CN116768472A - Method for producing molten glass, method for producing glass article, and glass article - Google Patents
Method for producing molten glass, method for producing glass article, and glass article Download PDFInfo
- Publication number
- CN116768472A CN116768472A CN202310254218.9A CN202310254218A CN116768472A CN 116768472 A CN116768472 A CN 116768472A CN 202310254218 A CN202310254218 A CN 202310254218A CN 116768472 A CN116768472 A CN 116768472A
- Authority
- CN
- China
- Prior art keywords
- glass
- less
- cullet
- article
- content
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 273
- 239000006060 molten glass Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000006063 cullet Substances 0.000 claims abstract description 101
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims description 26
- 239000011247 coating layer Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000002344 surface layer Substances 0.000 claims description 16
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 150000002221 fluorine Chemical class 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 20
- 239000010410 layer Substances 0.000 description 43
- 230000003373 anti-fouling effect Effects 0.000 description 30
- 239000000463 material Substances 0.000 description 17
- 238000011282 treatment Methods 0.000 description 17
- 239000010955 niobium Substances 0.000 description 15
- 238000005530 etching Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- -1 oxides Chemical class 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000006059 cover glass Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide 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
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
The application provides a method for producing molten glass with less impurities. A method for producing molten glass by melting a glass raw material composition and cullet, wherein the cullet is obtained by removing at least a part of the surface of a glass article.
Description
Technical Field
The present application relates to a method for producing molten glass, a method for producing a glass article, and a glass article.
Background
In paragraph [0025] of patent document 1, "a glass raw material composition and, if necessary, cullet having the same glass composition as the target molten glass are continuously fed into a melting furnace, and the glass is heated to about 1600 to 1700 ℃ to be melted, thereby producing a molten glass".
In paragraph [0026] of patent document 1, "the molten glass obtained in the above-mentioned melting step is molded into a target shape, and then, if necessary, subjected to a slow cooling step. Then, in the post-processing step, post-processing such as cutting and polishing is performed by a known method as needed, whereby a glass article is obtained.
Prior art literature
Patent literature
Patent document 1: international publication No. 2018/088503
Patent document 2: japanese patent application laid-open No. 2018-197176
Disclosure of Invention
Conventionally, glass articles having a coating (an antifouling film, an antireflection film, a printed portion, etc.) disposed on a surface of a glass plate have been used, for example, as cover glasses for display devices or the like (patent document 2).
When a crushed product obtained by crushing such a glass article with a hammer is used as the crushed glass, the obtained molten glass becomes more contaminated.
Accordingly, an object of the present application is to provide a method for producing molten glass with less impurities.
As a result of intensive studies, the present inventors have found that the above object can be achieved by adopting the following constitution, and have accomplished the present application.
That is, the present application provides the following [1] to [16].
[1] A method for producing molten glass by melting a glass raw material composition and cullet obtained by removing at least a part of the surface of a glass article.
[2] The method for producing molten glass according to the above [1], wherein the particle size distribution of the cullet has a D50 of 10 μm to 3000 μm.
[3] The method for producing molten glass according to the above [1] or [2], wherein the cullet is obtained by simultaneously removing the surface of the glass article and adjusting the particle size.
[4] The method for producing molten glass according to any one of [1] to [3], wherein the glass article has a glass plate, and the glass plate is subjected to a chemical strengthening treatment.
[5]According to [4] above]The method for producing molten glass, wherein the cullet is used as the glass cullet 2 The O content is expressed as A in mole percent K K is obtained by centering the thickness of the glass plate 2 The O content is expressed as B in mole percent K K for coating the surface layer of the glass plate 2 The O content is expressed as C in mol% units K When the value obtained by calculating the following formula (1) is less than 0.1000.
|(A K －B K )/(C K －B K )|(1)
[6]According to [4] above]～[5]The method for producing molten glass according to any one of claims, wherein Li is the cullet 2 The O content is expressed as A in mole percent Li Li at the center of the thickness of the glass plate 2 The O content is expressed as B in mole percent Li Li for the surface layer of the glass sheet 2 The O content is expressed as C in mol% units Li When the value obtained by calculating the following formula (2) is less than 0.1000.
|(A Li －B Li )/(C Li －B Li )|(2)
[7]According to [4] above]～[6]The method for producing molten glass according to any one of claims, wherein the cullet is Na 2 The O content is expressed as A in mole percent Na Na at the center of the thickness of the glass plate 2 The O content is expressed as B in mole percent Na Na on the surface layer of the glass plate 2 O content in unit moleThe mol% is set as C Na When the value obtained by calculating the following formula (3) is less than 0.1000.
|(A Na －B Na )/(C Na －B Na )|(3)
[8] The method for producing molten glass according to any one of [1] to [7], wherein the glass article comprises a glass plate and a coating layer disposed on a surface of the glass plate.
[9] The method for producing molten glass according to the above [8], wherein the cullet has fluorine.
[10] The method for producing a molten glass according to the above [9], wherein the cullet has the fluorine as a fluorine-containing organosilicon compound.
[11] The method for producing molten glass according to any one of the above [1] to [10], wherein a mass ratio of the cullet to the glass raw material composition is 20/80 to 80/20.
[12] A method for producing a glass article, comprising using the molten glass produced by the method according to any one of the above [1] to [11 ].
[13] A glass article comprising, in mass ppm, a material selected from the group consisting of Nb: less than 100ppm, cu: less than 100ppm, cr: less than 5ppm, ni: less than 5ppm, mn: less than 40ppm, co: less than 3ppm, fe: less than 100ppm, ti: less than 600ppm, P: less than 200ppm, and Zn: less than 200ppm of at least 5 elements.
