JPH0551542B2 - - Google Patents
Info
- Publication number
- JPH0551542B2 JPH0551542B2 JP16599384A JP16599384A JPH0551542B2 JP H0551542 B2 JPH0551542 B2 JP H0551542B2 JP 16599384 A JP16599384 A JP 16599384A JP 16599384 A JP16599384 A JP 16599384A JP H0551542 B2 JPH0551542 B2 JP H0551542B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fluorine
- porous glass
- glass layer
- present
- 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
Links
- 239000011521 glass Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000005373 porous glass Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000013307 optical fiber Substances 0.000 description 7
- 238000005253 cladding Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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]
- C03B37/01446—Thermal after-treatment of preforms, e.g. dehydrating, consolidating, sintering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
- C03B2201/14—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron and fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2203/00—Fibre product details, e.g. structure, shape
- C03B2203/10—Internal structure or shape details
- C03B2203/22—Radial profile of refractive index, composition or softening point
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は石英系多孔質ガラス層にフツ素をドー
プするための処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a treatment method for doping a silica-based porous glass layer with fluorine.
（従来技術）
石英系光フアイバにおいて、コア・クラツド相
互の相対的屈折率差を大きくすべく、あるいは光
フアイバの耐放射線性を高めるべく、そのクラツ
ド中にフツ素をドープすることがすでに実施され
ている。(Prior art) Fluorine has already been doped into the cladding of a silica optical fiber in order to increase the relative refractive index difference between the core and the cladding, or to improve the radiation resistance of the optical fiber. ing.
光フアイバ母材の製造に際してフツ素ドープト
石英を合成するとき、１例として火炎加水分解法
における火炎（酸水素炎）中に直接フツ素化合物
を混入し、その合成ガラス中にフツ素をドープす
る方法がとられている。 When synthesizing fluorine-doped quartz in the production of optical fiber base material, for example, a fluorine compound is directly mixed into the flame (oxyhydrogen flame) in the flame hydrolysis method, and fluorine is doped into the synthetic glass. A method is being taken.
この方法の場合、酸水素炎中にフツ素化合物を
混入しているため、きわめて容易に大量のHFガ
スが合成され、しかもそのHFがSiO2などの合成
ガラスを侵食してこれをSiF4などのガスに転換
し、揮散させてしまう。 In this method, since a fluorine compound is mixed into the oxyhydrogen flame, a large amount of HF gas is synthesized very easily, and the HF corrodes the synthetic glass such as SiO 2 and converts it into SiF 4 etc. It converts into gas and evaporates.
それゆえ上記方法の場合、反応収率が低い問題
があり、ガラス中にドープできるフツ素の量にも
限界があつた。 Therefore, in the case of the above method, there is a problem that the reaction yield is low, and there is also a limit to the amount of fluorine that can be doped into the glass.
（発明の目的）
本発明は上記の問題点に鑑み、ガラス揮散を抑
制して石英系ガラス中に必要かつ十分な量のフツ
素をドープすることのできる石英系多孔質ガラス
層の処理方法を提供しようとするものである。(Object of the Invention) In view of the above problems, the present invention provides a method for treating a porous silica glass layer that can suppress glass volatilization and dope a necessary and sufficient amount of fluorine into the silica glass. This is what we are trying to provide.
（発明の構成）
本発明に係る方法は、所定ハロゲン化原料の化
学反応により生成されたガラス微粒子を堆積して
B2O3−SiO2系多孔質ガラス層を形成し、該多孔
質ガラス層フツ素含有雰囲気中にて加熱処理する
ことを特徴としている。(Structure of the Invention) The method according to the present invention deposits glass fine particles produced by a chemical reaction of a predetermined halogenated raw material.
The method is characterized in that a B2O3 - SiO2- based porous glass layer is formed and the porous glass layer is heat-treated in a fluorine-containing atmosphere.
（実施例）
つぎに図面を参照して本発明方法の具体的な実
施例を説明する。(Example) Next, a specific example of the method of the present invention will be described with reference to the drawings.
第１図は、本発明方法の処理対象となる石英系
多孔質ガラス層１が石英系ガラス棒２の外周に堆
積形成された状態を示している。 FIG. 1 shows a state in which a silica-based porous glass layer 1 to be treated in the method of the present invention is deposited on the outer periphery of a quartz-based glass rod 2. As shown in FIG.
上記ガラス棒２は既知のMCVD法とか、VAD
法、OVD法などを介してつくられたものであり、
該棒２は１例として純SiO2からなる。 The above glass rod 2 is made using the known MCVD method or VAD method.
It was created through the law, OVD law, etc.
The rod 2 is made of pure SiO 2 by way of example.
一方、上記ガラス層１はOVD法、VAD法など
を介してガラス棒２の外周に前記のごとく形成さ
れているのであり、これはB2O5−SiO2系からな
る。 On the other hand, the glass layer 1 is formed on the outer periphery of the glass rod 2 by OVD method, VAD method, etc. as described above, and is made of B2O5 - SiO2 system.
多孔質ガラス層１をガラス棒２の外周に堆積形
成するとき、既知の多重管（三重管）構造からな
るバーナが用いられ、該バーナ中心にある第１流
道には原料ガスが、つぎの第２流道には酸素が、
さらに第３流道には水素がそれぞれ供給されると
ともにこれらの火炎加水分解反応により生成され
たガラス微粒子（スート状）がガラス棒２の外周
に堆積され、多孔質ガラス層１となる。 When depositing and forming the porous glass layer 1 on the outer periphery of the glass rod 2, a burner having a known multi-tube (triple tube) structure is used, and a first flow path in the center of the burner carries the raw material gas. Oxygen is in the second flow path,
Further, hydrogen is supplied to each of the third channels, and glass fine particles (soot-like) generated by these flame hydrolysis reactions are deposited on the outer periphery of the glass rod 2, forming the porous glass layer 1.
多孔質ガラス層１を形成する際のより具体的な
例として、四塩化ケイ素250cc／分と、三塩化ホ
ウ素50cc／分と、アルゴン900cc／分とを混合し
た原料ガスが第１流道へ供給され、第２流道、第
３流道にはそれぞれ61／分の水素、41／分の酸素
が供給される。 As a more specific example of forming the porous glass layer 1, a raw material gas containing 250 cc/min of silicon tetrachloride, 50 cc/min of boron trichloride, and 900 cc/min of argon is supplied to the first flow path. The second flow path and the third flow path are supplied with hydrogen at a rate of 61/min and oxygen at a rate of 41/min, respectively.
上記のようにしてガラス棒２の外周に形成され
た多孔質ガラス層１は、三フツ化ホウ素１％・残
部ヘリウムとした混合ガス、しかもその混合ガス
供給量が301／分である1400℃のフツ素含有雰囲
気中にて加熱処理されるのであり、ここで多孔質
ガラス層１にはフツ素がドープされ、同時に該層
１が透明ガラス化される。 The porous glass layer 1 formed on the outer periphery of the glass rod 2 as described above is made of a mixed gas of 1% boron trifluoride and the balance helium at a temperature of 1400°C with a gas supply rate of 301/min. Heat treatment is performed in a fluorine-containing atmosphere, where the porous glass layer 1 is doped with fluorine and at the same time the layer 1 is made into transparent glass.
この際の加熱処理に用いられる装置は、第２図
に例示するごとく下部に給気口３、上部に排気口
４を備なえた石英製炉心管５の外周に電気ヒータ
６が配置されたものであり、該炉心管５内には下
部の給気口３から上記混合ガスが供給されるとと
もにその上部から多孔質ガラス層１付のガラス棒
２が低速で挿入降下され、多孔質ガラス層１が電
気ヒータ６により加熱処理される。 The device used for this heat treatment is one in which an electric heater 6 is arranged around the outer periphery of a quartz furnace tube 5, which is equipped with an air supply port 3 at the bottom and an exhaust port 4 at the top, as shown in FIG. The above-mentioned mixed gas is supplied into the core tube 5 from the air supply port 3 at the lower part, and the glass rod 2 with the porous glass layer 1 is inserted and lowered from the upper part at a low speed, and the porous glass layer 1 is heated by an electric heater 6.
上記処理により得らたガラス棒を光フアイアバ
母材とし、これを紡糸して光フアイバにしたとこ
ろ、その屈折率分布は第３図イのごとく、SiO2
製コア７の屈折率＝1.46におけるクラツド８との
比屈折率差△が1.0％にもなり、クラツド８にフ
ツ素が十分ドープされていることが確認できた。 The glass rod obtained by the above treatment was used as an optical fiber base material, and when this was spun into an optical fiber, the refractive index distribution was as shown in Figure 3 A, SiO 2
The relative refractive index difference Δ with respect to the cladding 8 when the refractive index of the core 7 was 1.46 was as much as 1.0%, and it was confirmed that the cladding 8 was sufficiently doped with fluorine.
比較のため、フツ素化合物を含まない雰囲気中
で加熱処理することにより得られた上記母材を紡
糸し、光フアイバを製造したところ、この比較例
での△は第３図ロのごとく0.25％とかなり小さい
ものになつてしまつた。 For comparison, the above base material obtained by heat treatment in an atmosphere free of fluorine compounds was spun to produce an optical fiber, and the △ in this comparative example was 0.25% as shown in Figure 3 B. It has become quite small.
なお、B2O3−SiO2系でのB2O3の効果として、
B2O3はＦとの反応性が高く、これと容易に反応
してガラス中にＦを取りこむ。 In addition, the effect of B 2 O 3 in the B 2 O 3 −SiO 2 system is as follows:
B 2 O 3 has high reactivity with F and easily reacts with it to incorporate F into the glass.
換言すれば、わずかにＦが存在する処理雰囲気
中でも上記反応が進み、多量のＦをガラス中に取
りこむ。 In other words, the above reaction proceeds even in a processing atmosphere where a small amount of F is present, and a large amount of F is incorporated into the glass.
また、一般に純SiO2製とした多孔質ガラスを
フツ素化合物含有雰囲気中で加熱処理すると、そ
のガラスの大半が揮散してしまうが、本発明のご
とくB2O3を含むSiO2系の場合、上記処理による
ガラス揮散が10％以下であり、フツ素ドープ時の
ガラス歩どまりが高く、かつ、フツ素の反応収率
も高い。 Furthermore, when porous glass made of pure SiO 2 is generally heat treated in an atmosphere containing fluorine compounds, most of the glass evaporates, but in the case of SiO 2 containing B 2 O 3 as in the present invention, The glass volatilization due to the above treatment is 10% or less, the glass yield when doping with fluorine is high, and the reaction yield of fluorine is also high.
（発明の効果）
以上説明した通り、本発明方法によるときは、
B2O3−SiO2系の多孔質ガラスをフツ素含有雰囲
気中にて加熱処理するから、ガラス揮散を抑制し
て石英系ガラス中に必要かつ十分な量のフツ素を
ドープすることができる。(Effect of the invention) As explained above, when using the method of the present invention,
Since B 2 O 3 −SiO 2 -based porous glass is heat-treated in a fluorine-containing atmosphere, it is possible to suppress glass volatilization and dope the necessary and sufficient amount of fluorine into silica glass. .
第１図は本発明方法において処理対象となる多
孔質ガラス層の略示説明図、第２図は本発明方法
に用いる装置の略示説明図、第３図は本発明方法
での処理母材から得られた光フアイバとその比較
例における光フアイバのそれぞれ屈折率分布を示
した説明図である。
１……多孔質ガラス層、５……炉心管、６……
電気ヒータ。
FIG. 1 is a schematic explanatory diagram of a porous glass layer to be treated in the method of the present invention, FIG. 2 is a schematic explanatory diagram of the apparatus used in the method of the present invention, and FIG. 3 is a schematic diagram of the base material to be treated in the method of the present invention. FIG. 2 is an explanatory diagram showing the refractive index distributions of an optical fiber obtained from the above and a comparative example thereof. 1... Porous glass layer, 5... Furnace tube, 6...
electric heater.
Claims (1)
れたガラス微粒子を堆積してB2O3−SiO2系多孔
質ガラス層を形成し、該多孔質ガラスをフツ素含
有雰囲気中にて加熱処理することを特徴とする石
英系多孔質ガラス層の処理方法。1. Depositing glass particles generated by a chemical reaction of a predetermined halogenated raw material to form a B2O3 - SiO2- based porous glass layer, and heat-treating the porous glass in a fluorine-containing atmosphere. A method for processing a silica-based porous glass layer, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16599384A JPS6144725A (en) | 1984-08-08 | 1984-08-08 | Method of treating quartz porous glass layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16599384A JPS6144725A (en) | 1984-08-08 | 1984-08-08 | Method of treating quartz porous glass layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6144725A JPS6144725A (en) | 1986-03-04 |
| JPH0551542B2 true JPH0551542B2 (en) | 1993-08-02 |
Family
ID=15822874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16599384A Granted JPS6144725A (en) | 1984-08-08 | 1984-08-08 | Method of treating quartz porous glass layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6144725A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0776092B2 (en) * | 1985-10-09 | 1995-08-16 | 住友電気工業株式会社 | Glass manufacturing method |
| JP2580542Y2 (en) * | 1991-03-13 | 1998-09-10 | 日本精工株式会社 | Steering column support device |
| US5203898A (en) * | 1991-12-16 | 1993-04-20 | Corning Incorporated | Method of making fluorine/boron doped silica tubes |
| JP3713108B2 (en) * | 1996-08-14 | 2005-11-02 | 富士写真フイルム株式会社 | Pillow type packaging equipment |
-
1984
- 1984-08-08 JP JP16599384A patent/JPS6144725A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6144725A (en) | 1986-03-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |