CN1115308C - Method for fabricating silica glass - Google Patents
Method for fabricating silica glass Download PDFInfo
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- CN1115308C CN1115308C CN98117652A CN98117652A CN1115308C CN 1115308 C CN1115308 C CN 1115308C CN 98117652 A CN98117652 A CN 98117652A CN 98117652 A CN98117652 A CN 98117652A CN 1115308 C CN1115308 C CN 1115308C
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- gel
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- colloidal sol
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- 238000000034 method Methods 0.000 title claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 9
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001879 gelation Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229960001866 silicon dioxide Drugs 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims 2
- 239000004160 Ammonium persulphate Substances 0.000 claims 1
- -1 N, N '-methylene Chemical group 0.000 claims 1
- 235000019395 ammonium persulphate Nutrition 0.000 claims 1
- 239000010703 silicon Substances 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 239000003431 cross linking reagent Substances 0.000 abstract description 8
- 239000002270 dispersing agent Substances 0.000 abstract description 4
- 239000003505 polymerization initiator Substances 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- 208000037656 Respiratory Sounds Diseases 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000013307 optical fiber Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- CGDIOSRHLQWGQC-UHFFFAOYSA-N O(O)O.CN(C)C Chemical compound O(O)O.CN(C)C CGDIOSRHLQWGQC-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
-
- 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
- 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
- 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
- C03C2203/22—Wet processes, e.g. sol-gel process using colloidal silica sols
-
- 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
- C03C2203/30—Additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Melting And Manufacturing (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Compositions (AREA)
Abstract
一种制作石英玻璃的方法，包括以下步骤：向丙烯酸类树脂单体和交联剂溶解于蒸馏水中得到预混合溶液中添加硅和分散剂，并调节混合物的pH以形成溶胶；去除溶胶中气泡，并使之老化；在老化的溶胶中添加聚合引发剂；将混合物倒入塑模，使其形成胶凝；将凝胶老化、脱模、干燥；对干燥的凝胶进行热处理，去除有机物质，然后进行烧结，因此可获得高纯度石英玻璃管。此方法在干燥之后很少发生裂纹且收缩率很低，用此方法还可制作大型石英玻璃管。
A method for producing quartz glass, comprising the steps of: adding silicon and a dispersant to a premixed solution obtained by dissolving an acrylic resin monomer and a crosslinking agent in distilled water, and adjusting the pH of the mixture to form a sol; removing air bubbles in the sol , and make it age; add a polymerization initiator to the aged sol; pour the mixture into a mold to form a gel; age the gel, release it, and dry it; heat-treat the dried gel to remove organic substances , and then sintered, so high-purity quartz glass tubes can be obtained. This method has few cracks and low shrinkage after drying, and large quartz glass tubes can also be produced by this method.
Description
The present invention relates to make the method for silica glass by sol-gel technology.
Usually, silica glass is transparent and unreactiveness is arranged to have high-caliber thermostability and intensity, and low thermal expansivity.Because these characteristics, silica glass is widely used in the Optical devices as optical fiber or optical lens.
In essence, optical fiber is made up of the fuse at its center and (metal) coating layer with the specific refractory power that is different from fuse, so that light all reflects from fuse.In order to make optical fiber, it comprises the coating pipe of a plug and this plug of sealing to make a kind of optic fiber preformed article.Then, in addition thermal treatment and being elongated of optic fiber preformed article to form optical fiber.
By modified chemical vapor deposition (MCVD) method, vapor phase axial deposition (VAD) method or extension vapour deposition (OVD) manufactured optic fiber preformed article.
In chemical vapour deposition, optic fiber preformed article is to be made by the coating pipe that high-purity quartz glass is made.Here, the coating pipe of silica glass forms by sol-gel technology.
Sol-gel technology as a kind of liquid phase process, can improve the component that output is also freely controlled product.And because sol-gel technology carries out at low temperatures, this sol-gel technology is the method for very economical.And because high purity material is used as starting material, this method is widely used in makes semiconductor light mask and high-purity quartz glass.
Below the concise and to the point method of making the coating pipe that silica glass forms by sol-gel technology of describing.
At first, silicon grain is scattered in the water to form colloidal sol.The colloidal sol that forms is through the burin-in process of the scheduled time.Then, pour the colloidal sol that produces into mold and carry out gelation.Finish after the gelation, from mold, isolate gel and make it dry.
Then, the exsiccant gel is heat-treated so that remove organic substance from gel.Then, from the gel of removing organic substance, eliminate the reaction of oh group, and carry out a sintering process, thereby finished the coating pipe of making by silica glass.
The speed of response of above-described sol-gel technology depends on component, pH and the solvent of gelation reaction temperature, colloidal sol, is difficult to keep speed of response in OK range by controlling these factors.In addition, when molded gel drying, can produce many crackles, and in sintering, shrinkage and crackle can take place.In order to address these problems, developed a kind of dry control chemical additive (DCCA) or a kind of polymer-bonded agent method, or redispersion method and supercritical drying drying method.
Use method local difference the vaporator rate of solvent from gel of dry control chemical additive (DCCA) to minimize, thereby in drying process, also the difference of the local pressure of sample is minimized.Its result.Therefore the gel hardening has reduced cracking.
According to the redispersion method, the exsiccant fine silica powder, the silicon that promptly atomizes is scattered in and forms colloidal sol in the water, colloidal sol gelling subsequently.In gelatinization process, because hydrogen bond makes silicon grain form a kind of agglomerate.After the agglomerate drying, the exsiccant agglomerate stand thermal technology's preface and grinding step subsequently redispersion in water.The gelling in addition of the product of redispersion, molded sintering then.
Yet aforesaid method be not effectively preventing aspect the crackle, and preparation process is very complicated in the Drying of gels process.
In order to solve the above problems, the object of the present invention is to provide the method for making the high-density silica glass, after the drying process crackle taking place and got rid of, and has also reduced generation crackle and contraction after sintering circuit in this method.
Therefore, in order to reach the above object, provide a kind of method of making silica glass, it comprises following steps:
(1) silicon and a kind of dispersion agent are added to a kind of acrylic resin monomer of being dissolved in the distilled water and a kind of linking agent and a kind of aqueous premix of obtaining, disperse this mixing solutions, adjust the pH value of mixture, to form a kind of colloidal sol;
(2) from colloidal sol, remove bubble, make the colloidal sol that is produced aging then;
(3) in the colloidal sol that burin-in process is crossed, add a kind of polymerization starter, and the pH value of conditioned reaction mixture;
(4) this reaction mixture is poured in the mold, in thermostat container, at high temperature made miscellany aging, and make the resultant gelation then;
(5) gel that obtains is made it aging,, make the gel drying of the demoulding subsequently the gel demoulding that burin-in process is crossed;
(6) the exsiccant gel is heat-treated to remove organic substance from gel; And
(7) gel of removing organic substance is carried out oh group and eliminate reaction and sintering reaction.
Describe most preferred embodiment of the present invention in more detail by the reference accompanying drawing, will make above-mentioned purpose of the present invention and advantage become distincter:
Fig. 1 shows the schema of making the silica glass method by the present invention.
According to the method that the present invention makes quartz glass, chemical gelatification is that silicon is added to dissolving A kind of acrylic resin monomer of Yu Shuizhong and a kind of crosslinking agent and in the aqueous premix that obtains, And disperseed and polymerization and thermally gelling are to add a kind of gelling in the component of quartz glass Agent and the suitable pH value of adjusting products therefrom, both carry out simultaneously. Its result is by acrylic compounds The polymer adhesive with 3-dimension network structure that resin monomer and crosslinking agent form is whole solidifying Evenly distribute in the glue, therefore, can eliminate the common density level bands that is caused by sol-gel technology The degree problem. And, the intensity enhancing of gel, thus the crackle that produces between dry period eliminated also Shortened drying time.
Preferably, acrylic resin monomer inclusion accounts for take the 2-of aqueous premix weight as base 20 (weight) %, crosslinking agent then account for take the 0.05-1.0 of aqueous premix weight as base (weight) %.
Preferably, the concentration that contains the aqueous premix of acrylic resin monomer and crosslinking agent is wanted Low. If the concentration of aqueous premix is lower, in sol-gel process at the organic substance branch Do not retain carbon after separating, then after sintering circuit the transparency of quartz glass with regard to variation. In addition Outward, if use this dilution aqueous premix, moist gel just becomes smoothly, by control The pH value is carried out the intensity that Thermogelling can improve moist gel.
There is no particular limitation to acrylic resin monomer and crosslinking agent. Yet, the acrylic compounds tree Alicyclic monomer is acrylamide or Methacrylamide preferably, and crosslinking agent N preferably, N ＇-methylene Diacrylamine [(H2C＝CHCONH)
2CH
2]
Describe the method that the present invention makes quartz glass in detail referring to Fig. 1.
At first, a kind of acrylic resin monomer and a kind of crosslinking agent are dissolved in deionized water with system Standby aqueous premix. In aqueous premix, add atomizing silicon and dispersant, disperseed subsequently, The pH value of reactant mixture is adjusted to 11-13 to form colloidal sol. Here based on weight The hybrid ratio of atomizing silicon and premix solution is 4: 6-6: 4. Here, dispersant helps In atomizing silicon Uniform Dispersion in mixed solution. There is not special restriction can use any dispersion Agent. Yet, preferably use TMAH as dispersant.
Subsequently, use vavuum pump from colloidal sol, to remove bubble, and colloidal sol is carried out the old of the scheduled time Change is with the silicon grain of stable sol.
Subsequently, in this reactant mixture, add polymerization initiator and catalyst, also want if need Add gelling agent. Subsequently, the pH value of reactant mixture is adjusted to 9-11. With what obtain Mixture is poured into and is carried out gelation in the mold. And in insulating box, place to wear out subsequently. 60-100 ℃ of burin-in process of carrying out 30 minutes-3 hours. Subsequently, at room temperature put Putting gel wears out.
Here, use ammonium persulfate as polymerization initiator, use methyl formate, methyl lactate or ethyl lactate as gelling agent
Subsequently, the gel mold of burin-in process is taken off, subsequently in 20-50 ℃ of insulating box and Make it dry under relative humidity (RH) 70-95%. Then, in order to remove dry coagulating The organic substance that glue retains, such as additive and adhesive, here for first Technology for Heating Processing, With 50 ℃ speed per hour gel is heated to 300-700 ℃, keeps this temperature 2-8 hours. Then for through first heat treatment gel in remove the oh group retain, chlorine In the compression ring border temperature is elevated to 800-1200 ℃ with 100 ℃ speed per hour, And under this temperature, kept 1-8 hour. Then, in helium environment with temperature with per hour 1 00 ℃ speed is increased to 1,100-1, and 500 ℃, and under this temperature, keep 1-8 Hour, therefore finished the making of high density and highly purified quartz glass.
Below explanation the present invention makes the embodiment of the method for silica glass.Yet the present invention is not limited to following examples.
Embodiment 1
With the N of acrylamide and 0.2 (weight) % of 4.8 (weight) %, N ＇-methylene diacrylamine is dissolved in the deionized water of 95.0 (weight) % with the preparation aqueous premix.
With 500 milliliters of aqueous premix, TMA (TriMethylAmine) oxyhydroxide (TMAH) aqueous solution (accounting for the aqueous solution 25.0 (weight) %) of 500 gram atomizing silicon (the product A erosil OX-50 of Degussa company) and 52 milliliters uses strong shear mixer to mix and disperse to prepare colloidal sol.Then, from colloidal sol, remove bubble, and carry out wearing out in 10 hours with vacuum pump.8 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) as polymerization starter, and are added 8 gram methyl-formiates (is 1.6 (weight) % based on silicon weight) and and the burin-in process colloidal sol mixing of crossing.
Mixture is poured into and is carried out gelation in the mold.In the mold of dress mixture carry out one hour burin-in process at 70 ℃ thermostat container, and gelationization subsequently is with the wet gel stripping that obtains, 30 ℃ of thermostat containers and 90% time drying of relative humidity (RH) 4 days.Subsequently, gel is heated to 120 ℃, and under this temperature, keeps 5 hours removing residual moisture, thereby form the exsiccant gel with 20 ℃ speed per hour.
Subsequently, the exsiccant gel is heated to after 550 ℃, in this temperature gel is carried out 5 hours thermal treatment, from the exsiccant gel, to remove organic substance in speed with 50 ℃/hour.The gel of removing organic substance is heated to 1000 ℃ with 100 ℃/hour speed, and keeps making it to form in 5 hours vitrifying in this temperature.Here be in chlorine gas environment, to remove oh group to form glass.
At last, the speed with 100 ℃/hour in helium environment is heated to 1400 ℃ with products therefrom, and under this temperature gel is carried out 4 hours sintering, to form quartz glass tube.
Embodiment 2
Except that using methyl lactate rather than methyl-formiate, use same quadrat method as described in Example 1 to make quartz glass tube.
Embodiment 3
Except that using ethyl lactate rather than methyl-formiate, use same quadrat method as described in Example 4 to make quartz glass tube.
Embodiment 4
With the N of Methacrylamide and 0.16 (weight) % of 3.9 (weight) %, N ＇-methylene diacrylamine is dissolved in the deionized water of 95.94 (weight) % with the preparation aqueous premix.
With 500 milliliters of aqueous premix, the TMAH aqueous solution (25.0 (weight) % aqueous solution) of 500 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 52 milliliters mixes and uses strong shear mixer to disperse to prepare colloidal sol.
Then, use vacuum pump from colloidal sol, to remove bubble, and carry out wearing out in 10 hours.In aged colloidal sol, add 8 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution), from reaction mixture, remove bubble.Add 8 grams methyl-formiates (is that base is 1.6 (weight) % with silicon weight) and and reaction mixture mix.Subsequently the miscellany that obtains is poured in the mold, in 70 ℃ thermostat container, carried out 1 hour burin-in process, and gel changes into predetermined shape subsequently.
After the gel demoulding, dry 10 days of 30 ℃ of thermostat containers and 90%RH to the humidity that obtains.Then, resultant is heated to 700 ℃, and kept 4 hours in this temperature subsequently with 50 ℃ speed per hour.Then, the exsiccant gel is heated to 1100 ℃, the exsiccant gel is carried out thermal treatment in 5 hours at 1100 ℃ with 100 ℃ speed per hour.Here, under chlorine atmosphere, heat-treat the oh group that technology retains with removal.
At last, under helium atmosphere, resultant is heated to 1500 ℃, gel is carried out 5 hours sintering, improved with regard to having formed the intensity of comparing gel with the situation of routine in this temperature with 100 ℃ speed per hour, so the gel easy handling.
And, can observe the quartz glass tube of making by embodiment 1 to 4 and whether crack and shrinkage.
The result is that at the quartz glass tube of pressing embodiment 1 to 4 making, crackle and shrinkage after drying treatment have all reduced.
In the method for the silica glass of making by the present invention, can obtain a kind of high-purity quartz glass pipe, its after drying, seldom crack and the shrinkage ratio quite low, in addition, can make big quartz glass tube by this making method.
The silica glass that obtains by making method of the present invention can be applied to semiconducter device, a kind of optical lens etc. and optic fiber preformed article.
Claims (3)
1. method of making silica glass comprises following steps:
(1) silicon-dioxide and as the Tetramethylammonium hydroxide of dispersion agent be added in the distilled water that is dissolved in surplus based on a kind of acrylic resin monomer of 2-20 (weight) % of the weight of aqueous premix with and in a kind of aqueous premix that obtains based on a kind of linking agent of 0.05-1.0 (weight) % of the weight of aqueous premix, disperse this mixing solutions, the pH value of adjusting mixture is to 11-13, to form a kind of colloidal sol;
(2) from colloidal sol, remove bubble, make the colloidal sol that is produced aging then;
(3) in the colloidal sol that burin-in process is crossed, add ammonium persulphate, and the pH value of conditioned reaction mixture is to 9-11 as polymerization starter;
(4) reaction mixture is poured in the mold, in 60-100 ℃ pyritous thermostat container, mixture carried out burin-in process and subsequently with the resultant gelation.
(5) gel that obtains is made it aging, the gel demoulding that burin-in process is crossed makes the gel drying of the demoulding subsequently;
(6) the exsiccant gel is heat-treated to remove organic substance from gel; And
(7) gel of removing organic substance is carried out oh group and eliminates reaction and sintering reaction,
Wherein this acrylic resin monomer is to be selected from a kind of compound in the group of being made up of acrylamide and Methacrylamide, and this linking agent is N, N ＇-methylene diacrylamine.
2. in accordance with the method for claim 1, it is characterized in that in the step (3) also adding a kind of jelling agent except that polymerization starter, jelling agent wherein is a kind of compound of choosing from the group that methyl-formiate, methyl lactate and ethyl lactate are formed at least.
3. in accordance with the method for claim 1, the blending ratio that it is characterized in that silicon-dioxide and aqueous premix is based on 4 of weight: 6-6: 4.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR19970042751 | 1997-08-29 | ||
| KR42751/1997 | 1997-08-29 | ||
| KR42751/97 | 1997-08-29 | ||
| KR19263/98 | 1998-05-27 | ||
| KR19263/1998 | 1998-05-27 | ||
| KR1019980019263A KR100252185B1 (en) | 1997-08-29 | 1998-05-27 | Method of manufacturing silica glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1210825A CN1210825A (en) | 1999-03-17 |
| CN1115308C true CN1115308C (en) | 2003-07-23 |
Family
ID=26633040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98117652A Expired - Fee Related CN1115308C (en) | 1997-08-29 | 1998-08-28 | Method for fabricating silica glass |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2938058B2 (en) |
| KR (1) | KR100252185B1 (en) |
| CN (1) | CN1115308C (en) |
| CA (1) | CA2246153C (en) |
| FR (1) | FR2767808B1 (en) |
| GB (1) | GB2328685B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100322132B1 (en) * | 1999-01-29 | 2002-01-29 | 윤종용 | Silica glass composition for sol-gel process |
| KR20000074724A (en) * | 1999-05-25 | 2000-12-15 | 윤종용 | Manufacturing method of silica glass for sol-gel process |
| CN1107657C (en) * | 2000-04-17 | 2003-05-07 | 袁茂豪 | Production process of high-silicon quartzite powder |
| KR20050080879A (en) * | 2004-02-11 | 2005-08-18 | 삼성전자주식회사 | Method for fabricating holey fiber preform |
| CN107250069B (en) * | 2015-03-04 | 2021-06-29 | 国立大学法人九州大学 | Method for producing silica glass precursor, silica glass precursor, method for producing silica glass, and silica glass |
| DE102016012003A1 (en) * | 2016-10-06 | 2018-04-12 | Karlsruher Institut für Technologie | Composition and method for producing a shaped body from high-purity, transparent quartz glass by means of additive manufacturing |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2113200B (en) * | 1982-01-08 | 1985-06-19 | Hitachi Ltd | Process for producing optical glass |
| JP2635313B2 (en) * | 1986-05-14 | 1997-07-30 | 日立化成工業株式会社 | Method for producing silica glass |
| JPS6385018A (en) * | 1986-09-26 | 1988-04-15 | Harima Ceramic Co Ltd | Production of high purity silica glass |
| JPH01176235A (en) * | 1987-12-29 | 1989-07-12 | Hitachi Chem Co Ltd | Production of silica glass |
| JPH01176234A (en) * | 1987-12-29 | 1989-07-12 | Hitachi Chem Co Ltd | Production of silicate glass |
| US4894194A (en) * | 1988-02-22 | 1990-01-16 | Martin Marietta Energy Systems, Inc. | Method for molding ceramic powders |
| DE4130440A1 (en) * | 1991-09-13 | 1993-03-18 | Philips Patentverwaltung | METHOD FOR PRODUCING MOLDED BODIES FROM CERAMIC OR GLASS |
| FR2681534B1 (en) * | 1991-09-20 | 1995-01-27 | Rhone Poulenc Chimie | CONCENTRATED COLLOUIDAL SOLUTIONS OF NON-AGGREGATED MONOCRYSTALLINE PARTICLES OF METAL OXIDES, THEIR PREPARATION PROCESS AND THEIR APPLICATION FOR OBTAINING FILMS. |
| US5240488A (en) * | 1992-08-14 | 1993-08-31 | At&T Bell Laboratories | Manufacture of vitreous silica product via a sol-gel process using a polymer additive |
-
1998
- 1998-05-27 KR KR1019980019263A patent/KR100252185B1/en not_active IP Right Cessation
- 1998-08-20 JP JP10234619A patent/JP2938058B2/en not_active Expired - Fee Related
- 1998-08-20 GB GB9818056A patent/GB2328685B/en not_active Expired - Fee Related
- 1998-08-28 CN CN98117652A patent/CN1115308C/en not_active Expired - Fee Related
- 1998-08-28 FR FR9810826A patent/FR2767808B1/en not_active Expired - Fee Related
- 1998-08-28 CA CA002246153A patent/CA2246153C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2246153C (en) | 2001-11-27 |
| CN1210825A (en) | 1999-03-17 |
| JPH11147727A (en) | 1999-06-02 |
| KR19990023144A (en) | 1999-03-25 |
| GB9818056D0 (en) | 1998-10-14 |
| FR2767808A1 (en) | 1999-03-05 |
| JP2938058B2 (en) | 1999-08-23 |
| FR2767808B1 (en) | 2000-12-15 |
| GB2328685B (en) | 1999-09-29 |
| KR100252185B1 (en) | 2000-04-15 |
| GB2328685A (en) | 1999-03-03 |
| CA2246153A1 (en) | 1999-02-28 |
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