EP3060362B1 - Mehrkomponenten-system zur herstellung von formen und kernen und verfahren zur herstellung von formen und kernen - Google Patents
Mehrkomponenten-system zur herstellung von formen und kernen und verfahren zur herstellung von formen und kernen Download PDFInfo
- Publication number
- EP3060362B1 EP3060362B1 EP14796675.8A EP14796675A EP3060362B1 EP 3060362 B1 EP3060362 B1 EP 3060362B1 EP 14796675 A EP14796675 A EP 14796675A EP 3060362 B1 EP3060362 B1 EP 3060362B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- molding material
- component system
- molding
- mixture
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 34
- 239000000203 mixture Substances 0.000 claims description 92
- 239000012778 molding material Substances 0.000 claims description 76
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 239000011230 binding agent Substances 0.000 claims description 47
- 235000019353 potassium silicate Nutrition 0.000 claims description 39
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 36
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 34
- 150000001639 boron compounds Chemical class 0.000 claims description 29
- 239000002585 base Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000011734 sodium Chemical group 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 8
- -1 aluminum silicates Chemical class 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052700 potassium Chemical group 0.000 claims description 4
- 239000011591 potassium Chemical group 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052845 zircon Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001570 bauxite Inorganic materials 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 6
- 229910002923 B–O–B Inorganic materials 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 239000010431 corundum Substances 0.000 claims 2
- 239000011521 glass Substances 0.000 claims 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 239000011324 bead Substances 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000004005 microsphere Substances 0.000 claims 1
- 229910052863 mullite Inorganic materials 0.000 claims 1
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005266 casting Methods 0.000 description 79
- 238000004519 manufacturing process Methods 0.000 description 29
- 238000007792 addition Methods 0.000 description 15
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 12
- 235000010338 boric acid Nutrition 0.000 description 11
- 238000005058 metal casting Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000004328 sodium tetraborate Substances 0.000 description 9
- 229920000388 Polyphosphate Polymers 0.000 description 8
- 239000001205 polyphosphate Substances 0.000 description 8
- 235000011176 polyphosphates Nutrition 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 125000005619 boric acid group Chemical class 0.000 description 6
- 229910021487 silica fume Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 229960002645 boric acid Drugs 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 5
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 3
- 229910006501 ZrSiO Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 125000005341 metaphosphate group Chemical group 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- ILOKQJWLMPPMQU-UHFFFAOYSA-N calcium;oxido(oxo)borane Chemical compound [Ca+2].[O-]B=O.[O-]B=O ILOKQJWLMPPMQU-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910001392 phosphorus oxide Chemical class 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000896693 Disa Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910011131 Li2B4O7 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical class [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003111 delayed effect 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
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- YNPKJCSIKJCODK-UHFFFAOYSA-N disodium boric acid hydrogen borate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OB(O)O.OB(O)O.OB(O)O.OB([O-])[O-] YNPKJCSIKJCODK-UHFFFAOYSA-N 0.000 description 1
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical class O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
- B22C1/188—Alkali metal silicates
-
- 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
Definitions
- the invention relates to a multi-component system for obtaining molding material mixtures for the foundry industry, comprising one or more powdery oxidic boron compounds in combination with refractory molding raw materials, a water glass-based binder system and amorphous particulate silicon dioxide, in particular for the production of castings from aluminum, and a process for the production thereof of molds and cores from the molding material mixtures, which easily disintegrate after metal casting.
- Casting molds essentially consist of cores and molds, which represent the negative molds of the casting to be produced. These cores and molds consist of a refractory material, for example quartz sand, and a suitable binder, which gives the casting mold sufficient mechanical strength after removal from the mold.
- a refractory base material is used, which is coated with a suitable binder.
- the refractory mold raw material is preferably in a free-flowing form, so that it can be filled into a suitable hollow mold and compacted there.
- the binder creates a firm bond between the particles of the base material, so that the casting mold is given the required mechanical stability.
- Casting molds have to meet various requirements. During the casting process itself, they must first have sufficient strength and temperature resistance in order to be able to absorb the liquid metal into the cavity formed from one or more casting (partial) molds. After the solidification process begins, the mechanical stability of the casting is ensured by a solidified metal layer that forms along the walls of the casting mold. The material of the casting mold must now decompose under the influence of the heat given off by the metal in such a way that it loses its mechanical strength, that is to say the cohesion between individual particles of the refractory material is broken. Ideally, the mold disintegrates into fine sand that can be easily removed from the casting.
- inorganic binders Compared to organic binders, inorganic binders have the disadvantage that the casting molds produced therefrom have relatively low strengths. This is particularly evident immediately after the mold is removed from the tool. Good strengths at this point are particularly important for the production of complicated and / or thin-walled molded parts and their safe handling. The resistance to air humidity is also significantly reduced compared to organic binders.
- EP 1802409 B1 discloses that higher instant strengths and greater resistance to atmospheric moisture can be achieved by using a refractory molding base, a water glass-based binder and addition of particulate amorphous silicon dioxide. This addition ensures safe handling of even complicated molds.
- Inorganic binder systems have the disadvantage over organic binder systems that the coring behavior, i.e. the ability of the casting mold to disintegrate quickly (under mechanical stress) into a free-flowing form after casting, in purely inorganic casting molds (e.g. those that use water glass as a binder ) is often worse than in molds made with an organic binder.
- the invention was therefore based on the object of providing a multicomponent system for obtaining a molding material mixture for producing casting molds for metal processing, which particularly effectively improves the disintegration properties of the casting mold after metal casting and at the same time achieves a level of strength which is necessary in the automated production process is.
- casting molds with a complex geometry should be made possible, which can also include thin-walled sections, for example.
- the casting mold should also have a high storage stability and remain stable even at higher temperatures and air humidity.
- a key advantage is that the addition of powdered borates leads to significantly improved disintegration properties of the casting mold after metal casting. This advantage is associated with significantly lower costs for the production of a casting, in particular for castings which have a complex geometry with very small cavities from which the casting mold has to be removed.
- the multi-component system contains organic components with a proportion of up to a maximum of 0.49% by weight, in particular up to a maximum of 0.19% by weight, so that only very small amounts of emissions of CO 2 and other pyrolysis products are produced ,
- the use of the molding material mixture also contributes to the reduction of climate-damaging emissions from CO 2 and other organic pyrolysis products.
- Common and known materials can be used as the refractory mold base material for the production of casting molds. Suitable are, for example, quartz, zircon or chrome ore sand, olivine, vermiculite, bauxite, chamotte as well as artificial mold raw materials, in particular more than 50% by weight quartz sand based on the refractory mold raw material. It is not necessary to use only new sands. In terms of conserving resources and avoiding landfill costs, it is even advantageous to use the highest possible proportion of regenerated old sand, as can be obtained from used forms by recycling.
- a refractory molded raw material is understood to mean substances that have a high melting point (melting temperature).
- the melting point of the refractory mold base material is preferably greater than 600 ° C., preferably greater than 900 ° C., particularly preferably greater than 1200 ° C. and particularly preferably greater than 1500 ° C.
- the refractory molding base material preferably makes up greater than 80% by weight, in particular greater than 90% by weight, particularly preferably greater than 95% by weight, of the molding material mixture obtained from the multicomponent system according to the invention.
- regenerates can also be used, which can be obtained by washing and then drying shredded used molds. As a rule, the regenerates can make up at least about 70% by weight of the refractory base material, preferably at least about 80% by weight and particularly preferably greater than 90% by weight.
- the average diameter of the refractory mold raw materials is generally between 100 ⁇ m and 600 ⁇ m, preferably between 120 ⁇ m and 550 ⁇ m and particularly preferably between 150 ⁇ m and 500 ⁇ m.
- the particle size can e.g. determine by sieving according to DIN ISO 3310. Particle shapes with the greatest linear expansion to the smallest linear expansion (perpendicular to one another and in each case for all spatial directions) from 1: 1 to 1: 5 or 1: 1 to 1: 3, i.e. those that e.g. are not fibrous.
- the refractory molding base material preferably has a free-flowing state, in particular in order to be able to process the molding material mixture obtained from the multi-component system according to the invention in conventional core shooters.
- the water glasses contain dissolved alkali silicates and can be prepared by dissolving glass-like lithium, sodium and potassium silicates in water.
- the water glass preferably has a molar module SiO 2 / M 2 O (cumulative for different M's, ie in total) in the range from 1.6 to 4.0, in particular 2.0 to less than 3.5, where M is Lithium, sodium and / or potassium is available.
- a proportion of lithium ions in particular amorphous lithium silicates, lithium oxides and lithium hydroxide, or a ratio [Li 2 O] / [M 2 O] or [Li 2 O active ] / [M 2 O] as in FIG DE 102013106276 A1 described used.
- the water glasses have a solids content in the range from 25 to 65% by weight, preferably from 30 to 55% by weight, in particular from 30 to 50% by weight and very particularly preferably from 30 to 45% by weight.
- the solids content relates to the amount of SiO 2 and M 2 O contained in the water glass.
- the above values are based on a solids content of 35% by weight (see examples), regardless of which solids content is actually used.
- Powdery or particulate in each case means solid powder (including dusts) or also granules which can be poured and thus can also be sieved.
- the molding material mixture contains one or more powdery, oxidic boron compounds.
- the average particle size of the oxidic boron compounds is preferably less than 1 mm, preferably less than 0.5 mm, particularly preferably less than 0.25 mm.
- the particle size of the oxidic boron compounds is preferably greater than 0.1 ⁇ m, preferably greater than 1 ⁇ m and particularly preferably greater than 5 ⁇ m.
- the average particle size can be determined using a sieve analysis.
- the screen residue on a screen with a mesh size of 1.00 mm is preferably less than 5% by weight, particularly preferably less than 2.0% by weight and particularly preferably less than 1.0% by weight.
- the screen residue is less than 20% by weight, preferably less than 15% by weight, particularly preferably less than 10% by weight and particularly preferably less, regardless of the information given above on a screen with a mesh size of 0.5 mm than 5% by weight.
- the sieve residue is preferably less than 50% by weight, preferably less than 25% by weight and particularly preferably less than 15% by weight, independently of the preceding information on a sieve with a mesh size of 0.25 mm.
- the screening residue is determined using the machine screening method described in DIN 66165 (Part 2), with a chain ring also being used as a screening aid.
- Oxidic boron compounds are understood to mean compounds in which the boron is in the oxidation state +3. Furthermore, the boron is coordinated with oxygen atoms (in the first coordination sphere, i.e. as the closest neighbor) - either 3 or 4 oxygen atoms.
- the oxidic boron compound is preferably selected from the group of borates, boric acids, boric anhydrides, borosilicates, borophosphates, borophosphosilicates and mixtures thereof, the oxidic boron compound preferably not containing any organic groups.
- Boric acids are understood to mean orthoboric acid (empirical formula H 3 BO 3 ) and meta or polyboric acids (empirical formula (HBO 2 ) n ).
- Orthoboric acid occurs, for example, in water vapor sources and as a mineral sassolin. It can also be produced from borates (eg borax) by acid hydrolysis.
- meta or polyboric acids can be produced from orthoboric acid by intermolocular condensation by heating.
- Boric anhydride (empirical formula B 2 O 3 ) can be produced by annealing boric acids. Boric anhydride is obtained as a mostly glassy, hygroscopic mass that can then be crushed.
- borates are derived from boric acids. They can be of both natural and synthetic origin. Borates are made up, among other things, of borate structural units in which the boron atom is surrounded by either 3 or 4 oxygen atoms as the closest neighbors. The individual structural units are mostly anionic and can either be isolated within a substance, for example in the case of orthoborate [BO 3 ] 3- , or linked together, such as Metaborate [BO 2 ] n- n , whose units are linked to form rings or chains can be - if you look at such a linked structure with corresponding BOB bonds, it is anionic in the overall view.
- orthoborate [BO 3 ] 3- or linked together, such as Metaborate [BO 2 ] n- n , whose units are linked to form rings or chains can be - if you look at such a linked structure with corresponding BOB bonds, it is anionic in the overall view.
- Borates which contain linked BOB units are preferably used. Orthoborates are suitable, but not preferred. Counterions to the anionic borate units are, for example, alkali and / or alkaline earth cations, but also, for example, zinc cations.
- M x O B 2 O 3
- M stands for the cation and x for divalent cations 1 and for monovalent cations 2 is.
- the lower limit is preferably greater than 1:20, preferably greater than 1:10 and particularly preferably greater than 1: 5.
- Borates in which trivalent cations serve as counterions to the anionic borate units are also suitable, for example aluminum cations in the case of aluminum borates.
- Natural borates are mostly hydrated, ie water is contained as structural water (as OH groups) and / or as water of crystallization (H 2 O molecules).
- Borax or borax decahydrate (di-sodium tetraborate decahydrate) can be regarded as an example, the empirical formula in the literature either as [Na (H 2 O) 4 ] 2 [B 4 O 5 (OH) 4 ] or for the sake of simplicity is given as Na 2 B 4 O 7 ⁇ 10H 2 O. Both hydrated and non-hydrated borates can be used, but the hydrated borates are preferred.
- Amorphous borates are understood to mean, for example, alkali or alkaline earth borate glasses.
- Perborates are not preferred due to their oxidative properties.
- fluoroborates is also conceivable, but due to the fluorine content not particularly preferred in aluminum casting. Since the use of ammonium borate with an alkaline water glass solution produces significant amounts of ammonia, which endangers the health of the people working in the foundry, such a substance is not preferred.
- Borosilicates, borophosphates and borophosphosilicates are understood to mean compounds which are usually amorphous / glass-like.
- the structure of these compounds contains not only neutral and / or anionic boron-oxygen coordinates (eg neutral BO 3 units or anionic BO 4 - units), but also neutral and / or anionic silicon-oxygen and / or phosphorus - Oxygen coordinations - the silicon is in the oxidation level +4 and the phosphorus is in the oxidation level +5.
- the coordinations can be linked to one another via bridging oxygen atoms, such as for Si-OB or POB.
- Metal oxides, in particular alkali and alkaline earth metal oxides, which serve as so-called network modifiers, can be built into the structure of the borosilicates, borophosphates and borophosphosilicates.
- the proportion of boron (calculated as B 2 O 3 ) in the borosilicates, borophosphates and borophosphosilicates is preferably greater than 15% by weight, preferably greater than 30% by weight, particularly preferably greater than 40% by weight, based on the total mass of the corresponding borosilicate, borophosphate or borophosphosilicate.
- boric acids from the group of borates, boric acids, boric anhydride, borosilicates, borophosphates and / or borophosphosilicates, however, the borates, borophosphates and borophosphosilicates, and in particular the alkali and alkaline earth borates, are clearly preferred.
- One reason for this selection is the strong hygroscopicity of the boric anhydride, which impairs its possible use as a powder additive when it is stored for a long time. In casting experiments with an aluminum melt, it was also shown that borates lead to significantly better casting surfaces than boric acids, which is why the latter are less preferred. Borates are particularly preferably used. Alkali and / or alkaline earth borates are particularly preferred, of which sodium borates and / or calcium borates are preferred.
- the proportion of the oxidic boron compound, based on the refractory mold raw material is preferably less than 1.0% by weight, preferably less than 0.4% by weight, particularly preferably less than 0.2% by weight, particularly preferably less than 0.1% by weight and particularly preferably less than 0.075% by weight.
- the lower limit is preferably greater than 0.002% by weight, preferably greater than 0.005% by weight, particularly preferably greater than 0.01% by weight and particularly preferably greater than 0.02% by weight.
- alkaline earth borates in particular calcium metaborate, increase the strength of molds and / or cores which have been cured with acidic gases such as CO 2 . It has also surprisingly been found that the moisture resistance of the molds and / or cores is improved by the addition of oxidic boron compounds according to the invention.
- the molding material mixture contains a portion of a particulate amorphous silicon dioxide in order to increase the strength level of the casting molds produced with such molding material mixtures.
- An increase in the strengths of the casting molds, in particular the increase in the hot strengths, can be advantageous in the automated production process. Synthetically produced amorphous silicon dioxide is particularly preferred.
- the particle size of the amorphous silicon dioxide is preferably less than 300 ⁇ m, preferably less than 200 ⁇ m, particularly preferably less than 100 ⁇ m and has, for example, an average primary particle size between 0.05 ⁇ m and 10 ⁇ m.
- the sieve residue of the particulate amorphous SiO 2 when passing through a sieve with a mesh size of 125 ⁇ m (120 mesh) is preferably not more than 10% by weight, particularly preferably not more than 5% by weight and very particularly preferably not more than 2% by weight. %. Independently of this, the sieve residue on a sieve with a mesh size of 63 ⁇ m is less than 10% by weight, preferably less than 8% by weight.
- the screening residue is determined using the machine screening method described in DIN 66165 (Part 2), with a chain ring also being used as a screening aid.
- the particulate amorphous silicon dioxide which is preferably used according to the present invention has a water content of less than 15% by weight, in particular less than 5% by weight and particularly preferably less than 1% by weight.
- the particulate amorphous SiO 2 is used as a powder (including dusts).
- Both synthetically produced and naturally occurring silicas can be used as amorphous SiO 2 .
- the latter are out, for example DE 102007045649 are known, but are not preferred since they generally contain not insignificant crystalline components and are therefore classified as carcinogenic.
- Synthetic is not understood to mean naturally occurring amorphous SiO 2 , that is to say the production thereof comprises a deliberately carried out chemical reaction, as is caused by a human, For example, the production of silica sols by ion exchange processes from alkali silicate solutions, the precipitation from alkali silicate solutions, the flame hydrolysis of silicon tetrachloride, the reduction of quartz sand with coke in an electric arc furnace in the production of ferrosilicon and silicon.
- the amorphous SiO 2 produced by the latter two processes is also referred to as pyrogenic SiO 2 .
- amorphous silicon dioxide means only precipitated silica (CAS No. 112926-00-8) and flame-hydrolytically produced SiO 2 (pyrogenic silica, fumed silica, CAS No. 112945-52-5), while that in the case of ferrosilicon or Silicon production product is only referred to as amorphous silicon dioxide (Silica Fume, Microsilica, CAS No. 69012-64-12).
- the product formed in the manufacture of ferrosilicon or silicon is also understood to be amorphous SiO 2 .
- Precipitated silicas and pyrogenic, ie flame hydrolytic or arc-produced silicon dioxide are preferably used.
- Amorphous silicon dioxide produced by thermal decomposition of ZrSiO 4 (described in US Pat DE 102012020509 ) and SiO 2 produced by oxidation of metallic Si using an oxygen-containing gas (described in US Pat DE 102012020510 ).
- quartz glass powder mainly amorphous silicon dioxide, which was produced from crystalline quartz by melting and rapid cooling again, so that the particles are spherical and not splintered (described in US Pat DE 102012020511 ).
- the average primary particle size of the particulate amorphous silicon dioxide can be between 0.05 ⁇ m and 10 ⁇ m, in particular between 0.1 ⁇ m and 5 ⁇ m, particularly preferably between 0.1 ⁇ m and 2 ⁇ m.
- the primary particle size can be determined, for example, with the aid of dynamic light scattering (for example Horiba LA 950) and checked by scanning electron microscope images (SEM images with, for example, Nova Nano-SEM 230 from FEI). Furthermore, with the help of the SEM images, details of the primary particle shape down to the order of 0.01 ⁇ m could be made visible.
- the silicon dioxide samples were dispersed in distilled water and then applied to an aluminum holder stuck with copper tape before the water was evaporated.
- the specific surface area of the particulate amorphous silicon dioxide was determined using gas adsorption measurements (BET method) in accordance with DIN 66131.
- the specific surface area of the particulate amorphous SiO 2 is between 1 and 200 m 2 / g, in particular between 1 and 50 m 2 / g, particularly preferably between 1 and 30 m 2 / g. If necessary. the products can also be mixed, for example to obtain specific mixtures with specific particle size distributions.
- the purity of the amorphous SiO 2 can vary widely. Types with a content of at least 85% by weight of silicon dioxide have proven suitable, preferably of at least 90% by weight and particularly preferably of at least 95% by weight. Depending on the application and the desired level of strength, between 0.1% and 2% by weight of the particulate amorphous SiO 2 are used, preferably between 0.1% and 1.8%, particularly preferably between 0.1%. % and 1.5% by weight, based in each case on the basic molding material.
- the ratio of water glass binder to particulate amorphous silicon dioxide can be varied within wide limits. This offers the advantage that the initial strengths of the cores, i.e. improve the strength immediately after removal from the tool without significantly affecting the final strength. This is of particular interest in light metal casting. On the one hand, high initial strengths are desired so that the cores can be easily transported after assembly or assembled into whole core packages; on the other hand, the final strengths should not be too high to avoid difficulties in the core disintegration after casting, i.e. the base material of the mold should be able to be easily removed from the cavities of the mold after casting.
- the amorphous SiO 2 is preferably present in a proportion of 1 to 80% by weight, preferably 2 to 60% by weight, particularly preferably 3 to 55% by weight. % and particularly preferably between 4 to 50% by weight. Or independently of this, based on the ratio of solids content of the water glass (based on the oxides, ie total mass of alkali metal oxide and silicon dioxide) to amorphous SiO 2, from 10: 1 to 1: 1.2 (parts by weight) is preferred.
- the amorphous SiO 2 is preferably added to the refractory before the binder is added.
- barium sulfate can be added to the molding material mixture in order to further improve the surface of the casting, in particular made of aluminum.
- the barium sulfate can be synthetically produced as well as natural barium sulfate, ie added in the form of minerals that contain barium sulfate, such as heavy spar or barite. This, as well as other features of the suitable barium sulfate and the molding mixture produced with it, are described in the DE 102012104934 described in more detail and their disclosure content is thus made by reference to the disclosure of the present property right.
- the barium sulfate is preferably used in an amount of 0.02 to 5.0% by weight, particularly preferably 0.05 to 3.0% by weight, particularly preferably 0.1 to 2.0% by weight or 0.3 to 0 , 99% by weight, based in each case on the entire molding mixture, added.
- the additive component (A) as in the DE 102012113073 or the DE 102012113074 described in more detail.
- Such additives can be used to obtain castings, in particular made of iron or steel, with a very high surface quality after the metal casting, so that after the removal of the casting mold, little or no post-processing of the surface of the casting is required.
- the molding material mixture can comprise a phosphorus-containing compound .
- a phosphorus-containing compound preferably inorganic phosphorus compounds in which the phosphorus is preferably in the +5 oxidation state.
- the phosphorus-containing compound is preferably in the form of a phosphate or phosphorus oxide.
- the phosphate can be present as an alkali metal or as an alkaline earth metal phosphate, alkali metal phosphates and in particular the sodium salts being particularly preferred.
- Both orthophosphates and polyphosphates, pyrophophates or metaphosphates can be used as phosphates.
- the phosphates can be prepared, for example, by neutralizing the corresponding acids with an appropriate base, for example an alkali metal base, such as NaOH, or optionally also an alkaline earth metal base, it not necessarily being necessary for all the negative charges of the phosphate to be saturated by metal ions.
- Both the metal phosphates and the metal hydrogen phosphates and the metal dihydrogen phosphates can be used, such as Na 3 PO 4 , Na 2 HPO 4 , and NaH 2 PO 4 .
- the anhydrous phosphates and hydrates of the phosphates can also be used.
- the phosphates can be introduced into the molding material mixture both in crystalline and in amorphous form.
- Polyphosphates are understood to mean, in particular, linear phosphates which comprise more than one phosphorus atom, the phosphorus atoms in each case being connected to one another via oxygen bridges.
- Polyphosphates are obtained by the condensation of orthophosphate ions with elimination of water, so that a linear chain of PO 4 tetrahedra is obtained, which are each connected via corners.
- Polyphosphates have the general formula (O (PO 3 ) n) (n + 2) - , where n corresponds to the chain length.
- a polyphosphate can comprise up to several hundred PO 4 tetrahedra. However, polyphosphates with shorter chain lengths are preferably used.
- N preferably has values from 2 to 100, particularly preferably 5 to 50.
- Highly condensed polyphosphates can also be used, ie polyphosphates in which the PO 4 tetrahedra are connected to one another via more than two corners and therefore show polymerization in two or three dimensions.
- Metaphosphates are understood to be cyclic structures which are made up of PO 4 tetrahedra which are connected to one another via corners. Metaphosphates have the general formula ((PO 3 ) n) n- , where n is at least 3. N preferably has values from 3 to 10.
- Both individual phosphates and mixtures of different phosphates and / or phosphorus oxides can be used.
- the preferred proportion of the phosphorus-containing compound, based on the refractory base material, is between 0.05 and 1.0% by weight.
- the proportion of the phosphorus-containing compound is preferably chosen to be between 0.1 and 0.5% by weight.
- the phosphorus-containing, inorganic compound preferably contains between 40 and 90% by weight, particularly preferably between 50 and 80% by weight, phosphorus, calculated as P 2 O 5 .
- the phosphorus-containing compound can in itself be added to the molding material mixture in solid or dissolved form.
- the phosphorus-containing compound is preferably added to the molding material mixture as a solid.
- the molding material mixture according to the invention contains a proportion of platelet-shaped lubricants, in particular graphite or MoS 2 .
- the amount of the platelet-shaped lubricant, in particular graphite, added is preferably 0.05 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on the basic molding material.
- surface-active substances in particular surfactants
- surfactants can also be used which improve the flowability of the molding material mixture .
- Anionic surfactants are preferably used for the molding material mixture.
- Surfactants with sulfuric acid or sulfonic acid groups should be mentioned here in particular.
- the pure surface-active substance, in particular the surfactant, based on the weight of the refractory base material is preferably present in the molding material mixture in a proportion of 0.001 to 1% by weight, particularly preferably 0.01 to 0.2% by weight.
- the molding material mixture is an intensive mixture of at least the above-mentioned components of the multi-component system.
- the particles of the refractory molding material are preferably coated with a layer of the binder. By evaporating the water present in the binder (approx. 40-70% by weight, based on the weight of the binder), a firm cohesion can then be achieved between the particles of the refractory base material.
- the casting molds produced with the molding material mixture surprisingly show very good disintegration after casting, in particular when casting aluminum.
- the molding material mixture can be used to produce casting molds which also show very good disintegration when cast iron, so that the molding material mixture can be poured out again from narrow and angled sections of the casting mold after the casting.
- the use of the moldings produced from the molding material mixture is therefore not only restricted to light metal casting and / or non-ferrous metal casting.
- the casting molds are generally suitable for casting metals, such as non-ferrous metals or ferrous metals.
- the molding material mixture is particularly preferably suitable for the casting of aluminum.
- the procedure is generally such that the refractory molding raw material (component (F)) is initially introduced and then the binder or component (B) and the additive or component (A) are stirred is added.
- component (F) refractory molding raw material
- component (B) binder or component
- additive or component (A) are stirred is added.
- the additives described above can be added in any form to the molding material mixture. They can be added individually or as a mixture.
- the binder is provided as a two-component system, a first liquid component containing the water glass and possibly a surfactant (see above) (components (B)) and a second but solid component containing one or more oxidic boron Compounds and the particulate silicon dioxide (components (A)) and all other solid additives mentioned above, with the exception of the basic molding materials, in particular the particulate amorphous silicon dioxide and possibly a phosphate and possibly a preferably platelet-shaped lubricant and possibly barium sulfate or possibly other components such as described include.
- the refractory molding raw material is placed in a mixer and then preferably the solid component (s) of the binder is first added and mixed with the refractory molding material.
- the mixing time is chosen so that the refractory base material and solid binder component are thoroughly mixed.
- the mixing time depends on the amount of the molding material mixture to be produced and on the mixing unit used.
- the mixing time is preferably chosen between 1 and 5 minutes.
- the liquid component of the binder is then added, preferably with further movement of the mixture, and the mixture is then mixed further until a uniform layer of the binder has formed on the grains of the refractory base molding material.
- the mixing time depends on the amount of molding material mixture to be produced and on the mixing unit used.
- the duration for the mixing process is preferably chosen between 1 and 5 minutes.
- a liquid component is understood to mean both a mixture of different liquid components and the entirety of all liquid individual components, the latter also being able to be added individually.
- a solid component is understood to mean both the mixture of individual or all of the solid components described above and the entirety of all solid individual components, the latter being able to be added to the molding material mixture together or in succession.
- the liquid component of the binder can first be added to the refractory base material and only then can the solid component be added to the mixture.
- 0.05 to 0.3% by weight of water, based on the weight of the mold base is first added to the refractory mold base and only then are the solid and liquid components of the binder added.
- a surprising positive effect on the processing time of the molding material mixture can be achieved.
- the inventors believe that the dehydrating effect of the solid components of the binder is reduced in this way and the curing process is thereby delayed.
- the molding material mixture is then brought into the desired shape.
- the usual methods for shaping are used.
- the molding material mixture can be shot into the molding tool by means of a core shooting machine with the aid of compressed air.
- the molding material mixture is then cured, it being possible to use all processes which are known for binders based on water glass, for example hot curing, gassing with CO 2 or air or a combination of both, and curing by means of liquid or solid catalysts. Hot curing is preferred.
- the heating can take place, for example, in a mold which preferably has a temperature of 100 to 300 ° C., particularly preferably a temperature of 120 to 250 ° C. It is possible to fully harden the casting mold in the mold. However, it is also possible to harden the casting mold only in its edge region, so that it has sufficient strength to be able to be removed from the molding tool.
- the mold can then be fully cured by removing more water from it. This can be done in an oven, for example. The water can also be removed, for example, by evaporating the water under reduced pressure.
- the hardening of the casting molds can be accelerated by blowing heated air into the mold.
- the water contained in the binder is rapidly removed, as a result of which the casting mold is solidified in periods of time suitable for industrial use.
- the temperature of the air blown in is preferably 100 ° C. to 180 ° C., particularly preferably 120 ° C. to 150 ° C.
- the flow rate of the heated air is preferably set so that the casting mold is cured in time periods suitable for industrial use.
- the time periods depend on the size of the molds produced. The aim is to cure in a period of less than 5 minutes, preferably less than 2 minutes. For very large molds, however, longer periods of time may be required.
- the water can also be removed from the molding material mixture in such a way that the heating of the molding material mixture is effected or assisted by irradiation with microwaves. It would be conceivable, for example, to mix the basic molding material with the solid, powdery component (s), to apply this mixture in layers on a surface and to print the individual layers with the aid of a liquid binder component, in particular with the aid of water glass, the layer-by-layer application of the Solid mixture, one printing process with the help of the liquid binder follows.
- the entire mixture can be heated in a microwave oven.
- the methods according to the invention are suitable per se for the production of all casting molds customary for metal casting, that is to say for example of cores and molds. Casting molds which comprise very thin-walled sections can also be produced particularly advantageously.
- the casting molds produced from the molding material mixture or with the method according to the invention have a high strength immediately after production, without the strength of the casting molds being so high after curing that difficulties arise after the production of the casting when removing the casting mold. Furthermore, these molds have a high stability with increased air humidity, i.e. the casting molds can surprisingly be stored without problems for a long time. As an advantage, the casting mold has a very high stability under mechanical stress, so that thin-walled sections of the casting mold can also be realized without being deformed by the metallostatic pressure during the casting process. Another object of the invention is therefore a casting mold, which was obtained by the inventive method described above.
- Examples 1.01 and 1.02 illustrate that the addition of amorphous SiO 2 can achieve a significantly improved strength level (according to EP 1802409 B1 and DE 102012020509 A1 ).
- a comparison of Examples 1.02 to 1.14 shows that the strength level is not noticeably influenced by the addition of powdery oxidic boron compounds.
- Examples 1.06 and 1.11 to 1.14 show a slight deterioration in the strength levels with an increasing proportion of the additive according to the invention. However, the effect is very weak.
- Examples 1.01 and 1.02 show that adding a particulate, amorphous silicon dioxide to the molding material mixture significantly deteriorates the disintegration behavior of the molds produced with it.
- a comparison of Examples 1.02 to 1.09 clearly shows that the use of powdery oxidic boron compounds leads to significantly improved disintegration properties of the forms bonded with water glass.
- a comparison of Examples 1.07 and 1.10 shows that it makes a difference whether the borate (in this case) was pre-dissolved in the binder before use in the molding mixture or whether the borate was added to the molding mixture as a solid powder. Such an effect is surprising.
- Examples 1.06 and 1.11 to 1.14 illustrate that the disintegration behavior can be increased significantly with an increasing proportion of the additive according to the invention. It also becomes clear that even small additions are sufficient to significantly increase the disintegration ability of the hardened molding material mixture after thermal stress.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL14796675T PL3060362T3 (pl) | 2013-10-22 | 2014-10-21 | System wieloskładnikowy do wytwarzania form i rdzeni oraz sposób wytwarzania form i rdzeni |
SI201431522T SI3060362T1 (sl) | 2013-10-22 | 2014-10-21 | Večkomponentni sistem za izdelavo form in jeder ter postopek za izdelavo form in jeder |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE201310111626 DE102013111626A1 (de) | 2013-10-22 | 2013-10-22 | Formstoffmischungen enthaltend eine oxidische Bor-Verbindung und Verfahren zur Herstellung von Formen und Kernen |
PCT/DE2014/000530 WO2015058737A2 (de) | 2013-10-22 | 2014-10-21 | Formstoffmischungen enthaltend eine oxidische bor-verbindung und verfahren zur herstellung von formen und kernen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3060362A2 EP3060362A2 (de) | 2016-08-31 |
EP3060362B1 true EP3060362B1 (de) | 2020-01-01 |
Family
ID=51897022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14796675.8A Active EP3060362B1 (de) | 2013-10-22 | 2014-10-21 | Mehrkomponenten-system zur herstellung von formen und kernen und verfahren zur herstellung von formen und kernen |
Country Status (14)
Country | Link |
---|---|
US (1) | US9901975B2 (zh) |
EP (1) | EP3060362B1 (zh) |
JP (1) | JP6594308B2 (zh) |
KR (1) | KR102159614B1 (zh) |
CN (1) | CN105828973B (zh) |
BR (1) | BR112016008892B1 (zh) |
DE (1) | DE102013111626A1 (zh) |
ES (1) | ES2778075T3 (zh) |
HU (1) | HUE048328T2 (zh) |
MX (1) | MX359164B (zh) |
PL (1) | PL3060362T3 (zh) |
RU (1) | RU2703746C2 (zh) |
SI (1) | SI3060362T1 (zh) |
WO (1) | WO2015058737A2 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3159073B1 (en) * | 2014-06-20 | 2023-04-05 | Asahi Yukizai Corporation | Mold manufacturing method and mold |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10059614B2 (en) * | 2013-10-04 | 2018-08-28 | Corning Incorporated | Melting glass materials using RF plasma |
CN104942218A (zh) * | 2015-06-09 | 2015-09-30 | 含山县兴达球墨铸铁厂 | 一种大型钢铸件用高强度型砂 |
CN105665615B (zh) * | 2016-02-05 | 2018-10-02 | 济南圣泉集团股份有限公司 | 一种铸造水玻璃用固化剂及其制备方法和用途 |
WO2017152589A1 (zh) * | 2016-03-08 | 2017-09-14 | 沈阳汇亚通铸造材料有限责任公司 | 一种铸造用水玻璃砂吹气硬化的制型、芯方法 |
CN106001392A (zh) * | 2016-05-30 | 2016-10-12 | 柳州市柳晶科技有限公司 | 无机覆膜砂及其制造方法 |
CN110769951A (zh) * | 2017-01-11 | 2020-02-07 | Ha国际有限责任公司 | 用于高压模铸中的铸造型芯的组合物和方法 |
CN108393430B (zh) * | 2017-02-04 | 2020-05-08 | 济南圣泉集团股份有限公司 | 一种铸造水玻璃用固化剂 |
DE102017107531A1 (de) | 2017-04-07 | 2018-10-11 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verfahren zur Herstellung von Gießformen, Kernen und daraus regenerierten Formgrundstoffen |
DE102017114628A1 (de) | 2017-06-30 | 2019-01-03 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verfahren zur Herstellung einer Formstoffmischung und eines Formkörpers daraus in der Gießereiindustrie sowie Kit zur Anwendung in diesem Verfahren |
CN109420743A (zh) * | 2017-08-31 | 2019-03-05 | 沈阳汇亚通铸造材料有限责任公司 | 一种水玻璃砂吹气硬化的高效制芯方法 |
EP3501690A1 (en) * | 2017-12-20 | 2019-06-26 | Imertech Sas | Method of making particulate refractory material foundry articles, and product made by such method |
PL3620244T3 (pl) | 2018-09-07 | 2021-12-06 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Sposób wytwarzania cząsteczkowej kompozycji ogniotrwałej do zastosowania w produkcji form i rdzeni odlewniczych, odpowiednie zastosowania oraz mieszanina regeneracyjna do obróbki cieplnej |
DE102019113008A1 (de) | 2019-05-16 | 2020-11-19 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verwendung eines partikulären Materials umfassend ein teilchenförmiges synthetisches amorphes Siliciumdioxid als Additiv für eine Formstoffmischung, entsprechende Verfahren, Mischungen und Kits |
CN110064727A (zh) * | 2019-06-10 | 2019-07-30 | 沈阳汇亚通铸造材料有限责任公司 | 一种酯固化铸造用水玻璃砂组合物 |
DE102019116702A1 (de) | 2019-06-19 | 2020-12-24 | Ask Chemicals Gmbh | Geschlichtete Gießformen erhältlich aus einer Formstoffmischung enthaltend ein anorganisches Bindemittel und Phosphat- und oxidische Borverbindungen, ein Verfahren zu deren Herstellung und deren Verwendung |
DE102019131241A1 (de) | 2019-08-08 | 2021-02-11 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verfahren zur Herstellung eines Artikels zur Verwendung in der Gießereiindustrie, entsprechendes Granulat sowie Kit, Vorrichtungen und Verwendungen |
DE102019131676A1 (de) * | 2019-11-22 | 2021-05-27 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Kerne für den Druckguss |
DE102020118148A1 (de) | 2020-07-09 | 2022-01-13 | Bindur Gmbh | Formstoff zur Herstellung von Kernen und Verfahren zu dessen Härtung |
DE102020119013A1 (de) | 2020-07-17 | 2022-01-20 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verfahren zur Herstellung eines Artikels zur Verwendung in der Gießereiindustrie, entsprechende Form, Kern, Speiserelement oder Formstoffmischung sowie Vorrichtungen und Verwendungen |
RU2764908C1 (ru) * | 2021-07-30 | 2022-01-24 | Акционерное общество "Научно-производственная корпорация "Уралвагонзавод" имени Ф.Э. Дзержинского" | Способ отверждения жидкостекольной смеси при изготовлении форм и стержней |
CN114101593B (zh) * | 2021-11-26 | 2023-08-01 | 陕西科技大学 | 一种高溃散、可回收氧化硅基陶瓷型芯及其制备方法和应用 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1146081A (en) * | 1966-02-11 | 1969-03-19 | Foseco Int | Foundry moulds and cores |
AU2236370A (en) | 1969-11-17 | 1972-05-18 | Minerals, Binders, Clays (Proprietary) Limited | Improvements in the co2 process for bonding, moulding and core sands in foundries |
JPS51112425A (en) * | 1975-03-28 | 1976-10-04 | Hitachi Ltd | Method of manufacturing mold |
CH616450A5 (en) | 1975-11-18 | 1980-03-31 | Baerle & Cie Ag | Binder based on aqueous alkali metal silicate solutions |
US4226277A (en) * | 1978-06-29 | 1980-10-07 | Ralph Matalon | Novel method of making foundry molds and adhesively bonded composites |
DE3369257D1 (en) | 1982-12-11 | 1987-02-26 | Foseco Int | Alkali metal silicate binder compositions |
AT389249B (de) * | 1985-06-20 | 1989-11-10 | Petoefi Mgtsz | Zusatz zum regulieren der nach dem giessen zurueckbleibenden festigkeit von wasserglasgebundenen gussformen und/oder kernen |
SE520565C2 (sv) * | 2000-06-16 | 2003-07-29 | Ivf Industriforskning Och Utve | Sätt och apparat vid framställning av föremål genom FFF |
DE10085198D2 (de) | 2000-09-25 | 2003-08-21 | Generis Gmbh | Verfahren zum Herstellen eines Bauteils in Ablagerungstechnik |
JP2002219551A (ja) | 2001-01-22 | 2002-08-06 | Okamoto:Kk | 消失型中子及びそれを用いた鋳造方法 |
DE102004042535B4 (de) | 2004-09-02 | 2019-05-29 | Ask Chemicals Gmbh | Formstoffmischung zur Herstellung von Gießformen für die Metallverarbeitung, Verfahren und Verwendung |
DE102006036381A1 (de) | 2006-08-02 | 2008-02-07 | Minelco Gmbh | Formstoff, Gießerei-Formstoff-Gemisch und Verfahren zur Herstellung einer Form oder eines Formlings |
DE102006049379A1 (de) | 2006-10-19 | 2008-04-24 | Ashland-Südchemie-Kernfest GmbH | Phosphorhaltige Formstoffmischung zur Herstellung von Giessformen für die Metallverarbeitung |
DE102007008149A1 (de) | 2007-02-19 | 2008-08-21 | Ashland-Südchemie-Kernfest GmbH | Thermische Regenerierung von Gießereisand |
DE102007027577A1 (de) * | 2007-06-12 | 2008-12-18 | Minelco Gmbh | Formstoffmischung, Formling für Gießereizwecke und Verfahren zur Herstellung eines Formlings |
DE102007045649B4 (de) | 2007-09-25 | 2015-11-19 | H2K Minerals Gmbh | Verfahren zur Herstellung einer Form und/oder eines Kernes unter Verwendung von zerkleinerten natürlichen partikulären amorphen Kieselsäurematerialien im Gießereibereich und Binderzusammensetzung |
DE102007051850A1 (de) | 2007-10-30 | 2009-05-07 | Ashland-Südchemie-Kernfest GmbH | Formstoffmischung mit verbesserter Fliessfähigkeit |
ES2461115T3 (es) | 2009-10-05 | 2014-05-16 | Cognis Ip Management Gmbh | Disoluciones de vidrio soluble que contienen aluminio |
JP5933169B2 (ja) * | 2010-10-01 | 2016-06-08 | リグナイト株式会社 | 粘結剤コーテッド耐火物、鋳型、鋳型の製造方法 |
JP5972634B2 (ja) | 2012-03-29 | 2016-08-17 | 株式会社ロキテクノ | プリーツフィルターの製造方法 |
DE102012104934A1 (de) | 2012-06-06 | 2013-12-12 | Ask Chemicals Gmbh | Forstoffmischungen enthaltend Bariumsulfat |
DE102012020510B4 (de) | 2012-10-19 | 2019-02-14 | Ask Chemicals Gmbh | Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss |
DE102012020511A1 (de) | 2012-10-19 | 2014-04-24 | Ask Chemicals Gmbh | Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss |
DE102012020509A1 (de) | 2012-10-19 | 2014-06-12 | Ask Chemicals Gmbh | Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss |
DE102012113074A1 (de) | 2012-12-22 | 2014-07-10 | Ask Chemicals Gmbh | Formstoffmischungen enthaltend Metalloxide des Aluminiums und Zirkoniums in partikulärer Form |
DE102012113073A1 (de) | 2012-12-22 | 2014-07-10 | Ask Chemicals Gmbh | Formstoffmischungen enthaltend Aluminiumoxide und/oder Aluminium/Silizium-Mischoxide in partikulärer Form |
DE102013106276A1 (de) | 2013-06-17 | 2014-12-18 | Ask Chemicals Gmbh | Lithiumhaltige Formstoffmischungen auf der Basis eines anorganischen Bindemittels zur Herstellung von Formen und Kernen für den Metallguss |
-
2013
- 2013-10-22 DE DE201310111626 patent/DE102013111626A1/de not_active Withdrawn
-
2014
- 2014-10-21 WO PCT/DE2014/000530 patent/WO2015058737A2/de active Application Filing
- 2014-10-21 HU HUE14796675A patent/HUE048328T2/hu unknown
- 2014-10-21 PL PL14796675T patent/PL3060362T3/pl unknown
- 2014-10-21 ES ES14796675T patent/ES2778075T3/es active Active
- 2014-10-21 RU RU2016118813A patent/RU2703746C2/ru active
- 2014-10-21 JP JP2016525511A patent/JP6594308B2/ja active Active
- 2014-10-21 SI SI201431522T patent/SI3060362T1/sl unknown
- 2014-10-21 KR KR1020167013484A patent/KR102159614B1/ko active IP Right Grant
- 2014-10-21 CN CN201480068805.8A patent/CN105828973B/zh active Active
- 2014-10-21 MX MX2016005300A patent/MX359164B/es active IP Right Grant
- 2014-10-21 EP EP14796675.8A patent/EP3060362B1/de active Active
- 2014-10-21 US US15/030,691 patent/US9901975B2/en active Active
- 2014-10-21 BR BR112016008892-1A patent/BR112016008892B1/pt active IP Right Grant
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3159073B1 (en) * | 2014-06-20 | 2023-04-05 | Asahi Yukizai Corporation | Mold manufacturing method and mold |
Also Published As
Publication number | Publication date |
---|---|
DE102013111626A1 (de) | 2015-04-23 |
KR102159614B1 (ko) | 2020-09-28 |
CN105828973B (zh) | 2019-10-18 |
BR112016008892B1 (pt) | 2021-01-12 |
US9901975B2 (en) | 2018-02-27 |
JP2016533900A (ja) | 2016-11-04 |
SI3060362T1 (sl) | 2020-07-31 |
JP6594308B2 (ja) | 2019-10-23 |
RU2703746C2 (ru) | 2019-10-22 |
WO2015058737A3 (de) | 2015-06-18 |
US20160361756A1 (en) | 2016-12-15 |
MX2016005300A (es) | 2016-08-08 |
CN105828973A (zh) | 2016-08-03 |
RU2016118813A3 (zh) | 2018-05-25 |
HUE048328T2 (hu) | 2020-07-28 |
WO2015058737A2 (de) | 2015-04-30 |
RU2016118813A (ru) | 2017-11-28 |
ES2778075T3 (es) | 2020-08-07 |
EP3060362A2 (de) | 2016-08-31 |
PL3060362T3 (pl) | 2020-07-13 |
KR20160088315A (ko) | 2016-07-25 |
MX359164B (es) | 2018-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3060362B1 (de) | Mehrkomponenten-system zur herstellung von formen und kernen und verfahren zur herstellung von formen und kernen | |
EP2858770B9 (de) | Formstoffmischungen enthaltend bariumsulfat sowie verfahren zur herstellung von giessformen / kernen, verfahren zum aluminiumguss und form oder kern somit herstellbar | |
EP3010669B1 (de) | Verfahren zur herstellung von lithiumhaltigen formstoffmischungen auf der basis eines anorganischen bindemittels zur herstellung von formen und kernen für den metallguss | |
EP2097192B1 (de) | Phosphorhaltige formstoffmischung zur herstellung von giessformen für die metallverarbeitung | |
EP3230046B1 (de) | Verfahren zum schichtweisen aufbau von formen und kernen mit einem wasserglashaltigen bindemittel und ein wasserglashaltiges bindemittel | |
EP2934787B1 (de) | Formstoffmischungen enthaltend aluminiumoxide und/oder aluminium/silizium-mischoxide in partikulärer form | |
DE102004042535B4 (de) | Formstoffmischung zur Herstellung von Gießformen für die Metallverarbeitung, Verfahren und Verwendung | |
EP2209572B1 (de) | Formstoffmischung mit verbesserter fliessfähigkeit | |
EP2934788B9 (de) | Formstoffmischungen enthaltend metalloxide des aluminiums und zirkoniums in partikulärer form | |
DE102007045649B4 (de) | Verfahren zur Herstellung einer Form und/oder eines Kernes unter Verwendung von zerkleinerten natürlichen partikulären amorphen Kieselsäurematerialien im Gießereibereich und Binderzusammensetzung | |
EP3606690B1 (de) | Verfahren zur herstellung von giessformen, kernen und daraus regenerierten formgrundstoffen | |
DE102007008149A1 (de) | Thermische Regenerierung von Gießereisand | |
WO2014059968A2 (de) | Formstoffmischungen auf der basis anorganischer bindemittel und verfahren zur herstellung von formen und kerne für den metallguss | |
WO2014059969A2 (de) | Formstoffmischungen auf der basis anorganischer bindemittel und verfahren zur herstellung von formen und kerne für den metallguss | |
EP3092092B1 (de) | Verfahren zur herstellung von formen und kernen für den metallguss unter verwendung einer carbonylverbindung sowie nach diesem verfahren hergestellte formen und kerne | |
DE102013006135A1 (de) | Kerne auf der Basis von Salz, Verfahren zu ihrer Herstellung und deren Verwendung | |
WO2020253917A1 (de) | Geschlichtete giessformen erhältlich aus einer formstoffmischung enthaltend ein anorganisches bindemittel und phosphahaltige verbindungen und oxidische borverbindungen und verfahren zu deren herstellung und deren verwendung | |
DE102006061876A1 (de) | Kohlenhydrathaltige Formstoffmischung | |
DE102019116406A1 (de) | Additivmischung für Formstoffmischungen zur Herstellung wasserglasgebundener Gießereiformen und Gießereikerne | |
WO2004080145A2 (de) | Magnesium- und/oder aluminiumfathaltige formen und kerne mit phosphat/boratzusatz und ihre herstellung und verwendung |
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: 20160520 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AL 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 RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20170707 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20190715 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL 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 RS SE SI SK SM 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 Ref country code: AT Ref legal event code: REF Ref document number: 1219140 Country of ref document: AT Kind code of ref document: T Effective date: 20200115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502014013398 Country of ref document: DE |
|
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: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: SK Ref legal event code: T3 Ref document number: E 33968 Country of ref document: SK |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E048328 Country of ref document: HU |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS 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: 20200101 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: 20200101 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: 20200101 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: 20200527 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: 20200401 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2778075 Country of ref document: ES Kind code of ref document: T3 Effective date: 20200807 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200101 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: 20200501 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: 20200401 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: 20200402 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: 20200101 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502014013398 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM 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: 20200101 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: 20200101 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: 20200101 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: 20200101 |
|
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 |
|
26N | No opposition filed |
Effective date: 20201002 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20201015 Year of fee payment: 7 Ref country code: NL Payment date: 20201020 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20201022 Year of fee payment: 7 Ref country code: HU Payment date: 20201012 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SI Payment date: 20201012 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200101 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201021 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20201031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201021 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
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: 20200101 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: 20200101 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20211101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200101 Ref country code: AL 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: 20200101 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20211101 Ref country code: HU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211022 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20211022 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211031 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230517 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20230926 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SK Payment date: 20231016 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20231025 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20231117 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20231025 Year of fee payment: 10 Ref country code: IT Payment date: 20231031 Year of fee payment: 10 Ref country code: FR Payment date: 20231023 Year of fee payment: 10 Ref country code: CZ Payment date: 20231009 Year of fee payment: 10 Ref country code: AT Payment date: 20231019 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20231220 Year of fee payment: 10 |