JPS6138137B2 - - Google Patents
Info
- Publication number
- JPS6138137B2 JPS6138137B2 JP14822978A JP14822978A JPS6138137B2 JP S6138137 B2 JPS6138137 B2 JP S6138137B2 JP 14822978 A JP14822978 A JP 14822978A JP 14822978 A JP14822978 A JP 14822978A JP S6138137 B2 JPS6138137 B2 JP S6138137B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- particles
- optical transmission
- sio
- flame
- 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
- 239000011521 glass Substances 0.000 claims description 66
- 239000002245 particle Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 230000005540 biological transmission Effects 0.000 claims description 18
- 230000003287 optical effect Effects 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 12
- 238000005253 cladding Methods 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 8
- 239000005368 silicate glass Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 3
- 238000002074 melt spinning Methods 0.000 claims description 3
- 229910007926 ZrCl Inorganic materials 0.000 claims description 2
- 239000005388 borosilicate glass Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims 2
- 230000008023 solidification Effects 0.000 claims 2
- 238000010828 elution Methods 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 15
- 239000006060 molten glass Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000005373 porous glass Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- -1 FeCl3 Chemical class 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007670 refining Methods 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Description
【発明の詳細な説明】
本発明は光伝送用フアイバーの製造方法に関す
るものであり、溶融紡糸してフアイバーを作る素
材即ちプレフオームの製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a fiber for optical transmission, and more particularly to a method of manufacturing a material, ie, a preform, from which the fiber is made by melt spinning.
光伝送用ガラスフアイバーとしては表面にプラ
イマリー・コートを施して強度を保持した石英系
ガラス及び多成分ガラスからなるフアイバーがあ
るが、いずれも取り扱い易さの点から100〜150μ
ｍφのガラスの太さが採用されている。そのうち
光伝送に利用される光学的活性領域（例えばコア
とクラツド）は目的とする伝送損失、信号歪等か
らの設計によつて異るが、100〜150μｍφのよう
な大きさを必要としない。即ち最外層のある部分
は単に構造支持体としての役割だけを課されてい
る。 Glass fibers for optical transmission include fibers made of quartz-based glass and multi-component glass, which have a primary coat applied to the surface to maintain strength, but both have a diameter of 100 to 150μ for ease of handling.
The thickness of the glass is mφ. The optically active regions (for example, core and cladding) used for optical transmission do not need to be as large as 100 to 150 μmφ, although this varies depending on the design considering the intended transmission loss, signal distortion, etc. That is, certain portions of the outermost layer are solely tasked with the role of structural support.
時には、クラツドから僅か漏れてくるエネルギ
ーを損失させてかつ外部からの光の入り込みを防
ぐ目的でクラツドのガラスの屈折率よりも大きく
かつ光伝送損失の大きなガラスを最外層に意識的
に設けることもある。 Sometimes, a glass with a refractive index higher than that of the glass of the cladding and with a large optical transmission loss is intentionally provided in the outermost layer in order to lose a small amount of energy leaking from the cladding and to prevent light from entering from outside. be.
石英系ガラスフアイバーに於いて従来は前述の
ような目的に対しては、ロツド―イン―チユーブ
方法によつて製造を行つていた。まずロツドとし
ては、外ズケ法或は軸ズケ法により半径方向に所
定の屈折率分布を持つシリカ系ガラス棒を準備す
る（外ズケ法の場合には出発部材をくり抜いたま
まのときにはパイプ状であり、それをコラツプス
して中心孔をなくして充実すればロツドとなる）
多くの場合火炎加水分解によるガラススス照→焼
結による透明ガラス化→ロツド加工という工程で
作つている。プラズマ炎を用いてＮやＦをドープ
する時のみ焼結工程を省くことが出来る。 Conventionally, silica-based glass fibers have been manufactured by a rod-in-tube method for the above-mentioned purposes. First, as a rod, prepare a silica-based glass rod with a predetermined refractive index distribution in the radial direction by the outside-hole method or the shaft-hole method (in the case of the outside-hole method, if the starting member is hollowed out, it will be shaped like a pipe). Yes, if you collapse it and eliminate the central hole, it will become a rod)
In most cases, it is produced through the process of glass soot irradiation by flame hydrolysis, transparent glass formation by sintering, and rod processing. The sintering step can be omitted only when doping with N or F using a plasma flame.
次にパイプとしては、ブラジル産の水晶の細粒
化→ベルヌイ法による石英ガラス・ブロツクの作
製→パイプ加工という工程で作つた石英パイプを
準備する。 Next, a quartz pipe is prepared using the process of refining Brazilian quartz, creating a quartz glass block using the Bernoulli method, and then processing the pipe.
次にロツド―イン―チユーブ方式を第１図にて
説明する。 Next, the rod-in-tube method will be explained with reference to FIG.
前記ロツド１１をそのロツド径に極めて近い内
径をもつ一端を封じた前記パイプ１２の中に挿入
し、その中を減圧しながら高温加熱領域（ヒータ
ー１３は例えば2200℃と極めて高い温度を生ぜせ
しめる）に速度Ｕで送り込み、溶融したガラスは
速度ｖで紡糸してフアイバ１４をプライマリーコ
ートして巻取る。このようにして得られたフアイ
バーのガラスの部分の断面に於ける屈折率分布を
第２図に示す。２１はコア、２２はクラツド、２
３はジヤケツト層である。ここで２３のジヤケツ
ト層が構造支持及び光吸収の役割を果している。 The rod 11 is inserted into the pipe 12, which has an inner diameter very close to the diameter of the rod, and is sealed at one end, and is heated in a high-temperature heating region (the heater 13 generates an extremely high temperature of, for example, 2200° C.) while reducing the pressure inside the pipe 12. The molten glass is fed at a speed U, and the molten glass is spun at a speed v, and a fiber 14 is primary coated and wound. FIG. 2 shows the refractive index distribution in the cross section of the glass portion of the fiber thus obtained. 21 is core, 22 is clad, 2
3 is a jacket layer. Here, 23 jacket layers serve as structural support and light absorption.
しかしながらこのような従来の方法において
は、次のような欠点があつた。 However, such conventional methods have the following drawbacks.
ジヤケツト材質は主に石英ガラスに限られる
ので、クラツドとジヤケツトの屈折率差を制御
しようとするクラツドの屈折率の値は一定に限
られ、屈折率分布の設計上の許容範囲が小さ
い。 Since the jacket material is mainly limited to silica glass, the value of the refractive index of the clad in order to control the difference in refractive index between the clad and the jacket is limited to a constant value, and the tolerance range for the design of the refractive index distribution is small.
ジヤケツト材質は主に石英ガラスに限られる
ので、光伝送損失の値は小さく一定の値にな
る。光伝送損失を一定の大きな値に制御するこ
とは出来ない。 Since the jacket material is mainly limited to quartz glass, the value of optical transmission loss is small and constant. It is not possible to control optical transmission loss to a constant large value.
コアクラツドのガラスがドーパントを多く含
むガラスである場合、このガラスに比してジヤ
ケツト材質の石英ガラスは溶融温度が高く、こ
れをフアイバーに溶融紡糸しようとするとコア
グラツトのガラスは軟かくなりすぎ変形し、か
つ気泡も生じてくる。 When the core glass contains a large amount of dopants, the quartz glass used as the jacket material has a higher melting temperature than this glass, and when attempting to melt-spun it into a fiber, the core glass becomes too soft and deforms. Also, bubbles are generated.
ロツドとジヤケツトの境界には気泡や汚染等
のフアイバーとしたとき散乱の源となる欠陥が
導入される。 At the interface between the rod and the jacket, defects such as air bubbles and contamination are introduced which become a source of scattering when used as a fiber.
高精度のパイプを作る工程ではロスが出てく
る為原料は易いにもかかわらずパイプのコスト
は大きく、従つてフアイバーのコストにも影響
を与える。 The process of making high-precision pipes involves losses, so even though the raw materials are cheap, the cost of the pipes is high, and this also affects the cost of the fibers.
一方石英ガラス棒又は管の作り方は、古い歴史
をもつている。その一例はマンドレル上にブラジ
ル産水晶の細い粒子を酸水素炎等で溶融し吹き付
けてゆく方法である。 On the other hand, the method of making quartz glass rods or tubes has a long history. One example is a method in which fine particles of Brazilian quartz are melted using an oxyhydrogen flame and sprayed onto a mandrel.
もう一例はSiCl4やTiCl4を火炎加水分解して作
つたススをマンドレル上に吹き付けてゆき、同一
工程又は別工程で高温加熱して焼結してゆく方法
である。 Another example is a method in which soot made by flame hydrolysis of SiCl 4 or TiCl 4 is sprayed onto a mandrel and sintered by heating at high temperature in the same or separate process.
このような方法が光フアイバーに適用されてい
る例としてはコア・ガラス上にクラツドガラスを
積層する方法がある。 An example of such a method applied to optical fiber is a method in which a clad glass is laminated on a core glass.
本発明は前述のロツド―イン―チユーブ法の欠
点を改善する為に上述の方法を変形して適用する
ものである。 The present invention applies a modification of the above-mentioned method in order to improve the drawbacks of the above-mentioned rod-in-tube method.
本発明の目的は、クラツドの屈折率に対してそ
れに等しいか又は一定の差だけ高い屈折率を有す
る、光伝送損失を所定の値に制御したジヤケツト
層を設けることである。 An object of the present invention is to provide a jacket layer having a refractive index equal to or higher than the refractive index of the cladding by a certain difference, and with optical transmission loss controlled to a predetermined value.
またジヤケツトガラスを溶融しながら積層する
ことによつてロツド―イン―チユーブよりも経済
的な方法を提供することにある。そして半径方向
に所定の屈折率分布を有するガラス・ロツドの粘
性膨張係数、溶融温度に比較的近いジヤケツトガ
ラスを選び出し、ガラス積層後の冷却による歪割
れを無くし、また紡糸時にロツドの部分から気泡
が出ないような範囲の温度で紡糸出来るようにす
る方法を提供するものである。 Another object is to provide a more economical method than the rod in-tube method by laminating the jacket glass while melting it. Then, we select a jacket glass that has a predetermined refractive index distribution in the radial direction and is relatively close to the melting temperature and viscous expansion coefficient of the glass rod to eliminate strain cracks caused by cooling after glass lamination, and to eliminate air bubbles from the rod portion during spinning. The purpose of the present invention is to provide a method that allows spinning to be performed at a temperature within a range in which no
また積極的にはジヤケツト・ガラスを軟かくし
このジヤケツト・ガラスの外側部分の膨張係数は
小さく内側部分の膨張係数は大きくしてフアイバ
ーにしたとき表面のガラスは平滑にしかつ圧縮歪
が残るようにすることにより高強度のフアイバー
を作る方法にもなる。 In addition, we actively soften the jacket/glass so that the outer part of the jacket/glass has a smaller expansion coefficient and the inner part has a larger coefficient of expansion, so that when it is made into a fiber, the surface of the glass will be smooth and compressive strain will remain. This also provides a way to make high-strength fibers.
このようなことはドーパントを組合せて濃度分
布を変えれば容易に得られる。 This can be easily achieved by changing the concentration distribution by combining dopants.
第３図と第４図で本発明について説明する。第
３図に於いては半径方向に所定の屈折率分布を有
するガラスロツド３２（３１はダミー棒を示す）
を回転させておき、それと相対的に火炎バーナー
或はプラズマ炎トーチ３３を往復移動させる。ま
ずロツド表面を酸水素炎等の火炎或はプラズマ炎
であぶつた後、火炎或はプラズマ炎３４の中に後
述するガラス粒子３５をバーナー或はトーチの中
心孔を通して送り込み溶融したガラス３６をロツ
ド上に積層してゆく。３７は積層してゆくジヤケ
ツト層を表わす。 The present invention will be explained with reference to FIGS. 3 and 4. In Fig. 3, a glass rod 32 (31 indicates a dummy rod) has a predetermined refractive index distribution in the radial direction.
is rotated, and a flame burner or plasma flame torch 33 is reciprocated relative to it. First, the surface of the rod is heated with a flame such as oxyhydrogen flame or plasma flame, and then glass particles 35 (described later) are fed into the flame or plasma flame 34 through the center hole of a burner or torch, and the molten glass 36 is placed on the rod. The layers are stacked on top of each other. 37 represents the jacket layers that are being laminated.
第４図に於いては半径方向に所定の屈折率分布
を有するガラスロツド４２（４１はダミー棒を示
す）を回転させておき、それと相対的に火炎バー
ナー或はプラズマ炎トーチ４３を往復移動させ
る。まずロツド表面を火炎或はプラズマ炎であぶ
つた後火炎或はプラズマ炎４４の中に後述するガ
ラス粒子４６をノズル４５を通じて送り込み、溶
融したガラス４７をロツド上に積層してゆく。４
８は積層されたジヤケツト層を示す。なおここで
バーナーやトーチは１本乃至複数本でも良い。 In FIG. 4, a glass rod 42 (41 indicates a dummy rod) having a predetermined refractive index distribution in the radial direction is rotated, and a flame burner or plasma flame torch 43 is reciprocated relative to it. First, the surface of the rod is bombarded with flame or plasma flame, and then glass particles 46, which will be described later, are fed into the flame or plasma flame 44 through a nozzle 45, and molten glass 47 is laminated on the rod. 4
8 indicates the laminated jacket layers. Note that here, the number of burners and torches may be one or more.
次にこのような方法に於いて適用されるガラス
粒子について説明をする。 Next, the glass particles used in such a method will be explained.
このジヤケツトとして用いられるガラスの性質
に応じてガラスは次の３つに分けられる。 Depending on the properties of the glass used for this jacket, it can be divided into the following three types.
Ａ SiO2ガラス或は高ケイ酸ガラス（Vycor
etc）
Ｂ Ａに対し屈折率を調整し溶融温度を下げる為
にTiO2，Al2O3，ZrO2，B2O3，P2O5等の酸化
物を若干ドープしたシリカ系ガラス
Ｃ Ｂ又はＡのガラスにさらに伝送損失を引き起
す遷移金属の酸化物をドープしたシリカ系ガラ
ス
以下これらの具体的なガラス粒子の製法につい
て説明する。A SiO 2 glass or high silicate glass (Vycor
etc) B Silica-based glass C B slightly doped with oxides such as TiO 2 , Al 2 O 3 , ZrO 2 , B 2 O 3 , P 2 O 5 to adjust the refractive index and lower the melting temperature relative to A. or a silica-based glass doped with a transition metal oxide that further causes transmission loss.Specific methods for producing these glass particles will be described below.
Ａ―１ 従来の石英ガラスの作り方の直接的利用
天然水晶を細く砕き酸乃至アルカリで洗浄して
表面の不純物を除去してガラス粒子とする。A-1 Direct use of conventional methods for making quartz glass Natural quartz is crushed into fine pieces and washed with acid or alkali to remove surface impurities to form glass particles.
Ａ―２ 高ケイ酸ガラスの作り方の利用
分相性アルカリボロシリケートガラスを作
り、それを棒状、管状、板状、適当な形で引上
げ等で成形し、分相熱処理を施し、さらに酸に
て溶出を行い多孔質ガラスとし、粉砕して適当
な大きさの粒にした後洗浄を行う。この後乾燥
し高温にて熱固化させるとガラス粒子となる。
これは３％程度のB2O3を含むSiO2ガラスとな
り、純水石英ガラスよりも低屈折率となる。A-2 Use of method for making high silicate glass Make phase-splitting alkali borosilicate glass, shape it into a rod, tube, plate, or other suitable shape by drawing, perform phase-splitting heat treatment, and elute with acid. The glass is made into porous glass, which is crushed into particles of appropriate size and then washed. After this, it is dried and thermally solidified at a high temperature to become glass particles.
This becomes SiO 2 glass containing approximately 3% B 2 O 3 and has a lower refractive index than pure water silica glass.
Ａ―３ 低純度のSiCl4，SiHCl3，SiH4等を火炎
やプラズマ炎中で反応させ酸化物の微粒子とす
る。これは直接そのままロツド上に積層させ
る。A-3 Low-purity SiCl 4 , SiHCl 3 , SiH 4 , etc. are reacted in a flame or plasma flame to form fine oxide particles. This is directly laminated onto the rod.
Ｂ―１ Ａ―１のガラス粒子にチタニア、アルミ
ナ、ジルコニアの酸化物等の細く砕いて洗浄し
たものを良く混合する。B-1 Finely crushed and washed titania, alumina, zirconia oxides, etc. are mixed well with the glass particles of A-1.
Ｂ―２ Ａ―２の洗浄後の多孔質ガラスを例えば
ZrOCl2・8H2Oの水溶液に浸漬した後溶解度を
下げて細孔内表面にZr化合物を析出させ、しか
る後乾燥加熱してZrO2としてさらに熱固化し
てZrO2をドープした高ケイ酸ガラス粒子を作
る。B-2 For example, the porous glass after cleaning in A-2 is
High silicate glass doped with ZrO 2 by immersing it in an aqueous solution of ZrOCl 2 .8H 2 O, lowering its solubility and depositing Zr compounds on the inner surface of the pores, and then drying and heating to further thermally solidify it as ZrO 2 . create particles.
Ｂ―３ Ａ―３に於いて原料ガス中にTiCl4，
AlCl3，ZrCl4，POCl3，BCl3等原料ガスを混合
させることによつてTiO2―SiO2，Al2O3―
SiO2，ZrO2―SiO2，TiO2―Al2O3―ZrO2―
P2O5―B2O3等のガラス粒子を作る。B-3 In A-3, TiCl 4 ,
By mixing raw material gases such as AlCl 3 , ZrCl 4 , POCl 3 , BCl 3 etc., TiO 2 ―SiO 2 , Al 2 O 3 ―
SiO 2 , ZrO 2 ―SiO 2 , TiO 2 ―Al 2 O 3 ―ZrO 2 ―
Create glass particles such as P 2 O 5 -B 2 O 3 .
Ｃ―１ Ａ―１，Ｂ―１に於いてガラス粒子の中
にFe2O3等の遷移金属の酸化物を少量混ぜて混
合することによつて得るか或はＡ―１，Ｂ―１
の粒子の上に遷移金属の酸化物を薄くコーテイ
ングすることによつて粒子を作る。C-1 It is obtained by mixing a small amount of transition metal oxide such as Fe 2 O 3 into the glass particles in A-1 and B-1, or by mixing A-1 and B-1.
The particles are made by coating a thin layer of transition metal oxide on top of the particles.
Ｃ―２ Ａ―２，Ｂ―２に於いて洗浄後の多孔質
ガラスをFeCl3等の遷移金属の塩の水溶液に浸
漬した後溶解度を下げて細孔内表面にFeCl3等
を析出させしかる後乾燥加熱してFeO3或は
FeO等とし、さらに熱固化して酸化鉄をドープ
した高ケイ酸ガラス粒子を作る。C-2 After washing the porous glass in A-2 and B-2, the porous glass is immersed in an aqueous solution of a salt of a transition metal such as FeCl3 , and then the solubility is lowered to precipitate FeCl3, etc. on the inner surface of the pores. After drying and heating, FeO 3 or
FeO, etc. and further heat solidify to create high silicate glass particles doped with iron oxide.
Ｃ―３ Ａ―３，Ｂ―３に於いてFeCl3等の遷移
金属の化合物を火炎やプラズマ炎の中に送り込
んで酸化物の微粒子の中にこれら遷移金属を飛
び込ませる。勿論高温に加熱すれば蒸気となる
ので原料ガスの中に混ぜて送ることも出来る。C-3 In A-3 and B-3, compounds of transition metals such as FeCl 3 are sent into a flame or plasma flame to cause these transition metals to jump into fine particles of oxide. Of course, if it is heated to a high temperature, it becomes steam, so it can be mixed with the raw material gas and sent.
次にＣ―１，Ｃ―２，Ｃ―３のケースのそれぞ
れについて実施例を説明する。 Next, examples will be described for each of cases C-1, C-2, and C-3.
Ｃ―１のケース
ブラジル産水晶を細く砕き5NHNO3で酸洗いを
行い、同時にアルミナを細く砕き5NHNO3で酸洗
いを行い、95：５の割合に混合を行つた。Case C-1 Brazilian quartz was crushed finely and pickled with 5NHNO3 , and at the same time, alumina was crushed finely and pickled with 5NHNO3 , and mixed at a ratio of 95:5.
この後この混合粒子をFeCl3を溶かした水溶液
３％水溶液の中に入れ、NH4OHを加えてアルカ
リ性としたところFe2O3が混合粒子上に沈澱し
た。 Thereafter, the mixed particles were placed in a 3% aqueous solution containing FeCl 3 and NH 4 OH was added to make it alkaline, and Fe 2 O 3 was precipitated on the mixed particles.
これを乾そうした後プラズマ炎の中に第４図の
方法で送り込み溶融したガラスを直径10mmφのロ
ツド（コアはGeO2―SiO2，グラツドはSiO2）上に
積層して15mmφとした。 After this was dried, it was fed into a plasma flame using the method shown in Figure 4, and the molten glass was layered on a rod (core made of GeO 2 --SiO 2 and glass made of SiO 2 ) with a diameter of 10 mm to obtain a diameter of 15 mm.
このジヤケツトの屈折率はnd＝1.460＞nd＝
1.4585（SiO2）であり青かつ色の色がついてい
た。 The refractive index of this jacket is nd=1.460>nd=
1.4585 (SiO 2 ) and was blue and colored.
これを紡糸して出来たフアイバーは、クロス・
トークに対して強いという性質をもつことが分つ
た。 The fibers made by spinning this are cross-
It turns out that he has a strong personality when it comes to talk.
Ｃ―２のケース
3.6wt％Na2O―4.4wt％K2O―36.0wt％B2O3―
56wt％SiO2のガラスを白金るつぼで溶解し２mm
φ棒に引き上げた。これを550℃×24hr熱処理
し、3NHCl（90℃）で溶出を行い粉砕した後水で
洗浄した。この後５％FeCl3の水溶液の中に浸漬
し真空中に放置し水分を蒸発させ、高温に加熱し
てゆき1000℃まで加熱して細孔をつぶしてガラス
粒子とした。このガラス粒子茶かつ色の色をして
いた。Case C-2 3.6wt%Na 2 O-4.4wt%K 2 O-36.0wt%B 2 O 3 -
Melt 56wt%SiO 2 glass in a platinum crucible to 2mm
I pulled it up to the φ rod. This was heat-treated at 550°C for 24 hours, eluted with 3NHCl (90°C), pulverized, and washed with water. Thereafter, it was immersed in an aqueous solution of 5% FeCl 3 and left in vacuum to evaporate water, and then heated to a high temperature of 1000° C. to collapse the pores and form glass particles. This glass particle was brown and colored in color.
次にこれを第４図に示す酸水素炎の中に送り込
み溶融したガラスを直径100mmφのロツド（コア
はP2O5―B2O3―GiO2―SiO2グラツドはP2O5―
B2O3―SiO2）の上に積層して20mmφとした。 Next, this is sent into the oxyhydrogen flame shown in Figure 4, and the molten glass is made into a rod with a diameter of 100 mm (the core is P 2 O 5 - B 2 O 3 - GiO 2 - SiO 2 , and the glass is P 2 O 5 -
B 2 O 3 --SiO 2 ) to form a 20 mm diameter.
このジヤケツトの屈折率はnd＝1.4580＞nd＝
1.4570（クラツド・ガラス）であり、茶かつ色の
色をしていた。 The refractive index of this jacket is nd=1.4580>nd=
1.4570 (clad glass), and had a brown and colored color.
これを1850℃のヒーター温度で溶融紡糸してフ
アイバーを作ることが出来た。 We were able to make fiber by melt spinning this at a heater temperature of 1850°C.
一方この10mmφのロツドを11mmφ×21mmφの石
英パイプに入れて溶融紡糸したところロツドの内
部より気泡が発生して来て中断せざるを得なかつ
た。この時2000℃以下ではガラスは硬くて紡糸す
ることが出来なかつた。 On the other hand, when this 10 mmφ rod was placed in a quartz pipe of 11 mmφ×21 mmφ and melt-spun was performed, bubbles were generated from inside the rod and the process had to be discontinued. At this time, glass was too hard to spin at temperatures below 2000°C.
Ｃ―３のケース
SiCl4の中にTiCl4，BCl3をモル比で100：10：
５の割合で混合し、この原料ガスを少量の酸素と
ともに第３図に示すプラズマ炎の中に送り込み
TiO2―B2O3―SiO2の溶融ガラスを作り、これを
10mmφのロツド（コアはGeO2―B2O3―SiO2、ク
ラツドはB2O3―SiO2）上に積層して15mmφとし
た。このジヤケツトの屈折率はnd＝1.4595＞nd
＝1.480（クラツド・ガラス）でありTiの為ブル
ー色をしていた。Case C-3 TiCl 4 and BCl 3 in SiCl 4 in a molar ratio of 100:10:
This raw material gas is mixed at a ratio of 5:5 and sent into the plasma flame shown in Figure 3 together with a small amount of oxygen.
Make a molten glass of TiO 2 ―B 2 O 3 ―SiO 2 and
It was laminated on a 10 mmφ rod (core: GeO 2 --B 2 O 3 --SiO 2 , cladding: B 2 O 3 --SiO 2 ) to give a diameter of 15 mm. The refractive index of this jacket is nd=1.4595>nd
= 1.480 (clad glass) and had a blue color due to Ti.
これを溶融紡糸することは容易であつた。 It was easy to melt-spun this.
次に本発明の効果について述べる。 Next, the effects of the present invention will be described.
クラツドのガラスの屈折率に対して一定の屈
折率差を有するジヤケツトガラスを設けること
が出来る。 A jacket glass can be provided that has a constant refractive index difference with respect to the refractive index of the cladding glass.
光伝送損失を一定に調整したジヤケツト・ガ
ラスを設けることが出来る。 A jacket/glass whose optical transmission loss is adjusted to a constant value can be provided.
ロツドのガラスの溶融温度、粘度、膨脹係数
に近いガラスの組成を選ぶことが出来るので、
紡糸時の気泡発生やジヤケツトを付けた後の割
れを無くすることが出来る。 You can choose a glass composition that is close to the melting temperature, viscosity, and expansion coefficient of Rod glass.
It is possible to eliminate air bubbles during spinning and cracks after attaching a jacket.
従来のロツド―イン―チユーブの時の割れの
原因となるクラツドとジヤケツトの境界付整は
無くすることが出来る。 The boundary adjustment between the cladding and the jacket, which causes cracking in conventional rod in-tubes, can be eliminated.
水晶粉末や高ケイ酸ガラス粉末は安価なので
それらを直接ロツド上に付けていけばジヤケツ
ト部の費用は高いものとはならない。 Crystal powder and high silicate glass powder are inexpensive, so if they are applied directly to the rod, the cost of the jacket part will not be high.
SiCl4，TiCl4，AlCl3等も工業用の低品位の
ものは安価であるので、歩留よくこれらを酸化
物ガラスとして直接ロツド上に付けてゆけば、
ジヤケツト部の費用は高いものとはならない。 Industrial low-grade materials such as SiCl 4 , TiCl 4 , and AlCl 3 are inexpensive, so if they can be applied directly to the rod as oxide glass with a high yield,
The cost of the jacket part is not high.
ジヤケツト・ガラスを高温で軟かいものにし
ジヤケツト・ガラス外側部分で膨張係数を少さ
くしかつ内側部分で膨張係数を大きくすると高
強度のフアイバーが得られる。 A high-strength fiber can be obtained by making the jacket/glass soft at high temperatures, decreasing the coefficient of expansion in the outer part of the jacket/glass, and increasing the coefficient of expansion in the inner part.
第１図は従来のジヤケツト層の設け方の一つと
してロツド―イン―チユーブ法を示す。第２図は
このようにして得られるフアイバーの断面を示
す。第３図、第４図は本発明のジヤケツト層の設
け方を示す図である。
第１図中１１はコア／クラツドを有するロツ
ド、１２はジヤケツトの石英パイプ、１３はヒー
ターであり、１４はフアイバーである。第２図中
２１はコア、２２はクラツド、２３はジヤケツト
を示す。第３図中３１は支持棒、３２はロツド、
３３はバーナー或はトーチ、３４は火炎又はプラ
ズマ炎、３５はガラス粒子を送る孔、３６は溶融
されたガラス粒子、３７は積層されたジヤケツ
ト・ガラスを示す。第４図中４１は支持棒、４２
はロツド、４３はバーナー又はトーチ、４４は火
炎又はプラズマ炎、４５はノズル、４６はガラス
粒子送り、４７は溶融されたガラス粒子、４８は
積層されたジヤケツト・ガラスを示す。
FIG. 1 shows a rod-in-tube method as one of the conventional methods for forming a jacket layer. FIG. 2 shows a cross section of the fiber thus obtained. FIGS. 3 and 4 are diagrams showing how the jacket layer of the present invention is provided. In FIG. 1, 11 is a rod having a core/cladding, 12 is a quartz pipe of a jacket, 13 is a heater, and 14 is a fiber. In FIG. 2, 21 indicates a core, 22 a cladding, and 23 a jacket. In Figure 3, 31 is a support rod, 32 is a rod,
33 is a burner or torch, 34 is a flame or plasma flame, 35 is a hole through which glass particles are sent, 36 is a molten glass particle, and 37 is a laminated jacket glass. In Figure 4, 41 is a support rod, 42
43 is a burner or torch, 44 is a flame or plasma flame, 45 is a nozzle, 46 is a glass particle feeder, 47 is a molten glass particle, and 48 is a laminated jacket glass.
Claims (1)
びクラツドからなるガラス棒を回転させ、その外
側にクラツドの屈折率と等しいか又はそれより大
きな屈折率を有するガラスの粒子を溶融して積層
し、溶融紡糸することを特徴とする光伝送用ガラ
スフアイバーの製造方法。 ２ 火炎又はプラズマ炎の中にガラスの粒子を送
り込み、炎の熱でガラスの粒子を溶融することを
特徴とする特許請求の範囲第１項記載の光伝送用
ガラスフアイバーの製造方法。 ３ 前記ガラスの粒子が、石英結晶粒子又はそれ
と他の酸化物の混合粒子であることを特徴とする
特許請求の範囲第１項又は第２項記載の光伝送用
ガラスフアイバーの製造方法。 ４ 前記ガラスの粒子がホウケイ酸系ガラスを分
相熱処理、溶出、粉砕、洗浄、乾燥、熱固化して
作る高ケイ酸ガラスの粒子であることを特徴とす
る特許請求の範囲第１項、第２項記載の光伝送用
ガラスフアイバーの製造方法。 ５ 前記ガラスの粒子がSiCl4、TiCl4、AlCl3、
ZrCl4等を火炎加水分解して出来るSiO2、TiO2―
SiO2、Al2O3―SiO2、ZrO2―SiO2、Al2O3―TiO2
―ZrO2―SiO2のガラス微粒子であることを特徴
とする特許請求の範囲第１項又は第２項記載の光
伝送用ガラスフアイバーの製造方法。 ６ 石英結晶粒子又は混合粒子の精洗した後の表
面に遷移金属の酸化物をコーテイングした石英結
晶粒子であることを特徴とする特許請求の範囲第
１項、第２項又は第３項記載の光伝送用ガラスフ
アイバーの製造方法。 ７ 洗浄後屈折率を上げる元素及び又は遷移金属
の塩を含む水溶液に浸漬し、しかる後乾燥、熱固
化して作る遷移金属の酸化物をドープした高ケイ
酸ガラスの粒子であることを特徴とする特許請求
の範囲、第４項記載の光伝送用ガラスフアイバー
の製造方法。 ８ 火炎加水分解する時の原料の一部に遷移金属
のハロゲン化物を混入させ、遷移金属の酸化物を
ドープした合成ガラス微粒子であることを特徴と
する特許請求の範囲第１項、第２項又は第５項記
載の光伝送用ガラスフアイバーの製造方法。[Claims] 1. A glass rod consisting of a core and a cladding having a predetermined refractive index distribution in the radial direction is rotated, and glass particles having a refractive index equal to or larger than the refractive index of the cladding are placed on the outside of the rod. A method for producing a glass fiber for optical transmission, characterized by melting, laminating, and melt-spinning. 2. A method for manufacturing a glass fiber for optical transmission according to claim 1, characterized in that glass particles are fed into a flame or plasma flame, and the glass particles are melted by the heat of the flame. 3. The method for producing a glass fiber for optical transmission according to claim 1 or 2, wherein the glass particles are quartz crystal particles or mixed particles of quartz crystal particles and other oxides. 4. Claims 1 and 4, characterized in that the glass particles are particles of high silicate glass made by subjecting borosilicate glass to phase separation heat treatment, elution, pulverization, washing, drying, and thermal solidification. 2. A method for producing a glass fiber for optical transmission according to item 2. 5 The glass particles are SiCl 4 , TiCl 4 , AlCl 3 ,
SiO 2 and TiO 2 produced by flame hydrolysis of ZrCl 4 , etc.
SiO 2 , Al 2 O 3 ―SiO 2 , ZrO 2 ―SiO 2 , Al 2 O 3 ―TiO 2
3. The method for manufacturing a glass fiber for optical transmission according to claim 1 or 2, characterized in that the glass fibers are glass particles of -ZrO 2 -SiO 2 . 6. A quartz crystal particle according to claim 1, 2 or 3, which is a quartz crystal particle or a mixed particle whose surface is coated with a transition metal oxide after cleaning. A method of manufacturing glass fiber for optical transmission. 7. Particles of high silicate glass doped with a transition metal oxide produced by immersing in an aqueous solution containing an element that increases the refractive index and/or a salt of a transition metal after cleaning, followed by drying and thermal solidification. A method for manufacturing a glass fiber for optical transmission according to claim 4. 8. Claims 1 and 2, characterized in that they are synthetic glass fine particles doped with a transition metal oxide by mixing a transition metal halide into a part of the raw material for flame hydrolysis. Or the method for producing a glass fiber for optical transmission according to item 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14822978A JPS5575932A (en) | 1978-11-29 | 1978-11-29 | Production of glass fiber for light transmission |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14822978A JPS5575932A (en) | 1978-11-29 | 1978-11-29 | Production of glass fiber for light transmission |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5575932A JPS5575932A (en) | 1980-06-07 |
| JPS6138137B2 true JPS6138137B2 (en) | 1986-08-27 |
Family
ID=15448153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14822978A Granted JPS5575932A (en) | 1978-11-29 | 1978-11-29 | Production of glass fiber for light transmission |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5575932A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106452U (en) * | 1988-01-11 | 1989-07-18 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2521123A1 (en) * | 1982-02-09 | 1983-08-12 | Thomson Csf | PROCESS FOR PRODUCING DOPED SILICA GLASS FOR OPTICAL FIBER PREFORM PREPARATION |
| DE19936478A1 (en) * | 1999-08-03 | 2001-02-15 | Degussa | Sintered materials |
-
1978
- 1978-11-29 JP JP14822978A patent/JPS5575932A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106452U (en) * | 1988-01-11 | 1989-07-18 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5575932A (en) | 1980-06-07 |
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