JPH0648325B2 - Optical fiber and manufacturing method thereof - Google Patents
Optical fiber and manufacturing method thereofInfo
- Publication number
- JPH0648325B2 JPH0648325B2 JP63176941A JP17694188A JPH0648325B2 JP H0648325 B2 JPH0648325 B2 JP H0648325B2 JP 63176941 A JP63176941 A JP 63176941A JP 17694188 A JP17694188 A JP 17694188A JP H0648325 B2 JPH0648325 B2 JP H0648325B2
- Authority
- JP
- Japan
- Prior art keywords
- optical fiber
- fiber
- carbon
- glass
- containing hydrogen
- 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
- 239000013307 optical fiber Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003365 glass fiber Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- 238000002294 plasma sputter deposition Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 34
- 239000000835 fiber Substances 0.000 description 26
- 239000011521 glass Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 238000005253 cladding Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007069 methylation reaction Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- -1 Predieu and XGGlavas Proteins 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 230000011987 methylation Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 101150056682 Smo gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は高強度にして、長期的に強度低下の少ない光フ
アイバ及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to an optical fiber which has a high strength and exhibits little strength reduction over a long period of time, and a method for producing the same.
［従来の技術］ 石英系光フアイバでは引張り応力を付加した状態で放置
しておくと、長時間後に破断するという欠点（疲労と呼
ばれる）がある。[Prior Art] A silica-based optical fiber has a drawback (called fatigue) that it breaks after a long time if left in a state where tensile stress is applied.
この疲労を防ぐ第１の方法として、石英ガラスより熱膨
張係数が小さく、薄いガラス層を最外層として形成し、
伝送特性を劣化させることなく、光フアイバ表面に熱膨
張係数の差より生じる圧縮応力を働かせ、強度の向上と
疲労の抑制を図ろうとする光フアイバ構造が従来より提
案されている。As a first method for preventing this fatigue, a thin glass layer having a smaller coefficient of thermal expansion than quartz glass and being formed as an outermost layer,
Conventionally, an optical fiber structure has been proposed in which a compressive stress caused by a difference in thermal expansion coefficient is exerted on the surface of the optical fiber without deteriorating the transmission characteristics, thereby improving strength and suppressing fatigue.
第５図は従来の表面圧縮層を形成した光フアイバの一例
の断面図であり、51はSiO2−GeO2ガラス・コア、52は石
英ガラス・クラツド、53はSiO2−TiO2ガラスからなる最
外層である。FIG. 5 is a cross-sectional view of an example of a conventional optical fiber having a surface compression layer, where 51 is a SiO 2 —GeO 2 glass core, 52 is a quartz glass cladding, and 53 is a SiO 2 —TiO 2 glass. It is the outermost layer.
また、上記第１の方法の改良法としてクラツド層の最外
層をボロンを含有した石英ガラスとし、その外周にSiO2
−TiO2ガラス層を設けた例も提案されている［エス．エ
ム．オウ等、S.M.Oh,Predieu and X.G.Glavas,Opt.Let
t.7(1982)p.241]。Further, as an improved method of the above first method, the outermost layer of the cladding layer is made of quartz glass containing boron, and SiO 2 is formed on the outer periphery thereof.
An example in which a -TiO 2 glass layer is provided has also been proposed [S. M. Oh et al., SMOh, Predieu and XGGlavas, Opt.Let
t. 7 (1982) p. 241].
石英系光フアイバの疲労を防ぐ第２の方法は、光フアイ
バガラスの表面エネルギーを常に大きい状態に保つこと
で傷の成長を防ぐ方法であって、具体的には、例えば第
６図に示すようにドープトシリカからなるコア61とシリ
カからなるクラツド62を有するフアイバ60の外周に、水
分の透過しにくいグラフアイト膜63をＣＶＤ法により被
覆し、光フアイバの表面への水分の吸着を防ぐものであ
り、この例では外層としてシリコン層64及び熱可塑性樹
脂層65が設けられている。（米国特許第４，１８３，６
２１号明細書）。The second method for preventing the fatigue of the silica-based optical fiber is a method for preventing the growth of scratches by keeping the surface energy of the optical fiber glass large at all times. Specifically, for example, as shown in FIG. In the outer periphery of the fiber 60 having a core 61 made of doped silica and a cladding 62 made of silica, a graphite film 63 which is hard to transmit water is coated by a CVD method to prevent adsorption of water to the surface of the optical fiber. In this example, a silicon layer 64 and a thermoplastic resin layer 65 are provided as outer layers. (U.S. Pat. No. 4,183,6
21).
［発明が解決しようとする課題］ 石英系光フアイバの疲労を防ぐ上記第１の方法による、
第５図のフアイバではTiO2はSiO2より蒸気圧が高く、光
フアイバの紡糸時にSiO2−TiO2からなる最外層からTiO2
が蒸発するために、目的とする表面の圧縮応力がさほど
大きくならないという問題がある。前記のエス・エム・
オウ等の報告においては、第５図の光フアイバでは、強
度は約０．３GPa増加したにすぎず、疲労も僅かしか抑
制されないことが報告されている。[Problems to be Solved by the Invention] According to the first method for preventing the fatigue of the silica-based optical fiber,
The 5 TiO 2 in the fiber of figure higher vapor pressure than SiO 2, TiO 2 from the outermost layer consisting of SiO 2 -TiO 2 during spinning of the optical fiber
However, there is a problem in that the compressive stress on the target surface does not become so large due to the evaporation of the. The above-mentioned S.M.
In the report of Oh et al., It is reported that the optical fiber shown in FIG. 5 only increased the strength by about 0.3 GPa and the fatigue was suppressed only slightly.
該報告では、前記したようにこのクラツド層の最外層を
石英ガラスより熱膨張係数の大きなボロンを含有した石
英ガラスとし、その外側にSiO2−TiO2ガラス層を設けた
例が示されているが、このものもその効果は十分に大き
なものではない。In this report, as described above, an example is shown in which the outermost layer of the cladding layer is made of silica glass containing boron having a larger thermal expansion coefficient than silica glass, and an SiO 2 —TiO 2 glass layer is provided on the outside thereof. However, the effect of this one is not great enough.
またガラスの最高強度は破壊じん性値と密接な関係があ
るが、SiO2−TiO2ガスス層の破壊じん性値は石英ガラス
より低いため、第１の方法による第５図の光フアイバの
最高強度は原理的に向上しないという欠点がある。Although the maximum strength of glass is closely related to the fracture toughness value, the fracture toughness value of the SiO 2 -TiO 2 gas layer is lower than that of quartz glass, so the maximum of the optical fiber of Fig. 5 by the first method is shown. There is a drawback that the strength is not improved in principle.
さらに、第１の方法では線引き中にフアイバガラス表面
よりコアに向かって拡散するTiO2（TiO2となっているも
のもある），BiO3によって、伝送損失が増加する問題も
ある。BiO3が赤外域で大きな吸収を持つことはよく知ら
れている。Further, the first method has a problem that the transmission loss increases due to TiO 2 (some of which are TiO 2 ) and BiO 3 which diffuse toward the core from the fiber glass surface during drawing. It is well known that BiO 3 has a large absorption in the infrared region.
一方、第２の方法によるフアイバは、グラフアイト膜63
が水分を透過しにくいという好ましい性質を持ってい
る。しかし、このグラフアイト膜をＣＶＤ法によって作
成するためには１０００℃以上という高温を必要とする
ために、成膜時にフアイバ表面とカーボンとが以下の反
応式によって SiO2＋Ｃ → SiC＋O2↑ 反応することが避けられず、フアイバ表面の滑らかさが
失われ、初期強度（すなわち最高強度）の低下が避けら
れないという欠点がある。On the other hand, the fiber by the second method is
Has a desirable property that it is difficult for water to permeate. However, since a high temperature of 1000 ° C. or higher is required to form this graphite film by the CVD method, the fiber surface and carbon react SiO 2 + C → SiC + O 2 ↑ according to the following reaction formula during film formation. Inevitably, the smoothness of the fiber surface is lost and the initial strength (that is, the maximum strength) is inevitably reduced.
本発明は、最高強度が低下せず、伝送損失を増加させ
ず、尚且つ長期的な強度低下つまり疲労の少ない光フア
イバ及びその製造方法を新規に提供することを目的とし
ている。It is an object of the present invention to newly provide an optical fiber in which the maximum strength is not reduced, the transmission loss is not increased, and the long-term strength reduction, that is, fatigue is small, and a manufacturing method thereof.
［課題を解決するための手段］ 本発明者等は研究を重ねた結果、水分の透過を防ぐ膜と
して水素を含むカーボン膜を採用すれば上記の目的を達
成した光フアイバが得られることを見いだし、さらに、
このような光フアイバを有利に実現できる製造方法にも
到達できた。[Means for Solving the Problems] As a result of repeated studies, the present inventors have found that an optical fiber that achieves the above object can be obtained by adopting a carbon film containing hydrogen as a film that prevents the permeation of water. ,further,
We have also reached a manufacturing method that can advantageously realize such an optical fiber.
すなわち、本発明はコア及びクラツドを有する石英系ガ
ラスフアイバの外側に、Ｂ水素を含むカーボン層を有し
てなる光フアイバを提供するものである。水素を含むカ
ーボン層が炭素原子１原子当たり水素原子を０．３〜１
原子を含む上記光フアイバが特に好ましい。That is, the present invention provides an optical fiber having a carbon layer containing B hydrogen on the outside of a silica glass fiber having a core and a cladding. The carbon layer containing hydrogen contains 0.3 to 1 hydrogen atom per carbon atom.
The above-mentioned optical fibers containing atoms are particularly preferred.
さらに本発明はコア及びクラツドを有する石英系ガラス
フアイバの外側に、炭化水素の熱分解反応を利用して水
素を含むカーボン層を形成することを特徴とする上記光
フアイバの製造方法をも提供する。本発明の特に好まし
い実施態様としては、該石英系ガラスフアイバを６００
℃以上で１０００℃以下の温度範囲内で加熱し、この加
熱された石英系ガラスフアイバの外周に炭化水素ガスを
流すことにより熱分解する上記方法が挙げられる。また
本発明においては水素を含むカーボン層を形成する工程
の直前に、該石英系ガラスフアイバをAr等のプラズマ中
でのスパツタリング処理及び／又はメチル化処理してお
くことが、所期の効果を増大できるので特に好ましい。Furthermore, the present invention also provides a method for producing the above optical fiber, characterized in that a carbon layer containing hydrogen is formed on the outside of a silica glass fiber having a core and a cladding by utilizing a thermal decomposition reaction of hydrocarbon. . In a particularly preferred embodiment of the present invention, the quartz glass fiber is 600
The above-mentioned method of thermally decomposing by heating within a temperature range of not less than 1000 ° C. and not more than 1000 ° C. and flowing a hydrocarbon gas around the heated silica-based glass fiber can be mentioned. Further, in the present invention, immediately before the step of forming a carbon layer containing hydrogen, the silica glass fiber is subjected to a sputtering treatment and / or a methylation treatment in a plasma such as Ar, which has a desired effect. It is particularly preferable because it can be increased.
以下に本発明を図面を参照して詳細に説明する。Hereinafter, the present invention will be described in detail with reference to the drawings.
第１図は本発明の光フアイバの一具体例の断面図であっ
て、１は石英系ガラスからなるコア、２は石英系ガラス
からなるクラツドであり、この石英系ガラスフアイバの
外側に、水分の透過を防止するための炭化水素を熱分解
することにより形成された水素を含むカーボン層３を有
する点に本発明の特徴がある。FIG. 1 is a cross-sectional view of a specific example of the optical fiber of the present invention, in which 1 is a core made of silica glass and 2 is a cladding made of silica glass. The present invention is characterized in that it has a carbon layer 3 containing hydrogen formed by thermally decomposing a hydrocarbon for preventing the permeation of hydrogen.
本発明の光フアイバを製造するには、紡糸された石英系
ガラスフアイバの外側に水素を含むカーボン層を合成す
るが、炭化水素を原料としてＣＶＤ法により該炭化水素
の熱分解を利用して合成する。例えば石英系ガラスフア
イバを外部加熱手段を備えた反応管中を通過させ、この
反応管内に炭化水素ガスを導入することにより熱分解さ
せ、水素を含むカーボン層を石英系ガスフアイバ外周に
成長させる等の方法によればよい。In order to manufacture the optical fiber of the present invention, a carbon layer containing hydrogen is synthesized on the outer side of a spun silica glass fiber. The hydrocarbon is used as a raw material and is synthesized by utilizing the thermal decomposition of the hydrocarbon by the CVD method. To do. For example, a quartz glass fiber is passed through a reaction tube equipped with an external heating means, and a hydrocarbon gas is introduced into the reaction tube for thermal decomposition, and a carbon layer containing hydrogen is grown on the outer circumference of the quartz gas fiber. According to the method.
本発明に用いることのできる炭化水素としては、例えば
ＣＨ4，C3H8等の直鎖型飽和炭化水素、C2H6，C2H4等の
直鎖型不飽和炭化水素、C6H6等の芳香族炭化水素、ＣＨ
Ｃｌ＝ＣＨＣｌ等のハイドロクロロカーボン等が挙げら
れる。Examples of hydrocarbons that can be used in the present invention include linear saturated hydrocarbons such as CH 4 and C 3 H 8 , linear unsaturated hydrocarbons such as C 2 H 6 and C 2 H 4 , and C 6 Aromatic hydrocarbons such as H 6 , CH
Hydrochlorocarbons such as Cl = CHCl are exemplified.
本発明の光フアイバにおけるカーボン層の膜厚は５００
Å〜２０００Åの範囲内であることが好ましい。５００
Å未満ではＨ２分子の透過を十分に阻止することができ
ず、２０００Åを越えると膜合成時にガラスフアイバが
カーボン粒子で傷つけられるのが避けられないし、徐々
にではあるがＳｉＣとＣが反応してガラスフアイバの表
面がボロボロになるため、光フアイバの最高強度が小さ
くなってしまうので好ましくない。The thickness of the carbon layer in the optical fiber of the present invention is 500.
It is preferably in the range of Å to 2000Å. 500
If it is less than Å, the permeation of H 2 molecules cannot be sufficiently blocked, and if it exceeds 2000 Å, it is unavoidable that the glass fiber is damaged by the carbon particles during the film synthesis, and SiC and C gradually react with each other. Since the surface of the glass fiber is broken, the maximum strength of the optical fiber becomes small, which is not preferable.
本発明の光フアイバにおいては、この水素を含むカーボ
ン層の外側に更に通常の樹脂被覆層を設けることができ
る。In the optical fiber of the present invention, an ordinary resin coating layer can be further provided outside the carbon layer containing hydrogen.
［作用］ ガラスが乾燥空気と接している状態ではガラス表面は−
Ｓｉ−Ｏ−Ｓｉ−Ｏ−となっていて表面エネルギーが大
きいが、水分が存在すると、−Ｓｉ−Ｏ‥Ｈ−Ｏ−Ｈの
ように水素結合が生じて表面エネルギーが小さくなる。
ところで、「破壊により解放される弾性エネルギーが破
壊により生じる表面エネギーよりも大きい場合に破壊が
進行する」という、いわゆるグリフス理論がこの場合う
まく当て嵌まり、ガラスと水が境界を構成すると破壊
（疲労）し易くなることが分かっている。[Operation] When the glass is in contact with dry air, the glass surface is
Si-O-Si-O- has a large surface energy, but when water is present, a hydrogen bond is generated as in -Si-O ... H-O-H to reduce the surface energy.
By the way, the so-called glyphs theory that "the fracture progresses when the elastic energy released by the fracture is larger than the surface energy generated by the fracture" is successfully applied in this case, and when the glass and water form the boundary, the fracture (fatigue) occurs. I know it will be easier to do.
本発明の光フアイバは炭化水素を熱分解することにより
形成された水素を含むカーボン層を有することにより、
水分のガラス表面への透過を防止できるので、ガラスの
表面エネルギーが大きい状態を保てるので、疲労が少な
く、初期強度を保つことができる。The optical fiber of the present invention has a carbon layer containing hydrogen formed by thermally decomposing hydrocarbons,
Since water can be prevented from permeating to the glass surface, the surface energy of the glass can be kept high, so that fatigue can be reduced and the initial strength can be maintained.
また、本発明の光フアイバは製法の上でも、ガラス強度
の低下を防止できる点で従来法によるものより有利であ
る。即ち、本発明では炭化水素を原料として用いて、こ
れを熱分解して水素を含むカーボン膜を合成する方法に
よるので、既に説明したガラスフアイバ表面のカーボン
による還元反応 ＳｉＯ２＋Ｃ → ＳｉＣ ＋ Ｏ２↑ が起こらない１０００℃以下で合成できるので、得られ
た光フアイバの最高強度が低下しない。Also, the optical fiber of the present invention is advantageous over the conventional method in that it can prevent the decrease in glass strength even in the manufacturing method. That is, in the present invention, since hydrocarbon is used as a raw material and the carbon film containing hydrogen is synthesized by thermally decomposing it as a raw material, the reduction reaction of carbon on the glass fiber surface as described above SiO 2 + C → SiC + O 2 Since it can be synthesized at 1000 ° C or lower where ↑ does not occur, the maximum strength of the obtained optical fiber does not decrease.
本発明の光フアイバの炭化水素を熱分解することにより
形成された水素を含むカーボン膜において、水素原子の
量は炭素原子１に対して０．３〜１が好ましい。１を越
えると膜の水分透過防止効果が小さくなり、また膜が硬
くなり光フアイバにマイクロベンドロスを生じるので好
ましくない。一方、０．３未満の膜を合成するには１０
００℃以上の加熱を要するが１０００℃以上での加熱で
は上記の還元反応がおきて、フアイバがボロボロになる
ため好ましくない。In the carbon film containing hydrogen formed by thermally decomposing the hydrocarbon of the optical fiber of the present invention, the amount of hydrogen atoms is preferably 0.3 to 1 with respect to 1 carbon atom. If it exceeds 1, the effect of preventing moisture permeation of the film becomes small, and the film becomes hard to cause microbend loss in the optical fiber, which is not preferable. On the other hand, to synthesize a film of less than 0.3, 10
Heating at 00 ° C. or higher is required, but heating at 1000 ° C. or higher is not preferable because the above-described reduction reaction occurs and the fiber becomes tattered.
水素を含むカーボン膜合成工程直前にガラスフアイバの
ガラス表面をメチル化して疎水処理を施しておくと、万
が一水分が水素を含むカーボン膜を透過して来てもガラ
ス表面と水分・水素とが水素結合せず、ガラスの表面エ
ネルギーが減少しないので、光フアイバの疲労を抑える
ことができる。疎水化はジメチルジクロルシラン雰囲気
で光フアイバを５００℃に加熱することにより行うこと
が好ましい。If the glass surface of the glass fiber is methylated and subjected to a hydrophobic treatment immediately before the step of synthesizing the carbon film containing hydrogen, even if moisture penetrates the carbon film containing hydrogen, the glass surface and the moisture / hydrogen will be hydrogen. Since they are not bonded and the surface energy of the glass is not reduced, the fatigue of the optical fiber can be suppressed. The hydrophobization is preferably performed by heating the optical fiber to 500 ° C. in a dimethyldichlorosilane atmosphere.
また熱分解によるカーボン膜合成直前又は疎水化処理直
前にAr等のプラズマス中で光フアイバをスパツタリング
して表面を清浄にすることが有効である。It is also effective to sputter the optical fiber in plasma such as Ar to clean the surface immediately before synthesizing the carbon film by thermal decomposition or immediately before the hydrophobic treatment.
従って疎水化は、線引直後又はプラズマスパツタリング
の直後でカーボン膜合成前に行うことが好ましい。Therefore, the hydrophobization is preferably performed immediately after the drawing or immediately after the plasma sputtering and before the carbon film synthesis.
［実施例］ 実施例１ 第２図に示す装置を用いて光フアイバ用プリフオームを
溶融・紡糸してガラスファイバとし、しかる後にクラツ
ドガラスの外側に水素を含むカーボン層をＣＶＤ法によ
り成長させ、さらにその上を紫外線硬化樹脂で被覆し
て、本発明の光フアイバ素線を製造した。図中１は光フ
アイバ用プリフオーム、２は紡糸炉であり、ここで外径
３０mmφの光フアイバ用プリフオームを外径１２５mmφ
のガラスフアイバ11とした。ガラスの線速は３ｍ／sec
であった。このガラスフアイバ11は紡糸炉２直下の赤外
線加熱装置６を持つカーボンコーテイング装置５内に送
り込まれた。カーボンコーテイング装置５の入口・出口
には、ガラスフアイバ11の温度を測定する装置3,4が備
え付けられている。入口側測定装置３で測定したフアイ
バ温度は８５０℃であった。赤外線加熱装置６のパワー
は出口側測定装置４で測定したフアイバ温度が８００℃
になるように調節した。カーボンコーテイング装置５に
は、反応ガス入口７，出口８が設けられている。反応ガ
ス入口７はフアイバ出口近くに、反応ガス出口８はフア
イバ入口近くに設けられている。反応ガス入口７からは
ＣＨ４を１５００cc／secで導入した。カーボンコーテ
イング装置５の内径は２０mm、長さは５００mmである。
カーボンコーテイング装置５を通過した水素を含むカー
ボン層を被覆された被覆フアイバは、通常の紫外線樹脂
被覆装置９を経て、ここで紫外線硬化アクリル樹脂を６
２．５μｍの層厚で被覆され、次に巻き取り装置10で巻
き取られた。以上により得られた本発明の光フアイバの
構造、特性を調べたところ、次のような結果が得られ
た。Example 1 Example 1 Using the apparatus shown in FIG. 2, an optical fiber preform was melted and spun into a glass fiber, after which a carbon layer containing hydrogen was grown on the outside of the cladding glass by a CVD method, and The optical fiber of the present invention was manufactured by coating the above with an ultraviolet curable resin. In the figure, 1 is an optical fiber preform, and 2 is a spinning furnace, in which an optical fiber preform having an outer diameter of 30 mmφ is an outer diameter of 125 mmφ.
The glass fiber is 11. The linear velocity of glass is 3m / sec
Met. This glass fiber 11 was fed into a carbon coating device 5 having an infrared heating device 6 directly below the spinning furnace 2. At the inlet and outlet of the carbon coating device 5, devices 3 and 4 for measuring the temperature of the glass fiber 11 are provided. The fiber temperature measured by the inlet side measuring device 3 was 850 ° C. The power of the infrared heating device 6 is such that the fiber temperature measured by the outlet side measuring device 4 is 800 ° C.
Adjusted so that The carbon coating device 5 is provided with a reaction gas inlet 7 and an outlet 8. The reaction gas inlet 7 is provided near the fiber outlet, and the reaction gas outlet 8 is provided near the fiber inlet. CH 4 was introduced from the reaction gas inlet 7 at 1500 cc / sec. The carbon coating device 5 has an inner diameter of 20 mm and a length of 500 mm.
The coated fiber, which has passed through the carbon coating device 5 and is coated with the carbon layer containing hydrogen, is passed through a normal ultraviolet resin coating device 9 and then the ultraviolet curing acrylic resin 6 is added thereto.
It was coated with a layer thickness of 2.5 μm and then wound on a winding device 10. When the structure and characteristics of the optical fiber of the present invention obtained as described above were examined, the following results were obtained.
