CN112897888A - Method of making a glass substrate having a textured surface - Google Patents
Method of making a glass substrate having a textured surface Download PDFInfo
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- CN112897888A CN112897888A CN201911229117.6A CN201911229117A CN112897888A CN 112897888 A CN112897888 A CN 112897888A CN 201911229117 A CN201911229117 A CN 201911229117A CN 112897888 A CN112897888 A CN 112897888A
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- glass substrate
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- 239000011521 glass Substances 0.000 title claims abstract description 274
- 239000000758 substrate Substances 0.000 title claims abstract description 256
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000000243 solution Substances 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 120
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 73
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 72
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 72
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 72
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 72
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 229910003638 H2SiF6 Inorganic materials 0.000 claims abstract description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 87
- 229910052593 corundum Inorganic materials 0.000 claims description 83
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 83
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 74
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 61
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 36
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 36
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- 230000005540 biological transmission Effects 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000741 silica gel Substances 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 17
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 229910052788 barium Inorganic materials 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910052712 strontium Inorganic materials 0.000 claims description 15
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052792 caesium Inorganic materials 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 9
- 229910016341 Al2O3 ZrO2 Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 claims description 6
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 4
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000004436 sodium atom Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 83
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 64
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 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 11
- -1 Li)2O Inorganic materials 0.000 description 11
- 230000004313 glare Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 9
- 230000006870 function Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229910004074 SiF6 Inorganic materials 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000005407 aluminoborosilicate glass Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 159000000011 group IA salts Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 229910001409 divalent cation oxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000016776 visual perception Effects 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/08—Glass having a rough surface
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)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The present application relates to methods of making glass substrates having textured surfaces. A method of making a glass substrate having a textured surface comprises: contacting an initial surface of a glass substrate with a first solution comprising dissolved SiO2、H2SiF6And H3BO3Thereby forming a porous layer adjacent to the initial surface; and contacting the porous layer with a second solution comprising one or more basic salts, thereby removing the porous layer and creating a new surface that has an increased texture compared to the original surface. The first solution may be an aqueous solution comprising: 0.5 to 0.8M dissolved SiO20.5 to 2M H2SiF6And 20 to 60mM H3BO3. The temperature of the first solution is 25 ℃ to 40 ℃. The initial surface of the glass substrate may be contacted with the first solution for a period of time ranging from 5 minutes to 2.5 hours.
Description
Technical Field
The present invention relates generally to methods of making glass substrates having textured surfaces.
Background
There are many devices, applications and situations where it is desirable to view an object through an intervening transparent medium, such as glass. For example, some cell phones, computer displays, televisions, and appliances employ displays that include a transparent cover through which the display is viewed. Similarly, windows, windshields, glass for covering photographs and other art, and aquariums, among others, involve viewing objects through an intervening transparent medium.
However, glare is sometimes a problem when attempting to view a display in the open or brightly lit environment. Herein, "glare" may be defined as the substantially specular reflection of ambient light from one or more surfaces of the transparent cover on the viewer side of the transparent cover. Thus, glare passes through the light path from the ambient light source to the transparent covered surface and then to the viewer, with the angle of incidence substantially equal to the angle of reflection. Object light (object light), on the other hand, moves from an object (e.g., a display) through the transparent overlay to the viewer. When the optical paths of the glare and the object light substantially overlap in the area between the transparent cover and the viewer, the glare makes it more difficult to view the object through the intervening transparent cover.
To reduce such glare, the viewer side of the transparent cover is sometimes modified by removing material from the surface of the transparent cover to provide a new surface with increased texture (sometimes referred to as "roughening" or "texturing"). The modified surface converts light reflected from the surface to diffuse reflection rather than specular reflection. The amount of light reflected from the surface does not change. Instead, only the characteristics of the reflected light are changed, so that the reflected image has no sharp boundary. The modified surface is sometimes referred to as an "anti-glare" surface.
Heretofore, hydrofluoric acid (sometimes referred to as "wet chemical etching") has been used in certain processes to texture the desired surface of the transparent cover. In the case of glass, hydrofluoric acid (HF) dissolves the silica network. In addition to providing surface texture for anti-glare purposes, glass is wet etched with hydrofluoric acid to smooth out or polish out small defects (e.g., scratches in the glass surface) to improve strength. Frost-based hydrofluoric acid etchants are used by hobbyists to etch decorative designs in glass.
However, there is a problem in that hydrofluoric acid has been exposed to cold for various reasons. Non-hydrofluoric acid processes have been attempted. However, these processes take too long (up to 48 hours) and require elevated temperatures (e.g., 95 ℃), which in turn leads to increased energy costs. Therefore, a wet etching process that does not directly use hydrofluoric acid but is fast enough and energy efficient enough is needed for commercial production.
Disclosure of Invention
The present disclosure solves this problem by a two-solution method that uses a first solution comprising dissolved SiO to form a porous layer on a surface requiring texturing2(e.g. from SiO)2Dissolution of gel), H2SiF6And H3BO3. The method then uses a second solution comprising an alkaline salt (e.g., an alkaline hydroxide) to dissolve the porous layer and leave a more textured surface. A more textured surface produces less glare. Neither the first solution nor the second solution uses hydrofluoric acid directly. The porous layer may be created at room temperature and over a period of several hours.
According to a first aspect of the present disclosure, a method of making a glass substrate having a textured surface comprises: contacting an initial surface of a glass substrate with a first solution comprising dissolved SiO2、H2SiF6And H3BO3Thereby forming a porous layer adjacent to the initial surface; and contacting the porous layer with a second solution comprising one or more basic salts, thereby removing the porous layer and creating a new surface that has an increased texture compared to the original surface. In an embodiment, the thickness of the glass substrate is 100 μm to 2.1mm before contacting the initial surface of the glass substrate with the first solution. In an embodiment, the method further comprises: contacting the initial surface of the glass substrate with a decontaminating agent in an ultrasonic bath prior to contacting the initial surface of the glass substrate with the first solution. In embodiments, the first solution is an aqueous solution comprising: 0.5 to 0.8M dissolved SiO20.5 to 2 mol/L H2SiF6(ii) a And 20 to 60 mmoles/L H3BO3. In an embodiment, the method further comprises preparing the first solution by, prior to contacting the initial surface of the glass substrate with the first solution: (i) in the presence of H2SiF6In the aqueous solution of (2), SiO is dissolved from the silica gel2(ii) a And (ii) to contain H2SiF6And dissolved SiO2The aqueous solution of (a) contains H3BO3An aqueous solution of (a). In an embodiment, preparing the first solution further comprises: in the presence of H2SiF6From an aqueous solution of (A) dissolving SiO from a silica gel2Thereafter, but in the direction containing H2SiF6And dissolved SiO2The aqueous solution of (a) contains H3BO3Before the aqueous solution of (a), filtering the undissolved silica gel from the aqueous solution. In an embodiment, the temperature of the first solution is 25 ℃ to 40 ℃. In an embodiment, the initial surface of the glass substrate is contacted with the first solution for a period of time from 5 minutes to 6 hours. In an embodiment, the initial surface of the glass substrate is contacted with the first solution for a period of time from 5 minutes to 2.5 hours. In an embodiment, the method further comprises: after contacting the initial surface of the glass substrate with the first solution, but before contacting the porous layer with the second solution, the porous layer is washed with deionized water. In an embodiment, the one or more basic salts comprise KOH. In embodiments, the temperature of the second solution is from room temperature to 80 ℃. In an embodiment, the method further comprises: the new surface is washed with water and the glass substrate is subjected to a temperature of 70 ℃ to 130 ℃ for a period of 15 minutes to 45 minutes. In an embodiment, the porous layer has a thickness of 400nm to 600 nm.
In an embodiment, the composition of the glass substrate in the bulk comprises: 9.39 to 18 mol% alumina; 6 to 20 mol% Na2O; up to 9.01 mole% boron oxide; and at least one alkaline earth metal oxide, wherein-15 mol% < R2O+R′O-Al2O3-ZrO2)-B2O32 mol% or less, wherein R is Na and optionally one or more of: li, K, Rb and Cs, and R' is one or more of Mg, Ca, Sr and Ba. In an embodiment, the composition of the glass substrate in the bulk comprises: 1 to 10 mol% P2O5(ii) a MgO; and at least 5 mol% Al2O3(ii) a Wherein 77 mol% SiO is more than or equal to2+Al2O3Not less than 70 mol% and sigma R' O not more than 0.5P2O5(mol%), wherein R' is Mg, Ca, Ba and Sr, and wherein the glass comprises at least one monovalent metal oxide modifier R2O, wherein P2O5≤[Σ(R2O)-Al2O3]. In an embodiment, the composition of the glass substrate in the bulk comprises: 1 to 10 mol% P2O5(ii) a MgO; and 3 to 25 mol% Na2O; wherein 77 mol% SiO is more than or equal to2+Al2O3Not less than 70 mol% and sigma R' O not more than 0.5P2O5(mol%), wherein R' is Mg, Ca, Ba and Sr, wherein P is2O5≤[(Na2O+K2O+Rb2O+Ag2O+Cs2O)-Al2O3]. In an embodiment, the composition of the glass substrate in the bulk comprises: 60 to 72 mol% SiO2(ii) a 6 to 14 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 0 to 1 mol% Li2O; 0 to 20 mol% Na2O; 0 to 10 mol% K2O; 0 to 8 mol% MgO; 0 to 10 mol% CaO; 0 to 5 mol% ZrO2(ii) a 0 to 1 mol% SnO2(ii) a 0 to 1 mol% CeO2(ii) a Less than 50ppm As2O3(ii) a And less than 50ppm Sb2O3(ii) a Wherein, Li is more than or equal to 12 mol percent2O+Na2O+K2O is less than or equal to 20 mol percent; and wherein MgO + CaO is in a proportion of 0 mol% to 10 mol%. In an embodiment, the composition of the glass substrate in the bulk comprises: at least 50 mol% SiO2(ii) a Less than 10 mol% B2O3(ii) a And at least 8 mol% Na2O; at least 8 mol% Na2O, wherein
And wherein Al2O3(mol%)>B2O3(mol%) and the modifier is Na2O and optionally other than Na2O and Li2One or more alkali metal oxides R other than O2At least one of O, and one or more alkaline earth oxides. In an embodiment, the composition of the glass substrate in the bulk comprises: 50 to 72 mol% SiO2(ii) a 9 to 17 mol% Al2O3(ii) a Less than 10 mol% B2O3(ii) a 8 to 16 mol% Na2O; and 0 to 4 mol% K2O, wherein
Wherein, Al2O3(mol%)>B2O3(mol%) and the modifier is Na2O and optionally other than Na2O and Li2One or more alkali metal oxides R other than O2At least one of O, and one or more alkaline earth oxides RO; and wherein the aluminoborosilicate glass is lithium-free. In an embodiment, the composition of the glass substrate in the bulk comprises: at least about 50 mol% SiO2(ii) a At least about 10 mol% R2O, wherein R2O comprises Na2O；Al2O3Wherein Al is2O3(mol%)<R2O (mol%); 3 to 4.5 mol% B2O3(ii) a And at least 0.1 mol% of at least one of MgO and ZnO; wherein, B2O3(mol%) - (R)2O (mol%) -Al2O3(mol%)) is more than or equal to 3 mol%.
In an embodiment, the new surface has concave surface features.
In an embodiment, the composition of the glass substrate in the bulk comprises: 62 to 70 mol% SiO2(ii) a 0 to 18 mol% Al2O3(ii) a 0 to 10 mol% B2O3(ii) a 0 to 15Li2O; 0 to 20 mol% Na2O; 0 to 18 mol% K2O; 0 to 17 mol% MgO; 0 to 18 mol% CaO; and 0 to 5 mol% ZrO2(ii) a Wherein R is more than or equal to 14 mol percent2O + R 'O is less than or equal to 25 mol percent, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr; wherein, 10 mol percent is less than or equal to Al2O3+B2O3+ ZrO less than or equal to 30 mol%; and wherein-15 mol% < R2O+R′O-Al2O3-ZrO2)-B2O3Less than or equal to 4 mol percent; and wherein the new surface has concave surface features having an average diameter of 650nm to 750nm and an average peak to valley height of 60nm to 80 nm. In an embodiment, a glass substrate having a new surface has: distinctness of image from 92 to 99%, gloss-60 from 100 to 145GU, transmission haze from 0.25 to 7.5%, flash value less than 3.5% and transmission greater than 93%.
In an embodiment, the composition of the glass substrate in the bulk comprises: 62 to 67 mol% SiO2(ii) a 3 to 7 mol% B2O3(ii) a 12 to 15 mol% Al2O3(ii) a 12 to 15 mol% Na2O; 0 mol% K2O; 1 to 3.5 mol% MgO; 0 mol% CaO; 0.02 to 0.14 mol% SnO2(ii) a And the new surface has concave surface features having an average diameter of 2.5 μm to 3.5 μm and an average peak to valley height of 650nm to 850 nm.
In an embodiment, the composition of the glass substrate in the bulk comprises: 45 to 65 mol% SiO2(ii) a 14 to 25 mol% Al2O3(ii) a 4 to 15 mol% P2O5(ii) a And 14 to 20 mol% Na2O; wherein the new surface has concave surface features having an average diameter of 9 to 15 μm and an average peak to valley height of 3.5 to 7.5 μm. In an embodiment, the composition of the glass substrate in the bulk comprises: 57.43 mol% SiO2(ii) a 16.10 mol% Al2O3(ii) a 6.54 mol% P2O5(ii) a 17.05 mol% Na2O; 2.81 mol% MgO; and 0.07 mol% SnO2。
In an embodiment, the porous layer comprises fluorine atoms and hydrogen atoms in absolute concentrations greater than the bulk of the glass substrate. In an embodiment, the porous layer comprises aluminum atoms and sodium atoms at a concentration less than the bulk of the glass substrate.
According to a second aspect of the present disclosure, a method of making a glass substrate having a textured surface comprises: contacting the initial surface of the glass substrate with a first solution at a temperature of 25 ℃ to 40 ℃ and comprising 0.5 to 0.8M dissolved SiO for a period of time of 5 minutes to 2.5 hours20.5 to 2M H2SiF6And 20 to 60mM H3BO3Thereby forming a porous layer adjacent to the initial surface, the porous layer having a thickness of 400nm to 600nm and containing fluorine atoms and hydrogen atoms at a concentration greater than that of the bulk of the glass substrate; and contacting the porous layer with a second solution in an ultrasonic bath, the second solution having a temperature of 40 ℃ to 80 ℃ and comprising one or more alkaline hydroxides, thereby removing the porous layer and producing a new surface with increased texture compared to the original surface, the new surface having concave surface features.
In an embodiment, a glass substrate having a new surface has: distinctness of image from 92 to 99%, gloss-60 from 100 to 145GU, transmission haze from 0.25 to 7.5%, flash value less than 3.5% and transmission greater than 93%. In an embodiment, the concave surface feature has one of: (i) an average diameter of 650nm to 750nm, and an average peak-to-valley height of 60nm to 80 nm; (ii) an average diameter of 2.5 to 3.5 μm, and an average peak-to-valley height of 650 to 850 nm; or (iii) an average diameter of 9 μm to 15 μm and an average peak-to-valley height of 3.5 μm to 7.5 μm.
According to a third aspect of the present disclosure, a glass substrate comprises a bulk composition comprising: 45 to 65 mol% SiO2(ii) a 14 to 25 mol% Al2O3(ii) a 4 to 15 mol% P2O5(ii) a And 14 to 20 mol% Na2O; and a surface comprising concave surface features having an average diameter of 9 μm to 15 μm and 3.5 μm to 7An average peak to valley height of 5 μm. In an embodiment, the glass substrate further comprises: distinctness of image from 22 to 27%, gloss-60 from 95 to 105GU, transmission haze from 2.5 to 7.5%, flash value from 12 to 16%, and transmission from 93.5 to 94.5%.
According to a fourth aspect of the present disclosure, a glass substrate comprises a bulk composition comprising: 62 to 67 mol% SiO2(ii) a 3 to 7 mol% B2O3(ii) a 12 to 15 mol% Al2O3(ii) a 12 to 15 mol% Na2O; 0 mol% K2O; 1 to 3.5 mol% MgO; 0 mol% CaO; and 0.02 to 0.14 mol% SnO2(ii) a And a surface comprising concave surface features having an average diameter of 2.5 μ ι η to 3.5 μ ι η and an average peak to valley height of 650nm to 850 nm.
In a fifth aspect of the disclosure, a glass substrate comprises a bulk composition comprising: 62 to 70 mol% SiO2(ii) a 0 to 18 mol% Al2O3(ii) a 0 to 10 mol% B2O3(ii) a 0 to 15 mol% Li2O; 0 to 20 mol% Na2O; 0 to 18 mol% K2O; 0 to 17 mol% MgO; 0 to 18 mol% CaO; and 0 to 5 mol% ZrO2(ii) a Wherein R is more than or equal to 14 mol percent2O + R 'O is less than or equal to 25 mol percent, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr; wherein, 10 mol percent is less than or equal to Al2O3+B2O3+ ZrO less than or equal to 30 mol%; and a surface comprising concave surface features having an average diameter of 650nm to 750nm and an average peak to valley height of 60nm to 80 nm. In an embodiment, the glass substrate further comprises: distinctness of image from 92 to 99%, gloss-60 from 100 to 145GU, transmission haze from 0.25 to 7.5%, flash value less than 3.5% and transmission greater than 93%.
Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operations of the various embodiments.
Drawings
FIG. 1 is a flow chart of a method of making a glass substrate having a textured surface showing the steps of: contacting a glass substrate having an initial surface with a first solution to produce a porous layer adjacent to the initial surface; and thereafter contacting the glass substrate with a second solution to remove the porous layer and create a new surface having surface features that provide a texture that reduces glare;
FIG. 2 is a prospective view of an embodiment of a glass substrate modified according to the method of FIG. 1, showing that the glass substrate has major surfaces facing in opposite directions and separated by a thickness, and one of the major surfaces is an initial surface to be contacted with a first solution of the method of FIG. 1;
FIG. 3 is a cross-sectional view of the glass substrate of FIG. 2 taken along line CS-CS of FIG. 2, showing that the glass substrate comprises a bulk located at the center of the glass substrate and that the initial surface of the glass substrate has little surface roughness;
FIG. 4 is another cross-sectional view of the glass substrate of FIG. 2 taken along line CS-CS of FIG. 2, but after the step of creating the porous layer of the method of FIG. 1, showing the porous layer having a thickness adjacent to the initial layer and extending toward the bulk;
FIG. 5 is another cross-sectional view of the glass substrate of FIG. 2 taken along line CS-CS of FIG. 2, but after the step of removing the porous layer and creating a new surface of the method of FIG. 1, showing the new surface having concave surface features with peaks and valleys, an average diameter, and an average peak to valley height;
FIG. 6 is a graph of the results of a Secondary Ion Mass Spectrometry (SIMS) analysis of the glass substrate after the step of creating the porous layer of the method of FIG. 1, showing: (a) the relative concentration of atomic silicon in the porous layer is increased compared to the bulk due to leaching of other elements from the porous layer into the first solution; (b) the absolute concentrations of atomic hydrogen and fluorine in the porous layer are increased compared to the bulk due to migration from the first solution to the porous layer; and (c) the absolute concentrations of atomic aluminum and sodium in the porous layer are reduced compared to the bulk due to migration from the glass substrate into the first solution.
Fig. 7 is a scanning electron microscope picture array of the following glass substrates: after the step of the method of fig. 1 of creating a porous layer (panel a, cross-section); and after the step of the method of FIG. 1 to remove the porous layer to reveal a new surface (panels B and C, cross-section; and panel D top view), the porous layer is shown in panel A, and the surface features are shown in panels B-D;
FIG. 8 is an array of scanning electron microscope pictures of a glass substrate (different in composition from the glass substrate of FIG. 7) after the method of FIG. 1, showing surface features in pictures A-D, and those surface features having a wider diameter and a higher peak-to-valley height than the glass substrate of FIG. 7; and
fig. 9 is a scanning electron microscope picture array of a glass substrate (different in composition from the glass substrates of fig. 7 and 8) after the method of fig. 1, showing surface features in pictures a-D, and those surface features having a wider diameter and a higher peak to valley height than the glass substrates of fig. 7 and 8.
Detailed Description
Reference will now be made in detail to the preferred embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
A method overview and a glass substrate. Referring now to fig. 1-5, a method 10 of making a glass substrate 12 having a textured surface is described herein. Referring specifically to fig. 2 and 3, prior to the method 10, the glass substrate 12 includes an initial surface 14, which may be one of several major surfaces 16, 18 of the glass substrate 12. All or all of the major surfaces 16, 18 may be treated according to this method 10The portion is textured. The initial surface 14 of the glass substrate 12 will typically have less than desirable texture with insignificant surface features, through lower surface roughness (e.g., R)rmsValues 1 to 3 nm). In an embodiment, the glass substrate 12 is a sheet having a thickness 20 between opposing parallel major surfaces 16, 18 facing generally in opposite directions. In embodiments, the thickness 20 is 100 μm to 2.1mm, such as 0.4mm to 2.0mm, for example about 1.1 mm. However, the glass substrate 12 may have a thickness 20 greater than 2.1 mm. Herein, the surface roughness R is measured using an atomic force microscopermsSpecifically, an atomic force microscope controlled by a NanoVi control station distributed by Seiko Instruments Inc. (Qianye, Japan) was used. Herein, the thickness 20 was measured using a micrometer, specifically a 293-242 micrometer distributed by Mitutoyo Corporation (Mitutoyo Corporation), kawasaki, japan.
Referring specifically to fig. 4, during method 10, as further explained, a porous layer 22 is created adjacent to initial surface 14. Porous layer 22 has a thickness 24 that extends from initial surface 14 toward a bulk 26 of glass substrate 12. For purposes herein, the bulk 26 is a central region of the glass substrate 12. In an embodiment, porous layer 22 has a thickness 24 of 400nm to 600 nm. However, in other embodiments, the thickness 24 of porous layer 22 may be greater than 600nm or less than 400 nm. The thickness 24 is a function of the conditions of the method 10 and the composition of the bulk 26 of the glass substrate 12. As set forth in detail below, method 10 results in porous layer 22 having a chemical composition that is different than bulk 26 of glass substrate 12. Herein, thickness 24 of porous layer 22 is measured by a scanning electron microscope, specifically, an S-4800 scanning electron microscope distributed by Hitachi High-Technologies Corporation (Tokyo, Japan).
Referring specifically to fig. 5, method 10 removes porous layer 22 to create a new surface 28. In embodiments, method 10 removes all or substantially all of porous layer 22. The new surface 28 has an increased texture compared to the original surface 14; or the new surface 28 may have at least a desired texture as compared to the original surface 14. The new surface 28 has surface features 30. In an embodiment, the surface features 30 are generally concave with a plurality of peaks 32, each peak 32 being adjacent to one or more valleys 34. In an embodiment, the peaks 32 of the surface features 30 are substantially circular. In such embodiments, the surface features 30 have an average diameter 36 and an average peak-to-valley height 38. These structural aspects are discussed further below. Herein, the average diameter 36 and the average peak-to-valley height 38 are measured by a scanning electron microscope, specifically, an S-4800 scanning electron microscope distributed by Hitachi High-Technologies Corporation (Tokyo, Japan).
The method 10 is compatible with a wide variety of glass substrates 12, including those described below: corning, U.S. patent No. 8,969,226 (entitled "Glasses Having Improved Toughness and Scratch Resistance"); no. 9,540,278 entitled "Ion Exchangeable Glasses"; no. 8,158,543 (entitled "Fining Agents for Silicate Glasses"); no. 8,431,502 (entitled "Silicate Glasses Having Low Seed Concentration"); 8,586,492 (entitled "Crack and Scratch Resistant Glass and Enclosures Made Therefrom"); and No. 8,946,103 entitled "zirconium Compatible Glass With High large Resistance", which are all incorporated herein by reference in their entirety.
In an embodiment, the glass substrate 12 is an alkali aluminosilicate glass substrate. In an embodiment, the alkali of the alkali aluminosilicate glass substrate is sodium. In embodiments, the alkali aluminosilicate glasses described herein are substantially free of lithium. As used herein, "substantially free of lithium" means that lithium is not purposefully added to the glass or glass raw materials during any processing steps to form the alkali aluminosilicate glass. It is to be understood that glass substrates 12 that are substantially free of lithium may inadvertently contain small amounts of lithium due to contamination. In embodiments, the glass substrate 12 is an aluminoborosilicate glass, i.e., a glass that contains both alumina and boria. In an embodiment, the glass substrate 12 is a soda lime glass.
In an embodiment, the glass substrate 12 comprises: 62 to 70 mol% SiO2(ii) a 0 to 18 mol% Al2O3(ii) a 0 to 10 mol% B2O3(ii) a 0 to 15 mol% Li2O; 0 to 20 mol% Na2O; 0 to 18 mol% K2O; 0 to 17 mol% MgO; 0 to 18 mol% CaO; and 0 to 5 mol% ZrO2Wherein R is more than or equal to 14 mol percent2O + R 'O is less than or equal to 25 mol percent, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr; al is less than or equal to 10 mol percent2O3+B2O3+ ZrO less than or equal to 30 mol%; and-15 mol% or less (R)2O+R′O-Al2O3-ZrO2)-B2O3Less than or equal to 4 mol percent. Other oxides, such as, but not limited to, ZnO, SnO, and the like can also be added independently to the glass in amounts less than 5 mole percent2、Sb2O3、As2O3、La2O3、Y2O3And Fe2O3And the like. In an embodiment, the glass substrate 12 comprises: 60 to 70 mol% SiO2(ii) a 1 to 5 mol% B2O3(ii) a 10 to 15 mol% Al2O3(ii) a 10 to 15 mol% Na2O; 0.1 to 1 mol% K2O; 1-4 mol% MgO; 0.001 to 0.020 mol% Fe2O3(ii) a 0.001 to 0.020 mol% ZrO2(ii) a And 0.001 to 0.20 mol% SnO2. In an embodiment, the glass substrate 12 comprises: 67.55 mol% SiO2(ii) a 3.67 mol% B2O3(ii) a 12.67 mol% Al2O3(ii) a 13.66 mol% Na2O; 0.014 mol% K2O; 2.33 mol% MgO; 0 mol% CaO; 0.008 mol% Fe2O3(ii) a 0.005 mol% ZrO2(ii) a And 0.10 mol% SnO2。
In an embodiment, the glass substrate 12 comprises: 64 to 66 mol% SiO2(ii) a 8 to 12 mol% Al2O3(ii) a 1 to 11 mol% B2O3(ii) a 0 to 5 mol% Li2O; 6 to 12 mol% Na2O; 1 to 4 mol% K2O; 0 to 4 mol% MgO; 0 to 6 mol% CaO; and 0 to 2 mol% ZrO2Wherein R is more than or equal to 20 mol percent2O + R' O is less than or equal to 24 mol percent; and 16 mol% or less of Al2O3+B2O3+ZrO2Less than or equal to 29 mol%, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr.
In an embodiment, the glass substrate 12 comprises: 9.39 to 18 mol% Al2O3(ii) a 6 to 20 mol% Na2O; up to 9.01 mol% B2O3(ii) a And at least one alkaline earth metal oxide, wherein-15 mol% < R2O+R′O-Al2O3-ZrO2)-B2O32 mol% or less, wherein, where R is Na and optionally one or more of the following: li, K, Rb and Cs, and R' is one or more of Mg, Ca, Sr and Ba. The glass substrate 12 of these embodiments may comprise: 62 to 70 mol% SiO2(ii) a Up to 9.01 mol% B2O3(ii) a 0 to 15 mol% Li2O; 0 to 18 mol% K2O; less than 3 mol% MgO; less than 3 mol% CaO; and 0 to 5 mol% ZrO2. The glass substrate 12 of these embodiments may comprise: 64 to 66 mol% SiO2(ii) a 9.39 to 12 mol% Al2O3(ii) a 1 to 9.01 mol% B2O3(ii) a 0 to 5 mol% Li2O; 6 to 12 mol% Na2O; 1 to 4 mol% K2O; less than 3 mol% MgO; less than 3 mol% CaO; and 0 to 2 mol% ZrO2。
In an embodiment, the glass substrate 12 comprises: 56 to 72 mol% SiO2(ii) a 5 to 18 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 0.1 to 10 mol% P2O5(ii) a 3 to 25 mol% Na2O; 0 to 5 mol% K2O; 0 to 4 mol% CaO; 0 to 1 mol% MgO; and up to 0.5 mol% SnO2And does not contain lithium.
In an embodiment, the glass substrate 12 comprises: 56 to 72 mol% SiO2(ii) a 5 to 18 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 0.1 to 10 mol% P2O5(ii) a And 2 to 20 mol% Ag2And O. This glass substrate 12 may also be free of lithium.
In an embodiment, the glass substrate 12 comprises: 1 to 10 mol% P2O5(ii) a MgO; and at least 5 mol% Al2O3(ii) a Wherein 77 mol% SiO is more than or equal to2+Al2O3Not less than 70 mol% and sigma R' O not more than 0.5P2O5(mol%), wherein R' is Mg, Ca, Ba and Sr, and wherein the glass comprises at least one monovalent metal oxide modifier R2O, wherein P2O5≤[Σ(R2O)-Al2O3]。R2The sum of O will be (Na)2O+K2O+Rb2O+Ag2O+Cs2O). For example, this glass substrate 12 may comprise: 56 to 72 mol% SiO2(ii) a 5 to 18 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 1 to 10 mol% P2O5(ii) a 0 to 7 mol% Li2O; 3 to 25 mol% Na2O; and 0 to 5 mol% K2And O. As another example, the glass substrate 12 may comprise: 56 to 72 mol% SiO2(ii) a 5 to 18 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 1 to 10 mol% P2O5(ii) a And 2 to 20 mol% Ag2O。
In an embodiment, the glass substrate 12 comprises: 60 to 70 mol% SiO2(ii) a 6 to 14 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 0 to 15 mol% Li2O; 0 to 20 mol% Na2O; 0 to 10 mol% K2O; 0 to 8 mol% MgO; 0 to 10 mol% CaO; 0 to 5 mol% ZrO2(ii) a 0 to 1 mol% SnO2(ii) a 0 to 1 mol% CeO2(ii) a Less than 50ppm As2O3(ii) a And less than 50ppm Sb2O3(ii) a Therein, 12Li in mol% or less2O+Na2O+K2O is less than or equal to 20 mol percent, and MgO plus CaO is less than or equal to 0 mol percent and less than or equal to 10 mol percent. For example, the glass substrate 12 may comprise: 63.5 to 66.5 mol% SiO2(ii) a 8 to 12 mol% Al2O3(ii) a 0 to 3 mol% B2O3(ii) a 0 to 5 mol% Li2O; 8 to 18 mol% Na2O; 0 to 5 mol% K2O; 1 to 7 mol% MgO; 0 to 2.5 mol% CaO; 0 to 3 mol% ZrO2(ii) a 0.05 to 0.25 mol% SnO2(ii) a 0.05 to 0.5 mol% CeO2(ii) a Less than 50ppm As2O3(ii) a And less than 50ppm Sb2O3(ii) a Wherein, 14 mol percent is less than or equal to Li2O+Na2O+K2O is less than or equal to 18 mol percent, and MgO plus CaO is less than or equal to 2 mol percent and less than or equal to 7 mol percent.
In an embodiment, the glass composition comprises: 60 to 72 mol% SiO2(ii) a 6 to 14 mol% Al2O3(ii) a 0 to 15 mol% B2O3(ii) a 0 to 1 mol% Li2O; 0 to 20 mol% Na2O; 0 to 10 mol% K2O; 0 to 8 mol% MgO; 0 to 10 mol% CaO; 0 to 5 mol% ZrO2(ii) a 0 to 1 mol% SnO2(ii) a 0 to 1 mol% CeO2(ii) a Less than 50ppm As2O3(ii) a And less than 50ppm Sb2O3(ii) a Wherein, Li is more than or equal to 12 mol percent2O+Na2O+K2O is less than or equal to 20 mol percent, and MgO plus CaO is less than or equal to 0 mol percent and less than or equal to 10 mol percent.
In an embodiment, the glass substrate 12 comprises: 50 to 72 mol% SiO2(ii) a 9 to 17 mol% Al2O3(ii) a 2 to 12 mol% B2O3(ii) a 8 to 16 mol% Na2O; and 0 to 4 mol% K2O, wherein
Wherein the modifier is selected from the group consisting of: alkali metal oxides (e.g., Li)2O、Na2O、K2O、Rb2O、Cs2O) and alkaline earthMetal oxides (e.g., MgO, CaO, SrO, BaO). For example, the glass substrate 12 may comprise: 64 mol% SiO214.5 mol% Al2O38 mol% B2O311.5 mol% Na2O, 0.1 mol% SnO2In which ratio
These embodiments may also comprise 0 to 5 mole% of at least one of: p2O5MgO, CaO, SrO, BaO, ZnO and ZrO2. The glass substrate 12 of these embodiments may be substantially free of lithium. The glass substrate 12 of these embodiments may be substantially free of at least one of arsenic, antimony, and barium.
In an embodiment, the glass substrate 12 comprises: at least 50 mol% SiO2Less than 10 mol% B2O3And at least 8 mol% Na2O, wherein the aluminoborosilicate glass contains no lithium, wherein the ratio
Wherein, Al2O3(mol%)>B2O3(mol%) and the modifier is Na2O and optionally other than Na2O and Li2One or more alkali metal oxides R other than O2At least one of O, and one or more alkaline earth oxides. For example, the glass composition may comprise: 50 to 72 mol% SiO2(ii) a 9 to 17 mol% Al2O3(ii) a Less than 10 mol% B2O3(ii) a 8 to 16 mol% Na2O; and 0 to 4 mol% K2O, where the ratio is, for example, as described above, and-5.7 mol%<Sigma modifier-Al2O3<2.99 mol%.
In an embodiment, the glass substrate 12 comprises: at least about 50 mol% SiO2(ii) a At least about 10 mol% ofAt least one alkali metal oxide R2O, wherein R2O comprises Na2O, and optionally other alkali metal oxides (e.g., Li)2O、K2O、Ce2O、Rb2O); alumina (Al)2O3) Wherein, expressed in mol%, Al2O3In an amount less than the total amount of alkali metal oxide present in the glass (i.e., Al)2O3(mol%)<R2O (mole%)); and boron oxide (B)2O3) In which B is2O3(mol%) - (R)2O (mol%) -Al2O3(mol%)) is more than or equal to 3 mol%. These glass substrates 12 may include at least 0.1 mol% of at least one of MgO and ZnO. These glass substrates 12 may comprise 3 to 4.5 mol% B2O3。
In an embodiment, the glass substrate 12 comprises: at least about 50 mol% SiO2(ii) a 9 to 22 mol% Al2O3(ii) a 3 to 10 mol% B2O3(ii) a 10 to 20 mol% Na2O; 0 to 5 mol% K2O; at least about 0.1 mole% MgO and/or ZnO, wherein 0 mole% MgO (mole%) or more + ZnO (mole%) or less 6 mole%; and optionally, at least one of CaO, BaO and SrO, wherein 0 mol% or less CaO (mol%) + SrO (mol%) + BaO (mol%) + 2 mol%. These glass substrates 12 may comprise 66 to 74 mol% SiO2. These glass substrates 12 may include at least 0.1 mol% of at least one of MgO and ZnO.
In an embodiment, the glass substrate 12 comprises: 66 to 74 mol% SiO2(ii) a At least about 10 mol% R2O, wherein R2O comprises 9 to 20 mol% Na2O；Al2O3Wherein Al is2O3(mol%)<R2O (mol%); and B2O3Wherein 4.5 mol% is not less than B2O3(mol%) - (R)2O (mol%) -Al2O3(mol%)) is more than or equal to 3 mol%. For example, the glass substrate 12 may comprise: 9 to 22 mol% Al2O3(ii) a 3 to 10 mol% B2O3(ii) a 0 to 5 mol% K2O; at least 0.1 mol% MgO + ZnO, wherein MgO is more than or equal to 0 and less than or equal to 6, and ZnO is more than or equal to 0 and less than or equal to 6 mol%; and, optionally, at least one of CaO, BaO and SrO, wherein CaO + SrO + BaO is 0 mol% or more and 2 mol% or less. For another example, the glass substrate 12 may comprise: 66 to 74 mol% SiO2(ii) a At least about 10 mol% R2O, wherein R2O comprises Na2O；Al2O3Wherein Al is2O3(mol%)<R2O (mol%); and 3 to 4.5 mol% B2O3Wherein B is2O3(mol%) - (R)2O (mol%) -Al2O3(mol%)) is more than or equal to 3 mol%. These glass substrates 12 may include at least 0.1 mol% of at least one of MgO and ZnO. In some cases, B2O3(mol%) - (R)2O (mol%) -Al2O3(mol%)) is less than or equal to 4.5 mol%. In other examples, the glass substrate 12 comprises: 9 to 22 mol% Al2O3(ii) a 9 to 20 mol% Na2O; 0 to 5 mol% K2O; at least 0.1 mol% MgO + ZnO, wherein MgO is more than or equal to 0 and less than or equal to 6 and ZnO is more than or equal to 0 and less than or equal to 6; and, optionally, at least one of CaO, BaO and SrO, wherein CaO + SrO + BaO is 0 mol% or more and 2 mol% or less. In some cases, the glass substrate 12 includes 9 to 22 mol% Al2O3And 9 to 20 mol% Na2O。
In an embodiment, the glass substrate 12 comprises: 62 to 67 mol% SiO2(ii) a 3 to 7 mol% B2O3(ii) a 12 to 15 mol% Al2O3(ii) a 12 to 15 mol% Na2O; 0 mol% K2O; 1 to 3.5 mol% MgO; 0 mol% CaO; and 0.02 to 0.14 mol% SnO2. For example, the glass substrate 12 may comprise: 64.74 mol% SiO2(ii) a 5.14 mol% B2O3(ii) a 13.94 mol% Al2O3(ii) a 13.72 mol% Na2O; 0 mol% K2O; 2.38 mol% MgO; 0 mol% CaO; 0.08 mol% SnO2。
In an embodiment, the glass substrate 12 comprises:at least about 4 mol% P2O5And 0 mol% to about 4 mol% B2O3Wherein the glass substrate 12 does not contain Li2O, and wherein 1.3<[(P2O5+R2O)/M2O3]Less than or equal to 2.3; in the formula, M2O3＝Al2O3+B2O3And R2O is the sum of the monovalent cationic oxides present. In some cases, 1.5<[(P2O5+R2O)/M2O3]Less than or equal to 2.0. In some cases, this glass substrate 12 includes less than 1 mol% K2And O. In some cases, this glass substrate 12 comprises 0 mol% K2And O. In some cases, this glass substrate 12 includes less than 1 mol% B2O3. In some cases, this glass substrate 12 includes 0 mol% B2O3. In some cases, the monovalent and divalent cation oxides are selected from the group consisting of: na (Na)2O、K2O、Rb2O、Cs2O, MgO, CaO, SrO, BaO and ZnO. For example, the glass substrate 12 may comprise: 40 to 70 mol% SiO2(ii) a 11 to 25 mol% Al2O3(ii) a 4 to 15 mol% P2O5(ii) a And 13 to 25 mol% Na2And O. For another example, the glass substrate 12 may comprise: 45 to 65 mol% SiO2(ii) a 14 to 25 mol% Al2O3(ii) a 4 to 15 mol% P2O5(ii) a And 14 to 20 mol% Na2O。
In an embodiment, the glass substrate 12 comprises: 50 to 75 mol% SiO2(ii) a 10 to 20 mol% Al2O3(ii) a 0 to 5 mol% P2O5(ii) a 5 to 20 mol% Na2O; 5 to 10 mol% Li2O; and 0 to 5 mol% ZnO.
All of the above embodiments relating to the composition of the glass substrate 12 are with respect to the composition at the bulk 26.
Is contacted with the first solution to produce porous layer 22. In step 40, the method 10 includes contacting the initiation surface 14 of the glass substrate 12 with a first solution. First of allThe solution comprises: dissolved SiO2(e.g. from dissolution of silica gel), H2SiF6(also known as fluorosilicic acid) and H3BO3(also known as boric acid). In embodiments, the first solution is an aqueous solution comprising: 0.5 to 0.8M dissolved SiO20.5 to 2M H2SiF6And 20 to 60mM H3BO3. In an embodiment, the water of the aqueous solution is deionized water.
The first solution may be brought into contact with the initial surface 14 via various methods 10. One example is to submerge the initial surface 14 under a first solution contained in a container. As other examples, the first solution may be slot coated, spin coated, or spray coated onto the initial surface 14. If it is desired to only contact a particular surface (e.g., surface 16) or portion thereof of the glass substrate 12 with the first solution, an acid resistant film may be disposed on the surface (e.g., surface 18) that is not desired to be contacted with the first solution.
The first solution is in contact with the initial surface 14 for a period of time and has a temperature. In an embodiment, the time period is 5 minutes to 6 hours. In embodiments, the time period is 2.5 hours or less, such as 5 minutes to 2.5 hours and 1 to 2.5 hours. In some cases, the time period is 10 minutes, 20 minutes, 30 minutes, or 2 hours. In an embodiment, the temperature of the first solution is 25 to 40 ℃.
In an embodiment, the method 10 further comprises: a first solution is prepared at step 42. The preparation of the solution involves, in order: (i) in the presence of H2SiF6The aqueous solution of (a) dissolves the silica gel so that the aqueous solution has dissolved SiO2And H2SiF6(ii) a (ii) Filtering the undissolved silica gel from the aqueous solution; and (iii) to contain SiO2And H2SiF6The aqueous solution of (a) contains H3BO3An aqueous solution of (a). For example, it may contain H2SiF6For example, 30 wt% H in deionized water2SiF6Or 2 to 3M H in deionized water2SiF6) Adding the silica gel to the vessel and maintaining the temperature (e.g., room temperature)) Stirred for a period of time (e.g., 24 hours) to dissolve the SiO well from the silica gel2Into a vessel containing H2SiF6In an aqueous solution of (a). The contents of the vessel may then be passed through a filter to remove dissolved SiO2And H2SiF6The aqueous solution of (a) separates undissolved silica gel. Then, adding hydrogen to the mixture containing H2SiF6And dissolved SiO2Adding H to the aqueous solution of (1)3BO3E.g., 0.4 to 1M H in deionized water3BO3). The combined contents may then be mixed by stirring at a temperature (e.g., room temperature) for a period of time (e.g., 30 minutes).
In an embodiment, the method 10 further comprises: at step 44, the initial surface 14 of the glass substrate 12 is contacted with a degreaser in an ultrasonic bath. This step 44 cleans the initial surface 14 in preparation for contacting the initial surface 14 with the first solution at step 44. The ultrasonic bath may be at room temperature or some other temperature. The glass substrate 12 may be contacted with the stain remover for a period of time such as 5 minutes. However, this cleaning period may be shorter or longer.
The composition of porous layer 22 resulting from step 40, in which initial surface 14 of glass substrate 12 is contacted with the first solution, is different from the composition of glass substrate 12 at bulk 26. Secondary Ion Mass Spectrometry (SIMS) analysis of the glass substrate 12 after performing step 40 of method 10 confirms this compositional change. The figures reproduced in fig. 6 are examples of displaying such variations, which are discussed in more detail below in connection with the embodiments. The graph reveals that the composition of the glass substrate 12 is a function of depth from the initial surface 14 toward the bulk 26, specifically, (a) the absolute concentration of hydrogen, fluorine, sodium, and aluminum atoms is a function of depth; and (b) the relative concentration of silicon atoms is a function of depth. The portion of the graph from initial surface 14 (depth 0) to the dashed line (500nm) shows the concentration of the selected atoms as a function of depth in porous layer 22, and the remaining graph to the right of the dashed line shows the concentration of the selected atoms as a function of depth towards bulk 26. In this particular example, porous layer 22 comprises an absolute concentration of fluorine atoms and hydrogen atoms that is greater than bulk 26 of glass substrate 12, and a relative concentration of silicon atoms that is greater than bulk 26. Further, in this particular example, porous layer 22 comprises aluminum atoms and sodium atoms in absolute concentrations that are less than the absolute concentration of bulk 26 of glass substrate 12. If porous layer 22 results from the precipitation of the first solution (rather than as a result of the removal of material from glass substrate 12), then there will be no sodium or aluminum atoms in porous layer 22 (because the first solution is prepared without sodium or aluminum atoms).
The decrease in absolute concentration of sodium and aluminum atoms in porous layer 22 compared to bulk 26, combined with the increase in absolute concentration of hydrogen atoms in porous layer 22 compared to bulk 26, reveals (in a manner not bound by theory) that acid leaching of the first solution leaches hydrogen ions into glass substrate 12 (located in porous layer 22) and that sodium and aluminum ions leach from glass substrate 12 into the first solution. Such leaching processes are typically very slow and sometimes require high temperatures to accelerate the process. However, here, the increased absolute concentration of fluorine ions in porous layer 22 compared to bulk 26 (in a manner not limited by theory) suggests that fluorine ions enter glass substrate 12 through initial surface 14 along with hydrogen ions and accelerate leaching of sodium and aluminum, thereby forming porous layer 22. The water in the first solution causes H therein2SiF6Hydrolysis, as shown in equation (1) below:
without being bound by theory, it is believed that fluoride ions (anions) and hydrogen ions (cations) form small amounts of hydrofluoric acid (HF). Hydrofluoric acid (HF) etches SiO of the glass substrate 122The network and ultimately the leaching of aluminum and sodium ions, and thus the duration and temperature of forming porous layer 22, is reduced. However, dissolved SiO present in the first solution2H which would form hydrogen ions and fluorine ions according to the above equation (1) is limited2SiF6And thus limits the generation of hydrofluoric acid (HF). Furthermore, H present in the first solution3BO3By following the equationFormula (2) neutralizes hydrofluoric acid (HF), preventing the generated hydrofluoric acid (HF) from completely removing (etching) porous layer 22:
H3BO3+4HF→H[BF4]+3H2O (2)
thus, hydrofluoric acid (HF) is maintained at a very low concentration, but at a concentration sufficient to promote relatively rapid formation of porous layer 22, without the need to raise the temperature of the first solution.
The thickness and degree of porosity of porous layer 22 may be taken as the period of time that the first solution is in contact with initial surface 14 and the composition of the first solution (i.e., increasing or decreasing dissolved SiO in the first solution)2、H2SiF6And H3BO3Relative amount) of the first component. The longer the time period, the thicker the thickness, all other things being equal. Conversely, the shorter the period of time, the thinner the thickness, all other things being equal.
At step 46, method 10 further includes washing porous layer 22 with water. In an embodiment, the water is deionized. In an embodiment, the entire glass substrate 12 is washed with water (e.g., deionized water). This step 46 is performed before porous layer 22 is removed later in method 10, discussed below.
The second solution may be contacted with porous layer 22 via various methods 10. One example is to submerge the surface of porous layer 22 under a second solution contained in a container. As other examples, the second solution may be slit coated, spin coated, or spray coated onto the surface of porous layer 22. A film of alkali-resistant hydroxide may be disposed on the remaining portion of the glass substrate 12 other than the porous layer 22 to prevent contact and etching of the second solution. In embodiments, the second solution is disposed in an ultrasonic bath when in contact with porous layer 22.
In embodiments, the pH of the second solution is greater than or equal to 14. In embodiments, the one or more basic salts of the second solution is or includes KOH. In other embodiments, the one or more basic salts are one or more basic hydroxides, such as potassium hydroxide, sodium hydroxide, and compounds comprising basic hydroxides. The pH level can be determined using pH paper.
In embodiments, the second solution is an aqueous solution comprising 25 to 60 wt% of a basic salt. Higher concentrations of alkaline salts aid in the removal of porous layer 22. For example, the second solution may be an aqueous solution comprising 50 wt% KOH.
In embodiments, the second solution has a temperature and a duration of time when in contact with porous layer 22. In embodiments, the second solution is contacted with porous layer 22 for a period of 2 to 30 minutes. For example, the time period may be 10 minutes. In embodiments, the temperature of the second solution is from room temperature to 80 ℃, e.g., from 40 ℃ to 80 ℃. For example, the temperature of the second solution may be 60 ℃. For the purposes of this disclosure, room temperature may be assumed to be 25 ℃.
The second solution removes porous layer 22, leaving a new surface 28 with a different texture (e.g., more textured) than the original surface 14. The porous layer 22 created by the first solution allows the second solution to easily etch the glass substrate 12 (specifically, in the porous layer 22). As described, the method 10 produces concave surface features 30 that provide the texture of the new surface 28, and those surface features 30 may be quantified by their average diameter 36 and average peak-to-valley height 38. The average diameter 36 and average peak-to-valley height 38 are functions of various factors including: the composition of glass substrate 12, the period of time that the first solution is in contact with initial surface 14, the temperature of the first solution, the composition of the first solution, the temperature of the second solution, the concentration of the alkaline salt in the second solution, and the period of time that the second solution is in contact with porous layer 22. In an embodiment, the average diameter 36 of a surface feature 30 is 650nm to 750nm, while the average peak-to-valley height 38 of the same surface feature 30 is 60nm to 80 nm. In an embodiment, the average diameter 36 of a surface feature 30 is 2.5 μm to 3.5 μm, while the average peak-to-valley height 38 of the same surface feature 30 is 650nm to 850 nm. In an embodiment, the average diameter 36 of the surface features 30 is 9 μm to 15 μm and the average peak to valley height 38 is 3.5 μm to 7.5 μm.
At step 50, the method 10 further includes rinsing the new surface 28 with water. In an embodiment, the water is deionized. The water generally cleans the residue that remains on the new surface 28 and the glass substrate 12 after the contact with the second solution at step 48.
At step 52, the method 10 further includes drying the glass substrate 12. In embodiments, the glass substrate 12 may be placed in a heated environment (e.g., in the interior chamber of an oven), at a temperature, and for a period of time. In embodiments, the temperature is 70 ℃ to 130 ℃ and the time period is 15 minutes to 45 minutes. For example, the temperature may be 110 ℃ and the time period may be 30 minutes.
The anti-glare properties of the glass substrate 12 having the new surface 28. The new surface 28 produced by the method 10 provides the glass substrate 12 with anti-glare properties. As shown in the examples below, various anti-glare attributes can be adjusted by adjusting the component concentrations of the first solution, the period of time that the first solution is in contact with the glass substrate 12, and whether one or both of the initial surfaces 14 are in contact with the first solution. The adjustable anti-glare attributes include distinctness of image, gloss-60, transmission haze, and sparkle. The glass substrate 12 treated according to method 10 maintained acceptable visible light transmission.
As used herein, the term "Distinctness of Image" (abbreviated "DOI") is defined by method 10A of ASTM method D5767(ASTM 5767), entitled "Standard Test Methods for Instrument Measurements of Distinctness-of-Image Gloss of Coating Surfaces," which is incorporated herein by reference in its entirety. Measurements of glass reflection factors were made at the specular viewing angle and at angles slightly off the specular viewing angle on the new surface 28 of the glass substrate 12 according to method a of ASTM 5767. Light is incident on the glass substrate 12 at 20 ° from normal to the new surface 28 (the major surface closest to the incident light) as described in ASTM D5767. The values obtained by these measurements are combined to provide a DOI value. Specifically, DOI is calculated according to the following equation (3):
DOI＝(1-ROS/RS)x 100 (3)
in the formula, ROSIs the relative magnitude of the reflectivity from the specular direction, and RSIs the relative magnitude of the reflectivity in the specular direction. As described herein, R is calculated by averaging the reflectance over an angular range of 0.2 to 0.4 from the specular direction, unless otherwise specifiedOS. Rs is calculated by averaging the reflectances within an angular range of ± 0.05 ° centered on the mirror direction. RSAnd ROSA goniometer (Novo-gloss IQ, Rhopoint instruments) calibrated to certified black glass standards according to ASTM methods D523 and D5767 was used. The Novo-gloss instrument uses a detector array in which the specular angle is centered at the highest value in the detector array. DOI was evaluated using a two-sided approach, where reflections from both major surfaces were allowed. The two-sided measurement enables determination of gloss, reflectance, and DOI for the glass substrate 12 as a whole (not just as the major surface of the new surface 28). From the obtained R, as described aboveSAnd ROSCalculating R from the mean value ofOS/RS. The DOI measurement using the two-sided method 10 is preferably performed in a dark room or dark environment, such that when no sample is present, the measured values for these properties are zero.
For anti-glare surfaces, it is generally desirable that DOI be low and the reflectance Ros/Rs be high. This results in a visual perception of a blurred or unclear reflected image. In an embodiment, R of the glass substrate 12 at an angle of 20 ° from the specular direction using the double-sided method 10OS/RSThe ratio is greater than 0.003, for example, 0.003 to 0.10, including 0.003 to 0.08. In embodiments, using the two-sided approach, the DOI value of the glass substrate 12 at an angle of 20 ° from the specular direction is less than 99.7, e.g., 90 to 99.7, including 92 to 99.7 and including 92 to 99. In embodiments, using the two-sided approach, the DOI value for the glass substrate 12 at an angle of 20 ° from the specular aspect is 12 to 16.
"gloss" refers to specular reflectance measured according to ASTM method D523, calibrated with a standard (e.g., certified black glass standard), the entire contents of which are incorporated herein by reference. Herein, the gloss is measured using a goniophotometer (e.g., commercially available from Rhopoint instruments, mentioned above). Common gloss measurements are typically made at incident light angles of 20 °, 60 ° and 85 °, with the most common gloss measurement being made at 60 ° ("gloss-60" refers to this incident light angle measurement). In an embodiment, the glass substrate 12 treated according to method 10 has a gloss-60 of 100 to 145GU (gloss units), for example, 100 to 130GU, 100 to 125GU, 100 to 105GU, and 100 to 102 GU. In other embodiments, the glass substrate 12 treated according to method 10 has a gloss-60 of 95 to 105 GU.
"Transmission haze", "haze" or similar term refers to the percentage of transmitted light that is scattered outside a 4.0 ° cone according to ASTM D1003. Haze values were measured using a Haze-Guard Haze test apparatus (Elektron technologies, PLC). For optically smooth surfaces, transmission haze is typically near zero. Haze values are typically reported as percent haze. In an embodiment, the glass substrate 12 treated according to method 10 has a transmission haze of less than 7.5%, for example, 0.25 to 7.5%, 0.25 to 2.5%, 2 to 7.5%, 2 to 2.5%, and 2 to 7.5%. In other embodiments, the glass substrate 12 treated according to method 10 has a transmission haze of 2.5 to 7.5%, for example 5 to 6%.
"glare" is a generally undesirable side effect that can occur when introducing an anti-glare or light scattering surface to a pixelated display system (e.g., a Liquid Crystal Display (LCD), Organic Light Emitting Diode (OLED), or touch screen, etc.). Sparkle is associated with the very fine grainy appearance of a display, which may appear to shift the grain pattern as the viewing angle of the display changes. Display sparkle can be manifested as bright and dark spots or colored spots of an approximate pixel horizontal dimension specification. Herein, the glass substrate 12 was evaluated for sparkle value using a bench top sparkle measurement system ("SMS bench") (specifically, SMS-1000 available from Display-mestachnik and systems corporation (Display-Messtachnik & system GmBH)) and a Display light source of 140 ppi. The display light source may be a model association model Z510 screen. The glare value using an SMS table for the anti-glare surface disclosed herein is recorded as a percentage (%). In embodiments, the glass substrate 12 treated according to method 10 has a sparkle value of less than 3.5%, for example, 0.25 to 3.5%, 1.5 to 3.5%, 2 to 3.5%, 0.25 to 2.5%, and 1.5 to 2.5%. In other embodiments, the glass substrate 12 treated according to method 10 has a sparkle value of 12 to 16%, for example 14 to 15%.
"transmittance" refers to the percentage of incident optical power that is transmitted through the entire visible wavelength range of the glass substrate 12 according to ASTM D1003. In this context, the transmittance values are measured using the Haze-Guard test equipment (Elektron technologies, PLC) mentioned above. The transmission is reported as a percentage (%). In an embodiment, the glass substrate 12 treated according to method 10 has a transmittance of greater than 93%, for example, greater than 93.3%, 93 to 94%, and 93.3 to 94%. In other embodiments, the transmittance of the glass substrate 12 treated according to method 10 is 93.5 to 94.5%.
In an embodiment, when the glass substrate 12 has the following composition of the bulk 26: 62 to 70 mol% SiO2(ii) a 0 to 18 mol% Al2O3(ii) a 0 to 10 mol% B2O3(ii) a 0 to 15 mol% Li2O; 0 to 20 mol% Na2O; 0 to 18 mol% K2O; 0 to 17 mol% MgO; 0 to 18 mol% CaO; and 0 to 5 mol% ZrO2Wherein R is more than or equal to 14 mol percent2O + R 'O is less than or equal to 25 mol percent, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr; al is less than or equal to 10 mol percent2O3+B2O3+ ZrO less than or equal to 30 mol% and-15 mol% (R)2O+R′O-Al2O3-ZrO2)-B2O3At 4 mol% or less, the glass substrate 12 treated according to method 10 has: (1) with the two-sided approach, the DOI value at an angle of 20 ° from the specular direction is less than 99.7, such as 90 to 99.7, including 92 to 99.7 and including 92 to 99; (2) gloss-60 values are 100 to 145GU, e.g., 100 to 130GU, 100 to 125GU, 100 to 105GU and 100 to 102 GU; (3) transmission haze less than 7.5%, e.g. 0.25 to 7.5%0.25 to 2.5%, 2 to 7.5%, 2 to 2.5% and 2 to 7.5%; (4) a flash value of less than 3.5%, e.g., 0.25 to 3.5%, 1.5 to 3.5%, 2 to 3.5%, 0.25 to 2.5%, and 1.5% to 2.5%; and (5) a transmittance of greater than 93%, e.g., greater than 93.3%, 93 to 94%, and 93.3 to 94%.
In embodiments, when the glass substrate has a composition of bulk 26, it comprises: 45 to 65 mol% SiO2(ii) a 14 to 25 mol% Al2O3(ii) a 4 to 15 mol% P2O5(ii) a And 14 to 20 mol% Na2O, the glass substrate 12 treated according to method 10 has: (1) with the two-sided approach, the DOI value at an angle of 20 ° from the mirror direction is 22 to 27; (2) a gloss-60 value of 95 to 105 GU; (3) transmission haze is 2.5 to 7.5%, e.g., 5 to 6%; (4) flash value is 12 to 16%, e.g., 14 to 15%; and (5) the transmittance is 93.5 to 94.5%.
The benefits of method 10. The method 10 provides a number of benefits. First, the resulting antiglare properties (i.e., transmittance, haze, sparkle, and DOI value) of the glass substrate 12 meet the requirements of many antiglare applications. In other words, the method 10 functions to produce a glass substrate 12 having anti-glare properties.
Second, the method 10 functions without the need to directly use hydrofluoric acid. Thus, the method 10 avoids the disadvantages of purchasing, using, and discarding hydrofluoric acid. Any hydrofluoric acid generated during step 40 of creating porous layer 22 is of finite volume and is transient in nature. The acid used in step 40 is low in concentration and environmentally safe.
Third, the method 10 creates a new surface 28 (texturing) in an energy efficient and fast enough way for commercial production. Method 10 step 40 of using the first solution may be performed at room temperature up to 40 ℃ and for a period of time from 10 minutes to 6 hours. In some cases, step 40 may be performed at room temperature for 2 hours or less. Method 10 step 48 of using the second solution may be performed at room temperature up to 80 ℃ for a period of time of 2 to 30 minutes. In some cases, the entire process 10 may be conducted at room temperature (except for step 52 where drying is conducted), and may be completed in a period of 8 hours. The temperatures involved in steps 40, 48 are much lower than other attempts to create a new surface 28 (texturing) using chemistry without the use of hydrofluoric acid. Thus, the method 10 is more energy efficient than the prior art attempts to replace hydrofluoric acid. The time period is also shorter. Thus, the method 10 is a significant improvement over the prior art.
Fourth, for any given composition of the glass substrate 12, the average diameter 36 and average peak-to-valley height 38 of the surface features 30 produced by the method 10 are both less than other attempts to replace hydrofluoric acid. For many compositions of the glass substrate 12, the surface features 30 are less than 1 micron. The smaller surface features 30 have practical applications and may provide a basis for new applications requiring smaller surface features 30.
Finally, the method 10 is low cost and easily scalable. The raw materials used for steps 40, 48 of method 10 are readily available and inexpensive. The method 10 does not require expensive heating equipment for high temperature processing.
Examples
Example 1: for example 1: the glass substrate 12 includes: 67.55 mol% SiO2(ii) a 3.67 mol% B2O3(ii) a 12.67 mol% Al2O3(ii) a 13.66 mol% Na2O; 0.014 mol% K2O; 2.33 mol% MgO; 0 mol% CaO; 0.008 mol% Fe2O3(ii) a 0.005 mol% ZrO2(ii) a And 0.10 mol% SnO2. The glass substrate 12 is a sheet having major surfaces 16, 18 facing in opposite directions. The thickness 20 of the glass substrate 12 is 1.1 mm. In accordance with step 44 of method 10, the glass substrate 12 is contacted with a detergent and cleaned. More specifically, the glass substrate 12 was placed in an ultrasonic bath containing a detergent for 5 minutes at room temperature.
A first solution is prepared pursuant to step 42 of method 10. More specifically, 2.54M H2SiF6And deionized water was added to the silica gel so that the silica gel was 5% by weight of the aqueous solution. The aqueous solution with silica gel was mechanically stirred at room temperature for 24 hours,so that SiO2From the silica gel into the aqueous solution. Then, the undissolved silica gel was filtered from the aqueous solution. To contain dissolved SiO2、H2SiF6And deionized water with 0.8M H3BO3And another aqueous solution of deionized water. This mixed aqueous solution was mechanically stirred at room temperature for 30 minutes to give a certain amount of the first solution. The final composition of the first solution was 0.7M SiO2、1.57M H2SiF6And 40mM H3BO3。
The first solution is then contacted with the initial surface 14 (major surface) of the glass substrate 12, pursuant to step 40. More specifically, the glass substrate 12 is vertically immersed in a container containing the first solution for a period of 2 hours. The temperature of the first substrate was maintained at 40 ℃. After this period of time, the glass substrate 12 is removed from the container and the porous layer 22 has formed adjacent to the initial surface 14. The glass substrate 12 is washed three times with deionized water and then dried, as per step 46.
Referring now to fig. 7, picture a, the upper left corner, is a scanning electron microscope image of the glass substrate 12 after step 40 and before step 48 of the method 10. Porous layer 22 is clearly visible and is distinguished from bulk 26 of glass substrate 12. The thickness of the porous layer 22 is 400nm to 500 nm.
Pursuant to step 48 of method 10, glass substrate 12 having porous layer 22 is then contacted with a second solution, thereby removing porous layer 22 and creating a new surface 28 having an increased texture as compared to initial surface 14. More specifically, an aqueous second solution containing 50 wt% KOH in deionized water was prepared. The aqueous second solution was then heated to a temperature of 60 ℃ and placed in an ultrasonic bath. Then, the glass substrate 12 having the porous layer 22 was immersed in the ultrasonic bath having the second solution for 1 hour. The temperature of the second solution was maintained at 60 ℃. The second solution completely removes porous layer 22. The glass substrate 12 now having a new surface 28 is removed from the second solution. The glass substrate 12 is washed three times with deionized water, pursuant to step 50. The glass substrate 12 is then dried in an oven providing an environment heated to 110 ℃ for a period of 30 minutes, pursuant to step 52.
Referring again to fig. 7, panel B in the upper right corner is another scanning electron microscope image of the glass substrate 12 after completion of the method 10. The new surface 28 is shown with concave surface features 30 having peaks 32 and valleys 34. Panel C (lower left corner) of FIG. 7 is another scanning electron microscope image of new surface 28, showing surface features having a diameter 36 of 742nm and a peak to valley height 38 of 75.4 nm. Panel D (lower right corner) of fig. 7 is another scanning electron microscope image of new surface 28, this time a top view, showing concave surface features 30 having peaks 32 and valleys 34.
Returning to fig. 6, the composition of glass substrate 12 of example 1 after step 40 of creating porous layer 22 is analyzed. As discussed above, the absolute concentration of atomic aluminum and atomic sodium decreases from bulk 26 throughout porous layer 22 to initial surface 14 because a portion of glass substrate 12 leaches into the first solution, forming porous layer 22. The relative concentration of atomic silicon in porous layer 22 is slightly elevated compared to bulk 26, which is believed (in a manner not to be limited by theory) to be due to leaching of aluminum and sodium from glass substrate 12 into the first solution, thereby creating porous layer 22. The loss of the modifier sodium from the glass network of porous layer 22 allows the second solution to readily dissolve and remove porous layer 22 to reveal new surface 28. The absolute concentrations of atomic hydrogen and atomic fluorine in porous layer 22 are increased as compared to bulk 26 of glass substrate 12, as described above. The glass substrate 12 is formulated to be fluoride free so that all atomic fluorine present in porous layer 22 is from the first solution.
Example 2: example 2 is consistent with example 1, except that the composition of the glass substrate of example 2 is different from the glass substrate 12 of example 1. More specifically, the glass substrate 12 of example 2 had the following composition: 64.74 mol% SiO2(ii) a 5.14 mol% B2O3(ii) a 13.94 mol% Al2O3(ii) a 13.72 mol% Na2O; 0 mol% K2O; 2.38 mol% MgO; 0 mol% CaO; 0.08 mol% SnO2. The composition of example 2 contained more aluminum and boron and less than example 1Silicon, and the glass substrate 12 of example 2 was more easily etched than the glass substrate 12 of example 1.
Referring now to fig. 8, panels a-D are scanning electron microscope images of the glass substrate 12 after the method 10 is completed. The new surface 28 is shown with concave surface features 30 having peaks 32 and valleys 34. Panel C at the bottom left shows two surface features 30 having diameters 36 of 2.98 μm and 2.76 μm and peak-to-valley heights 38 of 774nm and 714nm, respectively. Because the glass substrate 12 of example 2 is more easily etched than the substrate 12 of example 1, the method 10 produces larger surface features 30.
Example 3: example 3 is consistent with examples 1 and 2, except that the composition of the glass substrate 12 of example 3 is different from the glass substrate 12 of examples 1 and 2. More specifically, the glass substrate 12 of example 3 had the following composition: 57.43 mol% SiO2(ii) a 16.10 mol% Al2O3(ii) a 6.54 mol% P2O5(ii) a 17.05 mol% Na2O; 2.81 mol% MgO; and 0.07 mol% SnO2. The composition of example 3 contained more aluminum and phosphorous and less silicon than examples 1 and 2, and the glass substrate 12 of example 3 was more easily etched than the glass substrates 12 of examples 1 and 2.
Referring now to fig. 9, panels a-D are scanning electron microscope images of the glass substrate 12 after the method 10 is completed. The new surface 28 is shown with concave surface features 30 having peaks 32 and valleys 34. Panel C at the bottom left shows two surface features 30, each having a diameter 36 of 10.2 μm to 13.5 μm and a peak to valley height 38 of 4.17nm to 6.94 nm. Because the glass substrate 12 of example 3 is more easily etched than the substrates 12 of examples 1 and 2, the method 10 produces larger surface features 30.
Examples 4 to 8: examples 4-7 all employed the same composition as the glass substrate 12 of example 1 above and are identified as composition "a" in table 1 below. Example 8 employed the same composition as the glass substrate 12 of example 3 above and was identified in table 1 below as composition "B".
In accordance with step 42 of method 10, silica gel is mixed into H in deionized water2SiF6In an aqueous solution of (a) so that the aqueous solution is SiO2And (4) saturation. The undissolved silica gel was filtered from the aqueous solution. This aqueous solution is then added with stirring to a solution having H3BO3And deionized water, thereby producing a first solution. Depending on the embodiment, the first solution has 40mM H3BO3And 1M or 2M of H2SiF6As shown in table 1 below. The temperature of the first solution was raised to 40 ℃ and maintained at this temperature. Pursuant to step 40 of method 10, for each example, the glass substrate 12 was immersed in the first solution contained in the container for a period of time as shown in table 1 below. For each embodiment, both major surfaces 16, 18 of the glass substrate 12 are the initial surfaces 14 that are in contact with the first solution (and subsequent second solution). For other embodiments, only the major surface 16 of the glass substrate 12 is the initial surface 14 that is in contact with the first solution (and subsequent second solution), and a protective film is disposed on the other major surface 18 of the glass substrate 12. This aspect is labeled in table 1 below as "single" side or "double-sided," single "meaning that only major surface 16 of glass substrate 12 is in contact with the first and second solutions, and the other major surface 18 is covered with a protective film. The first solution in contact with the initial surface 14 of the glass substrate 12 of each example creates a porous layer 22. After step 40 of method 10, the glass substrate 12 of each example is removed from contact with the first solution and cleaned according to step 46. Each glass substrate 12 having porous layer 22 is immersed in a vessel containing a second solution of 50 wt.% KOH in deionized water at a temperature of 60 ℃ for a period of 1 hour, pursuant to step 48. This step 48 removes porous layer 22, resulting in a new surface 28 having surface features 30. Each glass substrate 12 is then removed from contact with the second solution, cleaned (step 50) and dried (step 52). Each example was then tested for various optical properties. The results are shown in Table 1 below.
TABLE 1
| Examples | Haze (%) | Flashing (%) | Transmittance (%) |
| 4 | 0.30 | 0.43 | 93.70 |
| 5 | 2.42 | 1.91 | 93.40 |
| 6 | 2.21 | 2.19 | 93.60 |
| 7 | 7.20 | 3.12 | 93.90 |
| 8 | 5.35 | 14.60 | 93.90 |
TABLE 1 continuation
It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the claims.
Claims (36)
1. A method of making a glass substrate having a textured surface, comprising:
contacting an initial surface of a glass substrate with a first solution comprising dissolved SiO2、H2SiF6And H3BO3Thereby forming a porous layer adjacent to the initial surface; and
the porous layer is contacted with a second solution comprising one or more basic salts, thereby removing the porous layer and creating a new surface with increased texture compared to the original surface.
2. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the thickness of the glass substrate is 100 μm to 2.1mm before contacting the initial surface of the glass substrate with the first solution.
3. The method of claim 1, further comprising:
contacting the initial surface of the glass substrate with a decontaminating agent in an ultrasonic bath prior to contacting the initial surface of the glass substrate with the first solution.
4. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the first solution is an aqueous solution comprising:
0.5 to 0.8M dissolved SiO2；
0.5 to 2M H2SiF6(ii) a And
20 to 60mM H3BO3。
5. The method of claim 1, further comprising:
prior to contacting the initial surface of the glass substrate with the first solution, preparing the first solution by, in order: (i) in the presence of H2SiF6In the aqueous solution of (2), SiO is dissolved from the silica gel2(ii) a And (ii) to contain H2SiF6And dissolved SiO2The aqueous solution of (a) contains H3BO3An aqueous solution of (a).
6. The method of claim 5, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
preparing the first solution further comprises: in the presence of H2SiF6From an aqueous solution of (A) dissolving SiO from a silica gel2Thereafter, but in the direction containing H2SiF6And dissolved SiO2The aqueous solution of (a) contains H3BO3Before the aqueous solution of (a), filtering the undissolved silica gel from the aqueous solution.
7. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the temperature of the first solution is 25 ℃ to 40 ℃.
8. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the initial surface of the glass substrate is contacted with the first solution for a period of time from 5 minutes to 6 hours.
9. The method of claim 8, wherein the first and second light sources are selected from the group consisting of,
the initial surface of the glass substrate is contacted with the first solution for a period of time ranging from 5 minutes to 2.5 hours.
10. The method of claim 1, further comprising:
after contacting the initial surface of the glass substrate with the first solution, but before contacting the porous layer with the second solution, the porous layer is washed with deionized water.
11. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the one or more basic salts include KOH.
12. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the temperature of the second solution is room temperature to 80 ℃.
13. The method of claim 1, further comprising:
washing the new surface with water; and
the glass substrate is subjected to a temperature of 70 ℃ to 130 ℃ for a period of 15 minutes to 45 minutes.
14. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the porous layer has a thickness of 400nm to 600 nm.
15. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
9.39 to 18 mol% alumina;
6 to 20 mol% Na2O；
Up to 9.01 mole% boron oxide; and
at least one alkaline earth metal oxide;
wherein-15 mol% is less than or equal to (R)2O+R′O-Al2O3-ZrO2)-B2O32 mol% or less, wherein R is Na and optionally one or more of Li, K, Rb and Cs, and R' is one or more of Mg, Ca, Sr and Ba.
16. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
1 to 10 mol% P2O5；
MgO; and
at least 5 mol% Al2O3；
Wherein 77 mol% SiO is more than or equal to2+Al2O3Not less than 70 mol% and sigma R' O not more than 0.5P2O5(mol%), wherein R' is Mg, Ca, Ba and Sr, and wherein the composition of the mass further comprises at least one monovalent metal oxide modifier R2O, wherein P2O5≤[Σ(R2O)-Al2O3]。
17. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
1 to 10 mol% P2O5；
MgO; and
3 to 25 mol% Na2O；
Wherein 77 mol% SiO is more than or equal to2+Al2O3Not less than 70 mol% and sigma R' O not more than 0.5P2O5(mol%), wherein R' is Mg, Ca, Ba and Sr, wherein P is2O5≤[(Na2O+K2O+Rb2O+Ag2O+Cs2O)-Al2O3]。
18. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
60 to 72 mol% SiO2；
6 to 14 mol% Al2O3；
0 to 15 mol% B2O3；
0 to 1 mol% Li2O；
0 to 20 mol% Na2O；
0 to 10 mol% K2O；
0 to 8 mol% MgO;
0 to 10 mol% CaO;
0 to 5 mol% ZrO2；
0 to 1 mol% SnO2；
0 to 1 mol% CeO2；
Less than 50ppm As2O3(ii) a And
less than 50ppm Sb2O3；
Wherein, Li is more than or equal to 12 mol percent2O+Na2O+K2O is less than or equal to 20 mol percent; and
wherein, MgO + CaO is more than or equal to 0 mol% and less than or equal to 10 mol%.
19. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
at least 50 mol% SiO2；
Less than 10 mol% B2O3(ii) a And
at least 8 mol% Na2O；
Wherein the composition of the block is lithium-free;
wherein, the ratio
And wherein Al2O3(mol%)>B2O3(mol%) and the modifier is Na2O and optionally other than Na2O and Li2One or more alkali metal oxides R other than O2At least one of O, and one or more alkaline earth oxides.
20. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
50 to 72 mol% SiO2；
9 to 17 mol% Al2O3；
Less than 10 mol% B2O3；
8 to 16 mol% Na2O; and
0 to 4 mol% K2O；
Wherein, the ratio
Wherein, Al2O3(mol%)>B2O3(mol%) and the modifier is Na2O and optionally other than Na2O and Li2One or more alkali metal oxides R other than O2At least one of O, and one or more alkaline earth oxides RO; and
wherein the composition of the block is lithium-free.
21. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
at least about 50 mol% SiO2；
At least about 10 mol% R2O, wherein R2O comprises Na2O；
Al2O3Wherein Al is2O3(mol%)<R2O (mol%);
3 to 4.5 mol% B2O3(ii) a And
at least 0.1 mol% of at least one of MgO and ZnO;
wherein, B2O3(mol%) - (R)2O (mol%) -Al2O3(mol%)) is more than or equal to 3 mol%.
22. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the new surface has concave surface features.
23. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
62 to 70 mol% SiO2；
0 to 18 mol% Al2O3；
0 to 10 mol% B2O3；
0 to 15 mol% Li2O；
0 to 20 mol% Na2O；
0 to 18 mol% K2O；
0 to 17 mol% MgO;
0 to 18 mol% CaO; and
0 to 5 mol% ZrO2；
Wherein R is more than or equal to 14 mol percent2O + R 'O is less than or equal to 25 mol percent, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr;
wherein, 10 mol percent is less than or equal to Al2O3+B2O3+ ZrO less than or equal to 30 mol%; and
wherein-15 mol% is less than or equal to (R)2O+R′O-Al2O3-ZrO2)-B2O3Less than or equal to 4 mol percent;
the new surface has concave surface features having an average diameter of 650nm to 750nm and an average peak to valley height of 60nm to 80 nm.
24. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
62 to 67 mol% SiO2；
3 to 7 mol% B2O3；
12 to 15 mol% Al2O3；
12 to 15 mol% Na2O；
0 mol% K2O；
1 to 3.5 mol% MgO;
0 mol% CaO; and
0.02 to 0.14 mol% SnO2(ii) a And
the new surface has concave surface features having an average diameter of 2.5 to 3.5 μm and an average peak to valley height of 650 to 850 nm.
25. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the glass substrate has a composition in bulk comprising:
45 to 65 mol% SiO2；
14 to 25 mol% Al2O3；
4 to 15 mol% P2O5(ii) a And
14 to 20 mol% Na2O；
Wherein the new surface has concave surface features having an average diameter of 9 to 15 μm and an average peak to valley height of 3.5 to 7.5 μm.
26. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,
the porous layer contains silicon atoms, fluorine atoms, and hydrogen atoms in absolute concentrations greater than the bulk of the glass substrate.
27. The method of claim 26, wherein the first and second light sources are selected from the group consisting of,
the porous layer comprises aluminum atoms and sodium atoms in a concentration less than the bulk of the glass substrate.
28. The method of claim 23, wherein the step of,
the glass substrate having a new surface has: distinctness of image from 92 to 99%, gloss-60 from 100 to 145GU, transmission haze from 0.25 to 7.5%, flash value less than 3.5% and transmission greater than 93%.
29. A method of making a glass substrate having a textured surface, comprising:
contacting the initial surface of the glass substrate with a first solution at a temperature of 25 ℃ to 40 ℃ and comprising 0.5 to 0.8M dissolved SiO for a period of time of 5 minutes to 2.5 hours20.5 to 2M H2SiF6And 20 to 60mM H3BO3Thereby forming a porous layer adjacent to the initial surface, the porous layer having a thickness of 400nm to 600nm and comprising fluorine atoms and hydrogen atoms in absolute concentrations greater than the bulk of the glass substrate; and
contacting the porous layer with a second solution in an ultrasonic bath, the second solution having a temperature of 40 ℃ to 80 ℃ and comprising one or more alkaline hydroxides, thereby removing the porous layer and producing a new surface having increased texture compared to the original surface, the new surface having concave surface features.
30. The method of claim 29, wherein the step of,
the glass substrate having a new surface has: distinctness of image from 92 to 99%, gloss-60 from 100 to 145GU, transmission haze from 0.25 to 7.5%, flash value less than 3.5% and transmission greater than 93%.
31. The method of claim 29, wherein the step of,
the concave surface features have one of:
(i) an average diameter of 650nm to 750nm, and an average peak-to-valley height of 60nm to 80 nm;
(ii) an average diameter of 2.5 to 3.5 μm, and an average peak-to-valley height of 650 to 850 nm; or
(iii) The average diameter is 9 μm to 15 μm, and the average peak-to-valley height is 3.5 μm to 7.5 μm.
32. A glass substrate, comprising:
a composition at a block comprising:
45 to 65 mol% SiO2；
14 to 25 mol% Al2O3；
4 to 15 mol% P2O5(ii) a And
14 to 20 mol% Na2O; and
a surface comprising concave surface features having an average diameter of 9 μ ι η to 15 μ ι η and an average peak to valley height of 3.5 μ ι η to 7.5 μ ι η.
33. The glass substrate of claim 32, further comprising:
an image sharpness of 22 to 27%;
gloss-60 of 95 to 105 GU;
a transmission haze of 2.5 to 7.5%;
a flash value of 12 to 16%; and
93.5 to 94.5% transmission.
34. A glass substrate, comprising:
a composition at a block comprising:
62 to 67 mol% SiO2；
3 to 7 mol% B2O3；
12 to 15 mol% Al2O3；
12 to 15 mol% Na2O；
0 mol% K2O；
1 to 3.5 mol% MgO;
0 mol% CaO; and
0.02 to 0.14 mol% SnO2(ii) a And
a surface comprising concave surface features having an average diameter of 2.5 μ ι η to 3.5 μ ι η and an average peak to valley height of 650nm to 850 nm.
35. A glass substrate, comprising:
a composition at a block comprising:
62 to 70 mol% SiO2；
0 to 18 mol% Al2O3；
0 to 10 mol% B2O3；
0 to 15 mol% Li2O；
0 to 20 mol% Na2O；
0 to 18 mol% K2O；
0 to 17 mol% MgO;
0 to 18 mol% CaO; and
0 to 5 mol% ZrO2；
Wherein R is more than or equal to 14 mol percent2O + R 'O is less than or equal to 25 mol percent, wherein R is Li, Na, K, Cs or Rb, and R' is Mg, Ca, Ba or Sr;
wherein, 10 mol percent is less than or equal to Al2O3+B2O3+ ZrO less than or equal to 30 mol%; and
wherein-15 mol% is less than or equal to (R)2O+R′O-Al2O3-ZrO2)-B2O3Less than or equal to 4 mol percent; and
a surface comprising concave surface features having an average diameter of 650nm to 750nm and an average peak to valley height of 60nm to 80 nm.
36. The glass substrate of claim 32, further comprising:
an image sharpness of 92 to 99%;
gloss-60 of 100 to 145 GU;
a transmission haze of 0.25 to 7.5%;
a flash value of less than 3.5%; and
greater than 93% transmission.
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| PCT/US2020/062636 WO2021113196A1 (en) | 2019-12-04 | 2020-12-01 | Method of manufacturing a glass substrate with a textured surface |
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| CN107531559A (en) * | 2015-02-26 | 2018-01-02 | 康宁股份有限公司 | For the product for controlling the method for the surface characteristics body on glass and ceramic product and being formed using this method |
| CN108290775A (en) * | 2015-11-23 | 2018-07-17 | 康宁股份有限公司 | Inorganic coating is removed from glass baseplate |
| US20180282201A1 (en) * | 2017-03-28 | 2018-10-04 | Corning Incorporated | Textured glass articles and methods of making the same |
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