JPS62187132A - Production of glass for optical fiber - Google Patents
Production of glass for optical fiberInfo
- Publication number
- JPS62187132A JPS62187132A JP2756886A JP2756886A JPS62187132A JP S62187132 A JPS62187132 A JP S62187132A JP 2756886 A JP2756886 A JP 2756886A JP 2756886 A JP2756886 A JP 2756886A JP S62187132 A JPS62187132 A JP S62187132A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- water
- soln
- ammonia
- alkoxide
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 33
- 239000013307 optical fiber Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 25
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000005187 foaming Methods 0.000 abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000005491 wire drawing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 23
- 208000005156 Dehydration Diseases 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 230000005070 ripening Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 1
- 101100353042 Mycobacterium bovis (strain BCG / Pasteur 1173P2) lnt gene Proteins 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 101150028022 ppm1 gene Proteins 0.000 description 1
- -1 propatool Chemical compound 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/016—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by a liquid phase reaction process, e.g. through a gel phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は光ファイバ用ガラスの製造方法、さらに詳細に
は、アルコキシドを原料とするガラスの製造方法であっ
て、光学的に均一で高純度のガラスを製造することがで
き、しかも線引き時に発泡などの問題の生じることのな
い光ファイバ用ガラスの製造方法に関する。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for producing glass for optical fibers, and more particularly, a method for producing glass using an alkoxide as a raw material. The present invention relates to a method for producing glass for optical fibers, which can produce glass without causing problems such as foaming during drawing.
従来、光ファイバ用ガラスの製造方法としては気相軸付
は法（Ｖａｐｏｒ−Ｐｈａｓｅ Ａｘｉａｌ Ｄｅｐｏ
ｓｉｔｉｏｎ法：ＶＡＤ法）やＭＣＶＤ法（Ｍｏｄｉｆ
ｉｅｄ Ｃｈｅ＋＊１ｃａｌＶａｐｏｒ Ｄｅｐｏｓｉ
ｔｉｏｎ法）等が広く知られている。この方法で得られ
るガラスで特徴的なことは、光ファイバが低損失となる
ために吸収の原因となる不純物（水分や遷移元素）が極
限まで除去されており、しかも光学的にも散乱体がなく
、非常に均一であることである。Conventionally, the method for producing glass for optical fibers has been the Vapor-Phase Axial Depo method.
position method: VAD method) and MCVD method (Modif method)
ied Che+*1cal Vapor Deposit
tion method) etc. are widely known. The characteristic feature of the glass obtained by this method is that impurities that cause absorption (moisture and transition elements) are removed to the utmost to ensure that the optical fiber has low loss, and it is optically free from scatterers. It is very uniform.
近年、アルコキシドを原料として、これをゆっくりと加
水分解させ、１２００〜１４００℃の比較的低温で透明
な石英系ガラスを製造する方法（一般にゾル・ゲル法と
呼ばれる）が提案された。この方法では低温で、ガラス
が合成できるばらかでなく、ＶＡＤ法など気相で合成す
る方法に比較して、より高い収率でガラスを得ることが
できるというメリットがある。In recent years, a method (generally called the sol-gel method) has been proposed in which alkoxides are used as raw materials and are slowly hydrolyzed to produce transparent quartz glass at a relatively low temperature of 1200 to 1400°C. This method has the advantage of not only being able to synthesize glass at low temperatures, but also being able to obtain glass at a higher yield than a gas phase synthesis method such as the VAD method.
ところが、ゾル・ゲル法においては、吸収の原・因とな
る水分を除去するために、塩素県税水剤を導入しながら
ガラス化を行う方法が一般的であるが、この脱水処理を
行いながらガラス化したときには、光ファイバに線引き
する際（温度約２０００℃）発泡し、著しく散乱損失が
増加してしまうことが明らかになった。この発泡現象は
脱水処理時に多量に含有きれた塩素によるものと考えら
れている。このため、脱水処理を行ったのち、光ファイ
バに加工する際の発泡を防ぐ手段として、レル溶液を熟
成させ、得られる多孔質ゲルの比表面積を小さくする方
法が、本発明者等によって提案されている（特願昭６０
−１５５６９７号）。However, in the sol-gel method, in order to remove moisture that is the cause of absorption, vitrification is generally performed while introducing a chlorine prefectural water agent; It has become clear that when vitrified, foaming occurs during drawing into an optical fiber (at a temperature of approximately 2000° C.), resulting in a significant increase in scattering loss. This bubbling phenomenon is thought to be due to the large amount of chlorine contained during the dehydration process. For this reason, the present inventors have proposed a method to reduce the specific surface area of the resulting porous gel by aging the Rel solution as a means to prevent foaming during processing into optical fibers after dehydration. (Special request 1986)
-155697).
第１図にこの製造方法の各工程を模式図で示す。FIG. 1 schematically shows each step of this manufacturing method.
たとえば、Ｓｉ（ＯＣｇｌｌｓ）４をアルコールで希釈
し、低濃度のアンモニアを含む水により加水分解してゾ
ル溶液１を製造する（第■工程）。For example, Si(OCglls) 4 is diluted with alcohol and hydrolyzed with water containing a low concentration of ammonia to produce the sol solution 1 (Step (2)).
次ぎに、このゾル溶液１を外気を遮断して熟成させ（第
■工程）、その後ゲル化させて固体状の多孔質ゲル２を
得る（第■工程）。Next, this sol solution 1 is aged by blocking the outside air (step (2)), and then gelled to obtain a solid porous gel 2 (step (2)).
さらにゲル２をゆっくりと加熱して反応により生じるア
ルコールや余分な水分を揮発させることにより、乾燥ゲ
ル体３を得る（第■工程）。Furthermore, by slowly heating the gel 2 to volatilize the alcohol and excess water produced by the reaction, a dry gel body 3 is obtained (step (2)).
次ぎに、これを１２００〜１４００℃まで徐々に昇温さ
せて、ガラスを得る工程（第■工程）。Next, a step of gradually raising the temperature of this to 1200 to 1400° C. to obtain glass (step (2)).
この際、電気炉７にはガス導入口５、ガス排出口６を設
け、石英るつぼなどの容器８に乾燥ゲル体試料４を入れ
、塩素ガスを導入しなから脱水処理を行うのが一般的で
ある。At this time, the electric furnace 7 is generally provided with a gas inlet 5 and a gas outlet 6, the dried gel sample 4 is placed in a container 8 such as a quartz crucible, and dehydration is performed without introducing chlorine gas. It is.
ところで、前述の第■工程において、ゾル溶液を熟成し
て得られる多孔質ゲルの比表面積を小さくできることは
前述の如くである。この様子を第２図に示す。この図よ
り明らかなように、熟成する時間が増すにつれて比表面
積が小さくなることがわかる。By the way, as described above, in the above-mentioned step (1), the specific surface area of the porous gel obtained by aging the sol solution can be reduced. This situation is shown in FIG. As is clear from this figure, the specific surface area decreases as the aging time increases.
このように、比表面積を小さくすることによって、第一
に主にガラス微粒子の表面に吸着しているＯＨ基（水分
）を、特に脱水処理を行うことなく減少させることがで
きるという利点がある。第３図に多孔質ゲルの比表面積
と脱水処理を行わないで得たガラス中のＯＨ基濃度の関
係を示す、この図より明らかなように多孔質ゲルの比表
面積を小さくすることによってガラス中の水分を現象さ
せることが可能であることが判る。したがって、脱水処
理を行う場合においてもガラス中に含まれる塩素の量を
小さくすることができる。In this way, by reducing the specific surface area, there is an advantage that, first, the OH groups (water) mainly adsorbed on the surface of the glass particles can be reduced without particularly performing a dehydration treatment. Figure 3 shows the relationship between the specific surface area of porous gel and the OH group concentration in glass obtained without dehydration treatment.As is clear from this figure, by reducing the specific surface area of porous gel, It turns out that it is possible to make the moisture of Therefore, even when dehydrating the glass, the amount of chlorine contained in the glass can be reduced.
比表面積を小さくすることによって、第二に多孔質ゲル
体の平均細孔径が大きくなり、より高温まで細孔が閉じ
なくなるために、塩素が説出しやすくなるという利点が
ある。By reducing the specific surface area, the second advantage is that the average pore diameter of the porous gel becomes larger and the pores do not close even at higher temperatures, making it easier for chlorine to be expelled.