膜厚；フアイバの断面をＳＥＭ（走査型電子顕微鏡）で
撮映したところ、１５０nmであった。Film thickness: When a cross section of the fiber was photographed by SEM (scanning electron microscope), it was 150 nm.
水素含有量；カーボン層を燃焼させて、発生する水分量
を測定したところ、カーボン１原子当り０．５原子の水
素原子があった。Hydrogen content: When the carbon layer was burned and the amount of water produced was measured, 0.5 atom of hydrogen atom was present per atom of carbon.
フアイバ強度；フアイバを２０ｍ取り、その一端を固定
し、多端を荷重を計りながら１ｍ／secの速さで引っ張
り、最終的に破断させ、破断時の荷重を測定する引張り
試験を２０回（フアイバ20本分）行った。このデータに
より、荷重Ｐ（引張り強度PGa)の時何％のフアイバが破
断していたか（破断確率）をワイブル確率紙上にプロツ
トしたものを、第３図にＡとして示す。第３図のＢはカ
ーボン層を持たない通常のフアイバ（比較品）について
同様に試験した結果である。本発明品のＡは比較品のＢ
に比べて疲労が少ないことが分かる。なお、ｎ値（ワイ
ブル確率紙上に表れた傾きから求められるワイブル分布
の形状パラメータで、この場合は疲労しにくさを示す）
１８０、初期強度（破断確率１００％への外挿値）４．
８GPaであった。Fiber strength: 20m of fiber is taken, one end is fixed, and the other end is pulled at a speed of 1m / sec while measuring the load to finally break it, and the tensile test to measure the load at break is carried out 20 times (fiber 20 I went. Based on this data, what percentage of the fiber was broken at the load P (tensile strength PGa) (broken probability) was plotted on the Weibull probability paper and is shown as A in FIG. B of FIG. 3 is the result of the same test performed on a normal fiber (comparative product) having no carbon layer. A of the present invention is B of the comparative product
You can see that there is less fatigue compared to. In addition, n value (shape parameter of the Weibull distribution obtained from the inclination that appears on the Weibull probability paper, and in this case indicates the degree of fatigue)
180, initial strength (extrapolated value to 100% fracture probability) 4.
It was 8 GPa.
実施例２ 実施例１と同じ装置で水素を含むカーボン層を持つ本発
明の光フアイバ素線が作製したが、紡糸炉とカーボンコ
ーテイング装置との間の距離及び赤外線加熱装置の出力
を調節することにより、カーボンコーテイング装置の入
口及び出口でのフアイバ温度を表に示すように変化させ
た。得られたフアイバのそれぞれについて、水素量（炭
素原子に対する比），ｎ値，初期強度，損失，膜厚の各
項目につき測定を行った。この結果も表に併せて示す。Example 2 An optical fiber strand of the present invention having a carbon layer containing hydrogen was prepared in the same apparatus as in Example 1, but the distance between the spinning furnace and the carbon coating apparatus and the output of the infrared heating apparatus were adjusted. The fiber temperature at the inlet and the outlet of the carbon coating device was changed as shown in the table. Each of the obtained fibers was measured for each item of hydrogen content (ratio to carbon atom), n value, initial strength, loss, and film thickness. The results are also shown in the table.
上記の表から次のことが分かる。 The following can be seen from the above table.
即ち、フアイバ加熱温度が１０００℃を越すと、初期強
度の低下がみられ、一方１００℃未満ではｎ値が低くな
りマイクロベンドによるロス増加がある。従って、６０
０〜１０００℃の温度範囲内に加熱して炭化水素を分解
することが好ましいことが分かるが、この条件で得られ
る水素を含むカーボン膜中に水素原子量／炭素原子量は
０．３〜１である。膜厚は合成時の温度が高い程暑くな
る。That is, when the fiber heating temperature exceeds 1000 ° C., the initial strength is decreased, while when the fiber heating temperature is less than 100 ° C., the n value becomes low and the loss due to microbending increases. Therefore, 60
It can be seen that it is preferable to heat within the temperature range of 0 to 1000 ° C. to decompose hydrocarbons, but the hydrogen atom weight / carbon atom weight is 0.3 to 1 in the carbon film containing hydrogen obtained under these conditions. . The film thickness becomes hotter as the temperature during synthesis increases.
