CN117925242A - Etchant for making textured glass articles - Google Patents
Etchant for making textured glass articles Download PDFInfo
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- CN117925242A CN117925242A CN202211271275.XA CN202211271275A CN117925242A CN 117925242 A CN117925242 A CN 117925242A CN 202211271275 A CN202211271275 A CN 202211271275A CN 117925242 A CN117925242 A CN 117925242A
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- glass article
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- 239000011521 glass Substances 0.000 title claims abstract description 153
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 72
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 potassium hexafluorosilicate Chemical compound 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000741 silica gel Substances 0.000 claims abstract description 16
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 16
- JTDPJYXDDYUJBS-UHFFFAOYSA-N quinoline-2-carbohydrazide Chemical compound C1=CC=CC2=NC(C(=O)NN)=CC=C21 JTDPJYXDDYUJBS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 97
- 239000005354 aluminosilicate glass Substances 0.000 claims description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 230000005540 biological transmission Effects 0.000 claims description 22
- 230000003746 surface roughness Effects 0.000 claims description 21
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 19
- 238000007654 immersion Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002834 transmittance Methods 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 230000001351 cycling effect Effects 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229940050410 gluconate Drugs 0.000 claims description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 150000001720 carbohydrates Chemical class 0.000 claims description 6
- 159000000001 potassium salts Chemical class 0.000 claims description 6
- 239000000176 sodium gluconate Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 229960004063 propylene glycol Drugs 0.000 claims description 5
- 235000013772 propylene glycol Nutrition 0.000 claims description 5
- 235000012207 sodium gluconate Nutrition 0.000 claims description 5
- 229940005574 sodium gluconate Drugs 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 description 31
- 239000000843 powder Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 238000000879 optical micrograph Methods 0.000 description 13
- 238000003801 milling Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 229910004074 SiF6 Inorganic materials 0.000 description 4
- 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 4
- 239000000243 solution Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000004224 potassium gluconate Substances 0.000 description 2
- 235000013926 potassium gluconate Nutrition 0.000 description 2
- 229960003189 potassium gluconate Drugs 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 229940071260 lithium gluconate Drugs 0.000 description 1
- ZOTSUVWAEYHZRI-JJKGCWMISA-M lithium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Li+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O ZOTSUVWAEYHZRI-JJKGCWMISA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present application relates to etchants for use in the manufacture of textured glass articles. The etchant comprises: greater than or equal to 20wt% and less than or equal to 45 wt% ammonium bifluoride; greater than or equal to 0.25 wt% and less than or equal to 10 wt% silicon compound; greater than or equal to 5wt% and less than or equal to 30 wt% hydrochloric acid; greater than or equal to 25 wt% and less than or equal to 60 wt% water; and greater than or equal to 0.5 wt% and less than or equal to 20wt% of a polyhydroxy alcohol. The silicon compound includes: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof.
Description
Technical Field
The present specification relates generally to etchants, and in particular, to etchants for manufacturing textured glass articles having sufficient coverage and micro-uniformity of surface features thereon.
Background
Aluminosilicate glass articles can exhibit excellent ion exchange capacity and drop performance. Various industries, including the consumer electronics industry, require reflective materials that have the same or similar strength and fracture toughness properties. However, conventional textured etchants may not produce the coverage and micro-uniformity of surface features on certain aluminosilicate glass articles necessary to achieve a desired appearance.
Thus, there is a need for alternative etchants for producing aluminosilicate glass articles having sufficient coverage and micro-uniformity of surface features thereon.
Disclosure of Invention
According to aspect 1 A1, the etchant may comprise: greater than or equal to 20 wt% and less than or equal to 45 wt% ammonium bifluoride; greater than or equal to 0.25 wt% and less than or equal to 10 wt% of a silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof; greater than or equal to 5 wt% and less than or equal to 30 wt% hydrochloric acid; greater than or equal to 25 wt% and less than or equal to 60 wt% water; and greater than or equal to 0.5 wt% and less than or equal to 20 wt% of a polyhydroxy alcohol.
Aspect 2 A2 includes the etchant according to aspect 1 A1, wherein the polyhydric alcohol includes: pentaerythritol, ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol or combinations thereof.
Aspect 3 A3 includes the etchant according to aspect 1 A1 or aspect 2 A2, wherein the weight ratio of the sum of ammonium bifluoride and silicon compound to the sum of hydrochloric acid, water and polyhydroxy alcohol is 0.3 to 0.9.
Aspect 4 A4 includes the etchant according to any one of aspects 1 to 3 A1 to A3, wherein the etchant contains 0.5 wt% or more and 8 wt% or less of a silicon compound.
Aspect 5 A5 includes the etchant of aspect 4 A4, wherein the etchant comprises greater than or equal to 0.75 wt% and less than or equal to 6 wt% silicon compound.
Aspect 6 A6 includes the etchant according to any one of aspects 1 to 5 A1 to A5, wherein the etchant contains a polyhydric alcohol in an amount of 1% by weight or more and 15% by weight or less.
Aspect 7 A7 includes the etchant of aspect 6 A6, wherein the etchant contains greater than or equal to 1.5 wt% and less than or equal to 10 wt% of a polyhydric alcohol.
Aspect 8 A8 includes the etchant according to any one of aspects 1 to 7 A1 to A7, wherein the etchant contains greater than or equal to 23 wt% and less than or equal to 43 wt% ammonium bifluoride.
Aspect 9 A9 includes the etchant of aspect 8 A8, wherein the etchant comprises greater than or equal to 25 wt% and less than or equal to 40 wt% ammonium bifluoride.
Aspect 10 a10 includes the etchant according to any one of aspects 1 to 9 A1 to A9, wherein the etchant contains 7 wt% or more and 27 wt% or less of hydrochloric acid.
Aspect 11 a11 includes the etchant of aspect 10a 10, wherein the etchant comprises greater than or equal to 10 wt% and less than or equal to 25 wt% hydrochloric acid.
Aspect a12 includes the etchant according to any one of aspects A1 to a11, wherein the etchant contains 30 wt% or more and 55 wt% or less of water.
Aspect 13 a13 includes the etchant according to aspect 1 A1, wherein the etchant comprises: greater than or equal to 25 wt% and less than or equal to 40 wt% ammonium bifluoride; greater than or equal to 0.5 wt% and less than or equal to 4 wt% silica gel; greater than or equal to 13 wt% and less than or equal to 23 wt% hydrochloric acid; greater than or equal to 35 wt% and less than or equal to 55 wt% water; and greater than or equal to 1 wt% and less than or equal to 15 wt% glycerol.
Aspect 14a 14 includes the etchant according to any one of aspects 1 to 13 A1 to a13, wherein the etchant further comprises ammonium fluoride in an amount of 3% by weight or more and 30% by weight or less.
The 15 th aspect a15 includes the etchant according to any one of the 1 st to 14 th aspects A1-a14, wherein the etchant further comprises greater than or equal to 0.25 wt% and less than or equal to 20 wt% of at least one of sodium salt and potassium salt.
According to aspect 16 a16, a method of forming a textured glass article can include: immersing an aluminosilicate glass article in an etchant comprising: greater than or equal to 20 wt% and less than or equal to 45 wt% ammonium bifluoride, greater than or equal to 0.25 wt% and less than or equal to 10 wt% silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or a combination thereof, greater than or equal to 5wt% and less than or equal to 30 wt% hydrochloric acid, greater than or equal to 25wt% and less than or equal to 60 wt% water, and greater than or equal to 0.5 wt% and less than or equal to 20 wt% polyhydroxy alcohol; and cycling the aluminosilicate glass article in the etchant for a duration of time between an upper immersion depth and a lower immersion depth deeper than the upper immersion depth.
Aspect A17 includes the method of aspect A16 of 16, wherein the cycling is performed at a speed greater than or equal to 5cm/s and less than or equal to 30 cm/s.
Aspect 18a 18 includes the method according to aspect 16 a16 or aspect 17 a17, wherein the temperature of the etchant is greater than 10 ℃ and less than or equal to 30 ℃.
Aspect 19a 19 includes the method according to any one of aspects 16 to 18 a16-a18, wherein the cycle time is greater than or equal to 60s and less than or equal to 600s.
Aspect 20a 20 includes the method according to any one of aspects 16 to 19 a16 to a19, wherein the polyhydric alcohol includes: pentaerythritol, ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol or combinations thereof.
Aspect a21 includes the method according to any one of aspects a16 to a20, wherein the weight ratio of the sum of ammonium bifluoride and silicon compound to the sum of hydrochloric acid, water and polyhydroxy alcohol is 0.3 to 0.6.
Aspect 22 a22 includes the method according to any one of aspects 16 to 21 a16-a21, wherein the etchant comprises greater than or equal to 0.5 wt% and less than or equal to 8 wt% silicon compound.
Aspect a23 includes the method according to any one of aspects a16-a22 of 16 to 22, wherein the etchant comprises greater than or equal to 1 wt% and less than or equal to 17 wt% polyhydroxy alcohol.
Aspect 24 a24 includes the method according to any one of aspects 16 to 23 a16-a23, wherein the etchant comprises greater than or equal to 23 wt% and less than or equal to 43 wt% ammonium bifluoride.
Aspect 25 a25 includes the method according to any one of aspects 16 to 24 a16-a24, wherein the etchant comprises greater than or equal to 7 wt% and less than or equal to 27 wt% hydrochloric acid.
Aspect a26 includes the method according to any one of aspects a16-a25 of 16-25, wherein the etchant comprises greater than or equal to 30 wt% and less than or equal to 55 wt% water.
Aspect 27 a27 includes the method of any one of aspects 16-26 a16-a26, wherein the etchant further comprises greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride.
Aspect 28 a28 includes the method of any one of aspects 16-27 a 16-27, wherein the etchant further comprises greater than or equal to 0.25 wt% and less than or equal to 20 wt% of at least one of sodium and potassium salts.
Aspect 29 a29 includes the method of any one of aspects 16-28 a 16-28, wherein the aluminosilicate glass article comprises greater than or equal to 14 mol% Al 2O3.
Aspect 30 a30 includes the method according to any one of aspects 16-29 a16-a29, wherein the aluminosilicate glass article comprises: greater than or equal to 50 mole% and less than or equal to 70 mole% SiO 2; greater than or equal to 10 mole% and less than or equal to 22 mole% Al 2O3; greater than or equal to 0.5 mole% and less than or equal to 5 mole% P 2O5; greater than or equal to 0 mole% and less than or equal to 10 mole% B 2O5; greater than or equal to 0 mole% and less than or equal to 3 mole% MgO; greater than or equal to 0 mole% and less than or equal to 3 mole% ZnO; greater than or equal to 3 mole% and less than or equal to 12 mole% Li 2 O; greater than or equal to 4 mole% and less than or equal to 15 mole% Na 2 O; greater than or equal to 0 mole% and less than or equal to 2 mole% K 2 O; and greater than or equal to 0 mole% and less than or equal to 1 mole% TiO 2.
Aspect a31 includes the method of any one of aspects a16-a30 of aspects 16-30, wherein the textured glass article includes a plurality of polyhedral surface features extending from the first surface, the plurality of polyhedral surface features each comprising: a base on the first surface, a plurality of facets extending from the first surface, a surface feature size at the base of greater than or equal to 50 μιη and less than or equal to 300 μιη, and a surface feature height of greater than or equal to 10 μιη and less than or equal to 40 μιη, wherein the plurality of facets of each polyhedral surface feature converge toward each other.
Aspect a32 includes the method of any one of aspects a16-a30 of 16-30, wherein the textured glass article includes a plurality of polyhedral surface features extending from the first surface, the plurality of polyhedral surface features each comprising: a base on the first surface, a plurality of facets extending from the first surface, a surface feature size at the base of greater than or equal to 50 μιη and less than or equal to 300 μιη, and a surface feature height of greater than or equal to 8 μιη and less than or equal to 40 μιη, wherein the plurality of facets of each polyhedral surface feature converge toward each other.
Aspect 33 a33 includes the method according to aspect 31a 31 or aspect 32 a32, wherein the plurality of polyhedral surface features comprises triangular pyramids (triangular pyramid), rectangular pyramids (quadrangular pyramid), or a combination thereof.
Aspect a34 includes the method of any one of aspects a31-a33 of 31-33, wherein the plurality of polyhedral surface features comprises a face angle of greater than or equal to 13 ° and less than or equal to 20 °.
Aspect a35 includes the method according to any one of aspects a31-a34 of 31-34, wherein the plurality of polyhedral surface features includes a surface roughness of greater than or equal to 2 μιη and less than or equal to 7 μιη.
Aspect a36 includes the method of any one of aspects a31-a34 of 31-34, wherein the plurality of polyhedral surface features comprises a surface roughness greater than or equal to 1 μιη and less than or equal to 7 μιη.
Aspect a37 includes the method of any one of aspects a31-a36 of 31-36, wherein the plurality of polyhedral surface features comprises a transmittance of greater than or equal to 80% and less than or equal to 95%.
Aspect a38 includes the method of any one of aspects a31-a37 of 31-37, wherein the plurality of polyhedral surface features comprises a transmission haze of greater than or equal to 95% and less than or equal to 100%.
Aspect 39 a39 includes the method according to any one of aspects 31-38 a 31-38, wherein the plurality of polyhedral surface features comprises a transmission haze of greater than or equal to 80% and less than or equal to 100%.
Aspect a40 includes the method of any one of aspects a31-a39 of aspects 31-39, wherein the textured glass article has the plurality of polyhedral surface features with sufficient coverage and micro-uniformity.
