JPH03112831A - Fluoride optical fiber and its production - Google Patents
Fluoride optical fiber and its productionInfo
- Publication number
- JPH03112831A JPH03112831A JP1246572A JP24657289A JPH03112831A JP H03112831 A JPH03112831 A JP H03112831A JP 1246572 A JP1246572 A JP 1246572A JP 24657289 A JP24657289 A JP 24657289A JP H03112831 A JPH03112831 A JP H03112831A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fluoride
- oxide
- pbo
- optical fiber
- 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.)
- Granted
Links
- 239000013307 optical fiber Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title abstract description 7
- 239000005383 fluoride glass Substances 0.000 claims abstract description 71
- 239000000075 oxide glass Substances 0.000 claims abstract description 56
- 239000011247 coating layer Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims abstract description 4
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract 3
- 150000002367 halogens Chemical class 0.000 claims abstract 3
- 239000011521 glass Substances 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 208000005156 Dehydration Diseases 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 2
- -1 Tl2O Chemical compound 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910003069 TeO2 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 239000003365 glass fiber Substances 0.000 abstract 1
- 239000005304 optical glass Substances 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000004455 differential thermal analysis Methods 0.000 description 7
- 229910007998 ZrF4 Inorganic materials 0.000 description 4
- 229910001632 barium fluoride Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005491 wire drawing Methods 0.000 description 4
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000005387 chalcogenide glass Substances 0.000 description 1
- 150000005313 chalcohalides Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002411 thermogravimetry 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
- C03B37/01205—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments
- C03B37/01225—Means for changing or stabilising the shape, e.g. diameter, of tubes or rods in general, e.g. collapsing
- C03B37/0124—Means for reducing the diameter of rods or tubes by drawing, e.g. for preform draw-down
-
- 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
- C03B37/01205—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments
- C03B37/01211—Manufacture of preforms for drawing fibres or filaments starting from tubes, rods, fibres or filaments by inserting one or more rods or tubes into a tube
-
- 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
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/025—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from reheated softened tubes, rods, fibres or filaments, e.g. drawing fibres from preforms
- C03B37/027—Fibres composed of different sorts of glass, e.g. glass optical fibres
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/041—Non-oxide glass compositions
- C03C13/042—Fluoride glass compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/325—Fluoride glasses
-
- 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
- C03B2201/10—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron
-
- 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
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
-
- 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
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/32—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with aluminium
-
- 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
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
-
- 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
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/50—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with alkali metals
-
- 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
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/54—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with beryllium, magnesium or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/80—Non-oxide glasses or glass-type compositions
- C03B2201/82—Fluoride glasses, e.g. ZBLAN glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐候性に優れたフッ化物ガラス光ファイバお
よびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fluoride glass optical fiber with excellent weather resistance and a method for manufacturing the same.
（従来の技術）
フッ化物ガラス光ファイバは、赤外領域の透過特性に優
れているので、赤外光の伝送媒体、赤外イメージ導波媒
体、高出力赤外レーザのパワー伝送媒体、赤外光を利用
した各種光センシングシステム内の伝送媒体、またはそ
の超低損失性に着目して次世代の光通信伝送路としての
応用が期待されている。(Prior art) Fluoride glass optical fiber has excellent transmission characteristics in the infrared region, so it can be used as an infrared light transmission medium, an infrared image waveguide medium, a power transmission medium for high-output infrared lasers, and an infrared light transmission medium. It is expected to be applied as a transmission medium in various optical sensing systems that utilize light, or as a next-generation optical communication transmission line, focusing on its ultra-low loss property.
しかしながら、フッ化物ガラスを応用するうえで、耐候
性、特に耐水性が、酸化物ガラスより著しく劣ることが
問題となっている。このため、フッ化物ガラス光ファイ
バを空気中に放置するとファイバ表面が空気中の水分に
より加水分解し、伝送媒体の水酸基による吸収損失の増
大や、ファイバの機械的強度の劣化を引き起こすことが
知られている。特にフッ化物ガラス光ファイバを光通信
媒体として利用する場合、その通信媒体としての信頼性
を確保するうえから、耐候性を改善することが不可欠に
なる。However, when applying fluoride glass, there is a problem that its weather resistance, particularly water resistance, is significantly inferior to that of oxide glass. For this reason, it is known that if a fluoride glass optical fiber is left in the air, the fiber surface will be hydrolyzed by moisture in the air, causing an increase in absorption loss due to hydroxyl groups in the transmission medium and a deterioration in the mechanical strength of the fiber. ing. In particular, when fluoride glass optical fiber is used as an optical communication medium, it is essential to improve its weather resistance in order to ensure its reliability as a communication medium.
従来、フッ化物ガラス光ファイバにカルコゲナイドガラ
スを被覆したもの（特願昭５８−２３０５５５）は知ら
れているが、フッ化物と酸化物ガラスとを接触させると
酸化物ガラスが腐食されることから、フッ化物ガラス光
ファイバに酸化物ガラスを被覆することは試みられなか
った。しかし酸化物ガラスは、一般にフン化物ガラスよ
り格段に耐候性に優れているので、酸化物ガラスがフッ
化物ガラス光ファイバに被覆できれば、フッ化物ガラス
光ファイバの欠点は解決され、十分実用に耐えられるこ
とになる。Conventionally, a fluoride glass optical fiber coated with chalcogenide glass (Japanese Patent Application No. 58-230555) has been known, but since the oxide glass is corroded when the fluoride and oxide glass come into contact, No attempt has been made to coat fluoride glass optical fibers with oxide glasses. However, oxide glass generally has much better weather resistance than fluoride glass, so if oxide glass can be coated on fluoride glass optical fiber, the disadvantages of fluoride glass optical fiber will be solved and it will be suitable for practical use. It turns out.
また、酸化物ガラスグランド中でコアガラスを溶融しフ
ァイバ化する方法も知られているが（特願昭５４−１２
６８２１）、第１図に示す熱分析結果でもわかるように
、酸化物ガラスはフッ化物ガラスの融点で反応するので
、特願昭５４−１２６８２１に記載されている手法で、
フッ化物ガラス光ファイバに酸化物ガラスの被覆を施す
ことはできない。Additionally, a method is known in which core glass is melted in an oxide glass gland to form a fiber (Japanese Patent Application No. 54-12
6821), as can be seen from the thermal analysis results shown in Figure 1, oxide glass reacts at the melting point of fluoride glass.
Oxide glass coatings cannot be applied to fluoride glass optical fibers.
（発明が解決しようとする課題）
本発明は、従来、不可能であったフッ化物ガラス光ファ
イバへの酸化物ガラスの被覆を可能とし、耐候性の優れ
たフッ化物ガラス光ファイバを提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a fluoride glass optical fiber with excellent weather resistance by making it possible to coat a fluoride glass optical fiber with oxide glass, which was previously impossible. It is in.
（課題を解決するための手段）
第１図は、ＺｒＦ２− ＢａＦ２− ＬａＦ３− ＹＦ
、−Ａ ｆＦ３− ＬｉＦ系フッ化物ガラスの粉末とＢ
２Ｏ３− ＰｂＯ−Ｂ２Ｏ３ＴｅＯ２− ＺｎＯ系酸化
物ガラスの粉末とを混合し、脱水処理を施したもののＴ
Ｏ（熱重量）曲線■とＤＴＡ （示差熱分析）曲線■お
よび２ｒＦ、−ＢａＦ２ＬａＦ３− ＹＦ３−＾βＦ３
−ｈＦ系フッ化物ガラス単体のＤＴＡ曲線曲線水す図で
ある。(Means for solving the problem) Figure 1 shows ZrF2-BaF2-LaF3-YF
, -A fF3- LiF-based fluoride glass powder and B
2O3- PbO-B2O3TeO2- T
O (thermogravimetric) curve ■ and DTA (differential thermal analysis) curve ■ and 2rF, -BaF2LaF3- YF3-^βF3
- It is a DTA curve curve water diagram of hF type|system|group fluoride glass single substance.
第１図から明らかなように、５００℃のフッ化物ガラス
の融点で資料重量の減少の開始と吸熱反応の開始が観測
され、フッ化物ガラスと酸化物ガラスとが反応し始める
ことがわかる。As is clear from FIG. 1, the beginning of a decrease in the weight of the material and the start of an endothermic reaction were observed at the melting point of the fluoride glass of 500° C., indicating that the fluoride glass and the oxide glass begin to react.
しかし、フッ化物ガラス単体のＤＴＡ曲線曲線前記ＤＴ
Ａ曲線Ｏとを比べると、結晶化温度以下の温度で（線引
きはガラス転移温度と結晶化温度の間で行う＞ＤＴＡ曲
線の変化の差は見られず、フッ化物ガラスと酸化物ガラ
スとの反応は起こっていないことがわかる。一般にフッ
化物と酸化物の反応では、反応系に水分が存在すると両
者の反応は促進されるが、（Ｋ、Ｆｕｊｉｕｒａ、 ｅ
ｔａｌ、 Ｊ、 Ａｍｅ。However, the DTA curve of the fluoride glass alone
Comparing curve A with curve O, there is no difference in change in the DTA curve observed at temperatures below the crystallization temperature (drawing is done between the glass transition temperature and crystallization temperature), indicating that the difference between fluoride glass and oxide glass It can be seen that no reaction occurs.Generally, in the reaction between fluoride and oxide, the presence of water in the reaction system accelerates the reaction between the two.
tal, J., Ame.
Ｃｅｒａ、Ｓｏｃ、Ｖｏｌ、７１．４６０．（１９８８
）） この実験でフッ化物ガラスと酸化物ガラスとの
反応が認められなかったのは、混合粉末体に脱水処理を
施したためである。Cera, Soc, Vol, 71.460. (1988
)) The reason why no reaction between fluoride glass and oxide glass was observed in this experiment was because the mixed powder was subjected to dehydration treatment.
本発明のフッ化物ガラス光ファイバはその耐候性を向上
させるため、クラッド層の外側に酸化物ガラス被覆層を
設け、酸化物ガラス被覆はフッ化物ガラスプリフォーム
を酸化物ガラスチューブに挿入し、一体として線引きす
る。特に線引きする際に、酸化物ガラスチューブ内に脱
水処理を施しフッ化物ガラスと酸化物ガラスとの反応を
抑える。In order to improve the weather resistance of the fluoride glass optical fiber of the present invention, an oxide glass coating layer is provided on the outside of the cladding layer, and the oxide glass coating is made by inserting a fluoride glass preform into an oxide glass tube and integrally Draw a line as Particularly during wire drawing, dehydration treatment is performed inside the oxide glass tube to suppress the reaction between the fluoride glass and the oxide glass.
従来、フッ化物ガラスが酸化物ガラスと反応すると考え
られてきたのは、両者の接触が水分存在下で行われたた
めである。今回、水分を除去した系ではフッ化物ガラス
と酸化物ガラスはフッ化物ガラスの少なくとも線引き温
度（結晶化温度以下）では起こらないことを見出し、線
引きを無水系で行うことにより、フッ化物ガラスと酸化
物ガラスの一体線引きを可能とした。Conventionally, it has been thought that fluoride glass reacts with oxide glass because the two were brought into contact in the presence of moisture. This time, we discovered that fluoride glass and oxide glass do not form in a water-removed system, at least at the drawing temperature (lower than the crystallization temperature) of fluoride glass, and by performing drawing in an anhydrous system, fluoride glass and oxide glass This made it possible to draw lines on glass as one piece.
フッ化物光ファイバの線引き温度は、光フアイバ作製に
用いるフッ化物ガラスの組成により２５０℃から４５０
℃程度まで変化する（例えば１，１．Ｇ。The drawing temperature of fluoride optical fiber varies from 250°C to 450°C depending on the composition of the fluoride glass used to make the optical fiber.
It changes to about ℃ (for example, 1.1.G).
Ｄｒｅｘｈａｇｅ ”Ｔｒｅａｔｉｓｅ ｏｎ Ｍａｔ
ｅｒｉａｌｓ ５ｃｉｅｎｃｅ ａｎｄＴｅｃｈｎｏｌ
ｇｙ” Ｖｏｌ、２６ Ｇｌａｓｓ ＩＶ Ｐ、 １５
１〜Ｐ、２４３）。Drexhage ”Treatise on Mat
erials 5science and Technology
gy” Vol, 26 Glass IV P, 15
1-P, 243).
したがってプリフォームにより、被覆する酸化物ガラス
の軟化温度も変化させる必要がある。上記、線引き温度
をカバーするため、以下の系の酸化物ガラスを被覆材と
した。Therefore, it is necessary to change the softening temperature of the oxide glass to be coated depending on the preform. In order to cover the above-mentioned drawing temperature, the following oxide glass was used as a coating material.
Ｂ２Ｏ３−２：ｎｏ−Ｖ２Ｏ，系、Ｂ２Ｏ３ ＰｂＯ系
、Ｂ２Ｏ３−ＰｂＯ−ＴＮ２Ｏ−Ｖ２Ｏ５系、Ｂ２Ｏ３
ＰｂＯＴ ｊ２２Ｏ−Ａ ｊ！ ２Ｏ３ 系、Ｂ２Ｏ３
−Ｐｂ［１−Ｌｉ２［］系、Ｂ２Ｏ３イ１□［１−Ｃｄ
［ｌ系、Ｂ２Ｏ゜ＴＥ０１−Ｂ２Ｏ３系、Ｂ２Ｏ３−Ｐ
ｂＯ−Ｔ Ｒ２Ｏ系、Ｂ２Ｏ３−ＰｂＯＺｎＯ系、Ｂ２
Ｏ．−ＰｂＯ−Ｃ６０系、Ｂ２Ｏ３−ＰｂＯ−Ｎａ２Ｏ
系、Ｂ２Ｏ３−Ｂｉ、０３−Ｃｄ０系、Ｂ２Ｏ３−ＴＥ
０１−ＺｎＯ系、Ｂ２Ｏ３−ＴＥ０１−Ｌ２Ｏ系、Ｂ２
Ｏ３−ＰｂＯ−に２Ｏ系、ＢＪ３−ＰｂＯＢａＯ系、Ｂ
２Ｏ．−ＰｂＯ−Ｂ２Ｏ．系、Ｂ２Ｏ３ＴＥ０１−Ｂａ
Ｏ系、Ｂ２Ｏ３−Ｔ ４７２Ｏ−ＺｎＯ−３ｉｎ□系、
Ｂ２Ｏ３−ＰｂＯ−ＴｅＯ□−Ｂ２Ｏ３ＺｎＯ系
これら酸化物ガラス製のガラスチューブを作製すること
により、線引き温度が２５０℃〜４５０ ℃にあるフン
化物ガラスプリフォームを一体線引きできた。また、線
引き温度の上記温度域内での任意の変化は、上記酸化物
ガラス系のうち少なくとも二つの系を混合してガラスチ
ューブを作製することにより対応できた。B2O3-2: no-V2O, system, B2O3 PbO system, B2O3-PbO-TN2O-V2O5 system, B2O3
PbOT j22O-A j! 2O3 series, B2O3
-Pb[1-Li2[] system, B2O3i1□[1-Cd
[l series, B2O゜TE01-B2O3 series, B2O3-P
bO-T R2O system, B2O3-PbOZnO system, B2
O. -PbO-C60 system, B2O3-PbO-Na2O
system, B2O3-Bi, 03-Cd0 system, B2O3-TE
01-ZnO system, B2O3-TE01-L2O system, B2
O3-PbO- to 2O system, BJ3-PbOBaO system, B
2O. -PbO-B2O. system, B2O3TE01-Ba
O system, B2O3-T 472O-ZnO-3in□ system,
By producing a glass tube made of these oxide glasses of the B2O3-PbO-TeO□-B2O3ZnO system, it was possible to integrally draw a fluoride glass preform at a drawing temperature of 250°C to 450°C. Furthermore, arbitrary changes in the drawing temperature within the above-mentioned temperature range could be accommodated by mixing at least two of the above-mentioned oxide glass systems to prepare a glass tube.
