JPH04254420A - Production of quartz base glass body having refractive index distribution - Google Patents
Production of quartz base glass body having refractive index distributionInfo
- Publication number
- JPH04254420A JPH04254420A JP1644291A JP1644291A JPH04254420A JP H04254420 A JPH04254420 A JP H04254420A JP 1644291 A JP1644291 A JP 1644291A JP 1644291 A JP1644291 A JP 1644291A JP H04254420 A JPH04254420 A JP H04254420A
- Authority
- JP
- Japan
- Prior art keywords
- alkoxide
- gel
- immersed
- solution
- glass body
- 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
- 238000009826 distribution Methods 0.000 title abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000006121 base glass Substances 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 12
- 239000010453 quartz Substances 0.000 title description 7
- 239000011521 glass Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 29
- 239000010703 silicon Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 22
- -1 silicon alkoxide Chemical class 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011240 wet gel Substances 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 45
- 238000010828 elution Methods 0.000 description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004704 methoxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は屈折率分布を有する石英
系ガラス体の製造方法、特にドープ成分を含むシリコン
アルコキシドから屈折率分布を有する石英系ガラス体を
製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a quartz glass body having a refractive index distribution, and more particularly to a method for manufacturing a quartz glass body having a refractive index distribution from silicon alkoxide containing a dope component.
【０００２】0002
【従来の技術】ドープ成分を含むシリコンアルコキシド
からゾルゲル法により屈折率分布を有する石英系ガラス
体を製造するには、通常、シリコンアルコキシドとシリ
コン以外の金属のアルコキシドとの混合アルコール溶液
に水を添加し、これらの金属アルコキシド（以下、アル
コキシド類と言う）の加水分解と縮合を行わせ、内部に
水とアルコールを含む多孔質ウェットゲルを形成させる
。このウェットゲルを酸の水溶液に浸漬して、シリコン
以外の金属アルコキシドに由来するドープ成分の一部を
ウェットゲルから溶出させ、ウェットゲル内にドープ成
分の濃度分布を形成させる。この後、ゲルを乾燥してド
ライゲルとし、１２００℃以上の高温で焼結する。[Prior Art] In order to produce a quartz-based glass body with a refractive index distribution using a sol-gel method from silicon alkoxide containing a dope component, water is usually added to a mixed alcohol solution of silicon alkoxide and an alkoxide of a metal other than silicon. Then, these metal alkoxides (hereinafter referred to as alkoxides) are hydrolyzed and condensed to form a porous wet gel containing water and alcohol inside. This wet gel is immersed in an aqueous acid solution to elute a portion of the dope component derived from a metal alkoxide other than silicon from the wet gel, thereby forming a concentration distribution of the dope component within the wet gel. Thereafter, the gel is dried to form a dry gel, which is then sintered at a high temperature of 1200° C. or higher.
【０００３】シリコンアルコキシドはガラス体における
石英を生成し、シリコン以外の金属のアルコキシドは屈
折率分布を形成するドープ成分となる。アルコキシド類
の加水分解と縮合の結果生成したウェットゲルを酸の水
溶液に浸漬すると、シリコン以外の金属成分（すなわち
ドープ成分）の一部は、ウェットゲルの表面から溶出し
、表面の濃度低下によりウェットゲル内には拡散に基づ
くドープ成分の濃度分布が生ずる。このドープ成分の濃
度分布に基づき、ガラス体中に屈折率分布が得られる。[0003] Silicon alkoxide forms quartz in the glass body, and alkoxides of metals other than silicon serve as doping components that form a refractive index distribution. When a wet gel produced as a result of hydrolysis and condensation of alkoxides is immersed in an aqueous acid solution, some of the metal components other than silicon (i.e., dope components) are eluted from the surface of the wet gel, and the surface concentration decreases, causing the wet gel to become wet. A concentration distribution of the dope component occurs within the gel based on diffusion. Based on the concentration distribution of this dope component, a refractive index distribution is obtained in the glass body.
【０００４】0004
【発明が解決しようとする課題】しかしながら、上述の
方法により屈折率分布を有する石英系ガラス体を製造す
ると、シリコン以外の金属成分（ドープ成分）を溶出し
た後のゲル体の強度が溶出前と比較して小さくなるため
、その溶出後のゲル体の乾燥工程での割れの発生率が高
くなる。[Problems to be Solved by the Invention] However, when a quartz-based glass body having a refractive index distribution is manufactured by the method described above, the strength of the gel body after elution of metal components other than silicon (dope components) is not as high as before elution. Since it is comparatively smaller, the incidence of cracking during the drying process of the gel body after its elution increases.
【０００５】本発明の目的は、このような事情を考慮し
てなされたもので、割れの発生を抑制することを可能に
した屈折率分布を有する石英系ガラス体の製造方法を提
供することにある。[0005] The object of the present invention has been made in consideration of the above circumstances, and is to provide a method for manufacturing a silica-based glass body having a refractive index distribution that makes it possible to suppress the occurrence of cracks. be.
【０００６】[0006]
【課題を解決するための手段】本発明者は、屈折率分布
を有する石英系ガラス体を製造する知見を基に割れの発
生を抑制するために種々の研究開発を実施した結果、シ
リコン以外の金属の一部を溶出した後のゲル体を、シリ
コンアルコキシドのみの加水分解溶液又はモノアルコキ
シトリアルキルシランの溶液に浸漬させることを見出し
たのである。[Means for Solving the Problems] The present inventor conducted various research and development to suppress the occurrence of cracks based on the knowledge of manufacturing quartz-based glass bodies having a refractive index distribution. It was discovered that the gel body after a portion of the metal has been eluted can be immersed in a hydrolyzed solution of only silicon alkoxide or a solution of monoalkoxytrialkylsilane.
【０００７】すなわち、本発明の製造方法は、シリコン
アルコキシドとシリコン以外の金属のアルコキシドを含
む混合溶液をゲル化させ、得られたゲル体から前記金属
の一部を溶出させ、この溶出後のゲル体からガラス体を
得る製造方法において、前記溶出後のゲル体を、シリコ
ンアルコキシドのみの加水分解溶液又はモノアルコキシ
トリアルキルシランの溶液に浸漬させた後、乾燥、焼結
してガラス体を得るものである。That is, the manufacturing method of the present invention involves gelling a mixed solution containing a silicon alkoxide and an alkoxide of a metal other than silicon, eluting a portion of the metal from the resulting gel body, and dissolving the gel after this elution. A manufacturing method for obtaining a glass body from a body, in which the eluted gel body is immersed in a hydrolyzed solution of only silicon alkoxide or a solution of monoalkoxytrialkylsilane, and then dried and sintered to obtain a glass body. It is.
【０００８】本発明においてシリコンアルコキシドとシ
リコン以外の金属のアルコキシドを含む混合溶液におけ
る、シリコンアルコキシドの種類、シリコンアルコキシ
ド以外の金属アルコキシドの種類、アルコキシド類の混
合アルコール溶液の調製（アルコールの種類、濃度等）
、添加する水の量、添加速度、温度、撹拌等は、公知の
通常の態様に従って決定することができる。In the present invention, in a mixed solution containing silicon alkoxide and an alkoxide of a metal other than silicon, the type of silicon alkoxide, the type of metal alkoxide other than silicon alkoxide, and the preparation of a mixed alcohol solution of alkoxides (type of alcohol, concentration, etc.) )
, the amount of water to be added, the rate of addition, temperature, stirring, etc. can be determined according to known conventional methods.
【０００９】シリコンおよびそれ以外の金属のアルコキ
シドとしては、それらのメトキシド、エトキシド、プロ
ポキシド、ブトキシド等を用いることができる。シリコ
ン以外の金属としては、チタン、ゲルマニウム、ジルコ
ニウム、タンタル等を用いることができる。As the alkoxides of silicon and other metals, their methoxides, ethoxides, propoxides, butoxides, etc. can be used. As metals other than silicon, titanium, germanium, zirconium, tantalum, etc. can be used.
【００１０】その混合溶液をゲル化することにより、不
完全網目構造から成るゲル体が形成され、このゲル体を
酸に浸漬させ、ゲル体からシリコン以外の金属の一部を
溶出させる。By gelling the mixed solution, a gel body having an incomplete network structure is formed, and this gel body is immersed in acid to elute a portion of metals other than silicon from the gel body.
【００１１】ゲル体からのシリコン以外の金属成分（ド
ープ成分）の溶出における、酸としては、塩酸、硫酸、
硝酸、弗酸等を用いることができ、酸の濃度、温度、浸
漬時間等は、通常の態様に従って決定することができる
。[0011] Examples of acids for elution of metal components other than silicon (dope components) from the gel body include hydrochloric acid, sulfuric acid,
Nitric acid, hydrofluoric acid, etc. can be used, and the acid concentration, temperature, immersion time, etc. can be determined according to usual methods.
【００１２】これにより、ゲル体内にドープ成分の濃度
分布が形成される。この溶出後のゲル体をアルコキシド
の加水分解アルコール溶液に浸漬させることで、溶出に
より弱くなったゲル体の網目構造が修復強化されること
になり、乾燥時の割れが抑制される。[0012] As a result, a concentration distribution of the dope component is formed within the gel body. By immersing the gel body after elution in a hydrolyzed alcohol solution of alkoxide, the network structure of the gel body weakened by the elution is repaired and strengthened, and cracking during drying is suppressed.
【００１３】また、溶出後のゲル体をモノアルコキシト
リアルキルシラン溶液に浸漬させることで、ゲル体中の
ＯＨ基がトリアルキルシロキサン基で置換され、水やア
ルコールに対する親和性の減少及び立体障害により乾燥
時の毛細管力と収縮率の低下が生じることになり、乾燥
時の割れが抑制される。Furthermore, by immersing the gel body after elution in a monoalkoxytrialkylsilane solution, the OH groups in the gel body are substituted with trialkylsiloxane groups, resulting in decreased affinity for water and alcohol and steric hindrance. This results in a reduction in capillary force and shrinkage during drying, which suppresses cracking during drying.
【００１４】従って、溶出後のゲル体をシリコンアルコ
キシドのみの加水分解溶液又はモノアルコキシトリアル
キルシランの溶液に浸漬させてから、これを乾燥、焼結
するため、乾燥工程での割れの発生が抑制されるので、
割れのないガラス体を得ることが可能となる。[0014] Therefore, since the eluted gel body is immersed in a hydrolysis solution containing only silicon alkoxide or a solution of monoalkoxytrialkylsilane and then dried and sintered, the occurrence of cracks during the drying process is suppressed. Because it is done,
It becomes possible to obtain a glass body without cracks.
【００１５】尚、本発明の製造方法におけるゲル体の洗
浄、乾燥、焼結等は、通常の態様に従って行うことがで
きる。[0015] In the manufacturing method of the present invention, washing, drying, sintering, etc. of the gel body can be carried out according to conventional methods.
【００１６】[0016]
【実施例】以下、本発明の実施例を説明する。[Examples] Examples of the present invention will be described below.
【００１７】（実施例１）シリコンテトラメトキシド、
チタンテトラ−ｎ−ブトキシド、水及びｎ−プロピルア
ルコールを、モル比で ０．８：０．２ ：４：４にな
るように混合して、シリカゾルを調製し、これを内径１
５ｍｍのガラス管中に密封してゲル化させ、室温に３日
放置した。
尚、ゾルは約１時間でゲル化した。このシリカゾルをゲ
ル化して得たウェットゲルは、シリコンテトラメトキシ
ドとチタンテトラ−ｎ−ブトキシドの部分加水分解と縮
合の結果生じた不完全ガラス網目構造体で、水とｎ−プ
ロピルアルコールを含むものである。(Example 1) Silicon tetramethoxide,
Titanium tetra-n-butoxide, water and n-propyl alcohol were mixed in a molar ratio of 0.8:0.2:4:4 to prepare a silica sol, which was
The mixture was sealed in a 5 mm glass tube, allowed to gel, and left at room temperature for 3 days. Note that the sol gelled in about 1 hour. The wet gel obtained by gelling this silica sol is an incomplete glass network structure formed as a result of partial hydrolysis and condensation of silicon tetramethoxide and titanium tetra-n-butoxide, and contains water and n-propyl alcohol. .
【００１８】そして、ゲル体をガラス管から取り出し、
これを５％塩酸に２０時間浸漬して、ゲル体からチタン
成分を溶出させた。このように、ゲル体を５％塩酸に２
０時間浸漬することにより、不完全網目構造体から成る
ゲルの表面付近のチタン成分が溶出し、ゲル体内部にチ
タン成分の濃度勾配が形成される。[0018] Then, the gel body is taken out from the glass tube,
This was immersed in 5% hydrochloric acid for 20 hours to elute the titanium component from the gel body. In this way, the gel body is diluted with 5% hydrochloric acid.
By immersing for 0 hours, the titanium component near the surface of the gel consisting of an incomplete network structure is eluted, and a concentration gradient of the titanium component is formed inside the gel body.
【００１９】そのチタン成分溶出後のゲル体を水に浸漬
して洗浄し、ゲル体に含まれる塩酸を除去する。洗浄後
、シリコンテトラメトキシド、水及びｎ−プロピルアル
コールをモル比で１：４：４になるように混合して調製
したシリカゾルにゲル体を３０分間浸漬する。浸漬後、
これを乾燥させる。これにより、ウェットゲルに含まれ
る水とｎ−プロピルアルコールとが除去される。After the titanium component has been eluted, the gel body is immersed in water and washed to remove hydrochloric acid contained in the gel body. After washing, the gel body is immersed for 30 minutes in a silica sol prepared by mixing silicon tetramethoxide, water, and n-propyl alcohol in a molar ratio of 1:4:4. After soaking,
Let this dry. As a result, water and n-propyl alcohol contained in the wet gel are removed.
【００２０】この乾燥ゲルを常法により焼結して、直径
５ｍｍ、長さ８０ｍｍのガラス体を得た。このガラス体
は、半径方向に放物線状の屈折率分布を有する透明の石
英系ガラス体であった。This dried gel was sintered by a conventional method to obtain a glass body with a diameter of 5 mm and a length of 80 mm. This glass body was a transparent quartz-based glass body having a parabolic refractive index distribution in the radial direction.
【００２１】このような一連の製造工程により１０本の
ガラス体（直径５ｍｍ、長さ８０ｍｍ）を製作し、これ
らの割れの程度を調べた。その結果、各ガラス体につい
て割れは全く発生しなかった。Ten glass bodies (diameter 5 mm, length 80 mm) were manufactured through this series of manufacturing steps, and the degree of cracking in these bodies was examined. As a result, no cracks occurred in each glass body.
【００２２】（比較例１）実施例１の一連の製造工程の
うち、溶出洗浄後のゲル体をシリコンテトラメトキシド
の加水分解アルコール溶液に浸漬する工程以外はほぼ同
じ製造工程により１０本のガラス体を製作し、これらの
割れの程度を調べた。その結果、１０本のうち６本に割
れが発生した。(Comparative Example 1) Ten pieces of glass were manufactured using almost the same manufacturing process as in Example 1, except for the step of immersing the gel body after elution and cleaning in a hydrolyzed alcohol solution of silicon tetramethoxide. The body was fabricated and the extent of these cracks was investigated. As a result, cracks occurred in 6 out of 10 pieces.
【００２３】（実施例２）シリコンテトラメトキシド、
チタンテトラ−ｎ−ブトキシド、水及びｎ−プロピルア
ルコールを、モル比で ０．８：０．２ ：４：４にな
るように混合して、シリカゾルを調製し、これを内径１
５ｍｍのガラス管中に密封してゲル化させ、室温に３日
放置した。(Example 2) Silicon tetramethoxide,
Titanium tetra-n-butoxide, water and n-propyl alcohol were mixed in a molar ratio of 0.8:0.2:4:4 to prepare a silica sol, which was
The mixture was sealed in a 5 mm glass tube, allowed to gel, and left at room temperature for 3 days.
【００２４】そして、ゲル体をガラス管から取り出し、
これを５％塩酸に２０時間浸漬して、ゲル体からチタン
成分を溶出させた。[0024] Then, the gel body is taken out from the glass tube,
This was immersed in 5% hydrochloric acid for 20 hours to elute the titanium component from the gel body.
【００２５】そのチタン成分溶出後のゲル体を水に浸漬
して洗浄し、ゲル体に含まれる塩酸を除去する。洗浄後
、モノメトキシトリエチルシランのｎ−プロピルアルコ
ールのモル比で１：４の混合液にゲル体を３０分間浸漬
する。浸漬後、これを乾燥させ、この乾燥ゲルを常法に
より焼結して、直径５ｍｍ、長さ８０ｍｍのガラス体を
得た。
このガラス体は、半径方向に放物線状の屈折率分布を有
する透明の石英系ガラス体であった。After the titanium component has been eluted, the gel body is immersed in water and washed to remove hydrochloric acid contained in the gel body. After washing, the gel body is immersed for 30 minutes in a mixture of monomethoxytriethylsilane and n-propyl alcohol in a molar ratio of 1:4. After immersion, this was dried, and the dried gel was sintered by a conventional method to obtain a glass body with a diameter of 5 mm and a length of 80 mm. This glass body was a transparent quartz-based glass body having a parabolic refractive index distribution in the radial direction.
