CA2021601A1 - Translucent silicon-oxy-carbide glass and articles - Google Patents
Translucent silicon-oxy-carbide glass and articlesInfo
- Publication number
- CA2021601A1 CA2021601A1 CA002021601A CA2021601A CA2021601A1 CA 2021601 A1 CA2021601 A1 CA 2021601A1 CA 002021601 A CA002021601 A CA 002021601A CA 2021601 A CA2021601 A CA 2021601A CA 2021601 A1 CA2021601 A1 CA 2021601A1
- Authority
- CA
- Canada
- Prior art keywords
- glass
- resin
- percent
- silicon
- heating
- 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 143
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 29
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 105
- 239000011347 resin Substances 0.000 claims description 105
- 239000002243 precursor Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000919 ceramic Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 230000004580 weight loss Effects 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims 1
- 229920002050 silicone resin Polymers 0.000 abstract description 17
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 13
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000004031 devitrification Methods 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 29
- 238000000197 pyrolysis Methods 0.000 description 25
- -1 carbon modified vitreous silica Chemical class 0.000 description 19
- 229910010271 silicon carbide Inorganic materials 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000004429 atom Chemical group 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- 150000003254 radicals Chemical group 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229940105305 carbon monoxide Drugs 0.000 description 4
- 125000005587 carbonate group Chemical group 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- YSMODUONRAFBET-UHFFFAOYSA-N 5-hydroxylysine Chemical group NCC(O)CCC(N)C(O)=O YSMODUONRAFBET-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241000153282 Theope Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 208000028462 aluminosis Diseases 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004212 difluorophenyl group Chemical group 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960003903 oxygen Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/045—Silicon oxycarbide, oxynitride or oxycarbonitride glasses
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/02—Fibres; Filaments; Yarns; Felts; Woven material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
- Ceramic Products (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42871189A | 1989-10-30 | 1989-10-30 | |
| US428,711 | 1989-10-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2021601A1 true CA2021601A1 (en) | 1991-05-01 |
Family
ID=23700077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002021601A Abandoned CA2021601A1 (en) | 1989-10-30 | 1990-07-19 | Translucent silicon-oxy-carbide glass and articles |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH03183637A (de) |
| CA (1) | CA2021601A1 (de) |
| DE (1) | DE4033493A1 (de) |
| FR (1) | FR2654424A1 (de) |
| GB (1) | GB2238046A (de) |
| IT (1) | IT1243995B (de) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020430A1 (en) * | 1987-01-09 | 1994-09-15 | Allied-Signal Inc. | Carbon-containing black glass monoliths |
| US5328976A (en) * | 1987-01-09 | 1994-07-12 | Allied-Signal Inc. | Carbon-containing black glass monoliths |
| US5629249A (en) * | 1988-04-25 | 1997-05-13 | Alliedsignal Inc. | Silicon carboxide fibers from gel spinning cyclosiloxane polymer precursors |
| US5512359A (en) * | 1990-01-12 | 1996-04-30 | Alliedsignal Inc. | High flexural strength ceramic fiber reinforced silicon carboxide composite |
| DE4112244A1 (de) * | 1990-05-15 | 1993-11-18 | Allied Signal Inc | Faserverstärkter Glasverbundstoff und Verfahren zu dessen Herstellung |
| CA2023380A1 (en) * | 1990-08-16 | 1993-10-07 | Roger Y. Leung | Silicon carboxide fibers from gel spinning cyclosiloxane polymer precursors |
| US5244720A (en) * | 1991-04-19 | 1993-09-14 | Allied-Signal Inc. | Fiber-reinforced glass composite for protecting polymeric substrates |
| EP0688307B2 (de) * | 1993-03-12 | 2000-06-14 | AlliedSignal Inc. | Verstärkter siliziumcarboxid verbundwerkstoff, enthaltend mit bornitrid beschichtete keramische fasern |
| EP0691942B1 (de) * | 1993-04-01 | 1997-10-08 | AlliedSignal Inc. | Kohlenstofffaser verstärkter silicium-carboxide-verbundwerkstoff mit hoher biegefestigkeit |
| DE19951375A1 (de) * | 1999-10-26 | 2001-05-17 | Fraunhofer Ges Forschung | Glasartiger anorganischer Festkörper, Verfahren zur Herstellung eines solchen Festkörpers und dessen Verwendung |
-
1990
- 1990-07-19 CA CA002021601A patent/CA2021601A1/en not_active Abandoned
- 1990-10-17 FR FR9012833A patent/FR2654424A1/fr not_active Withdrawn
- 1990-10-20 DE DE4033493A patent/DE4033493A1/de not_active Withdrawn
- 1990-10-24 JP JP2284540A patent/JPH03183637A/ja active Pending
- 1990-10-25 GB GB9023284A patent/GB2238046A/en not_active Withdrawn
- 1990-10-30 IT IT02193090A patent/IT1243995B/it active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| FR2654424A1 (fr) | 1991-05-17 |
| GB9023284D0 (en) | 1990-12-05 |
| IT1243995B (it) | 1994-06-28 |
| DE4033493A1 (de) | 1991-05-02 |
| IT9021930A0 (it) | 1990-10-30 |
| JPH03183637A (ja) | 1991-08-09 |
| IT9021930A1 (it) | 1992-04-30 |
| GB2238046A (en) | 1991-05-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |