CN101495306B - 制备多层玻璃结构的方法 - Google Patents
制备多层玻璃结构的方法 Download PDFInfo
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- CN101495306B CN101495306B CN2006800170909A CN200680017090A CN101495306B CN 101495306 B CN101495306 B CN 101495306B CN 2006800170909 A CN2006800170909 A CN 2006800170909A CN 200680017090 A CN200680017090 A CN 200680017090A CN 101495306 B CN101495306 B CN 101495306B
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- glass
- nitrate
- oxidant
- composition
- sodium
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- 239000011521 glass Substances 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 105
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 58
- 238000010304 firing Methods 0.000 claims abstract description 32
- 239000004615 ingredient Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 71
- 239000007800 oxidant agent Substances 0.000 claims description 67
- 230000001590 oxidative effect Effects 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 30
- 239000000049 pigment Substances 0.000 claims description 27
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 21
- 239000000470 constituent Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000005034 decoration Methods 0.000 claims description 8
- -1 fluorate Chemical compound 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 6
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 239000005387 chalcogenide glass Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000005388 borosilicate glass Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- NNRLDGQZIVUQTE-UHFFFAOYSA-N gamma-Terpineol Chemical compound CC(C)=C1CCC(C)(O)CC1 NNRLDGQZIVUQTE-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 claims description 4
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 2
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 claims description 2
- 239000004343 Calcium peroxide Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 2
- 229940088601 alpha-terpineol Drugs 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019402 calcium peroxide Nutrition 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 claims description 2
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 2
- 229940105296 zinc peroxide Drugs 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 239000002320 enamel (paints) Substances 0.000 description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 239000011651 chromium Substances 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 14
- 229910052804 chromium Inorganic materials 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 239000010955 niobium Substances 0.000 description 6
- 239000000075 oxide glass Substances 0.000 description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- 238000000576 coating method Methods 0.000 description 4
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- 239000000395 magnesium oxide Substances 0.000 description 4
- 235000012245 magnesium oxide Nutrition 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
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- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 description 2
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 2
- 238000007688 edging Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000011022 opal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000005336 safety glass Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- ZEARRFOSVATHLW-UHFFFAOYSA-L O[Cr](O)=O Chemical compound O[Cr](O)=O ZEARRFOSVATHLW-UHFFFAOYSA-L 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- RAGDLRRCYVRFQS-UHFFFAOYSA-L [Co].[Fe].[Cr](=O)(O)O Chemical compound [Co].[Fe].[Cr](=O)(O)O RAGDLRRCYVRFQS-UHFFFAOYSA-L 0.000 description 1
- BIMBXACELLEXFS-UHFFFAOYSA-N [Cr].[Nb].[Ti] Chemical compound [Cr].[Nb].[Ti] BIMBXACELLEXFS-UHFFFAOYSA-N 0.000 description 1
- SJXYEDZBGOVJEW-UHFFFAOYSA-N [Cr].[W].[Ti] Chemical compound [Cr].[W].[Ti] SJXYEDZBGOVJEW-UHFFFAOYSA-N 0.000 description 1
- RHQKKJPJCHGKQO-UHFFFAOYSA-N [Cu+2].[O-][Cr]([O-])=O Chemical compound [Cu+2].[O-][Cr]([O-])=O RHQKKJPJCHGKQO-UHFFFAOYSA-N 0.000 description 1
- WYWXJXXVNATOED-UHFFFAOYSA-L [Fe].[Zn].[Cr](=O)(O)O Chemical compound [Fe].[Zn].[Cr](=O)(O)O WYWXJXXVNATOED-UHFFFAOYSA-L 0.000 description 1
- 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 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical compound [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- DQSZTYQROOAPEX-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2].[Bi+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2].[Bi+3] DQSZTYQROOAPEX-UHFFFAOYSA-N 0.000 description 1
- ATGLZGGYYRAGGV-UHFFFAOYSA-N [Sb].[Ti].[Cr] Chemical compound [Sb].[Ti].[Cr] ATGLZGGYYRAGGV-UHFFFAOYSA-N 0.000 description 1
- RGJFIBUEZUKXSQ-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[O-2].[Al+3].[B+3] Chemical compound [Si]([O-])([O-])([O-])[O-].[O-2].[Al+3].[B+3] RGJFIBUEZUKXSQ-UHFFFAOYSA-N 0.000 description 1
- NRWNVALJYWIWEH-UHFFFAOYSA-N [Ti].[Ba].[Ni] Chemical compound [Ti].[Ba].[Ni] NRWNVALJYWIWEH-UHFFFAOYSA-N 0.000 description 1
- LTRVYMQEYWYTFM-UHFFFAOYSA-N [Ti].[Mn].[Sb] Chemical compound [Ti].[Mn].[Sb] LTRVYMQEYWYTFM-UHFFFAOYSA-N 0.000 description 1
- XHFQVKIBTSHQHN-UHFFFAOYSA-N [Ti].[Nb].[Mn] Chemical compound [Ti].[Nb].[Mn] XHFQVKIBTSHQHN-UHFFFAOYSA-N 0.000 description 1
- XFRSLLLNVCTDKR-UHFFFAOYSA-N [Ti].[Sb].[Cr].[Mn] Chemical compound [Ti].[Sb].[Cr].[Mn] XFRSLLLNVCTDKR-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- TUFZVLHKHTYNTN-UHFFFAOYSA-N antimony;nickel Chemical compound [Sb]#[Ni] TUFZVLHKHTYNTN-UHFFFAOYSA-N 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- XTUHPOUJWWTMNC-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)chromium Chemical compound [Co+2].[O-][Cr]([O-])(=O)=O XTUHPOUJWWTMNC-UHFFFAOYSA-N 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 239000010952 cobalt-chrome Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- QZVSYHUREAVHQG-UHFFFAOYSA-N diberyllium;silicate Chemical compound [Be+2].[Be+2].[O-][Si]([O-])([O-])[O-] QZVSYHUREAVHQG-UHFFFAOYSA-N 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- FEBJSGQWYJIENF-UHFFFAOYSA-N nickel niobium Chemical compound [Ni].[Nb] FEBJSGQWYJIENF-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- UMTMDKJVZSXFNJ-UHFFFAOYSA-N nickel;trihydrate Chemical compound O.O.O.[Ni] UMTMDKJVZSXFNJ-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
- B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
- B32B17/10266—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on glass pane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
- B32B17/10348—Specific parts of the laminated safety glass or glazing being colored or tinted comprising an obscuration band
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
- C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
本发明提供了一种使用单一烧制步骤制备装饰多层玻璃结构的方法,该方法包括使用含有确保该组合物的有机部分在烧制和成对的玻璃片材弯曲时会完全烧尽的组分的结晶玻璃瓷漆组合物。该组合物的优点在于,当涂覆到成对的玻璃片材的其中一片上时,在烧制和该对片材弯曲的过程中它们会完全烧尽。在组合物中较高含量的氧化剂的存在确保了氧气的供给,使得在玻璃片材烧制时和在将该瓷漆组合物烧结到该成对的装饰和彩色玻璃片材的仅一块玻璃片材中之前能够使有机载体燃烧。
Description
技术领域
本发明涉及多层玻璃结构,特别涉及制备使用结晶的瓷漆装饰的多层玻璃结构的方法。
背景技术
结晶的玻璃瓷漆组合物是现有技术中已知的,它们可以用于多种应用领域,例如玻璃器皿、陶瓷器具等的装饰性涂层。它们特别适用于在用作汽车挡风玻璃、侧灯和背灯的玻璃片材周围形成彩色边缘。该彩色边缘增加了美观,同时防止了其下的粘结剂的UV降解。该结晶的玻璃瓷漆是活性组合物,因为它们包含在烧制时会进行反应和结晶的组分。
通常,这些瓷漆组合物主要由玻璃料、着色剂和有机载体构成。将它们涂覆到基体,例如玻璃片材上,然后烧制使有机载体被烧尽并使该玻璃料熔合,由此将瓷漆涂覆到基体上。通常将瓷漆组合物涂覆到用于汽车用途的玻璃片材上,然后在高温下进行成形工艺。在该处理过程中,瓷漆熔化,并熔合到玻璃基体上,玻璃形成所需的最终形状。在将各层堆积在一起之前,也可以将这种组合物涂覆到多层层压材料(例如安全玻璃挡风板)中的一层上,由此该颜料/颜色位于所形成的多层层压材料的内部。
在这种情况下,通过例如丝网印刷涂覆瓷漆之后,在低温或用UV光使该湿膜干燥或固化,以去除溶剂并产生干燥的未烧制瓷漆,其中颗粒由高分子量的有机粘结剂分子结合在一起。在产生该未烧制瓷漆层之后,可以在其上印刷导电的银层,需要在较高温度下进行至少三个另外的加热步骤。第一次加热烧掉较高温度的高分子量有机粘结剂分子,将瓷漆组合物粘结到第一基体层上。第二次加热使第二玻璃基体与第一玻璃基体一起配合并弯曲。在第一和第二玻璃片材之间插入乙烯基片材(例如聚乙烯醇缩丁醛)之后,然后需要第三次低温加热,使两个玻璃片材和乙烯基片材熔合以形成玻璃整块,即层压的玻璃挡风窗。
当使用常规结晶瓷漆组合物(在仍未烧制时)堆叠玻璃基体,在烧制时形成配合的一套时,结果是较高温度的有机粘结剂的不完全去除(即燃烧),这会造成明显的碳滞留以及所需的瓷漆黑色的退化。此外,底部片材上的瓷漆会不适宜地粘结到顶部片材上,导致对任一片材或对两者都产生损害。
Tünker的美国专利5443669公开了一种制备装饰的多层玻璃结构的方法,其中两个玻璃块一起烧制。然而,Tünker的方法会导致两块的粘附,因为这种方法不使用结晶的玻璃瓷漆。此外,Tünker的方法使用了包含特定硅胶的无机粘结剂,其不能容易地与瓷漆组合物的其它组分混合。此外,Tünker的专利教导使用含铅的氧化剂和含少量氧的氧化剂,但该氧化剂与常规的粘结剂材料的反应并不充分。
发明内容
本发明提供一种使用单一烧制步骤来制备装饰的多层玻璃结构的方法,该方法包括使用结晶的玻璃瓷漆组合物,所述组合物包含确保在烧制和成对的玻璃片材弯曲时完全烧掉该组合物的有机部分的组分。该组合物的优点在于,当涂覆到成对的玻璃片材的一片上时,在烧制和成对片材弯曲的过程中它会被完全烧掉。组合物中高含量氧化剂的存在确保了氧气的供给,使得在玻璃片材烧制时和在将该瓷漆组合物烧结到该成对的装饰或彩色玻璃片材的仅一块玻璃片材上之前能够燃烧有机载体。该瓷漆组合物使用常规的有机粘结剂材料,其不需要使用无机粘结剂如硅胶。此外,该瓷漆组合物和该氧化剂是不含铅的。
通常,该结晶的瓷漆组合物在烧制之前包括活性玻璃料、氧化剂组分、颜料和有机载体。如果需要,该组合物可以进一步包含籽晶材料。制备结晶的瓷漆组合物的方法包括将前述组分以无特别的顺序和以所需的量进行混合。
本发明还包括将瓷漆与玻璃基体熔合的方法,所述玻璃基体如用于汽车、建筑/结构、家用设施和饮料工业中的那些玻璃基体,例如汽车挡风玻璃和其它的汽车玻璃、住宅和商用窗户、陶瓷炉灶面和饮料瓶。例如,该瓷漆组合物可以用于在汽车玻璃板的外周围形成彩色和/或防UV的装饰边。
特别地,该未烧制的瓷漆组合物(在烧制之前)包括活性玻璃组分、包含氧化剂的氧化剂组分、颜料和有机载体。该活性玻璃组分包括氧化物玻璃料或硫化物玻璃料或它们两者。该氧化剂组分包括选自以下组成组的无铅氧化剂: 氧化物、硝酸盐、碳酸盐、硼酸盐、氟酸盐、氯酸盐、溴酸盐、碘酸盐、硫酸盐、磷酸盐和高锰酸盐,条件是每分子氧化剂中包括至少两个氧原子。该瓷漆组合物可以任选地还包括籽晶材料,它促进该瓷漆组合物结晶,所述籽晶材料选自以下组成的组:硅酸盐、钛酸盐、铝酸盐、铌酸盐和铋酸盐及其混合物。
具体实施方式
本发明方法包括使用含有以下组分的瓷漆组合物:(1)至少一种活性玻璃料(氧化物或硫化物或它们两者);(2)至少一种氧化剂;(3)着色剂(颜料);和(4)用于组分(1)-(3)的载体。氧化剂被认为提供分子氧,由于它在烧制循环过程中会分解,这促使在该瓷漆组合物烧结到玻璃基体上之前将有机载体完全消除(燃烧和/或挥发)。通常将该瓷漆组合物涂覆到成对片材中的一个片材上(“底部片材”)。在涂覆该瓷漆组合物之后,将该底部片材与该对片材中的另一片材(“顶部片材”)紧密配合。该组合物可以任选地包含籽晶材料,它被认为有助于晶体结构的成核和生长,这有利于防治顶部片材熔合到底部片材上。
通常,该瓷漆组合物在烧制之前以重量计包括20~80%的含有一种或多种活性玻璃料的玻璃组分、0.01~7%的氧化剂组分、10~40%的颜料和10~40%的有机载体。该瓷漆组合物可以进一步包括0.1~20%的籽晶材料。可替代地,该瓷漆组合物以重量计可以包括20~80%的较低熔点(450~550℃)的活性玻璃料和10~50%的较高熔点(580~680℃)的活性玻璃料。所有组成百分比都是以重量计的,且都是对于烧制前的混合物而给出的。所有百分比、温度、时间、颗粒尺寸和其它数值的范围都假定为带有修饰语“约”。下面给出了对各组分的详述。
玻璃组分。包含活性玻璃料的玻璃组分以重量计占瓷漆组合物的约20~80%。该活性玻璃料可以包含氧化物玻璃料、硫化物玻璃料或两者的组合。术语“活性玻璃料”是指该玻璃料中所含氧化物的至少30wt%在烧制时会反应形成结晶产物。适合的氧化物玻璃料包括硼硅酸盐玻璃料,例如硼硅酸铋玻璃料和硼硅酸锌玻璃料。在美国专利5153150(Ruderer等)和6207285(Sakoske等)中可以发现关于适合的玻璃料的更多细节,两篇文献都与此共有,全部引入此处作为参考。可用于本发明的代表性的氧化物玻璃料在烧制前具有如下表 1中所示的组成:
表1.氧化物玻璃料的组成(组分范围以重量百分比计)
组分 | 范围1 | 范围2 | 范围3 | 范围4 | 范围5 | 范围6 | 范围7 | 范围8 |
Bi2O3+ZnO | 1-99 | 5-95 | ||||||
B2O3 | 1-20 | 10-35 | 0.1-9 | 0.1-9 | 21-60 | 21-60 | ||
SiO2 | 0.1-28 | 0.1-28 | 5-50 | 5-50 | 0.1-28 | 0.1-28 | 0.1-28 | 0.1-28 |
Bi2O3 | 15-60 | 9-75 | 9-75 | 9-75 | ||||
ZnO | 5-50 | 5-50 | 0.1-11 | 0.1-11 | 21-50 |
从上面可以看到,玻璃料的组成不是苛刻的。每个玻璃料组分可以另外包含现有技术中已知的玻璃改性氧化物和/或硫化物组分。示例性的玻璃改性氧化物包括TiO2、ZrO2、Al2O3、K2O、Li2O、Na2O、F2、Nb2O5、CeO2、Sb2O3、BaO、CaO、SrO、MgO、SnO、Cr2O3、NiO、CoO、锰的氧化物(例如MnO或Mn2O3)、铁的氧化物(例如Fe2O3或FeO)、铜的氧化物(例如CuO或Cu2O)、钼的氧化物(例如MoO或Mo2O3)、钨的氧化物(例如WO3或WO2)。也可以预见前述金属不同氧化态的氧化物。还可以预见有意包含PbO和/或CdO的玻璃料、或者特意不包含PbO和/或CdO的玻璃料,这取决于所需的性能和环境的考虑。
广泛地,这种添加剂氧化物的用量包括0~10%的TiO2、0~7%的ZrO2、0~7%的Al2O3、0~10%的K2O、0~5%的Li2O、0~15%的Na2O、0~7%的F2、0~4%的Nb2O5、0~4%的CeO2、0~4%的Sb2O3、0~20%的BaO、0~20%的CaO、0~20%的SrO、0~10%的MgO、0~20%的SnO、0~10%的Cr2O3、0~8%的NiO、0~10%的CoO、0~25%的锰的氧化物、0~20%的铁的氧化物、0~10%的铜的氧化物、0~4%的钼的氧化物、0~5%的钨的氧化物。优选地,在该段落中的每个范围的下限不是0而是0.1%。
硫化物玻璃料是包含金属硫化物组分的玻璃料。在Antequil等的美国专利535071 8中公开了适用于此处的硫化物玻璃料,该专利引入此处作为参考。在这种玻璃料中的示例性的硫化物包括ZnS、MnS、FeS、CoS、NiS、Cu2S、CdS、Sb2S3和Bi2S3。优选地,所述硫化物是ZnS。包含氧化物和硫化物玻璃料的玻璃组分也是可预见的。适用于此处的玻璃料的熔点范围为约450℃~约750℃, 或者任何中间温度,例如500℃、550℃、580℃、600℃、630℃、650℃、680℃或700℃,各种玻璃料在这些温度下可以有效地烧制。
该玻璃料以已知方式制成,例如在1000~1300℃的温度下将原料(氧化物和/或硫化物)混合并熔合在一起约40分钟,以形成具有所想要组成的熔融玻璃。然后可以以已知方式(例如水淬火)将形成的熔融玻璃突然冷却,以形成玻璃料。然后可以使用常规的磨碎技术将该玻璃料磨碎到约1~约8微米,优选2~约6微米,更优选约3~约5微米的粒径。
氧化剂组分。氧化剂组分包括一种或多种氧化剂,即在分解时释放出分子氧的化合物。该氧化剂是不含铅的(与瓷漆组合物一样),这种氧化剂分子中包含至少两个氧原子。当涂覆瓷漆的玻璃基体被烧制时,释放的氧气会引发和保持有机载体的燃烧。根据该瓷漆组合物的烧制情况,选择适当的氧化剂组合,以提供足够的氧气来确保完全烧掉有机载体。在玻璃料烧结开始之前需要氧化剂分解以及有机载体烧尽。如果在氧化剂分解之前烧结,那么碳灰会在烧结的最后时刻滞留在瓷漆中,因此造成黑色瓷漆变灰和起泡。这种结果在任何应用中都是不可接受的。这种多孔玻璃陶瓷膜将具有较差的抗划伤性和机械完整性,并且不能充分地粘结到它所涂覆的玻璃片材上,和/或在层压加热过程中不能充分地粘结到该层压制品上,这最终会造成较差的结构完整性或者分层。
颗粒尺寸对氧化剂的效果会产生影响。氧化剂颗粒尺寸应当与玻璃料颗粒尺寸大致相同。事实上,该氧化剂可以与玻璃料一起研磨,以确保氧化剂均匀地分散到在烧制之前涂覆到玻璃片材上的整个瓷漆糊组合物中。研磨到平均粒径(D50)为8~13μm的氧化剂(例如碱式硝酸铋)是适用的。发现其它的例如D50在1~5μm范围内的二氧化锰颗粒也是适用的。适用于实施本发明的氧化剂包括在装饰性瓷漆组合物的烧制温度曲线内的温度下释放出氧气的任何物质。
通常,适合的氧化剂包括氧化物、过氧化物、硝酸盐、碱式硝酸盐、氯酸盐、溴酸盐、硫酸盐和磷酸盐,条件是在制备层压玻璃结构的过程中用于烧制和将该瓷漆组合物熔合到玻璃片材上的烧制温度范围内适合使有机组分分解的温度下分解时会释放分子氧。特别地,预期适用于本发明的氧化剂包括锑、铋、钙、镁、锰、镍、钾、钠、锶、碲或锌的氧化物和过氧化物;钡、铋、钙、 铯、钴、铜、锂、镁、钾、钠、锶或锡的硝酸盐和碱式硝酸盐;钠或钾的氯酸盐;钠或钾的溴酸盐;钠或钾的硫酸盐;和钠或钾的磷酸盐。对于第二表面瓷漆涂覆,碱式硝酸铋、硝酸钠和硝酸铵各自单独或其任意组合的性能是最好的。表2中列举了示例性的氧化物。在一种实施方式中,所述氧化剂组分包括重量比为约1∶2~约2∶1的碱式硝酸铋和二氧化锰。在另一实施方式中,所述氧化剂组分包括重量比为约15∶1~约2∶1的二氧化锰和硝酸钠。
表2.氧化剂及其分解温度
化合物 | 分子式 | 熔点℃(分解) | 沸点℃(分解) |
硝酸铵 | NH4NO3 | 169.6 | 210 |
五氧化二锑 | Sb2O5 | 380 | |
硝酸钡 | Ba(NO3)2 | 592 | |
五氧化二铋 | Bi2O5 | 150 | 357 |
碱式硝酸铋 | BiONO3 | 260 | 335 |
四氧化二铋 | Bi2O4 | 305 | |
硝酸钙 | Ca(NO3)2 | 561 | |
过氧化钙 | CaO2 | 275 | |
硝酸铯 | CsNO3 | 414 | |
硝酸钴 | Co(NO3)2 | 100 | |
硝酸铜 | Cu(NO3)2 | 255 | |
硝酸锂 | LiNO3 | 253 | |
过氧化镁 | MgO2 | 100 | |
二氧化锰 | MnO2 | 535 | |
氧化镍(III) | Ni2O3 | 600 | |
二氧化铂 | PtO2 | 450 | |
溴酸钾 | KBrO3 | 370 | 434 |
氯酸钾 | KClO3 | 368 | 400 |
碘酸钾 | K1O3 | 560 | |
硝酸钾 | KNO3 | 337 | 400 |
过氧化钾 | K2O2 | 490 |
[0025]
硝酸银 | AgNO3 | 212 | |
溴酸钠 | NaBrO3 | 381 | |
氯酸钠 | NaClO3 | 248 | |
硝酸钠 | NaNO3 | 306.8 | 380 |
过碳酸钠 | 2Na2CO3·3H2O2 | 50 | |
过氧化钠 | Na2O2 | 460 | 657 |
硝酸锶 | Sr(NO3)2 | 570 | 645 |
过氧化锶 | SrO2 | 215 | |
三氧化碲 | TeO3 | 430 | |
硝酸锡 | Sn(NO3)4 | 50 | |
过氧化锌 | ZnO2 | 150 | 212 |
颜料。精细研磨的玻璃料可以与混合的金属氧化物颜料进行混合。通常在汽车工业中用于产生黑色的混合金属氧化物颜料包括铜、铬、钴、镍、锰和其它过渡金属的氧化物。尽管在汽车工业中优选使用黑色尖晶石颜料,但是产生非黑色的颜色的金属氧化物颜料可以与此处的玻璃料进行混合。根据所需的颜色、光泽度和不透明度的范围,所述颜料通常构成此处的瓷漆组合物的约10~约40%。
使用的颜料可以来自几种主要种类的复合无机颜料,包括刚玉-赤铁矿、橄榄石、柱红石、烧绿石、金红石、尖晶石和尖晶石,尽管其它种类如斜锆石、硼酸盐、石榴石、方镁石、硅铍石、磷酸盐、榍石和锆石可以适用于某些应用领域中。例如,硅酸钴蓝色橄榄石Co2SiO4;镍钡钛淡黄色柱红石2NiO:3BaO:17TiO2;亚锑酸铅黄色烧绿石Pb2SbO7;镍锑钛黄色金红石(Ti,Ni,Nb)O2;镍铌钛黄色金红石(Ti,Ni,Nb)O2;镍钨黄色金红石(Ti,Ni,W)O2;铬锑钛浅黄色金红石(Ti,Cr,Sb)O2;铬铌钛浅黄色金红石(Ti,Cr,Nb)O2;铬钨钛浅黄色金红石(Ti,Cr,W)O2;锰锑钛浅黄色金红石(Ti,Mn,Sb)O2;钛钒灰色金红石(Ti,V,Sb)O2;锰铬锑钛棕色金红石(Ti,Mn,Cr,Sb)O2;锰铌钛棕色金红石(Ti,Mn,Nb)O2;铝酸钴蓝色尖晶石CoAl2O4;锌铬钴铝尖晶石(Zn,Co)(Cr,Al)2O4;铬酸钴蓝绿色尖晶石CoCr2O4;钛酸钴绿色尖晶石Co2TiO4;亚铬酸铁棕色尖晶石Fe(Fe,Cr)2O4;钛酸铁棕色尖晶石Fe2TiO4;铁酸镍棕色尖晶石NiFe2O4; 铁酸锌棕色尖晶石(Zn,Fe)Fe2O4;亚铬酸锌铁棕色尖晶石(Zn,Fe)(Fe,Cr)2O4;亚铬酸铜黑色尖晶石CuCr2O4;亚铬酸铁钴黑色尖晶石(Co,Fe)(Fe,Cr)2O4;铬铁锰棕色尖晶石(Fe,Mn)(Cr,Fe)2O4;铬铁镍黑色尖晶石(Ni,Fe)(Cr,Fe)2O4;和铬锰锌棕色尖晶石(Zn,Mn)(Cr2O4)。
本发明的瓷漆组合物还可以包含最高约15%的一种或多种填料(例如二氧化硅和氧化铝)以及其它的常规添加剂(例如铁、硅、铁等),以提高所需的性质,例如对抗银渗透性。可替代地,该填料可以是高熔点的氧化物填料,例如硼-氧化铝-硅酸盐、氧化铝-硅酸盐、硅酸钙、苏打-氧化钙-氧化铝-硅酸盐、硅灰石、长石、钛酸酯及其组合。
籽晶材料。瓷漆组合物可以任选地包含最高约20%(例如0.1~20%或2~10%)的籽晶材料,例如硅酸铋、硅酸锌和钛酸铋。该籽晶材料可以非限制性地包括一种或多种以下材料:Zn2SiO4、Bi12SiO20、Bi4(SiO4)3、Bi2SiO5、2ZnO·3TiO2、Bi2O3·SiO2、Bi2O3·2TiO2、2Bi2O3·3TiO2、Bi7Ti4NbO21、Bi4Ti3O12、Bi2Ti2O7、Bi12TiO20、Bi4Ti3O12和Bi2Ti4O11。美国专利6624104(Sakoske等)和5208191(Ruderer等)提供了籽晶材料的进一步信息;两篇专利都与此共有,并引入作为参考。
有机载体。前述固体组分与有机载体一起结合,以形成糊状的未烧制瓷漆组合物。该未烧制瓷漆糊总共包括60~90%如上所述的固体和10~40%有机载体。调节该糊的粘度以使其可以丝网印刷、辊涂或喷涂到所需的基体上。
有机载体包括粘结剂和溶剂,它们是根据所需的应用而选择的。必须的是,该载体足以悬浮颗粒(即玻璃料、氧化剂、颜料、籽晶)并且在烧制时会完全燃烧。特别地,可以使用包括甲基纤维素、乙基纤维素和羟丙基纤维素以及它们的组合。适合的溶剂包括丙二醇、二甘醇丁基醚、2,2,4-三甲基戊二醇单异丁酸酯(TexanolTM)、α-萜品醇、β-萜品醇、γ-萜品醇、十三烷醇、二甘醇乙基醚(CarbitolTM)、二甘醇丁基醚(Butyl CarbitolTM)、松油、植物油、矿物油、低分子量的石油馏分、十三烷醇、合成和天然的树脂以及它们的混合物。也可以包含表面活性剂和/或其它的成膜改性剂。溶剂和粘结剂可以以约50∶1~约20∶1的重量比存在。优选的载体是重量比为约200∶1~约20∶1、50∶1~约20∶1、更优选约40∶1~约25∶1的Butyl CarbitolTM(二甘醇一丁基醚)和乙基纤维素的混合物。
瓷漆组合物不需要使用无机粘结剂如硅胶。优选地,该瓷漆组合物包含少于3wt%的硅胶,因为这种材料难于与该瓷漆组合物的其它组分相混合。更优选地,所述瓷器组合物基本上没有硅胶。优选地,可以在小于200℃的温度下对该载体进行干燥,除去几乎所有溶剂。
通常,该瓷漆糊的性质是粘性的,它的粘度取决于所使用的涂覆方法和最终用途。为了进行丝网印刷,在布氏粘度计,#29轴和10rpm下测定的20℃时粘度在10000~80000,优选在15000~35000厘泊,更优选在18000~28000厘泊的范围内是适当的。
方法。可以通过将包含颜料的瓷漆组合物涂覆到玻璃片材的至少一个表面上并将该玻璃片材烧制,来为玻璃基体着色或装饰。特别是,形成装饰的玻璃结构的方法包括在第一玻璃基体上涂覆在烧制前包含以下组分的未烧制结晶的瓷漆组合物:玻璃组分、有机载体、氧化剂组分和颜料;在低温下干燥该载体以去除溶剂;将该第二玻璃基体与第一玻璃基体堆叠一起,其中该未烧制的结晶的瓷漆组合物位于第一和第二玻璃基体之间;使所堆叠的玻璃基体进行煅烧操作,由此该瓷漆仅熔合到一块玻璃基体上,有机载体完全烧尽,并且该玻璃基体不会粘结在一起。该瓷漆组合物可以进一步包含籽晶材料。该氧化剂组分包括分解释放分子氧的氧化剂,所述氧化剂选自以下组成的组:氧化物、硝酸盐、碳酸盐、硼酸盐、氟酸盐、氯酸盐、溴酸盐、碘酸盐、硫酸盐、磷酸盐、锰酸盐和高锰酸盐。所述方法可以包括玻璃形成步骤,由此将玻璃块弯曲在一起以形成配合的一对。
此外,形成具有瓷漆涂层的玻璃基体的方法是可以预见的,该方法包括(a)将未烧制的结晶瓷漆组合物涂覆到玻璃基体上;(b)将该涂覆的玻璃加热到高温,优选至少约570℃;(c)使用成型冲模使该加热的玻璃承受成型压力,例如重力下垂或在0.1~5psi之间,通常约2psi的冲压弯曲;以及(d)将该成型的玻璃与冲模分开。该瓷漆组合物可以涂覆到玻璃基体的整个表面上,或者仅涂覆到其一部分上,例如其周围。
还提供了一种使玻璃基体涂覆和着色的方法,其中将该瓷漆组合物涂覆到第一玻璃基体(例如玻璃片材)的第一侧。通常,这是本领域公知的汽车挡风 板的“第二表面”。将第二基体与第一玻璃基体堆叠一起,由此该瓷漆组合物位于第一和第二基体之间。将该堆叠的基体放置在模具中,在足以使该瓷漆烧结并熔合到第一玻璃基体上的温度下(例如约570℃~约680℃)进行煅烧。其中一个玻璃片材具有陶瓷装饰的所述配对的玻璃片材与模具和另一片材分开,由此它们不会与冲模或另一个片材粘结一起。其优点在于,在烧制后片材不会彼此粘结,因为它们通常进一步处理以制成层压的挡风玻璃(安全玻璃)。在这种情况下,在玻璃片材之间插入诸如聚乙烯醇缩丁醛(PVB)的层压薄膜,将该片材和PVB加热到使其熔合在一起。如果在上述烧制步骤之后该片材彼此粘结,进一步的处理会失败或不可能,会发生机械和/或光学缺陷。
为了制备本发明的瓷漆组合物,使用常规方法将玻璃料粉碎成细粉,将其与籽晶材料、颜料、任选的填料和载体以任何顺序混合。可以添加如上所讨论的其它氧化物、以及防治银渗透的材料。在该瓷漆组合物中可以存在此处所述的各组分的多种以上的各组分。在将所有瓷漆组合物组分混合之前,可以首先将氧化剂与溶剂(例如丙二醇,或其它前述溶剂)紧密混合。通常,在该混合中氧化剂与溶剂的比例为约1∶20~约1∶4,优选为约1∶15~约1∶5。当与有机载体混合时,可以在瓷漆混合物中添加氧化剂和玻璃料。或者,可以在与剩余组分混合之前将氧化剂溶解或分散在有机载体中。
该瓷漆组合物可以以常规方式涂覆到玻璃基体上,例如通过丝网印刷、贴花涂覆、喷涂、刷涂、辊涂等。当将该组合物涂覆到玻璃基体上时,丝网印刷是优选的。在将该组合物以所需的图案涂覆到基体上时,然后将该涂覆的涂层烧制,以将该瓷漆粘合到基体上。通常烧结温度是由玻璃料熟化温度决定的。典型地,该组合物的烧结温度为约570℃~680℃,更优选为约570℃~650℃,最优选为约570℃~620℃。
实施例
以下组合物表示本发明的示例性实施方式。它们用于更详细地解释本发明,并不是用于限定本发明。
表中的缩略语具有以下含义:玻璃组分是硼硅酸锌玻璃料和硼硅酸铋玻璃料的混合物。颜料是黑色无机亚铬酸铜尖晶石颜料。颜料+NH4NO3是用黑色颜料干磨的0.3%硝酸铵。籽晶1是硅酸铋籽晶材料。籽晶2是硅酸锌籽晶材 料。有机载体是97.25%的丁基卡必醇和2.75%的乙基纤维素,标准等级45。BiONO3是D50粒径为8~13微米的碱式硝酸铋(也称为含氧硝酸铋)。MnO2 是D50粒径小于5微米的二氧化锰。
称量如表3中所示的玻璃料、颜料和籽晶材料(籽晶1到籽晶2)以及下面的(“干瓷漆”),并且在混合机中混合在一起。使用Hobart型混合机将所混合的干瓷漆与有机载体进行混合,使干瓷漆材料润湿。在该混合物润湿之后,添加氧化剂BiONO3、MnO2和氧化剂混合物NaNO3+丙二醇(PG)和/或NH4NO3+PG,同时加入另外部分的丁基卡必醇,以对其粘度进行略微调节。然后在三辊研磨机上研磨该湿糊材料。通过添加丁基卡必醇溶剂进行最终的粘度调节。该糊批料包含下表3和4中所示的组分。
表3.瓷漆组合物干组分
组分 | 重量(克) |
玻璃组分 | 5292.5 |
颜料 | 1667.5 |
籽晶1 | 217.5 |
籽晶2 | 72.5 |
BiONO3氧化剂 | 7.2 |
MnO2氧化剂 | 7.2 |
总干瓷漆+氧化剂 | 7264.4 |
在该混合的玻璃料、颜料和籽晶材料中,依照表4来添加有机载体、氧化剂和其它的溶剂。
表4.添加形成糊料的有机载体、氧化剂和溶剂
组分 | 重量(克) |
有机载体 | 1338.0 |
6%NaNO3+94%PG | 104.1 |
溶剂 | 48.0 |
最终得到的糊料的配比如下表5所示。
表5.最终的糊料组合物
组分 | 重量(克) |
瓷漆+氧化剂 | 7264.4 |
有机载体 | 1338.0 |
10%NH4NO3+90%PG | 104.0 |
丁基卡必醇 | 48.0 |
总的糊料组合物 | 8754.4 |
当取样用于第二表面烧结和测试时,该配比按照下表6进行变化。各样品含有6克的干组分和特定量的其它组分。称量玻璃组分(即玻璃料)、颜料和籽晶材料,并在混合机中将它们混合在一起,以形成上述干组分的均匀混合物。在下面的样品1和2的情况中,在混合步骤中添加BiONO3和MnO2。将干粉末与有机载体和氧化剂溶液一起放入混合容器中。将该材料混合在一起10分钟,用有机载体和氧化剂溶液润湿该干材料。使用三辊研磨机研磨混合的糊状材料,以进一步润湿该瓷漆材料并将其分散到载体中。使用丁基卡必醇溶剂进行最终的粘度调节。
表6.示例性测试的瓷漆组合物
样品号 | 1 | 2 | 3 | 4 |
组分(wt%) | ||||
玻璃组分 | 59.13 | 59.09 | 59.18 | 57.63 |
颜料 | 18.63 | 18.62 | 18.16 | |
颜料+0.3%NH4NO3 | 18.65 | |||
籽晶1 | 2.43 | 2.43 | 2.43 | 2.37 |
籽晶2 | 0.81 | 0.81 | 0.81 | 0.79 |
BiONO3 | 0.05 | 0.08 | ||
MnO2 | 0.05 | 0.08 | ||
6%NaNO3+94%丙二醇 | 1.35 | |||
10%NH4NO3+90%丙二醇 | 1.35 | 1.35 | 2.63 | |
有机载体 | 17.55 | 17.54 | 17.57 | 18.42 |
使用230目的聚酯丝网,将上述糊状组合物以3”×3”(7.6cm×7.6cm) 平方的尺寸丝网印刷到4”×4”(10.2cm×10.2cm)的碱石灰玻璃板上,并在115℃下干燥8分钟。将该印刷的板放平,并使印刷的侧面朝上,将另一未印刷的4”×4”(10.2cm×10.2cm)的碱石灰玻璃板叠放在印刷表面之上。然后将该叠放的玻璃板在特定的温度(例如1100、1120、1140(593℃、604℃、616℃))下烧制特定的时间(6或8分钟)。表7显示了在将玻璃板分开之后特定的瓷漆组合物的烧制形成的外观。
表7.烧制的瓷漆外观(颜色和烧尽)
本领域的技术人员容易想到其它的优点和改进。因此,本发明在较宽的范围内并不限定于此处所显示和所述的特定细节和实施例。因此,在不脱离由后附权利要求及其等价物所限定的一般发明概念的精神和范围的情况下,可以进行各种改进。
Claims (19)
1.一种形成装饰的玻璃结构的方法,包括:
a.在第一玻璃基体上涂覆结晶的瓷漆组合物,所述结晶的瓷漆组合物在烧制前包括:
i.20~80wt%的活性玻璃组分,
ii.0.01~7wt%的氧化剂组分,
iii.10~40wt%的颜料,
iv.10~40wt%的有机载体,和
v.小于3wt%的硅胶,
其中,各组分含量之和为100%,
b.将第二玻璃基体与第一玻璃基体堆叠,其中,该未烧制的结晶瓷漆组合物位于该第一和第二玻璃基体之间,以及
c.使所堆叠的玻璃基体进行烧制操作,由此:
i.未烧制的结晶瓷漆组合物熔合到第一玻璃基体上,
ii.所述有机载体被完全烧掉,以及
iii.所述玻璃基体没有彼此粘结。
2.如权利要求1的方法,其中,所述氧化剂组分包括分解释放出分子氧的无铅氧化剂,所述氧化剂具有每分子氧化剂至少2个氧原子,所述氧化剂选自以下组成的组:氧化物、硝酸盐、碳酸盐、硼酸盐、氟酸盐、氯酸盐、溴酸盐、碘酸盐、硫酸盐、磷酸盐、锰酸盐、高锰酸盐以及它们的组合。
3.如权利要求2的方法,其中,所述氧化剂独立地选自以下组成的组:
a.锑、铋、钙、镁、锰、镍、钾、钠、锶、碲或锌的氧化物和过氧化物;
b.钡、铋、钙、铯、钴、铜、锂、镁、钾、钠、锶或锡的硝酸盐和碱式硝酸盐;
c.钠或钾的氯酸盐;
d.钠或钾的溴酸盐;
e.钠或钾的硫酸盐;和
f.钠或钾的磷酸盐。
4.如权利要求1的方法,其中,所述氧化剂组分包括选自以下组成的组的氧化剂:硝酸铵、五氧化二锑、硝酸钡、五氧化二铋、碱式硝酸铋、四氧化二铋、硝酸钙、过氧化钙、硝酸铯、硝酸钴、硝酸铜、硝酸锂、过氧化镁、二氧化锰、氧化镍III、一氧化铂、二氧化铂、硝酸钾、过氧化钾、硝酸钠、过碳酸钠、过氧化钠、硝酸锶、过氧化锶、硝酸银、三氧化碲、硝酸锡、和过氧化锌以及它们的组合。
5.如权利要求1的方法,其中,所述氧化剂组分包括选自以下组成的组的氧化剂:硝酸铵、碱式硝酸铋、硝酸钠和二氧化锰以及它们的组合。
6.如权利要求1的方法,其中,所述氧化剂组分包括重量比为1∶2~2∶1的碱式硝酸铋和二氧化锰。
7.如权利要求1的方法,其中,所述氧化剂组分包括重量比为15∶1~2∶1的二氧化锰和硝酸钠。
8.如权利要求1的方法,其中,所述玻璃组分包括玻璃料,其中该玻璃料选自以下组成的组:硼硅酸铋玻璃料和硼硅酸锌玻璃料或它们的组合,其中:
a.所述硼硅酸铋玻璃料包括
i.9~75wt%的Bi2O3,
ii.0.1~28wt%的SiO2,和
iii.0.1~9wt%的B2O3,
b.所述硼硅酸锌玻璃料包括
i.21~50wt%ZnO,
ii.0.1~28wt%SiO2,和
iii.21~60wt%B2O3。
9.如权利要求1的方法,其中,所述该玻璃组分包括:
a.15~60wt%的Bi2O3,
b.5~50wt%的SiO2,
c.1~20wt%的B2O3,和
d.5~50wt%的ZnO。
10.如权利要求1的方法,其中,所述有机载体包括:
a.选自以下组成的组的粘结剂:甲基纤维素、乙基纤维素、和羟丙基纤
维素以及它们的组合,和
b.选自以下组成的组的溶剂:二甘醇丁基醚、2,2,4-三甲基戊二醇单异丁酸酯、α-萜品醇、β-萜品醇、γ-萜品醇、十三烷醇、二甘醇乙基醚、二甘醇二丁基醚以及它们的混合物。
11.如权利要求10的方法,其中,所述溶剂和所述粘结剂的重量比为50∶1~20∶1。
12.如权利要求1的方法,其中,所述未烧制的结晶瓷漆组合物进一步包含1~20wt%的籽晶材料,其中所述籽晶材料含有至少一种选自以下的相:Zn2SiO4、Bi12SiO20、Bi4(SiO4)3、Bi2SiO5、2ZnO·3TiO2、Bi2O3·SiO2、Bi2O3·2TiO2、2Bi2O3·3TiO2、Bi7Ti4NbO21、Bi4Ti3O12、Bi2Ti2O7、Bi12TiO20、Bi4Ti3O12和Bi2Ti4O11。
13.如权利要求1的方法,其中,所述烧制操作是在500℃~750℃的设定温度下进行的。
14.如权利要求1的方法,其中,在烧制前,所述结晶的瓷漆组合物包括:
a.20~80wt%的具有450℃~550℃的熔点的活性氧化物或硫化物玻璃料,
b.0.1~7wt%的氧化剂组分,其中该氧化剂组分包括至少一种以下组分:
i.D50为8~13微米的碱式硝酸铋,
ii.D50为1~5微米的二氧化锰,
iii.硝酸铵,和
iv.硝酸钠,
c.10~30wt%的无机颜料
d.1~5wt%的含铋籽晶材料
e.0~7wt%的含锌籽晶材料,和
f.10~40wt%的有机载体,其中该有机载体包括
i.0.5~5wt%的乙基纤维素,和
ii.95~99.5wt%的二甘醇一丁基醚。
15.如权利要求14的方法,其中,所述玻璃料进一步包含10~50wt%的具有580℃~680℃的熔点的活性玻璃料。
16.如权利要求14的方法,其中,该方法进一步包括通过以下工艺使加热的玻璃成形,所述工艺选自以下组成的组:用冲模使该玻璃经受成形压力,以及将该成形的玻璃与该冲模分开;或者使该玻璃经受重力下垂。
17.由权利要求1的方法所获得的装饰的玻璃结构。
18.如权利要求17的玻璃结构,其中,所述结构是汽车玻璃。
19.如权利要求18的玻璃结构,其中,所述瓷漆组合物被涂覆到玻璃基体的外围。
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US11/131,919 US7832233B2 (en) | 2005-05-18 | 2005-05-18 | Method of making staged burnout enamels for second surface firing of multilayer glass structures |
PCT/US2006/005288 WO2006124088A2 (en) | 2005-05-18 | 2006-02-15 | Method of making multilayer glass structures |
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EP1888333A4 (en) | 2011-08-31 |
PL1888333T3 (pl) | 2014-01-31 |
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US7832233B2 (en) | 2010-11-16 |
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WO2006124088A3 (en) | 2009-04-16 |
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