【００２６】このような一連の製造工程により１０本の
ガラス体（直径５ｍｍ、長さ８０ｍｍ）を製作し、これ
らの割れの程度を調べた。その結果、各ガラス体につい
て割れは全く発生しなかった。Ten glass bodies (diameter 5 mm, length 80 mm) were produced through this series of manufacturing steps, and the degree of cracking in these bodies was examined. As a result, no cracks occurred in each glass body.
【００２７】（比較例２）実施例２の一連の製造工程の
うち、溶出洗浄後のゲル体をモノメトキシトリエチルシ
ランのアルコール溶液に浸漬する工程以外はほぼ同じ製
造工程により１０本のガラス体を製作し、これらの割れ
の程度を調べた。その結果、１０本のうち６本に割れが
発生した。(Comparative Example 2) Ten glass bodies were manufactured using almost the same manufacturing process as in Example 2, except for the step of immersing the gel body after elution and cleaning in an alcoholic solution of monomethoxytriethylsilane. The degree of these cracks was investigated. As a result, cracks occurred in 6 out of 10 pieces.
【００２８】したがって、ゲル化した混合溶液からチタ
ン成分を溶出させたゲル体を洗浄後、これを、シリコン
テトラメトキシドの加水分解アルコール溶液又はモノメ
トキシトリエチルシラン溶液に浸漬することにより、乾
燥時の割れを抑制することができ、割れのない光学特性
のよい屈折率分布を有する石英系ガラス体を得ることが
できる。すなわち、溶出洗浄後のゲル体をシリコンテト
ラメトキシドの加水分解アルコール溶液に浸漬すること
により、チタン成分の溶出のため弱くなったゲル体の網
目構造が修復強化されるので、乾燥時の割れが抑制され
ることになる。また、溶出洗浄後のゲル体をモノメトキ
シトリエチルシラン溶液に浸漬させることで、ゲル体中
のＯＨ基がトリアルキルシロキサン基で置換され、水や
アルコールに対する親和性の減少及び立体障害により乾
燥時の毛細管力と収縮率の低下が生じるので、乾燥時の
割れが抑制されることになる。Therefore, after washing the gel body from which the titanium component has been eluted from the gelled mixed solution, it is immersed in a hydrolyzed alcohol solution of silicone tetramethoxide or a monomethoxytriethylsilane solution to improve the drying time. Cracks can be suppressed, and a silica-based glass body without cracks and having good optical properties and a refractive index distribution can be obtained. In other words, by immersing the gel body after elution and cleaning in a hydrolyzed alcohol solution of silicone tetramethoxide, the network structure of the gel body, which has become weak due to the elution of titanium components, is repaired and strengthened, thereby preventing cracks during drying. It will be suppressed. In addition, by immersing the gel body after elution and washing in a monomethoxytriethylsilane solution, the OH groups in the gel body are substituted with trialkylsiloxane groups, which reduces the affinity for water and alcohol and causes steric hindrance during drying. Since the capillary force and shrinkage rate are reduced, cracking during drying is suppressed.
【００２９】[0029]
【発明の効果】以上要するに本発明によれば、シリコン
以外の金属の一部を溶出させたゲル体を、シリコンアル
コキシドのみの加水分解溶液又はモノアルコキシトリア
ルキルシランの溶液に浸漬させた後、これを乾燥、焼結
するので、乾燥時の割れの発生が抑制され、割れのない
屈折率分布を有するガラス体が得られるという優れた効
果を発揮する。[Effects of the Invention] In summary, according to the present invention, a gel body from which a part of metal other than silicon has been eluted is immersed in a hydrolysis solution of only silicon alkoxide or a solution of monoalkoxytrialkylsilane. Since it is dried and sintered, the occurrence of cracks during drying is suppressed and a glass body with a crack-free refractive index distribution can be obtained, which is an excellent effect.
Claims (2)
の金属のアルコキシドを含む混合溶液をゲル化させ、得
られたゲル体から前記金属の一部を溶出させ、この溶出
後のゲル体からガラス体を得る製造方法において、前記
溶出後のゲル体を、シリコンアルコキシドのみの加水分
解溶液に浸漬させた後、乾燥、焼結してガラス体を得る
ことを特徴とする屈折率分布を有する石英系ガラス体の
製造方法。1. A process for producing a glass body by gelling a mixed solution containing a silicon alkoxide and an alkoxide of a metal other than silicon, eluting a portion of the metal from the resulting gel body, and obtaining a glass body from the eluted gel body. In the method, the eluted gel body is immersed in a hydrolysis solution containing only silicon alkoxide, and then dried and sintered to obtain a glass body. Method.
の金属のアルコキシドを含む混合溶液をゲル化させ、得
られたゲル体から前記金属の一部を溶出させ、この溶出
後のゲル体からガラス体を得る製造方法において、前記
溶出後のゲル体を、モノアルコキシトリアルキルシラン
の溶液に浸漬させた後、乾燥、焼結してガラス体を得る
ことを特徴とする屈折率分布を有する石英系ガラス体の
製造方法。2. A process for producing a glass body by gelling a mixed solution containing a silicon alkoxide and an alkoxide of a metal other than silicon, eluting a portion of the metal from the resulting gel body, and obtaining a glass body from the eluted gel body. In the method, the eluted gel body is immersed in a solution of monoalkoxytrialkylsilane, and then dried and sintered to obtain a glass body. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1644291A JPH04254420A (en) | 1991-02-07 | 1991-02-07 | Production of quartz base glass body having refractive index distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1644291A JPH04254420A (en) | 1991-02-07 | 1991-02-07 | Production of quartz base glass body having refractive index distribution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04254420A true JPH04254420A (en) | 1992-09-09 |
Family
ID=11916355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1644291A Pending JPH04254420A (en) | 1991-02-07 | 1991-02-07 | Production of quartz base glass body having refractive index distribution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04254420A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6178780B1 (en) * | 1993-11-12 | 2001-01-30 | Olympus Optical Co., Ltd. | Method of solution doping a sol gel body via immersion |
-
1991
- 1991-02-07 JP JP1644291A patent/JPH04254420A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6178780B1 (en) * | 1993-11-12 | 2001-01-30 | Olympus Optical Co., Ltd. | Method of solution doping a sol gel body via immersion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3040278B2 (en) | Method for producing product made of high silica glass | |
| US4786618A (en) | Sol-gel method for making ultra-low expansion glass | |
| US5068208A (en) | Sol-gel method for making gradient index optical elements | |
| RU2141928C1 (en) | Method of preparing monolithic quartz glass using sol-gel process | |
| US5919280A (en) | Method for fabricating silica glass | |
| US5294573A (en) | Sol-gel process of making gradient-index glass | |
| JPH04254420A (en) | Production of quartz base glass body having refractive index distribution | |
| US5308802A (en) | Sol-gel process of making glass, particulary gradient-index glass | |
| JPH0421526A (en) | Production of quartz-based glass body having refractive index distribution | |
| JP3209534B2 (en) | Method of manufacturing refractive index distribution type optical element | |
| JP3209533B2 (en) | Method of manufacturing refractive index distribution type optical element | |
| JPH059036A (en) | Production of quartz glass having refractive index distribution | |
| JPS6027615A (en) | Production of optical glass | |
| KR100248062B1 (en) | Composition for forming silica glass and the method for preparing silica glass using the same | |
| KR100549422B1 (en) | silica glass composition and manufacturing method of silica glass using the same | |
| JPH06115949A (en) | Production of silica glass form with refractive index distribution | |
| KR100337703B1 (en) | Composition for making silica glass with sol-gel process | |
| JPH0812342A (en) | Production of glass | |
| JPH06321548A (en) | Production of glass | |
| JPH05306126A (en) | Distributed index optical element and its production | |
| JPH05178622A (en) | Production of quartz glass having refractive index distribution | |
| JP3153814B2 (en) | Method of manufacturing refractive index distribution type optical element | |
| JPH0517163A (en) | Production of quartz-based glass body having refractive index distribution | |
| JPH05306125A (en) | Production of glass | |
| KR100243327B1 (en) | Method of preparing silica glass with sol-gel process |