[14] The glass article according to the above [13], wherein the glass article further comprises, in mass ppm, li: less than 700ppm.
[15] The glass article according to the above [13] or [14], wherein the glass article comprises a glass and a coating layer disposed on a surface of the glass, and the coating layer contains at least 1 element selected from Nb, cu, cr, ni, mn, co, fe, ti, P and Zn in an amount of 10 mass ppm or more.
[16] The glass article according to the above [13] or [14], wherein the glass article comprises a glass and a coating layer disposed on a surface of the glass, and the coating layer contains at least 2 elements selected from Nb, cu, cr, ni, mn, co, fe, ti, P and Zn in an amount of 10 mass ppm or more, respectively.
According to the present application, a molten glass with less impurities is obtained.
Detailed Description
Hereinafter, preferred embodiments of the present application will be described.
However, the present application is not limited to the following embodiments. Various modifications and substitutions may be added to the following embodiments without departing from the spirit of the application.
The glass composition (oxide basis) of the glass raw material composition, cullet, and molten glass was determined by a known measurement method. Specifically, the measurement method is obtained by using, for example, a measurement method such as an X-ray fluorescence spectrum (XRF) analysis method or an ICP (inductively coupled plasma) luminescence spectrometry method, alone or in combination.
[ method for producing molten glass ]
The method for producing molten glass according to the present embodiment is a method for producing molten glass by melting a glass raw material composition and cullet obtained by removing at least a part of the surface of a glass article.
As described above, glass articles are known in which a coating (an antifouling film, an antireflection film, a printed portion, or the like) is disposed on the surface of a glass plate.
When a crushed product obtained by crushing such a glass article with a hammer is used as the crushed glass, the obtained molten glass becomes more contaminated.
However, according to the present embodiment, since the crushed material obtained by removing at least a part of the surface (coating layer in this case) of such a glass article is used as the crushed glass, impurities in the obtained molten glass are reduced.
Specifically, for example, when the content (unit: mass ppm) of the elements shown below is within the range shown below, it can be evaluated that the impurities are small in the obtained molten glass.
Nb: less than 100ppm
Cu: less than 100ppm
Cr: less than 5ppm
Ni: less than 5ppm
Mn: less than 40ppm
Co: less than 3ppm
Fe: less than 100ppm
Ti: less than 600ppm
P: less than 200ppm
Zn: less than 200ppm
Hereinafter, the method for producing molten glass according to the present embodiment will be described in more detail.
Glass raw material composition
The glass raw material composition contains a glass raw material. The kind and content of the glass raw material and the like are appropriately selected according to the composition (glass composition) of the target molten glass.
Silicon Source and aluminium Source
The glass raw material composition preferably contains a silicon source and an aluminum source as glass raw materials.
The silicon source is formed into SiO by melting 2 Examples of the compound (b) include silica sand.
The aluminum source is melted to become Al 2 O 3 Examples of the compound (d) include alumina.
The silicon source and the aluminum source may be used alone or in combination of 2 or more. The particle size is not particularly limited, and may be appropriately selected.
The ratio of silicon source to aluminum source (silicon source/aluminum source) is calculated as mole ratio on oxide basis (SiO 2 /Al 2 O 3 ) The total amount is preferably 2.5 or more, more preferably 4 or more. If it is within this range, the aluminum source is less likely to undergo melting residues.
On the other hand, for the reason that the silicon source is less likely to generate melting residues, it is preferably 15 or less, more preferably 12 or less.
Alkali Metal Source
The glass raw material composition may contain an alkali metal source as a glass raw material.
In the present specification, alkali metal means lithium (Li), sodium (Na) and potassium (K).
The alkali metal source is Li formed by melting 2 O、Na 2 O or K 2 O.
Examples of the alkali metal source include alkali metal carbonates, sulfates, nitrates, oxides, hydroxides, chlorides, and fluorides.
The alkali metal source may be used alone or in combination of 2 or more. The particle size is not particularly limited, and may be appropriately selected.
Alkaline-earth metal source
The glass raw material composition may contain an alkaline earth metal source as a glass raw material.
In the present specification, alkaline earth metal means magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).
The alkaline earth metal source is a compound that becomes MgO, caO, srO or BaO by melting.
Examples of the alkaline earth metal source include carbonates, sulfates, nitrates, oxides, hydroxides, chlorides, and fluorides of alkaline earth metals. In addition, a complex carbonate such as dolomite and a complex oxide such as calcined dolomite may be used.
The alkaline earth metal source may be used alone or in combination of 2 or more. The particle size is not particularly limited, and may be appropriately selected.
Other glass materials
The glass raw material composition may further contain other glass raw materials according to the target glass composition.
Specific examples of the other glass raw materials include tin oxide, titanium oxide, zirconium oxide, zircon, cerium oxide, antimony oxide, iron oxide, cobalt oxide, chromium oxide, copper oxide, nickel oxide, and yttrium oxide, and 1 kind of these may be used alone or 2 or more kinds may be used in combination.
Broken glass
Cullet is a glass-like article formed from 1 or 2 or more glass raw material compositions containing silicon, and is mainly glass cullet discharged during the process of producing glass or the like.
In recent years, glass articles having a coating layer (an anti-fouling film, an anti-reflective film, a printed portion, etc.) disposed on the surface of a glass plate have been used, for example, as cover glass for display devices, and the use of such glass articles as broken glass has been studied.
In contrast, cullet in the present embodiment is obtained by removing at least a part of the surface of a glass article (hereinafter, also referred to as "glass article for cullet") that is cullet. As described above, the impurity content of the molten glass obtained thereby becomes small.
Glass articles for cullet
In the present embodiment, as a glass article for cullet, a coated glass sheet having a glass sheet and a coating layer (an anti-fouling film, an anti-reflective film, a printed portion, or the like) disposed on a surface of the glass sheet is preferable.
Specific examples of the coated glass sheet include glass used as cover glass for display devices, and the like, and defective products generated during the production of such glass.
(glass plate)
Examples of the glass plate include glass plates made of a glass such as usual glass mainly composed of silica, for example, soda lime silicate glass, aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass.
The glass composition of the glass sheet is preferably a composition that is formable and strengthened by a chemical strengthening treatment.
(chemical strengthening treatment)
The glass sheet is preferably subjected to a chemical strengthening treatment.
The chemical strengthening treatment may be performed by a conventionally known method, for example, ion exchange is performed on the principal surface of the glass plate to form a surface layer having residual compressive stress. Specifically, alkali metal ions (e.g., li ions and/or Na ions) having a smaller ion radius, which are contained in the glass in the vicinity of the main surface of the glass sheet, are replaced with alkali metal ions (e.g., na ions and/or K ions) having a larger ion radius at a temperature equal to or lower than the glass transition point. Thereby, compressive stress remains on the principal surface of the glass plate, and the strength of the glass plate is improved.
The glass plate contains Li 2 In the case of O, the strength can be further improved by performing the chemical strengthening treatment 2 times or more. Specifically, for example, at the first timeIn the treatment, for example, the glass plate is brought into contact with an inorganic salt composition mainly containing sodium nitrate to perform ion exchange between Na and Li. Next, in the second treatment, for example, the glass plate is contacted with an inorganic salt composition mainly containing potassium nitrate to perform ion exchange between K and Na.
The surface Compressive Stress (CS) and depth of surface compressive stress layer (DOL) of the glass sheet after the chemical strengthening treatment are appropriately adjusted, CS is preferably 300MPa or more, and DOL is preferably 10 μm or more.
The thickness of the glass plate is, for example, 0.1mm to 5mm.
The size of the glass plate is appropriately selected according to the purpose.
(antifouling film)
The anti-fouling film easily eliminates contamination (fingerprints of people, etc.).
As a method for forming the antifouling film, any of dry methods such as vacuum vapor deposition, ion beam assisted vapor deposition, ion plating, sputtering, and plasma CVD, spin coating, dip coating, casting, slit coating, and spray coating can be used.
The constituent material of the antifouling film may be appropriately selected from materials capable of imparting antifouling property, water repellency, and oil repellency. Specifically, a fluorine-containing organosilicon compound is exemplified.
As the fluorine-containing organosilicon compound, for example, an organosilicon compound having at least 1 group selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group is suitably exemplified. The polyfluoropolyether group is a divalent group having a structure in which polyfluoropolyalkylene groups and etheric oxygen atoms are alternately bonded. The polyfluoroalkylene and polyfluoroalkyl groups may be perfluoroalkylene and perfluoroalkyl groups, respectively.
As the fluorine-containing organosilicon compound having at least 1 group selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group and a polyfluoroalkyl group, commercially available products can be used, and specific examples thereof include KP-801, KY178, KY-130, KY185 (manufactured by Xinyue chemical Co., ltd.), OPTOOL DSX, OPTOOL AES (manufactured by Dain Co., ltd.), S550 (manufactured by AGC Co., ltd.), and the like.
The thickness of the antifouling film is preferably 2nm or more, more preferably 4nm or more. On the other hand, the wavelength is preferably 20nm or less, more preferably 15nm or less, and still more preferably 10nm or less.
(antireflection film)
The antireflection film is a film that suppresses light reflection, and has a structure in which a high refractive index layer and a low refractive index layer are laminated, for example.
The high refractive index layer is, for example, a layer having a refractive index of 1.9 or more at a wavelength of 550nm, and the low refractive index layer is, for example, a layer having a refractive index of 1.6 or less at a wavelength of 550 nm.
The antireflection film may have a structure having 1 layer each of the high refractive index layer and the low refractive index layer, or may have a structure having 2 or more layers each of the high refractive index layer and the low refractive index layer. When the composition includes 2 or more layers of each of the high refractive index layer and the low refractive index layer, the high refractive index layer and the low refractive index layer are preferably alternately laminated.
The materials of the high refractive index layer and the low refractive index layer are selected in consideration of the degree of antireflection required, productivity, and the like.
Examples of the material constituting the high refractive index layer include materials containing an element such as Nb, ti, zr, ta, si, and specific examples thereof include niobium oxide (Nb 2 O 5 ) Titanium oxide (TiO) 2 ) Zirconium oxide (ZrO) 2 ) Tantalum oxide (Ta) 2 O 5 ) Silicon nitride, and the like.
As a material constituting the low refractive index layer, for example, a Si-containing material is exemplified, and as a specific example thereof, silicon oxide (SiO 2 ) Mixed oxides of Si and Sn, mixed oxides of Si and Zr, mixed oxides of Si and Al, and the like.
As a method for forming the antireflection film (high refractive index layer and low refractive index layer), for example, a conventionally known method using magnetron sputtering, pulse sputtering, AC sputtering, digital sputtering, or the like is given. For example, a glass plate is placed in a chamber filled with a mixed gas atmosphere of an inert gas and oxygen, and each layer is formed using a target containing a desired element.
The thickness of the antireflection film is, for example, 100 to 300nm.
(printing section)
The printed portion is formed in a frame shape on the surface of the glass plate to shield wiring of the display device and the like.
The printing portion is formed by printing a colored ink on a glass plate.
Examples of the printing method include bar coating, reverse coating, gravure coating, die coating, roll coating, and screen coating.
Examples of the coloring ink include organic inks containing a coloring material such as a dye or a pigment and an organic resin. The coloring ink is black or white in many cases, but the color thereof is not particularly limited.
The dye or pigment may be used without particular limitation.
Examples of the organic resin include homopolymers such as epoxy resins, acrylic resins, polyethylene terephthalate, polyethersulfone, polyarylate, polycarbonate, transparent ABS resins, phenol resins, acrylonitrile-butadiene-styrene resins, polyurethane, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, polyether ether ketone, polyethylene, polyester, polypropylene, polyamide, polyimide, and the like; copolymers of monomers of these resins with copolymerizable monomers, and the like.
The thickness of the printed portion is preferably 2 μm or more, more preferably 4 μm or more. On the other hand, the particle size is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less.
Treatment of glass articles for cullet
A case is considered in which the above-mentioned glass article for cullet (specifically, for example, a glass article having a coating layer on the surface of a glass plate) is crushed by a hammer to use a crushed product having a rough particle size adjusted as cullet.
In this case, the impurities in the obtained molten glass become large.
Accordingly, the surface of the glass article for cullet is removed to obtain cullet. Thus, the coating layer such as the anti-fouling film or the printed portion of the cullet is removed, and thus the impurity of the molten glass obtained is reduced.
The glass cullet article may be crushed, and the surface may be removed before or after crushing the glass cullet article.
As described later, the removal of the surface may be performed simultaneously with the pulverization or the particle size adjustment.
The glass article for cullet is preferably subjected to surface removal and particle size adjustment, and more preferably to surface removal and particle size adjustment simultaneously.
In this case, for example, a commercially available pulverizing apparatus (product name: micro-Sizer, manufactured by DONICO INTER Co.) can be suitably used.
In the Micro-Sizer, a plurality of impellers rotate, and a sample (for example, glass for crushed glass) to be put into the impeller is rubbed against each other by the force of the impellers and the wind of the impellers. According to the principle of air separation, only materials with the size below a specified size can be rolled up. Thus, the surface of the glass article for cullet is removed and the particle size is adjusted at the same time.
Particle size adjustment may be performed simultaneously with pulverization. That is, the glass cullet may be directly put into a Micro-Sizer and the particle size may be adjusted while being pulverized.
The surface of the glass article for cullet may be removed by other treatments, for example, sand blast treatment, acid treatment (etching), and the like.
The blasting treatment is a treatment of blasting abrasive grains (abrasive materials) such as steel grains and sand on the surface of a sample (glass article for cullet) with compressed air. Thereby, (at least a part of) the surface of the glass article for cullet is removed.
In the acid treatment (etching), specifically, an aqueous solution containing an acid is used as an etching solution to etch a sample (glass article for cullet). Thereby, the surface of the glass article for cullet is dissolved. That is, (at least a part of) the surface of the glass article for cullet is removed.
Examples of the acid contained in the etching solution include Hydrogen Fluoride (HF), sulfuric acid, nitric acid, hydrochloric acid, hexafluorosilicic acid, and the like, and hydrogen fluoride is preferable.
The etching method is not particularly limited, and for example, a method of immersing a sample (glass article for cullet) in an etching liquid is preferable.
The conditions such as the acid content in the etching liquid, the temperature of the etching liquid, and the immersion time (etching time) in the etching liquid can be appropriately adjusted.
The surface of the glass article for cullet may be removed by a treatment such as a blast treatment or an acid treatment, and then the particle size may be adjusted. Particle size adjustment is performed, for example, using the Micro-Sizer described above.
Particle size distribution of cullet
The particle size distribution of the cullet is preferably D50 of 10 μm to 3000 μm. Thus, the cullet is easily melted.
The D50 is more preferably 100 μm or more, still more preferably 200 μm or more. On the other hand, the D50 is more preferably 2500 μm or less, and still more preferably 2000 μm or less.
"D50" is 50% of the diameter of the cumulative ratio of the volume basis obtained by measuring the particle diameter by the laser diffraction method.
However, when glass articles for cullet are treated with Micro-sizers, impurities such as iron (Fe), chromium (Cr), and nickel (Ni) may be mixed into the resulting cullet. Therefore, it is preferable to remove these impurities from the cullet after the Micro-Sizer treatment by using a magnetic separator such as an electromagnetic separator.
In this case, the maximum particle diameter of the cullet is preferably 2000 μm or less, more preferably 1000 μm or less, for the reason that the cullet can be removed effectively.
The maximum particle size of the cullet is measured or controlled by, for example, sieving.
In addition, when the cullet is subjected to component inspection, the smaller the D50 of the cullet is, the better for the reason of reducing the deviation in sampling inspection.
Specifically, it is preferably 800 μm or less, more preferably 400 μm or less, further preferably 200 μm or less, particularly preferably 100 μm or less.
When the glass article for cullet has an anti-fouling film, cullet has fluorine as a constituent material of the anti-fouling film (for example, a fluorine-containing organosilicon compound).
Of course, the cullet may have fluorine in a form other than the constituent material of the anti-fouling film.
Formula (1), formula (2) and formula (3)
As described above, when the glass sheet of the glass article for cullet is subjected to the chemical strengthening treatment, the K amount of the surface layer (surface compressive stress layer) of the glass sheet is larger than the K amount of the center of the sheet thickness (the original K amount of the glass sheet). In addition, the Li amount and Na amount of the surface layer (surface compressive stress layer) of the glass plate are smaller than those of the center of the plate thickness (original Li amount and Na amount of the glass plate), respectively.
When such a glass sheet is directly formed into cullet, there is a possibility that a deviation from the target glass composition may occur.
Therefore, the potassium formula (1) (also simply referred to as "formula (1)"), the lithium formula (2) (also simply referred to as "formula (2)") and the sodium formula (3) (also simply referred to as "formula (3)") described below preferably satisfy the requirements described below.
Specifically, K of cullet 2 The O content is expressed as A in mole percent K K is obtained by centering the thickness of the glass plate 2 The O content is expressed as B in mole percent K K for coating the surface layer (surface compressive stress layer) of a glass sheet 2 The O content is expressed as C in mol% units K In the case of calculating the following formula (1), the value obtained is preferably less than 0.1000.
|(A K －B K )/(C K －B K )|(1)
In this case, the surface layer (surface compressive stress layer) of the glass plate is sufficiently removed.
The lower limit is not particularly limited, and for example, the calculated value of formula (1) exceeds 0.0001.
Also, li of cullet 2 The O content is expressed as A in mole percent Li Li at the center of the thickness of the glass plate 2 The O content is expressed as B in mole percent Li Li for coating the surface layer (surface compressive stress layer) of a glass sheet 2 The O content is expressed as C in mol% units Li In the case of calculating the following formula (2), the value obtained is preferably less than 0.1000.
|(A Li －B Li )/(C Li －B Li )|(2)
In this case, the surface layer (surface compressive stress layer) of the glass plate is sufficiently removed.
The lower limit is not particularly limited, and for example, the calculated value of formula (2) exceeds 0.0001.
Also, na of cullet 2 The O content is expressed as A in mole percent Na Na at the center of the thickness of the glass plate 2 The O content is expressed as B in mole percent Na Na of the surface layer (surface compressive stress layer) of the glass plate 2 The O content is expressed as C in mol% units Na In the case of calculating the following formula (3), the value obtained is preferably less than 0.1000.
|(A Na －B Na )/(C Na －B Na )|(3)
In this case, the surface layer (surface compressive stress layer) of the glass plate is sufficiently removed.
The lower limit is not particularly limited, and for example, the calculated value of formula (3) exceeds 0.0001.
Mass ratio
The mass ratio of the cullet to the glass raw material composition is preferably 20/80 to 80/20, more preferably 30/70 to 70/30.
Melting
The method for melting the glass raw material composition and cullet is not particularly limited, and conventionally known methods can be employed, and a method in which the glass raw material composition and cullet are charged into a melting furnace to be melted is preferable.
The mode of the melting furnace is not particularly limited, and may be a batch type or a continuous type.
For example, a glass raw material composition and cullet are continuously charged into a melting furnace according to a target glass composition, and are heated to a temperature of about 1600 to 1700 ℃ to be melted, thereby obtaining molten glass.
[ method for producing glass article and glass article ]
The method for producing a glass article according to the present embodiment is a method for producing a glass article using a molten glass produced by the method for producing a molten glass according to the present embodiment described above.
Specifically, for example, the obtained molten glass is molded into a desired shape, then slowly cooled as necessary, and then optionally subjected to post-processing such as cutting and polishing according to a known method. This gives a glass article (hereinafter, also simply referred to as "final glass article").
For example, when the final glass article is a glass sheet, the molten glass is formed into a plate shape by a known method such as a float method, a downdraw method, or a fusion method. Then, if necessary, the glass sheet is obtained by slow cooling.
The composition of the final glass article obtained by shaping the molten glass is substantially the same as the composition of the molten glass.
Therefore, the final glass article obtained in this embodiment has fewer impurities.
The final glass article is used as, for example, a glass for electronic devices (cover glass for display, etc.) which is a part of electronic devices such as a solar cell, a Liquid Crystal Display (LCD), an organic EL display (OLED), etc.
However, as described above, in the method for producing molten glass according to the present embodiment, a glass article from which a coating layer of a glass article for cullet (coated glass plate) is removed is used as cullet.
When the coating of the coated glass sheet is not completely removed, the resulting molten glass, and thus the final glass article, contains a certain amount of elements (trace elements) from the coating. In this case, the amount of change in trace elements becomes small, so that the quality of the final glass article as glass is stable.
Specifically, for example, the final glass article may contain, in mass ppm, a material selected from the group consisting of Nb: less than 100ppm, cu: less than 100ppm, cr: less than 5ppm, ni: less than 5ppm, mn: less than 40ppm, co: less than 3ppm, fe: less than 100ppm, ti: less than 600ppm, P: less than 200ppm, and Zn: less than 200ppm of at least 5 elements.
When the final glass article contains Nb, the Nb content exceeds 3ppm, for example.
When the final glass article contains Cu, the Cu content is, for example, more than 2ppm.
When the final glass article contains Cr, the Cr content exceeds 1ppm, for example.
When the final glass article contains Ni, the Ni content exceeds, for example, 0.5ppm.
When the final glass article contains Mn, the Mn content exceeds 7ppm, for example.
When the final glass article contains Co, the Co content is, for example, more than 0.5ppm.
When the final glass article contains Fe, the Fe content exceeds 30ppm, for example.
When the final glass article contains Ti, the Ti content is, for example, more than 2ppm.
When the final glass article contains P, the P content is, for example, more than 20ppm.
When the final glass article contains Zn, the Zn content is, for example, more than 5ppm.
The final glass article may further contain less than 700ppm by mass of Li. When the final glass article contains Li, the Li content exceeds 10ppm, for example.
The final glass article may have glass (e.g., a glass plate) and a coating (a printed portion, an antireflection film, an antifouling film, etc.) disposed on a surface of the glass.
The coating layer of the final glass article may be a coating layer containing at least 1 element selected from Nb, cu, cr, ni, mn, co, fe, ti, P and Zn in an amount of 10 mass ppm or more.
The coating layer of the final glass article may contain at least 2 elements selected from Nb, cu, cr, ni, mn, co, fe, ti, P and Zn in an amount of 10 mass ppm or more, respectively.
Examples
Hereinafter, embodiments of the present application will be specifically described with reference to examples. However, the present application is not limited to the following examples. Examples 1 to 7 are examples and example 8 is a comparative example.
Preparation of glass articles for cullet (coated glass sheets)
As a glass article for cullet, a coated glass sheet can be produced as follows.
Composition of glass plate
The composition of the glass plate (compositions A, B and E) is shown in Table 1 below.
TABLE 1
Chemical strengthening treatment
A glass plate (plate thickness: 0.7mm, dimensions: 70 mm. Times.140 mm) was subjected to a chemical strengthening treatment.
The glass sheets of compositions a and B were subjected to a 1-stage chemical strengthening treatment.
Specifically, the glass plate is treated with potassium nitrate (KNO 3 ) Immersing in molten salt melted by heating to 450 ℃ for 150 minutes. Then, the glass plate was pulled up from the molten salt and cooled slowly to room temperature over 1 hour.
The glass sheet of composition E was subjected to a 2-stage chemical strengthening treatment.
Specifically, first, a glass plate is subjected to a reaction between sodium nitrate (NaNO 3 ) Immersing in the molten salt melted by heating to 450 ℃ for 2.5 hours. Then, the glass plate was pulled up from the molten salt and cooled slowly to room temperature over 1 hour.
Next, the glass plate is subjected to a treatment of potassium nitrate (KNO 3 ) Immersing in molten salt melted by heating to 425 ℃ for 1.5 hours. Then, the glass plate was pulled up from the molten salt and cooled slowly to room temperature over 1 hour.
Table 2 below shows the surface Compressive Stress (CS) and depth of surface compressive stress layer (DOL) of the glass sheet subjected to the chemical strengthening treatment.
CS and DOL of compositions A and B and CS of composition E were measured using a surface stress meter (FSM-6000, manufactured by the folding source manufacturing company).
DOL of the composition E was measured using a scattered light photoelastic stress meter (SLP-2000, manufactured by the folding source manufacturing company).
TABLE 2
Coating (coating)
A coated glass sheet was produced by forming a coating layer (a printed portion, an antireflection film, and an antifouling film) on a glass sheet as follows.
The coating layer contains Ti and Nb in an amount of 10 mass ppm or more in total.
(printing section)
The printing was performed in a frame shape having a width of 10mm on one main surface (first main surface) of the glass plate in accordance with the following procedure to form a printed portion.
First, a black ink was applied to a thickness of 5 μm by a screen printer, and then kept at 150 ℃ for 10 minutes to dry, thereby forming a 1 st printing layer. Next, after the black ink was applied to the 1 st printing layer at a thickness of 5 μm in the same manner as above, the mixture was kept at 150 ℃ for 40 minutes and dried to form a 2 nd printing layer. Thus, a printed portion in which the 1 st printed layer and the 2 nd printed layer are laminated is formed.
As the black ink, a Ti-containing black ink (HFGV 3RX01, manufactured by Seiko corporation) was used.
(antireflection film)
Sequentially forming a high refractive index layer (Nb) on the other main surface (second main surface) of the glass plate by magnetron sputtering 2 O 5 ) A low refractive index layer (SiO 2 ) High refractive index layer (Nb) 2 O 5 ) A low refractive index layer (SiO 2 ) An antireflection film was formed at a total thickness of 250 nm.
(antifouling film)
An antifouling film was formed on the other main surface (second main surface) of the glass plate and on the antireflection film according to the following procedure.
First, as a material of the anti-fouling film, a solution of a fluorine-containing organosilicon compound is introduced into a heating vessel. Then, the heated vessel was degassed by a vacuum pump for 10 hours or longer to remove the solvent from the solution, and the solvent was used as an antifouling film forming composition.
KY185 (manufactured by Xinyue chemical Co., ltd.) was used as a material of the anti-fouling film.
Next, the heating vessel containing the composition for forming an antifouling film was heated to 270 ℃, and after reaching 270 ℃, the state was maintained for 10 minutes until the temperature was stable. Next, the glass plate is set in a vacuum chamber. Then, the antifouling film forming composition is supplied to the main surface (second main surface) of the glass plate from a nozzle connected to a heating vessel containing the antifouling film forming composition, thereby forming an antifouling film.
The thickness of the anti-fouling film was measured by a crystal oscillator tester provided in a vacuum chamber, and the anti-fouling film was formed until the thickness of the anti-fouling film reached 4nm.
Next, the glass plate taken out of the vacuum chamber was set on a hot plate with the anti-fouling film facing upward, and heat-treated in the atmosphere at 150 ℃ for 60 minutes.
Thus, an antifouling film is formed on the entire main surface (second main surface) of the glass plate.
Example 1
Molten glass was produced as follows.
Composition (target) of molten glass
As the composition of the target molten glass, a composition E is selected from the above compositions A, B and E. The composition (target) of the selected molten glass is shown in table 3 below.
The following glass raw materials were blended according to the target glass composition to prepare a glass raw material composition.
Silicon source: silica sand
Aluminum source: alumina oxide
Alkali metal source: lithium carbonate, sodium carbonate and potassium carbonate
Alkaline earth metal source: magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate
Other glass raw materials: zirconia, titania and yttria
Treatment of glass articles for cullet
The coated glass plate (glass article for cullet) of composition E was subjected to surface removal and particle size adjustment by 10 minutes treatment using a crushing apparatus (Micro-Sizer). Thus, cullet is obtained.
Broken glass
The D50 of the resultant cullet is shown in table 3 below.
Further, the calculated values of the above-mentioned potassium formula (1), lithium formula (2) and sodium formula (3) were obtained for the obtained cullet. The results are shown in Table 3 below.
The obtained cullet was passed through a sieve having a mesh size of 2mm, whereby cullet having a maximum particle diameter of 2000 μm or less was obtained.
The cullet was subjected to magnetic separation using a magnetic separator (model: DVF50-6, manufactured by Japanese Eriez Manufacturing Co., ltd.) and a drum separator (model: SREX12"ΦX12" W+NBR3t Liner), whereby impurities such as chromium (Cr) were removed.
The Cr content of the cullet was measured before and after the magnetic separation using an ICP mass spectrometer (manufactured by Agilent 8800,Agilent Technologies Co.). As a result, the Cr content of the cullet was 4.8 mass ppm before magnetic separation and 1.3 mass ppm after magnetic separation.
The Cr content of the cullet after magnetic separation was the same as that of the glass article for cullet before the Micro-Sizer treatment.
From this, it can be seen that: the use of a magnetic separator can effectively remove impurities by making the maximum particle diameter of the cullet be 2000 μm or less.
Mass ratio and melting
The glass raw material composition and cullet were mixed at a mass ratio of 60/40 (cullet/glass raw material composition) and placed in a crucible, and melted using a melting furnace.
The total amount of the glass raw material composition and cullet was set to 2kg in terms of glass mass.
As the crucible, an alumina crucible (product name: SSA-S, manufactured by NIKKATO Co., ltd., inner diameter 240mm, height 245 mm) was used.
As the melting furnace, a large electric furnace having two chambers of a traveling crucible holder and a heater provided in the upper part of each chamber is used. This is to reproduce the heating state of the upper combustion space for heating the molten glass from above in the continuous melting furnace.
To reproduce the temperature history of the melting furnace, first, heating was performed in the 1 st furnace chamber at 1350℃for 30 minutes (dew point 50 ℃) and then in the 2 nd furnace chamber at 1600℃for 180 minutes (dew point 50 ℃). Thereby obtaining molten glass.
Example 2
Molten glass was obtained in the same manner as in example 1 except that the mass ratio (cullet/glass raw material composition) was changed to 40/60.
Example 3
Molten glass was obtained in the same manner as in example 1 except that the mass ratio (cullet/glass raw material composition) was changed to 30/70.
Case 4
Molten glass was obtained in the same manner as in example 1 except that the treatment time with the crushing apparatus was changed to 7 minutes.
Example 5
Composition a was selected as the composition of the target molten glass, and a coated glass sheet of composition a was used as a glass article for cullet. Except for this, molten glass was obtained in the same manner as in example 1.
Example 6
The composition A was selected as the composition of the target molten glass, the coated glass sheet of the composition B was used as a glass article for cullet, and the mass ratio (cullet/glass raw material composition) was changed to 10/90. Except for this, molten glass was obtained in the same manner as in example 1.
Example 7
The glass article for cullet is first etched using an etching liquid. As the etching solution, an aqueous solution of 6 mass% Hydrogen Fluoride (HF) (liquid temperature: 25 ℃ C.) was used. The surface layer (surface) of the glass article for cullet was removed by etching to a thickness of 100. Mu.m.
Further, the glass article for cullet after etching was subjected to a treatment for 2 minutes using a crushing apparatus (Micro-Sizer). Thus, cullet is obtained.
Except for these points, molten glass was obtained in the same manner as in example 1.
Example 8
The crushed glass was obtained by treatment using a crushing apparatus (Micro-Sizer), and at this time, only the particle size adjustment was performed. That is, the removal of the surface is not performed. Except for this, molten glass was obtained in the same manner as in example 1.
Evaluation
The obtained molten glass was subjected to measurement using an inductively coupled plasma mass spectrometry device (ICP-MS) and an inductively coupled plasma emission spectrometry device (ICP-AES), and the contents (unit: mass ppm) of each element of Nb, cu, cr, ni, mn, co, fe, ti, P and Zn were obtained.
The content of each element is described as "a" in table 3 below when the content is within the range of the impurity concentration described below, and the content of any element is described as "C" in table 3 below when the content is outside the range of the upper limit value of the impurity concentration described below. As long as "A", a molten glass having less impurities can be produced.
Impurity concentration
Nb: less than 100ppm
Cu: less than 100ppm
Cr: less than 5pm
Ni: less than 5pm
Mn: less than 40ppm
Co: less than 3ppm
Fe: less than 100ppm
Ti: less than 600ppm
P: less than 200ppm
Zn: less than 200ppm
TABLE 3
Summary of evaluation results
From the above table 3, it can be seen that: the impurity concentration of example 8 was "C". In contrast, the impurity concentration of examples 1 to 7 was "a", and molten glass with few impurities could be produced.
While the application has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various modifications and alterations can be made therein without departing from the spirit and scope thereof.
The present application is based on Japanese patent applications 2022-44270 and 2023-6607 of 18/3/18/2023/1/19, the contents of which are incorporated herein by reference.
Claims (16)
1. A method for producing molten glass by melting a glass raw material composition and cullet obtained by removing at least a part of the surface of a glass article.
2. The method for producing molten glass according to claim 1, wherein the crushed glass has a particle size distribution D50 of 10 μm to 3000 μm.
3. The method for producing molten glass according to claim 1, wherein the cullet is obtained by simultaneously removing a surface of the glass article and adjusting a particle size.
4. The method for producing molten glass according to claim 1, wherein the glass article has a glass plate, and the glass plate is subjected to a chemical strengthening treatment.
5. The method for producing molten glass according to claim 4, wherein the cullet is K 2 The O content is expressed as A in mole percent K K is obtained by centering the thickness of the glass plate 2 The O content is expressed as B in mole percent K K for coating the surface layer of the glass plate 2 The O content is expressed as C in mol% units K When the value obtained by calculating the following formula (1) is less than 0.1000,
|(A K －B K )/(C K －B K )|(1)。
6. the method for producing molten glass according to claim 4, wherein Li of the cullet is 2 The O content is expressed as A in mole percent Li Li at the center of the thickness of the glass plate 2 The O content is expressed as B in mole percent Li Li for the surface layer of the glass sheet 2 The O content is expressed as C in mol% units Li When the value obtained by calculating the following formula (2) is less than 0.1000,
|(A Li －B Li )/(C Li －B Li )|(2)。
7. the method for producing molten glass according to claim 4, wherein the cullet is Na 2 The O content is expressed as A in mole percent Na Na at the center of the thickness of the glass plate 2 The O content is expressed as B in mole percent Na Na of the surface layer of the glass plate 2 The O content is expressed as C in mol% units Na When the value obtained by calculating the following formula (3) is less than 0.1000,
|(A Na －B Na )/(C Na －B Na )|(3)。
8. the method for producing molten glass according to claim 1, wherein the glass article has a glass plate and a coating layer disposed on a surface of the glass plate.
9. The method for producing molten glass according to claim 8, wherein the cullet has fluorine.
10. The method for producing molten glass according to claim 9, wherein the cullet has the fluorine in the form of a fluorine-containing organosilicon compound.
11. The method for producing molten glass according to claim 1, wherein a mass ratio of the cullet to the glass raw material composition is 20/80 to 80/20.
12. A method for producing a glass article, using the molten glass produced by the method according to any one of claims 1 to 11.
13. A glass article contains, in mass ppm, at least 5 elements selected from the group consisting of less than 100ppm Nb, less than 100ppm Cu, less than 5ppm Cr, less than 5ppm Ni, less than 40ppm Mn, less than 3ppm Co, less than 100ppm Fe, less than 600ppm Ti, less than 200ppm P, and less than 200ppm Zn.
14. The glass article of claim 13, wherein the glass article further comprises less than 700ppm Li in mass ppm.
15. The glass article according to claim 13, wherein the glass article comprises a glass and a coating layer disposed on a surface of the glass, wherein the coating layer contains at least 1 element selected from Nb, cu, cr, ni, mn, co, fe, ti, P and Zn in an amount of 10 mass ppm or more.
16. The glass article according to claim 13, wherein the glass article comprises a glass and a coating layer disposed on a surface of the glass, wherein the coating layer contains at least 2 elements selected from Nb, cu, cr, ni, mn, co, fe, ti, P and Zn in an amount of 10 mass ppm or more, respectively.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-044270 | 2022-03-18 | ||
| JP2023006607A JP2023138333A (en) | 2022-03-18 | 2023-01-19 | Manufacturing method of molten glass, manufacturing method of glass article and glass article |
| JP2023-006607 | 2023-01-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116768472A true CN116768472A (en) | 2023-09-19 |
Family
ID=87993781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310254218.9A Pending CN116768472A (en) | 2022-03-18 | 2023-03-16 | Method for producing molten glass, method for producing glass article, and glass article |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116768472A (en) |
-
2023
- 2023-03-16 CN CN202310254218.9A patent/CN116768472A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109415242B (en) | Chemically temperable glass sheet | |
| CN111718131B (en) | Cover glass | |
| JP6582974B2 (en) | Cover glass and manufacturing method thereof | |
| CN107531546B (en) | Chemically temperable glass sheet | |
| CN107082562B (en) | Optical glass, optical element, and preform for precision press molding | |
| DE112016002132T5 (en) | Base with a film with low reflection | |
| CN107001111A (en) | The glass plate being chemically tempered | |
| CN113233789B (en) | Recycling method of reinforced microcrystalline glass | |
| KR20180004141A (en) | Glass plate that can control warp through chemical strengthening | |
| CN114590996A (en) | Optical glass, preform, and optical element | |
| EP3303237B1 (en) | Glass sheet capable of having controlled warping through chemical strengthening | |
| TW201900405A (en) | Covering member, manufacturing method of cover member, and display device | |
| DE102017010360A1 (en) | SUBSTRATE WITH THE CHARACTER OF A LOW REFLECTION AND METHOD OF MANUFACTURING THEREOF | |
| CN111727177A (en) | Cover glass and in-cell liquid crystal display device | |
| JP2020033202A (en) | Crystallized glass substrate, chemically strengthened glass plate, and method for producing the same | |
| EP3747840B1 (en) | Optical glass and optical component | |
| CN116768472A (en) | Method for producing molten glass, method for producing glass article, and glass article | |
| JP2018080096A (en) | Cover glass, display device and manufacturing method of cover glass | |
| WO2024004807A1 (en) | Manufacturing method of glass plate | |
| JP2023138333A (en) | Manufacturing method of molten glass, manufacturing method of glass article and glass article | |
| WO2022025011A1 (en) | Chemically strengthened crystallized glass and method for manufacturing same | |
| CN113454040B (en) | Glass substrate with antifouling layer and method for producing glass substrate with antifouling layer | |
| CN111683907A (en) | Dimensionally stable and fast etching of glass | |
| CN116924683B (en) | Magnesium aluminum silicon microcrystalline glass with high transparency and high strength and preparation method thereof | |
| JP4370704B2 (en) | Glass coloring method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |