CA3026834A1 - Glass components with custom-tailored composition profiles and methods for preparing same - Google Patents
Glass components with custom-tailored composition profiles and methods for preparing same Download PDFInfo
- Publication number
- CA3026834A1 CA3026834A1 CA3026834A CA3026834A CA3026834A1 CA 3026834 A1 CA3026834 A1 CA 3026834A1 CA 3026834 A CA3026834 A CA 3026834A CA 3026834 A CA3026834 A CA 3026834A CA 3026834 A1 CA3026834 A1 CA 3026834A1
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- CA
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- Prior art keywords
- glass
- recited
- ink
- forming material
- ldf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011521 glass Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims description 72
- 239000000463 material Substances 0.000 claims abstract description 82
- 238000007496 glass forming Methods 0.000 claims abstract description 77
- 238000007639 printing Methods 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000010146 3D printing Methods 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 16
- -1 polydimethylsiloxanes Polymers 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000008119 colloidal silica Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 238000000518 rheometry Methods 0.000 claims description 4
- 150000004770 chalcogenides Chemical class 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- YHBWXWLDOKIVCJ-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]acetic acid Chemical compound COCCOCCOCC(O)=O YHBWXWLDOKIVCJ-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229940093915 gynecological organic acid Drugs 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- KVIKMJYUMZPZFU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O KVIKMJYUMZPZFU-UHFFFAOYSA-N 0.000 claims 1
- 239000000976 ink Substances 0.000 description 91
- 238000013459 approach Methods 0.000 description 47
- 239000000377 silicon dioxide Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 19
- 238000012545 processing Methods 0.000 description 19
- 238000009472 formulation Methods 0.000 description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 13
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- 239000010931 gold Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 11
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- 239000005304 optical glass Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
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- 238000000151 deposition Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraethylene glycol dimethyl ether Natural products COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OLRBYEHWZZSYQQ-VVDZMTNVSA-N (e)-4-hydroxypent-3-en-2-one;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O OLRBYEHWZZSYQQ-VVDZMTNVSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 239000010432 diamond Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 229910052732 germanium Inorganic materials 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
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- 229910052769 Ytterbium Inorganic materials 0.000 description 1
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- 239000000010 aprotic solvent Substances 0.000 description 1
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
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- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/01—Other methods of shaping glass by progressive fusion or sintering of powdered glass onto a shaping substrate, i.e. accretion, e.g. plasma oxidation deposition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
- C03B19/066—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction for the production of quartz or fused silica articles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
Abstract
According to one embodiment, a method includes forming a structure by printing an ink, the ink including a glass-forming material, and heat treating the formed structure for converting the glass-forming material to glass.
Description
GLASS COMPONENTS WITH CUSTOM-TAILORED
COMPOSITION PROFILES AND METHODS FOR
PREPARING SAME
moll The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and Lawrence Livermore National Security, LLC for the operation of Lawrence Livermore National Laboratory.
FIELD OF THE INVENTION
100021 The present invention relates to glass components , and more particularly, this invention relates optical and non-optical glass components with custom-tailored composition profiles and methods for preparing same.
BACKGROUND
10001¨ Conventionally, gradients in material compositions are introduced either (1) axially, by fusing together multiple layers containing uniform composition, or
COMPOSITION PROFILES AND METHODS FOR
PREPARING SAME
moll The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and Lawrence Livermore National Security, LLC for the operation of Lawrence Livermore National Laboratory.
FIELD OF THE INVENTION
100021 The present invention relates to glass components , and more particularly, this invention relates optical and non-optical glass components with custom-tailored composition profiles and methods for preparing same.
BACKGROUND
10001¨ Conventionally, gradients in material compositions are introduced either (1) axially, by fusing together multiple layers containing uniform composition, or
(2) radially, by diffusing species (typically small, fast diffusing ions) into or out of rod-shaped silica sol-gels or solids at elevated temperatures. Unfortunately, purely diffusion-based gradients are limited to symmetric, parabolic profiles and have maximum achievable diameters (in the case of radial gradient refractive index lenses) of ¨20 mm, with most commercial versions being <2 mm in diameter. Introduction of larger, slower diffusing species proves challenging.
[0004] Some attempts have been made to create single-composition glasses via additive manufacturing. Silica glass of a single composition has been prepared via additive manufacturing using the selective laser melting (SLM) to melt and fuse silica particles in a silica powder bed. In addition, glass of a single composition has been prepared via an additive manufacturing method (G3DP) that melts silica in a kiln-like high temperature reservoir and deposits a ribbon of molten glass through a nozzle. These methods leave the filaments or selectively melted regions vulnerable to thermally induced stresses on cooling, which can prevent the part from achieving optical quality, for example, by creating undesirable refractive index gradients across the thickness of the part. Moreover, the selective melted regions may also leave trapped porosity between segments thereby resulting in resistance in merging the segments. In addition, these methods are not amenable to tightly controlled introduction of different compositions. It would be desirable to print and completely form the structure in the absence of high temperature.
[0005] Various embodiments described herein use direct ink writing (DIW) additive manufacturing to introduce the composition gradient into an amorphous, low density form (LDF). Following complete formation, the LDF is heat treated to transparency as a whole structure, thus reducing edge effects.
100061 Current methods to form glass of gradient composition have also proven challenging. In a slurry-based 3D printing (S-3DP) system, the dopants are added after the LDF is built from a slurry and dried. This process challenges the structural integrity within the LDF. In addition, the introduction of the dopant in low viscosity droplets over the dried body leaves the potential for the species of interest to diffuse radially and axially and to fill the pores of the dried structure beneath by capillary forces, leading to reduced control over the introduced compositional gradient. Composition gradients may also be limited to material that can incorporate readily into the LDF by diffusion (e.g.
small molecules, ions). Thus, it would be desirable to develop a process that forms a glass of gradient composition in which the dopants are a component of the mixture during formation of the LDF and before drying the LIN%
[0004] Some attempts have been made to create single-composition glasses via additive manufacturing. Silica glass of a single composition has been prepared via additive manufacturing using the selective laser melting (SLM) to melt and fuse silica particles in a silica powder bed. In addition, glass of a single composition has been prepared via an additive manufacturing method (G3DP) that melts silica in a kiln-like high temperature reservoir and deposits a ribbon of molten glass through a nozzle. These methods leave the filaments or selectively melted regions vulnerable to thermally induced stresses on cooling, which can prevent the part from achieving optical quality, for example, by creating undesirable refractive index gradients across the thickness of the part. Moreover, the selective melted regions may also leave trapped porosity between segments thereby resulting in resistance in merging the segments. In addition, these methods are not amenable to tightly controlled introduction of different compositions. It would be desirable to print and completely form the structure in the absence of high temperature.
[0005] Various embodiments described herein use direct ink writing (DIW) additive manufacturing to introduce the composition gradient into an amorphous, low density form (LDF). Following complete formation, the LDF is heat treated to transparency as a whole structure, thus reducing edge effects.
100061 Current methods to form glass of gradient composition have also proven challenging. In a slurry-based 3D printing (S-3DP) system, the dopants are added after the LDF is built from a slurry and dried. This process challenges the structural integrity within the LDF. In addition, the introduction of the dopant in low viscosity droplets over the dried body leaves the potential for the species of interest to diffuse radially and axially and to fill the pores of the dried structure beneath by capillary forces, leading to reduced control over the introduced compositional gradient. Composition gradients may also be limited to material that can incorporate readily into the LDF by diffusion (e.g.
small molecules, ions). Thus, it would be desirable to develop a process that forms a glass of gradient composition in which the dopants are a component of the mixture during formation of the LDF and before drying the LIN%
- 3 -SUMMARY
[0007] Various embodiments described herein enable (1) the formation of optical or non-optical glass with custom composition profiles that are not achievable by conventional glass processing techniques, (2) the introduction of species that cannot be introduced easily by diffusion methods, and (3) the creation of glass optics containing custom patterned material properties that are far larger than those achievable by diffusion methods.
100081 Some embodiments described herein introduce a gradient via NW
additive manufacturing and use continuous in-line mixing of glass-forming species, with or without dopant, to achieve the desired composition changes. The LDF is fully formed before drying. The dopant itself can be an ion, molecule, and/or particle, and it may be premixed with the glass-forming species in a high viscosity suspension, which limits its diffusion at low temperature within the LDF.
[0009] According to one embodiment, a method includes forming a structure by printing an ink, the ink including a glass-forming material, and heat treating the formed structure for converting the glass-forming material to glass.
[0010] According to another embodiment, a product includes a monolithic glass structure having physical characteristics of formation by three dimensional printing of an ink comprising a glass-forming material. Other aspects and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
[0007] Various embodiments described herein enable (1) the formation of optical or non-optical glass with custom composition profiles that are not achievable by conventional glass processing techniques, (2) the introduction of species that cannot be introduced easily by diffusion methods, and (3) the creation of glass optics containing custom patterned material properties that are far larger than those achievable by diffusion methods.
100081 Some embodiments described herein introduce a gradient via NW
additive manufacturing and use continuous in-line mixing of glass-forming species, with or without dopant, to achieve the desired composition changes. The LDF is fully formed before drying. The dopant itself can be an ion, molecule, and/or particle, and it may be premixed with the glass-forming species in a high viscosity suspension, which limits its diffusion at low temperature within the LDF.
[0009] According to one embodiment, a method includes forming a structure by printing an ink, the ink including a glass-forming material, and heat treating the formed structure for converting the glass-forming material to glass.
[0010] According to another embodiment, a product includes a monolithic glass structure having physical characteristics of formation by three dimensional printing of an ink comprising a glass-forming material. Other aspects and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
- 4 -BRIEF DESCRIPTION OF THE DRAWINGS
[00111 FIG. 1 is a flow chart of a method to prepare glass components with custom-tailored composition profiles, according to one embodiment.
100121 FIG. 2A is a schematic drawing of a method to prepare a single composition glass components, according to one embodiment.
[0013] FIG. 2B is a schematic drawing of a method to prepare a multiple composition glass components, according to one embodiment.
[0014] FIG. 3A is an image of an extrusion of glass-forming ink onto a substrate, according to one embodiment.
[0015] FIG. 3B is an image of a printed low density form, according to one embodiment.
[0016] FIG. 3C is an image of a glass form following heat treatment of a printed low density form, according to one embodiment.
[0017] FIG. 4A is a schematic drawing of a low density form that includes a gradient in a material property of the low density form along an axial direction, according to one embodiment.
[0018] FIG. 4B is a schematic drawing of a low density form that includes a gradient in a material property of the low density form along a radial direction, according to one embodiment.
[0019] FIG. 5A is an image of a low density form with a gradient in the axial direction following multiple component printing, according to one embodiment.
[00111 FIG. 1 is a flow chart of a method to prepare glass components with custom-tailored composition profiles, according to one embodiment.
100121 FIG. 2A is a schematic drawing of a method to prepare a single composition glass components, according to one embodiment.
[0013] FIG. 2B is a schematic drawing of a method to prepare a multiple composition glass components, according to one embodiment.
[0014] FIG. 3A is an image of an extrusion of glass-forming ink onto a substrate, according to one embodiment.
[0015] FIG. 3B is an image of a printed low density form, according to one embodiment.
[0016] FIG. 3C is an image of a glass form following heat treatment of a printed low density form, according to one embodiment.
[0017] FIG. 4A is a schematic drawing of a low density form that includes a gradient in a material property of the low density form along an axial direction, according to one embodiment.
[0018] FIG. 4B is a schematic drawing of a low density form that includes a gradient in a material property of the low density form along a radial direction, according to one embodiment.
[0019] FIG. 5A is an image of a low density form with a gradient in the axial direction following multiple component printing, according to one embodiment.
- 5 -[0020] FIG. 5B is an image of a glass form with a gradient in the axial direction following heat treatment of a printed low density form, according to one embodiment.
100211 FIG. 5C is an image of a low density form with a gradient in the radial direction following multiple component printing, according to one embodiment.
[0022] FIG. 4B is an image of a glass form with a gradient in the radial direction following heat treatment of a printed low density form, according to one embodiment.
[0023] FIGS. 6A-6C are images of printed parts formed with a silica composition, according to one embodiment.
[0024] FIGS. 6D-6E are images of printed parts formed with a silica-titania composition, according to one embodiment.
[0025] FIG. 7A is a plot of refractive index profile verses titania concentration of glass formed according to one embodiment.
[0026] FIG. 7B is an image of the resultant glass structures formed with different titania concentrations, according to one embodiment.
[0027] FIG. 8 is a plot of the thermal treatment profile of the formation of a consolidated structure according to one embodiment. Images of each step are included as insets on the profile plot.
[0028] FIG. 9A is an image of a gradient refractive index silica-titania glass lens prepared by direct ink writing, according to one embodiment.
[0029] FIG. 9B is a surface-corrected interferogram of the glass lens of FIG. 9A.
[0030] FIG. 9C is an image of the 300-pm focal spot from the lens of FIG.
9A.
[0031] FIG. 10A is an image of a composite glass comprised of a gold-doped silica glass core, according to one embodiment.
100211 FIG. 5C is an image of a low density form with a gradient in the radial direction following multiple component printing, according to one embodiment.
[0022] FIG. 4B is an image of a glass form with a gradient in the radial direction following heat treatment of a printed low density form, according to one embodiment.
[0023] FIGS. 6A-6C are images of printed parts formed with a silica composition, according to one embodiment.
[0024] FIGS. 6D-6E are images of printed parts formed with a silica-titania composition, according to one embodiment.
[0025] FIG. 7A is a plot of refractive index profile verses titania concentration of glass formed according to one embodiment.
[0026] FIG. 7B is an image of the resultant glass structures formed with different titania concentrations, according to one embodiment.
[0027] FIG. 8 is a plot of the thermal treatment profile of the formation of a consolidated structure according to one embodiment. Images of each step are included as insets on the profile plot.
[0028] FIG. 9A is an image of a gradient refractive index silica-titania glass lens prepared by direct ink writing, according to one embodiment.
[0029] FIG. 9B is a surface-corrected interferogram of the glass lens of FIG. 9A.
[0030] FIG. 9C is an image of the 300-pm focal spot from the lens of FIG.
9A.
[0031] FIG. 10A is an image of a composite glass comprised of a gold-doped silica glass core, according to one embodiment.
- 6 -100321 FIG. 10B is a plot of the absorbance as a function of wavelength of light of the composite glass of FIG. 10A.
100331 FIG. NC is a plot of the absorbance at 525 nm versus position along the glass surface of the composite glass of FIG. 10A.
100331 FIG. NC is a plot of the absorbance at 525 nm versus position along the glass surface of the composite glass of FIG. 10A.
- 7 -DETAILED DESCRIPTION
[0034] The following description is made for the purpose of illustrating the general principles of the present invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations.
100351 Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defmed in dictionaries, treatises, etc.
[0036] It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless otherwise specified.
[0037] The following description discloses several preferred embodiments of preparing optical and non-optical glass components with custom-tailored composition profiles, and/or related systems and methods.
100381 In one general embodiment, a method includes forming a structure by printing an ink, the ink including a glass-forming material, and heat treating the formed structure for converting the glass-forming material to glass.
[0039] in another general embodiment, a product includes a monolithic glass structure having physical characteristics of formation by three dimensional printing of an ink comprising a glass-forming material.
[0034] The following description is made for the purpose of illustrating the general principles of the present invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations.
100351 Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defmed in dictionaries, treatises, etc.
[0036] It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless otherwise specified.
[0037] The following description discloses several preferred embodiments of preparing optical and non-optical glass components with custom-tailored composition profiles, and/or related systems and methods.
100381 In one general embodiment, a method includes forming a structure by printing an ink, the ink including a glass-forming material, and heat treating the formed structure for converting the glass-forming material to glass.
[0039] in another general embodiment, a product includes a monolithic glass structure having physical characteristics of formation by three dimensional printing of an ink comprising a glass-forming material.
- 8 -
9 PCT/US2017/036197 100401 A list of acronyms used in the description is provided below.
3D Three dimensional DIW Direct ink write FDM Fused deposition modeling IR Infrared G3DP Glass three dimensional printing GRIN Gradient index glass LDF Low density form Si Silicon S-3DP Slurry-based three dimensional printing SLM Selective laser melting Ti Titanium UV Ultraviolet 100411 =Various embodiments described herein provide methods for fabricating active or passive optical or non-optical glass components and/or glass sensors with custom material composition profiles in 1-, 2-, or 3-dimensions. Various embodiments described herein enable the three dimensional (3D) printing of a variety of inorganic glasses, with or without compositional changes. Depending on glass composition and processing conditions, the glasses may appear either transparent or opaque to the htunan eye.
However, the term "optical glass" does not refer only to glasses useful in the visible portion of the spectrum, but may also be extended to UV, visible, near-IR, mid-IR, and farl R.
100421 FIG. 1 shows a method 100 for preparing optical glass components with custom-tailored composition profiles in accordance with one embodiment. As an option, the present method 100 may be implemented to devices such as those shown in the other FIGS. described herein. Of course, however, this method 100 and others presented herein may be used to form structures for a wide variety of devices and/or purposes which may or may not be related to the illustrative embodiments listed herein.
Further, the methods presented herein may be carried out in any desired environment.
Moreover, more or less operations than those shown in FIG. 1 may be included in method 100, according to various embodiments. It should also be noted that any of the aforementioned features may be used in any of the embodiments described in accordance with the various methods.
100431 In one embodiment as shown in FIG. 1, a method 100 begins with an operation 102 that includes forming a structure by printing an ink. According to various embodiments, printing an ink may involve one of the following additive manufacturing techniques that may have an ink mixing capability: direct ink writing (DIW), stereolithography in 3D systems, projection microstereolithography, fused deposition modeling, electrophoretic deposition, PolyJet processing, Direct Deposition, inkjet printing, inkjet powder bed printing, aerosol jet printing, etc. One could imagine combining these processes as well.
[0044] According to various embodiments, the method 100 may be used to create filaments, films, and/or 3D monolithic or spanning free-forms.
[0045] According to one embodiment, the ink includes a glass-forming material.
According to another embodiment, the glass-forming material includes prepared
3D Three dimensional DIW Direct ink write FDM Fused deposition modeling IR Infrared G3DP Glass three dimensional printing GRIN Gradient index glass LDF Low density form Si Silicon S-3DP Slurry-based three dimensional printing SLM Selective laser melting Ti Titanium UV Ultraviolet 100411 =Various embodiments described herein provide methods for fabricating active or passive optical or non-optical glass components and/or glass sensors with custom material composition profiles in 1-, 2-, or 3-dimensions. Various embodiments described herein enable the three dimensional (3D) printing of a variety of inorganic glasses, with or without compositional changes. Depending on glass composition and processing conditions, the glasses may appear either transparent or opaque to the htunan eye.
However, the term "optical glass" does not refer only to glasses useful in the visible portion of the spectrum, but may also be extended to UV, visible, near-IR, mid-IR, and farl R.
100421 FIG. 1 shows a method 100 for preparing optical glass components with custom-tailored composition profiles in accordance with one embodiment. As an option, the present method 100 may be implemented to devices such as those shown in the other FIGS. described herein. Of course, however, this method 100 and others presented herein may be used to form structures for a wide variety of devices and/or purposes which may or may not be related to the illustrative embodiments listed herein.
Further, the methods presented herein may be carried out in any desired environment.
Moreover, more or less operations than those shown in FIG. 1 may be included in method 100, according to various embodiments. It should also be noted that any of the aforementioned features may be used in any of the embodiments described in accordance with the various methods.
100431 In one embodiment as shown in FIG. 1, a method 100 begins with an operation 102 that includes forming a structure by printing an ink. According to various embodiments, printing an ink may involve one of the following additive manufacturing techniques that may have an ink mixing capability: direct ink writing (DIW), stereolithography in 3D systems, projection microstereolithography, fused deposition modeling, electrophoretic deposition, PolyJet processing, Direct Deposition, inkjet printing, inkjet powder bed printing, aerosol jet printing, etc. One could imagine combining these processes as well.
[0044] According to various embodiments, the method 100 may be used to create filaments, films, and/or 3D monolithic or spanning free-forms.
[0045] According to one embodiment, the ink includes a glass-forming material.
According to another embodiment, the glass-forming material includes prepared
- 10-dispersions of particles, where the particles range in size from nanometers to microns. In some approaches, particles may be mono-dispersed. In other approaches, particles may be poly-dispersed. In another approach, particles may be agglomerated.
[0046] In another embodiment, the glass-forming material may be a single composition of inorganic particles, for example, but not limited to, fumed silica, colloidal silica, LUDOX colloidal silica dispersion, titania particles, zirconia particles, alumina particles, metal chalcogenide particles (e.g. CdS, CdSe, ZnS, PbS), etc. In yet other embodiments, the glass-forming material may be a single composition of inorganic-containing particles.
[0047] In one embodiment, the glass-forming material may be a plurality of a mixed composition particle, for example, but not limited to, a binary silica-titania particle, silica-germanium oxide particle, and/or may be a particle with an inorganic or organic chemically modified surface (i.e. titania-modified silica particles; silica-modified titania particles; 3-aminopropyltriethoxysilane modified silica particles).
[0048] In some embodiments, the glass-forming material may be a mixture of particles of different compositions, for example but not limited to, a silica particle plus titania particle mixture that when fused together forms silica-titania glass.
[0049] According to one embodiment, the glass-forming material may be a single composition of glass-forming material that may not be in the form of particles. In some embodiments, a dopant may be directly incorporated into polymers, for example but not limited to, silica, silica-titania containing polymers, silica-germanium oxide polymers, silica-aluminum oxide polymers, silica-boron trioxide polymers, etc.
[0046] In another embodiment, the glass-forming material may be a single composition of inorganic particles, for example, but not limited to, fumed silica, colloidal silica, LUDOX colloidal silica dispersion, titania particles, zirconia particles, alumina particles, metal chalcogenide particles (e.g. CdS, CdSe, ZnS, PbS), etc. In yet other embodiments, the glass-forming material may be a single composition of inorganic-containing particles.
[0047] In one embodiment, the glass-forming material may be a plurality of a mixed composition particle, for example, but not limited to, a binary silica-titania particle, silica-germanium oxide particle, and/or may be a particle with an inorganic or organic chemically modified surface (i.e. titania-modified silica particles; silica-modified titania particles; 3-aminopropyltriethoxysilane modified silica particles).
[0048] In some embodiments, the glass-forming material may be a mixture of particles of different compositions, for example but not limited to, a silica particle plus titania particle mixture that when fused together forms silica-titania glass.
[0049] According to one embodiment, the glass-forming material may be a single composition of glass-forming material that may not be in the form of particles. In some embodiments, a dopant may be directly incorporated into polymers, for example but not limited to, silica, silica-titania containing polymers, silica-germanium oxide polymers, silica-aluminum oxide polymers, silica-boron trioxide polymers, etc.
- 11 -According to some embodiments the glass-forming material of the ink may include large molecules and/or polymers (linear or branched) prepared from smaller metal-containing organic precursors. Examples of polymers include poly(dimethylsiloxane), silicones, diethoxysiloxane-ethyltitanate copolymer, polyhedral oligomeric silsesquioxane polymers and copolymers. Examples of large molecules include polyoxometalate clusters, oxoalkoxometalate clusters. Designer Si/Ti containing polymers may be synthesized via acid-catalyzed hydrolysis of organosilicates and organotitanates, e.g., tetraethylorthosilicate and titanium isopropoxide, with additional transesterification steps if necessary. Modifications to this process include:
utilizing organometallic chemistries containing bonds other than metal-oxygen, e.g., (3-aminopropyl)triethoxysilane; doping via direct addition of salts to the polymer solution, e.g., NaF, Cu(NO3)2, Li2CO3; doping via inclusion of metal species into polymer chain during acid-catalyzed hydrolysis; replacement of major (for example, silicon (Si)), and minor (for example titanium (Ti)) glass components with alternatives that are able to undergo linear polymerization, e.g., Ge, Zr, V, Fe.
[0050] According to some embodiments the glass-forming material of the ink may include small metal-containing organic precursors and/or inorganic precursors, such as metalalkoxides, siloxanes, silicates, phosphates, chalcogenides, metal-hydroxides, metal salts, etc. Examples may include silicon alkoxides, boron alkoxides, titanium alkoxides, germanium alkoxides. In some approaches, the glass-forming material of the ink may include titanium isopropoxide, titanium diisopropoxide bis(acetylacetonate), tetraethyl orthosilicate, zinc chloride, titanium chloride.
utilizing organometallic chemistries containing bonds other than metal-oxygen, e.g., (3-aminopropyl)triethoxysilane; doping via direct addition of salts to the polymer solution, e.g., NaF, Cu(NO3)2, Li2CO3; doping via inclusion of metal species into polymer chain during acid-catalyzed hydrolysis; replacement of major (for example, silicon (Si)), and minor (for example titanium (Ti)) glass components with alternatives that are able to undergo linear polymerization, e.g., Ge, Zr, V, Fe.
[0050] According to some embodiments the glass-forming material of the ink may include small metal-containing organic precursors and/or inorganic precursors, such as metalalkoxides, siloxanes, silicates, phosphates, chalcogenides, metal-hydroxides, metal salts, etc. Examples may include silicon alkoxides, boron alkoxides, titanium alkoxides, germanium alkoxides. In some approaches, the glass-forming material of the ink may include titanium isopropoxide, titanium diisopropoxide bis(acetylacetonate), tetraethyl orthosilicate, zinc chloride, titanium chloride.
- 12 -100511 In one embodiment, the glass-forming material may be suspended in a solvent. In one embodiment in which the glass-forming material is a polar and/or hydrophilic glass-forming material, the solvent is preferably a polar, aprotic solvent. In one approach, the solvent may be a pure component or mixture of the following:
propylene carbonate, dimethyl ethers (e.g. tetra (ethylene glycol) dimethyl ether), and/or dimethylformamide. In another approach, the solvent may be a polar, protic solvent, for example, alcohol and/or water. In one embodiment in which the glass-forming material is hydrophobic, the solvent may be a non-polar solvent, for example, but not limited to, xylenes, alkanes.
[0052] According to one embodiment, the ink may be a combination of the glass-forming material and at least one second component that alters a property of the heat treated glass structure. In some embodiments, the second component may be a property altering dopant. In other embodiments, more than one material property may be affected by the addition of a second component. In various embodiments, the second component may affect the material property (e.g. characteristics) of the resulting structure in terms of one or more of the following: optical, mechanical, magnetic, thermal, electrical, chemical characteristics, etc.
[0053] In one approach, the second component may be in the form of ions. In another approach, the second component may be molecules. In yet another approach, the second component may be particles.
[0054] In some embodiments, the ink may contain an effective amount of one or more second components that may alter a property of the heat treated glass structure. The effective amount of a second component is an amount that alters a property of the heat
propylene carbonate, dimethyl ethers (e.g. tetra (ethylene glycol) dimethyl ether), and/or dimethylformamide. In another approach, the solvent may be a polar, protic solvent, for example, alcohol and/or water. In one embodiment in which the glass-forming material is hydrophobic, the solvent may be a non-polar solvent, for example, but not limited to, xylenes, alkanes.
[0052] According to one embodiment, the ink may be a combination of the glass-forming material and at least one second component that alters a property of the heat treated glass structure. In some embodiments, the second component may be a property altering dopant. In other embodiments, more than one material property may be affected by the addition of a second component. In various embodiments, the second component may affect the material property (e.g. characteristics) of the resulting structure in terms of one or more of the following: optical, mechanical, magnetic, thermal, electrical, chemical characteristics, etc.
[0053] In one approach, the second component may be in the form of ions. In another approach, the second component may be molecules. In yet another approach, the second component may be particles.
[0054] In some embodiments, the ink may contain an effective amount of one or more second components that may alter a property of the heat treated glass structure. The effective amount of a second component is an amount that alters a property of the heat
- 13 -treated glass structure may be readily determined without undue experimentation following the teachings herein and varying the concentration of the additive, as would become apparent to one skilled in the art upon reading the present description.
[0055] In one embodiment, the color of the resulting structure may be affected by the addition of one or more second components selected from the following group:
metal nanoparticles (gold, silver) of various sizes, sulfur, metal sulfides (cadmium sulfide), metal chlorides (gold chloride), metal oxides (copper oxides, iron oxides).
[0056] In one embodiment, the absorptivity (linear or nonlinear) of the resulting structure may be affected by the addition of a one or more second components selected from the following group: cerium oxide, iron, copper, chromium, silver, and gold.
[0057] In one embodiment, the refractive index of the resulting structure may be affected by the addition of one or more second components selected from the following group: titanium, zirconium, aluminum, lead, thorium, barium.
[0058] in one embodiment, the dispersion of the resulting structure may be affected by the addition of one or more second components selected from the following group:
barium, thorium.
[0059] In one embodiment, the attenuation/optical density of the resulting structure may be affected by the addition of one or more second components selected from the following group: alkaline metals and alkaline earth metals.
[0060] In one embodiment, the photosensitivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: silver, cerium, fluorine.
[0055] In one embodiment, the color of the resulting structure may be affected by the addition of one or more second components selected from the following group:
metal nanoparticles (gold, silver) of various sizes, sulfur, metal sulfides (cadmium sulfide), metal chlorides (gold chloride), metal oxides (copper oxides, iron oxides).
[0056] In one embodiment, the absorptivity (linear or nonlinear) of the resulting structure may be affected by the addition of a one or more second components selected from the following group: cerium oxide, iron, copper, chromium, silver, and gold.
[0057] In one embodiment, the refractive index of the resulting structure may be affected by the addition of one or more second components selected from the following group: titanium, zirconium, aluminum, lead, thorium, barium.
[0058] in one embodiment, the dispersion of the resulting structure may be affected by the addition of one or more second components selected from the following group:
barium, thorium.
[0059] In one embodiment, the attenuation/optical density of the resulting structure may be affected by the addition of one or more second components selected from the following group: alkaline metals and alkaline earth metals.
[0060] In one embodiment, the photosensitivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: silver, cerium, fluorine.
- 14 -[0061] In one embodiment, the electrical conductivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: alkali metal ions, fluorine, carbon nanotubes.
[0062] In one embodiment, the birefringence, such as having a refractive index that depends on polarization and propagation direction of light imparted by the crystalline phase formed from the second component, of the resulting structure may be affected by the addition of one or more second components selected from the following group:
titanium, zirconium, zinc, niobium, strontium, lithium, in combination with silicon and oxygen.
[0063] In one embodiment, the thermal conductivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: carbon nanotubes, metals.
[0064] In one embodiment, the thermal emissivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: tin oxide, iron.
[0065] In one embodiment, the thermal expansion of the resulting structure may be affected by the addition of a one or more second components selected from the following group: boron oxide, titanium oxide.
[0066] In one embodiment, the glass transition temperature of the resulting structure may be affected by the addition of sodium carbonate as the second component.
[0067] In one embodiment, the melting point of the resulting structure may be affected by the addition of one or more second components selected from the following group: sodium, aluminum, lead.
[0062] In one embodiment, the birefringence, such as having a refractive index that depends on polarization and propagation direction of light imparted by the crystalline phase formed from the second component, of the resulting structure may be affected by the addition of one or more second components selected from the following group:
titanium, zirconium, zinc, niobium, strontium, lithium, in combination with silicon and oxygen.
[0063] In one embodiment, the thermal conductivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: carbon nanotubes, metals.
[0064] In one embodiment, the thermal emissivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: tin oxide, iron.
[0065] In one embodiment, the thermal expansion of the resulting structure may be affected by the addition of a one or more second components selected from the following group: boron oxide, titanium oxide.
[0066] In one embodiment, the glass transition temperature of the resulting structure may be affected by the addition of sodium carbonate as the second component.
[0067] In one embodiment, the melting point of the resulting structure may be affected by the addition of one or more second components selected from the following group: sodium, aluminum, lead.
- 15 -[0068] In one embodiment, the gain coefficient of the resulting structure may be affected by the addition of one or more second components selected from the following group: rare earth ions (e.g. neodymium, erbium, ytterbium); transition metal ions (e.g.
chromium).
[0069] In one embodiment, the photoemission of the resulting structure may be affected by the addition of a second component. In another embodiment, the luminescence of the resulting structure may be affected by the addition of a second component. In yet another embodiment, the fluorescence of the resulting structure may be affected by the addition of a second component.
[0070] In one embodiment, the chemical reactivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: alkaline metals, alkaline earth metals, silver.
[0071] In one embodiment, the density of the resulting structure may be affected by the addition of one or more second components selected from the following group:
titanium, zirconium, aluminum, lead, thorium, barium.
[0072] In one embodiment, the concentration of the second component in the ink may change during the printing for creating a compositional gradient in the printed structure.
In some approaches, the second component in the ink may create a compositional gradient in the final heat treated structure.
[0073] In some embodiments, the concentration of the second component in the ink may create a compositional change (e.g. gradient, pattern, etc.) that may not be symmetrical about any axis, for example but not limited to, a pattern may change radially around the structure, a pattern may be formed as a complete 3D structure, etc.).
chromium).
[0069] In one embodiment, the photoemission of the resulting structure may be affected by the addition of a second component. In another embodiment, the luminescence of the resulting structure may be affected by the addition of a second component. In yet another embodiment, the fluorescence of the resulting structure may be affected by the addition of a second component.
[0070] In one embodiment, the chemical reactivity of the resulting structure may be affected by the addition of one or more second components selected from the following group: alkaline metals, alkaline earth metals, silver.
[0071] In one embodiment, the density of the resulting structure may be affected by the addition of one or more second components selected from the following group:
titanium, zirconium, aluminum, lead, thorium, barium.
[0072] In one embodiment, the concentration of the second component in the ink may change during the printing for creating a compositional gradient in the printed structure.
In some approaches, the second component in the ink may create a compositional gradient in the final heat treated structure.
[0073] In some embodiments, the concentration of the second component in the ink may create a compositional change (e.g. gradient, pattern, etc.) that may not be symmetrical about any axis, for example but not limited to, a pattern may change radially around the structure, a pattern may be formed as a complete 3D structure, etc.).
- 16 -[0074] In some embodiments, the ink may contain an effective amount of one or more additional additives that may perform specific functions. For example, but not limited to, the additives may enhance dispersion, phase stability, and/or network strength;
control and/or change pH; modify rheology; reduce crack formation during drying; aid in sintering; etc. The effective amount of an additive is an amount that imparts the desired function or result, and may be readily determined without undue experimentation following the teachings herein and varying the concentration of the additive, as would become apparent to one skilled in the art upon reading the present description.
[0075] In one embodiment, the ink may include one or more of the following additives to enhance dispersion: surfactants (e.g. 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEAA)), polyelectrolytes (e.g. polyacrylic acid), inorganic acids (e.g.
citric acid, ascorbic acid).
[0076] In one embodiment, the ink may include an additive (e.g. boric anhydride (B203)) to enhance phase stabilization (i.e. to prevent phase/composition separation, which may or may not be a crystalline phase separation). Another example is ZnO, which can act as a phase stabilizer for alkali silicate.
[0077] In one embodiment, the ink may include an additive (e.g. boric anhydride B203) to inhibit crystallization. Other crystallization inhibitors include A1203 and Ga203.
[0078] In one embodiment, the ink may include an additive (e.g.
polydimethylsiloxanes) to strengthen the network.
[0079] In one embodiment, the ink may include one or more of the following additives to control pH: organic acids, inorganic acids, bases (e.g. acetic acid, HCI, 1(011, NH4OH).
control and/or change pH; modify rheology; reduce crack formation during drying; aid in sintering; etc. The effective amount of an additive is an amount that imparts the desired function or result, and may be readily determined without undue experimentation following the teachings herein and varying the concentration of the additive, as would become apparent to one skilled in the art upon reading the present description.
[0075] In one embodiment, the ink may include one or more of the following additives to enhance dispersion: surfactants (e.g. 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEAA)), polyelectrolytes (e.g. polyacrylic acid), inorganic acids (e.g.
citric acid, ascorbic acid).
[0076] In one embodiment, the ink may include an additive (e.g. boric anhydride (B203)) to enhance phase stabilization (i.e. to prevent phase/composition separation, which may or may not be a crystalline phase separation). Another example is ZnO, which can act as a phase stabilizer for alkali silicate.
[0077] In one embodiment, the ink may include an additive (e.g. boric anhydride B203) to inhibit crystallization. Other crystallization inhibitors include A1203 and Ga203.
[0078] In one embodiment, the ink may include an additive (e.g.
polydimethylsiloxanes) to strengthen the network.
[0079] In one embodiment, the ink may include one or more of the following additives to control pH: organic acids, inorganic acids, bases (e.g. acetic acid, HCI, 1(011, NH4OH).
- 17 -100801 In one embodiment, the ink may include one or more of the following additives to modify rheology: polymers (e.g. cellulose, polyethylene glycols, poly vinyl alcohols); surfactants (e.g. MEEAA, sodium dodecyl sulfate, glycerol, ethylene glycol);
metal alkoxides (e.g. titanium diisopropoxide bis(acetylacetonate)).
[0081] In one embodiment, the ink may include one or more of the following additives as a drying aid to increase resistance to cracking and/or reduce crack formation during drying: polymers (e.g. polyethylene glycol, polyacrylates), cross-linkable monomers or polymers and crosslinking reagents (e.g. polyethylene glycol diacrylate (PEGDA)).
[0082] In one embodiment, the ink may include an additive as a sintering aid.
Sintering aids enhance the sintering/densification process. In the case of glass, a sintering aid may lower the viscosity of the material being sintered to glass. For example, boric anhydride (B203) may be included as a sintering aid.
[0083] in various embodiments, the formulation of glass-forming ink (i.e.
glass-forming material) is optimized for the following combination of factors:
printability (depending on the method of 3D printing), resistance to cracking, and sintering to transparency. In some approaches, volumetric loading of the formulation of glass-forming ink is optimized. In sonic approaches, the characteristics of the composition gradient of the glass-forming material may be optimized.
[0084] According to one embodiment, a formulation of glass-forming material may include: glass-forming, inorganic species in the range of about 5 vol% to about 50 vol%
of total volume; solvent in the range of about 30 vol% to about 95 vol%; a second
metal alkoxides (e.g. titanium diisopropoxide bis(acetylacetonate)).
[0081] In one embodiment, the ink may include one or more of the following additives as a drying aid to increase resistance to cracking and/or reduce crack formation during drying: polymers (e.g. polyethylene glycol, polyacrylates), cross-linkable monomers or polymers and crosslinking reagents (e.g. polyethylene glycol diacrylate (PEGDA)).
[0082] In one embodiment, the ink may include an additive as a sintering aid.
Sintering aids enhance the sintering/densification process. In the case of glass, a sintering aid may lower the viscosity of the material being sintered to glass. For example, boric anhydride (B203) may be included as a sintering aid.
[0083] in various embodiments, the formulation of glass-forming ink (i.e.
glass-forming material) is optimized for the following combination of factors:
printability (depending on the method of 3D printing), resistance to cracking, and sintering to transparency. In some approaches, volumetric loading of the formulation of glass-forming ink is optimized. In sonic approaches, the characteristics of the composition gradient of the glass-forming material may be optimized.
[0084] According to one embodiment, a formulation of glass-forming material may include: glass-forming, inorganic species in the range of about 5 vol% to about 50 vol%
of total volume; solvent in the range of about 30 vol% to about 95 vol%; a second
- 18 -component(s) (i.e. dopants) in the range of 0 wt% to about 20 wt%; and an additive(s) from 0 wt% to about 10 wt%.
[0085] Example Formulation 1 of Ink 5-15 vol% Fumed Silica (Cabosil EH-5 or Cabosil OX-50) 30-95 vol% Tetraethylene glycol dimethyl ether 0-20 wt% Titanium diisopropixide bis(acetylacetonate) 0-6 wt% Ethylene glycol 0-2 wt% Poly(dimethylsiloxane) [0086] Example Formulation 2 of Ink 75-95 vol% Silica-titania-containing polymers 10-25 vol% Tetraethylene glycol dimethyl ether 0-10 vol% H20 for prehydrolysis [0087] Example Formulation 3 of Ink 5-20 vol% 25-nm titania-coated silica particles 25-45 vol% Propylene carbonate 25-45 vol% Tetraethylene glycol dimethyl ether 0-5 wt% MEEAA
[0088] According to one embodiment, the concentration of the second component in the ink may change during the printing for creating a compositional gradient in the structure and thus, the final heat treated structure.
[0089] In one embodiment, the temperature of the ink may be less than about during the printing.
[0085] Example Formulation 1 of Ink 5-15 vol% Fumed Silica (Cabosil EH-5 or Cabosil OX-50) 30-95 vol% Tetraethylene glycol dimethyl ether 0-20 wt% Titanium diisopropixide bis(acetylacetonate) 0-6 wt% Ethylene glycol 0-2 wt% Poly(dimethylsiloxane) [0086] Example Formulation 2 of Ink 75-95 vol% Silica-titania-containing polymers 10-25 vol% Tetraethylene glycol dimethyl ether 0-10 vol% H20 for prehydrolysis [0087] Example Formulation 3 of Ink 5-20 vol% 25-nm titania-coated silica particles 25-45 vol% Propylene carbonate 25-45 vol% Tetraethylene glycol dimethyl ether 0-5 wt% MEEAA
[0088] According to one embodiment, the concentration of the second component in the ink may change during the printing for creating a compositional gradient in the structure and thus, the final heat treated structure.
[0089] In one embodiment, the temperature of the ink may be less than about during the printing.
- 19 -100901 In one embodiment, the method 100 includes drying the formed structure for removing a sacrificial material, where the drying is done prior to heat treating the formed structure. Ideally, the fully formed structure is dried in a single process.
[0091] According to one embodiment as shown in FIG. 1, method 100 includes operation 104 that involves heat treating the formed structure for converting the glass-forming material to glass.
[0092] In one embodiment, the method includes additional processing of the heat-treated glass structure. In one approach, the method includes grinding the heat-treated glass structure. In another approach, the method includes polishing the heat-treated glass structure. In yet another approach the method includes grinding and polishing the heat-treated glass structure.
[0093] In one embodiment, the heat-treated glass structure may be in the form of a fiber.
[0094] In another embodiment, the heat-treated glass structure may be in the form of a sheet.
[0095] In one embodiment, the heat-treated glass structure may be in the form of a three-dimensional monolith.
[0096] In another embodiment, the heat-treated glass structure may be in the form of a coating on a substrate such as a part, a tool, etc.
[0097] FIGS. 2A-2B depict methods 200 and 250 for preparing an optical glass component with custom-tailored composition profiles in accordance with one embodiment. As an option, the present methods 200 and 250 may be implemented in conjunction with features from any other embodiment listed herein, such as those
[0091] According to one embodiment as shown in FIG. 1, method 100 includes operation 104 that involves heat treating the formed structure for converting the glass-forming material to glass.
[0092] In one embodiment, the method includes additional processing of the heat-treated glass structure. In one approach, the method includes grinding the heat-treated glass structure. In another approach, the method includes polishing the heat-treated glass structure. In yet another approach the method includes grinding and polishing the heat-treated glass structure.
[0093] In one embodiment, the heat-treated glass structure may be in the form of a fiber.
[0094] In another embodiment, the heat-treated glass structure may be in the form of a sheet.
[0095] In one embodiment, the heat-treated glass structure may be in the form of a three-dimensional monolith.
[0096] In another embodiment, the heat-treated glass structure may be in the form of a coating on a substrate such as a part, a tool, etc.
[0097] FIGS. 2A-2B depict methods 200 and 250 for preparing an optical glass component with custom-tailored composition profiles in accordance with one embodiment. As an option, the present methods 200 and 250 may be implemented in conjunction with features from any other embodiment listed herein, such as those
- 20 -described with reference to the other FIGS. Of course, however, such methods 200 and 250 and others presented herein may be used in various applications and/or in permutations which may or may not be specifically described in the illustrative embodiments listed herein. Further, the methods 200 and 250 presented herein may be used in any desired environment.
100981 An exemplary embodiment of method 200 to prepare a single component silica glass is illustrated in FIG. 2A. According to one embodiment, the method to print the ink involves DIW printing as shown in steps 222 and 224. DIW is a 3D
printing process based on extrusion of viscoelastic material. Air pressure or positive displacement pushes the ink 202 through a small nozzle 208. In some approaches, the nozzle 208 is controlled by a computer and has three degrees of freedom (x, y, and z). In other approaches the nozzle 208 may be expanded to have six axes for printing. The nozzle 208 may be positioned to extrude the ink in a controlled spatial pattern.
100991 In steps 222 and 224, DIW deposits filaments 212 of rheologically tuned glass-forming DIW ink 202 containing glass-forming species in a prescribed geometry to create a weakly associated, near net-shaped, porous amorphous low density form (LDF) 214. In some approaches, there is rapid solidification of the extruded filament 212 into the LDF 214. In some approaches, the LDF 214 may be referred to as a green body, glass-forming species, etc. The glass-forming species may be introduced as either precursors and/or as colloids/particles. In some approaches, the glass-forming DIW ink 202 may be colloidal silica ink.
1001001 According to one embodiment, the formulation of the glass-forming DIW
ink is optimized for printability, drying/bakeout, and sintering. The formulation of the glass-
100981 An exemplary embodiment of method 200 to prepare a single component silica glass is illustrated in FIG. 2A. According to one embodiment, the method to print the ink involves DIW printing as shown in steps 222 and 224. DIW is a 3D
printing process based on extrusion of viscoelastic material. Air pressure or positive displacement pushes the ink 202 through a small nozzle 208. In some approaches, the nozzle 208 is controlled by a computer and has three degrees of freedom (x, y, and z). In other approaches the nozzle 208 may be expanded to have six axes for printing. The nozzle 208 may be positioned to extrude the ink in a controlled spatial pattern.
100991 In steps 222 and 224, DIW deposits filaments 212 of rheologically tuned glass-forming DIW ink 202 containing glass-forming species in a prescribed geometry to create a weakly associated, near net-shaped, porous amorphous low density form (LDF) 214. In some approaches, there is rapid solidification of the extruded filament 212 into the LDF 214. In some approaches, the LDF 214 may be referred to as a green body, glass-forming species, etc. The glass-forming species may be introduced as either precursors and/or as colloids/particles. In some approaches, the glass-forming DIW ink 202 may be colloidal silica ink.
1001001 According to one embodiment, the formulation of the glass-forming DIW
ink is optimized for printability, drying/bakeout, and sintering. The formulation of the glass-
- 21 -forming DIW ink may be optimized for printability in terms of shear thinning, ability to flow (steady flow), ability to hold shape (shape retention), low agglomeration, long print time, stable pot life (stability), etc. The formulation of the glass-forming DIW ink may be optimized for drying in terms of robustness to handling, crack resistance, low/uniform shrinkage, porosity suited to organic removal, etc. The formulation of the glass-forming DIW ink may be optimized for sintering in terms of crack resistance, low/uniform shrinkage, able to densify/become transparent, low tendency to phase separate, etc.
1001011 According to one embodiment, step 222 involves the glass-forming DIW
ink 202 extruded through a nozzle 208 to deposit filaments 212 onto a substrate 210 in a single layer.
1001021 Step 224 of method 200 involves building layer upon layer of glass-forming DIW ink 202 to form a LDF 214. FIG. 3A shows an image of the colloidal silica ink being extruded onto the substrate.
1001031 The LDF 214 may be treated to multiple steps to consolidate and convert the LDF 214 to the heat-treated glass form 216.
1001041 Optionally, the LDF 214, either before or after drying, may undergo additional processing to further change the composition of the part. In some approaches, additional processing may include diffusion, leaching, etching, etc. in other approaches, additional processing may include light, sound, vibration to alter the characteristics of the printed form, or a combination thereof. In yet other approaches, a chemical treatment before closing the porosity of the LDF by heat treatment may define the optical quality of the resulting glass form.
1001011 According to one embodiment, step 222 involves the glass-forming DIW
ink 202 extruded through a nozzle 208 to deposit filaments 212 onto a substrate 210 in a single layer.
1001021 Step 224 of method 200 involves building layer upon layer of glass-forming DIW ink 202 to form a LDF 214. FIG. 3A shows an image of the colloidal silica ink being extruded onto the substrate.
1001031 The LDF 214 may be treated to multiple steps to consolidate and convert the LDF 214 to the heat-treated glass form 216.
1001041 Optionally, the LDF 214, either before or after drying, may undergo additional processing to further change the composition of the part. In some approaches, additional processing may include diffusion, leaching, etching, etc. in other approaches, additional processing may include light, sound, vibration to alter the characteristics of the printed form, or a combination thereof. In yet other approaches, a chemical treatment before closing the porosity of the LDF by heat treatment may define the optical quality of the resulting glass form.
- 22 -1001051 In step 226, the LDF may be dried, calcined (i.e. removal of residual solvents/organics at elevated temperature), etc. During drying, the liquid/solvent phase may be removed. The LDF 214 may be released from the substrate 210 on which the LDF 214 was printed. In some approaches, the drying step 226 may involve dwelling hours to weeks at temperatures below the boiling point of the solvent.
1001061 In some embodiments, a processing step 226 may involve a lower heating step (i.e. burnout) to remove organics as well as any residual and/or adsorbed water/solvent phase. In some approaches, the burnout step may involve dwelling 0.5 to 24 hours at 250-600 C.
1001071 In some embodiments, the processing step 226 may include heating the LDF
214 under alternate gas atmospheres for chemically converting the surface (e.g.
conversion of free surface hydroxyls to dehydrated siloxanes). In some approaches, the processing step 226 may include heating the LDF 214 under oxidative gas atmospheres (e.g. 02 gas). In other approaches, the processing step 226 may include heating the LDF
214 under reducing gas atmospheres (e.g. H2 gas). In yet other approaches, the processing step 226 may include heating the LDF 214 under non-reactive gas atmospheres (e.g. Ar, He). In yet other approaches, the processing step 226 may include heating the under reactive gas atmospheres (e.g. N2, C12). In yet other approaches, the processing step 226 may include heating the LDF 214 under vacuum.
1001081 In some embodiments, the processing step 226 may also include compacting the parts (i.e. reducing porosity) of the LDF 214 using uniaxial pressure or isostatic pressure thereby resulting in a compact form. In some approaches, the processing step
1001061 In some embodiments, a processing step 226 may involve a lower heating step (i.e. burnout) to remove organics as well as any residual and/or adsorbed water/solvent phase. In some approaches, the burnout step may involve dwelling 0.5 to 24 hours at 250-600 C.
1001071 In some embodiments, the processing step 226 may include heating the LDF
214 under alternate gas atmospheres for chemically converting the surface (e.g.
conversion of free surface hydroxyls to dehydrated siloxanes). In some approaches, the processing step 226 may include heating the LDF 214 under oxidative gas atmospheres (e.g. 02 gas). In other approaches, the processing step 226 may include heating the LDF
214 under reducing gas atmospheres (e.g. H2 gas). In yet other approaches, the processing step 226 may include heating the LDF 214 under non-reactive gas atmospheres (e.g. Ar, He). In yet other approaches, the processing step 226 may include heating the under reactive gas atmospheres (e.g. N2, C12). In yet other approaches, the processing step 226 may include heating the LDF 214 under vacuum.
1001081 In some embodiments, the processing step 226 may also include compacting the parts (i.e. reducing porosity) of the LDF 214 using uniaxial pressure or isostatic pressure thereby resulting in a compact form. In some approaches, the processing step
- 23 -226 may also include compacting the parts (i.e. reducing porosity) of the LDF
214 under vacuum.
1001091 FIG. 3B shows an image of a LDF that has been dried.
1001101 According to one embodiment, the method involves heat treating the dried LDF 214, as shown in step 228 of FIG. 2A, to close the remaining porosity and form a consolidated, transparent glass part. In some approaches, a compact form of the LDF
may be heat treated.
1001111 The heat treating step 228 may involve sintering, in which the LDF 214 (i.e.
inorganic, glass-forming species) completely densifies into a solid glass consolidated form 216 at elevated temperatures. In some approaches, sintering the LDF may involve dwelling minutes to hours at 500-1600 C. The temperature for sintering depends on material composition and initial inorganic loading and porosity of the LDF. In some approaches, the sintering of the LDF may involve simultaneous use of applied pressure.
In some approaches, the heat treating step 228 may occur under different atmospheric conditions. In other approaches, the heat treating step 228 may occur under vacuum.
1001121 In some embodiments, the heat treated glass form 216 may be a monolithic glass structure.FIG. 3C shows an image of a monolithic glass structure after heat treatment of the LDF shown in FIG. 3B. In some embodiments, the resultant glass consolidated form 216 may retain the characteristics of the ink 202 that may have been imparted during DIW printing (steps 222 224).
1001131 In one embodiment, the glass consolidated form 216 may have a physical characteristic of the LDF 214 including spiral-shaped, arcuate and/or straight ridges along one surface of the glass form 216.
214 under vacuum.
1001091 FIG. 3B shows an image of a LDF that has been dried.
1001101 According to one embodiment, the method involves heat treating the dried LDF 214, as shown in step 228 of FIG. 2A, to close the remaining porosity and form a consolidated, transparent glass part. In some approaches, a compact form of the LDF
may be heat treated.
1001111 The heat treating step 228 may involve sintering, in which the LDF 214 (i.e.
inorganic, glass-forming species) completely densifies into a solid glass consolidated form 216 at elevated temperatures. In some approaches, sintering the LDF may involve dwelling minutes to hours at 500-1600 C. The temperature for sintering depends on material composition and initial inorganic loading and porosity of the LDF. In some approaches, the sintering of the LDF may involve simultaneous use of applied pressure.
In some approaches, the heat treating step 228 may occur under different atmospheric conditions. In other approaches, the heat treating step 228 may occur under vacuum.
1001121 In some embodiments, the heat treated glass form 216 may be a monolithic glass structure.FIG. 3C shows an image of a monolithic glass structure after heat treatment of the LDF shown in FIG. 3B. In some embodiments, the resultant glass consolidated form 216 may retain the characteristics of the ink 202 that may have been imparted during DIW printing (steps 222 224).
1001131 In one embodiment, the glass consolidated form 216 may have a physical characteristic of the LDF 214 including spiral-shaped, arcuate and/or straight ridges along one surface of the glass form 216.
-24 -1001141 In one embodiment, in the post-processing step 230, the glass form 216 may be post-processed, for example to achieve the desired figure and/or surface finish of a final polished optic form 218 through techniques such as grinding and/or polishing. In one embodiment, the polished optic 218 is a polished formation by 3D printing and heat treatment, such that the properties of the LDF 214 remain and are not removed by polishing. In one embodiment, the polished optic 218 is a monolithic glass structure that has been polished.
1001151 In some approaches, the glass form 216 may be treated as bolt glass, thereby allowing removal any of the evidence of the printing process by conventional techniques known in the art. hi other approaches, the glass form 216 retains features achievable only by the printing processes described herein, even after post-processing.
1001161 According to one embodiment, a schematic representation of a method 250 to form a gradient and/or a spatial pattern in a glass product is illustrated in FIG. 2B. In other embodiments, the method may create a compositional change (e.g.
gradient, pattern, etc.) that may not be symmetrical about any axis, for example but not limited to, a pattern may change radially around the structure, a pattern may be formed as a complete 3D structure, etc.).
1001171 In one approach, the method may form a gradient index (GRIN) glass.
Printing a GRIN glass involves printing a monolith with no porosity in which the characteristics of the formation of the LDF result in favorable elastic modulus/viscosity as indicated by space filling, high aspect ratio, and spanning. In addition, the method may involve matching the rheology of the two :DIW inks desired to create the gradient. In
1001151 In some approaches, the glass form 216 may be treated as bolt glass, thereby allowing removal any of the evidence of the printing process by conventional techniques known in the art. hi other approaches, the glass form 216 retains features achievable only by the printing processes described herein, even after post-processing.
1001161 According to one embodiment, a schematic representation of a method 250 to form a gradient and/or a spatial pattern in a glass product is illustrated in FIG. 2B. In other embodiments, the method may create a compositional change (e.g.
gradient, pattern, etc.) that may not be symmetrical about any axis, for example but not limited to, a pattern may change radially around the structure, a pattern may be formed as a complete 3D structure, etc.).
1001171 In one approach, the method may form a gradient index (GRIN) glass.
Printing a GRIN glass involves printing a monolith with no porosity in which the characteristics of the formation of the LDF result in favorable elastic modulus/viscosity as indicated by space filling, high aspect ratio, and spanning. In addition, the method may involve matching the rheology of the two :DIW inks desired to create the gradient. In
- 25 -some embodiments, two, three, four, etc. inks may be combined by mixing before extrusion of the filament onto the substrate.
1001181 According to one embodiment, during DIW printing, steps 232, 234, the filament composition 213 may be tuned during printing by adjusting the flow rates of separate streams to introduce desired composition changes within the LDF 214 at the desired locations.
100119] In some approaches, different inks 203, 204 may be introduced separately to create the LDF 215. As shown illustrated in a schematic representation of a side view in FIG. 4A, in one approach, a monolithic glass structure 400 with the physical characteristics of formation by 3D printing (LDF 215 of FIG. 2B) may include a gradient in a refractory index of the monolithic glass structure 400 along an axial direction of the monolithic glass structure 400. The axial 408 direction is perpendicular to the plane 410 of deposition.
1001201 Looking back to FIG. 2B, the glass structure is formed as a LDF (LDF
215 in FIG. 2B) in which a first glass-forming ink 203 may be extruded followed by extrusion of a second glass-forming ink 204. The resulting glass structure 400 in FIG. 4A
has a first glass 403 and a second glass 404, from the first glass-forming ink 203 and second glass-forming ink 204, respectively.
1001211 Moreover, the resulting glass structure 400 of FIG. 4A may include an interface 406 between first glass 403 formed from the glass-forming material and second glass 404 formed from a second glass-forming material having a different composition than the glass-forming material. In some approaches, there may be no intermixing of the first glass 403 in the second glass 404 because there may no migration of the second
1001181 According to one embodiment, during DIW printing, steps 232, 234, the filament composition 213 may be tuned during printing by adjusting the flow rates of separate streams to introduce desired composition changes within the LDF 214 at the desired locations.
100119] In some approaches, different inks 203, 204 may be introduced separately to create the LDF 215. As shown illustrated in a schematic representation of a side view in FIG. 4A, in one approach, a monolithic glass structure 400 with the physical characteristics of formation by 3D printing (LDF 215 of FIG. 2B) may include a gradient in a refractory index of the monolithic glass structure 400 along an axial direction of the monolithic glass structure 400. The axial 408 direction is perpendicular to the plane 410 of deposition.
1001201 Looking back to FIG. 2B, the glass structure is formed as a LDF (LDF
215 in FIG. 2B) in which a first glass-forming ink 203 may be extruded followed by extrusion of a second glass-forming ink 204. The resulting glass structure 400 in FIG. 4A
has a first glass 403 and a second glass 404, from the first glass-forming ink 203 and second glass-forming ink 204, respectively.
1001211 Moreover, the resulting glass structure 400 of FIG. 4A may include an interface 406 between first glass 403 formed from the glass-forming material and second glass 404 formed from a second glass-forming material having a different composition than the glass-forming material. In some approaches, there may be no intermixing of the first glass 403 in the second glass 404 because there may no migration of the second
-26 -glass-forming material into the first glass-forming material across the interface, or vice versa.
1001221 In one embodiment, the interface 406 may be oriented substantially along a plane 410 of deposition of the monolithic glass structure 400 thereby bifurcating the monolithic glass structure into two portions, the first glass 403 and the second glass 404, having different compositions directly adjacent the interface.
100123] As shown in FIGS. 5A-5D, two different inks, silica and silica with 20 nm gold nanoparticles were used to form a compositional change leading to a change in material property in the final heat-treated structure. FIGS 5A-5B show the formation of an axial step in absorption in a final heat-treated structure. As shown in FIG. 5A, the LDF was formed with a conformational change in which the first ink silica was used to form a portion of the LDF (bottom of LDF in FIG. 5A), and then the ink was switched to the second ink, silica/gold nanoparticle ink (top of LDF in FIG. 5A). The LDF
was then consolidated to glass by sintering in the heat treatment (step 238 of FIG.
2B). A resultant monolithic glass structure with a gradient in absorbance along an axial direction is shown in FIG. 5B in which the silica/gold nanoparticle portion of the glass is up in FIG. 5B.
100124] In one embodiment a physical characterization of the monolithic glass structure 217 includes a gradient comprising two or more glass-forming materials such that the interface between a first glass-forming material and a second glass-forming material that is uniform. As illustrated in FIG. 5A, there is an interface between the upper glass-forming material (silica/gold nanoparticles) and the lower material (silica).
Moreover, there is no migration of the first glass-forming material (silica) into the second glass-forming material (silica/gold nanoparticles), and vice versa, there is no migration of
1001221 In one embodiment, the interface 406 may be oriented substantially along a plane 410 of deposition of the monolithic glass structure 400 thereby bifurcating the monolithic glass structure into two portions, the first glass 403 and the second glass 404, having different compositions directly adjacent the interface.
100123] As shown in FIGS. 5A-5D, two different inks, silica and silica with 20 nm gold nanoparticles were used to form a compositional change leading to a change in material property in the final heat-treated structure. FIGS 5A-5B show the formation of an axial step in absorption in a final heat-treated structure. As shown in FIG. 5A, the LDF was formed with a conformational change in which the first ink silica was used to form a portion of the LDF (bottom of LDF in FIG. 5A), and then the ink was switched to the second ink, silica/gold nanoparticle ink (top of LDF in FIG. 5A). The LDF
was then consolidated to glass by sintering in the heat treatment (step 238 of FIG.
2B). A resultant monolithic glass structure with a gradient in absorbance along an axial direction is shown in FIG. 5B in which the silica/gold nanoparticle portion of the glass is up in FIG. 5B.
100124] In one embodiment a physical characterization of the monolithic glass structure 217 includes a gradient comprising two or more glass-forming materials such that the interface between a first glass-forming material and a second glass-forming material that is uniform. As illustrated in FIG. 5A, there is an interface between the upper glass-forming material (silica/gold nanoparticles) and the lower material (silica).
Moreover, there is no migration of the first glass-forming material (silica) into the second glass-forming material (silica/gold nanoparticles), and vice versa, there is no migration of
- 27 -the second glass-forming material (silica/gold nanoparticles) into the first glass-forming material (silica).
1001251 The prior art methods to 3D print optical glass have not been able to achieve embodiments described herein because the prior art methods have difficulty controlling thermal gradients during 3D printing, have a non-uniform interface between filaments, and/or lack the capability to incorporate multiple materials within the green body or LDF.
1001261 In other approaches, a smooth composition change may be created by blending inline the ink streams from the different inks 203, 204 via active mixing with a mixing paddle 206 near the tip of the nozzle 208. As illustrated in a schematic representation of a top view in FIG. 4B, in one approach, a monolithic glass structure 420 with physical characteristics of formation by 3D printing (LDF 215 of FIG. 2B) may include a gradient in the refractive index, or another material property such as absorbance, along a radial direction of the monolithic glass structure 420. A
radial 412 direction is along the plane 410 of deposition in any direction. Looking back to MG. 2B, the glass structure is formed as a LDF (LDF 215 in FIG. 2B) in which a radial step in refractive index in which the two inks 203, 204 in FIG. 2B were blended inline the ink streams. The resulting glass structure 420 in FIG. 4B has a first glass 414 and a second glass 413, from the first glass-forming ink 203 and second glass-forming ink 204, respectively.
1001271 Moreover, the resulting glass structure 420 of FIG. 4B includes an interface 416 between first glass 414 formed from the glass-forming material and second glass 413 formed from a second glass-forming material having a different composition than the glass-forming material. In some approaches, there may be no intermixing of the first
1001251 The prior art methods to 3D print optical glass have not been able to achieve embodiments described herein because the prior art methods have difficulty controlling thermal gradients during 3D printing, have a non-uniform interface between filaments, and/or lack the capability to incorporate multiple materials within the green body or LDF.
1001261 In other approaches, a smooth composition change may be created by blending inline the ink streams from the different inks 203, 204 via active mixing with a mixing paddle 206 near the tip of the nozzle 208. As illustrated in a schematic representation of a top view in FIG. 4B, in one approach, a monolithic glass structure 420 with physical characteristics of formation by 3D printing (LDF 215 of FIG. 2B) may include a gradient in the refractive index, or another material property such as absorbance, along a radial direction of the monolithic glass structure 420. A
radial 412 direction is along the plane 410 of deposition in any direction. Looking back to MG. 2B, the glass structure is formed as a LDF (LDF 215 in FIG. 2B) in which a radial step in refractive index in which the two inks 203, 204 in FIG. 2B were blended inline the ink streams. The resulting glass structure 420 in FIG. 4B has a first glass 414 and a second glass 413, from the first glass-forming ink 203 and second glass-forming ink 204, respectively.
1001271 Moreover, the resulting glass structure 420 of FIG. 4B includes an interface 416 between first glass 414 formed from the glass-forming material and second glass 413 formed from a second glass-forming material having a different composition than the glass-forming material. In some approaches, there may be no intermixing of the first
- 28 -glass 414 in the second glass 413 because there may no migration of the second glass-forming material into the first glass-forming material across the interface, or vice versa.
[00128] In one embodiment, the interface 416 may be oriented substantially perpendicular to a plane 410 of deposition of the monolithic glass structure 420 thereby bifurcating the monolithic glass structure 420 into two portions, the first glass 413 and the second glass 414, having different compositions directly adjacent the interface 416.
[00129] According to one embodiment, two different inks may be used to print a conformational change in a LDF that leads to a material property of a radial step in absorbance in the final heat-treated structure. As shown in FIGS. 5C-5D , a first ink of silica and a second ink of silica/gold nanoparticles were used to print a radial step in absorbance in which the two inks were blended inline the ink streams. FIG. 5C
shows the LDF form with the silica/gold nanoparticle ink in the center of the LDF and the silica ink on the outer portions of the LDF. A resultant monolithic glass structure with a gradient in the absorbance along a radial direction is shown in FIG. 5D.
[00130] The compositional changes may not be limited to axial and/or radial gradients (such as those that can be achieved by diffusion techniques) but rather can be made to create arbitrary profiles in the LDF.
[00131] Compositional changes in the LDF 215 may lead to varying material properties within the formed glass 217. Examples of material properties that may be affected by compositional changes in the LDF 215 are detailed more fully above, and may include, but may not be limited to: absorptivity, transmission, refractive index, dispersion, scatter, electrical conductivity, thermal conductivity, thermal expansion, gain
[00128] In one embodiment, the interface 416 may be oriented substantially perpendicular to a plane 410 of deposition of the monolithic glass structure 420 thereby bifurcating the monolithic glass structure 420 into two portions, the first glass 413 and the second glass 414, having different compositions directly adjacent the interface 416.
[00129] According to one embodiment, two different inks may be used to print a conformational change in a LDF that leads to a material property of a radial step in absorbance in the final heat-treated structure. As shown in FIGS. 5C-5D , a first ink of silica and a second ink of silica/gold nanoparticles were used to print a radial step in absorbance in which the two inks were blended inline the ink streams. FIG. 5C
shows the LDF form with the silica/gold nanoparticle ink in the center of the LDF and the silica ink on the outer portions of the LDF. A resultant monolithic glass structure with a gradient in the absorbance along a radial direction is shown in FIG. 5D.
[00130] The compositional changes may not be limited to axial and/or radial gradients (such as those that can be achieved by diffusion techniques) but rather can be made to create arbitrary profiles in the LDF.
[00131] Compositional changes in the LDF 215 may lead to varying material properties within the formed glass 217. Examples of material properties that may be affected by compositional changes in the LDF 215 are detailed more fully above, and may include, but may not be limited to: absorptivity, transmission, refractive index, dispersion, scatter, electrical conductivity, thermal conductivity, thermal expansion, gain
-29 -coefficient, glass transition temperature (Tg) melting point, photoemission, fluorescence, chemical reactivity (e.g. etch rate), density/porosity.
1001321 As shown in FIG. 2B, DIW printing in steps 232, 234 may involve forming the LDF 215, according to one embodiment. The LDF begins in the first step 232 of DIW
printing as a single layer on a substrate 210. As the DIW printing continues in step 234, the LDF 215 may be formed layer by layer until the desired LDF 215 (i.e. green body) is formed.
1001331 In some embodiments, formation of a LDF with single composition (method 200) or a multiple composition (for example, a gradient) (method 250) may involve fused deposition modeling (FDM). FDM uses thermoplastic filament, that may be a composite mixture of several materials combined with a mixing paddle similar to the ink mixture of DIW (see steps 232-234 of FIG. 2B). The resulting filament may be extruded through a heated nozzle to form a LDF on a substrate as shown in steps 222-224 or steps in FIGS. 2A and 2B, respectively. The heated nozzle, at temperatures in the range of about 150 C to 200 C, partially heats the filament for extrusion. In some approaches, a sacrificial support material may be extruded by a second nozzle to provide a support for the glass-forming material extruded by the mixing nozzle. In some approaches, the polymer of the extruded filament and/or support material may be removed after formation of the LDF.
1001341 In various embodiments, the LDF may be formed in a complex shape, for example, but not limited to, a conical form, a corkscrew pattern, a cylinder, etc.
1001351 The LDF 215 may be treated to multiple steps to consolidate and convert the Lllf= 215 to the heat-treated glass form 217.
1001321 As shown in FIG. 2B, DIW printing in steps 232, 234 may involve forming the LDF 215, according to one embodiment. The LDF begins in the first step 232 of DIW
printing as a single layer on a substrate 210. As the DIW printing continues in step 234, the LDF 215 may be formed layer by layer until the desired LDF 215 (i.e. green body) is formed.
1001331 In some embodiments, formation of a LDF with single composition (method 200) or a multiple composition (for example, a gradient) (method 250) may involve fused deposition modeling (FDM). FDM uses thermoplastic filament, that may be a composite mixture of several materials combined with a mixing paddle similar to the ink mixture of DIW (see steps 232-234 of FIG. 2B). The resulting filament may be extruded through a heated nozzle to form a LDF on a substrate as shown in steps 222-224 or steps in FIGS. 2A and 2B, respectively. The heated nozzle, at temperatures in the range of about 150 C to 200 C, partially heats the filament for extrusion. In some approaches, a sacrificial support material may be extruded by a second nozzle to provide a support for the glass-forming material extruded by the mixing nozzle. In some approaches, the polymer of the extruded filament and/or support material may be removed after formation of the LDF.
1001341 In various embodiments, the LDF may be formed in a complex shape, for example, but not limited to, a conical form, a corkscrew pattern, a cylinder, etc.
1001351 The LDF 215 may be treated to multiple steps to consolidate and convert the Lllf= 215 to the heat-treated glass form 217.
- 30 -100 361 Once formed, the LDF 215 may be dried and/or receive additional processing as described above for step 226 in method 200 in FIG. 2A.
1001371 Referring back to FIG. 2B, according to one embodiment, step 238 of method 250 includes heat treating the dried LDF 215 to close the remaining porosity and form a consolidated, transparent glass part. The resultant glass consolidated form 217 may retain the compositional variation that may have been imparted during DI W printing (steps 232, 234).
1001381 In one embodiment, the glass consolidated form 217 may have a physical characteristic of the LDF 215 including spiral-shaped, arcuate and/or straight ridges along one surface of the glass form 217.
1001391 According to one embodiment, in a post-processing step 240, the glass form 217 may be further processed, for example to achieve the desired figure and/or surface finish of a final polished optic 220 through techniques such as grinding and/or polishing.
In one embodiment, the polished optic 220 is a polished formation by 3D
printing and heat treatment, such that the properties of the LDF 215 remain and are not removed by polishing. In one embodiment, the polished optic 220 is a monolithic glass structure that has been polished.
1001401 The various embodiments described herein may be extended to a variety of (predominantly) amorphous, inorganic glass materials in addition to silica-based glasses, including phosphate-based glasses, borate glasses, germanium oxide glasses, fluoride glasses, aluminosilicate glasses, and chalcogenide glasses.
1001411 Example 1 of Heat Treatment
1001371 Referring back to FIG. 2B, according to one embodiment, step 238 of method 250 includes heat treating the dried LDF 215 to close the remaining porosity and form a consolidated, transparent glass part. The resultant glass consolidated form 217 may retain the compositional variation that may have been imparted during DI W printing (steps 232, 234).
1001381 In one embodiment, the glass consolidated form 217 may have a physical characteristic of the LDF 215 including spiral-shaped, arcuate and/or straight ridges along one surface of the glass form 217.
1001391 According to one embodiment, in a post-processing step 240, the glass form 217 may be further processed, for example to achieve the desired figure and/or surface finish of a final polished optic 220 through techniques such as grinding and/or polishing.
In one embodiment, the polished optic 220 is a polished formation by 3D
printing and heat treatment, such that the properties of the LDF 215 remain and are not removed by polishing. In one embodiment, the polished optic 220 is a monolithic glass structure that has been polished.
1001401 The various embodiments described herein may be extended to a variety of (predominantly) amorphous, inorganic glass materials in addition to silica-based glasses, including phosphate-based glasses, borate glasses, germanium oxide glasses, fluoride glasses, aluminosilicate glasses, and chalcogenide glasses.
1001411 Example 1 of Heat Treatment
- 31 -1001421 Printed monolithic silica or silica-titania green-bodies (25 mm diameter, 5 mm thick) are placed onto a hot-plate at 100 C. After 3 hours, the printed green bodies are released from the substrate. The green bodies are then dried in a box furnace at 100 C
for 110 hours. Next, the liquid-free green bodies are heated to 600 C at a ramp rate of 10 C/min and left to dwell for 1 hour to burn out remaining organic components.
The green bodies are then ramped at 100 C/hr to 1000 C and held for 1 hr under vacuum.
Last, the part is sintered in a preheated furnace at 1500 C for 3-10 minutes. The parts are then removed and rapidly cooled to room temperature. All non-vacuum processing steps are performed in air.
1001431 Example 2 of Heat Treatment 1001441 Printed monolithic silica green-bodies composed of 25-nm diameter silica or silica-titania particles (25 mm diameter, 5 mm thick) ramped in a box furnace to 75 C at a rate of 3 C/h. Once the oven reaches 75 C, the printed green bodies are released from the substrate. The green bodies are then dried in a drying oven at 75 C for 120 hours.
Next, the liquid-free green bodies are heated to 600 C at a ramp rate of 1 C/min and left to dwell for 1 hour to burn out remaining organic components. Last, the part is sintered in a preheated furnace at 1150 C for 1 hour. The parts are then removed and rapidly cooled to room temperature. All non-vacuum processing steps are performed in air.
1001451 Experiments 1001461 FIGS. 6A-6F are images of printed parts made with Formulation 3 of Ink (as described above). FIGS. 6A-6C are images of printed parts formed with a silica-only composition. FIG. 6A is an images of the green body formed after printing.
FIG. 6B is an
for 110 hours. Next, the liquid-free green bodies are heated to 600 C at a ramp rate of 10 C/min and left to dwell for 1 hour to burn out remaining organic components.
The green bodies are then ramped at 100 C/hr to 1000 C and held for 1 hr under vacuum.
Last, the part is sintered in a preheated furnace at 1500 C for 3-10 minutes. The parts are then removed and rapidly cooled to room temperature. All non-vacuum processing steps are performed in air.
1001431 Example 2 of Heat Treatment 1001441 Printed monolithic silica green-bodies composed of 25-nm diameter silica or silica-titania particles (25 mm diameter, 5 mm thick) ramped in a box furnace to 75 C at a rate of 3 C/h. Once the oven reaches 75 C, the printed green bodies are released from the substrate. The green bodies are then dried in a drying oven at 75 C for 120 hours.
Next, the liquid-free green bodies are heated to 600 C at a ramp rate of 1 C/min and left to dwell for 1 hour to burn out remaining organic components. Last, the part is sintered in a preheated furnace at 1150 C for 1 hour. The parts are then removed and rapidly cooled to room temperature. All non-vacuum processing steps are performed in air.
1001451 Experiments 1001461 FIGS. 6A-6F are images of printed parts made with Formulation 3 of Ink (as described above). FIGS. 6A-6C are images of printed parts formed with a silica-only composition. FIG. 6A is an images of the green body formed after printing.
FIG. 6B is an
- 32 -image after drying of the green body of FIG. 6A. FIG. 6C is an image after consolidation of the dried green body of FIG. 6B.
[00147] FIGS. 6D-6F are images of printed parts formed with a silica-titania composition. FIG. 6D is an image of the green body formed after printing. FIG.
6E is an image after drying of the green body of FIG. 6D. FIG. 6F is an image after consolidation of the dried green body of HG. 6E.
[00148] FIG. 7A is a plot of refractive index profile (y-axis) versus titania (h02) concentration (wt%, x-axis) in a resultant glass. Glasses made from the inks of Formulation 1 (as described above) are represented on the plot as diamonds (*, solid line) and have a variation in refractive index comparable to commercial silica (A) and silica-titanate glasses (0, o) (dotted line). FIG. 7B is an image of the resultant glass structures formed from the ink formulations represented by the diamonds (*) of FIG. 7A at different concentrations of wt% TiO2 (2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 9 wt%, 10 wt%).
[00149] FIG. 8 is a plot of the thermal treatment profile of the formation process of a consolidated printed parts using Formulation 1 Ink (as described above). The volumetric shrinkage (Vink) of the structure at each step during the heat treatment process is shown next to the image of the structure.
[00150] FIG. 9A is an optical image of a gradient refractive index silica-titania glass lens prepared by direct ink writing the LDF while blending two inks inline at the printhead in the required ratio to deposit a radial gradient in TiO2 concentration. Two inks were used from the Formulation 1 Ink (described above), Ink A contained 0%
titanium alkoxide and ink B contained enough titanium alkoxide to result in 1.6 wt%
TiO2 in the final consolidated glass. The glass was consolidated using the heat treatment
[00147] FIGS. 6D-6F are images of printed parts formed with a silica-titania composition. FIG. 6D is an image of the green body formed after printing. FIG.
6E is an image after drying of the green body of FIG. 6D. FIG. 6F is an image after consolidation of the dried green body of HG. 6E.
[00148] FIG. 7A is a plot of refractive index profile (y-axis) versus titania (h02) concentration (wt%, x-axis) in a resultant glass. Glasses made from the inks of Formulation 1 (as described above) are represented on the plot as diamonds (*, solid line) and have a variation in refractive index comparable to commercial silica (A) and silica-titanate glasses (0, o) (dotted line). FIG. 7B is an image of the resultant glass structures formed from the ink formulations represented by the diamonds (*) of FIG. 7A at different concentrations of wt% TiO2 (2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 9 wt%, 10 wt%).
[00149] FIG. 8 is a plot of the thermal treatment profile of the formation process of a consolidated printed parts using Formulation 1 Ink (as described above). The volumetric shrinkage (Vink) of the structure at each step during the heat treatment process is shown next to the image of the structure.
[00150] FIG. 9A is an optical image of a gradient refractive index silica-titania glass lens prepared by direct ink writing the LDF while blending two inks inline at the printhead in the required ratio to deposit a radial gradient in TiO2 concentration. Two inks were used from the Formulation 1 Ink (described above), Ink A contained 0%
titanium alkoxide and ink B contained enough titanium alkoxide to result in 1.6 wt%
TiO2 in the final consolidated glass. The glass was consolidated using the heat treatment
- 33 -profile shown in FIG. 8 and then polished using ceria pad polishing. FIG. 9B
is a surface-corrected interferogram, which shows how the refractive index changes within the bulk of the material shown in the image of FIG. 9A. The refractive index is highest at the center, where the TiO2 composition is highest, and lowest at the edges, where the TiO2 concentration is lowest. A lineout across the center shows that the refractive index change across the center is parabolic, as shown by the inset plot of FIG. 9B (8n/(no-1) on y-axis, Distance (mm) on x-axis), which suggests the part can function as a lens. FIG.
9C is an image of the 300-ttm focal spot from the lens, which has a focal length of 62 cm.
1001511 FIG. 10A is an optical image of a composite glass comprised of a gold-doped silica glass core with an undoped silica glass cladding, which was prepared by direct ink writing the composition change into the LDF. Two silica inks were used, with one ink containing gold nanoparticles. FIG. 10B is a plot of the absorbance as a function of wavelength of light, with each spectrum corresponding to the indicated positions across the glass. The peaks at 525 nm were attributed to absorbance from the gold nanoparticles.
FIG. 10C is a plot of the absorbance at 525 nm (y-axis) versus position along the glass surface (x-axis, with the position 0 being the center of the glass). The plot of FIG. 10C
represents that the absorbance at 525 nm was tuned within this glass. The spot size measured was an average over a ¨ I mm diameter spot.
1001521 In Use 1001531 Various embodiments described herein may be used to make active or passive optical glass components (e.g. lenses, corrector plates, windows, screens, collectors, waveguides, mirror blanks, sensors, etc.) with specialized compositions and material properties for both commercial or government applications. These methods may be used
is a surface-corrected interferogram, which shows how the refractive index changes within the bulk of the material shown in the image of FIG. 9A. The refractive index is highest at the center, where the TiO2 composition is highest, and lowest at the edges, where the TiO2 concentration is lowest. A lineout across the center shows that the refractive index change across the center is parabolic, as shown by the inset plot of FIG. 9B (8n/(no-1) on y-axis, Distance (mm) on x-axis), which suggests the part can function as a lens. FIG.
9C is an image of the 300-ttm focal spot from the lens, which has a focal length of 62 cm.
1001511 FIG. 10A is an optical image of a composite glass comprised of a gold-doped silica glass core with an undoped silica glass cladding, which was prepared by direct ink writing the composition change into the LDF. Two silica inks were used, with one ink containing gold nanoparticles. FIG. 10B is a plot of the absorbance as a function of wavelength of light, with each spectrum corresponding to the indicated positions across the glass. The peaks at 525 nm were attributed to absorbance from the gold nanoparticles.
FIG. 10C is a plot of the absorbance at 525 nm (y-axis) versus position along the glass surface (x-axis, with the position 0 being the center of the glass). The plot of FIG. 10C
represents that the absorbance at 525 nm was tuned within this glass. The spot size measured was an average over a ¨ I mm diameter spot.
1001521 In Use 1001531 Various embodiments described herein may be used to make active or passive optical glass components (e.g. lenses, corrector plates, windows, screens, collectors, waveguides, mirror blanks, sensors, etc.) with specialized compositions and material properties for both commercial or government applications. These methods may be used
-34 -to introduce ions, molecules, or particles in arbitrary (i.e. custom) locations within the glass components (monoliths, films, or free-forms) to achieve spatially varying material properties within the glass, including: absorptivity, transmission, refractive index, dispersion, scatter, electrical conductivity, thermal conductivity, thermal expansion, gain coefficient, glass transition temperature (Tg), melting point, photoemission, fluorescence, chemical reactivity (e.g. etch rate), or density/porosity.
[00154] Various embodiments described herein provide methods for preparing intricate 3D and controlled color glass art, jewelry, etc. The control of the dopants of silver and gold nanoparticles allows control of the reflective and transmissivity properties of the art piece.
[00155] Further embodiments include active or passive optical glass components useful for lenses, corrector plates, windows, screens, collectors, waveguides, mirror blanks, sensors, etc., as well as non-optical glass components useful in conventional applications.
[00156] The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, embodiments, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure.
[00154] Various embodiments described herein provide methods for preparing intricate 3D and controlled color glass art, jewelry, etc. The control of the dopants of silver and gold nanoparticles allows control of the reflective and transmissivity properties of the art piece.
[00155] Further embodiments include active or passive optical glass components useful for lenses, corrector plates, windows, screens, collectors, waveguides, mirror blanks, sensors, etc., as well as non-optical glass components useful in conventional applications.
[00156] The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, embodiments, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure.
- 35 -1001571 While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation.
Thus, the breadth and scope of an embodiment of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.
Thus, the breadth and scope of an embodiment of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.
-36 -
Claims (21)
1. A method, comprising:
forrning a structure by printing an ink, the ink comprising a glass-forming material; and heat treating the formed structure for converting the glass-forming material to glass.
forrning a structure by printing an ink, the ink comprising a glass-forming material; and heat treating the formed structure for converting the glass-forming material to glass.
2. The method as recited in claim 1, comprising drying the formed structure for removing a sacrificial material, wherein the drying is done prior to heat treating the formed structure.
3. The method as recited in claim 1, wherein the ink is a combination of the glass-fonning rnaterial and a second component that alters a property to the heat treated structure.
4. The method as recited in claim 3, wherein a concentration of the second component in the ink changes during the printing for creating a compositional gradient in the structure.
5. The method as recited in claim 1, wherein a temperature of the ink is less than about 200 °C during the printing.
6. The method as recited in claim 1, wherein the glass-forming material is selected from a group of materials consisting of: silica, fumed silica, colloidal silica, LUDOX colloidal silica dispersion, titania particles, zirconia particles, alumina particles, and metal chalcogenide particles.
7. The method as recited in claim 1, wherein the glass-forming material is suspended in a solvent during forming.
8. The method as recited in claim 1, comprising at least one of grinding and polishing the heat-treated structure.
9. The method as recited in claim 1, wherein the heat-treated structure is in the form of a fiber.
10. The method as recited in claim 1, wherein the heat-treated structure is in the form of a sheet.
11. The method as recited in claim 1, wherein the heat-treated structure is in the form of a three-dimensional monolith.
12. The method as recited in claim 1, wherein the heat-treated structure is in the form of a coating on a substrate.
13. The method as recited in claim 1, wherein the ink comprises an effective amount of an additive that imparts at least one of the following characteristics:
enhance dispersion, enhance phase stability, enhance network strength, control pH, change pH, modify rheology, reduce crack formation during drying, and aid in sintering.
enhance dispersion, enhance phase stability, enhance network strength, control pH, change pH, modify rheology, reduce crack formation during drying, and aid in sintering.
14. A product, comprising:
a monolithic glass structure having physical characteristics of formation by three dimensional printing of an ink comprising a glass-forming material.
a monolithic glass structure having physical characteristics of formation by three dimensional printing of an ink comprising a glass-forming material.
15. The product as recited in claim 14, wherein the physical characteristics of formation by three dimensional printing include ridges along one surface of the monolithic glass structure.
16. The product as recited in claim 14, wherein the monolithic glass structure comprises an additive selected from a group of additives consisting of: 2-[2-(2-methoxyethoxy)ethoxy]acetic acid, polyelectrolytes, polyacrylic acid, inorganic acids, citric acid, ascorbic acid, boric anhydride, polydimethylsiloxanes, organic acids, bases, acetic acid, HCl, KOH, NH4OH, cellulose, polyethylene glycols, poly vinylalcohols, sodium dodecyl sulfate, glycerol, ethyleneglycol, metal alkoxides, titanium diisopropoxide bis(acetylacetonate, polymers, polyethylene glycol, polyacrylates, crosslinkable monomersor polymers, and polyethylene glycol diacrylate.
17. The product as recited in claim 14, wherein the physical characteristics of formation by three dimensional printing include a gradient in a refractive index of the monolithic glass structure along an axial direction of the rnonolithic glass structure.
18. The product as recited in claim 14, wherein the physical characteristics of forrnation by three dimensional printing include a gradient in the refractive index along a radial direction of the monolithic glass structure.
19. The product as recited in claim 14, wherein the physical characteristics of formation by three dimensional printing include an interface between first glass forrned from the glass-forrning material and second glass forrned from a second glass-forming material having a different composition than the glass-forming material, wherein there is no intermixing of the first glass in the second glass.
20. The product as recited in claim 19, wherein the interface is oriented substantially along a plane of deposition of the monolithic glass structure thereby bifurcating the monolithic glass structure into two portions having different compositions directly adjacent the interface.
21. The product as recited in claim 19, wherein the interface is oriented substantially perpendicular to a plane of deposition of the monolithic glass structure thereby bifurcating the monolithic glass structure into two portions having different compositions directly adjacent the interface.
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Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10807119B2 (en) | 2013-05-17 | 2020-10-20 | Birmingham Technologies, Inc. | Electrospray pinning of nanograined depositions |
US10559864B2 (en) | 2014-02-13 | 2020-02-11 | Birmingham Technologies, Inc. | Nanofluid contact potential difference battery |
US20200024465A1 (en) | 2016-06-06 | 2020-01-23 | Lawrence Livermore National Security, Llc | Engineered feedstocks for additive manufacture of glass |
US10950706B2 (en) | 2019-02-25 | 2021-03-16 | Birmingham Technologies, Inc. | Nano-scale energy conversion device |
US11101421B2 (en) | 2019-02-25 | 2021-08-24 | Birmingham Technologies, Inc. | Nano-scale energy conversion device |
US11244816B2 (en) | 2019-02-25 | 2022-02-08 | Birmingham Technologies, Inc. | Method of manufacturing and operating nano-scale energy conversion device |
WO2020236776A1 (en) * | 2019-05-20 | 2020-11-26 | Birmingham Technologies, Inc. | Apparatus for engineered electrospray depositions, and method of fabricating nano-structures with engineered nano-scale electrospray depositions |
US11046578B2 (en) | 2019-05-20 | 2021-06-29 | Birmingham Technologies, Inc. | Single-nozzle apparatus for engineered nano-scale electrospray depositions |
US11124864B2 (en) | 2019-05-20 | 2021-09-21 | Birmingham Technologies, Inc. | Method of fabricating nano-structures with engineered nano-scale electrospray depositions |
US20210032767A1 (en) * | 2019-08-01 | 2021-02-04 | Lawrence Livermore National Security, Llc | Additive manufacturing of microanalytical reference materials |
CN111018321A (en) * | 2019-12-31 | 2020-04-17 | 北京工业大学 | Method for preparing glass through 3D printing and photocuring molding |
US11649525B2 (en) | 2020-05-01 | 2023-05-16 | Birmingham Technologies, Inc. | Single electron transistor (SET), circuit containing set and energy harvesting device, and fabrication method |
US11417506B1 (en) | 2020-10-15 | 2022-08-16 | Birmingham Technologies, Inc. | Apparatus including thermal energy harvesting thermionic device integrated with electronics, and related systems and methods |
US11616186B1 (en) | 2021-06-28 | 2023-03-28 | Birmingham Technologies, Inc. | Thermal-transfer apparatus including thermionic devices, and related methods |
WO2023285340A1 (en) | 2021-07-14 | 2023-01-19 | Michael Fokine | Method and apparatus for additive manufacturing of a glass object |
KR20240035451A (en) | 2021-07-14 | 2024-03-15 | 마이클 포킨 | Additive manufacturing method and device |
CN114426392B (en) * | 2022-01-25 | 2024-03-05 | 中国科学院宁波材料技术与工程研究所 | Microscale glass based on three-dimensional direct writing and manufacturing method thereof |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU65910A1 (en) * | 1944-09-27 | 1945-11-30 | А.П. Белопольский | Method for producing soda-lime glass |
US5121329A (en) * | 1989-10-30 | 1992-06-09 | Stratasys, Inc. | Apparatus and method for creating three-dimensional objects |
JP4339982B2 (en) | 2000-05-16 | 2009-10-07 | 株式会社フジ電科 | Airtight terminal |
JP4201544B2 (en) * | 2002-08-07 | 2008-12-24 | 信越石英株式会社 | Multi-layer quartz glass plate manufacturing apparatus and method |
RU2370464C2 (en) * | 2004-06-24 | 2009-10-20 | Бенек Ой | Method of alloying and alloyed material |
CN1862289A (en) * | 2005-05-13 | 2006-11-15 | 鸿富锦精密工业(深圳)有限公司 | Gradient refractive index lens and preparing method thereof |
RU2302066C1 (en) * | 2005-09-22 | 2007-06-27 | Научный центр волоконной оптики при Институте общей физики им. А.М. Прохорова Российской академии наук | Fiber optic conductor for optical intensification of radiation at wavelengths ranging between 1000 and 1700 nm, methods for its manufacture, and fiber laser |
US20080090034A1 (en) * | 2006-09-18 | 2008-04-17 | Harrison Daniel J | Colored glass frit |
US20080132150A1 (en) * | 2006-11-30 | 2008-06-05 | Gregory John Arserio | Polishing method for extreme ultraviolet optical elements and elements produced using the method |
US8308993B2 (en) * | 2008-01-30 | 2012-11-13 | Basf Se | Conductive inks |
CN102439509B (en) | 2009-05-05 | 2015-07-22 | 英特尔公司 | Passive alignment method and its application in micro projection devices |
EP2292357B1 (en) | 2009-08-10 | 2016-04-06 | BEGO Bremer Goldschlägerei Wilh.-Herbst GmbH & Co KG | Ceramic article and methods for producing such article |
US8991211B1 (en) * | 2009-11-01 | 2015-03-31 | The Exone Company | Three-dimensional printing glass articles |
RU2463264C2 (en) * | 2010-09-15 | 2012-10-10 | Общество С Ограниченной Ответственностью "Димонта" | OPTICAL GLASS, CAPABLE OF LUMINESCENCE IN 1000-1700 nm RANGE, METHODS OF PRODUCING SAID GLASS (VERSIONS) AND FIBRE LIGHT GUIDE |
EP2529694B1 (en) * | 2011-05-31 | 2017-11-15 | Ivoclar Vivadent AG | Method for generative production of ceramic forms by means of 3D jet printing |
US9419502B2 (en) * | 2012-08-03 | 2016-08-16 | Hamilton Sundstrand Corporation | Additive manufacturing of a component having a laminated stack of layers |
JP6261112B2 (en) * | 2013-07-23 | 2018-01-17 | キヤノンファインテックニスカ株式会社 | Image sensor unit and image reading apparatus |
US10377090B2 (en) * | 2013-10-08 | 2019-08-13 | Lawrence Livermore National Security, Llc | Multifunctional reactive inks, methods of use and manufacture thereof |
WO2015120429A1 (en) * | 2014-02-10 | 2015-08-13 | President And Fellows Of Harvard College | Three-dimensional (3d) printed composite structure and 3d printable composite ink formulation |
US20150239767A1 (en) * | 2014-02-26 | 2015-08-27 | Corning Incorporated | HEAT TREATING SILICA-TITANIA GLASS TO INDUCE A Tzc GRADIENT |
WO2015141779A1 (en) * | 2014-03-19 | 2015-09-24 | シーメット株式会社 | Recoater unit, three-dimensional-layer shaping device, three-dimensional-layer shaping method, and shaped article |
US20160009029A1 (en) * | 2014-07-11 | 2016-01-14 | Southern Methodist University | Methods and apparatus for multiple material spatially modulated extrusion-based additive manufacturing |
US20170246686A1 (en) * | 2014-09-26 | 2017-08-31 | Hewlett-Packard Development Company, L.P. | Pastes for printing three-dimensional objects in additive manufacturing processes |
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CN109641442A (en) | 2019-04-16 |
RU2018143304A3 (en) | 2020-07-09 |
AU2017277281A2 (en) | 2019-01-17 |
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