolharze zeigen eine relativ hohe Viskosität, die bei längerem Lagern des Harzes noch zunimmt. Insbesondere bei Temperaturen unterhalb von 20 °C nimmt die Viskosität stark zu, sodass der Sand erwärmt werden muss, um das Bindemittel gleichmäßig auf der Oberfläche der Sandkörner auftragen zu können. Nachdem das Phenol-No-Bake-Bindemittel auf dem feuerfesten Formstoff aufgetragen wurde, sollte die Formstoffmischung möglichst umgehend verarbeitet werden, um keine Verschlechterung der Qualität der Formstoffmischung durch vorzeitige Aushärtung in Kauf nehmen zu müssen, was zu einer Verschlechterung der Festigkeit der aus der Formstoffmischung hergestellten Gießformen führen kann. Bei Verwendung von Phenol-No-Bake-Bindemitteln ist die Fließfähigkeit der Formstoffmischung meist schlecht. Bei der Herstellung der Gießform muss die Formstoffmischung daher sorgfältig verdichtet werden, um eine hohe Festigkeit der Gießform erreichen zu können.Phenolic resins as the second large group of acid-catalyzed curable no-bake binders contain resoles as reactive resin components, ie phenolic resins which have been prepared with an excess of formaldehyde. Phenol resins show a significantly lower reactivity compared to furan resins and require strong sulfonic acids as catalysts. Phenolic resins show a relatively high viscosity, which increases with prolonged storage of the resin. Especially at temperatures below 20 ° C, the viscosity increases sharply, so that the sand must be heated in order to apply the binder evenly on the surface of the grains of sand can. After the phenol no-bake binder has been applied to the refractory molding material, the molding material mixture should be processed as soon as possible, so as not to impair the quality of the molding compound by premature Curing to accept, which can lead to a deterioration in the strength of the molds produced from the molding material mixture. When using phenol no-bake binders, the flowability of the molding material mixture is usually poor. In the production of the mold, the molding material mixture must therefore be carefully compacted in order to achieve a high strength of the mold can.
Die Herstellung und Verarbeitung der Formstoffmischung sollte bei Temperaturen im Bereich von 15 bis 35 °C erfolgen. Bei zu niedriger Temperatur lässt sich die Formstoffmischung wegen der hohen Viskosität des Phenol-No-Bake-Harzes schlecht verarbeiten. Bei Temperaturen von mehr als 35 °C verkürzt sich die Verarbeitungszeit durch vorzeitige Aushärtung des Bindemittels.The preparation and processing of the molding material mixture should be carried out at temperatures in the range of 15 to 35 ° C. If the temperature is too low, the molding material mixture is difficult to process because of the high viscosity of the phenol no-bake resin. At temperatures of more than 35 ° C, the processing time is shortened by premature curing of the binder.
Nach dem Abguss lassen sich Formstoffmischungen auf der Basis von Phenol-No-Bake-Bindemitteln ebenfalls wieder aufarbeiten, wobei auch hier mechanische oder thermische bzw. kombinierte mechanisch/thermische Verfahren verwendet werden können.After casting, molding mixtures based on phenol no-bake binders can also be worked up again, in which case mechanical or thermal or combined mechanical / thermal processes can also be used.
Auf den rieselfähigen Feuerfeststoff wird dann eine Säure aufgebracht, wobei ein säurebeschichteter feuerfester Formstoff erhalten wird. Die Säure wird mit üblichen Verfahren auf den feuerfesten Formstoff aufgebracht, beispielsweise indem die Säure auf den feuerfester Formstoff aufgesprüht wird. Die Menge der Säure wird bevorzugt im Bereich von 5 bis 45 Gew.-%, besonders bevorzugt im Bereich von 20 bis 30 Gew.-% gewählt, bezogen auf das Gewicht des Bindemittels und berechnet als reine Säure, also ohne Berücksichtigung eines ggf. verwendeten Lösungsmittels. Sofern die Säure nicht bereits in flüssiger Form vorliegt und eine ausreichend niedrige Viskosität aufweist, um in Form eines dünnen Films auf den Körnern des feuerfesten Formstoffs verteilt werden zu können, wird die Säure in einem geeigneten Lösungsmittel gelöst. Beispielhafte Lösungsmittel sind Wasser oder Alkohole oder Gemische aus Wasser und Alkohol. Insbesondere bei Verwendung von Wasser wird die Lösung jedoch möglichst konzentriert hergestellt, um die in das Bindemittel bzw. die Formstoffmischung eingeschleppte Wassermenge möglichst gering zu halten. Zur gleichmäßigen Verteilung der Säure auf den Körnern wird das Gemisch aus feuerfestem Formstoff und Säure gut homogenisiert.An acid is then applied to the free-flowing refractory to obtain an acid-coated refractory molding material. The acid is applied by conventional methods on the refractory molding material, for example by the acid is sprayed onto the refractory molding material. The amount of acid is preferably selected in the range of 5 to 45 wt .-%, particularly preferably in the range of 20 to 30 wt .-%, based on the weight of the binder and calculated as the pure acid, ie without taking into account any used solvent. If the acid is not already in liquid form and has a sufficiently low viscosity to be distributed in the form of a thin film on the grains of the refractory molding material, the acid is dissolved in a suitable solvent. Exemplary solvents are water or alcohols or mixtures of water and alcohol. Especially when using however, the solution is prepared as concentrated as possible in order to minimize the amount of water entrained into the binder or the molding material mixture. For uniform distribution of the acid on the grains, the mixture of refractory molding material and acid is well homogenized.
Auf den mit Säure beschichteten feuerfesten Formstoff wird dann ein durch Säure aushärtbares Bindemittel aufgebracht. Die Menge des Bindemittels wird bevorzugt im Bereich von 0,25 bis 5 Gew.-%, besonders bevorzugt im Bereich von 1 bis 3 Gew.-% gewählt, bezogen auf den feuerfesten Formstoff und berechnet als Harzkomponente. Als durch Säure aushärtbares Bindemittel können an sich alle Bindemittel verwendet werden, die durch Säure aushärtbar sind, insbesondere solche durch Säure aushärtbare Bindemittel, die bereits für die Herstellung von Formstoffmischungen für die Gießereiindustrie üblich sind. Das Bindemittel kann neben einem vernetzbaren Harz auch noch weitere übliche Komponenten enthalten, beispielsweise Lösungsmittel zur Einstellung der Viskosität oder Streckmittel, die einen Teil des vernetzbaren Harzes ersetzen.An acid-curable binder is then applied to the acid-coated refractory molding material. The amount of the binder is preferably selected in the range of 0.25 to 5 wt .-%, particularly preferably in the range of 1 to 3 wt .-%, based on the refractory molding material and calculated as the resin component. As the acid-curable binder, it is possible to use, as such, all acid-curable binders, especially those acid-curable binders which are already customary for the production of molding compounds for the foundry industry. In addition to a crosslinkable resin, the binder may also contain other customary components, for example solvents for adjusting the viscosity or extenders which replace part of the crosslinkable resin.
Das Bindemittel wird auf den mit Säure beschichteten feuerfesten Formstoff aufgegeben und durch Bewegen der Mischung auf den Körnern des feuerfesten Formstoffs in Form eines dünnen Films verteilt.The binder is applied to the acid-coated refractory molding material and distributed by moving the mixture on the grains of the refractory molding material in the form of a thin film.
Die Mengen an Bindemittel und Säure werden so gewählt, dass einerseits eine ausreichende Festigkeit der Gießform und andererseits eine ausreichende Verarbeitungszeit der Formstoffmischung erreicht wird. Geeignet ist beispielsweise eine Verarbeitungszeit im Bereich von 5 bis 45 Minuten.The amounts of binder and acid are chosen so that on the one hand sufficient strength of the casting mold and on the other hand a sufficient processing time of the molding material mixture is achieved. For example, a processing time in the range of 5 to 45 minutes is suitable.
Der mit dem Bindemittel beschichtete feuerfeste Formstoff wird dann mit üblichen Verfahren zu einem Formkörper geformt. Dazu kann die Formstoffmischung in eine geeignete Form eingebracht und dort verdichtet werden. Der dabei erhaltene Formkörper wird dann aushärten gelassen.The coated with the binder refractory molding material is then formed by conventional methods to a shaped body. For this purpose, the molding material mixture can be introduced into a suitable mold and be condensed there. The resulting molded body is then allowed to cure.
Als Furan-No-Bake-Bindemittel können an sich alle Furanharze verwendet werden, wie sie bereits in Furan-No-Bake Bindemittelsystemen verwendet werden.As furan no-bake binder, all furan resins can be used per se, as they are already used in furan no-bake binder systems.
Die in technischen Furan-No-Bake-Bindemitteln eingesetzten Furanharze sind meist Vorkondensate oder Mischungen von Furfurylalkohol mit weiteren Monomeren oder Vorkondensaten. Die in Furan-No-Bake-Bindemitteln enthaltenen Vorkondensate werden in an sich bekannter Weise hergestellt.The furan resins used in technical furan no-bake binders are usually precondensates or mixtures of furfuryl alcohol with other monomers or precondensates. The precondensates contained in furan no-bake binders are prepared in a manner known per se.
Gemäß einer bevorzugten Ausführungsform wird Furfurylalkohol in Kombination mit Harnstoff und/oder Formaldehyd bzw. Harnstoff / Formaldehyd-Vorkondensaten eingesetzt. Formaldehyd kann sowohl in monomerer Form eingesetzt werden, beispielsweise in Form einer Formalinlösung, als auch in Form seiner Polymeren, wie Trioxan oder Paraformaldehyd. Neben bzw. an Stelle von Formaldehyd können auch andere Aldehyde oder auch Ketone verwendet werden. Geeignete Aldehyde sind beispielsweise Acetaldehyd, Propionaldehyd, Butyraldehyd, Acrolein, Crotonaldehyd, Benzaldehyd, Salicylaldehyd, Zimtaldehyd, Glyoxal und Gemische dieser Aldehyde. Formaldehyd ist bevorzugt, wobei dieser vorzugsweise in Form von Paraformaldehyd eingesetzt wird.According to a preferred embodiment, furfuryl alcohol is used in combination with urea and / or formaldehyde or urea / formaldehyde precondensates. Formaldehyde can be used both in monomeric form, for example in the form of a formalin solution, as well as in the form of its polymers, such as trioxane or paraformaldehyde. In addition to or instead of formaldehyde, other aldehydes or ketones can be used. Suitable aldehydes are, for example, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, crotonaldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde, glyoxal and mixtures of these aldehydes. Formaldehyde is preferred, this being preferably used in the form of paraformaldehyde.
Als Ketonkomponente können alle Ketone eingesetzt werden, die eine ausreichend hohe Reaktivität aufweisen. Beispielhafte Ketone sind Methylethylketon, Methylpropylketon und Aceton, wobei Aceton bevorzugt verwendet wird.As ketone component, all ketones can be used which have a sufficiently high reactivity. Exemplary ketones are methyl ethyl ketone, methyl propyl ketone and acetone, with acetone being preferred.
Die genannten Aldehyde und Ketone können als einzelne Verbindung aber auch im Gemisch miteinander eingesetzt werden.The said aldehydes and ketones can be used as a single compound but also in admixture with each other.
Das Molverhältnis von Aldehyd, insbesondere Formaldehyd, bzw. Keton zu Furfurylalkohol kann innerhalb weiter Bereiche gewählt werden. Bei der Herstellung der Furanharze können pro Mol Aldehyd vorzugsweise 0,4 bis 4 Mol Furfurylalkohol, bevorzugt 0,5 bis 2 Mol Furfurylalkohol verwendet werden.The molar ratio of aldehyde, in particular formaldehyde, or ketone to furfuryl alcohol can be selected within wide ranges. In the preparation of the furan resins, 0.4 to 4 moles of furfuryl alcohol, preferably 0.5 to 2 moles of furfuryl alcohol, may be used per mole of aldehyde.
Zur Herstellung der Vorkondensate können Furfurylalkohol, Formaldehyd und Harnstoff beispielsweise nach Einstellung eines pH-Werts von mehr als 4,5 zum Sieden erhitzt werden, wobei kontinuierlich Wasser aus dem Reaktionsgemisch abdestilliert wird. Die Reaktionszeit kann dabei mehrere Stunden betragen, beispielsweise 2 Stunden. Bei diesen Reaktionsbedingungen tritt nahezu keine Polymerisation des Furfurylalkohols ein. Der Furfurylalkohol wird jedoch zusammen mit dem Formaldehyd und dem Harnstoff in ein Harz einkondensiert.To produce the precondensates, furfuryl alcohol, formaldehyde and urea can be heated to boiling, for example, after the pH has been adjusted to more than 4.5, water being continuously distilled off from the reaction mixture. The reaction time can be several hours, for example 2 hours. Under these reaction conditions occurs almost no polymerization of furfuryl alcohol. However, the furfuryl alcohol is condensed into a resin together with the formaldehyde and the urea.
Nach einem alternativen Verfahren werden Furfurylalkohol, Formaldehyd und Harnstoff bei einem pH-Wert von deutlich unterhalb 4,5, beispielsweise bei einem pH-Wert von 2,0, in der Hitze umgesetzt, wobei das bei der Kondensation entstehende Wasser unter reduziertem Druck abdestilliert werden kann. Das Reaktionsprodukt weist eine relativ hohe Viskosität auf und wird zur Herstellung des Bindemittels mit Furfurylalkohol verdünnt, bis die gewünschte Viskosität eingestellt ist.According to an alternative method furfuryl alcohol, formaldehyde and urea are reacted at a pH of well below 4.5, for example at a pH of 2.0, in the heat, wherein the water formed in the condensation are distilled off under reduced pressure can. The reaction product has a relatively high viscosity and is diluted with furfuryl alcohol to produce the binder until the desired viscosity is achieved.
Mischformen dieser Herstellungsverfahren können ebenfalls angewandt werden.Mixed forms of these production methods can also be used.
Es ist auch möglich, Phenol in das Vorkondensat einzuführen. Dazu kann das Phenol unter alkalischen Bedingungen zunächst mit Formaldehyd zu einem Resolharz umgesetzt werden. Dieses Resol kann dann mit Furfurylalkohol oder einem furangruppenhaltigen Harz umgesetzt oder vermischt werden. Solche furangruppenhaltigen Harze können beispielsweise mit den oben beschriebenen Verfahren erhalten werden. Für die Herstellung des Vorkondensats können auch höhere Phenole eingesetzt werden, beispielsweise Resorcin, Kresole oder auch Bisphenol A. Der Anteil des Phenols bzw. der höheren Phenole am Bindemittel wird vorzugsweise im Bereich von bis zu 45 Gew.-%, bevorzugt bis zu 20 Gew.-%, besonders bevorzugt bis zu 10 Gew.-% gewählt. Gemäß einer Ausführungsform kann der Anteil des Phenols bzw. der höheren Phenole größer als 2 Gew.-%, gemäß einer weiteren Ausführungsform größer als 4 Gew.-% gewählt werden.It is also possible to introduce phenol into the precondensate. For this purpose, the phenol can be reacted under alkaline conditions, first with formaldehyde to a resole resin. This resol can then be reacted or mixed with furfuryl alcohol or a furan group-containing resin. Such furan group-containing resins can be obtained, for example, by the methods described above. For the production of the precondensate It is also possible to use higher phenols, for example resorcinol, cresols or also bisphenol A. The proportion of phenol or higher phenols in the binder is preferably in the range of up to 45% by weight, preferably up to 20% by weight, especially preferably chosen up to 10 wt .-%. According to one embodiment, the proportion of phenol or higher phenols can be greater than 2 wt .-%, according to a further embodiment greater than 4 wt .-% can be selected.
Weiter ist auch möglich, Kondensate aus Aldehyden und Ketonen zu verwenden, die zur Herstellung des Bindemittels dann mit Furfurylalkohol vermischt werden. Solche Kondensate lassen sich durch Umsetzung von Aldehyden und Ketonen unter alkalischen Bedingungen herstellen. Als Aldehyd wird bevorzugt Formaldehyd, insbesondere in Form von Paraformaldehyd verwendet. Als Keton wird bevorzugt Aceton eingesetzt. Andere Aldehyde bzw. Ketone können jedoch ebenfalls verwendet werden. Das relative Molverhältnis von Aldehyd zu Keton wird vorzugsweise im Bereich von 7 : 1 bis 1 : 1, bevorzugt 1,2 : 1 bis 3,0 : 1 gewählt. Die Kondensation wird vorzugsweise unter alkalischen Bedingungen bei pH-Werten im Bereich von 8 bis 11,5, bevorzugt 9 bis 11 durchgeführt. Eine geeignete Base ist beispielsweise Natriumcarbonat.It is also possible to use condensates of aldehydes and ketones, which are then mixed with furfuryl alcohol to produce the binder. Such condensates can be prepared by reacting aldehydes and ketones under alkaline conditions. The aldehyde used is preferably formaldehyde, in particular in the form of paraformaldehyde. The ketone used is preferably acetone. However, other aldehydes or ketones can also be used. The relative molar ratio of aldehyde to ketone is preferably selected in the range of 7: 1 to 1: 1, preferably 1.2: 1 to 3.0: 1. The condensation is preferably carried out under alkaline conditions at pH values in the range of 8 to 11.5, preferably 9 to 11. A suitable base is, for example, sodium carbonate.
Die Menge des Furfurylalkohols, welche im Furan-No-Bake-Bindemittel enthalten ist, wird einerseits bestimmt von dem Bestreben, den Anteil aus Kostengründen möglichst gering zu halten. Andererseits wird durch einen hohen Anteil an Furfurylalkohol eine Verbesserung der Festigkeit der Gießform erreicht. Bei sehr hohem Anteil an Furfurylalkohol im Bindemittel werden jedoch sehr spröde Gießformen erhalten, welche sich schlecht verarbeiten lassen. Vorzugsweise wird der Anteil des Furfurylalkohols am Bindemittel im Bereich von 30 bis 95 Gew.-%, bevorzugt 50 bis 90 Gew.-%, besonders bevorzugt 60 bis 85 Gew.-% gewählt. Der Anteil an Harnstoff und/oder Formaldehyd am Bindemittel wird vorzugsweise im Bereich von 2 bis 70 Gew.-%, bevorzugt 5 bis 45 Gew.-%, besonders bevorzugt 15 bis 30 Gew.-% gewählt. Die Anteile umfassen sowohl die im Bindemittel enthaltenen ungebundenen Anteile dieser Verbindungen als auch die Anteile, die im Harz gebunden sind.The amount of furfuryl alcohol, which is contained in the furan no-bake binder, on the one hand determined by the endeavor to keep the proportion as low as possible for cost reasons. On the other hand, an improvement in the strength of the casting mold is achieved by a high proportion of furfuryl alcohol. However, with a very high proportion of furfuryl alcohol in the binder, very brittle casting molds are obtained which are difficult to process. Preferably, the proportion of furfuryl alcohol in the binder in the range of 30 to 95 wt .-%, preferably 50 to 90 wt .-%, particularly preferably 60 to 85 wt .-% is selected. The proportion of urea and / or formaldehyde on the binder is preferably in the range of 2 to 70 wt .-%, preferably 5 to 45 wt .-%, particularly preferably 15 to 30 wt .-% selected. The proportions include both the unbound portions of these compounds contained in the binder and those bound in the resin.
Den Furanharzen können weitere Zusätze zugesetzt werden, wie Ethylenglycol oder ähnliche aliphatische Polyole, beispielsweise Zuckeralkohole, wie Sorbitol, die als Streckmittel dienen und einen Teil des Furfurylalkohols ersetzen. Ein zu hoher Zusatz derartiger Streckmittel kann im ungünstigen Fall zu einer Verringerung der Festigkeit der Gießform und Absenkung der Reaktivität führen. Der Anteil dieser Streckmittel am Bindemittel wird daher vorzugsweise geringer als 25 Gew.-%, bevorzugt geringer als 15 Gew.-% und besonders bevorzugt geringer als 10 Gew.-% gewählt. Um eine Kostenersparnis zu erreichen ohne dabei einen übermäßigen Einfluss auf die Festigkeit der Gießform in Kauf nehmen zu müssen, wird der Anteil der Streckmittel gemäß einer Ausführungsform größer als 5 Gew.-% gewählt.Other additives can be added to the furan resins, such as ethylene glycol or similar aliphatic polyols, for example, sugar alcohols, such as sorbitol, which serve as an extender and replace part of the furfuryl alcohol. Too high an addition of such extenders can lead to a reduction in the strength of the mold and lowering the reactivity in the worst case. The proportion of these extenders in the binder is therefore preferably less than 25% by weight, preferably less than 15% by weight and more preferably less than 10% by weight. In order to achieve a cost saving without having to put an excessive influence on the strength of the mold, the proportion of extenders is chosen according to an embodiment greater than 5 wt .-%.
Die Furan-No-Bake-Bindemittel können weiterhin Wasser enthalten. Da Wasser die Aushärtung der Formstoffmischung jedoch verlangsamt und bei der Aushärtung Wasser als Reaktionsprodukt entsteht, wird der Anteil des Wassers bevorzugt möglichst gering gewählt. Vorzugsweise beträgt der Anteil des Wassers am Bindemittel weniger als 20 Gew.-%, bevorzugt weniger als 15 Gew.-%. Unter wirtschaftlichen Gesichtspunkten kann eine Wassermenge von mehr als 5 Gew.-% im Bindemittel toleriert werden.The furan no-bake binders may further contain water. However, since water slows the curing of the molding material mixture and water is formed as a reaction product during curing, the proportion of water is preferably chosen as low as possible. The proportion of water in the binder is preferably less than 20% by weight, preferably less than 15% by weight. From an economic point of view, an amount of water of more than 5% by weight in the binder can be tolerated.
Als Phenolharze werden im erfindungsgemäßen Verfahren Resole verwendet. Resole sind Gemische von Hydroxymethylphenolen, die über Methylen- und Methylenetherbrücken verknüpft sind und durch Reaktion von Aldehyden und Phenolen im Molverhältnis von 1 : <1, gegebenenfalls in Gegenwart eines Katalysators, z.B. eines basischen Katalysators, erhältlich sind. Sie weisen ein Molgewicht Mw von ≤ 10.000 g/mol auf.As phenolic resins resoles are used in the process according to the invention. Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and by reaction of aldehydes and phenols in a molar ratio of 1: <1, if appropriate in the presence of a catalyst, for example a basic Catalyst, are available. They have a molecular weight M w of ≦ 10,000 g / mol.
Zur Herstellung der Phenolharze sind alle herkömmlich verwendeten Phenole geeignet, wobei Phenol besonders bevorzugt ist. Als Aldehydkomponente wird bevorzugt Formaldehyd eingesetzt, insbesondere in form von Paraformaldehyd. Alternative Phenole und Aldehyde wurden bereits in Zusammenhang mit den Polyurethanbindemitteln erläutert. Auf die entsprechenden Passagen wird Bezug genommen.For the preparation of the phenolic resins, all conventionally used phenols are suitable, with phenol being particularly preferred. The aldehyde component used is preferably formaldehyde, in particular in the form of paraformaldehyde. Alternative phenols and aldehydes have already been explained in connection with the polyurethane binders. The corresponding passages are referred to.
Die Bindemittel können weitere übliche Zusätze enthalten, beispielsweise Silane als Haftvermittler. Geeignete Silane sind beispielsweise Aminosilane, Epoxysilane, Mercaptosilane, Hydroxysilane und Ureidosilane, wie γ-Hydroxypropyltrimethoxysilan, γ-Aminopropyltrimethoxysilan, 3-Ureidopropyltriethoxysilan, γ-Mercaptopropyltrimethoxysilan, γ-Glycidoxypropyltrimethoxysilan, β-(3,4-Epoxycyclohexyl)trimethoxysilan, N-β-(Aminoethyl)-γ-aminopropyltrimethoxysilan.The binders may contain other customary additives, for example silanes as adhesion promoters. Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as γ-hydroxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane.
Sofern ein solches Silan verwendet wird, wird es dem Bindemittel in einem Anteil von 0,1 bis 3 Gew.-%, vorzugsweise 0,1 bis 1 Gew.-% zugegeben.If such a silane is used, it is added to the binder in a proportion of 0.1 to 3% by weight, preferably 0.1 to 1% by weight.
Die Bindemittel können auch noch weitere übliche Komponenten enthalten, wie beispielsweise Aktivatoren oder Weichmacher.The binders may also contain other conventional components, such as activators or plasticizers.
Die Formstoffmischung kann neben dem feuerfesten Formstoff, dem Bindemittel und ggf. dem Katalysator noch weitere übliche Bestandteile enthalten. Beispielhafte weitere Bestandteile sind Eisenoxid, gemahlene Flachsfasern, Holzmehlgranulate, gemahlene Kohle oder Ton.The molding material mixture, in addition to the refractory molding material, the binder and optionally the catalyst may contain other conventional ingredients. Exemplary further constituents are iron oxide, ground flax fibers, wood flour granules, ground coal or clay.
Die Formstoffmischung wird dann mit üblichen Verfahren zu einer GGrundform oder einem Teil einer Grundform geformt und ggf. ausgehärtet. Die Grundform kann dann ggf. ganz oder teilweise zusammengebaut werden und der in der Grundform vorgesehene Formhohlraum mit der oben beschriebenen Schlichtezusammensetzung insgesamt oder abschnittsweise beschichtet werden. Hierzu können übliche Verfahren verwendet werden. Die Schlichtezusammensetzung kann beispielsweise durch Tauchverfahren, Fluten, Aufpinseln oder durch Aufsprühen aufgetragen werden.The molding material mixture is then shaped by conventional methods into a basic shape or a part of a basic shape and optionally cured. If appropriate, the basic shape can then be completely or partially assembled and the mold cavity provided in its basic form can be coated in its entirety or in sections with the sizing composition described above. For this purpose, conventional methods can be used. The sizing composition can be applied, for example, by dipping, flooding, brushing or by spraying.
Bei Tauchen als Aufbringungsverfahren wird die Gießform, in deren Formhohlraum gegebenenfalls eine Grundbeschichtung aufgebracht worden ist, für etwa 2 Sekunden bis 2 Minuten in ein Behältnis eingetaucht, das mit einer gebrauchsfertigen, erfindungsgemäßen Schlichtezusammensetzung gefüllt ist. Die Gießform wird dann aus der Schlichtezusammensetzung herausgenommen und überschüssige Schlichtezusammensetzung von der Gießform ablaufen gelassen. Die Zeit, die das Ablaufen der überschüssigen Schlichtezusammensetzung nach dem Tauchen in Anspruch nimmt, richtet sich nach dem Ablaufverhalten der verwendeten Schlichtezusammensetzung.When immersed as an application method, the mold, in the mold cavity of which optionally a base coat has been applied, is immersed for about 2 seconds to 2 minutes in a container filled with a ready-to-use sizing composition according to the invention. The mold is then removed from the sizing composition and excess sizing composition drained from the mold. The time taken to drain the excess sizing composition after dipping depends on the flow behavior of the sizing composition used.
Beim Sprühen als Aufbringungsverfahren werden handelsübliche Druckkesselsprühgeräte verwendet. Hierbei wird die Schlichtezusammensetzung im verdünnten Zustand in einen Drückkessel gefüllt. Über den einzustellenden Überdruck kann die Schlichte in eine Sprühpistole gedrückt werden, wo Sie mit Hilfe von separat regulierbarer Zerstäuberluft versprüht wird. Beim Sprühen werden die Bedingungen vorzugsweise so gewählt dass der Druck für Schlichtezusammensetzung und Zerstäuberluft so an der Pistole eingestellt ist, dass die versprühte Schlichtezusammensetzung noch nass auf der Form oder dem Kern auftrifft, aber einen gleichmäßigen Auftrag ergibt.In spraying as the application method commercial pressure sprayers are used. Here, the sizing composition is filled in a dilute state in a pressure vessel. The sizing can be pressed into a spray gun via the overpressure to be set, where it is sprayed with the aid of separately adjustable atomizing air. When spraying, the conditions are preferably chosen so that the pressure for size composition and atomizing air is adjusted to the gun such that the sprayed size composition still wet on the mold or the core, but gives a uniform application.
Die in der Schlichte enthaltene Trägerflüssigkeit wird anschließend verdampft, sodass eine trockene Schlichteschicht erhalten wird. Als Trocknungsverfahren können alle konventionellen Trocknungsverfahren verwendet werden, wie beispielsweise Trocknen lassen an der Luft, Trocknung mit entfeuchteter Luft, Trocknen mit Mikrowellen- oder Infrarotstrahlung, Trocknen im Konvektionsofen, und vergleichbare Verfahren.The carrier liquid contained in the size is then evaporated so that a dry sizing layer is obtained. As a drying process, all conventional drying methods may be used, such as air drying, dehumidified air drying, microwave or infrared radiation drying, convection oven drying, and similar methods.
In einer bevorzugten Ausführungsform der Erfindung wird die beschichtete Gießform bei 100 bis 250 °C, bevorzugt bei 120 bis 180 °C, in einem Konvektionsofen getrocknet. Bei der Verwendung von Alkoholschlichten wird die erfindungsgemäße Schlichtezusammensetzung bevorzugt durch Abbrennen des Alkohols oder Alkoholgemischs getrocknet. Hierbei wird die beschichtete Gießform durch die Verbrennungswärme zusätzlich erwärmt. In einer weiteren bevorzugten Ausführungsform wird die beschichtete Gießform ohne weiter Behandlung an der Luft getrocknet.In a preferred embodiment of the invention, the coated casting mold is dried at 100 to 250 ° C, preferably at 120 to 180 ° C, in a convection oven. When using alcohol sizes, the size composition according to the invention is preferably dried by burning off the alcohol or alcohol mixture. In this case, the coated casting mold is additionally heated by the heat of combustion. In a further preferred embodiment, the coated casting mold is dried in the air without further treatment.
Ggf. kann die Schlichteschicht anschließend noch gehärtet werden, beispielsweise durch Bestrahlen mit UV-Strahlung, wenn ein entsprechendes härtbares Bindemittel in der Schlichtezusammensetzung enthalten ist.Possibly. The sizing layer can then be further cured, for example by irradiation with UV radiation, if a corresponding curable binder is included in the sizing composition.
Die Schlichte kann in Form einer einzelnen Schicht oder auch in Form mehrerer übereinander angeordneter Schichten aufgebracht werden. Dabei können die einzelnen Schichten in ihrer Zusammensetzung gleich oder verschieden sein. Beispielsweise kann zunächst eine Grundbeschichtung aus einer handelsüblichen Schlichte hergestellt werden, welche kein erfindungsgemäßes metallisches Additiv enthält. Als Grundbeschichtung können beispielsweise Wasserschlichten oder auch Alkoholschlichten verwendet werden. Es ist aber auch möglich, alle Schichten aus der erfindungsgemäßen Schlichtezusammensetzung herzustellen. Die Schicht, welche später mit dem flüssigen Metall in Berührung gelangt, wird jedoch immer aus der erfindungsgemäßen Schlichte hergestellt. Beim Aufbringen mehrerer Schichten kann jede einzelne Schicht nach dem Aufbringen vollständig oder teilweise getrocknet werden.The size can be applied in the form of a single layer or in the form of several layers arranged one above the other. The individual layers may be the same or different in their composition. For example, first a base coat can be made from a commercially available size which does not contain a metallic additive according to the invention. As a primer coating, for example, water-based or alcohol-based sizing can be used. However, it is also possible to prepare all layers from the size composition according to the invention. However, the layer which later comes in contact with the liquid metal is always made from the size of the invention. When applying several layers, each individual layer can be completely or partially dried after application.
Die aus der Schlichtezusammensetzung hergestellte Beschichtung weist vorzugsweise eine Trockenschichtdicke von zumindest 0,1 mm, bevorzugt zumindest 0,2 mm, besonders bevorzugt zumindest 0,45 mm, insbesondere bevorzugt zumindest 0,55 mm auf. Gemäß einer Ausführungsform wird die Dicke der Beschichtung kleiner als 1,5 mm gewählt. Die Trockenschichtstärke ist hierbei die Schichtstärke der getrockneten Beschichtung, welche durch Trocknen der Schlichtezusammensetzung durch im Wesentlichen vollständiges Entfernen der Lösungsmittelkomponente und gegebenenfalls anschließendem Härten erhalten wurde. Die Trockenschichtstärke der Grundbeschichtung und der Deckbeschichtung werden vorzugsweise durch Messung mit dem Nassschichtdickenkamm ermittelt.The coating prepared from the sizing composition preferably has a dry film thickness of at least 0.1 mm, preferably at least 0.2 mm, more preferably at least 0.45 mm, most preferably at least 0.55 mm. According to one embodiment, the thickness of the coating is chosen to be less than 1.5 mm. The dry layer thickness here is the layer thickness of the dried coating, which was obtained by drying the sizing composition by substantially complete removal of the solvent component and optionally subsequent curing. The dry layer thickness of the base coat and the top coat are preferably determined by measurement with the wet film thickness comb.
Die Gießform kann anschließend ggf. vollständig zusammengebaut werden.If necessary, the casting mold can then be completely assembled.
Ein weiterer Gegenstand der Erfindung betrifft die Verwendung der oben beschriebenen Gießform zur Herstellung eines Gussstücks.Another object of the invention relates to the use of the casting mold described above for the production of a casting.
Dazu wird zunächst eine Gießform bereitgestellt. Dies kann eine verlorene Form sein, die wie oben beschrieben aus einem Feuerfestmaterial, beispielsweise Quarzsand, und einem Bindemittel hergestellt wurde, oder auch eine Dauerform, wie sie üblicherweise zur Herstellung von Rohren, Lagern oder Hülsen verwendet wird, wobei der Formhohlraum mit der oben beschriebenen Schlichtezusammensetzung ausgekleidet wurde. Die Gießform weist auf zumindest den Flächen, welche mit dem flüssigen Metall in Kontakt gelangen, eine Schutzbeschichtung auf, welche das flüssige Metall von der Gießform isoliert und welche die Oberflächenbeschaffenheit des Gussstücks positiv beeinflussen kann. In die vorbereitete Gießform wird nun flüssiges Metall eingeleitet, vorzugsweise Eisen oder einer Eisenlegierung. Das flüssige Metall wird anschließend zu einem Gussstück erstarren gelassen und dann das Gussstück von der Gießform getrennt. Dazu werden übliche Verfahren angewendet. Bei verlorenen Formen wird die Gießform mechanisch zerstört, beispielsweise durch Rütteln. Bei Dauerformen wird das Gussstück mit üblichen Verfahren aus der Gießform gezogen.For this purpose, a casting mold is first provided. This may be a lost mold made as described above from a refractory material, such as quartz sand, and a binder, or even a permanent mold commonly used to make pipes, bearings or sleeves, the mold cavity having the shape described above Sizing composition was lined. The mold has a protective coating on at least the surfaces which contact the liquid metal, which isolates the liquid metal from the mold and which can positively influence the surface finish of the casting. In the prepared mold now liquid metal is introduced, preferably iron or an iron alloy. The liquid metal is then allowed to solidify into a casting and then the casting is separated from the casting mold. These are usual Method applied. In lost molds, the mold is mechanically destroyed, for example by shaking. In permanent molds, the casting is pulled out of the mold by conventional methods.
Ein weiterer Gegenstand der Erfindung betrifft eine Gießform, welche einen Formüberzug aufweist, der aus der oben beschriebenen Schlichte hergestellt worden ist. Eine derartige Gießform weist vorteilhaft eine Isolierung zwischen dem flüssigen Metall und der Gießform auf, wodurch die thermische Belastung der Gießform beim Gussvorgang vermindert wird und sich dadurch die Haltbarkeit der Gießform erhöht. Als weiterer Vorteil weist der Formüberzug ein metallisches Additiv auf, welches die Oberflächeneigenschaften des Gussstücks positiv beeinflussen kann, insbesondere die Ausbildung einer narbigen Oberfläche auf dem Gussstück zurückdrängt.Another object of the invention relates to a mold having a mold coating which has been prepared from the size described above. Such a mold advantageously has an insulation between the liquid metal and the casting mold, whereby the thermal load of the casting mold is reduced during the casting process and thereby increases the durability of the casting mold. As a further advantage, the mold coating has a metallic additive which can positively influence the surface properties of the casting, in particular suppressing the formation of a scarred surface on the casting.
Gießformen, welche eine Deckbeschichtung aufweisen, welche aus der erfindungsgemäßen Schlichtezusammensetzung hergestellt wurde, werden unter anderem zur Herstellung von Windkraftnarben, Mahlschüsseln, Motoren und Motorkomponenten, Maschinenbetten und Turbinen, allgemeine Maschinenkomponenten oder Presswerkzeuge verwendet.Molds having a topcoat made from the sizing composition of the present invention are used, inter alia, to make wind force scars, grinding bowls, engines and engine components, machine beds and turbines, general machine components or dies.
Die Erfindung wird im weiteren anhand von Beispielen näher erläutert.The invention will be explained in more detail by way of examples.
Die in den nachstehenden Beispielen verwendete Kernschlichte weist die in Tabelle 1 angegebene Zusammensetzung auf.
Die Formgussschlichte wurde wie folgt hergestellt: Isopropanol wird vorgelegt und hierin wird der Ton durch Verwendung eines hochscherenden Rührers mindestens 15 Minuten aufgeschlossen. Anschließend werden die Feuerfestkomponenten, Pigmente, Mangan und Farbstoffe mindestens 15 Minuten eingerührt, bis eine homogene Mischung entsteht. Zum Schluss werden Ethanol, rheologische Additive und Bindemittel eingerührt.The cast molding stock was prepared as follows: isopropanol is charged and the clay is digested for at least 15 minutes using a high shear stirrer. Subsequently, the refractory components, pigments, manganese and dyes are stirred for at least 15 minutes until a homogeneous mixture is formed. Finally, ethanol, rheological additives and binders are stirred in.
Claims (15)
- Coating composition for casting moulds and cores comprising at least one carrier liquid and a metal additive that comprises at least one metal or a compound of the at least one metal, wherein the metal is selected from the group of manganese and copper, and wherein the fraction of the metal additive is less than 50 wt. % based on the solid content of the coating composition.
- Coating composition according to claim 1, wherein the metal is manganese or the compound of a metal comprising manganese.
- Coating composition according to claim 1 or 2, wherein the metal is employed in pure form or in the form of an alloy with other metals.
- Coating composition according to one of the preceding claims, wherein the metal or the metal compound is contained in the metal additive in a fraction of at least 10 wt. %, determined as metal and based on the weight of the metal additive.
- Coating composition according to one of the preceding claims, wherein the metal additive is contained in the coating composition in a fraction of at least 10 wt. % based on the solid fraction of the coating composition.
- Coating composition according to one of the preceding claims, wherein the metal is contained in the metal additive in the form of an iron alloy.
- Coating composition according to one of the preceding claims, wherein the metal additive has a medium particle size (D50) in the range from 0.5 to 5000 µm.
- Coating composition according to one of the preceding claims, wherein the coating composition contains a solvent and the solvent is formed, at least partially of at least one alcohol.
- Coating composition according to claim 8, wherein the at least one alcohol forms a fraction of at least 50 wt. % in the solvent.
- The coating composition according to one of the claims 1 to 9, wherein the fraction of the metal additive in the coating composition is less than 40 wt. %, preferably less than 35 wt. % based on the solid content of the coating composition.
- The coating composition according to one of the claims 1 to 10, wherein the composition further contains a binder.
- Method for producing a casting mould, wherein a mould material mixture is provided that contains at least one refractory mould material and a binder, the mould material mixture is shaped to a basic mould comprising a mould cavity, and at least the surfaces of the mould cavity of the basic mould are coated with a coating composition according to one of the claims 1 to 11.
- Casting mould with a mould cavity, wherein at least the surfaces of the mould cavity are coated with a coating according to one of the claims 1 to 11.
- Use of a casting mould according to claim 13 for metal casting.
- Use according to claim 14, wherein the metal casting is an iron- or a steel casting.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008025460 | 2008-05-28 | ||
PCT/EP2009/056434 WO2009144242A1 (en) | 2008-05-28 | 2009-05-27 | Coating compositions for casting moulds and cores for avoiding maculate surfaces |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2300177A1 EP2300177A1 (en) | 2011-03-30 |
EP2300177B1 true EP2300177B1 (en) | 2016-01-27 |
Family
ID=40977587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09753897.9A Not-in-force EP2300177B1 (en) | 2008-05-28 | 2009-05-27 | Coating compositions for casting moulds and cores for avoiding maculate surfaces |
Country Status (11)
Country | Link |
---|---|
US (2) | US20110073270A1 (en) |
EP (1) | EP2300177B1 (en) |
JP (1) | JP5701751B2 (en) |
KR (1) | KR20110020279A (en) |
CN (1) | CN102105242A (en) |
BR (1) | BRPI0912323A2 (en) |
EA (1) | EA023525B1 (en) |
MX (1) | MX2010012994A (en) |
UA (1) | UA101663C2 (en) |
WO (1) | WO2009144242A1 (en) |
ZA (1) | ZA201008144B (en) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120199309A1 (en) * | 2011-02-04 | 2012-08-09 | Ask Chemicals L.P. | Sand additives for molds/cores for metal casting |
DE102011115025A1 (en) * | 2011-10-07 | 2013-04-11 | Ask Chemicals Gmbh | Coating compositions for inorganic casting molds and cores containing salts and their use |
CN102491785B (en) * | 2011-12-06 | 2013-02-27 | 辽宁速航特铸材料有限公司 | Method for improving property of ceramic core through high-temperature inorganic coating |
DE102012204614A1 (en) * | 2012-03-22 | 2013-09-26 | Man Diesel & Turbo Se | Manufacturing cast part used as cylinder heads for diesel engine, comprises introducing melted cast material into cavity of mold, solidifying cast material, and partially introducing additive into cast material to modify properties |
MX2015006148A (en) * | 2012-11-19 | 2015-10-22 | Sintokogio Ltd | Sand for casting mold, manufacturing method for sand casting-mold, and core for metal casting. |
CN103264142B (en) * | 2013-05-30 | 2015-05-13 | 苏州兴业材料科技股份有限公司 | Zircon power alternative coating for casting and preparation method thereof |
US10471497B2 (en) | 2013-08-16 | 2019-11-12 | The Exone Company | Three-dimensional printed metal-casting molds and methods for making the same |
CN103706757B (en) * | 2013-12-26 | 2015-07-08 | 南昌航空大学 | Magnesium alloy evaporative pattern casting coating and preparation method thereof |
JP2015131310A (en) * | 2014-01-10 | 2015-07-23 | 三菱重工業株式会社 | Casting mold forming slurry, method of manufacturing casting mold, casting mold, and method of manufacturing casting mold formation slurry |
KR101575314B1 (en) * | 2014-03-18 | 2015-12-07 | 현대자동차 주식회사 | Aluminium wheel for vehicle and the manufacturing method |
CN110052180B (en) * | 2014-04-18 | 2021-09-28 | 三菱化学株式会社 | Porous support-zeolite membrane composite and method for separating gas or liquid mixture |
CN104096793A (en) * | 2014-06-16 | 2014-10-15 | 芜湖市鸿坤汽车零部件有限公司 | Waste glass ceramic chip alcohol-based casting paint and production method thereof |
CN104889317A (en) * | 2015-06-24 | 2015-09-09 | 梁胜光 | Coating for casting sand molds |
CN105665615B (en) * | 2016-02-05 | 2018-10-02 | 济南圣泉集团股份有限公司 | A kind of casting waterglass curing agent and its preparation method and application |
DE102016015852B4 (en) | 2016-06-30 | 2024-05-29 | Refratechnik Holding Gmbh | Use of a heat-insulating molded body |
DE102016112044B4 (en) | 2016-06-30 | 2019-01-03 | Refratechnik Holding Gmbh | Use of a heat-insulating plate for insulating molten metal from the atmosphere or a metallurgical vessel |
CN106424538B (en) * | 2016-08-31 | 2018-12-11 | 金塔县黑石矿业有限责任公司 | A method of penetration-prevention cast paint is prepared by raw material of andalusite |
DE102017107658A1 (en) * | 2017-01-04 | 2018-07-05 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | A sizing composition for the foundry industry containing particulate amorphous silica and acid |
DE102017107655A1 (en) * | 2017-01-04 | 2018-07-05 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Use of an acid-containing sizing composition in the foundry industry |
CN107584068A (en) * | 2017-08-31 | 2018-01-16 | 山东鲁达轿车配件股份有限公司 | A kind of method that brake disc is produced using resin sand |
DE102018118291A1 (en) * | 2018-07-27 | 2020-01-30 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Sizing composition to reduce formaldehyde emissions |
CN108941445B (en) * | 2018-07-31 | 2020-12-18 | 铜陵旭时新材料科技有限公司 | Application method of release agent for disc casting machine |
CN108941446B (en) * | 2018-07-31 | 2020-11-27 | 铜陵旭时新材料科技有限公司 | Mold release agent for disc casting machine |
JP6910332B2 (en) * | 2018-11-26 | 2021-07-28 | 花王株式会社 | Binder composition for molding |
RU2722845C1 (en) * | 2019-11-27 | 2020-06-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Магнитогорский государственный технический университет им. Г.И. Носова" | Parting paint for molds and rods |
CN111302754B (en) * | 2020-03-31 | 2021-08-17 | 汉江弘源襄阳碳化硅特种陶瓷有限责任公司 | Lost foam coating for silicon carbide ceramic casting molding and preparation method thereof |
CN112692227B (en) * | 2020-12-30 | 2022-05-17 | 刘玉满 | Reinforcer for casting coating material for preventing sand from flaky peeling and shelling and preparation and use method thereof |
CN113976828A (en) * | 2021-11-19 | 2022-01-28 | 桂林中铸机械科技有限公司 | Carbon-free precision casting method for evaporative shell of evaporative pattern by adopting high-temperature ceramic coating gasification |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1678931A (en) * | 1924-05-03 | 1928-07-31 | Smith Corp A O | Production of pipe couplings by centrifugal casting |
US2313672A (en) * | 1941-08-06 | 1943-03-09 | Borden Co | Coating sand mold surfaces |
US2658834A (en) * | 1951-01-08 | 1953-11-10 | Jack F Govan | Method of protecting metal surfaces, composition therefor, and article resulting therefrom |
US3055761A (en) * | 1956-09-26 | 1962-09-25 | Exxon Research Engineering Co | Core molding composition |
FR1257063A (en) * | 1960-02-13 | 1961-03-31 | Renault | Foundry mold preparation process |
GB1211994A (en) * | 1969-01-11 | 1970-11-11 | British Cast Iron Res Ass | A method of making cast iron castings |
US3687739A (en) * | 1970-12-10 | 1972-08-29 | Diamond Shamrock Corp | Coated metal and method |
CA971398A (en) * | 1971-03-18 | 1975-07-22 | Robert Grierson | Tungsten-nickel-iron-molybdenum alloys |
US3748110A (en) * | 1971-10-27 | 1973-07-24 | Gen Motors Corp | Ductile corrosion resistant coating for nickel base alloy articles |
SU737098A1 (en) * | 1975-05-11 | 1980-05-30 | Научно-исследовательский конструкторско-технологический институт тракторных и комбайновых двигателей | Paste for moulds |
JPS5365220A (en) * | 1976-11-25 | 1978-06-10 | Nippon Steel Corp | Mold paint for steel ingot casting |
JPS5375118A (en) * | 1976-12-16 | 1978-07-04 | Hitachi Shipbuilding Eng Co | Castings of grate* etc* and its casting method |
JPS5446131A (en) * | 1977-09-20 | 1979-04-11 | Mishima Kosan Co Ltd | Method of making mold for continuous casting process |
SU899224A1 (en) * | 1979-09-26 | 1982-01-23 | Всесоюзный Научно-Исследовательский И Проектный Институт По Очистке Технологических Газов,Сточных Вод И Использованию Вторичных Энергоресурсов Предприятий Черной Металлургии | Lubricant for ingot moulds |
JPS5653843A (en) * | 1979-10-06 | 1981-05-13 | Toyota Motor Corp | Mold coating material countermeasure against casting defect |
JPS583746A (en) * | 1981-06-26 | 1983-01-10 | Mitsubishi Heavy Ind Ltd | Alloying material for surface layer of casting |
JPS606734B2 (en) * | 1982-12-22 | 1985-02-20 | 大平洋特殊鋳造株式会社 | Anti-sulfurization coating for organic binder molds |
JPS6415249A (en) * | 1987-07-07 | 1989-01-19 | Kao Corp | Sulfurizing prevented facing for organic binder mold |
US5039477A (en) * | 1989-06-02 | 1991-08-13 | Sugitani Kinzoku Kogyo Kabushiki Kaisha | Powdered metal spray coating material |
CN1050343A (en) * | 1989-09-21 | 1991-04-03 | 陈启星 | The mold coating produces the method for foundry goods coating or infiltration layer |
JPH04147744A (en) * | 1990-10-08 | 1992-05-21 | Kobe Rikagaku Kogyo Kk | Facing agent composition |
JPH115151A (en) * | 1997-06-17 | 1999-01-12 | Honda Motor Co Ltd | Method for casting mold |
DE10221074B4 (en) * | 2002-05-10 | 2004-08-05 | Dihag Deutsche Giesserei- Und Industrie-Holding Ag | Casting mold for the production of a casting using the basic molding material and using such a casting mold |
JP2004122181A (en) * | 2002-10-02 | 2004-04-22 | Ninomiya Sangyo Kk | Metal-coated cast iron molding, metal cast steel molding and production method therefor |
US7028744B2 (en) * | 2004-03-17 | 2006-04-18 | National Research Council Of Canada | Surface modification of castings |
US20100224756A1 (en) * | 2006-10-19 | 2010-09-09 | Ashland-Sudchemie-Kernfest Gmbh | Moulding material mixture containing carbohydrates |
-
2009
- 2009-05-27 JP JP2011510999A patent/JP5701751B2/en not_active Expired - Fee Related
- 2009-05-27 US US12/994,578 patent/US20110073270A1/en not_active Abandoned
- 2009-05-27 EP EP09753897.9A patent/EP2300177B1/en not_active Not-in-force
- 2009-05-27 WO PCT/EP2009/056434 patent/WO2009144242A1/en active Application Filing
- 2009-05-27 CN CN200980129351XA patent/CN102105242A/en active Pending
- 2009-05-27 EA EA201071346A patent/EA023525B1/en not_active IP Right Cessation
- 2009-05-27 UA UAA201015650A patent/UA101663C2/en unknown
- 2009-05-27 KR KR1020107029375A patent/KR20110020279A/en active IP Right Grant
- 2009-05-27 MX MX2010012994A patent/MX2010012994A/en active IP Right Grant
- 2009-05-27 BR BRPI0912323A patent/BRPI0912323A2/en not_active IP Right Cessation
-
2010
- 2010-11-15 ZA ZA2010/08144A patent/ZA201008144B/en unknown
-
2015
- 2015-12-23 US US14/757,818 patent/US20160129496A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP2300177A1 (en) | 2011-03-30 |
EA201071346A1 (en) | 2011-06-30 |
CN102105242A (en) | 2011-06-22 |
WO2009144242A1 (en) | 2009-12-03 |
KR20110020279A (en) | 2011-03-02 |
JP2011521786A (en) | 2011-07-28 |
EA023525B1 (en) | 2016-06-30 |
JP5701751B2 (en) | 2015-04-15 |
US20110073270A1 (en) | 2011-03-31 |
BRPI0912323A2 (en) | 2015-10-06 |
UA101663C2 (en) | 2013-04-25 |
US20160129496A1 (en) | 2016-05-12 |
ZA201008144B (en) | 2011-09-28 |
MX2010012994A (en) | 2010-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2300177B1 (en) | Coating compositions for casting moulds and cores for avoiding maculate surfaces | |
EP2142322B1 (en) | Coating compounds for casting moulds and cores that prevent reaction gas defects | |
EP2274122B1 (en) | Coating composition which adsorbs odourous and harmful substances and is intended for the box casting of metals | |
EP1841556B1 (en) | Highly insulating and fireproof coating materials for casting moulds | |
CN110719838B (en) | Method for producing three-dimensional layered mold body | |
EP2296836B1 (en) | Catalysts comprising methane sulfonic acid for the acid hardening method | |
EP2249982B1 (en) | Use of branched alkane diol carboxylic acid diesters in polyurethane-based foundry binders | |
CA1128687A (en) | Novolak catechol resin blends and coated sand for shell moulding | |
EP3823774B1 (en) | Sizing composition for casting moulds for metal casting, use thereof, and casting moulds provided with the sizing composition | |
DE202015105368U1 (en) | Casting molds and kits for the suppression of pitted surfaces on castings | |
US20150298200A1 (en) | Coating compounds for casting moulds and cores that prevent reaction gas defects | |
DE102019002802A1 (en) | Sizing composition, method for coating a casting mold, use of the sizing composition for coating a casting mold and casting mold | |
WO2018002206A1 (en) | Wash composition for making facings on temporary molds or on cores for iron and steel casting operations | |
WO2023217325A1 (en) | Process for layer-by-layer building of built articles with a viscosity-modified binder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20101203 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
17Q | First examination report despatched |
Effective date: 20110608 |
|
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ASK CHEMICALS GMBH |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20150623 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20151104 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 772456 Country of ref document: AT Kind code of ref document: T Effective date: 20160215 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502009012092 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20160127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160428 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160427 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160527 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160527 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160531 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502009012092 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160527 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
26N | No opposition filed |
Effective date: 20161028 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160531 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160531 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160427 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160527 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160527 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 772456 Country of ref document: AT Kind code of ref document: T Effective date: 20160527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20090527 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20160127 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20220623 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502009012092 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231201 |