JPS6240303B2 - - Google Patents
Info
- Publication number
- JPS6240303B2 JPS6240303B2 JP56029628A JP2962881A JPS6240303B2 JP S6240303 B2 JPS6240303 B2 JP S6240303B2 JP 56029628 A JP56029628 A JP 56029628A JP 2962881 A JP2962881 A JP 2962881A JP S6240303 B2 JPS6240303 B2 JP S6240303B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fiber
- temperature
- glass tube
- reaction
- 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 40
- 239000003365 glass fiber Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 19
- 239000005387 chalcogenide glass Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910003902 SiCl 4 Inorganic materials 0.000 description 5
- 229910052798 chalcogen Inorganic materials 0.000 description 4
- 150000001787 chalcogens Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- -1 GeH 4 Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000004804 winding 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]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01807—Reactant delivery systems, e.g. reactant deposition burners
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01861—Means for changing or stabilising the diameter or form of tubes or rods
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01884—Means for supporting, rotating and translating tubes or rods being formed, e.g. lathes
-
- 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
- C03C13/043—Chalcogenide 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
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
-
- 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
- C03B2201/86—Chalcogenide glasses, i.e. S, Se or Te glasses
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
本発明は赤外線を透過するガラスフアイバの製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a glass fiber that is transparent to infrared radiation.
従来、赤外線を透過するガラス材料としては、
カルコゲナイドガラスがよく知られている。これ
らのガラスは、それぞれの原料を粉末またはブロ
ツク状で、石英ガラス管内に真空封入し、長時間
高温度で溶融し、その後、空冷することにより得
られていた。 Traditionally, glass materials that transmit infrared rays include:
Chalcogenide glass is well known. These glasses were obtained by vacuum-sealing the respective raw materials in powder or block form in a quartz glass tube, melting them at high temperatures for a long time, and then cooling them in air.
光を伝播するガラスフアイバにおいては、用い
る波長域内で低い光損失値であることが要求さ
れ、このためには、吸収を示す不純物、たとえば
希土類金属、遷移金属および水分等の含有量を極
端に減少させたフアイバを製造しなければならな
い。不純物含有量を少なくする観点から考える
と、前述の製造方法は、はなはだ不十分な方法で
ある。現在、光フアイバには主としてSiO2系ガ
ラスフアイバが使用されているが、この場合には
以下に説明するようなCVD法（Chemical
Vapour Deposition法）によつて高純度なガラス
フアイバが製造されている。 Glass fibers that propagate light are required to have low optical loss values within the wavelength range used, and to achieve this, the content of absorbing impurities such as rare earth metals, transition metals, and water must be drastically reduced. The fiber must be manufactured in such a way that the From the point of view of reducing the impurity content, the above-mentioned production methods are extremely unsatisfactory. Currently, SiO 2 -based glass fibers are mainly used as optical fibers, but in this case, the CVD method (Chemical
High purity glass fibers are manufactured using the vapor deposition method.
すなわちCVD法による光フアイバ作製では、
SiCl4やGeCl4等、液体原料の蒸気を、Ar、O2等
の輸送ガスとともに、高温部に導入し、加熱分解
して高純度の酸化物を得る。この場合の高純度性
は、容易に蒸留精製が可能な原料を使用すること
と、精製によつて高純度化された原料から、すな
わち汚染なしに、所望の物質形態である酸化物に
変換できることによつて保障されている。 In other words, in optical fiber production using the CVD method,
The vapor of a liquid raw material such as SiCl 4 or GeCl 4 is introduced into a high-temperature section along with a transport gas such as Ar or O 2 and is thermally decomposed to obtain a high-purity oxide. High purity in this case means the use of raw materials that can be easily purified by distillation, and the fact that raw materials that have been highly purified through purification can be converted into the desired substance form, ie, oxides, without contamination. guaranteed by.