このようなゾル溶液の熟成は、比表面積の小さな（粒径
の大きな）乾燥ゲル体を製造できるために、水分除去お
よび塩素除去の見地から非常に有用であり、脱水処理後
のファイバ加工時に発生する発泡を著しく低減すること
が可能になった。Aging of such a sol solution is very useful from the viewpoint of removing water and chlorine because it can produce a dry gel body with a small specific surface area (large particle size), and it is very useful from the standpoint of removing water and chlorine, which occurs during fiber processing after dehydration. It has become possible to significantly reduce foaming.
しかしこの方法で得られる乾燥ゲルの比表面積は通常３
００ ｒｒｆ／ｇ程度であって、いわゆるＶＡＤ法で製
造されたガラス微粒子の１００ ｒｒｒ／ｇに比較して
は大きな値になる。すなわち、上述のような熟成を行う
ゾル・ゲル法において、さらに比表面積の小さなガラス
体を製造できれば、ＶＡＤ法と同様に脱水処理を行って
も線引き時において完全に発泡のないガラスを得ること
が可能になると考えられる。However, the specific surface area of the dry gel obtained by this method is usually 3
00 rrrf/g, which is a large value compared to 100 rrr/g of glass fine particles manufactured by the so-called VAD method. In other words, if it is possible to produce a glass body with a smaller specific surface area in the sol-gel method that performs aging as described above, it is possible to obtain a glass that is completely free of foaming during drawing even if it is dehydrated as in the VAD method. It is thought that it will be possible.
本発明は上述の点に鑑みなされたものであり、充分に脱
水が可能で、しかも線引き時に発泡などの問題を生じる
ことのない、ゾル・ゲル法における光ファイバ用ガラス
の製造方法を提供することを目的とする。The present invention has been made in view of the above points, and an object of the present invention is to provide a method for manufacturing optical fiber glass using the sol-gel method, which allows sufficient dehydration and does not cause problems such as foaming during drawing. With the goal.
したがって、本発明による光ファイバ用ガラスの製造方
法によれば、アンモニアを含むアルコキシド溶液を加水
分解して均一なゾル溶液を作製したのち、前記ゾル溶液
を熟成させ、次いで熟成が終了したゾル溶液に、少なく
とも一回以上、水もしくはアンモニア水溶液を添加して
さらに熟成させ、その後ゲル化、乾燥して多孔質ゲル体
を形成し、この多孔質ゲル体を高温処理して透明ガラス
化することを特徴とするものである。Therefore, according to the method for manufacturing optical fiber glass according to the present invention, after hydrolyzing an ammonia-containing alkoxide solution to prepare a uniform sol solution, the sol solution is aged, and then the aged sol solution is , is characterized by adding water or aqueous ammonia solution at least once and further aging, then gelling and drying to form a porous gel body, and treating this porous gel body at high temperature to make it transparent vitrified. That is.
本発明による光ファイバ用ガラスの製造方法によれば、
比表面積の小さな多孔質ゲル体を製造でき、親水処理を
行いながらガラス化を行った場合においても、ファイバ
加工時に発泡等の問題を生じないガラスを製造できると
いう利点がある。According to the method for manufacturing optical fiber glass according to the present invention,
This method has the advantage that a porous gel body with a small specific surface area can be manufactured, and even when vitrification is performed while performing hydrophilic treatment, glass can be manufactured without problems such as foaming during fiber processing.
本発明による光ファイバ用ガラスの製造方法によれば、
まずアルコキシドを加水分解し、ゾル溶液を生成させる
。According to the method for manufacturing optical fiber glass according to the present invention,
First, the alkoxide is hydrolyzed to generate a sol solution.
このような本発明において用いられるアルコキトは、基
本的に限定されるものではなく、従来この種のガラスを
製造するために用いられるアルコキシドを有効に用いる
ことができる。たとえばＳｉ （ＯＲ） ａ 、＾ｌ
（ＯＲ） ３あるいはＧｅ （ＯＲ） ４ （ただし
Ｒはメチル、エチル、プロピル、ブチルなどのアルキル
基を示す）などの一種以上のアルコキシドに水および必
要ならばメタノール、エタノール、プロパツール、ブタ
ノールなどのアルコール系溶媒の一種以上、さらには酸
あるいは塩基を添加したアルコキシド原料にアンモニア
を添加したものであることができる。The alkoxide used in the present invention is not fundamentally limited, and alkoxides conventionally used for producing this type of glass can be effectively used. For example, Si (OR) a , ^l
(OR) 3 or Ge (OR) 4 (wherein R represents an alkyl group such as methyl, ethyl, propyl, butyl), water and, if necessary, methanol, ethanol, propatool, butanol, etc. Ammonia may be added to an alkoxide raw material to which one or more alcoholic solvents, an acid or a base have been added.
このようなアルコキシドを加水分解し、ゾル溶液を生成
させたのち、このゾル溶液の水（溶媒が添加されている
ときには水と溶媒）を蒸発させてゲル化し、多孔質ゲル
体を形成させるわけであるが、本発明においては、ゾル
溶液をゲル化させるに先立って前記ゾル溶液を熟成させ
る。After hydrolyzing such an alkoxide to generate a sol solution, the water in this sol solution (or water and solvent if a solvent is added) is evaporated to form a gel, forming a porous gel body. However, in the present invention, the sol solution is aged prior to gelling the sol solution.
ｌこのような熟成によって、乾燥ゲルの比表面積′を小
さくする手段としては、ゾル溶液を熟成させる際に添加
する水の量を多くすることが予想されるが、しかし、ア
ルコキシド１モルに対し、水を４モルを超えて添加する
と、ゾル溶液が分離して均一な乾燥ゲル体かえられにく
いことが、本発明者らの検討で明らかになった。したが
って、この第一の熟成工程は、好ましくはアルコキシド
１モルに対し水４モル以下の割合のアルコキシド溶液で
あることが好ましい。One way to reduce the specific surface area of the dried gel through such aging is to increase the amount of water added when aging the sol solution; however, for every mol of alkoxide, Studies by the present inventors have revealed that when more than 4 moles of water is added, the sol solution separates and it is difficult to obtain a uniform dry gel. Therefore, in this first aging step, the alkoxide solution preferably has a ratio of 4 moles or less of water to 1 mole of alkoxide.
また、このようなゾル溶液に含有されるアンモニアは、
好ましくは０．００１〜０．０１ｍｏｌ ／ ｌである
のがよい。アンモニア濃度が０．００１ ｓｏｌ ／
Ｉｔより小さいと、ゲル化時間が長くなりすぎる虞を生
じ、一方０．０１ｍｏｌ ／ ｌを超えると、乾燥およ
び高温処理工程において割れを生じる虞がある。In addition, the ammonia contained in such a sol solution is
Preferably it is 0.001 to 0.01 mol/l. Ammonia concentration is 0.001 sol/
If it is smaller than It, the gelation time may become too long, while if it exceeds 0.01 mol/l, cracks may occur during drying and high temperature treatment steps.
また熟成温度は、好ましくは５０℃以上であるのがよい
。５０℃未満であると熟成時間が掛りすぎる虞があるか
らである。このような熟成は、ゾル溶液の比表面積が一
定になるまで続けられる。この熟成時間は、通常４日以
上である。４日未満であると充分に熟成されない虞があ
るからである。Further, the ripening temperature is preferably 50°C or higher. This is because if the temperature is less than 50°C, there is a risk that the aging time will be too long. Such aging is continued until the specific surface area of the sol solution becomes constant. This aging time is usually 4 days or more. This is because if it is less than 4 days, there is a risk that it will not be matured sufficiently.
このように第一の熟成が終了したのち、本発明にあって
は、さらに水またはアンモニア水溶液を前記ゾル溶液に
添加して熟成する。この熟成工程は、第一熟成工程とほ
ぼ同様の条件で行われる。After the first ripening is completed in this manner, in the present invention, water or ammonia aqueous solution is further added to the sol solution for ripening. This ripening step is performed under substantially the same conditions as the first ripening step.
すなわち、アンモニア水溶液を用いる場合には、アンモ
ニア濃度は好ましく ０．００１〜０．０１ｍｏｌ ／
１であり、熟成温度は５０℃以上であるのがよい。ま
た、熟成時間は４日以上であるのが好ましい。That is, when using an ammonia aqueous solution, the ammonia concentration is preferably 0.001 to 0.01 mol/
1, and the ripening temperature is preferably 50°C or higher. Moreover, it is preferable that the aging time is 4 days or more.
しかしながら、このように添加される水またはアンモニ
ア水溶液の水の量は、好ましくはアルコキシド１モルに
対し５０モル以下と多量の水またはアンモニア水溶液を
添加することができる。添加量が５０モルを超えると、
前述のように分離を生じて均一は乾燥ゲル体が得られに
くいからである。However, the amount of water or ammonia aqueous solution added in this way is preferably 50 mol or less per 1 mol of alkoxide, and a large amount of water or ammonia aqueous solution can be added. If the amount added exceeds 50 moles,
This is because separation occurs as described above and it is difficult to obtain a uniform dry gel body.
第一の熟成を行ったのちには、アルコキシド１モルに対
し４モルを超える水を添加しても、分離は生じないこと
が明らかになうん。このため、多量の水（またはアンモ
ニア水溶液）を添加して、熟成させることによって、充
分に小さな比表面積の乾燥ゲル体が得られるのである。After the first ripening, it is clear that no separation occurs even if more than 4 moles of water are added per mole of alkoxide. Therefore, by adding a large amount of water (or ammonia aqueous solution) and aging it, a dry gel body with a sufficiently small specific surface area can be obtained.
この第二の熟成工程は繰り返すことが可能であることは
言うまでもない。It goes without saying that this second ripening step can be repeated.
このように、ゾル溶液をすくなくとも二度にわたって熟
成することにより、初期の比表面積が小さく、かつ高温
において閉孔する多孔質ゲル体を製造することができ、
したがって高温処理をして透明ガラス化する場合、孔は
ゆっくりと閉孔することになる。このため多孔質ゲル体
に含まれる水ないし脱水剤が良好に除去されるのである
。In this way, by aging the sol solution at least twice, it is possible to produce a porous gel body that has a small initial specific surface area and closes its pores at high temperatures.
Therefore, when high-temperature treatment is performed to make transparent glass, the pores close slowly. For this reason, water or dehydrating agent contained in the porous gel body can be effectively removed.
このような多孔質ゲル体をハロゲン系脱水剤雰囲気中で
高温処理し、透明ガラス化することができる。上述のよ
うに脱水剤を用いなくとも水のある程度の除去は可能で
あるが、さらに良好に脱水するためにはハロゲン系脱水
剤雰囲気において高温処理し、脱水するのがよい。この
ようなハロゲン系脱水剤としては、塩素などのハロゲン
元素・および高温において塩素あるいはフン素などのハ
ロゲン元素を出すハロゲン化合物を有効に用いることが
できる。たとえば、５ＯＣ１２、ＳＰｅ 、ＳｉＦ ４
などの一種以上を有効に用いることができる。Such a porous gel body can be treated at high temperature in an atmosphere of a halogen-based dehydrating agent to be made into transparent glass. As mentioned above, it is possible to remove a certain amount of water without using a dehydrating agent, but in order to achieve even better dehydration, it is preferable to perform high temperature treatment in an atmosphere of a halogen-based dehydrating agent. As such a halogen-based dehydrating agent, halogen elements such as chlorine and halogen compounds that release halogen elements such as chlorine or fluorine at high temperatures can be effectively used. For example, 5OC12, SPe, SiF4
One or more of the following can be effectively used.
実施例Ｉ
Ｓｉ （ＯＣ２Ｈ５） ４をエチルンアルコールで希釈
し、０．００３ ｍｏｌ ／ ｊ！のアンモニアを含む
アンモニア水溶液をアルコキシド１モルに対し４モルの
割合で添加し、混合して均一なゾル溶液を得た。Example I Si (OC2H5) 4 was diluted with ethyl alcohol to give 0.003 mol/j! An ammonia aqueous solution containing ammonia was added at a ratio of 4 mol to 1 mol of alkoxide, and mixed to obtain a uniform sol solution.
この混合溶液を容器に入れ、蓋をしたのち、恒温槽中で
熟成させた。熟成の温度は７０℃であり、熟成時間は２
週間であった。This mixed solution was placed in a container, covered with a lid, and then aged in a constant temperature bath. The temperature of aging is 70℃, and the aging time is 2
It was a week.
熟成が終了し、比表面積が一定に達したゾル溶液に、さ
らにアンモニア水溶液（アンモニア濃度０．００３５ｍ
ｏｌ ／ ｌ ）を添加量を変化サセテ添加シ、７０℃
の温度で３週間恒温槽で熟成を行った。この場合、アル
コキシド１モルに対し、水４モル以上添加してもゾル溶
液の分離は生じなかった。その後、ゾル溶液をゲル化さ
せ、乾燥し、多孔質ゲル体を得た。この多孔質ゲル体を
５００℃で恒温処理した試料の比表面積をＢＥＴ法によ
って測定した。After completion of aging, the sol solution with a constant specific surface area is further added with an ammonia aqueous solution (ammonia concentration 0.0035 m
ol/l) was added at 70°C.
Aging was performed in a constant temperature bath for 3 weeks at a temperature of . In this case, no separation of the sol solution occurred even when 4 moles or more of water was added to 1 mole of alkoxide. Thereafter, the sol solution was gelatinized and dried to obtain a porous gel body. The specific surface area of a sample of this porous gel body subjected to constant temperature treatment at 500° C. was measured by the BET method.
結果を第４図に示す。第４図は添加した全ての水とＳｉ
（ＯＣｔ Ｈｓ ） ４のモル比（）Ｉ ｔ Ｏ／Ｓ
ｉ （ＯＣｇＨｓ）ａ）と多孔質ゲル体に比表面積の関
係を示したグラフである。The results are shown in Figure 4. Figure 4 shows all the added water and Si
(OCt Hs ) Molar ratio of 4 ()I t O/S
It is a graph showing the relationship between i (OCgHs) a) and the specific surface area of a porous gel body.
この図より明らかなように添加する水の量が増加するこ
とによって、比表面積は低下し、Ｓｉ （ＯＣＩＩＨ５
）４１モルに対し、水またはアンモニア水溶液を１６モ
ル加えた場合、比表面積は１４０ ｄｌｇと、ＶＡＤ法
で得られる比表面積に近い値を得た。As is clear from this figure, as the amount of water added increases, the specific surface area decreases and Si (OCIIH5
) When 16 mol of water or ammonia aqueous solution was added to 41 mol of the sample, the specific surface area was 140 dlg, which is close to the specific surface area obtained by the VAD method.
このような方法で製造された多孔質ゲル体に脱水処理を
施し、１３００〜１４００℃でガラスを行うことによっ
て、透明な石英ガラスロッドを得ることができた。A transparent quartz glass rod could be obtained by subjecting the porous gel body produced in this manner to dehydration treatment and glassing at 1300 to 1400°C.
このガラスロッドに気相法で弗素をドープして弗素ドー
プシリカクランドを形成し、プリフォームとした。この
プリフォームを通常の方法でファイバ加工し、シングル
モード光ファイバ（比屈折率差Δｎ ＝０．３６％、長
さ２．３ Ｋｍ＋）を得た。線引き時に発泡は見られな
かった。This glass rod was doped with fluorine by a vapor phase method to form a fluorine-doped silica gland, thereby forming a preform. This preform was processed into a fiber by a conventional method to obtain a single mode optical fiber (relative refractive index difference Δn = 0.36%, length 2.3 Km+). No foaming was observed during drawing.
この光ファイバの損失波長特性を測定したところ、１．
３９μｍに見られるＯＨ吸収ピークから求めた水分顔料
は０．１ ｐｐｍ１以下であった。When the loss wavelength characteristics of this optical fiber were measured, 1.
The water pigment content determined from the OH absorption peak observed at 39 μm was 0.1 ppm1 or less.
このように、熟成工程を少なくとも二度行うことによっ
て、アルコキシドと水の割合を多くすることが可能にな
り、これによって、比表面積の小さい乾燥ゲル体を得る
ことが可能になる。したがって、脱水をほぼ完全に行う
ことが可能になるとともに、線引き時に発泡などの問題
を生じることがなくなることが確認された。By performing the aging step at least twice in this way, it becomes possible to increase the ratio of alkoxide to water, thereby making it possible to obtain a dry gel body with a small specific surface area. Therefore, it has been confirmed that it is possible to perform almost complete dehydration and that problems such as foaming do not occur during wire drawing.
以上説明したように、本発明による光ファイバ用ガラス
の製造方法によれば、アルコキシド溶液を熟成させたの
ち、さらに水またはアンモニア水溶液を添加して、再び
熟成させたのち、ゲル化乾燥することによって比表面積
の小さな（１００ｒｒｒ／ｇ程度）多孔質ゲル体をえる
ことが可能になる。As explained above, according to the method for manufacturing optical fiber glass according to the present invention, after aging the alkoxide solution, water or ammonia aqueous solution is further added, the aqueous ammonia solution is further added, the alkoxide solution is aged again, and then gelation and drying are performed. It becomes possible to obtain a porous gel body with a small specific surface area (about 100 rrr/g).
このため、この多孔質ゲル体を用いることによって脱水
処理を行いながら、ガラス化を行った場合においても、
線引き時に完全に発泡のないファイバをえることができ
るという利点がある。Therefore, even when vitrification is performed while dehydration treatment is performed using this porous gel body,
The advantage is that a fiber completely free of foaming can be obtained during drawing.
歯面の簡単な説明
第１図はゾル・ゲル法によるガラスの製造方法を模式的
に示した説明図、第２図は第一の熟成のみを行って製造
された乾燥ゲル体の比表面積と熟成時間の関係を示す図
、第３図は比表面積と水分顔料との関係を示す図、第４
図は添加した水の量と比表面積の関係を示す図である。Brief explanation of the tooth surface Figure 1 is an explanatory diagram schematically showing the glass manufacturing method by the sol-gel method, and Figure 2 shows the specific surface area and specific surface area of the dry gel body manufactured by performing only the first aging. Figure 3 is a diagram showing the relationship between aging time, Figure 3 is a diagram showing the relationship between specific surface area and water pigment, and Figure 4 is a diagram showing the relationship between specific surface area and water pigment.
The figure shows the relationship between the amount of water added and the specific surface area.
１ ・・・ゾル溶液、２ ・・・ゲル、３ ・・・乾燥
ゲル体、４ ・・・試料、５ ・・・ガス導入口、６・
・・ガス排出口、７ ・・・電気炉、８ ・・・容器、
９ ・・・ガラス試料。1... Sol solution, 2... Gel, 3... Dry gel body, 4... Sample, 5... Gas inlet, 6...
・・Gas exhaust port, 7 ・・Electric furnace, 8 ・・Container,
9...Glass sample.
出願人代理人 雨 宮 正 事 業２図 ち威晴間 第１ ＩＩＩ Ｍ 図 ルApplicant's representative: Tadashi Ame Miya Figure 2 Chii Haruma 1st III M figure le
Claims (1)
て均一なゾル溶液を作製したのち、前記ゾル溶液を熟成
させ、次いで熟成が終了したゾル溶液に、少なくとも一
回以上、水もしくはアンモニア水溶液を添加してさらに
熟成させ、その後ゲル化、乾燥して多孔質ゲル体を形成
し、この多孔質ゲル体を高温処理して透明ガラス化する
ことを特徴とする光ファイバ用ガラスの製造方法。(1) After hydrolyzing an ammonia-containing alkoxide solution to prepare a uniform sol solution, the sol solution is aged, and then water or ammonia aqueous solution is added at least once to the aged sol solution. 1. A method for producing glass for optical fibers, which comprises further aging, gelling and drying to form a porous gel body, and subjecting the porous gel body to high temperature treatment to turn it into transparent glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2756886A JPS62187132A (en) | 1986-02-10 | 1986-02-10 | Production of glass for optical fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2756886A JPS62187132A (en) | 1986-02-10 | 1986-02-10 | Production of glass for optical fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62187132A true JPS62187132A (en) | 1987-08-15 |
Family
ID=12224622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2756886A Pending JPS62187132A (en) | 1986-02-10 | 1986-02-10 | Production of glass for optical fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62187132A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939451A (en) * | 2021-03-25 | 2021-06-11 | 泰安顺茂新材料技术有限公司 | Glass fiber drawing machine capable of reducing moisture of yarn cluster and using method thereof |
-
1986
- 1986-02-10 JP JP2756886A patent/JPS62187132A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939451A (en) * | 2021-03-25 | 2021-06-11 | 泰安顺茂新材料技术有限公司 | Glass fiber drawing machine capable of reducing moisture of yarn cluster and using method thereof |
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