実施例３ 第４図の装置を用いて、光フアイバ用プリフオームを溶
融・紡糸し、ガラスフアイバとし、しかも後クラツドガ
ラスの外側に水素を含むカーボン層をＣＶＤ法により成
長させ、さらにその上に紫外線硬化樹脂で被覆して本発
明の光フアイバ素線を製造した。紡糸炉２で線速３ｍ／
secで紡糸された外径１２５μｍのガラスフアイバ11
は、Arガス０．１ torrに保たれたArスパツタリング装
置12に導入され、しかる後カーボンコーテイング装置13
へ導入される。カーボンコーテイング装置13は２個の反
応容器14，15より成り立っており、該反応容器14内では
ジメチルジクロルシランを用いてフアイバ表面の疎水化
（メチル化）を行った。なお、第４図において１〜４及
び６〜11の符号の意味するところは第２図と同じであ
り、16はメチル化用ガス入口、17は同出口である。Example 3 Using the apparatus shown in FIG. 4, a preform for an optical fiber is melted and spun to form a glass fiber, and a carbon layer containing hydrogen is grown on the outer side of the post-clad glass by a CVD method, and further UV-cured thereon. The optical fiber wire of the present invention was manufactured by coating with a resin. Spinning furnace 2 linear speed 3m /
Glass fiber with an outer diameter of 125 μm spun in sec 11
Is introduced into the Ar sputtering device 12 where the Ar gas is kept at 0.1 torr, and then the carbon coating device 13
Be introduced to. The carbon coating device 13 is composed of two reaction vessels 14 and 15. In the reaction vessel 14, dimethyldichlorosilane was used to hydrophobize (methylate) the fiber surface. In FIG. 4, the reference numerals 1 to 4 and 6 to 11 are the same as those in FIG. 2, 16 is a methylation gas inlet, and 17 is the same outlet.
この方法で得た本発明の光フアイバにおいては、ガラス
フアイバと水素を含むカーボンコーテイング層は完全に
化学的結合によりつながっている。以上で得られた光フ
アイバの構造、特性は以下の通りであった。In the optical fiber of the present invention obtained by this method, the glass fiber and the carbon coating layer containing hydrogen are completely connected by a chemical bond. The structure and characteristics of the optical fiber obtained above were as follows.
膜厚；１５０nm 水素量；カーボン１原子当り０．５個 フアイバ強度；ｎ値２５０ 初期強度４．８GPa ［発明の効果］ 本発明は最高強度（初期強度）が低下せず、従来のTiO2
やBiO3を含有する層を持つものにみられた伝送損失の増
加がなく、しかも長期的な強度低下即ち疲労の少ないフ
アイバの新規な構造を提供できる。また本発明の製造方
法は本発明の構造をフアイバの特性を損なうことなく有
利に実現できるものである。Film thickness: 150 nm Hydrogen amount: 0.5 per carbon atom Fiber strength: n value 250 Initial strength 4.8 GPa [Effect of the invention] In the present invention, the maximum strength (initial strength) does not decrease, and conventional TiO 2
It is possible to provide a novel fiber structure in which there is no increase in transmission loss, which is found in a layer having a layer containing BiO 3 or BiO 3 , and in which long-term strength reduction, that is, fatigue is reduced. Further, the manufacturing method of the present invention can advantageously realize the structure of the present invention without deteriorating the characteristics of the fiber.
第１図は本発明の光フアイバを説明する断面図、第２図
は本発明の方法が実施態様を説明する図、第３図は本発
明の実施例２で作製した本発明品の引張り強度(GPa)と
破壊確率（％）の関係Ａと、比較品の同関係Ｂを示す
図、第４図は本発明の方法の別の実施態様であって、予
めArスパツタリング処理とメチル化処理を施す例の説明
図、第５図及び第６図は従来の光フアイバを説明する断
面図である。 １…光フアイバ用プリフオーム、２…紡糸炉、３…入口
側温度測定装置、４…出口側温度測定装置、５…カーボ
ンコーテイング装置、６…赤外線加熱装置、７…反応ガ
ス入口、８…反応ガス出口、９…紫外線硬化樹脂被覆装
置、10…巻き取り装置、11…ガラスフアイバ、12…Arス
パツタリング装置、13…カーボンコーテイング装置、14
…メチル化用反応容器、15…カーボンコーテイング用反
応容器、16…メチル化用ガス入口、17…メチル化用ガス
出口。FIG. 1 is a cross-sectional view for explaining the optical fiber of the present invention, FIG. 2 is a view for explaining an embodiment of the method of the present invention, and FIG. 3 is a tensile strength of the product of the present invention produced in Example 2 of the present invention. FIG. 4 is a diagram showing a relation A between (GPa) and the destruction probability (%) and a relation B of the comparative product, and FIG. 4 shows another embodiment of the method of the present invention, in which Ar sputtering treatment and methylation treatment are performed beforehand. FIGS. 5 and 6 are sectional views for explaining a conventional optical fiber. DESCRIPTION OF SYMBOLS 1 ... Preform for optical fiber, 2 ... Spinning furnace, 3 ... Entrance temperature measuring device, 4 ... Exit temperature measuring device, 5 ... Carbon coating device, 6 ... Infrared heating device, 7 ... Reaction gas inlet, 8 ... Reaction gas Outlet, 9 ... UV curable resin coating device, 10 ... Winding device, 11 ... Glass fiber, 12 ... Ar sputtering device, 13 ... Carbon coating device, 14
… Methylation reaction vessel, 15… Carbon coating reaction vessel, 16… Methylation gas inlet, 17… Methylation gas outlet.
Claims (6)
アイバの外側に、炭化水素を熱分解することにより形成
された水素を含むカーボン層を有してなる光フアイバ。1. An optical fiber having a carbon layer containing hydrogen formed by thermally decomposing a hydrocarbon on the outside of a silica glass fiber having a core and a clad.
たり水素原子を０．３〜１原子含むことを特徴とする特
許請求の範囲第１項記載の光フアイバ。2. The optical fiber according to claim 1, wherein the carbon layer containing hydrogen contains 0.3 to 1 atom of hydrogen per atom of carbon.
アイバの外側に、炭化水素を熱分解することにより水素
を含むカーボン層を成長させることを特徴とする光フア
イバの製造方法。3. A method for producing an optical fiber, which comprises growing a carbon layer containing hydrogen by thermally decomposing a hydrocarbon on the outside of a silica glass fiber having a core and a clad.
１０００℃以下の温度範囲内で加熱し、この加熱された
石英系ガラスフアイバの外周に炭化水素を流して熱分解
することを特徴とする特許請求の範囲第３項記載の光フ
アイバの製造方法。4. The quartz glass fiber is heated within a temperature range of 600 ° C. or higher and 1000 ° C. or lower, and a hydrocarbon is caused to flow around the heated quartz glass fiber for thermal decomposition. A method for manufacturing an optical fiber according to claim 3.
ーボン層を成長させる直前にプラズマスパツタリング処
理されていることを特徴とする特許請求の範囲第３又は
４項に記載の光フアイバの製造方法。5. The optical fiber according to claim 3, wherein the silica glass fiber is subjected to plasma sputtering treatment immediately before growing a carbon layer containing hydrogen. Production method.
はプラズマスパツタリング処理直後で水素を含むカーボ
ン層を成長させる直前にメチル化処理されていることを
特徴とする特許請求の範囲第３乃至５項のいずれに記載
の光フアイバの製造方法。6. The silica glass fiber is methylated immediately after drawing or immediately after growing a carbon layer containing hydrogen immediately after drawing or plasma sputtering. Item 6. A method for producing an optical fiber according to any one of items 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63176941A JPH0648325B2 (en) | 1988-07-18 | 1988-07-18 | Optical fiber and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63176941A JPH0648325B2 (en) | 1988-07-18 | 1988-07-18 | Optical fiber and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0227308A JPH0227308A (en) | 1990-01-30 |
| JPH0648325B2 true JPH0648325B2 (en) | 1994-06-22 |
Family
ID=16022415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63176941A Expired - Lifetime JPH0648325B2 (en) | 1988-07-18 | 1988-07-18 | Optical fiber and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0648325B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0235404A (en) * | 1988-07-26 | 1990-02-06 | Fujikura Ltd | Optical fiber |
| JP2644018B2 (en) * | 1988-12-13 | 1997-08-25 | 株式会社フジクラ | Optical fiber manufacturing method |
| US5628940A (en) * | 1994-07-11 | 1997-05-13 | Reno & Son, Inc. | Process for applying low-cement castable refractory material |
| JPH0925175A (en) * | 1995-05-11 | 1997-01-28 | Asahi Glass Co Ltd | Spraying method for irregular refractories |
| US5783510A (en) * | 1995-07-04 | 1998-07-21 | Asahi Glass Company Ltd. | Monolithic refractory composition wall |
| JP3046251B2 (en) * | 1996-10-15 | 2000-05-29 | 大光炉材株式会社 | Wet spraying method of dense pouring refractory composition |
| JP4728009B2 (en) * | 2005-02-16 | 2011-07-20 | オリンパス株式会社 | Fiber manufacturing method and fiber |
| CN102203647B (en) * | 2008-09-26 | 2014-04-30 | 康宁股份有限公司 | High numerical aperture multimode optical fiber |
| JP2011102964A (en) | 2009-10-14 | 2011-05-26 | Sumitomo Electric Ind Ltd | Optical fiber and method of manufacturing optical fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512629A (en) * | 1982-03-30 | 1985-04-23 | Hewlett-Packard Company | Optical fiber with hermetic seal and method for making same |
| JPH0646251B2 (en) * | 1985-05-22 | 1994-06-15 | 株式会社フジクラ | Light fiber |
| JPS6283339A (en) * | 1985-10-08 | 1987-04-16 | Yokogawa Hewlett Packard Ltd | Formation of coating on optical fiber |
| DE3885827T2 (en) * | 1987-09-18 | 1994-03-17 | American Telephone & Telegraph | Hermetically sealed, optical fibers. |
-
1988
- 1988-07-18 JP JP63176941A patent/JPH0648325B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0227308A (en) | 1990-01-30 |
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