塩化物を出発原料として、CVD法によるカル
コゲナイドガラスを材料とする低損失な赤外線透
過ガラスフアイバの製造が提案されている（特開
昭53−83639）。しかしこれらは、塩化物を熱分解
する反応にその基礎を置いているので、以下に述
べる致命的欠点を有し、この方法ではカルコゲナ
イドガラスおよびガラスフアイバの製造は不可能
である。すなわちカルコゲナイドガラスの場合に
は、カルコゲン成分（硫黄、セレン、テルル）の
揮発性が高いので、高温下においてはカルコゲン
成分が容易に揮発し、ガラス状態を保つことが不
可能になる。ところが、GeCl4、SiCl4等カルコゲ
ナイドガラスを形成する陽イオン成分の原料の分
解温度はGeCl4で800℃以上、SiCl4で1000℃以上
となり、カルコゲナイドガラスの揮発が活発化す
る温度（600〜700℃）に比較して、非常に高温で
ある。 It has been proposed to produce a low-loss infrared transmitting glass fiber made of chalcogenide glass using a CVD method using chloride as a starting material (Japanese Patent Application Laid-Open No. 83639/1983). However, since these methods are based on a reaction that thermally decomposes chlorides, they have the following fatal drawbacks, and chalcogenide glasses and glass fibers cannot be produced using this method. That is, in the case of chalcogenide glass, the chalcogen components (sulfur, selenium, tellurium) have high volatility, so the chalcogen components easily volatilize at high temperatures, making it impossible to maintain the glass state. However, the decomposition temperature of the raw materials for cationic components forming chalcogenide glasses such as GeCl 4 and SiCl 4 is over 800°C for GeCl 4 and over 1000°C for SiCl 4 , which is the temperature at which volatilization of chalcogenide glass becomes active (600-700°C). The temperature is very high compared to ℃).
このため、Ge、Si等を熱分解によつて形成せ
しめる温度に反応系を置くと、部分的にカルコゲ
ナイドガラスが生じたにしても、たちまちカルコ
ゲン成分が揮発し、ガラスの形成は起こらない。
またカルコゲナイドガラスのカルコゲン成分が揮
発しない温度（たとえば600℃）に反応系を保持
すると、今度はGeCl4、SiCl4の分解反応は起こら
ず、カルコゲナイドガラスは形成されない。 Therefore, if the reaction system is placed at a temperature that causes Ge, Si, etc. to be formed by thermal decomposition, even if chalcogenide glass is partially formed, the chalcogen component immediately volatilizes and no glass is formed.
Furthermore, if the reaction system is maintained at a temperature at which the chalcogen component of chalcogenide glass does not volatilize (for example, 600°C), the decomposition reaction of GeCl 4 and SiCl 4 will not occur, and chalcogenide glass will not be formed.
実際、「特開昭53−83639」の実施例に記述され
ている方法に従つて、GeS2およびGe−Ｐ−Ｓの
作製を試みたが、ガラス状物質の製造は不可能で
あつた。さらに流量比、加熱温度等を種々に変化
させたが、塩化物を用いる限りでは、ガラス状物
質は形成されなかつた。 In fact, attempts were made to produce GeS 2 and Ge-P-S according to the method described in the examples of ``Japanese Patent Application Laid-Open No. 53-83639,'' but it was impossible to produce a glassy substance. Furthermore, although the flow rate ratio, heating temperature, etc. were varied, no glassy substance was formed as long as chloride was used.
本発明はこのように、従来のCVD法、すなわ
ちハロゲン化物同志の熱分解反応では、カルコゲ
ナイドガラスが形成されないという致命的欠点を
解決するため、GeH4、SiH4、PH3等の水素化物
を用い、CVD法によりカルコゲナイドガラスを
生成せしめ、さらにガラスフアイバを製造したも
のである。以下実施例について詳しく説明する。 In this way, the present invention uses hydrides such as GeH 4 , SiH 4 , and PH 3 to solve the fatal drawback that chalcogenide glass is not formed in the conventional CVD method, that is, thermal decomposition reaction of halides. , chalcogenide glass was produced using the CVD method, and glass fiber was further manufactured. Examples will be described in detail below.
実施例 １
第１図は本発明のCVD法によるガラス薄膜作
製装置の構成図で、１は液体原料用容器、２は原
料ガスボンベ、３は流量調節器、４は減圧弁、５
は原料輸送用パイプ、６はパイプとガラス管をつ
なぐ接続部（回転コネクタ）、７はガラス管、８
はバーナ、９はガラス管をおさえ、回転させる平
行旋盤のチヤツクである。Embodiment 1 FIG. 1 is a block diagram of a glass thin film production apparatus using the CVD method of the present invention, in which 1 is a liquid raw material container, 2 is a raw material gas cylinder, 3 is a flow rate regulator, 4 is a pressure reducing valve, and 5
is a pipe for transporting raw materials, 6 is a connection part (rotary connector) that connects the pipe and glass tube, 7 is a glass tube, 8
is a burner, and 9 is a chuck for a parallel lathe that holds and rotates the glass tube.
液体原料S2Cl2を容器１に入れ、Arガスで輸送
し、同時に原料ガスボンベ２からGeH4ガスを、
減圧弁４を通して、原料輸送用パイプ５によつ
て、ガラス管７の中へ送り込んだ。それぞれの流
量は流量調節器により、精密に制御した。 Liquid raw material S 2 Cl 2 is placed in container 1 and transported with Ar gas, and at the same time GeH 4 gas is supplied from raw material gas cylinder 2.
The material was fed through a pressure reducing valve 4 and into a glass tube 7 via a raw material transport pipe 5. Each flow rate was precisely controlled using a flow rate controller.
一方、原料を送り込まれたガラス管７は、旋盤
によつて50rpmの速度で回転し、その下部から移
動式の酸水素炎バーナ８で、ガラス管７を加熱
し、ガラス管７の中で以下の反応を起こさせた。 On the other hand, the glass tube 7 into which the raw materials have been fed is rotated by a lathe at a speed of 50 rpm, and a mobile oxyhydrogen flame burner 8 heats the glass tube 7 from the bottom. caused a reaction.
GeH4→Ge＋2H2↑
（反応に必要な温度約500℃）
S2Cl2→2S＋Cl2↑
（反応に必要な温度400〜500℃）
ｘ・Ｓ＋Ge→GeSx
第２図に輸送した原料比（S2Cl2／GeH4）を横
軸にとり、加熱温度を縦軸にとつたときのガラス
化範囲を示した。第２図において〇印はガラス化
した状態、×印はガラス化しない状態、△印はガ
ラス化が不十分な状態を示すそれぞれ実験値であ
る。GeH 4 →Ge＋2H 2 ↑ (Temperature required for reaction: approximately 500℃) S 2 Cl 2 →2S＋Cl 2 ↑ (Temperature required for reaction: 400-500℃) x・S＋Ge→GeSx Figure 2 shows the ratio of raw materials transported (S 2 Cl 2 /GeH 4 ) is plotted on the horizontal axis and the vitrification range is plotted when the heating temperature is plotted on the vertical axis. In FIG. 2, the ◯ mark indicates a vitrified state, the x mark indicates a non-vitrified state, and the △ mark indicates an insufficiently vitrified state, respectively, which are experimental values.
ガラス化の判定は、堆積したガラスの透明度、
均質度から行つたが、同時にＸ線回折により結晶
ピークの現われないことを確認している（第３
図）。 Vitrification is determined by the transparency of the deposited glass,
This was done based on homogeneity, but at the same time it was confirmed by X-ray diffraction that no crystal peaks appeared (3rd
figure).
比較例 １
第１図において、液体原料容器を２個用いて、
S2Cl2とGeCl4をArガスで同時にガラス管内に輸
送し、バーナで加熱することにより、透明なガラ
スが作製可能かどうかの判定を行つた。種々の流
量および流量比（S2Cl2／GeCl4）で作製を試みた
が、透明なガラス膜は形成できなかつた。光温度
計で、ガラス管表面の温度を測定して反応との対
応を観察した。Comparative Example 1 In Fig. 1, using two liquid raw material containers,
We determined whether transparent glass could be produced by simultaneously transporting S 2 Cl 2 and GeCl 4 into a glass tube using Ar gas and heating them with a burner. Attempts were made using various flow rates and flow rate ratios (S 2 Cl 2 /GeCl 4 ), but a transparent glass film could not be formed. The temperature on the surface of the glass tube was measured using a photothermometer and the correspondence with the reaction was observed.
S2Cl2とGeCl4の組合わせでは、800℃以上で反
応が起こつた。約900℃で黄白色、約1000℃で乳
白色の不透明な付着物が発生したが、ガラス化
は、ついに起こらなかつた。これはGeCl4の反応
開始温度が800℃と高温であるので、生成したGe
−Ｓ系のＳ成分がたちまち揮発するためである。 In the combination of S 2 Cl 2 and GeCl 4 , the reaction occurred at temperatures above 800°C. At about 900°C, a yellowish-white and milky-white opaque deposit occurred at about 1000°C, but vitrification did not occur at all. This is because the reaction initiation temperature of GeCl 4 is as high as 800℃, so the generated Ge
This is because the S component of the -S system immediately evaporates.
実施例 ２
実施例１と同様の装置を用い、S2Cl2（液体）、
GeH4（ガス）、SH3（ガス）の３種類の原料で
CVD法を行つた。流量調節器によつてS2Cl2容器
にはArガスが200ml／分（40℃）、GeH4（10％の
濃度）は100ml／分、PH3（10％濃度）は10ml／
分の割合で流れるようにした。バーナでガラス管
表面の温度が約550℃になるように加熱すること
により、薄黄色の透明ガラス膜を、ガラス管内に
生成した。PH3の代わりにPCl3を用いた場合は、
前記（比較例１）の例と同様に反応温度が約700
〜800℃と高温になる。このため生成した硫黄の
揮発が著しく、ガラスの堆積は観察されなかつ
た。Example 2 Using the same apparatus as in Example 1, S 2 Cl 2 (liquid),
With three types of raw materials: GeH 4 (gas) and SH 3 (gas).
CVD method was performed. The flow rate regulator allows Ar gas to flow into the S 2 Cl 2 container at 200 ml/min (at 40°C), GeH 4 (10% concentration) at 100 ml/min, and PH 3 (10% concentration) at 10 ml/min.
I made it flow at a rate of 1 minute. By heating the glass tube surface with a burner to a temperature of approximately 550°C, a pale yellow transparent glass film was formed inside the glass tube. If PCl3 is used instead of PH3 ,
Similar to the example above (Comparative Example 1), the reaction temperature was about 700℃.
The temperature reaches ~800℃. Therefore, the generated sulfur volatilized significantly, and no glass deposition was observed.
実施例 ３
実施例１と同様の方法で、軟化点約500〜550℃
のガラス管内にGe−Ｓ系ガラス膜を堆積した。
堆積の温度は500℃、バーナの送り速度は150mm／
分であつた。その後、温度600℃、バーナの送り
速度75mm／分で、ガラス管を堆積したGe−Ｓ系
のガラス膜とともに、棒状に中実化し、中心部に
Ge−Ｓ系ガラスを、その外側に酸化物ガラス層
を有するフアイバ用母材を作製した。中実化に用
いた温度は、Ge−Ｓ系ガラスのＳ成分が揮発す
る温度650℃より低く、このため、Ge−Ｓガラス
は透明なガラス状態のまま、酸化物ガラス中に閉
じ込められた。Example 3 Using the same method as Example 1, the softening point was about 500 to 550°C.
A Ge-S glass film was deposited inside the glass tube.
The deposition temperature was 500℃, and the burner feed speed was 150mm/
It was hot in minutes. Then, at a temperature of 600℃ and a burner feed rate of 75mm/min, the glass tube is solidified into a rod shape along with the deposited Ge-S glass film, and the center
A fiber base material having an oxide glass layer on the outside was prepared from Ge-S glass. The temperature used for solidification was lower than 650° C., the temperature at which the S component of the Ge-S glass volatilizes, and therefore the Ge-S glass was confined in the oxide glass while remaining in a transparent glass state.
このフアイバ用母材の一部を加熱し、下に引き
出して、ボビンに巻き取ることにより、約100ｍ
長のガラスフアイバを得ることができた。コア径
は25μｍ、フアイバの外径は200μｍであつた。 By heating a part of this fiber base material, pulling it out, and winding it onto a bobbin, it is possible to
I was able to obtain a long glass fiber. The core diameter was 25 μm and the outer diameter of the fiber was 200 μm.
以上説明したように、Ge、Si、Ｐのハロゲン
化物（たとえばGeCl4、SiCl4等）をCVD法に用
いた場合、反応開始温度が高すぎて、カルコゲナ
イドガラスの成分が揮発し、ガラスの堆積が不可
能であつたが、本発明の方法のように、Ge、
Si、Ｐの水素化物、すなわちGeH4、SiH4、PH3
を用いることによつて、カルコゲナイドガラスの
揮発が活発化する温度以下で、CVD法によりガ
ラス薄膜をガラス管内部に堆積することができ
る。 As explained above, when halides of Ge, Si, and P (e.g., GeCl 4 , SiCl 4 , etc.) are used in the CVD method, the reaction initiation temperature is too high, and the components of chalcogenide glass volatilize, resulting in glass deposition. However, as in the method of the present invention, Ge,
Hydride of Si, P, i.e. GeH 4 , SiH 4 , PH 3
By using this method, a glass thin film can be deposited inside a glass tube by CVD at a temperature below which volatilization of chalcogenide glass becomes active.
さらに堆積したガラス膜を該ガラス管ととも
に、棒状に中実化し、ついで繊維状に線引きする
ことにより、ガラスフアイバを製造できる。 Furthermore, a glass fiber can be manufactured by solidifying the deposited glass film together with the glass tube into a rod shape and then drawing it into a fiber shape.
第１図はCVD法によるガラス薄膜作製装置の
構成図、第２図は輸送した原料の比（1/2S2Cl2／
GeH4）と加熱温度を変数としたときのガラス化範
囲を示す図、第３図は作製したガラス膜のＸ線回
折スペクトルを示す図である。
１……液体原料用容器、２……原料ガスボン
ベ、３……流量調節器、４……減圧弁、５……原
料輸送用パイプ、６……回転コネクタ、７……ガ
ラス管、８……バーナ、９……平行旋盤のチヤツ
ク。
Figure 1 is a configuration diagram of a glass thin film production apparatus using the CVD method, and Figure 2 shows the ratio of transported raw materials (1/2S 2 Cl 2 /
Fig. 3 is a diagram showing the vitrification range when GeH 4 ) and heating temperature are used as variables, and Fig. 3 is a diagram showing the X-ray diffraction spectrum of the produced glass film. DESCRIPTION OF SYMBOLS 1... Liquid raw material container, 2... Raw material gas cylinder, 3... Flow rate regulator, 4... Pressure reducing valve, 5... Raw material transport pipe, 6... Rotating connector, 7... Glass tube, 8... Burner, 9... Parallel lathe chuck.
Claims (1)
種以上と、気化した硫黄、セレン、テルルまたは
そのハロゲン化物の１種以上の組み合わせからな
るものを加熱分解することにより、気相からガラ
ス物質を形成した後、繊維状に線引きすることを
特徴とする赤外線透過ガラスフアイバの製造方
法。 ２ 特許請求の範囲第１項記載の赤外線透過ガラ
スフアイバの製造方法によつて、ガラス管の内側
に、ガラス膜を形成せしめ、該ガラス管とともに
棒状に中実化した繊維状に線引きすることによ
り、ガラスフアイバを製造することを特徴とする
赤外線透過ガラスフアイバの製造方法。[Claims] 1. Hydride of germanium, silicon, and phosphorus 1
A glass material is formed from a gas phase by thermally decomposing a combination of at least one species and one or more of vaporized sulfur, selenium, tellurium, or a halide thereof, and then drawn into a fiber shape. A method for manufacturing an infrared transmitting glass fiber. 2. By forming a glass film on the inside of a glass tube by the method for manufacturing an infrared transmitting glass fiber according to claim 1, and drawing it together with the glass tube into a solid rod-like fiber. , a method for producing an infrared transmitting glass fiber, the method comprising producing a glass fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56029628A JPS57145042A (en) | 1981-03-02 | 1981-03-02 | Production of glass fiber transmitting infrared rays |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56029628A JPS57145042A (en) | 1981-03-02 | 1981-03-02 | Production of glass fiber transmitting infrared rays |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57145042A JPS57145042A (en) | 1982-09-07 |
| JPS6240303B2 true JPS6240303B2 (en) | 1987-08-27 |
Family
ID=12281346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56029628A Granted JPS57145042A (en) | 1981-03-02 | 1981-03-02 | Production of glass fiber transmitting infrared rays |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57145042A (en) |
-
1981
- 1981-03-02 JP JP56029628A patent/JPS57145042A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57145042A (en) | 1982-09-07 |
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