JPH039046B2 - - Google Patents
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- Publication number
- JPH039046B2 JPH039046B2 JP59216773A JP21677384A JPH039046B2 JP H039046 B2 JPH039046 B2 JP H039046B2 JP 59216773 A JP59216773 A JP 59216773A JP 21677384 A JP21677384 A JP 21677384A JP H039046 B2 JPH039046 B2 JP H039046B2
- Authority
- JP
- Japan
- Prior art keywords
- gel
- glass body
- och
- bulk density
- types
- 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 - Lifetime
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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)
- Silicon Compounds (AREA)
- Glass Melting And Manufacturing (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Description
【発明の詳細な説明】
［発明の背景と目的］
本発明は、光学ガラス体の製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Background and Objects of the Invention] The present invention relates to a method of manufacturing an optical glass body.
最近、シリコンアルコキシドを加水分解して得
られる多孔質ゲルを焼結し、透明なガラス体を製
造する方法（以下ゾル・ゲル法と称す）が提案さ
れ、このゾル・ゲル法による光フアイバ製造の試
みも、Electronics Letters18［12］、499（1982）
により報告されている。 Recently, a method of manufacturing a transparent glass body by sintering a porous gel obtained by hydrolyzing silicon alkoxide (hereinafter referred to as the sol-gel method) has been proposed. Attempts too, Electronics Letters 18 [12], 499 (1982)
Reported by.
上記ゾル・ゲル法で得られるシリカ乾燥ゲルは
作成条件にも依存するが、Si（OC2H5）4の原料を
使う場合には、乾燥ゲルのかさ密度が、0.7ｇ／
cm3であり、Si（OCH3）4の原料を使う場合にはよ
り低いかさ密度のゲルができ、0.6ｇ／cm3のかさ
密度が得られ、この低かさ密度乾燥ゲルより光フ
アイバの作製が可能と上記文献に報告されてい
る。 The dry silica gel obtained by the above-mentioned sol-gel method depends on the preparation conditions, but when using Si(OC 2 H 5 ) 4 raw material, the bulk density of the dry gel is 0.7 g/
cm 3 , and when Si(OCH 3 ) 4 raw material is used, a gel with a lower bulk density is obtained, and a bulk density of 0.6 g/cm 3 is obtained, and optical fibers can be fabricated from this low bulk density dried gel. It is reported in the above literature that this is possible.
一般には、乾燥ゲルのかさ密度が小さいほど、
高温における焼結ガラス体の発泡が少なくなる。
従つて、無発泡ガラスを作るためにはなるべく低
いかさ密度のゲル作成が要求される。シリコンア
ルコキシドの原料を１種類単独に使用するゲル製
造方法では、0.6ｇ／cm3のかさ密度の乾燥ゲルが
限界であり、このゲルより作成したガラスは、
1300℃で発泡しないものでも約2000℃の高温で加
熱するとガラス体に気泡が発生するという発泡現
象がしばしば生じている。 In general, the lower the bulk density of the dry gel, the
Foaming of the sintered glass body at high temperatures is reduced.
Therefore, in order to produce non-foamed glass, it is required to produce a gel with as low a bulk density as possible. In the gel production method that uses only one type of silicon alkoxide raw material, the limit is a dry gel with a bulk density of 0.6 g/cm 3 , and the glass made from this gel has a
Even if a glass body does not foam at 1300°C, when heated at a high temperature of approximately 2000°C, a foaming phenomenon often occurs in which air bubbles are generated in the glass body.
本発明は、上記の状況に鑑みて成されたもので
あり、特に約2000℃の加熱時においても気泡の発
生を防止できる光学カラス体の製造方法を提供す
ることを目的としたものである。 The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a method for manufacturing an optical glass body that can prevent the generation of bubbles even when heated to approximately 2000°C.
［発明の概要］
本発明の要旨は、加水分解速度の異なる２種類
のシリコンアルコキシドSi（OC2H5）4及びSi
（OCH3）4を加水分解して多孔質ゲルとし、該多
孔質ゲルを加熱焼結し、光学ガラス体の酸化物ブ
ロツク体を製造する方法において、上記２種類の
シリコンアルコキシドのモル比Si（OC2H5）4／Si
（OCH3）4を４以上としたことにある。[Summary of the Invention] The gist of the present invention is that two types of silicon alkoxides, Si(OC 2 H 5 ) 4 and Si
(OCH 3 ) 4 is hydrolyzed to form a porous gel, and the porous gel is heated and sintered to produce an oxide block body for an optical glass body. OC 2 H 5 ) 4 /Si
(OCH 3 ) This is because 4 was set to 4 or more.
［実施例］
以下、本発明の光学ガラス体の製造方法を実施
例を用いて図面により説明する。[Example] Hereinafter, the method for manufacturing an optical glass body of the present invention will be explained using examples and drawings.
図は、ゾル・ゲル法のプロセスの概要図であ
る。シリコンアルコキシドを主原料とし、アルコ
ール及びH2Oを混合撹拌して得られた原料混合
液１を適宜ガラス容器２に移し、ガラス容器２を
アルミホイル３によりほぼ密閉、放置してゲル化
させる。ゲル化完了後の溶媒及び水を多量に含ん
でいるウエツト（Wet）ゲル４を乾燥工程で乾燥
させ、溶媒のアルコールや水を蒸発させ、焼結用
の多孔質の乾燥（Dry）ゲル５を作る。 The figure is a schematic diagram of the sol-gel process. A raw material mixture 1 obtained by mixing and stirring alcohol and H 2 O using silicon alkoxide as the main raw material is appropriately transferred to a glass container 2, and the glass container 2 is almost sealed with aluminum foil 3 and left to gel. After the gelation is complete, the wet gel 4 containing a large amount of solvent and water is dried in a drying process, and the solvent alcohol and water are evaporated to form a porous dry gel 5 for sintering. make.
次に、乾燥ゲル５を約1300℃で焼結、ガラス化
し透明ガラス体６を作る。そして、光フアイバを
作る場合には、透明ガラス体６から従来の光フア
イバのロツドインチユーブ法などにより、約2000
℃で光フアイバが製造される。 Next, the dried gel 5 is sintered and vitrified at about 1300°C to form a transparent glass body 6. When making an optical fiber, about 200
Optical fibers are manufactured at ℃.
加水分解速度の速いSi（OCH3）4と、遅いSi
（OC2H5）4との混合液に、溶媒としてのエタノー
ルC3H5OHを加え撹拌しながら、約0.05モル／
のNH3濃度のアンモニア水を加えて均一な混合
液とした。そして、Si（OC2H5）4とSi（OCH3）4合
計１モルに対して、エタノールが４モルとアンモ
ニヤ水が４モルの組成になるように混合液を作成
した。また、Si（OC2H5）4／Si（OCH3）4のモル比
率が、０／1.0、0.2／0.8、0.4／0.6、0.6／0.4、
0.8／0.2になるように５種類の組成の混合液を調
整作成した。 Si( OCH3 ) 4 has a fast hydrolysis rate and Si has a slow hydrolysis rate.
Add ethanol C 3 H 5 OH as a solvent to the mixture with (OC 2 H 5 ) 4 and add about 0.05 mole/C 3 H 5 OH while stirring.
Aqueous ammonia with a concentration of NH 3 was added to make a homogeneous mixture. Then, a mixed solution was prepared such that the composition was 4 moles of ethanol and 4 moles of aqueous ammonia per 1 mole of Si(OC 2 H 5 ) 4 and Si(OCH 3 ) 4 in total. Moreover, the molar ratio of Si(OC 2 H 5 ) 4 /Si(OCH 3 ) 4 is 0/1.0, 0.2/0.8, 0.4/0.6, 0.6/0.4,
Mixed liquids with five different compositions were prepared so that the ratio was 0.8/0.2.
このようにして得られた均一な混合液を、内径
10mm×長さ200mmのガラスの溶液２に入れ、アル
ミホイル３により上端部をほぼ密閉した後室温で
約１日放置してゲル化させた。次に、容器２のア
ルミホイル３の部分にピンホールを数個あけ、70
℃の恒温槽（図示せず）内に10日間、120℃の恒
温槽内に１日間、それぞれ保持しゲルに残留して
いる水及びエタノールを蒸発させ乾燥させた。こ
のようにして得た５種類の乾燥ゲルのかさ密度
は、縦軸にゲルのかさ密度を取り、横軸に、Si
（OC2H5）4／Si（OCH3）4のモル比をとつて示した
第２図の曲線Ａに示す如くである。即ち、加水分
解速度の速いSi（OCH3）4を単独に使用した場合
には、かさ密度は0.6ｇ／cm3であり、また、加水
分解速度の遅いSi（OC2H5）4を単独に使用する場
合にはゲル化に用する時間は著しく長く、しか
も、ゲルの作成は良好にできなかつた。これに対
し、Si（OC2H5）4／Si（OCH3）4のモル比が、0.8／
0.2＝４の組成では、0.40ｇ／cm3の最少の低かさ
密度のゲルが得られた。 The homogeneous mixture obtained in this way was
It was placed in a glass solution 2 measuring 10 mm x 200 mm in length, and the upper end was almost sealed with aluminum foil 3, and then left at room temperature for about 1 day to gel. Next, make several pinholes in the aluminum foil 3 of the container 2, and
The gel was kept in a constant temperature bath (not shown) at 120°C for 10 days and for 1 day in a constant temperature bath at 120°C to evaporate water and ethanol remaining in the gel and dry it. The bulk density of the five types of dry gels obtained in this way is determined by taking the bulk density of the gel on the vertical axis and Si
The molar ratio of (OC 2 H 5 ) 4 /Si(OCH 3 ) 4 is shown in curve A of FIG. 2. That is, when Si(OCH 3 ) 4 with a fast hydrolysis rate is used alone, the bulk density is 0.6 g/cm 3 , and when Si(OC 2 H 5 ) 4 with a slow hydrolysis rate is used alone. When used for gelation, the time required for gelation was extremely long, and the gel could not be formed well. On the other hand, the molar ratio of Si(OC 2 H 5 ) 4 /Si(OCH 3 ) 4 is 0.8/
The composition 0.2=4 gave the lowest bulk density gel of 0.40 g/cm 3 .
上記５種類のゲルを同じ条件で焼結したガラス
には気泡が全く無かつたが、約2000℃の高温で加
熱すると、かさ密度の小さいほどガラスの発泡が
少なく、Ｐ＝0.4ｇ／cm3のゲル、即ちSi
（OC2H5）4／Si（OCH3）4のモル比が、４のゲルか
ら作成したガラスには発泡がなく、きれいな無孔
透明ガラス体であつた。上記５種類の組成で作成
したガラスの発泡の比較は、第２図の○印内の黒
塗り量の大小で示してあり、黒塗り量の大きいほ
ど発泡が多く○印内の黒塗り部分の全くないもの
は無発泡を示す。上記のSi（OC2H5）4／Si
（OCH3）4のモル比が、４である無発泡のシリカ
ガラスロツドを、公知の技術でプリフオームした
後フアイバ化して光フアイバを作成した。フアイ
バの線引温度は約2000℃であるが発泡がなく、光
フアイバに利用できるガラスであることが確認さ
れた。 Glass obtained by sintering the above five types of gel under the same conditions had no bubbles at all, but when heated at a high temperature of about 2000℃, the lower the bulk density, the less foaming the glass had, P = 0.4g/cm 3 gel, i.e. Si
A glass prepared from a gel having a molar ratio of (OC 2 H 5 ) 4 /Si(OCH 3 ) 4 of 4 had no foaming and was a clean, non-porous, transparent glass body. A comparison of the foaming of glasses made with the above five compositions is shown by the amount of black paint inside the ○ mark in Figure 2. The larger the black paint amount, the more foaming occurs. If there is no foam at all, it indicates no foaming. Above Si(OC 2 H 5 ) 4 /Si
An optical fiber was prepared by preforming a non-foamed silica glass rod having a molar ratio of (OCH 3 ) 4 to 4 using a known technique and then forming it into a fiber. Although the drawing temperature of the fiber was approximately 2000℃, there was no foaming, and it was confirmed that the glass could be used for optical fibers.
このように本実施例の光学ガラス体の製造方法
によれば、酸化物の原料として同一元素で、加水
分解速度が異なる２種類のシリコンアルコキシド
を用いて加水分解を行いゲル作成を行う方法（以
下、異加水分解速度法と称す）において、加水分
解速度が異なる２種類のアルコキシドSi
（OC2H5）4／Si（OCH3）4のモル比を４以上とする
ことにより、約2000℃の加熱においても気泡の発
生を防止できた。従つて、光フアイバの製造時に
おいても、発泡することがない光学ガラス体を得
ることができる。 As described above, according to the method for manufacturing an optical glass body of this example, two types of silicon alkoxides, which are the same element but have different hydrolysis rates, are used as raw materials for the oxide to perform hydrolysis to create a gel (hereinafter referred to as (referred to as the different hydrolysis rate method), two types of alkoxides with different hydrolysis rates, Si
By setting the molar ratio of (OC 2 H 5 ) 4 /Si(OCH 3 ) 4 to 4 or more, generation of bubbles could be prevented even when heated to about 2000°C. Therefore, it is possible to obtain an optical glass body that does not foam even during the production of optical fibers.
因に、本実施例の異加水分解速度法のゲルが、
原料１元素に対し１種類の金属アルコキシドのみ
を用いて作成したゲルよりも更に低いかさ密度が
できる理由は、加水分解速度の遅いアルコキシド
原料によるゲルの強化効果によるものと考えられ
る。加水分解速度の速いアルコキシド原料は先に
反応してゲルの網目構造を形成するが、加水分解
速度の遅いものは、後に反応して既に形成された
網目構造の表面に堆積し、ゲルの構造全体を強化
する結果となると思われる。従つて、同じ溶媒の
表面張力による収縮力に対して、強いゲル程ゲル
の収縮が小さくその結果、低かさ密度のゲルが実
現できるのである。 Incidentally, the gel of the heterohydrolysis rate method of this example is
The reason why the bulk density is even lower than that of a gel made using only one type of metal alkoxide for one raw material element is thought to be due to the strengthening effect of the gel by the alkoxide raw material, which has a slow hydrolysis rate. Alkoxide raw materials with a fast hydrolysis rate react first to form a gel network structure, while those with a slow hydrolysis rate react later and deposit on the surface of the already formed network structure, destroying the entire gel structure. This is expected to result in the strengthening of Therefore, the stronger the gel, the smaller the shrinkage of the gel with respect to the shrinkage force due to the surface tension of the same solvent, and as a result, a gel with a lower bulk density can be realized.
上記実施例では、Si（OCH3）4とSi（OC2H5）4の
２種類のシリコンアルコキシドの場合を説明した
が、Si（OR）4（Ｒ：アルキル基）の３種類以上の
混合の場合も当然この異加水分解速度法の適用が
可能であると考えられる。 In the above example, the case of two types of silicon alkoxides, Si(OCH 3 ) 4 and Si(OC 2 H 5 ) 4, was explained, but a mixture of three or more types of Si(OR) 4 (R: alkyl group) was explained. Naturally, this heterohydrolysis rate method can also be applied to the case of
また、シリコンアルコキシドの他に、ゾル・ゲ
ル法に使用できる例えば、Ge（OR）4、Ti（OR）5、
Ta（OR）5等の金属アルコキシドも上記Si（OR）4
の場合と同じく異加水分解速度法の効果が期待で
きると考えられる。 In addition to silicon alkoxide, there are also other materials that can be used in the sol-gel method, such as Ge(OR) 4 , Ti(OR) 5 ,
Metal alkoxides such as Ta(OR) 5 and the above Si(OR) 4
It is thought that the effect of the heterohydrolysis rate method can be expected as in the case of .
［発明の効果］
以上述べたように、本発明の光学ガラス体の製
造方法によれば、約2000℃の高温で加熱しても気
泡の発生を防止できる光学ガラス体を製造するこ
とができる。[Effects of the Invention] As described above, according to the method for producing an optical glass body of the present invention, it is possible to produce an optical glass body that can prevent the generation of bubbles even when heated at a high temperature of about 2000°C.
そして、約2000℃の製造工程を有する光フアイ
バの生産においても、該光学ガラス体をその材料
に用いれば、光フアイバの製造工程で発泡するこ
とはなくなり、その結果、品質の良い無孔透明な
光フアイバを提供することができるという優れた
効果を奏する。 Even in the production of optical fiber, which requires a manufacturing process of approximately 2000°C, if this optical glass body is used as the material, foaming will not occur during the manufacturing process of optical fiber, and as a result, a high-quality, non-porous, transparent product will be produced. This has the excellent effect of being able to provide optical fibers.
図は本発明の光学ガラス体の製造方法のプロセ
スの概要図、第２図は第１図の方法を実施する加
水分解速度の速いシリコンアルコキシドと遅いシ
リコンアルコキシドのモル比及び乾燥ゲルのかさ
密度との関係を示すグラフである。
１：原料混合液、２：ウエツトゲル、５：乾燥
ゲル、６：透明ガラス体。
The figure is a schematic diagram of the process of the method for producing an optical glass body of the present invention, and Figure 2 shows the molar ratio of silicon alkoxide with a fast hydrolysis rate and silicon alkoxide with a slow hydrolysis rate and the bulk density of the dry gel in which the method of Figure 1 is carried out. It is a graph showing the relationship. 1: Raw material mixture, 2: Wet gel, 5: Dry gel, 6: Transparent glass body.
Claims (1)
コキシドSi（OC2H5）4及びSi（OCH3）4を加水分解
して多孔質ゲルとし、該多孔質ゲルを加熱焼結
し、光学ガラス体の酸化物ブロツク体を製造する
方法において、上記２種類のシリコンアルコキシ
ドのモル比Si（OC2H5）4／Si（OCH3）4を４以上と
したことを特徴とする光学ガラス体の製造方法。1 Two types of silicon alkoxides, Si(OC 2 H 5 ) 4 and Si(OCH 3 ) 4 , which have different hydrolysis rates, are hydrolyzed to form a porous gel, and the porous gel is heated and sintered to form an optical glass body. A method for producing an optical glass body, characterized in that the molar ratio Si(OC 2 H 5 ) 4 /Si(OCH 3 ) 4 of the two types of silicon alkoxides is 4 or more in the method for producing an oxide block body. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21677384A JPS6197138A (en) | 1984-10-16 | 1984-10-16 | Method for manufacturing optical glass bodies |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21677384A JPS6197138A (en) | 1984-10-16 | 1984-10-16 | Method for manufacturing optical glass bodies |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6197138A JPS6197138A (en) | 1986-05-15 |
| JPH039046B2 true JPH039046B2 (en) | 1991-02-07 |
Family
ID=16693667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21677384A Granted JPS6197138A (en) | 1984-10-16 | 1984-10-16 | Method for manufacturing optical glass bodies |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6197138A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791069B2 (en) * | 1985-11-05 | 1995-10-04 | 住友電気工業株式会社 | Glass manufacturing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56155038A (en) * | 1980-04-30 | 1981-12-01 | Hitachi Cable Ltd | Preparation of base material for optical fiber |
-
1984
- 1984-10-16 JP JP21677384A patent/JPS6197138A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6197138A (en) | 1986-05-15 |
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