JPH0328133A - Production of colored quartz glass - Google Patents
Production of colored quartz glassInfo
- Publication number
- JPH0328133A JPH0328133A JP16106389A JP16106389A JPH0328133A JP H0328133 A JPH0328133 A JP H0328133A JP 16106389 A JP16106389 A JP 16106389A JP 16106389 A JP16106389 A JP 16106389A JP H0328133 A JPH0328133 A JP H0328133A
- Authority
- JP
- Japan
- Prior art keywords
- silicate
- solution
- transition metal
- methyl
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 13
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011521 glass Substances 0.000 abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 abstract description 10
- -1 transition metal salts Chemical class 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000005187 foaming Methods 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000010937 tungsten Substances 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011240 wet gel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QYIBXNARBGCCNX-UHFFFAOYSA-N [V+3].CCCC[O-].CCCC[O-].CCCC[O-] Chemical compound [V+3].CCCC[O-].CCCC[O-].CCCC[O-] QYIBXNARBGCCNX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- GQNYZFMTYSVKQV-UHFFFAOYSA-N [Mo+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] Chemical compound [Mo+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] GQNYZFMTYSVKQV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- SFVJVIQIWGMENJ-UHFFFAOYSA-N butan-1-olate;iron(3+) Chemical compound [Fe+3].CCCC[O-].CCCC[O-].CCCC[O-] SFVJVIQIWGMENJ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- JUUPRTCPRDGKER-UHFFFAOYSA-N cerium(4+);2-methylpropan-2-olate Chemical compound [Ce+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] JUUPRTCPRDGKER-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWXKYODXCCJWNF-UHFFFAOYSA-N ethanol tungsten Chemical compound [W].CCO.CCO.CCO.CCO.CCO AWXKYODXCCJWNF-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
-
- 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
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
- C03C2201/3423—Cerium
-
- 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
- C03C2201/3435—Neodymium
-
- 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/40—Doped silica-based glasses containing metals containing transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
-
- 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
- C03C2203/00—Production processes
- C03C2203/20—Wet processes, e.g. sol-gel process
- C03C2203/26—Wet processes, e.g. sol-gel process using alkoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性、耐薬品性のすぐれた着色石英ガラスの
製造方法、特に大型の着色石英ガラス体を製造するに適
した方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing colored quartz glass having excellent heat resistance and chemical resistance, and particularly to a method suitable for producing large-sized colored quartz glass bodies.
着色石英ガラスの製造方法として、従来、米国コーニン
グ社の開発した、気相中で四塩化珪素を酸素で分解して
多孔質シリカを作り．これに遷移金属塩の溶液を含浸さ
せ、高温で焼或する方法があって、米国窯業協会誌，第
５７巻．第３０９〜３１３ページに記載されている。The conventional method for manufacturing colored quartz glass was developed by Corning Corporation in the United States, in which silicon tetrachloride is decomposed with oxygen in the gas phase to create porous silica. There is a method of impregnating this with a solution of a transition metal salt and firing it at high temperature, as described in Journal of the American Ceramics Association, Vol. 57. It is described on pages 309-313.
また珪酸エチル、エタノール、水の混合液に、遷移金属
塩を溶解し（遷移金属はイオン状態となる）、液のｐＨ
を３ないし６として加水分解し、ゲル化させた後、高温
に加熱しガラス化させる方法があり、特開昭５７−１１
８４５に記載されている。In addition, a transition metal salt is dissolved in a mixture of ethyl silicate, ethanol, and water (the transition metal is in an ionic state), and the pH of the solution is
There is a method of hydrolyzing 3 to 6, gelling it, and then heating it to a high temperature to vitrify it.
845.
しかし上記のコーニング社開発の方法は、気相反応を必
要とし、一定量を製造するのに多くの時間を要するので
、原価が高くなる。However, the method developed by Corning Inc. requires a gas phase reaction and takes a long time to produce a certain amount, resulting in high cost.
一方、特開昭５７−１１８４５の方法は液相での反応を
用いているが、酸性媒体中での加水分解のため、得られ
るゲルを高温で加熱処理する際に発泡や割れが起こり易
く、大型の着色ガラス体を作ることが困難であった。On the other hand, the method of JP-A-57-11845 uses reaction in a liquid phase, but because of hydrolysis in an acidic medium, foaming and cracking are likely to occur when the resulting gel is heated at high temperatures. It was difficult to make large colored glass bodies.
それ故、本発明の目的は、液相での反応を利用して、安
い原価で、製造時の発泡や割れを生ずることなく大型の
着色ガラス体を作ることが可能な、着色石英ガラスの製
造方法を提供することである。Therefore, an object of the present invention is to produce colored quartz glass, which can produce large colored glass bodies at low cost and without foaming or cracking during production, by utilizing reactions in the liquid phase. The purpose is to provide a method.
上記目的を解決するため、本発明では着色石英ガラスの
製造方法を、珪酸メチルまたは珪酸エチルのエタノール
溶液に遷移金属の硝酸塩、塩酸塩またはアルコキシドを
添加し、激しく撹拌しながら、ｐＨ１０ないし１１に調
整されたアンモニア水等のアルカリ水溶液を添加し、加
水分解して得られる多孔質のゲルを高温に加熱し、ガラ
ス化させる工程から構成した。In order to solve the above object, the present invention provides a method for producing colored quartz glass by adding a transition metal nitrate, hydrochloride, or alkoxide to an ethanol solution of methyl silicate or ethyl silicate, and adjusting the pH to 10 to 11 while stirring vigorously. The process consisted of adding an alkaline aqueous solution such as aqueous ammonia, and heating the porous gel obtained by hydrolysis to a high temperature to vitrify it.
本発明の着色石英ガラスの製造方法は以下の各過程から
或る。The method for producing colored quartz glass of the present invention includes the following steps.
（１）珪酸メチルまたは珪酸エチルのアルコール溶液に
遷移金属の硝酸塩、塩酸塩またはアルコキシドを添加す
る過程
珪酸メチルまたは珪酸エチルのアルコール溶液を調製す
るためのアルコールとしてはメチルアルコール、エチル
アルコール、ｎ−プロビルアルコール、イソプロビルア
ルコール等を用いることができるが、エチルアルコール
が好ましい。(1) Process of adding transition metal nitrate, hydrochloride, or alkoxide to an alcoholic solution of methyl silicate or ethyl silicate. Alcohols for preparing an alcoholic solution of methyl silicate or ethyl silicate include methyl alcohol, ethyl alcohol, n-propylene Viru alcohol, isopropyl alcohol, etc. can be used, but ethyl alcohol is preferred.
溶液の濃度は、珪酸メチルまたは珪酸エチル１モルに対
し、アルコールを２ないし６モル程度とする。The concentration of the solution is approximately 2 to 6 moles of alcohol per 1 mole of methyl silicate or ethyl silicate.
遷移金属として銅、チタン、鉄、コバルト、ニッケル、
マンガン、バナジウム、タングステン、モリブデン、ネ
オジム、セリウム等を用いることができる。遷移金属の
硝酸塩の具体例は硝酸銅、硝酸ニッケル、硝酸コバルト
、硝酸マンガン．硝酸ネオジム、硝酸セリウム等である
。また遷移金属塩酸塩の具体例は塩化銅、塩化チタン、
塩化鉄、塩化コバルト、塩化ニッケル、塩化マンガン、
塩化バナジウム、塩化モリブデン、塩化タングステン、
塩化ネオジム、塩化セリウム等である。Copper, titanium, iron, cobalt, nickel, as transition metals
Manganese, vanadium, tungsten, molybdenum, neodymium, cerium, etc. can be used. Specific examples of transition metal nitrates include copper nitrate, nickel nitrate, cobalt nitrate, and manganese nitrate. These include neodymium nitrate and cerium nitrate. Specific examples of transition metal hydrochlorides include copper chloride, titanium chloride,
Iron chloride, cobalt chloride, nickel chloride, manganese chloride,
Vanadium chloride, molybdenum chloride, tungsten chloride,
These include neodymium chloride and cerium chloride.
遷移金属アルコキシドの具体例は鉄トリーｎーブトキシ
ド、コバルトジイソプロボキシド、バナジウムトリーｎ
−ブトキシド、、タングステンベンタエトキシド、モリ
ブデンペンタエトキシド、セリウムテトラーｔ−ブトキ
シドである。Specific examples of transition metal alkoxides include iron tri-butoxide, cobalt diisoproboxide, and vanadium tri-butoxide.
-butoxide, tungsten pentaethoxide, molybdenum pentaethoxide, and cerium tetrat-butoxide.
遷移金属硝酸塩、塩酸塩またはアルコキシドの添加量は
、希望する着色濃度に依存するが、珪酸メチルまたは珪
酸エチル１モルに対し通常、１０００分の２ないし２０
モル程度である。The amount of transition metal nitrate, hydrochloride or alkoxide added depends on the desired coloring density, but is usually 2/1000 to 20% per mole of methyl silicate or ethyl silicate.
It is on the order of moles.
添加中および添加後は、硝酸塩、塩酸塩またはアルコキ
シドを充分に分散または溶解させるため、よく撹拌する
ことが望ましい。During and after the addition, it is desirable to stir well in order to sufficiently disperse or dissolve the nitrate, hydrochloride, or alkoxide.
添加された遷移金属硝酸塩または塩酸塩は、珪酸メチル
または珪酸エチルのアルコール溶液中に溶解はせず、分
散するだけであって、次の加水分解の過程で溶解される
。The added transition metal nitrate or hydrochloride is not dissolved in the alcohol solution of methyl silicate or ethyl silicate, but only dispersed, and is dissolved in the subsequent hydrolysis process.
（２）ｐＨ１０ないしｌ１のアルカリ水溶液を加えて加
水分解により多孔質のゲルを得る過程：上記（１）で得
られた遷移金属硝酸塩、塩酸塩またはアルコキシドを含
む珪酸メチルまたは珪酸エチルのアルコール溶液に、激
しく撹拌しながら、ｐＨ１０ないし１ｌのアルカリ水溶
液を加えて、珪酸メチルまたは珪酸エチルを加水分解さ
せる。(2) A process of adding an alkaline aqueous solution with a pH of 10 to 11 to obtain a porous gel by hydrolysis: to the alcohol solution of methyl silicate or ethyl silicate containing the transition metal nitrate, hydrochloride, or alkoxide obtained in (1) above. Then, while vigorously stirring, an aqueous alkali solution having a pH of 10 to 1 liter is added to hydrolyze the methyl silicate or ethyl silicate.
ｐＨ１０ないしＩ１のアルカリ水溶液は、緩衝能力を有
することが好ましく、アンモニア水がこの目的に適する
。ｐＨをこの範囲に保つことは重要で、これより低いｐ
Ｈにすると乾燥後のゲルのかさ密度が大きくなり、焼結
の過程で発泡や割れを生じ、これより高いｐＨではゲル
化が速すぎ、作業が困難になる。The alkaline aqueous solution having a pH of 10 to 11 preferably has a buffering capacity, and aqueous ammonia is suitable for this purpose. It is important to keep the pH within this range; lower p
If the pH is higher than this, the bulk density of the gel after drying will increase, causing foaming or cracking during the sintering process, and if the pH is higher than this, gelation will be too rapid and the work will be difficult.
アルカリ水溶液、例えばアンモニア水の量は、珪酸メチ
ルまたは珪酸エチル溶液のアルコール１モルに対し０．
５ないし２モル程度が適当である。The amount of alkaline aqueous solution, such as aqueous ammonia, is 0.0% per mole of alcohol in the methyl silicate or ethyl silicate solution.
Approximately 5 to 2 moles are appropriate.
アルカリ水溶液、例えばアンモニア水は、珪酸メチルま
たは珪酸エチル溶液を激しく撹拌しながら、その中にゆ
っくり加えることが望ましい。It is desirable to slowly add an alkaline aqueous solution, such as aqueous ammonia, to the methyl silicate or ethyl silicate solution while stirring the solution vigorously.
アルカリを添加後の溶液は適当な容器中で室温で放置す
れば，ゲル化する。After adding the alkali, the solution will gel if left in a suitable container at room temperature.
（３）多孔質のゲルを高温に加熱しガラス化させる過程
：
上記（２）の過程で得られたウェットゲルを徐々に乾燥
させ、その後さらに１２００゜Ｃ付近まで加熱して焼結
し、ガラス化させる。(3) Process of heating porous gel to high temperature and vitrifying it: The wet gel obtained in the process of (2) above is gradually dried, and then further heated to around 1200°C to sinter and form glass. to become
添加された遷移金属塩の種類により得られたガラスの色
は、添加された遷移金属塩の種類により異なる。例えば
硝酸ネオジムや塩化銅を用いれば淡青色に、バナジウム
アルコキシドを用いれば黄色が得られる。The color of the resulting glass varies depending on the type of transition metal salt added. For example, if neodymium nitrate or copper chloride is used, a pale blue color will be obtained, and if vanadium alkoxide is used, a yellow color will be obtained.
〔実施例１〕
１モルの珪酸メチルに０．０１モルの６水硝酸ネオジム
を加え、４モルのエタノールを加えてよく撹拌する。こ
の混合液を激しく撹拌しながら、水４モルに相当する量
のｐＨ１０．５のアンモニア水を、ゆっくり加える。こ
れによって珪酸メチルは加水分解される。[Example 1] Add 0.01 mole of neodymium hexahydrate nitrate to 1 mole of methyl silicate, add 4 moles of ethanol, and stir well. While stirring the mixture vigorously, aqueous ammonia having a pH of 10.5 in an amount equivalent to 4 moles of water is slowly added. This hydrolyzes the methyl silicate.
得られた液は淡青色を呈している。この液を第１図に示
すように、内径１５０ｍｍ、高さ５０ｍｍのテフロン樹
脂の容器ｌに、容積の８割を占めるように注いだ。容器
の上部をアルミニウム箔２で覆って密閉し、室温に放置
してゲル化させ、ウエットゲル３を得た。The obtained liquid has a pale blue color. As shown in FIG. 1, this liquid was poured into a Teflon resin container l having an inner diameter of 150 mm and a height of 50 mm so as to occupy 80% of the volume. The upper part of the container was covered with aluminum foil 2 to seal it, and the container was allowed to stand at room temperature to gel, thereby obtaining wet gel 3.
容器を覆ったアルξニウム箔に直径０．５ｍｍ程の孔を
１０個開けた上で、１時間にｌ″Ｃの割合で室温から１
２０゜Ｃまで温度を上昇させて、ゲルを乾燥させた。After making 10 holes with a diameter of about 0.5 mm in the aluminum foil that covered the container, the water was heated from room temperature to 1"C per hour.
The gel was dried by increasing the temperature to 20°C.
得られたドライゲル４を、電気炉５内で酸素雰囲気中で
加熱し、毎時１００゜Ｃの割で６００℃まで温度を上昇
させ、その後ヘリウム雰囲気中で同じ割合で１２００″
Ｃまで温度を上昇させて焼結させた。ゲルはガラス化し
、直径５０ｍｍ，厚さ１０ｍｍの淡青色透明のガラス円
板が得られた。The obtained dry gel 4 was heated in an oxygen atmosphere in an electric furnace 5 to raise the temperature to 600°C at a rate of 100°C per hour, and then heated at a rate of 1200°C at the same rate in a helium atmosphere.
Sintering was carried out by increasing the temperature to C. The gel was vitrified to obtain a pale blue transparent glass disc with a diameter of 50 mm and a thickness of 10 mm.
ガラスの密度は２．２０ｇｒ／ｃｍ’であった。The density of the glass was 2.20 gr/cm'.
ガラス板には気泡は見られず、割れもなかった．〔実施
例２〕
実施例１における６水硝酸ネオジムの代わりに０．００
５モルの２水塩化銅を用いたこと、アンモニア水のｐＨ
を１０．０としたこと以外は、実施例ｌと同様にして乾
燥ゲルを得た。There were no bubbles or cracks on the glass plate. [Example 2] 0.00 in place of neodymium hexahydrate nitrate in Example 1
Using 5 mol of copper dichloride, pH of ammonia water
A dried gel was obtained in the same manner as in Example 1, except that 10.0 was used.
得られたドライゲル４を電気炉５内で酸素雰囲気中で加
熱し、毎時１００゜Ｃの割で６００℃まで温度を上昇さ
せ、その後ヘリウム雰囲気中で毎時５０″Ｃの割合で１
２００゜Ｃまで温度を上昇させて焼結させた．
実施例１と同じ大きさの淡青色透明のガラス円板が得ら
れ、ガラスの密度は２．２３ ｇ ｒ／ ｃｍ３であっ
た．ガラス板には気泡は見られず、割れもなかった。The obtained dry gel 4 was heated in an oxygen atmosphere in an electric furnace 5 to raise the temperature to 600°C at a rate of 100°C per hour, and then heated at a rate of 100°C per hour in a helium atmosphere.
The temperature was raised to 200°C for sintering. A pale blue transparent glass disk of the same size as in Example 1 was obtained, and the density of the glass was 2.23 g r/cm3. No air bubbles were observed on the glass plate, and there were no cracks.
〔実施例３〕
実施例２における２水塩化銅の代わりに、０．００５モ
ルのバナジウムトリーｎ−ブトキシドを用いたこと以外
は、実施例２と同様にして着色ガラス手反をイ乍った。[Example 3] A colored glass fabric was prepared in the same manner as in Example 2, except that 0.005 mol of vanadium tri-n-butoxide was used instead of copper dichloride in Example 2. .
実施例１と同じ大きさの淡黄色透明のガラス円板が得ら
れ、ガラスの密度は２．１９ ｇ ｒ／ｃｍ３であった
。ガラス板には気泡は見られず、割れもなかった。A pale yellow transparent glass disk of the same size as in Example 1 was obtained, the density of the glass being 2.19 g r/cm 3 . No air bubbles were observed on the glass plate, and there were no cracks.
本発明では液相反応を利用しており、気相反応を利用す
る場合のような特別な装置を必要としないから、比較的
安価に着色石英ガラスを製造できる．
本発明の方法によると、一度に大量の着色ガラスを製造
できるから、量産により低価格も実現できる。The present invention uses a liquid phase reaction and does not require special equipment unlike when using a gas phase reaction, so colored quartz glass can be produced at a relatively low cost. According to the method of the present invention, a large amount of colored glass can be manufactured at one time, so mass production can also achieve low prices.
また製造時の発泡や割れを生ずることなく大型の着色ガ
ラス体を作ることができる．従って、大型の着色ガラス
体の製造における歩留まりが極めて高い。Additionally, large colored glass bodies can be made without foaming or cracking during manufacturing. Therefore, the yield in manufacturing large colored glass bodies is extremely high.
本発明の方法で製造される着色石英ガラスは、耐候性、
耐熱性、耐薬品性がすぐれている。従って、例えば高温
の環境下での使用に適する。The colored quartz glass produced by the method of the present invention has weather resistance,
Excellent heat resistance and chemical resistance. Therefore, it is suitable for use in a high temperature environment, for example.
第１図はゲル化に用いた容器を示す断面略図、第２図は
焼結に用いた装置の断面略図である。
符号の説明
■−・・−・−一−一一容器 ２−・・−・・
−−−−−アルミニウム箔３・・一一−−−・−ウェッ
トゲル
４−・−−−−一−−−ドライゲルFIG. 1 is a schematic cross-sectional view of a container used for gelling, and FIG. 2 is a schematic cross-sectional view of the apparatus used for sintering. Explanation of symbols■−・・−・−1−11 Container 2−・・−・・
------Aluminum foil 3...11-----Wet gel 4-----1---Dry gel
Claims (2)
遷移金属の硝酸塩、塩酸塩またはアルコキシドを添加し
、激しく撹拌しながらｐＨ１０ないし１１のアルカリ水
溶液を添加し、加水分解して得られる多孔質のゲルを高
温に加熱しガラス化させる工程から成る着色石英ガラス
の製造方法。(1) Add a transition metal nitrate, hydrochloride or alkoxide to an alcoholic solution of methyl silicate or ethyl silicate, add an alkaline aqueous solution of pH 10 to 11 while stirring vigorously, and hydrolyze the resulting porous gel. A method for producing colored quartz glass, which consists of a process of heating to high temperatures and vitrifying it.
第１項の着色石英ガラスの製造方法。(2) The method for producing colored quartz glass according to claim 1, wherein the alkaline aqueous solution is aqueous ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16106389A JPH0328133A (en) | 1989-06-23 | 1989-06-23 | Production of colored quartz glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16106389A JPH0328133A (en) | 1989-06-23 | 1989-06-23 | Production of colored quartz glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0328133A true JPH0328133A (en) | 1991-02-06 |
Family
ID=15727909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16106389A Pending JPH0328133A (en) | 1989-06-23 | 1989-06-23 | Production of colored quartz glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0328133A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5818644A (en) * | 1995-11-02 | 1998-10-06 | Olympus Optical Co., Ltd. | Gradient index optical element and method for making the same |
| US6244074B1 (en) * | 1997-12-25 | 2001-06-12 | Nippon Sheet Glass Co., Ltd. | Method of manufacturing glass plate with light-transmissive colored film |
-
1989
- 1989-06-23 JP JP16106389A patent/JPH0328133A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5818644A (en) * | 1995-11-02 | 1998-10-06 | Olympus Optical Co., Ltd. | Gradient index optical element and method for making the same |
| US6244074B1 (en) * | 1997-12-25 | 2001-06-12 | Nippon Sheet Glass Co., Ltd. | Method of manufacturing glass plate with light-transmissive colored film |
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