（実施例）
以下、本発明の実施例を図面を参照して詳細に説明する
が、本発明はもとより実施例により限定されるものでは
ない。(Example) Hereinafter, examples of the present invention will be described in detail with reference to the drawings, but the present invention is not limited to the examples.
実施例１
フッ化物ガラスプリフォームのガラスとして、ＺｒＦ４
− ＢａＦ２− ＹＦ３− Ａ ｎＦ３系ガラスを用い
た。コアガラス組成はＺｒＦ、（４５ｍｏ１％）−Ｂａ
Ｆ２（３８ｍａ１％）ＹＦ３（ｌｌｍｏｌ％）−八ｊ！
Ｐ、（５ｍｏ１％）、タララドガラス組成はＺｒＦａ（
４５ｍｏ１％）−ＢａＦａ（３６ｍｏ１％）−ＹＦ。Example 1 ZrF4 as glass for fluoride glass preform
- BaF2- YF3- AnF3-based glass was used. Core glass composition is ZrF, (45 mo1%)-Ba
F2 (38ma1%) YF3 (llmol%) - 8j!
P, (5 mo1%), Talarado glass composition is ZrFa (
45 mo1%)-BaFa (36 mo1%)-YF.
（ｌｌｍｏｌ％）−Ａｊ！Ｆ３（８ｍｏ１％）である。(llmol%)-Aj! F3 (8mol%).
酸化物ガラスとしてＢ２Ｏ３− ＰｂＯ−ＴｅＯ□−Ｂ
ｉ□０．−２ｎＯ系ガラスまたはＢ２Ｏ３−Ｂｉ２Ｏ，
−ＣｄＯ系ガラスを用いた。B2O3-PbO-TeO□-B as oxide glass
i□0. -2nO glass or B2O3-Bi2O,
-CdO glass was used.
第２図は本発明のフッ化物ガラス光ファイバを製造する
装置の構成を示す概略図であって、■はガス導入管、２
はガス排出管、３は支持管本体、４はコネクタ、５は炉
芯管、６は線引き炉、７は酸化物ガラスチューブ、８は
フッ化物ガラスプリフォーム、９はノズル、１０・・・
はシーリング、１１は酸化物ガラス被覆フッ化物光ファ
イバを示す。FIG. 2 is a schematic diagram showing the configuration of an apparatus for producing a fluoride glass optical fiber of the present invention, in which ■ is a gas introduction tube;
3 is a gas discharge pipe, 3 is a support tube body, 4 is a connector, 5 is a furnace core tube, 6 is a drawing furnace, 7 is an oxide glass tube, 8 is a fluoride glass preform, 9 is a nozzle, 10...
11 indicates a sealing, and 11 indicates an oxide glass coated fluoride optical fiber.
まず酸化物ガラスを９００℃で溶融し、得られたガラス
溶液を予加熱した金属鋳型（図を省略）に流し込み、そ
の直後にその金属鋳型をその中心軸の回りに２Ｏ０Ｏｒ
ｐｍの速度で回転させ、酸化物ガラスチューブを作製し
た。以上の工程は、乾燥Ｎ２ガス雰囲気で行われた。First, oxide glass is melted at 900°C, and the resulting glass solution is poured into a preheated metal mold (not shown).
The tube was rotated at a speed of pm to produce an oxide glass tube. The above steps were performed in a dry N2 gas atmosphere.
次に、Ｚｒ０ＣＩ！ ２の塩酸水溶液でフフ化物ガラス
プリフォームの表面をエツチングした後、第２図に示す
ように酸化物ガラスチューブ７に挿入し、酸化物ガラス
チューブ７を支持管本体３に接続した。ガス導入管１か
ら＾ｒガスで希釈した塩素ガスを導入しつつ、線引き炉
６により、３００℃で３時間酸化物ガラスチューブ内を
脱水処理した。この後、線引き炉を３８０℃に昇温し、
酸化物ガラスチューブ内を除圧に保ちつつ、フッ化物ガ
ラスプリフォームと酸化物ガラスチューブとを一体とし
て線引きした。線引き速度は１０ｍ／分であり、ファイ
バ外径１２５μｍであった。また線引き中、炉芯管５内
はノズル９からＡｒ−４ｉｅガスを導入し、不活性ガス
雰囲気とした。線引き中、フッ化物ガラスプリフォーム
と酸化物ガラスチューブとは反応することなく平滑に接
触し、界面での不整は発生しなかった。Next, Zr0CI! After etching the surface of the fluoride glass preform with an aqueous hydrochloric acid solution in step 2, it was inserted into an oxide glass tube 7 as shown in FIG. 2, and the oxide glass tube 7 was connected to the support tube body 3. While introducing chlorine gas diluted with ^r gas through the gas introduction pipe 1, the inside of the oxide glass tube was subjected to dehydration treatment at 300° C. for 3 hours in the drawing furnace 6. After this, the temperature of the drawing furnace was raised to 380°C,
The fluoride glass preform and the oxide glass tube were drawn as one body while keeping the inside of the oxide glass tube at a reduced pressure. The drawing speed was 10 m/min, and the fiber outer diameter was 125 μm. During wire drawing, Ar-4ie gas was introduced into the furnace core tube 5 through the nozzle 9 to create an inert gas atmosphere. During wire drawing, the fluoride glass preform and the oxide glass tube were in smooth contact without any reaction, and no irregularities occurred at the interface.
得られたいずれのファイバを水の中に長時間放置しても
、叶基による吸収損失の増大、およびファイバ強度の劣
化は認められなかった。Even when any of the obtained fibers was left in water for a long time, no increase in absorption loss due to leaf bases or deterioration of fiber strength was observed.
実施例２
コアガラスとしてＺｒＦ４（４９ｍｏ１％）−ＢａＦ２
（２５ｍｏ１％）−ＬｉＦ３（３，５ｍｏ１％）−ＹＦ
、 （２ｍｏ１％）−１Ｆ。Example 2 ZrF4 (49 mo1%)-BaF2 as core glass
(25mo1%)-LiF3 (3,5mo1%)-YF
, (2mo1%)-1F.
（２，５ｍｏ１％）−ＬｉＦ （１８ｍｏ１％）、タラ
ラドガラスとしてＺｒＦ、（４７，５ｍｏ１％）−Ｂａ
Ｆｚ（２３，５ｍｏ１％） ＬｉＦ３（２，５ｍｏ１％
） ＹＦｚ（２ｍｏ１％）−Ａ １２ Ｆ３ （４，４
ｍｏ１％）−ＮａＦ （２Ｏｍｏ１％）を用いたフッ化
物ガラスプリフォームを８．０．− ＰｂＯ−Ｌｉ２Ｏ
系ガラスまたはＢ２Ｏ３Ｔｌ２Ｏ− Ｂ；２Ｏ３系ガラ
スまたはＢ２Ｏ３− ＰｂＯ系ガラスで作製された酸化
物ガラスチューブに挿入し、２９０℃で線引きしても界
面の不整発生は認められず、耐候性の優れたフッ化物ガ
ラス光ファイバが得られた。(2,5 mo1%)-LiF (18 mo1%), ZrF as Talarado glass, (47,5 mo1%)-Ba
Fz (23,5mo1%) LiF3 (2,5mo1%
) YFz (2mo1%)-A 12 F3 (4,4
Fluoride glass preform using mo1%)-NaF (2Omo1%) was prepared at 8.0%. -PbO-Li2O
Even when inserted into an oxide glass tube made of 2O3 series glass or B2O3Tl2O- B;2O3 series glass or B2O3-PbO series glass and drawn at 290°C, no irregularities were observed at the interface, making it a highly weather resistant fluorocarbon tube. A compound glass optical fiber was obtained.
また、曲げ法により強度を測定したところ、いずれのフ
ァイバもＩ ＧＰａ以上の強度があることが確δ忍でき
た。Furthermore, when the strength was measured by the bending method, it was confirmed that all fibers had a strength of IGPa or higher.
実施例３
塩素ガスの代わりにＨＣＥ、 Ｂｒ２． Ｉ２． ＨＢ
ｒ、旧。Example 3 HCE, Br2. instead of chlorine gas. I2. H.B.
r, old.
ＣＣＲ４，５ＯＣＬ、 Ｆ２． ＨＦ、 ＣＦ４． Ｎ
Ｆ３またはＳＦ６のガスを不活性ガス（例えば后ガス）
で希釈したものをガス導入管１から導入し、脱水処理を
施した後、線引きしても界面の不整発生は見られず、フ
ァイバ化することができた。CCR4,5OCL, F2. HF, CF4. N
Convert F3 or SF6 gas to inert gas (e.g. post gas)
After the diluted material was introduced through the gas introduction pipe 1, dehydrated, and then drawn, no irregularities were observed at the interface, and it was possible to form a fiber.
実施例４
コアガラスとしてＺｒＦ＜（４５ｍｏ１％） ＢａＦ
ｚ（３８ｍｏ１％）−ＹＦ＋（ｌｌｍｏｌ％）−Ａ Ｉ
Ｆ ３ （６ｍｏ１％）、タララドガラスとしてＺｒ
Ｆ４（４７，５ｍｏ１％）−ＢａＦ２（２３，５ｍｏ１
％） ＹＦ３（ｌｌｍｏｌ％Ｅ Ａ Ｉ Ｆ３ （８ｍ
ｏ１％） ＬｉＰ（１０ｍｏ１％）を用いたフッ化物
ガラスプリフォームをＢ２Ｏ．− ＰｂＯ−Ｔ ｆ 、
０− Ａ ｆ ２Ｏ系ガラスまたはＢ２Ｏ３−ＴＥ０１
− ＣｄＯ系ガラスまたはＢ２Ｏ３− ＰｂＯＣｄ０系
ガラスまたはＢ２Ｏ３− ＰｂＯ−ＺｎＯ系ガラスまた
はＢ、０３− ＰｂＯ−Ｂｉ２Ｏ３系ガラスで作製され
た酸化物ガラスチューブに挿入し、３８０℃で線引きし
ても界面の不整発生は認められず、耐候性の優れたフッ
化物ガラス光ファイバが得られた。Example 4 ZrF < (45 mo1%) BaF as core glass
z(38mol%)-YF+(llmol%)-A I
F3 (6mo1%), Zr as Talarado glass
F4 (47,5 mo1%)-BaF2 (23,5 mo1
%) YF3(llmol%E A I F3 (8m
o1%) A fluoride glass preform using LiP (10mo1%) was heated in B2O. - PbO-T f ,
0- A f 2O glass or B2O3-TE01
- Even if it is inserted into an oxide glass tube made of CdO-based glass, B2O3- PbOCd0-based glass, B2O3- PbO-ZnO-based glass, or B,03- PbO-Bi2O3-based glass and drawn at 380°C, there will be no irregularity at the interface. No generation was observed, and a fluoride glass optical fiber with excellent weather resistance was obtained.
また、曲げ法により強度を測定したところ、いずれのフ
ァイバもＩＧＰａ以上の強度があることがＴｉｆｉ認で
きた。Furthermore, when the strength was measured by a bending method, it was confirmed that all fibers had a strength of IGPa or higher.
実施例５
コアガラスとしてＺｒＦ４（４５ｍｏ１％）−ＢａＦ２
（３８ｍｏ１％）−ＹＦｓ（１１ｍＯ１％）−Ａｊ！Ｆ
、（６ｍｏ１％）、タララドガラスとしてＺｒＦ４（４
７，５ｍｏ１％）−ＢａＦ２（２３，５ｍｏ１％）−Ｙ
ｈ （ｌｌｍｏｌ％）−１Ｆ３（８ｍｏ１％） −Ｌｉ
Ｆ（ｌＱｍｏ１％）を用いたフッ化物ガラスプリフォー
ムをＢ２Ｏ３−Ｔ Ｒ２Ｏ−ＺｎＯ系ガラスまたは［１
２Ｏ，−Ｔ ｌ 、０−ＺｎＯ−３ｔ０２系ガラスまた
はＢ２Ｏ３−Ｐ ｂｏ−ＢａＯ系ガラスまたはＢ２Ｏ３
− ＴＥ０１− ＢａＯ系ガラスで作製された酸化物ガ
ラスチューブに挿入し、３８０℃で線引きしても界面の
不整発生は認められず、耐候性の優れたフッ化物ガラス
光ファイバが得られた。Example 5 ZrF4 (45 mo1%)-BaF2 as core glass
(38mo1%)-YFs (11mO1%)-Aj! F
, (6mo1%), ZrF4 (4
7,5 mo1%)-BaF2 (23,5 mo1%)-Y
h (llmol%) -1F3 (8mol%) -Li
A fluoride glass preform using F (lQmo 1%) is converted into B2O3-T R2O-ZnO glass or [1
2O, -T l , 0-ZnO-3t02 glass or B2O3-P bo-BaO glass or B2O3
-TE01- Even when inserted into an oxide glass tube made of BaO-based glass and drawn at 380°C, no irregularities were observed at the interface, and a fluoride glass optical fiber with excellent weather resistance was obtained.
また、曲げ法により強度を測定したところ、いずれのフ
ァイバもＩＧＰａ以上の強度があることが確Ｓ忍できた
。Furthermore, when the strength was measured by a bending method, it was confirmed that all fibers had a strength of IGPa or higher.
以上の実施例ではフッ化物ガラスとしてＺｒＦ４ＢａＦ
２− ＹＦ３−へｌＦ３系、ＺｒＦ４− ＢａＦ２−
ＬａＦｔ−ＹＦ３−Ａ Ｉ！ Ｆ３ＮａＦ系およびＺｒ
Ｆ４ＢａＦ２ＬａＦ、＋ ＹＦ３−ＡｌＦ２− ＬｉＦ
系のものを使用したが、ＺｒＬ−ＢａＦｚＬａＦ、
Ａｌ１Ｆ３− ＮａＦ系、ＨｆＦ４− ＢａＦ２− Ｌ
ａＦ３Ａ ｊ！ Ｆ３系、ＢａＦ、 ＣａＦ、 ＹＦ３
−ＩＦ５系、ＣｄＦ２− ＬｉＰ−ＡＩ！Ｐ３ＰｂＦ２
系、等のガラスを用いたプリフォームを使用しても酸化
物ガラスの熱特性をそれらに合わせることは可能となり
、フッ化物ガラスプリフォームの組成によらず、酸化物
ガラス被覆は実施できた。In the above examples, ZrF4BaF is used as the fluoride glass.
2- YF3- to lF3 system, ZrF4- BaF2-
LaFt-YF3-A I! F3NaF system and Zr
F4BaF2LaF, + YF3-AlF2- LiF
ZrL-BaFzLaF,
Al1F3- NaF system, HfF4- BaF2- L
aF3A j! F3 series, BaF, CaF, YF3
-IF5 series, CdF2- LiP-AI! P3PbF2
It became possible to match the thermal properties of oxide glass to those using preforms using glasses such as fluoride glass, etc., and coating with oxide glass was possible regardless of the composition of the fluoride glass preform.
また本発明は、フッ化物ガラス光ファイバのみに適用可
能だけでなく、塩化物ガラスまたはヨウ化物ガラスまた
はカルコハライドガラス製光ファイバへの適用も可能で
あることを付記する。It should be noted that the present invention is not only applicable to fluoride glass optical fibers, but also to optical fibers made of chloride glass, iodide glass, or chalcohalide glass.
〈発明の効果〉
以上説明したように、本発明によれば、フッ化物ガラス
光ファイバの耐候性を著しく改善できるとともに、機械
的強度の向上も可能であるので、赤外センシングシステ
ムや長距離光通信システムにおいて実用可能なフッ化物
ガラス光ファイバを供給できるという利点がある。<Effects of the Invention> As explained above, according to the present invention, it is possible to significantly improve the weather resistance of fluoride glass optical fibers, as well as improve mechanical strength. An advantage is that it provides a fluoride glass optical fiber that can be used in communication systems.
第１図はフン化物ガラス粉末と酸化物ガラス粉末とを混
合し、脱水処理を施した一例のＴＧ曲線■とＤＴＡ曲線
曲線上びフッ化物ガラス単体のＤＴＡ曲線曲線水す図、
第２図は本発明のフッ化物ガラス光ファイ製造する装置
の構成を示す概略図である。
１・・・ガス導入管 ２・・・ガス排気管３・・
・支持管本体 ４・・・炉芯管５・・・コネクタ
６・・・線引き炉７・・・酸化物ガラスチ
ューブ
８・・・フッ化物ガラスプリフォーム
９・・・ノズル
１０・・・支持管本体３と炉芯管４のシーリング１１・
・・酸化物ガラス被覆フッ化物光ファイババを
特
許
出
願
人
日本電信電話株式会社Figure 1 shows the TG and DTA curves of an example of a mixture of fluoride glass powder and oxide glass powder subjected to dehydration treatment, and the DTA curve of fluoride glass alone. 1 is a schematic diagram showing the configuration of an apparatus for manufacturing a fluoride glass optical fiber according to the present invention. 1...Gas inlet pipe 2...Gas exhaust pipe 3...
- Support tube body 4... Furnace core tube 5... Connector 6... Wire drawing furnace 7... Oxide glass tube 8... Fluoride glass preform 9... Nozzle 10... Support tube Sealing 11 of main body 3 and furnace core tube 4
...Oxide glass coated fluoride optical fiber fiber patent applicant Nippon Telegraph and Telephone Corporation
Claims (6)
からなる被覆層をフッ化物ガラスクラッド層の外側に有
することを特徴とするフッ化物ガラス光ファイバ。1. A fluoride glass optical fiber comprising a coating layer made of oxide glass on the outside of a fluoride glass cladding layer.
、被覆層がＳｉＯ＿２、Ｂ＿２Ｏ＿３、ＰｂＯ、Ｔｌ＿
２ＯＢｉ＿２Ｏ＿３、ＣｄＯ、ＺｎＯ、ＢａＯ、Ｌｉ＿
２Ｏ、Ｎａ＿２Ｏ、Ｋ＿２Ｏ、Ｖ＿２Ｏ＿５、Ａｌ＿２
Ｏ＿３またはＴｅＯ＿２の内の少なくとも一つを含む酸
化物ガラスであることを特徴とするフッ化物ガラス光フ
ァイバ。2. The fluoride glass optical fiber according to claim 1, wherein the coating layer is SiO_2, B_2O_3, PbO, Tl_
2OBi_2O_3, CdO, ZnO, BaO, Li_
2O, Na_2O, K_2O, V_2O_5, Al_2
A fluoride glass optical fiber characterized in that it is an oxide glass containing at least one of O_3 and TeO_2.
、被覆層の酸化物ガラス成分が Ｂ＿２Ｏ＿３−ＺｎＯ−Ｖ＿２Ｏ＿５系ガラスＢ＿２Ｏ
＿３−ＰｂＯ系ガラス Ｂ＿２Ｏ＿３−ＰｂＯ−Ｔｌ＿２Ｏ−Ｖ＿２Ｏ＿５系ガ
ラスＢ＿２Ｏ＿３−ＰｂＯ−Ｔｌ＿２Ｏ−Ａｌ＿２Ｏ＿
３系ガラスＢ＿２Ｏ＿３−ＰｂＯ−Ｌｉ＿２Ｏ系ガラス
Ｂ＿２Ｏ＿３−Ｔｌ＿２Ｏ−ＣｄＯ系ガラスＢ＿２Ｏ＿
３−Ｔｌ＿２Ｏ−Ｂｉ＿２Ｏ＿３系ガラスＢ＿２Ｏ＿３
−ＰｂＯ−Ｔｌ＿２Ｏ系ガラスＢ＿２Ｏ＿３−ＰｂＯ−
ＺｎＯ系ガラス Ｂ＿２Ｏ＿３−ＰｂＯ−ＣｄＯ系ガラス Ｂ＿２Ｏ＿３−ＰｂＯ−Ｎａ＿２Ｏ系ガラスＢ＿２Ｏ＿
３−Ｂｉ＿２Ｏ＿３−ＣｄＯ系ガラスＢ＿２Ｏ＿３−Ｔ
ｌ＿２Ｏ−ＺｎＯ系ガラスＢ＿２Ｏ＿３−Ｔｌ＿２Ｏ−
Ｌｉ＿２Ｏ系ガラスＢ＿２Ｏ＿３−ＰｂＯ−Ｋ＿２Ｏ系
ガラス Ｂ＿２Ｏ＿３−ＰｂＯ−ＢａＯ系ガラス Ｂ＿２Ｏ＿３−ＰｂＯ−Ｂｉ＿２Ｏ＿３系ガラスＢ＿２
Ｏ＿３−Ｔｌ＿２Ｏ−ＢａＯ系ガラスＢ＿２Ｏ＿３−Ｔ
ｌ＿２Ｏ−ＺｎＯ−ＳｉＯ＿２系ガラスＢ＿２Ｏ＿３−
ＰｂＯ−ＴｅＯ＿２−Ｂｉ＿２Ｏ＿３−ＺｎＯ系ガラス
の内の一つの系または少なくとも二つの系を混合させた
ガラス系の成分を有することを特徴とするフッ化物ガラ
ス光ファイバ。3. In the fluoride glass optical fiber according to claim 1, the oxide glass component of the coating layer is B_2O_3-ZnO-V_2O_5-based glass B_2O.
_3-PbO-based glass B_2O_3-PbO-Tl_2O-V_2O_5-based glass B_2O_3-PbO-Tl_2O-Al_2O_
3-based glass B_2O_3-PbO-Li_2O-based glass B_2O_3-Tl_2O-CdO-based glass B_2O_
3-Tl_2O-Bi_2O_3 glass B_2O_3
-PbO-Tl_2O glass B_2O_3-PbO-
ZnO-based glass B_2O_3-PbO-CdO-based glass B_2O_3-PbO-Na_2O-based glass B_2O_
3-Bi_2O_3-CdO glass B_2O_3-T
l_2O-ZnO glass B_2O_3-Tl_2O-
Li_2O-based glass B_2O_3-PbO-K_2O-based glass B_2O_3-PbO-BaO-based glass B_2O_3-PbO-Bi_2O_3-based glass B_2
O_3-Tl_2O-BaO glass B_2O_3-T
l_2O-ZnO-SiO_2-based glass B_2O_3-
A fluoride glass optical fiber characterized by having a glass-based component that is a mixture of one or at least two of PbO-TeO_2-Bi_2O_3-ZnO-based glasses.
化物ガラスチューブに挿入し、一体としてガラス転移温
度と結晶化温度の間の温度で線引きすることを特徴とす
るフッ化物ガラス光ファイバの製造方法。4. 1. A method for producing a fluoride glass optical fiber, which comprises inserting a fluoride glass preform having a waveguide structure into an oxide glass tube, and drawing the whole body at a temperature between a glass transition temperature and a crystallization temperature.
法において、フッ化物ガラスプリフォームを酸化物ガラ
スチューブに挿入した後、酸化物ガラスチューブ内に含
ハロゲンガスを流し込み、フッ化物ガラスプリフォーム
および酸化物ガラスチューブの軟化温度領域よりも低温
でフッ化物ガラスプリフォームおよび酸化物ガラスチュ
ーブを加熱した後、一体として線引きすることを特徴と
するフッ化物ガラス光ファイバの製造方法。5. In the method for manufacturing a fluoride glass optical fiber according to claim 4, after the fluoride glass preform is inserted into the oxide glass tube, a halogen-containing gas is poured into the oxide glass tube, and the fluoride glass preform and the oxide A method for producing a fluoride glass optical fiber, which comprises heating a fluoride glass preform and an oxide glass tube at a temperature lower than the softening temperature range of the glass tube, and then drawing them as one unit.
法において、含ハロゲンガスとしてＣｌ＿２、ＨＣｌ、
Ｂｒ＿２、Ｉ＿２、ＨＢｒ、ＨＩ、Ｆ＿２、ＨＦ、ＣＦ
＿４、ＮＦ＿３、ＳＦ＿６、ＣＣｌ＿４、ＳＯＣｌ＿２
の少なくとも一つを不活性ガスで希釈したものを使用す
ることを特徴とするフッ化物ガラス光ファイバの製造方
法。6. In the method for manufacturing a fluoride glass optical fiber according to claim 5, the halogen-containing gas includes Cl_2, HCl,
Br_2, I_2, HBr, HI, F_2, HF, CF
_4, NF_3, SF_6, CCl_4, SOCl_2
1. A method for producing a fluoride glass optical fiber, comprising using at least one of the above diluted with an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246572A JP2815924B2 (en) | 1989-09-25 | 1989-09-25 | Manufacturing method of fluoride glass optical fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246572A JP2815924B2 (en) | 1989-09-25 | 1989-09-25 | Manufacturing method of fluoride glass optical fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03112831A true JPH03112831A (en) | 1991-05-14 |
| JP2815924B2 JP2815924B2 (en) | 1998-10-27 |
Family
ID=17150412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1246572A Expired - Lifetime JP2815924B2 (en) | 1989-09-25 | 1989-09-25 | Manufacturing method of fluoride glass optical fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2815924B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653575A (en) * | 1992-07-28 | 1994-02-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical amplifier |
| KR101645171B1 (en) * | 2015-04-02 | 2016-08-03 | 주식회사 이우이엔티 | NON-DEGRADABLE HAZARDOUS GAS PURIFICATION SYSTEM GENERATED IN THE SEMICONDUCTOR AND VOCs EMISSION PROCESS |
| KR20190057940A (en) * | 2017-11-21 | 2019-05-29 | (주)옵토네스트 | method of manufacturing glass fiber for optical fiber |
-
1989
- 1989-09-25 JP JP1246572A patent/JP2815924B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653575A (en) * | 1992-07-28 | 1994-02-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical amplifier |
| KR101645171B1 (en) * | 2015-04-02 | 2016-08-03 | 주식회사 이우이엔티 | NON-DEGRADABLE HAZARDOUS GAS PURIFICATION SYSTEM GENERATED IN THE SEMICONDUCTOR AND VOCs EMISSION PROCESS |
| KR20190057940A (en) * | 2017-11-21 | 2019-05-29 | (주)옵토네스트 | method of manufacturing glass fiber for optical fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2815924B2 (en) | 1998-10-27 |
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