According to aspect 41 a41, the etchant may comprise: greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride; greater than or equal to 0.25 wt% and less than or equal to 10 wt% of a silicon compound comprising silicon dioxide, a silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or a combination thereof; greater than or equal to 15 wt% and less than or equal to 45 wt% sulfuric acid; greater than or equal to 25 wt% and less than or equal to 60wt% water; and greater than or equal to 0.1 wt% and less than or equal to 10 wt% of a viscosity additive.
Aspect 42 a42 includes the etchant of aspect 41 a41, wherein the viscosity additive comprises: saccharides, metal gluconate, polydiallyl dimethyl ammonium chloride (PDADMAC), or combinations thereof.
Aspect 43 a43 includes the etchant of aspect 11 a41 or 42 a42, wherein the etchant contains greater than or equal to 0.25 wt% and less than or equal to 8 wt% silicon compound.
Aspect 44 a44 includes the etchant of aspect 43 a43, wherein the etchant comprises greater than or equal to 0.5 wt% and less than or equal to 6 wt% silicon compound.
Aspect 45 a45 includes the etchant according to any one of aspects 41 to 44 a41-a44, wherein the etchant comprises greater than or equal to 0.25 wt% and less than or equal to 8 wt% of a viscosity additive.
Aspect a46 includes the etchant of aspect a45, wherein the etchant comprises greater than or equal to 0.5 wt% and less than or equal to 6 wt% of a viscosity additive.
Aspect a47 includes the etchant according to any one of aspects a41 to a46, wherein the etchant contains ammonium fluoride in an amount of 5wt% or more and 27 wt% or less.
Aspect a48 includes the etchant of aspect a47 according to aspect a47, wherein the etchant comprises greater than or equal to 7wt% and less than or equal to 25 wt% ammonium fluoride.
Aspect 49 a49 includes the etchant according to any one of aspects 41 to 48 a41 to a48, wherein the etchant contains sulfuric acid of greater than or equal to 17 wt% and less than or equal to 43 wt%.
Aspect 50 a50 includes the etchant of aspect 49 a49, wherein the etchant comprises greater than or equal to 20 wt% and less than or equal to 40 wt% sulfuric acid.
Aspect 51 a51 includes the etchant according to any one of aspects 41 to 50 a41 to a50, wherein the etchant contains 30 wt% or more and 60 wt% or less of water.
Aspect 52a 52 includes the etchant of aspect 41 a41, wherein the etchant comprises: greater than or equal to 10 wt% and less than or equal to 25 wt% ammonium fluoride; greater than or equal to 0.25 wt% and less than or equal to 2 wt% ammonium hexafluorosilicate; greater than or equal to 25 wt% and less than or equal to 40 wt% sulfuric acid; greater than or equal to 40 wt% and less than or equal to 60 wt% water; and greater than or equal to 0.1 wt% and less than or equal to 4 wt% of at least one of sodium gluconate and polydiallyl dimethyl ammonium chloride (PDADMAC).
According to aspect 53 a53, a method of forming a textured glass article can comprise: immersing an aluminosilicate glass article in an etchant comprising: greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride, greater than or equal to 0.25 wt% and less than or equal to 10 wt% silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or a combination thereof, greater than or equal to 15 wt% and less than or equal to 45 wt% sulfuric acid, greater than or equal to 25wt% and less than or equal to 60 wt% water, and greater than or equal to 0.1 wt% and less than or equal to 10 wt% viscosity additive; and cycling the aluminosilicate glass article in the etchant for a duration of time between an upper immersion depth and a lower immersion depth deeper than the upper immersion depth.
54 Th aspect A54 includes the method according to 53 th aspect A53, wherein the circulating is performed at a speed of greater than or equal to 3cm/s and less than or equal to 30 cm/s.
Aspect 55 a55 includes the method according to aspect 53 a53 or aspect 54 a54, wherein the temperature of the etchant is greater than or equal to 10 ℃ and less than or equal to 30 ℃.
56 Th aspect a56 includes the method according to any one of the 53 th to 55 th aspects a53-a55, wherein the cycle time is greater than or equal to 30s and less than or equal to 600s.
Aspect 57 a57 includes the method according to any one of aspects 53-56 a53-a56, wherein the viscosity additive comprises: saccharides, metal gluconate, polydiallyl dimethyl ammonium chloride (PDADMAC), or combinations thereof.
Aspect 58 a58 includes the method according to any one of aspects 53-57 a53-a57, wherein the etchant comprises greater than or equal to 0.25 wt% and less than or equal to 8 wt% silicon compound.
Aspect a59 includes the method of any one of aspects a53-a58 of aspects 53-58, wherein the etchant comprises greater than or equal to 0.25 wt% and less than or equal to 8 wt% of a viscosity additive.
Aspect 60 a60 includes the method of any one of aspects 53-a59, wherein the etchant comprises greater than or equal to 5wt% and less than or equal to 27 wt% ammonium fluoride.
Aspect 61 a61 includes the method according to any one of aspects 53-60 a 53-60, wherein the etchant comprises greater than or equal to 17 wt% and less than or equal to 43 wt% sulfuric acid.
Aspect 62 a62 includes the method according to any one of aspects 53-61 a 53-61, wherein the etchant comprises greater than or equal to 40 wt% and less than or equal to 60 wt% water.
Aspect 63 a63 includes the method of any one of aspects 53-a62, wherein the aluminosilicate glass article comprises greater than or equal to 14 mol% Al 2O3.
Aspect 64 a64 includes the method of any one of aspects 53-a63, wherein the aluminosilicate glass article comprises: greater than or equal to 50 mole% and less than or equal to 70 mole% SiO 2; greater than or equal to 10 mole% and less than or equal to 22 mole% Al 2O3; greater than or equal to 0.5 mole% and less than or equal to 5 mole% P 2O5; greater than or equal to 0 mole% and less than or equal to 10 mole% B 2O5; greater than or equal to 0 mole% and less than or equal to 3 mole% MgO; greater than or equal to 0 mole% and less than or equal to 3 mole% ZnO; greater than or equal to 4 mole% and less than or equal to 15 mole% Na 2 O; greater than or equal to 0 mole% and less than or equal to 2 mole% K 2 O; and greater than or equal to 0 mole% and less than or equal to 1 mole% TiO 2.
Aspect a65 includes the method according to any one of aspects a53-a64, wherein the textured glass article includes a plurality of polyhedral surface features extending from the first surface, the plurality of polyhedral surface features each comprising: a base on the first surface, a plurality of facets extending from the first surface, a surface feature size at the base that is greater than or equal to 50 μm and less than or equal to 300 μm, wherein the plurality of facets of each polyhedral surface feature converge toward each other.
Aspect 66 a66 includes the method according to aspect 65 a65, wherein the plurality of polyhedral surface features comprises triangular pyramids (triangular pyramid), rectangular pyramids (quadrangular pyramid), or a combination thereof.
Aspect 67 a67 includes the method of any one of aspects 63-66, wherein the textured glass article has the plurality of polyhedral surface features with sufficient coverage and micro-uniformity.
Additional features and advantages of the etchants described herein are 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 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 describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of various embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter.
Drawings
FIG. 1 schematically illustrates an etchant that reacts with an aluminosilicate glass article according to one or more embodiments shown and described herein;
FIG. 2 is a flow chart of a method of forming a textured glass article according to one or more embodiments shown and described herein;
FIG. 3 schematically illustrates method steps for forming a textured glass article according to one or more embodiments shown and described herein;
FIG. 4 schematically illustrates another step of a method of forming a textured glass article according to one or more embodiments shown and described herein;
FIG. 5 schematically illustrates another step of a method of forming a textured glass article according to one or more embodiments shown and described herein;
FIG. 6 schematically illustrates a plan view of a textured glass article according to one or more embodiments shown and described herein;
FIG. 7 schematically illustrates a plan view of a polyhedral surface feature according to one or more embodiments shown and described herein;
FIG. 8 schematically illustrates a plan view of another polyhedral surface feature according to one or more embodiments shown and described herein;
FIG. 9 is a plan view of an exemplary electronic device incorporating any textured glass article according to one or more embodiments described herein;
FIG. 10 is a perspective view of the exemplary electronic device of FIG. 9;
FIG. 11 is a perspective view of the exemplary electronic device of FIG. 9;
FIG. 12 is an optical microscope image at 100 times magnification of a textured glass article according to one or more embodiments shown and described herein;
FIG. 13 is an optical microscope image at 100 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 14 is an optical microscope image at 100 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 15 is an optical microscope image at 100 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 16 is an optical microscope image at 100 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 17 is an optical microscope image at 100 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 18 is an optical microscope image at 100 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 19 is an optical microscope image at 50 times magnification of a comparative textured glass article;
FIG. 20 is an optical microscope image at 50 times magnification of another textured glass article according to one or more embodiments shown and described herein;
FIG. 21 is an optical microscope image at 50 times magnification of another textured glass article according to one or more embodiments shown and described herein; and
FIG. 22 is an optical microscope image at 50 times magnification of another textured glass article according to one or more embodiments shown and described herein.
Detailed Description
Reference will now be made in detail to various embodiments of etchants for forming textured glass articles having substantially covered and micro-uniform polyhedral surface features thereon. According to an embodiment, the etchant comprises: greater than or equal to 20 wt% and less than or equal to 45 wt% ammonium bifluoride; greater than or equal to 0.25 wt% and less than or equal to 10 wt% silicon compound; greater than or equal to 5 wt% and less than or equal to 30 wt% hydrochloric acid; greater than or equal to 25 wt% and less than or equal to 60 wt% water; and greater than or equal to 0.5 wt% and less than or equal to 20 wt% of a polyhydroxy alcohol. The silicon compound includes: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof.
According to other embodiments, the etchant comprises: greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride; greater than or equal to 0.25 wt% and less than or equal to 10 wt% silicon compound; greater than or equal to 15 wt% and less than or equal to 45 wt% sulfuric acid; greater than or equal to 25 wt% and less than or equal to 75 wt% water; and greater than or equal to 0.1 wt% and less than or equal to 10 wt% of a viscosity additive. The silicon compound includes: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof.
Various embodiments of etchants and methods of forming textured glass articles are described herein with particular reference to the accompanying drawings.
Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will also be understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
Directional terms used herein, such as up, down, right, left, front, back, top, bottom, are merely with reference to the drawings being drawn and are not intended to imply absolute orientation.
Unless explicitly stated otherwise, any method described herein should not be understood as requiring that its steps be performed in a specific order or that any apparatus be brought into a particular orientation. Accordingly, no order or orientation is to be inferred in any respect if the method claims do not actually recite an order to be followed by the steps of the method claims, or any device claims do not actually recite an order or orientation of the components, or no additional specific order to be understood by the claims or descriptions is intended to be limited to a specific order or orientation of the components of the device. The same applies to any possible non-explicitly stated interpretation basis including: logic regarding set steps, operational flows, component order, or component orientation; the general meaning obtained from grammatical structures or punctuation; and the number or variety of embodiments described in the specification.
As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a" component includes aspects having two or more such components unless the context clearly indicates otherwise.
In the embodiments of aluminosilicate glass articles described herein, the concentrations of the constituent components (e.g., siO 2 and Al 2O3, etc.) are specified as mole percent (mole%) based on oxide unless otherwise indicated.
As described herein, optical microscope images were obtained by a nikon Eclipse L200N optical microscope at 10 x objective and eyepiece magnification (total 100 x magnification).
As described herein, the "surface feature size" is measured using an optical microscope image at 200 x magnification. Images were obtained with two different 500 μm m x 1000 μm scan areas. In each image, the maximum distance over the cross section of the base of the 10 largest surface features is measured. "surface feature size" refers to the average maximum distance across the cross-section of the base of 20 surface features from these two scans. For example, for a surface feature with a triangular base, the maximum distance across the cross section of the base is the height of the triangular base. For surface features with rectangular pedestals, the maximum distance across the cross section of the pedestal is measured diagonally across the pedestal.
As used herein, "surface feature height" refers to the average polyhedral surface feature distance between the base of a surface feature and the highest vertex of the surface feature.
As used herein, "face angle (FACET ANGLE)" refers to the average polyhedral surface angle between a plane normal to the first surface of the aluminosilicate glass article and a face (facet). The face angle is measured by arctan (height/half length) of the surface features. As used herein, "triangular pyramid face angle" refers to the average face angle of triangular pyramids present on an aluminosilicate glass article. As used herein, "pyramid face angle" refers to the average face angle of a square pyramid present on an aluminosilicate glass article.
As used herein, "surface roughness" refers to the surface texture of a textured glass article quantified by: the arithmetic mean of the absolute values of the profile heights recorded over the evaluation length, which deviate from the mean line, is measured by a Mitutoyo SJ-310 surface roughness meter and according to ISO 1997. Unless otherwise indicated, the values reported herein are micrometers or μm.
As used herein, "transmittance" refers to the average proportion of incident light transmitted over a given wavelength range. As used herein, unless otherwise indicated, "transmittance" is measured by BYK Hazeguard at a thickness of 0.8mm in the wavelength range of 380nm to 720nm according to ASTM D1003.
As used herein, "transmission haze" refers to the ratio of transmitted light scattered at an angle greater than 2.5 ° relative to normal to all transmitted light for the entire transmission. As used herein, transmission haze is measured by standard CIE-C illuminant at a thickness of 0.8mm in the 380nm to 720nm wavelength range according to ASTM D1003, unless otherwise specified.
When used herein to describe a textured glass article, a plurality of polyhedral surface features is "substantially covered" it is meant that the polyhedral surface features cover greater than or equal to 90% of the major surface of the textured glass article.
When used herein to describe a textured glass article, a plurality of polyhedral surface features are "micro-uniform," it is meant that the individual feature sizes do not vary by more than 20%.
When used to describe the structure of a surface feature on a textured glass article, "polyhedral" refers to a three-dimensional shape having flat polygonal faces and straight sides.
When used to describe the structure of a surface feature on a textured glass article, "dendritic" refers to a branched structure.
The etchant is used to achieve a textured surface on the glass article. The properties of the textured surface (including the structure, size, coverage, and micro-uniformity of the surface features) can affect the appearance (e.g., reflectivity or "luminescent effect") of the textured glass article. Polyhedral surface features can achieve better "lighting effects" than dendritic surface features due to their flat polygonal faces and straight sides. While conventional textured etchants may result in polyhedral surface features, such etchants may not result in adequate coverage and micro-uniformity of polyhedral surface features necessary to achieve a desired appearance.
The etchant and method of forming a textured glass article disclosed herein alleviate the above problems so that aluminosilicate glass can be treated to have polyhedral surface features of sufficient coverage and micro-uniformity thereon. In particular, to achieve surface features of sufficient coverage and micro-uniformity to achieve the desired "luminescent effect", the etchants described herein are prepared such that the etchants preferentially produce silicon-based precipitates and such that the amount of aluminum-based precipitates is minimized. Silicon-based precipitates (e.g., metal fluorosilicates (MSiF 6)) result in large polyhedral surface features, which reflect more light than dendritic surface features. Aluminum-based precipitates (e.g., aluminum metal fluoride salts (MAlF 5)) result in small dendritic surface features. Thus, in embodiments, the etchant comprises ammonium bifluoride, a silicon compound, a polyhydroxy alcohol, hydrochloric acid and water. In other embodiments, the etchant comprises ammonium fluoride, silicon compounds, viscosity additives, sulfuric acid, and water.
Ammonium bifluoride and/or ammonium fluoride
Referring now to fig. 1, ammonium bifluoride includes hydrofluoric acid (HF) species and ammonium (NH 4) ions. The etchant 100 reacts with the aluminosilicate glass article 102, which causes HF species from the etchant 100 to diffuse into the aluminosilicate glass article 102 and corrode the Si-O network. SiF 4 is released from the aluminosilicate glass article 102 and reacts with HF to produce SiF 6 2- ions. NH 4 ions from the etchant 100 diffuse to the interface 104 of the etchant 100 and the aluminosilicate glass article 102 and react with SiF 6 2- ions to produce ammonium fluorosilicate (NH 4)2SiF6 precipitates because these precipitates have low solubility in the etchant 100, whereby they deposit onto the surface of the aluminosilicate glass article 102 to form seed crystals 106 (e.g., salt shells (salt crust)).
As the etchant 100 continues to react with the aluminosilicate glass article 102, the seed crystal 106 grows. Since the seed 106 is insoluble in the etchant, the seed 106 acts as an in situ mask. The seed 106 seals a portion of the surface of the aluminosilicate glass article 102. Glass is etched away around seed 106 to create polyhedral surface features 108. The shape of the polyhedral surface features 108 may be determined by the shape of the seed 106, which may be adjusted by varying the composition of the etchant 100 and/or varying the length of time the etchant contacts the aluminosilicate glass article 102.
Thus, the ammonium bifluoride present in etchant 100 acts as a crystallization promoter, encouraging the formation of seed crystals 106. The amount of ammonium bifluoride in etchant 100 should be high enough (e.g., greater than or equal to 20 wt%) to ensure formation of seed 106. The amount of ammonium bifluoride (less than or equal to 45 wt%) may be limited to reduce or prevent undissolved salts that may precipitate out once solubility is reached. Etching of undissolved salts may be different from the etchant and may result in lack of micro-uniformity.
In an embodiment, the etchant 100 may include greater than or equal to 20 wt% and less than or equal to 45 wt% ammonium bifluoride. In an embodiment, the etchant 100 may include greater than or equal to 23 wt% and less than or equal to 43 wt% ammonium bifluoride. In an embodiment, the etchant 100 may include greater than or equal to 25 wt% and less than or equal to 41 wt% ammonium bifluoride. In embodiments, the amount of ammonium bifluoride in etchant 100 may be greater than or equal to 20 wt%, greater than or equal to 23 wt%, greater than or equal to 25 wt%, or even greater than or equal to 27 wt%. In embodiments, the amount of ammonium bifluoride in etchant 100 may be less than or equal to 45 wt%, less than or equal to 43 wt%, less than or equal to 40 wt%, less than or equal to 37 wt%, or even less than or equal to 35 wt%. In an embodiment, the amount of ammonium bifluoride in etchant 100 may be: more than or equal to 20 weight percent and less than or equal to 45 weight percent, more than or equal to 20 weight percent and less than or equal to 43 weight percent, more than or equal to 20 weight percent and less than or equal to 40 weight percent, more than or equal to 20 weight percent and less than or equal to 37 weight percent, more than or equal to 20 weight percent and less than or equal to 35 weight percent, more than or equal to 23 weight percent and less than or equal to 45 weight percent, more than or equal to 23 weight percent and less than or equal to 43 weight percent, more than or equal to 23 weight percent and less than or equal to 40 weight percent, more than or equal to 23 weight percent and less than or equal to 37 weight percent, more than or equal to 23 weight percent and less than or equal to 35 weight percent, more than or equal to 25 weight percent and less than or equal to 45 weight percent, greater than or equal to 25 wt% and less than or equal to 43 wt%, greater than or equal to 25 wt% and less than or equal to 40 wt%, greater than or equal to 25 wt% and less than or equal to 37 wt%, greater than or equal to 25 wt% and less than or equal to 35 wt%, greater than or equal to 27 wt% and less than or equal to 45 wt%, greater than or equal to 27 wt% and less than or equal to 43 wt%, greater than or equal to 27 wt% and less than or equal to 40 wt%, greater than or equal to 27 wt% and less than or equal to 37 wt%, or even greater than or equal to 27 wt% and less than or equal to 35 wt%, or any and all subranges formed by any of these endpoints.
In an embodiment, the etchant 100 may include ammonium fluoride in addition to or instead of ammonium bifluoride. Like ammonium bifluoride, ammonium fluoride is a source of hydrofluoric acid (HF) species and ammonium (NH 4) ions and acts as a crystallization promoter, encouraging the formation of seed crystals. The amount of ammonium fluoride should be high enough (e.g., greater than or equal to 3 wt%) to ensure formation of seed 106. The amount of ammonium fluoride (less than or equal to 30 wt%) may be limited to reduce or prevent undissolved salts that may precipitate out once solubility is achieved. Etching of undissolved salts may be different from the etchant and may result in lack of micro-uniformity.
In an embodiment, the etchant 100 may include greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride. In an embodiment, the etchant 100 may include greater than or equal to 5 wt% and less than or equal to 27 wt% ammonium fluoride. In an embodiment, the etchant 100 may include greater than or equal to 7 wt% and less than or equal to 25 wt% ammonium fluoride. In an embodiment, the etchant 100 may include greater than or equal to 10 wt% and less than or equal to 25 wt% ammonium fluoride. In embodiments, the amount of ammonium fluoride in the etchant 100 can be greater than or equal to 2 wt%, greater than or equal to 7 wt%, greater than or equal to 10 wt%, greater than or equal to 13 wt%, or even greater than or equal to 15 wt%. In embodiments, the amount of ammonium fluoride in the etchant 100 can be less than or equal to 30 wt%, less than or equal to 27 wt%, less than or equal to 25 wt%, less than or equal to 23 wt%, less than or equal to 20 wt%, less than or equal to 17 wt%, less than or equal to 15 wt%, less than or equal to 13 wt%, or even less than or equal to 10 wt%. In an embodiment, the amount of ammonium fluoride in the etchant 100 may be: 3 wt% or more and 30 wt% or less, 3 wt% or more and 27 wt% or less, 3 wt% or less and 25 wt% or less, 3 wt% or less and 23 wt% or less, 3 wt% or less and 20 wt% or less, 3 wt% or less and 17 wt% or less, 3 wt% or less and 15 wt% or less, 3 wt% or less and 13 wt% or less, 3 wt% or less and 10 wt% or less, 5 wt% or less and 30 wt% or less, 5 wt% or less and 27 wt% or less, 5 wt% or less and 25 wt% or less, 5 wt% or less and 23 wt% or less, greater than or equal to 5 weight percent and less than or equal to 20 weight percent, greater than or equal to 5 weight percent and less than or equal to 17 weight percent, greater than or equal to 5 weight percent and less than or equal to 15 weight percent, greater than or equal to 5 weight percent and less than or equal to 13 weight percent, greater than or equal to 5 weight percent and less than or equal to 10 weight percent, greater than or equal to 7 weight percent and less than or equal to 30 weight percent, greater than or equal to 7 weight percent and less than or equal to 27 weight percent, greater than or equal to 7 weight percent and less than or equal to 25 weight percent, greater than or equal to 7 weight percent and less than or equal to 23 weight percent, greater than or equal to 7 weight percent and less than or equal to 20 weight percent, greater than or equal to 7 weight percent and less than or equal to 17 weight percent, greater than or equal to 7 weight percent and less than or equal to 15 weight percent, greater than or equal to 7 weight percent and less than or equal to 13 weight percent, more than or equal to 7 weight percent and less than or equal to 10 weight percent, more than or equal to 10 weight percent and less than or equal to 30 weight percent, more than or equal to 10 weight percent and less than or equal to 27 weight percent, more than or equal to 10 weight percent and less than or equal to 25 weight percent, more than or equal to 10 weight percent and less than or equal to 23 weight percent, more than or equal to 10 weight percent and less than or equal to 20 weight percent, more than or equal to 10 weight percent and less than or equal to 17 weight percent, more than or equal to 10 weight percent and less than or equal to 15 weight percent, more than or equal to 10 weight percent and less than or equal to 13 weight percent, more than or equal to 13 weight percent and less than or equal to 27 weight percent, more than or equal to 13 weight percent and less than or equal to 25 weight percent, greater than or equal to 13 wt% and less than or equal to 23 wt%, greater than or equal to 13 wt% and less than or equal to 20 wt%, greater than or equal to 13 wt% and less than or equal to 17 wt%, greater than or equal to 13 wt% and less than or equal to 15 wt%, greater than or equal to 15 wt% and less than or equal to 30 wt%, greater than or equal to 15 wt% and less than or equal to 27 wt%, greater than or equal to 15 wt% and less than or equal to 25 wt%, greater than or equal to 15 wt% and less than or equal to 23 wt%, greater than or equal to 15 wt% and less than or equal to 20 wt%, or even greater than or equal to 15 wt% and less than or equal to 17 wt%, or any and all subranges formed by any of these endpoints.
In embodiments where the etchant 100 comprises ammonium bifluoride, the amount of ammonium fluoride in the etchant 100 may be: 3 wt% or more and 30 wt% or less, 3 wt% or more and 27 wt% or less, 3 wt% or less and 25 wt% or less, 3 wt% or less and 23 wt% or less, 3 wt% or less and 20 wt% or less, 3 wt% or less and 17 wt% or less, 3 wt% or less and 15 wt% or less, 3 wt% or less and 13 wt% or less, 3 wt% or less and 10 wt% or less, 5 wt% or less and 30 wt% or less, greater than or equal to 5 wt% and less than or equal to 27 wt%, greater than or equal to 5 wt% and less than or equal to 25 wt%, greater than or equal to 5 wt% and less than or equal to 23 wt%, greater than or equal to 5 wt% and less than or equal to 20 wt%, greater than or equal to 5 wt% and less than or equal to 17 wt%, greater than or equal to 5 wt% and less than or equal to 15 wt%, greater than or equal to 5 wt% and less than or equal to 13 wt%, greater than or equal to 5 wt% and less than or equal to 10 wt%, or any and all subranges formed by any of these endpoints.
In embodiments where the etchant 100 does not include ammonium bifluoride, the amount of ammonium fluoride in the etchant 100 may be: 3 wt% or more and 30 wt% or less, 3 wt% or more and 27 wt% or less, 3 wt% or less and 25 wt% or less, 3 wt% or less and 23 wt% or less, 3 wt% or less and 20 wt% or less, 5 wt% or less and 30 wt% or less, 5 wt% or less and 27 wt% or less, 5 wt% or less and 25 wt% or less, 5 wt% or less and 23 wt% or less, 5 wt% or less and 20 wt% or less, 7 wt% or less and 30 wt% or less, 7 wt% or less and 27 wt% or less, or 7 wt% or less and 25 wt% or less, more than or equal to 7 weight percent and less than or equal to 23 weight percent, more than or equal to 7 weight percent and less than or equal to 20 weight percent, more than or equal to 10 weight percent and less than or equal to 30 weight percent, more than or equal to 10 weight percent and less than or equal to 27 weight percent, more than or equal to 10 weight percent and less than or equal to 25 weight percent, more than or equal to 10 weight percent and less than or equal to 23 weight percent, more than or equal to 10 weight percent and less than or equal to 20 weight percent, more than or equal to 13 weight percent and less than or equal to 30 weight percent, more than or equal to 13 weight percent and less than or equal to 27 weight percent, more than or equal to 13 weight percent and less than or equal to 25 weight percent, more than or equal to 13 weight percent and less than or equal to 23 weight percent, more than or equal to 13 weight percent and less than or equal to 20 weight percent, more than or equal to 15 weight percent and less than or equal to 30 weight percent, greater than or equal to 15 wt% and less than or equal to 27 wt%, greater than or equal to 15 wt% and less than or equal to 25 wt%, greater than or equal to 15 wt% and less than or equal to 23 wt%, or even greater than or equal to 15 wt% and less than or equal to 20 wt%, or any and all subranges formed by any of these endpoints.
Silicon compound
The silicon compounds in the etchant 100 may be used to increase the concentration of Si ions (e.g., silica and silica gel) or SiF 6 ions (e.g., ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, or magnesium hexafluorosilicate) to accelerate the precipitation of ammonium fluorosilicate on the aluminosilicate glass article 102. In an embodiment, the silicon compound may include: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof.
The amount of silicon compound in the etchant 100 should be high enough (e.g., greater than or equal to 0.25 wt%) to ensure an increased concentration of Si or SiF 6 ions. The amount of silicon compound (e.g., less than or equal to 10 wt%) may be limited so that the viscosity of the etchant 100 does not increase to a point where adequate coverage and micro-uniformity of the resulting polyhedral surface features cannot be achieved.
In an embodiment, the etchant 100 may include greater than or equal to 0.25 wt% and less than or equal to 10 wt% silicon compound. In an embodiment, the etchant 100 may include greater than or equal to 0.5 wt% and less than or equal to 8 wt% silicon compound. In an embodiment, the etchant 100 may include greater than or equal to 0.75 wt% and less than or equal to 6 wt% silicon compound. In embodiments, the amount of silicon compound in the etchant 100 may be greater than or equal to 0.25 wt%, greater than or equal to 0.5 wt%, greater than or equal to 0.75 wt%, or even greater than or equal to 1 wt%. In embodiments, the amount of silicon compound in the etchant 100 may be less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 6 wt%, or even less than or equal to 4 wt%. In an embodiment, the amount of silicon compound in the etchant 100 may be: greater than or equal to 0.25 wt% and less than or equal to 10 wt%, greater than or equal to 0.25 wt% and less than or equal to 8 wt%, greater than or equal to 0.25 wt% and less than or equal to 6 wt%, greater than or equal to 0.25 wt% and less than or equal to 4 wt%, greater than or equal to 0.5 wt% and less than or equal to 10 wt%, greater than or equal to 0.5 wt% and less than or equal to 8 wt%, greater than or equal to 0.5 wt% and less than or equal to 6 wt%, greater than or equal to 0.5 wt% and less than or equal to 4 wt%, greater than or equal to 0.75 wt% and less than or equal to 10 wt%, greater than or equal to 0.75 wt% and less than or equal to 8 wt%, greater than or equal to 0.75 wt% and less than or equal to 6 wt%, greater than or equal to 0.75 wt% and less than or equal to 4 wt%, greater than or equal to 1 wt% and less than or equal to 10 wt%, greater than or equal to 1 wt% and less than or equal to 8 wt%, greater than or equal to 1 wt% and less than or equal to 6 wt%, or even greater than or equal to 1 wt% and less than or equal to 4 wt%, or any and all subranges formed by any of these endpoints.
Polyhydroxy alcohols or viscosity additives
Polyhydroxy alcohols may be used in etchant 100 to increase the viscosity of the etchant to help regulate the flow of the etchant. Polyhydroxy alcohols may also be used in etchant 100 to reduce the solubility of ammonium fluorosilicate, thereby increasing the precipitation of ammonium fluorosilicate. In an embodiment, the polyhydric alcohol may include: pentaerythritol, ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol or combinations thereof.
The amount of polyol in the etchant 100 should be high enough (e.g., greater than or equal to 0.5 wt%) to ensure an increase in etchant viscosity. The amount of polyhydroxy alcohol (e.g., less than or equal to 20 wt.%) may be limited so that the viscosity of the etchant 100 does not increase to a point where adequate coverage and micro-uniformity of the resulting polyhedral surface features cannot be achieved. In an embodiment, the etchant 100 may include greater than or equal to 0.5 wt% and less than or equal to 20 wt% of a polyhydroxy alcohol. In an embodiment, the etchant 100 may include greater than or equal to 1wt% and less than or equal to 15 wt% of a polyhydroxy alcohol. In an embodiment, the etchant 100 may include greater than or equal to 1.5 wt% and less than or equal to 10 wt% of a polyhydroxy alcohol. In embodiments, the amount of polyhydroxy alcohol in etchant 100 may be greater than or equal to 0.5 wt.%, greater than or equal to 1 wt.%, greater than or equal to 1.5 wt.%, or even greater than or equal to 2 wt.%. In embodiments, the amount of polyhydroxy alcohol in etchant 100 may be less than or equal to 20 wt%, less than or equal to 15 wt%, less than or equal to 10 wt%, or even less than or equal to 5 wt%. In an embodiment, the amount of polyhydroxy alcohol in etchant 100 may be: 0.5 wt% and less than or equal to 20 wt%, 0.5 wt% and less than or equal to 15 wt%, 0.5 wt% and less than or equal to 10 wt%, 0.5 wt% and less than or equal to 5wt%, 1wt% and less than or equal to 20 wt%, 1wt% and less than or equal to 15 wt%, 1wt% and less than or equal to 10 wt%, 1wt% and less than or equal to 5wt%, 1.5 wt% and less than or equal to 20 wt%, 1.5 wt% and less than or equal to 15 wt%, 1.5 wt% and less than or equal to 10 wt%, 1.5 wt% and less than or equal to 5wt%, 2 wt% and less than or equal to 20 wt%, 2 wt% and less than or equal to 15 wt%, and even any of these ranges form any of equal to or less than or equal to 1wt% and less than or equal to 15 wt%, 1.5 wt% and less than or equal to 20 wt%, and 1.5 wt% and 15 wt% or less than or equal to 10 wt%, and 1.5 wt% or equal to 2 wt% and less than or equal to 20 wt%, and any of these ranges.
Instead of a polyhydroxy alcohol, a viscosity additive may be used to increase the viscosity of the etchant to help regulate the flow of the etchant. In an embodiment, the viscosity additive may include: saccharides, metal gluconate, polydiallyl dimethyl ammonium chloride (PDADMAC), or combinations thereof. In an embodiment, the metal gluconate may comprise: sodium gluconate, lithium gluconate, potassium gluconate, calcium gluconate, gluconic acid, or a combination thereof. In an embodiment, the saccharide may include: glucose, sucrose, fructose, or a combination thereof. In embodiments, the viscosity additive may include at least one of sodium gluconate and PDADMAC. The amount of viscosity additive should be high enough (e.g., greater than or equal to 0.1 wt%) to ensure an increase in etchant viscosity. The amount of viscosity additive (e.g., less than or equal to 10 wt%) may be limited so that the viscosity of the etchant 100 does not increase to a point where adequate coverage and micro-uniformity of the resulting polyhedral surface features is not achieved.
In an embodiment, the etchant 100 may include greater than or equal to 0.1 wt% and less than or equal to 10 wt% of a viscosity additive. In an embodiment, the etchant 100 may include greater than or equal to 0.25 wt% and less than or equal to 8 wt% of a viscosity additive. In an embodiment, the etchant 100 may include greater than or equal to 0.5 wt% and less than or equal to 6 wt% of a viscosity additive. In an embodiment, the etchant 100 may include greater than or equal to 0.1 wt% and less than or equal to 4 wt% of a viscosity additive. In an embodiment, the amount of viscosity additive in etchant 100 may be: greater than or equal to 0.1 wt%, greater than or equal to 0.25 wt%, greater than or equal to 0.5 wt%, greater than or equal to 0.75 wt%, or even greater than or equal to 1 wt%. In an embodiment, the amount of viscosity additive in etchant 100 may be: less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 6 wt%, less than or equal to 4 wt%, or even less than or equal to 2 wt%. In an embodiment, the amount of viscosity additive in etchant 100 may be: 0.1 wt% and 10 wt% or less, 0.1 wt% and 8 wt% or less, 0.1 wt% and 6 wt% or less, 0.1 wt% and 4 wt% or less, 0.1 wt% and 8 wt% or less, 0.25 wt% and 10 wt% or less, 0.25 wt% and 8 wt% or less, 0.25 wt% and 6 wt% or less, 0.25 wt% and 4 wt% or less, 0.25 wt% and 2 wt% or less, 0.5 wt% and 10 wt% or less, 0.5 wt% and 8 wt% or less, 0.5 wt% and 6 wt% or less, 0.5 wt% and 4 wt% or less, or 0.75 wt% or 75 wt% or less, or any of these ranges, 0.25 wt% and 6 wt% or less, 0.25 wt% and 0.25 wt% or less, 0.25 wt% and 4 wt% or less, 0.5 wt% or 0.5 wt% and 10 wt% or less, or 0.5 wt% and 8 wt% or 0.5 wt% or less and 6 wt% or less, or 0.5 wt% and 6 wt% or more, or 0.5 wt% or 75 wt% or more, or less, or 0.5 wt% or 75 wt% or more, or less, and any of these.
Hydrochloric acid or sulfuric acid
The hydrochloric acid present in the etchant 100 may function to dissolve the components of the glass network of the aluminosilicate glass article 102 and form the polyhedral surface features 108. The amount of hydrochloric acid in the etchant 100 should be high enough (e.g., greater than or equal to 5 wt.%) to ensure etching of the glass and formation of the textured glass article. The amount of hydrochloric acid (e.g., less than or equal to 30 wt%) may be limited to ensure that polyhedral surface features are created. When excess hydrochloric acid is added, polyhedral surface features may erode to small dimensions, losing their reflective appearance.
In an embodiment, the etchant 100 may include greater than or equal to 5 wt% and less than or equal to 30 wt% hydrochloric acid. In an embodiment, the etchant 100 may include greater than or equal to 7 wt% and less than or equal to 27 wt% hydrochloric acid. In an embodiment, the etchant 100 may include greater than or equal to 10 wt% and less than or equal to 25 wt% hydrochloric acid. In embodiments, the amount of hydrochloric acid in the etchant 100 may be greater than or equal to 5 wt%, greater than or equal to 7 wt%, greater than or equal to 10 wt%, greater than or equal to 13 wt%, or even greater than or equal to 15 wt%. In embodiments, the amount of hydrochloric acid in the etchant 100 may be less than or equal to 30 wt%, less than or equal to 27 wt%, less than or equal to 25 wt%, less than or equal to 23 wt%, or even less than or equal to 20 wt%. In an embodiment, the amount of hydrochloric acid in etchant 100 may be: greater than or equal to 5 weight percent and less than or equal to 30 weight percent, greater than or equal to 5 weight percent and less than or equal to 27 weight percent, greater than or equal to 5 weight percent and less than or equal to 25 weight percent, greater than or equal to 5 weight percent and less than or equal to 23 weight percent, greater than or equal to 5 weight percent and less than or equal to 20 weight percent, greater than or equal to 7 weight percent and less than or equal to 30 weight percent, greater than or equal to 7 weight percent and less than or equal to 27 weight percent, greater than or equal to 7 weight percent and less than or equal to 25 weight percent, greater than or equal to 7 weight percent and less than or equal to 23 weight percent, greater than or equal to 7 weight percent and less than or equal to 20 weight percent, greater than or equal to 10 weight percent and less than or equal to 30 weight percent, greater than or equal to 10 weight percent and less than or equal to 27 weight percent, greater than or equal to 10 weight percent and less than or equal to 25 weight percent, greater than or equal to 10 wt% and less than or equal to 23 wt%, greater than or equal to 10 wt% and less than or equal to 20 wt%, greater than or equal to 13 wt% and less than or equal to 30 wt%, greater than or equal to 13 wt% and less than or equal to 27 wt%, greater than or equal to 13 wt% and less than or equal to 25 wt%, greater than or equal to 13 wt% and less than or equal to 23 wt%, greater than or equal to 13 wt% and less than or equal to 20 wt%, greater than or equal to 15 wt% and less than or equal to 30 wt%, greater than or equal to 15 wt% and less than or equal to 27 wt%, greater than or equal to 15 wt% and less than or equal to 25 wt%, greater than or equal to 15 wt% and less than or equal to 23 wt%, or even greater than or equal to 15 wt% and less than or equal to 20 wt%, or any and all subranges formed by any of these endpoints.
Instead of hydrochloric acid, in an embodiment sulfuric acid may be present in the etchant 100, functioning to dissolve the components of the glass network of the aluminosilicate glass article 102 and to form the polyhedral surface features 108. The amount of sulfuric acid in the etchant 100 should be high enough (e.g., greater than or equal to 15 wt.%) to ensure etching of the glass and formation of the textured glass article. The amount of sulfuric acid (e.g., less than or equal to 45 wt%) may be limited to ensure that polyhedral surface features are created. When excess sulfuric acid is added, polyhedral surface features may erode to small dimensions, losing their reflective appearance.
In an embodiment, the etchant 100 may include greater than or equal to 15 wt% and less than or equal to 45 wt% sulfuric acid. In an embodiment, the etchant 100 may include greater than or equal to 17 wt% and less than or equal to 43 wt% sulfuric acid. In an embodiment, the etchant 100 may include greater than or equal to 20 wt% and less than or equal to 40 wt% sulfuric acid. In an embodiment, the etchant 100 may include greater than or equal to 25 wt% and less than or equal to 40 wt% sulfuric acid. In embodiments, the amount of sulfuric acid in the etchant 100 may be greater than or equal to 15 wt%, greater than or equal to 17 wt%, greater than or equal to 20 wt%, greater than or equal to 23 wt%, or even greater than or equal to 25 wt%. In embodiments, the amount of sulfuric acid in the etchant 100 may be less than or equal to 45 wt%, less than or equal to 43 wt%, less than or equal to 40 wt%, less than or equal to 37 wt%, or even less than or equal to 35 wt%. In an embodiment, the amount of sulfuric acid in the etchant 300 may be: 15% by weight or more and 45% by weight or less, 15% by weight or more and 43% by weight or less, 15% by weight or less and 40% by weight or less, 15% by weight or less and 37% by weight or less, 15% by weight or less and 35% by weight or less, 17% by weight or less and 45% by weight or less, 17% by weight or less and 43% by weight or less, 17% by weight or less and 40% by weight or less, 17% by weight or less and 37% by weight or less, 17% by weight or less and 35% by weight or less, 20% by weight or less and 45% by weight or less, 20% by weight or less and 43% by weight or less, 20% by weight or less and 40% by weight or less, more than or equal to 20 wt% and less than or equal to 37 wt%, more than or equal to 20 wt% and less than or equal to 35 wt%, more than or equal to 23 wt% and less than or equal to 45 wt%, more than or equal to 23 wt% and less than or equal to 43 wt%, more than or equal to 23 wt% and less than or equal to 40 wt%, more than or equal to 23 wt% and less than or equal to 37 wt%, more than or equal to 23 wt% and less than or equal to 35 wt%, more than or equal to 25 wt% and less than or equal to 45 wt%, more than or equal to 25 wt% and less than or equal to 43 wt%, more than or equal to 25 wt% and less than or equal to 40 wt%, more than or equal to 25 wt% and less than or equal to 37 wt%, or even more than or equal to 25 wt% and less than or equal to 35 wt%, or any and all subranges formed by any of these endpoints.
Water and its preparation method
The water present in the etchant 100 may act as a solvent. In an embodiment, the etchant 100 may include greater than or equal to 25 wt% and less than or equal to 60 wt% water. In an embodiment, the etchant 100 may include greater than or equal to 30 wt% and less than or equal to 55 wt% water. In embodiments, the amount of water in the etchant 100 may be greater than or equal to 25 wt%, greater than or equal to 30 wt%, greater than or equal to 35 wt%, or even greater than or equal to 40 wt%. In embodiments, the amount of water in the etchant 100 may be less than or equal to 60 wt%, less than or equal to 55 wt%, or even less than or equal to 50 wt%. In an embodiment, the amount of water in the etchant 100 may be: greater than or equal to 25 wt% and less than or equal to 60 wt%, greater than or equal to 25 wt% and less than or equal to 55 wt%, greater than or equal to 25 wt% and less than or equal to 50wt%, greater than or equal to 30 wt% and less than or equal to 60 wt%, greater than or equal to 30 wt% and less than or equal to 55 wt%, greater than or equal to 30 wt% and less than or equal to 50wt%, greater than or equal to 35 wt% and less than or equal to 60 wt%, greater than or equal to 35 wt% and less than or equal to 55 wt%, greater than or equal to 35 wt% and less than or equal to 50wt%, greater than or equal to 40wt% and less than or equal to 60 wt%, greater than or equal to 40wt% and less than or equal to 55 wt%, or even greater than or equal to 40wt% and less than or equal to 50wt%, or any and all subranges formed by any and all of these endpoints.
In embodiments, the etchant 100 disclosed herein may have a higher viscosity and may be a slurry due to the presence and amount of ammonium bifluoride and silicon compounds. The higher viscosity of the etchant 100 may help regulate the flow of the etchant, resulting in adequate coverage and micro-uniformity of the resulting polyhedral surface features. In embodiments, the weight ratio of the sum of ammonium bifluoride and silicon compound to the sum of hydrochloric acid, water and polyhydroxy alcohol may be from 0.3 to 0.9 or even from 0.3 to 0.6.
Sodium or potassium salts
In an embodiment, the etchant 100 disclosed herein may further include at least one of sodium and potassium salts, and ammonium bifluoride and/or ammonium fluoride, acting as a crystallization promoter, encouraging the formation of seed crystals. In an embodiment, at least one of the sodium salt and the potassium salt may include: sodium chloride, sodium sulfate, sodium thiosulfate, sodium nitrate, sodium fluoride, sodium bifluoride, sodium carbonate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium gluconate, sodium citrate, sodium acetate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, potassium chloride, potassium sulfate, potassium sulfite, potassium nitrate, potassium fluoride, potassium hydrogen fluoride, potassium carbonate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium gluconate, potassium citrate, potassium acetate, or a combination thereof. When present, the amount of at least one of the sodium and potassium salts present in the etchant should ensure seed formation (e.g., greater than or equal to 0.25 wt%). The amount of at least one of the sodium and potassium salts (e.g., less than or equal to 20 wt%) may be limited to reduce or prevent undissolved salts that may precipitate out once solubility is achieved. Etching of undissolved salts may be different from the etchant and may result in lack of micro-uniformity. In embodiments, the etchant may include greater than or equal to 0.25 wt% and less than or equal to 20 wt% of at least one of the sodium salt and the potassium salt. In embodiments, the amount of at least one of the sodium salt and the potassium salt may be greater than or equal to 0.25 wt%, greater than or equal to 0.5 wt%, greater than or equal to 1 wt%, greater than or equal to 1.5 wt%, or even greater than or equal to 2 wt%. In embodiments, the amount of at least one of the sodium salt and the potassium salt may be less than or equal to 20 wt%, less than or equal to 17 wt%, less than or equal to 15 wt%, less than or equal to 13 wt%, less than or equal to 10 wt%, or even less than or equal to 7 wt%. In an embodiment, the amount of at least one of the sodium salt and the potassium salt may be: more than or equal to 0.25 wt% and less than or equal to 20 wt%, more than or equal to 0.25 wt% and less than or equal to 17 wt%, more than or equal to 0.25 wt% and less than or equal to 15 wt%, more than or equal to 0.25 wt% and less than or equal to 13 wt%, more than or equal to 0.25 wt% and less than or equal to 10 wt%, more than or equal to 0.25 wt% and less than or equal to 7 wt%, more than or equal to 0.5 wt% and less than or equal to 20 wt%, more than or equal to 0.5 wt% and less than or equal to 17 wt%, more than or equal to 0.5 wt% and less than or equal to 15 wt%, more than or equal to 0.5 wt% and less than or equal to 13 wt%, more than or equal to 0.5 wt% and less than or equal to 10 wt%, more than or equal to 0.5 wt% and less than or equal to 7 wt%, more than or equal to 1 wt% and less than or equal to 20 wt%, 1% by weight or more and 17% by weight or less, 1% by weight or more and 15% by weight or less, 1% by weight or less and 13% by weight or less, 1% by weight or less and 10% by weight or less, 1% by weight or less and 7% by weight or less, 1.5% by weight or less and 20% by weight or less, 1.5% by weight or less and 17% by weight or less, 1.5% by weight or less and 15% by weight or less, 1.5% by weight or less and 13% by weight or less, 1.5% by weight or less and 10% by weight or less, 1.5% by weight or less and 7% by weight or less, 2% by weight or less and 20% by weight or 2% by weight or less and 17% by weight or less, greater than or equal to 2 wt% and less than or equal to 15 wt%, greater than or equal to 2 wt% and less than or equal to 13 wt%, greater than or equal to 2 wt% and less than or equal to 10 wt%, or even greater than or equal to 2 wt% and less than or equal to 7 wt%, or any and all subranges formed by any of these endpoints.
In an embodiment, the etchant may comprise: greater than or equal to 25 wt% and less than or equal to 40 wt% ammonium bifluoride; greater than or equal to 0.5 wt% and less than or equal to 4 wt% silica gel; greater than or equal to 13 wt% and less than or equal to 23 wt% hydrochloric acid; greater than or equal to 35 wt% and less than or equal to 25 wt% water; and greater than or equal to 1 wt% and less than or equal to 15 wt% glycerol.
In an embodiment, the etchant may comprise: greater than or equal to 10wt% and less than or equal to 25 wt% ammonium fluoride; greater than or equal to 0.25 wt% and less than or equal to 2 wt% ammonium hexafluorosilicate; greater than or equal to 25 wt% and less than or equal to 40 wt% sulfuric acid; greater than or equal to 40 wt% and less than or equal to 60 wt% water; and greater than or equal to 0.1 wt% and less than or equal to 4 wt% of at least one of metal gluconate and polydiallyl dimethyl ammonium chloride (PDADMAC).
Method of forming textured glass articles
Referring now to fig. 2 and 3, a method 200 of forming a textured glass article begins at block 202: the aluminosilicate glass article 102 is laminated with the laminate 320. The aluminosilicate glass article 102 may be in the form of a sheet. In an embodiment, the laminate 320 may be a polyethylene film having an adhesive layer. In an embodiment, lamination of the aluminosilicate glass article 102 may be performed in a roll lamination machine.
In an embodiment, the aluminosilicate glass article 102 can comprise greater than or equal to 14 mole% Al 2O3. In an embodiment, the aluminosilicate glass article 102 can comprise: greater than or equal to 50 mole% and less than or equal to 70 mole% SiO 2; greater than or equal to 10 mole% and less than or equal to 22 mole% Al 2O3; greater than or equal to 0.5 mole% and less than or equal to 5 mole% P 2O5; greater than or equal to 0 mole% and less than or equal to 10 mole% B 2O5; greater than or equal to 0 mole% and less than or equal to 3 mole% MgO; greater than or equal to 0 mole% and less than or equal to 3 mole% ZnO; greater than or equal to 3 mole% and less than or equal to 12 mole% Li 2 O; greater than or equal to 4 mole% and less than or equal to 15 mole% Na 2 O; greater than or equal to 0 mole% and less than or equal to 2 mole% K 2 O; and greater than or equal to 0 mole% and less than or equal to 1 mole% TiO 2.
Returning to fig. 2, in an embodiment, the method 200 may optionally proceed to block 204: the aluminosilicate glass article 102 is pre-cleaned (e.g., after washing with DI water, for example) in an aqueous solution and dried (e.g., in an oven).
Returning to FIG. 2 and referring now to FIG. 4, the method 200 continues with block 206: the aluminosilicate glass article 102 is immersed in the etchant 100. Etchant 100 may be an etchant as disclosed herein. In an embodiment, the etchant 100 may be prepared by: the components in powder form are blended by hand milling and the components in liquid/solvent form are pre-mixed and stirred to a homogeneous state. The mixture of powder and liquid may be poured and stirred. The resulting etchant 100 may age for greater than or equal to 2 hours before immersing the aluminosilicate glass article 102.
In an embodiment, the temperature of the etchant 100 may be greater than or equal to 10 ℃ and less than or equal to 30 ℃. In embodiments, the temperature of the etchant 100 may be greater than or equal to 10 ℃, greater than or equal to 12 ℃, greater than or equal to 14 ℃, or even greater than or equal to 16 ℃. In embodiments, the temperature of the etchant 100 may be less than or equal to 30 ℃, less than or equal to 28 ℃, less than or equal to 26 ℃, or even less than or equal to 24 ℃. In an embodiment, the temperature of the etchant 100 may be: greater than or equal to 10 ℃ and less than or equal to 30 ℃, greater than or equal to 10 ℃ and less than or equal to 28 ℃, greater than or equal to 10 ℃ and less than or equal to 26 ℃, greater than or equal to 10 ℃ and less than or equal to 24 ℃, greater than or equal to 12 ℃ and less than or equal to 30 ℃, greater than or equal to 12 ℃ and less than or equal to 28 ℃, greater than or equal to 12 ℃ and less than or equal to 26 ℃, greater than or equal to 12 ℃ and less than or equal to 24 ℃, greater than or equal to 14 ℃ and less than or equal to 30 ℃, greater than or equal to 14 ℃ and less than or equal to 28 ℃, greater than or equal to 14 ℃ and less than or equal to 26 ℃, greater than or equal to 14 ℃ and less than or equal to 24 ℃, greater than or equal to 16 ℃ and less than or equal to 30 ℃, greater than or equal to 16 ℃ and less than or equal to 28 ℃, greater than or equal to 16 ℃ and less than or equal to 24 ℃, or equal to 16 ℃ or equal to or greater than or equal to 16 ℃ and less than or equal to 24 ℃, or any and all subranges formed by any and all of these endpoints.
In an embodiment, as shown in fig. 4, aluminosilicate glass article 102 may be secured to arms 322 to aid in immersing aluminosilicate glass article 102 in etchant 100. For example, in an embodiment, an adhesive or suction cup 324 may be disposed between the stack 324 and the arm 320 to secure the aluminosilicate glass article 102 to the arm 322. The arm 322 may be lowered into a tank 326 containing the etchant 100 to immerse the aluminosilicate glass article 102 in the etchant 100.
Returning to fig. 2 and 4 and referring now to fig. 5, the method continues with block 208: the aluminosilicate glass article 102 is caused to circulate in the etchant 100 between an upper immersion depth D1 (shown in fig. 4) and a lower immersion depth D2 (shown in fig. 5) for a circulation time. In an embodiment, the cycling of the aluminosilicate glass article 102 is performed by the repeated up-and-down motion of the arm 322. The lower immersion depth D2 is deeper than the upper immersion depth D1 relative to the surface 328 of the etchant 100.
In embodiments, the circulation may be performed at a speed of greater than or equal to 5cm/s and less than or equal to 30 cm/s. In embodiments, the circulation speed may be greater than or equal to 5cm/s or even greater than or equal to 10cm/s. In embodiments, the circulation speed may be less than or equal to 30cm/s, less than or equal to 25cm/s, or even less than or equal to 20cm/s. In an embodiment, the speed at which the cycle is performed may be: greater than or equal to 5cm/s and less than or equal to 30cm/s, greater than or equal to 5cm/s and less than or equal to 25cm/s, greater than or equal to 5cm/s and less than or equal to 20cm/s, greater than or equal to 10cm/s and less than or equal to 30cm/s, greater than or equal to 10cm/s and less than or equal to 25cm/s, or even greater than or equal to 10cm/s and less than or equal to 20cm/s, or any and all subranges formed by any of these endpoints.
In embodiments, the circulation may be performed at a speed of greater than or equal to 3cm/s and less than or equal to 30 cm/s. In embodiments, the circulation speed may be greater than or equal to 3cm/s, greater than or equal to 5cm/s, or even greater than or equal to 10cm/s. In embodiments, the circulation speed may be less than or equal to 30cm/s, less than or equal to 25cm/s, or even less than or equal to 20cm/s. In an embodiment, the speed at which the cycle is performed may be: greater than or equal to 3cm/s and less than or equal to 30cm/s, greater than or equal to 3cm/s and less than or equal to 25cm/s, greater than or equal to 3cm/s and less than or equal to 20cm/s, greater than or equal to 5cm/s and less than or equal to 30cm/s, greater than or equal to 5cm/s and less than or equal to 25cm/s, greater than or equal to 5cm/s and less than or equal to 20cm/s, greater than or equal to 10cm/s and less than or equal to 30cm/s, greater than or equal to 10cm/s and less than or equal to 25cm/s, or even greater than or equal to 10cm/s and less than or equal to 20cm/s, or any and all subranges formed by any of these endpoints.
The cycling helps achieve adequate coverage and micro-uniformity of the polyhedral surface features. In an embodiment, the cycle time may be greater than or equal to 60s and less than or equal to 600s. In embodiments, the cycle time may be greater than or equal to 60s, greater than or equal to 120s, greater than or equal to 180s, or even greater than or equal to 240s. In embodiments, the cycle time may be less than or equal to 600s, less than or equal to 480s, or even less than or equal to 360s. In an embodiment, the cycle time may be: greater than or equal to 60s and less than or equal to 600s, greater than or equal to 60s and less than or equal to 480s, greater than or equal to 60s and less than or equal to 360s, greater than or equal to 120s and less than or equal to 600s, greater than or equal to 120s and less than or equal to 480s, greater than or equal to 360s, greater than or equal to 180s and less than or equal to 600s, greater than or equal to 180s and less than or equal to 480s, or even greater than or equal to 180s and less than or equal to 360s, or any and all subranges formed by any of these endpoints.
In an embodiment, the cycle time may be greater than or equal to 30s and less than or equal to 600s. In embodiments, the cycle time may be greater than or equal to 30s, greater than or equal to 60s, greater than or equal to 120s, greater than or equal to 180s, or even greater than or equal to 240s. In embodiments, the cycle time may be less than or equal to 600s, less than or equal to 480s, or even less than or equal to 360s. In an embodiment, the cycle time may be: greater than or equal to 30s and less than or equal to 600s, greater than or equal to 30s and less than or equal to 480s, greater than or equal to 30s and less than or equal to 360s, greater than or equal to 60s and less than or equal to 600s, greater than or equal to 60s and less than or equal to 480s, greater than or equal to 360s, greater than or equal to 120s and less than or equal to 600s, greater than or equal to 120s and less than or equal to 480s, greater than or equal to 120s and less than or equal to 360s, greater than or equal to 180s and less than or equal to 600s, greater than or equal to 180s and less than or equal to 480s, or even greater than or equal to 180s and less than or equal to 360s, or any and all subranges formed by any of these endpoints.
Returning to fig. 2 and 6, the method 200 continues with block 210: the aluminosilicate glass article 102 is removed from the etchant 100, the aluminosilicate glass article 102 is cleaned to remove the etchant 100 and seed 106 from the surface, and the article is dried to form a textured glass article 340 having polyhedral surface features 108. The aluminosilicate glass article 102 may be removed from the arm 322. In an embodiment, the etchant may be rinsed from the aluminosilicate glass article 102 by Deionized (DI) water. In an embodiment, the seed crystals 106 adhering to the aluminosilicate glass article 102 may be removed or washed away by, for example, a wash sponge. In an embodiment, the laminate 320 may be removed. In embodiments, the aluminosilicate glass article 102 can be dried in ambient conditions or in an oven.
As shown in fig. 6, the resulting textured glass article 340 includes a plurality of polyhedral surface features 108 extending from a first surface 342. Each of the plurality of polyhedral surface features 108 includes a base 344 on the first surface 342, a plurality of faces 346 extending from the first surface 342, and at least one vertex 348.
In an embodiment, the faces 346 of each polyhedral surface feature 108 extend from the first surface 342 and converge toward one another to form a polyhedral topography (e.g., having a pyramid shape that is triple-symmetrical or quadruple-symmetrical) of the polyhedral surface feature 108. For example, as shown in fig. 7 and 8, in an embodiment, the polyhedral surface features 108 may comprise triangular pyramids 108a, rectangular pyramids 108b, or a combination thereof.
In an embodiment, the surface feature size at the base 344 may be greater than or equal to 50 μm and less than or equal to 300 μm. In embodiments, the surface feature size at the base 344 may be greater than or equal to 50 μm, greater than or equal to 75 μm, or even greater than or equal to 100 μm. In embodiments, the surface feature size at the pedestals 344 can be less than or equal to 300 μm, less than or equal to 250 μm, less than or equal to 200 μm, or even less than or equal to 150 μm. In an embodiment, the surface feature dimensions at the base 344 may be: greater than or equal to 50 μm and less than or equal to 300 μm, greater than or equal to 50 μm and less than or equal to 250 μm, greater than or equal to 50 μm and less than or equal to 200 μm, greater than or equal to 50 μm and less than or equal to 150 μm, greater than or equal to 75 μm and less than or equal to 300 μm, greater than or equal to 75 μm and less than or equal to 250 μm, greater than or equal to 75 μm and less than or equal to 200 μm, greater than or equal to 75 μm and less than or equal to 150 μm, greater than or equal to 100 μm and less than or equal to 300 μm, greater than or equal to 100 μm and less than or equal to 250 μm, greater than or equal to 100 μm and less than or equal to 200 μm, or even greater than or equal to 100 μm and less than or equal to 150 μm, or any and all subranges formed by any of these endpoints.
In an embodiment, the surface feature height may be greater than or equal to 10 μm and less than or equal to 40 μm. In an embodiment, the surface feature height may be greater than or equal to 8 μm and less than or equal to 40 μm. In an embodiment, the surface feature height may be: greater than or equal to 8 μm, greater than or equal to 10 μm, greater than or equal to 12 μm, or even greater than or equal to 15 μm. In an embodiment, the surface feature height may be: less than or equal to 40 μm, less than or equal to 35 μm, less than or equal to 30 μm, less than or equal to 25 μm, or even less than or equal to 20 μm. In some embodiments, the surface feature height may be: 8 μm and 40 μm or less, 8 μm and 35 μm or less, 8 μm and 30 μm or less, 8 μm and 25 μm or less, 8 μm and 20 μm or less, 10 μm and 40 μm or less, 10 μm and 35 μm or less, 10 μm and 30 μm or less, 10 μm and 25 μm or less, 20 μm or less, 40 μm or less, 15 μm or less, or any of these ranges, 10 μm or more and 25 μm or less, 10 μm or less and 20 μm or less, 12 μm or less and 40 μm or less, 12 μm or less and 35 μm or less, 12 μm or less, 30 μm or less, 25 μm or less, 15 μm or less, or 15 μm or more, or any of which is equal to the range, 15 μm or less.
In an embodiment, the polyhedral surface features 108 may comprise a face angle of greater than or equal to 13 ° and less than or equal to 20 °. In an embodiment, the polyhedral surface features 108 may comprise a face angle of greater than or equal to 13 °, or even greater than or equal to 15 °. In an embodiment, the polyhedral surface features 108 may comprise a face angle of less than or equal to 20 °, or even less than or equal to 18 °. In an embodiment, the polyhedral surface features 108 may include the following angles: greater than or equal to 13 ° and less than or equal to 20 °, greater than or equal to 13 ° and less than or equal to 18 °, greater than or equal to 15 ° and less than or equal to 20 °, or even greater than or equal to 15 ° and less than or equal to 18 °, or any and all subranges formed by any of these endpoints.
In an embodiment, the polyhedral surface features 108 may comprise a surface roughness of greater than or equal to 2 μm and less than or equal to 7 μm. In an embodiment, the polyhedral surface features 108 may comprise a surface roughness of greater than or equal to 2 μm or even greater than or equal to 4 μm. In an embodiment, the polyhedral surface features 108 may comprise a surface roughness of less than or equal to 7 μm or even less than or equal to 6 μm. In an embodiment, the polyhedral surface features 108 may include the following surface roughness: greater than or equal to 2 μm and less than or equal to 7 μm, greater than or equal to 2 μm and less than or equal to 6 μm, greater than or equal to 4 μm and less than or equal to 7 μm, or even greater than or equal to 4 μm and less than or equal to 6 μm, or any and all subranges formed by any of these endpoints.
In an embodiment, the polyhedral surface features 108 may comprise a surface roughness of greater than or equal to 1 μm and less than or equal to 7 μm. In an embodiment, the polyhedral surface features 108 may comprise a surface roughness of greater than or equal to 1 μm or even greater than or equal to 3 μm. In an embodiment, the polyhedral surface features 108 may comprise a surface roughness of less than or equal to 7 μm or even less than or equal to 6 μm. In an embodiment, the polyhedral surface features 108 may include the following surface roughness: greater than or equal to 1 μm and less than or equal to 7 μm, greater than or equal to 1 μm and less than or equal to 6 μm, greater than or equal to 3 μm and less than or equal to 7 μm, or even greater than or equal to 3 μm and less than or equal to 6 μm, or any and all subranges formed by any of these endpoints.
In an embodiment, the polyhedral surface features 108 may comprise a transmittance of greater than or equal to 80% and less than or equal to 95%. In an embodiment, the polyhedral surface features 108 may comprise a transmittance of greater than or equal to 80%, or even greater than or equal to 85%. In an embodiment, the polyhedral surface features 108 may comprise a transmittance of less than or equal to 95%, or even less than or equal to 90%. In an embodiment, the polyhedral surface features 108 may comprise the following transmittance: greater than or equal to 80% and less than or equal to 95%, greater than or equal to 80% and less than or equal to 90%, greater than or equal to 85% and less than or equal to 95%, or even greater than or equal to 85% and less than or equal to 90%, or any and all subranges formed by any of these endpoints.
In an embodiment, the polyhedral surface features 108 may comprise a transmission haze of greater than or equal to 95% and less than or equal to 100%. In an embodiment, the polyhedral surface features 108 may comprise a transmission haze of greater than or equal to 95%, greater than or equal to 97%, or even greater than or equal to 99%. In an embodiment, the polyhedral surface features 108 may comprise a transmission haze of less than or equal to 100%. In an embodiment, the polyhedral surface features 108 include the following transmission haze: greater than or equal to 95% and less than or equal to 100%, greater than or equal to 97% and less than or equal to 100%, or even greater than or equal to 99% and less than or equal to 100%, or any and all subranges formed by any of these endpoints.
In an embodiment, the polyhedral surface features 108 may comprise a transmission haze of greater than or equal to 80% and less than or equal to 100%. In an embodiment, the polyhedral surface features 108 may comprise a transmission haze of greater than or equal to 80%, greater than or equal to 85%, or even greater than or equal to 90%. In an embodiment, the polyhedral surface features 108 may comprise a transmission haze of less than or equal to 100%. In an embodiment, the polyhedral surface features 108 include the following transmission haze: greater than or equal to 80% and less than or equal to 100%, greater than or equal to 85% and less than or equal to 100%, or even greater than or equal to 90% and less than or equal to 100%, or any and all subranges formed by any of these endpoints.
The structure and size of each polyhedral surface feature 108 and its sufficient coverage micro-uniformity helps achieve enhanced luminescence.
The textured glass articles described herein can be used in a variety of applications including, for example: back overlay applications in consumer or business electronics devices (e.g., smartphones, tablets, personal computers, superbooks, televisions, and cameras). An exemplary article incorporating any textured glass article as disclosed herein is shown in fig. 9-11. In particular, fig. 9-11 show a consumer electronic device 400 comprising: a housing 402 having a front surface 404, a back surface 406, and side surfaces 408; an electronic assembly (not shown) located at least partially or entirely within the housing and including at least a controller, a memory, and a display 410 located at or adjacent to a front surface of the housing; and a cover substrate 412 positioned on or over the front surface of the housing so as to be positioned over the display. In an embodiment, a portion of the housing 402 (e.g., the back surface 406) may comprise any textured glass article as disclosed herein.
Examples
For easier understanding of the various embodiments, reference is made to the following examples, which illustrate various embodiments of the etchant described herein.
Table 1 shows the compositions (in mole%) of glass articles A, B, C and D treated as described below. It is to be noted that references to "glass article a", "glass article B", "glass article C" and "glass article D" refer to glass articles having the corresponding compositions as shown in table 1. References to glass articles a-D do not refer to the same glass articles a-D, respectively, which are treated multiple times with various etchants.
TABLE 1
Table 2 shows the compositions (in weight%) of example etchants A-I and comparative etchant X.
TABLE 2
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Table 2 (subsequent)
Table 3 shows the properties of example articles A-G formed as described in examples 1-7 below.
TABLE 3 Table 3
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Table 3 (subsequent)
Example 1: example textured article A (example etchant A and glass article A)
To obtain example etchant a, 616g of blended powder comprising 97.5 wt% NH 4HF2 and 2.5 wt% SiO 2 gel was obtained by hand milling. 1212g of premix solvent containing 26.0 wt% HCl, 71.0 wt% H 2 O and 3.0 wt% C 3H8O3 are obtained and stirred thoroughly. The mixing of the powder and solvent was performed at 24 ℃. The etchant was cooled to 12 ℃.
Glass article a was cut to a size of 50x50mm and laminated on one side. The laminated glass article a was sonicated in a 3% parker aqueous solution for 10 minutes, followed by extensive rinsing with flowing DI water. After this, glass article a was dried in an oven at 60 ℃ and then placed under ambient conditions until glass article a cooled to 24 ℃.
Glass article A was immersed and circulated in example etchant A at a circulation rate of 20cm/s for a period of 240 seconds. Example etchant a temperature was 12 ℃.
The etched glass article a was rinsed with flowing DI water. The precipitate on the etched glass article was removed by scraping and the laminate was peeled off. The glass article was placed in a 60 ℃ oven until dry.
Referring now to fig. 12, example textured article a resulted from treating glass article a with example etchant a with sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 12, the example textured article a includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article a had: a surface feature size of 140 μm, a surface feature height of 30 μm, a triangular pyramid face angle of 18.5 °, a rectangular pyramid face angle of 19.0 °, a surface roughness of 6.0 μm, a transmittance of 91.5%, and a transmission haze of 100.0%.
Example 2: example textured article B (example etchant B and glass article B)
To obtain example etchant B, 153g of blended powder comprising 98.0 wt% NH 4HF2 and 2.5 wt% SiO 2 gel was obtained by hand milling. 351g of premix solvent containing 27.0 wt% HCl, 59.4 wt% H 2 O, and 13.6 wt% C 3H8O3 were obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etchant was cooled to 16 ℃.
Before etching, the glass article B was subjected to the same treatment as the glass article a in example 1.
The glass article B was immersed and circulated in example etchant B at a circulation rate of 10cm/s for a period of 120 s. The temperature of example etchant B was 16 ℃.
After etching, the etched glass article B was subjected to the same treatment as that of the glass article a in example 1.
Referring now to fig. 13, example textured article B resulted from treating glass article B with example etchant B with sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 13, the example textured article B includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article B had: 115 μm surface feature size, 13 μm surface feature height, 15.0 ° triangular pyramid face angle, 15.0 ° rectangular pyramid face angle, 4.0 μm surface roughness, 90.2% transmittance, and 99.5% transmission haze.
Example 3: example textured article C (example etchant C and glass article C)
To obtain example etchant C, 616g of blended powder comprising 92.5 wt% NH 4HF2 and 7.5 wt% SiO 2 gel was obtained by hand milling. 1114g of premix solvent containing 25.1 wt% HCl, 71.4 wt% H 2 O and 3.5 wt% C 3H8O3 were obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etchant was cooled to 14 ℃.
Before etching, the glass article C was subjected to the same treatment as the glass article a in example 1.
The glass article C was immersed and circulated in the example etchant C for a period of 300 seconds at a circulation rate of 15 cm/s. The temperature of etchant C was 14 ℃.
After etching, the etched glass article C was subjected to the same treatment as that of the glass article a in example 1.
Referring now to fig. 14, example textured article C resulted from treating glass article C with example etchant C with sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 14, the example textured article C includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article C has: a surface feature size of 89 μm, a surface roughness of 4.6 μm, a transmittance of 89.5%, and a transmission haze of 99.5%.
Example 4: example textured article D (example etchant D and glass article D)
Example etchant C was prepared as described in example 3.
Before etching, the glass article D was subjected to the same treatment as the glass article a in example 1.
The glass article D was immersed and circulated in the example etchant C for a period of 300 seconds at a circulation rate of 15 cm/s. The temperature of etchant C was 14 ℃.
After etching, the etched glass article D was subjected to the same treatment as that of the glass article a in example 1.
Referring now to fig. 15, example textured article D resulted from treating glass article D with example etchant C with sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 15, the example textured article D includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article D has: a surface feature size of 105 μm, a surface roughness of 4.5 μm, a transmittance of 90%, and a transmission haze of 99.7%.
Example 5: example textured article E (example etchant D and glass article B)
To obtain example etchant D, 195g of blended powder comprising 69.5 wt% NH 4HF2, 28 wt% NaF, and 2.5 wt% SiO 2 gel was obtained by hand milling. 306g of premix solvent containing 22.7 wt% HCl, 68.1 wt% H 2 O and 9.2 wt% C 3H8O3 were obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etchant was maintained at 24 ℃.
Before etching, the glass article B was subjected to the same treatment as the glass article a in example 1.
The glass article B was immersed and circulated in the example etchant D at a circulation rate of 10cm/s for a period of 120 s. The temperature of etchant D was 24 ℃.
After etching, the glass article B was subjected to the same treatment as that of the glass article a in example 1.
Referring now to fig. 16, example textured article E resulting from treatment of glass article B with example etchant D has sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 16, the example textured article E includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article E has: a surface feature size of 90 μm, a surface feature height of 15 μm, a surface roughness of 2.7 μm, a transmittance of 91.5%, and a transmission haze of 86.6%.
Example 6: example textured article F (example etchant E and glass article B)
To obtain example etchant E, 183g of blended powder comprising 88.5 wt% NH 4HF2, 8.7 wt% KHF 2, and 2.7 wt% SiO 2 gel was obtained by hand milling. 410g of a premix solvent containing 21.7 wt% HCl, 50.7 wt% H 2 O, and 27.6 wt% C 3H8O3 was obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The mixture was heated to 28 ℃.
Before etching, the glass article B was subjected to the same treatment as the glass article a in example 1.
The glass article B was immersed and circulated in the example etchant E at a circulation rate of 20cm/s for a period of 120 s. The temperature of etchant E was 28 ℃.
After etching, the glass article B was subjected to the same treatment as that of the glass article a in example 1.
Referring now to fig. 17, example textured article F resulting from treatment of glass article B with example etchant E has sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 17, the example textured article F includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article F had: a surface feature size of 65 μm, a surface feature height of 9 μm, a surface roughness of 1.4 μm, a transmittance of 90.6%, and a transmission haze of 93.5%.
Example 7: example textured article G (example etchant F and glass article A)
To obtain example etchant F, 164.5g of blended powder comprising 60.8 wt% NH 4HF2, 18.5 wt% NH 4 F, 17.6 wt% NaF, and 1.2 wt% SiO 2 gel was obtained by hand milling. 323g of premix solvent containing 22.8 wt% HCl, 68.2 wt% H 2 O and 9.0 wt% C 3H8O3 was obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etchant was cooled to 16 ℃.
Before etching, the glass article a was subjected to the same treatment as that of the glass article a in example 1.
The glass article A was immersed and circulated in the example etchant F at a circulation rate of 10cm/s for a period of 200 s. The temperature of etchant F was 16 ℃.
After etching, the glass article B was subjected to the same treatment as that of the glass article a in example 1.
Referring now to fig. 18, example textured article G resulting from treatment of glass article a with example etchant F has sufficient coverage and micro-uniformity of the resulting polyhedral surface features. As shown in fig. 18, the example textured article G includes triangular pyramids and rectangular pyramids.
As shown in table 3 above, example textured article G has: a surface feature size of 96 μm, a surface feature height of 17 μm, a surface roughness of 3.3 μm, a transmittance of 91.0%, and a transmission haze of 98.5%.
Comparative example 1: comparative textured article X (comparative etchant X and glass article A)
To obtain comparative etchant X, a blended powder comprising 89.7g NH 4 F and 3g (NH) 2SiF6 was obtained by hand milling. A premix solvent containing 167.08g (96.5 wt%) H 2SO4 and 238.7g H 2 O was obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etching solution was aged for 2 hours.
Glass article a was cut to 50x50mm size and sonicated in 3-4% Parker aqueous solution for 4 minutes before final soaking in ultra pure water for 6 minutes. After this, glass article a was dried in an oven at 120 ℃ and then placed under ambient conditions until glass article a cooled to 24 ℃.
The comparative etchant X was precipitated for 300s before etching. The glass article A was immersed and circulated in the comparative etchant X at a circulation rate of 4cm/s for a period of 30 seconds. Then, glass article a remained stable (i.e., without cycling) in comparative etchant X for 30s. The temperature of comparative etchant X was 12 ℃.
The etched glass article a was rinsed with flowing DI water. The precipitate on the etched glass article was removed by scraping and the laminate was peeled off. The glass article was placed in a 60 ℃ oven until dry.
Referring now to fig. 19, treatment of glass article a with comparative etchant X resulted in comparative textured article X lacking adequate coverage and micro-uniformity of the resulting polyhedral surface features. The comparative textured article X included triangular and rectangular pyramids and had a surface feature size of 75 μm.
Example 8: example textured article H (example etchant G and glass article A)
To obtain example etchant G, a blended powder comprising 89.7G NH 4F、3g(NH)2SiF6 and 10G NaC 6H11O7 was obtained by hand milling. A premix solvent containing 167.08g (96.5 wt%) H 2SO4 and 238.7g H 2 O was obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etching solution was aged for 2 hours.
Before etching, the glass article a was subjected to the same treatment as that of the glass article a in comparative example 1.
The example etchant G was precipitated for 300s before etching. The glass article A was immersed and circulated in the example etchant G at a circulation rate of 4cm/s for a period of 30s. The glass article a was then held stable (i.e., without cycling) in example etchant G for 30s. The temperature of example etchant G was 12 ℃.
After etching, the etched glass article a was subjected to the same treatment as that of the glass article a in comparative example 1.
Referring now to fig. 20, example textured article H resulting from treating glass article a with example etchant G has sufficient coverage and micro-uniformity of the resulting polyhedral surface features. The example textured article H included triangular and rectangular pyramids and had a surface feature size of 100 μm.
Example 9: example textured article I (example etchant H and glass article A)
To obtain example etchant H, a blended powder comprising 89.7g NH 4F、3g(NH)2SiF6 and 1.5g PDADMAC was obtained by hand milling. A premix solvent containing 167.08g (96.5 wt%) H 2SO4 and 238.7g H 2 O was obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etching solution was aged for 2 hours.
Before etching, the glass article a was subjected to the same treatment as that of the glass article a in comparative example 1.
The example etchant H was precipitated for 300s before etching. The glass article A was immersed and circulated in the example etchant H at a circulation rate of 4cm/s for a period of 30s. The glass article a was then held stable (i.e., without cycling) in example etchant H for 30s. The temperature of example etchant H was 12 ℃.
After etching, the etched glass article a was subjected to the same treatment as that of the glass article a in comparative example 1.
Referring now to fig. 21, example textured article I resulting from treatment of glass article a with example etchant H has sufficient coverage and micro-uniformity of the resulting polyhedral surface features. Example textured article I included triangular and rectangular pyramids and had a surface feature size of 50 μm.
Example 10: example textured article J (example etchant I and glass article A)
To obtain example etchant I, a blended powder comprising 89.7g NH 4F、3g(NH)2SiF6、10g NaC6H11O7 and 1.5g PDADMAC was obtained by hand milling. A premix solvent containing 167.08g (96.5 wt%) H 2SO4 and 238.7g H 2 O was obtained and thoroughly stirred. The mixing of the powder and solvent was performed at 24 ℃. The etching solution was aged for 2 hours.
Before etching, the glass article a was subjected to the same treatment as that of the glass article a in comparative example 1.
Example etchant I was precipitated for 300s prior to etching. The glass article A was immersed and circulated in example etchant I at a circulation rate of 4cm/s for a period of 30s. The glass article a was then held stable (i.e., without cycling) in example etchant I for 30s. The temperature of example etchant I was 12 ℃.
After etching, the etched glass article a was subjected to the same treatment as that of the glass article a in comparative example 1.
Referring now to fig. 22, example textured article J resulting from treatment of glass article a with example etchant I has sufficient coverage and micro-uniformity of the resulting polyhedral surface features. Example textured article J included triangular and rectangular pyramids and had a surface feature size of 90 μm.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Accordingly, this specification is intended to cover modifications and variations of the various embodiments described herein provided such modifications and variations fall within the scope of the appended claims and their equivalents.
Claims (67)
1. An etchant, comprising:
greater than or equal to 20 wt% and less than or equal to 45 wt% ammonium bifluoride;
Greater than or equal to 0.25 wt% and less than or equal to 10 wt% of a silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof;
greater than or equal to 5 wt% and less than or equal to 30 wt% hydrochloric acid;
greater than or equal to 25 wt% and less than or equal to 60 wt% water; and
Greater than or equal to 0.5 wt% and less than or equal to 20 wt% of a polyhydric alcohol.
2. The etchant of claim 1, wherein the polyhydric alcohol comprises: pentaerythritol, ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol or combinations thereof.
3. The etchant as claimed in claim 1 or 2, wherein the weight ratio of the sum of ammonium bifluoride and silicon compound to the sum of hydrochloric acid, water and polyhydroxy alcohol is 0.3 to 0.9.
4. The etchant of any of claims 1-3, wherein the etchant comprises greater than or equal to 0.5 wt% and less than or equal to 8 wt% silicon compound.
5. The etchant of claim 4, wherein the etchant comprises greater than or equal to 0.75 wt% and less than or equal to 6 wt% silicon compound.
6. The etchant of any one of claims 1-5, wherein the etchant comprises greater than or equal to 1 wt% and less than or equal to 15wt% of the polyhydroxy alcohol.
7. The etchant of claim 6, wherein the etchant comprises greater than or equal to 1.5 wt% and less than or equal to 10 wt% of the polyhydric alcohol.
8. The etchant of any of claims 1-7, wherein the etchant comprises greater than or equal to 23 wt% and less than or equal to 43 wt% ammonium bifluoride.
9. The etchant of claim 8, wherein the etchant comprises greater than or equal to 25 wt% and less than or equal to 40 wt% ammonium bifluoride.
10. The etchant of any of claims 1-9, wherein the etchant comprises greater than or equal to 7 wt% and less than or equal to 27 wt% hydrochloric acid.
11. The etchant of claim 10, wherein the etchant comprises greater than or equal to 10 wt% and less than or equal to 25 wt% hydrochloric acid.
12. The etchant of any of claims 1-11, wherein the etchant comprises greater than or equal to 30 wt% and less than or equal to 55 wt% water.
13. The etchant of claim 1, wherein the etchant comprises:
greater than or equal to 25 wt% and less than or equal to 40 wt% ammonium bifluoride;
greater than or equal to 0.5 wt% and less than or equal to 4 wt% silica gel;
Greater than or equal to 13 wt% and less than or equal to 23 wt% hydrochloric acid;
greater than or equal to 35 wt% and less than or equal to 55 wt% water; and
Greater than or equal to 1 wt% and less than or equal to 15 wt% glycerol.
14. The etchant of any of claims 1-13, wherein the etchant further comprises greater than or equal to 3wt% and less than or equal to 30wt% ammonium fluoride.
15. The etchant of any of claims 1-14, wherein the etchant further comprises greater than or equal to 0.25 wt% and less than or equal to 20 wt% of at least one of sodium or potassium salts.
16. A method of forming a textured glass article, the method comprising:
immersing an aluminosilicate glass article in an etchant comprising:
greater than or equal to 20 wt% and less than or equal to 45 wt% ammonium bifluoride;
Greater than or equal to 0.25 wt% and less than or equal to 10 wt% of a silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof;
greater than or equal to 5 wt% and less than or equal to 30 wt% hydrochloric acid;
greater than or equal to 25 wt% and less than or equal to 60 wt% water; and
Greater than or equal to 0.5 wt% and less than or equal to 20 wt% of a polyhydroxy alcohol; and
The aluminosilicate glass article is circulated in the etchant between an upper immersion depth and a lower immersion depth deeper than the upper immersion depth for a continuous cycle time.
17. The method of claim 16, wherein the cycling is performed at a speed greater than or equal to 5cm/s and less than or equal to 30 cm/s.
18. The method of claim 16 or 17, wherein the temperature of the etchant is greater than 10 ℃ and less than or equal to 30 ℃.
19. The method of any one of claims 16-18, wherein the cycle time is greater than or equal to 60s and less than or equal to 600s.
20. The method of any of claims 16-19, wherein the polyhydroxy alcohol comprises: pentaerythritol, ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol or combinations thereof.
21. The process of any one of claims 16-20, wherein the weight ratio of the sum of ammonium bifluoride and silicon compound to the sum of hydrochloric acid, water and polyhydroxy alcohol is from 0.3 to 0.6.
22. The method of any of claims 16-21, wherein the etchant comprises greater than or equal to 0.5 wt% and less than or equal to 8 wt% silicon compound.
23. The method of any of claims 16-22, wherein the etchant comprises greater than or equal to 1 wt% and less than or equal to 17 wt% polyhydroxy alcohol.
24. The method of any of claims 16-23, wherein the etchant comprises greater than or equal to 23 wt% and less than or equal to 43 wt% ammonium bifluoride.
25. The method of any of claims 16-24, wherein the etchant comprises greater than or equal to 7 wt% and less than or equal to 27 wt% hydrochloric acid.
26. The method of any of claims 16-25, wherein the etchant comprises greater than or equal to 30 wt% and less than or equal to 55 wt% water.
27. The method of any of claims 16-26, wherein the etchant further comprises greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride.
28. The method of any of claims 16-27, wherein the etchant further comprises greater than or equal to 0.25 wt% and less than or equal to 20 wt% of at least one of a sodium or potassium salt.
29. The method of any one of claims 16-28, wherein the aluminosilicate glass article comprises greater than or equal to 14 mol% ai 2O3.
30. The method of any one of claims 16-29, wherein the aluminosilicate glass article comprises:
Greater than or equal to 50 mole% and less than or equal to 70 mole% SiO 2;
Greater than or equal to 10 mole% and less than or equal to 22 mole% Al 2O3;
Greater than or equal to 0.5 mole% and less than or equal to 5 mole% P 2O5;
Greater than or equal to 0 mole% and less than or equal to 10 mole% B 2O5;
greater than or equal to 0 mole% and less than or equal to 3 mole% MgO;
Greater than or equal to 0 mole% and less than or equal to 3 mole% ZnO;
greater than or equal to 3 mole% and less than or equal to 12 mole% Li 2 O;
Greater than or equal to 4 mole% and less than or equal to 15 mole% Na 2 O;
greater than or equal to 0 mole% and less than or equal to 2 mole% K 2 O; and
Greater than or equal to 0 mole% and less than or equal to 1 mole% TiO 2.
31. The method of any of claims 16-30, wherein the textured glass article comprises a plurality of polyhedral surface features extending from the first surface, the plurality of polyhedral surface features each comprising: a base on the first surface, a plurality of facets extending from the first surface, a surface feature size at the base of greater than or equal to 50 μιη and less than or equal to 300 μιη, and a surface feature height of greater than or equal to 10 μιη and less than or equal to 40 μιη, wherein the plurality of facets of each polyhedral surface feature converge toward each other.
32. The method of any of claims 16-30, wherein the textured glass article comprises a plurality of polyhedral surface features extending from the first surface, the plurality of polyhedral surface features each comprising: a base on the first surface, a plurality of facets extending from the first surface, a surface feature size at the base of greater than or equal to 50 μιη and less than or equal to 300 μιη, and a surface feature height of greater than or equal to 8 μιη and less than or equal to 40 μιη, wherein the plurality of facets of each polyhedral surface feature converge toward each other.
33. The method of claim 31 or 32, wherein the plurality of polyhedral surface features comprise triangular pyramids, rectangular pyramids, or combinations thereof.
34. The method of any of claims 31-33, wherein the plurality of polyhedral surface features comprises a face angle greater than or equal to 13 ° and less than or equal to 20 °.
35. The method of any of claims 31-34, wherein the plurality of polyhedral surface features comprises a surface roughness greater than or equal to 2 μιη and less than or equal to 7 μιη.
36. The method of any of claims 31-34, wherein the plurality of polyhedral surface features comprises a surface roughness greater than or equal to 1 μιη and less than or equal to 7 μιη.
37. The method of any of claims 31-36, wherein the plurality of polyhedral surface features comprises a transmittance of greater than or equal to 80% and less than or equal to 95%.
38. The method of any of claims 31-37, wherein the plurality of polyhedral surface features comprises a transmission haze of greater than or equal to 95% and less than or equal to 100%.
39. The method of any of claims 31-37, wherein the plurality of polyhedral surface features comprises a transmission haze of greater than or equal to 80% and less than or equal to 100%.
40. The method of any of claims 31-39, wherein the textured glass article has sufficient coverage and micro-uniformity of the plurality of polyhedral surface features.
41. An etchant, comprising:
Greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride;
Greater than or equal to 0.25 wt% and less than or equal to 10 wt% of a silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof;
Greater than or equal to 15 wt% and less than or equal to 45 wt% sulfuric acid;
greater than or equal to 25 wt% and less than or equal to 60 wt% water; and
Greater than or equal to 0.1 wt% and less than or equal to 10 wt% of a viscosity additive.
42. The etchant of claim 41 wherein the viscosity additive comprises: saccharides, metal gluconate, polydiallyl dimethyl ammonium chloride (PDADMAC), or combinations thereof.
43. The etchant of claim 41 or 42 wherein the etchant contains greater than or equal to 0.25 wt% and less than or equal to 8 wt% silicon compound.
44. The etchant of claim 43 wherein the etchant comprises greater than or equal to 0.5 wt% and less than or equal to 6 wt% silicon compound.
45. The etchant of any of claims 41-44, wherein the etchant contains greater than or equal to 0.25 wt% and less than or equal to 8 wt% of the viscosity additive.
46. The etchant of claim 45 wherein the etchant comprises greater than or equal to 0.5wt% and less than or equal to 6wt% of the viscosity additive.
47. The etchant of any of claims 41-46, wherein the etchant comprises greater than or equal to 5wt% and less than or equal to 27 wt% ammonium fluoride.
48. The etchant of claim 47 wherein the etchant comprises greater than or equal to 7 wt% and less than or equal to 25 wt% ammonium fluoride.
49. The etchant of any of claims 41-48, wherein the etchant comprises greater than or equal to 17 wt% and less than or equal to 43 wt% sulfuric acid.
50. The etchant of claim 49, wherein the etchant comprises greater than or equal to 20 wt% and less than or equal to 40 wt% sulfuric acid.
51. The etchant of any of claims 41-50, wherein the etchant contains greater than or equal to 30 wt% and less than or equal to 60 wt% water.
52. The etchant of claim 41, wherein the etchant comprises:
Greater than or equal to 10 wt% and less than or equal to 25 wt% ammonium fluoride;
Greater than or equal to 0.25 wt% and less than or equal to 2 wt% ammonium hexafluorosilicate;
greater than or equal to 25 wt% and less than or equal to 40 wt% sulfuric acid;
greater than or equal to 40 wt% and less than or equal to 60 wt% water; and
Greater than or equal to 0.1wt% and less than or equal to 4 wt% of at least one of sodium gluconate and polydiallyl dimethyl ammonium chloride (PDADMAC).
53. A method of forming a textured glass article, the method comprising:
immersing an aluminosilicate glass article in an etchant comprising:
Greater than or equal to 3 wt% and less than or equal to 30 wt% ammonium fluoride;
Greater than or equal to 0.25 wt% and less than or equal to 10 wt% of a silicon compound comprising: silica, silica gel, ammonium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, magnesium hexafluorosilicate, or combinations thereof;
Greater than or equal to 15 wt% and less than or equal to 45 wt% sulfuric acid;
greater than or equal to 25 wt% and less than or equal to 60 wt% water; and
Greater than or equal to 0.1 wt% and less than or equal to 10 wt% of a viscosity additive; and
The aluminosilicate glass article is circulated in the etchant between an upper immersion depth and a lower immersion depth deeper than the upper immersion depth for a continuous cycle time.
54. The method of claim 53, wherein cycling is performed at a rate greater than or equal to 3cm/s and less than or equal to 30 cm/s.
55. The method of claim 53 or 54, wherein the etchant has a temperature greater than 10 ℃ and less than or equal to 30 ℃.
56. The method of any of claims 53-55, wherein the cycle time is greater than or equal to 30s and less than or equal to 600s.
57. The method of any of claims 53-56, wherein the viscosity additive comprises: saccharides, metal gluconate, polydiallyl dimethyl ammonium chloride (PDADMAC), or combinations thereof.
58. The method of any of claims 53-57, wherein the etchant comprises greater than or equal to 0.25 wt% and less than or equal to 8 wt% silicon compound.
59. The method of any of claims 53-58, wherein the etchant comprises greater than or equal to 0.25 wt% and less than or equal to 8 wt% of the viscosity additive.
60. The method of any of claims 53-59, wherein the etchant comprises greater than or equal to 5 wt% and less than or equal to 27 wt% ammonium fluoride.
61. The method of any of claims 53-60, wherein the etchant comprises greater than or equal to 17 wt% and less than or equal to 43 wt% sulfuric acid.
62. The method of any of claims 53-61, wherein the etchant comprises greater than or equal to 40 wt% and less than or equal to 60 wt% water.
63. The method of any one of claims 53-62, wherein the aluminosilicate glass article comprises greater than or equal to 14 mol% ai 2O3.
64. The method of any one of claims 53-63, wherein the aluminosilicate glass article comprises:
Greater than or equal to 50 mole% and less than or equal to 70 mole% SiO 2;
Greater than or equal to 10 mole% and less than or equal to 22 mole% Al 2O3;
Greater than or equal to 0.5 mole% and less than or equal to 5 mole% P 2O5;
Greater than or equal to 0 mole% and less than or equal to 10 mole% B 2O5;
greater than or equal to 0 mole% and less than or equal to 3 mole% MgO;
Greater than or equal to 0 mole% and less than or equal to 3 mole% ZnO;
greater than or equal to 3 mole% and less than or equal to 12 mole% Li 2 O;
Greater than or equal to 4 mole% and less than or equal to 15 mole% Na 2 O;
greater than or equal to 0 mole% and less than or equal to 2 mole% K 2 O; and
Greater than or equal to 0 mole% and less than or equal to 1 mole% TiO 2.
65. The method of any of claims 53-64, wherein the textured glass article comprises a plurality of polyhedral surface features extending from the first surface, the plurality of polyhedral surface features each comprising: a base on the first surface, a plurality of facets extending from the first surface, a surface feature size at the base that is greater than or equal to 50 μm and less than or equal to 300 μm, wherein the plurality of facets of each polyhedral surface feature converge toward each other.
66. The method of claim 65, wherein the plurality of polyhedral surface features comprise triangular pyramids, rectangular pyramids, or a combination thereof.
67. The method of any of claims 63-66, wherein the textured glass article has sufficient coverage and micro-uniformity of the plurality of polyhedral surface features.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211271275.XA CN117925242A (en) | 2022-10-17 | 2022-10-17 | Etchant for making textured glass articles |
| US18/076,511 US20230183570A1 (en) | 2021-12-15 | 2022-12-07 | Etchants for making textured glass articles |
| PCT/US2022/052620 WO2023114162A1 (en) | 2021-12-15 | 2022-12-13 | Etchants for making textured glass articles |
| TW111147758A TW202330431A (en) | 2021-12-15 | 2022-12-13 | Etchants for making textured glass articles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211271275.XA CN117925242A (en) | 2022-10-17 | 2022-10-17 | Etchant for making textured glass articles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117925242A true CN117925242A (en) | 2024-04-26 |
Family
ID=90763239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211271275.XA Pending CN117925242A (en) | 2021-12-15 | 2022-10-17 | Etchant for making textured glass articles |
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| Country | Link |
|---|---|
| CN (1) | CN117925242A (en) |
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- 2022-10-17 CN CN202211271275.XA patent/CN117925242A/en active Pending
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