JPS6351976B2 - - Google Patents
Info
- Publication number
- JPS6351976B2 JPS6351976B2 JP57006824A JP682482A JPS6351976B2 JP S6351976 B2 JPS6351976 B2 JP S6351976B2 JP 57006824 A JP57006824 A JP 57006824A JP 682482 A JP682482 A JP 682482A JP S6351976 B2 JPS6351976 B2 JP S6351976B2
- Authority
- JP
- Japan
- Prior art keywords
- doped silica
- silica glass
- sol
- transparent
- gas
- 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.)
- Expired
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- -1 alkyl silicate Chemical compound 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910005793 GeO 2 Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Compositions (AREA)
- Silicon Compounds (AREA)
Description
【発明の詳細な説明】
本発明は良好な光学特性を有するドープトシリ
カガラスの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing doped silica glass having good optical properties.
従来、アルキルシリケートと他の金属アルコキ
シドを含む混合液を加水分解するに際しては、該
混合液に直接、水または希アンモニア水または希
塩酸水を少量ずつ加えて加水分解反応を行つてい
た。この場合、アンモニアまたは塩酸は加水分解
を促進する効果を有するものである。 Conventionally, when hydrolyzing a liquid mixture containing an alkyl silicate and another metal alkoxide, the hydrolysis reaction was carried out by directly adding water, dilute ammonia water, or dilute hydrochloric acid water little by little to the mixture. In this case, ammonia or hydrochloric acid has the effect of promoting hydrolysis.
しかし、この従来の手法で該混合液を加水分解
した場合、混合液に相分離が生ずるという欠点が
あつた。 However, when the mixed liquid is hydrolyzed using this conventional method, there is a drawback that phase separation occurs in the mixed liquid.
たとえばSi（OC2H5）4とGe（OC4H9）4との混合
液（混合比９：１）を１％のNH4OHを含むアン
モニア水で加水分解した場合、混合液中にはアン
モニア水添加と同時に相分離が生じ、Ge
（OC4H9）4のみ先行して加水分解されるという欠
点があつた。このため加水分解して得られたりゾ
ル液では、Si（OH）4とGe（OH）4とがそれぞれ独
立に存在し、さらに乾燥、焼結後に得られるガラ
ス体においても、GeO2が相分離して析出し、白
濁するという欠点があつた。 For example, when a mixture of Si(OC 2 H 5 ) 4 and Ge(OC 4 H 9 ) 4 (mixing ratio 9:1) is hydrolyzed with aqueous ammonia containing 1% NH 4 OH, Phase separation occurs simultaneously with the addition of ammonia water, and Ge
The drawback was that only (OC 4 H 9 ) 4 was hydrolyzed first. Therefore, in the sol obtained by hydrolysis, Si(OH) 4 and Ge(OH) 4 exist independently, and even in the glass body obtained after drying and sintering, GeO 2 undergoes phase separation. The problem was that it precipitated and became cloudy.
したがつて従来の方法による加水分解では、良
好な光学特性を有するドープトシリカガラスが得
られないという問題点があつた。 Therefore, the conventional hydrolysis method has the problem that doped silica glass having good optical properties cannot be obtained.
本発明はこれら欠点を除去するため、アルキル
シリケートと他の金属アルコキシドを含む混合液
を加水分解するに先だち、密閉された容器内で水
蒸気を含む気体に所定の時間曝らして透明なゾル
状体を合成するもので、その目的は加水分解に際
して生ずる前記相分離を防止し、透明で、良好な
光学特性を有するドープトシリカガラス体を提供
することにある。 In order to eliminate these drawbacks, the present invention aims to produce a transparent sol by exposing a liquid mixture containing an alkyl silicate and other metal alkoxide to a gas containing water vapor for a predetermined period of time in a sealed container before hydrolyzing it. The purpose is to prevent the phase separation that occurs during hydrolysis and to provide a doped silica glass body that is transparent and has good optical properties.
図は本発明の一実施例を示し、１はガス流量調
節器、２はバブリング用容器、３は水、４は反応
容器、５はSi（OC2H5）4とGe（OC4H9）4の混合液、
６は連結配管、７は排気管である。図において流
量調節器１によつて流量制御した不活性ガスまた
は酸素ガスをバブリング容器２内に送り込み、水
３の中をバブリングすることによつて気体中に水
蒸気を含ませた後、連結配管６によつて水蒸気を
含んだ気体を反応容器４内に供給し、Si
（OC2H5）4とGe（OC4H9）4の混合液５を該気体に
曝らし、該混合液を予備加水分解するものであ
る。反応後のガスは排気管７より排出される。 The figure shows an embodiment of the present invention, in which 1 is a gas flow rate regulator, 2 is a bubbling container, 3 is water, 4 is a reaction container, and 5 is Si(OC 2 H 5 ) 4 and Ge(OC 4 H 9 ) 4 mixture,
6 is a connecting pipe, and 7 is an exhaust pipe. In the figure, inert gas or oxygen gas whose flow rate is controlled by a flow rate controller 1 is sent into a bubbling container 2, and water vapor is included in the gas by bubbling in water 3, and then the connecting pipe 6 A gas containing water vapor is supplied into the reaction vessel 4 by
A mixed solution 5 of (OC 2 H 5 ) 4 and Ge(OC 4 H 9 ) 4 is exposed to the gas to preliminarily hydrolyze the mixed solution. The gas after the reaction is exhausted from the exhaust pipe 7.
たとえば、水５を入れたバブリング容器に毎
分50のアルゴンガスを送り込み、温度50℃でバ
ブリングすると、アルゴンガス中には約12mol％
の水蒸気が含まれる。この12％H2Oを含んだア
ルゴンガスを連結管により、Si（OC2H5）4とGe
（OC4H9）4とを９：１（体積比）の割合で混ぜた混
合液５を入れた反応容器内に供給し、該混合液
を温度30℃下で５時間、該アルゴンガスに曝ら
し、予備加水分解を施すと、該混合液は反応後約
１時間で透明なゾル状体となつた。この透明なゾ
ル状体では、Si（OH）4とGe（OH）4とが相分離す
ることなく、分子レベルで混合した２成分ゾル状
体となつている。このためこの透明なゾル状体
を、NH4OHを1mol％含むアンモニア水によつ
て加水分解しても、相分離を生じず、透明な
GeO2ドープトシリカゲルが得られた。さらにこ
の透明なドープトシリカゲル体を1500℃で２時間
焼結した結果、屈折率が1.462の透明なGeO2ドー
プトシリカガラス体が得られた。 For example, if 50% of argon gas is sent per minute into a bubbling container containing 5% of water and bubbled at a temperature of 50°C, approximately 12 mol% of argon gas will be present in the argon gas.
Contains water vapor. This argon gas containing 12% H 2 O was transferred through a connecting pipe to Si(OC 2 H 5 ) 4 and Ge.
(OC 4 H 9 ) 4 at a ratio of 9:1 (volume ratio) was supplied into a reaction vessel containing a mixture 5, and the mixture was heated to 30°C for 5 hours in the argon gas. When exposed and pre-hydrolyzed, the mixture turned into a transparent sol about 1 hour after the reaction. In this transparent sol, Si(OH) 4 and Ge(OH) 4 are mixed at the molecular level without phase separation, resulting in a two-component sol. Therefore, even if this transparent sol-like material is hydrolyzed with aqueous ammonia containing 1 mol% of NH 4 OH, no phase separation occurs and a transparent sol remains.
GeO 2 doped silica gel was obtained. Furthermore, as a result of sintering this transparent doped silica gel body at 1500° C. for 2 hours, a transparent GeO 2 doped silica glass body with a refractive index of 1.462 was obtained.
金属アルコキシドとして、ゲルマニウムアルコ
オキサイドの代わりに、チタン、アルミニウム、
りん、ほう素、アンチモン、すず、鉛、タンタル
のアルコオキサイドをそれぞれ使用した場合に
も、ほぼ同一の反応条件で透明なゾル状体が得ら
れ、さらに焼結して透明なドープトシリカガラス
体が得られた。 As metal alkoxides, instead of germanium alkoxide, titanium, aluminum,
Even when phosphorus, boron, antimony, tin, lead, and tantalum alkoxides are used, a transparent sol-like body can be obtained under almost the same reaction conditions, and a transparent doped silica glass body can be obtained by sintering. was gotten.
前記の本発明により作製したドープトシリカガ
ラス体は組成の均一性が極めて良い。またアルコ
キシド原料として高純物を用いれば、極めて高い
透過率を有していた。 The doped silica glass body produced according to the present invention has extremely good compositional uniformity. Furthermore, if a highly purified alkoxide raw material was used, it had an extremely high transmittance.
また前記屈折率1.462のGeO2ドープトシリカガ
ラス体をコア材として、また市販の石英管をクラ
ツド材として使用して作製したコア径50μm、外
径125μmの光フアイバの損失は１Km当り5dB／Km
（波長0.85μm）であつた。 Furthermore, the loss of an optical fiber with a core diameter of 50 μm and an outer diameter of 125 μm manufactured using the GeO 2 doped silica glass body with a refractive index of 1.462 as a core material and a commercially available quartz tube as a cladding material is 5 dB/Km per 1 km.
(wavelength: 0.85 μm).
以上説明したように、本発明のドープトシリカ
ガラスの製造方法では、相分離を生ずることな
く、混合液を加水分解できるので、材料組成が均
一で、良好な光学特性を有するドープトシリカガ
ラス体を製造できる利点がある。また本発明は大
量のゾル状体を一度に合成できるので、良好な光
学特性を有するドープトシリカガラス体を量産で
きる利点がある。さらに大量に製造したドープト
シリカガラス体を光フアイバコア材に使用すれ
ば、安価な光フアイバを大量に製造できる利点が
ある。 As explained above, in the method for producing doped silica glass of the present invention, a mixed liquid can be hydrolyzed without causing phase separation, so that the doped silica glass has a uniform material composition and good optical properties. It has the advantage of being able to manufacture Furthermore, the present invention has the advantage of being able to mass-produce doped silica glass bodies with good optical properties, since a large amount of sol-like bodies can be synthesized at one time. Furthermore, if the doped silica glass body manufactured in large quantities is used as the optical fiber core material, there is an advantage that inexpensive optical fibers can be manufactured in large quantities.
図は本発明の一実施例図である。
１…ガス流量調整器、２…バブリング用容器、
３…水、４…反応容器、５…Si（OC2H5）4とGe
（OC4H9）4の混合液、６…連結配管、７…排気管。
The figure shows an embodiment of the present invention. 1... Gas flow rate regulator, 2... Bubbling container,
3...Water, 4...Reaction vessel, 5...Si(OC 2 H 5 ) 4 and Ge
(OC 4 H 9 ) Mixed liquid of 4 , 6...connection pipe, 7...exhaust pipe.
Claims (1)
を含む混合液を、密封された容器内で水蒸気を含
む気体に曝して透明なゾル状体を合成した後、該
ゾル状体を加水分解、乾燥、焼結を経て透明なガ
ラス体とすることを特徴とするドープトシリカガ
ラスの製造方法。1 A mixed solution containing an alkyl silicate and another metal alkoxide is exposed to a gas containing water vapor in a sealed container to synthesize a transparent sol-like material, and then the sol-like material is hydrolyzed, dried, and sintered. 1. A method for producing doped silica glass, which is characterized in that it is made into a transparent glass body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP682482A JPS58125634A (en) | 1982-01-21 | 1982-01-21 | Preparation of doped silica glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP682482A JPS58125634A (en) | 1982-01-21 | 1982-01-21 | Preparation of doped silica glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58125634A JPS58125634A (en) | 1983-07-26 |
| JPS6351976B2 true JPS6351976B2 (en) | 1988-10-17 |
Family
ID=11648963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP682482A Granted JPS58125634A (en) | 1982-01-21 | 1982-01-21 | Preparation of doped silica glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58125634A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2153848C (en) * | 1994-07-18 | 2003-05-13 | Motoyuki Tanaka | Oxide thin film having quartz crystal structure and process for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5782137A (en) * | 1980-09-17 | 1982-05-22 | Pasare Mishieru | Manufacture of glass pipe having at least one dope silica layers and manufacture of preform available foroptical fiber production |
-
1982
- 1982-01-21 JP JP682482A patent/JPS58125634A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5782137A (en) * | 1980-09-17 | 1982-05-22 | Pasare Mishieru | Manufacture of glass pipe having at least one dope silica layers and manufacture of preform available foroptical fiber production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58125634A (en) | 1983-07-26 |
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