JPH0667765B2 - Quartz glass manufacturing method and manufacturing apparatus - Google Patents
Quartz glass manufacturing method and manufacturing apparatusInfo
- Publication number
- JPH0667765B2 JPH0667765B2 JP19576485A JP19576485A JPH0667765B2 JP H0667765 B2 JPH0667765 B2 JP H0667765B2 JP 19576485 A JP19576485 A JP 19576485A JP 19576485 A JP19576485 A JP 19576485A JP H0667765 B2 JPH0667765 B2 JP H0667765B2
- Authority
- JP
- Japan
- Prior art keywords
- additive
- gas
- glass
- pressure
- quartz glass
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/01446—Thermal after-treatment of preforms, e.g. dehydrating, consolidating, sintering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
-
- 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
- C03B37/0128—Manufacture of preforms for drawing fibres or filaments starting from pulverulent glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/01446—Thermal after-treatment of preforms, e.g. dehydrating, consolidating, sintering
- C03B37/0146—Furnaces therefor, e.g. muffle tubes, furnace linings
-
- 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]
- C03B37/016—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 a liquid phase reaction process, e.g. through a gel phase
-
- 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
- C03B2201/12—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with fluorine
-
- 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
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/24—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with nitrogen, e.g. silicon oxy-nitride glasses
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Light Guides In General And Applications Therefor (AREA)
- Glass Melting And Manufacturing (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】 〔発明の技術分野〕 本発明は、石英ガラスの製造方法およびその製造装置に
関するものである。Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing quartz glass and an apparatus for producing the same.
F、N、Ne、Ar、Xe、Kr、Nd、Yb、Euなどの元素を含む石
英ガラスの製造方法としては、従来、下記のような方法
が知られていた。The following methods have been conventionally known as methods for producing silica glass containing elements such as F, N, Ne, Ar, Xe, Kr, Nd, Yb, and Eu.
(1)SiCl4などのガラス形成用原料化合物を火炎加水分解
などによって作製した多孔質ガラス体を常圧（１気圧）
下で該元素を含む気体ガスに曝しながら、焼結、透明ガ
ラス化する方法（いわゆる「気相添加法」）。(1) Atmospheric pressure (1 atm) of a porous glass body produced by flame hydrolysis of a raw material compound for glass formation such as SiCl 4
A method of sintering and vitrifying while exposing it to a gas containing the element below (so-called "gas phase addition method").
(2)火炎加水分解などによって作製した多孔質ガラス体
中に、該元素を含む液体を含浸させたのち、焼結、透明
ガラス化する方法（いわゆる「液浸法」）。(2) A method in which a porous glass body produced by flame hydrolysis or the like is impregnated with a liquid containing the element, followed by sintering and vitrification (so-called "immersion method").
(3)該添加元素を含む原料ガスを供給して多孔質ガラス
体を形成し、焼結、透明ガラス化する方法。(3) A method in which a raw material gas containing the additive element is supplied to form a porous glass body, which is then sintered and made into a transparent glass.
しかしながら、上述の方法はいずれも前記元素を１気圧
または１気圧以下で加熱焼結しているため、該元素の添
加量を充分大きくできず、また蒸気圧の高い元素は添加
できないという欠点があった。たとえばフッ素を添加し
た石英ガラスを気相添加法で製造する場合、１気圧の圧
力下で多孔質ガラス体をフッ素を含む雰囲気ガスに曝
し、1500〜1600℃に加熱焼結すると、比屈折率差△ｎに
して△ｎ＝−0.7％程度のフッ素添加石英ガラスは得ら
れるが、△ｎが−１％以上の石英ガラスをえることは極
めて困難であった。However, all of the above-mentioned methods have the drawback that the amount of addition of the element cannot be sufficiently increased and the element having a high vapor pressure cannot be added because the element is heated and sintered at 1 atm or less than 1 atm. It was For example, in the case of producing silica glass with fluorine added by the vapor phase addition method, if the porous glass body is exposed to an atmosphere gas containing fluorine under a pressure of 1 atm and heated and sintered at 1500 to 1600 ° C, the relative refractive index difference Fluorine-doped quartz glass having Δn of about Δn = −0.7% can be obtained, but it was extremely difficult to obtain quartz glass having Δn of −1% or more.
本発明は上述の点に鑑みなされたものであり、り、F、
N、Ne、Ar、Xe、Kr、Nd、Yb、Euなどの元素を適当量含
有させることのできる石英ガラスの製造方法およびその
方法を実施するための製造装置を提供することを目的と
する。The present invention has been made in view of the above points, and R, F,
An object of the present invention is to provide a method for producing silica glass that can contain an appropriate amount of elements such as N, Ne, Ar, Xe, Kr, Nd, Yb, and Eu, and an apparatus for implementing the method.
したがって、本発明による石英ガラスの製造方法は、多
孔質ガラス体を電気炉内で高温に加熱・焼結し透明ガラ
ス化する石英ガラスの製造方法において、前記焼結・透
明ガラス化は、１気圧を超える添加剤含有雰囲気ガス中
で行うことを特徴とするものである。Therefore, the method for producing quartz glass according to the present invention is the method for producing quartz glass in which a porous glass body is heated and sintered at a high temperature in an electric furnace to be transparent vitrified. It is characterized in that it is carried out in an additive-containing atmosphere gas exceeding the above range.
また本発明による石英ガラスの製造装置は、電気炉内に
設けられ、かつ多孔質ガラス体をその内部に設置可能な
密閉容器と、この密閉容器を加熱するための発熱体と、
前記電気炉内と密閉容器内の圧力をほぼ等しくなるよう
に調整でき、かつ前記容器内の添加物含有雰囲気ガスを
１気圧を超えた圧力に加圧可能な圧力調整装置とを有す
ることを特徴とするものである。Further, the quartz glass manufacturing apparatus according to the present invention is provided in an electric furnace, and a closed container in which a porous glass body can be installed, and a heating element for heating the closed container,
A pressure adjusting device capable of adjusting the pressure in the electric furnace and the pressure in the closed container to be substantially equal, and capable of pressurizing the additive-containing atmosphere gas in the container to a pressure exceeding 1 atm. It is what
本発明による石英ガラスの製造方法によれば、多孔質ガ
ラスを高温高圧下において添加剤を含む雰囲気ガスに曝
すので、所定量の添加剤を容易に添加可能であるという
利点がある。According to the method for producing quartz glass according to the present invention, since the porous glass is exposed to the atmospheric gas containing the additive under high temperature and high pressure, there is an advantage that a predetermined amount of the additive can be easily added.
また本発明による石英ガラスの製造装置によれば、１気
圧を超える添加剤雰囲気ガスの状態を達成でき、簡便
に、かつ良好に前記添加剤を添加した石英ガラスを製造
できるという利点がある。Further, according to the apparatus for producing quartz glass of the present invention, there is an advantage that the state of the additive atmosphere gas exceeding 1 atm can be achieved, and the quartz glass to which the additive is added can be easily and favorably produced.
本発明による石英ガラスの製造方法によれば、まず、多
孔質ガラス体を用意する。According to the method for producing quartz glass according to the present invention, first, a porous glass body is prepared.
このような多孔質ガラス体の製造方法は、本発明におい
て限定されるものではなく、従来の多孔質ガラス体を製
造する方法を有効に用いることができる。たとえばガラ
ス形成用原料化合物を火炎加水分解あるいは単に加水分
解（ゾル・ゲル法など）して製造した多孔質石英ガラス
であることができる。The method for producing such a porous glass body is not limited in the present invention, and the conventional method for producing a porous glass body can be effectively used. For example, it may be a porous quartz glass produced by flame hydrolysis or simply hydrolysis (sol-gel method, etc.) of a glass forming raw material compound.
次ぎにこのような多孔質ガラス体を、１気圧を超える添
加剤含有雰囲気ガス中に、高温下において曝して、前記
多孔質ガラスを焼結、透明ガラス化する。Next, such a porous glass body is exposed to an additive-containing atmosphere gas exceeding 1 atm at a high temperature to sinter the porous glass into a transparent glass.
一般に火炎加水分解あるいは単なる加水分解になどの方
法によって合成した多孔質ガラス体を添加剤を含む雰囲
気ガス中に曝しながら、焼結透明ガラス化して該添加剤
をガラス中に混入するメカニズム（気相添加法）は、次
のようなものであると考えられている。In general, a mechanism in which a porous transparent glass body synthesized by a method such as flame hydrolysis or simple hydrolysis is exposed to an atmospheric gas containing an additive to form a transparent transparent glass and the additive is mixed into the glass (gas phase The addition method) is considered to be as follows.
すなわち、炉内で添加剤を含む雰囲気ガス中に曝された
多孔質ガラス体は、炉内温度が上昇するにつれ、収縮
し、透明なガラス体になるが、この過程はつぎの４つの
工程に分けられる（文献、Ｓ．SUDO：他“Sintering pr
ocess of porous prefor ms made by VAD method for o
ptical fiber fabrication”Trams.IECE Japan.Vol.E6
3,No.10.p.731） (1)多孔質ガラス体の収縮、 (2)開孔状態、 (3)閉孔状態、 (4)閉孔の収縮。That is, the porous glass body exposed to the atmosphere gas containing the additive in the furnace shrinks into a transparent glass body as the temperature in the furnace rises. This process is divided into the following four steps. (Reference, S. SUDO: others “Sintering pr
ocess of porous prefor ms made by VAD method for o
ptical fiber fabrication ”Trams.IECE Japan.Vol.E6
(3) No.10.p.731) (1) Shrinkage of porous glass, (2) Open state, (3) Closed state, (4) Shrinkage of closed hole.
このような過程において、(1)、(2)の段階では、添加剤
を含んだ雰囲気ガスは多孔質ガラス体の空隙を自由に移
動しうるが、多孔質ガラス体がさらに収縮して(3)の閉
孔状態になると雰囲気ガスはガス体中の閉孔内に閉じ込
められることになる。さらに、温度が上昇して該閉孔が
収縮する段階で閉孔内の添加剤はガラス体中へ溶解する
こととなる。したがって、ガラス体中へ溶解あるいは混
入する添加剤の量は閉孔内に閉じ込められる雰囲気ガス
中の添加剤の量に依存することになる。In such a process, in the steps (1) and (2), the atmospheric gas containing the additive can move freely in the voids of the porous glass body, but the porous glass body further contracts (3 In the closed state of), the atmospheric gas is confined in the closed holes in the gas body. Further, at the stage where the temperature rises and the closed pores shrink, the additive in the closed pores dissolves in the glass body. Therefore, the amount of the additive dissolved or mixed in the glass body depends on the amount of the additive in the atmospheric gas trapped in the closed hole.
従来、上記気相添加は、１気圧の圧力下で行われていた
ため、閉孔中に閉じ込められる添加剤の量は制限され、
したがって最終的に得られるガラス体中の添加剤濃度を
高くすることは困難であった。Conventionally, the gas phase addition has been performed under a pressure of 1 atm, so that the amount of additive trapped in the closed pores is limited,
Therefore, it was difficult to increase the additive concentration in the finally obtained glass body.
本発明は、前述のような従来技術の問題点を解決するた
め、多孔質ガラス体を高温下において、１気圧を超える
添加剤含有ガス雰囲気中に曝し、焼結・透明ガラス化す
るものであり、この結果、閉孔内に閉じ込められる添加
剤を所望の量とすることができるとともに、最終的に得
られるガラス体の添加剤の量を増加できるものである。In order to solve the above-mentioned problems of the prior art, the present invention exposes a porous glass body to a gas atmosphere of an additive-containing gas exceeding 1 atm at a high temperature to sinter / transparent vitrify. As a result, the amount of the additive that is confined in the closed hole can be set to a desired amount, and the amount of the additive of the glass body finally obtained can be increased.
本発明によって多孔質ガラス体に添加される添加剤とし
ては、たとえば前述のF、N、Ne、Ar、Xe、Kr、Nd、Yb、
Euなどの元素を例として挙げることができる。前述の添
加剤は、単体あるいは高温中で分解し、単体を生じるよ
うな化合物の形で雰囲気ガスに添加される。As the additive added to the porous glass body according to the present invention, for example, the aforementioned F, N, Ne, Ar, Xe, Kr, Nd, Yb,
Elements such as Eu can be mentioned as an example. The above-mentioned additives are added to the atmospheric gas in the form of a simple substance or a compound that decomposes at high temperature to generate a simple substance.
この添加剤を含む雰囲気ガスの添加剤量は、たとえば光
学ガラスを製造する場合は、５〜９５％であるのが好ま
しい。５％未満であると、多孔質ガラス体に充分に添加
剤を添加できない虞があり、一方９５％を超えると、製
造された石英ガラスの光学特性に問題を生じる虞があ
る。The additive amount of the atmospheric gas containing this additive is preferably 5 to 95% in the case of producing optical glass, for example. If it is less than 5%, the additive may not be sufficiently added to the porous glass body, while if it exceeds 95%, there may be a problem in the optical properties of the manufactured quartz glass.
多孔質ガラス体は、このような添加剤を含む雰囲気ガス
中に高圧下で曝されるものであるが、このような圧力
は、多孔質ガラス体に添加される添加剤の量、種類、多
孔質ガラス体の嵩密度などにによって変化し、種々選択
可能である。しかしながら、通常圧力は２〜８気圧であ
るのが好ましい。２気圧未満であると、通常の気相添加
とあまり変化がなくなり、８気圧を超えると、光学ガラ
スの特性損なう虞を生じる。The porous glass body is exposed to an atmospheric gas containing such an additive under high pressure, but such a pressure causes the amount, kind, and porosity of the additive added to the porous glass body. It varies depending on the bulk density of the vitreous body and can be selected in various ways. However, it is generally preferred that the pressure is between 2 and 8 atmospheres. If it is less than 2 atm, there is not much change from the usual gas phase addition, and if it exceeds 8 atm, the characteristics of the optical glass may be impaired.
また、前記多孔質ガラスの嵩密度は、好ましくは0.1〜
1.5g/cm3であるのがよい。前記嵩密度が小さい程、基本
的に添加剤量は多くなるが、嵩密度が0.1g/cm3を超える
と、多孔質ガラスの形状を保持するのが困難になる。ま
た、1.5g/cm3を超えると、前記多孔質ガラス体中への添
加剤の添加が極めて困難になるからである。The bulk density of the porous glass is preferably 0.1 to
It should be 1.5 g / cm 3 . Basically, the smaller the bulk density, the larger the amount of the additive, but if the bulk density exceeds 0.1 g / cm 3 , it becomes difficult to maintain the shape of the porous glass. On the other hand, if it exceeds 1.5 g / cm 3 , it becomes extremely difficult to add the additive to the porous glass body.
次ぎに本発明の石英ガラスの製造装置について説明す
る。Next, a quartz glass manufacturing apparatus of the present invention will be described.
第１図は本発明による石英ガラスの製造装置の一実施例
の断面図であり、図中、１は炉体、２は断熱材、３は発
熱体、４は石英ガラスの製などの密閉容器、５は多孔質
ガラス体、６は添加物ガス導入管、７は添加物ガス圧力
調整器、８、９は雰囲気ガス導入管、１０は雰囲気ガス
圧力調整器、１１、１２はリークバルブである。FIG. 1 is a sectional view of an embodiment of a quartz glass manufacturing apparatus according to the present invention, in which 1 is a furnace body, 2 is a heat insulating material, 3 is a heating element, and 4 is a closed container made of quartz glass or the like. 5 is a porous glass body, 6 is an additive gas introducing pipe, 7 is an additive gas pressure regulator, 8 and 9 are atmospheric gas introducing pipes, 10 is an atmospheric gas pressure regulator, and 11 and 12 are leak valves. .
この第１図より明らかなように、本発明による石英ガラ
スの製造装置においては、密閉された炉体１内に断熱材
２が備えられており、炉体１内の温度が一定に保持され
るようになっている。そして前記断熱材２の内側には、
この炉体１内を加熱するための発熱体３が設けられてお
り、この発熱体３に囲まれた位置に密閉容器４が設置さ
れている。この密閉容器４は、その内部に多孔質ガラス
体５が設置可能になっている。さらに、前記炉体１の上
部には添加物（あるいは添加物を含む化合物）を密閉容
器４内に供給するための添加物ガス導入管６が設けら
れ、前記添加物ガス導入管６は添加物ガス圧力調整器７
を介し、前記密閉容器４内に添加剤ガスを導入可能にな
っている。このガス導入管６は雰囲気ガス導入管８と連
通しており、この雰囲気ガス導入管８はガス導入管９を
介して雰囲気ガス調整器１０に接続している。このため
前記密閉容器４内に雰囲気ガスと添加剤ガスの混合ガ
ス、すなわち添加剤含有ガスを導入可能になる。さら
に、ガス導入管９は密閉容器４の周囲の炉体１内部にも
連通しているため、前記炉体１と密閉容器４はほぼ等し
い圧力になる。As is clear from FIG. 1, in the apparatus for producing quartz glass according to the present invention, the heat insulating material 2 is provided in the closed furnace body 1, and the temperature in the furnace body 1 is kept constant. It is like this. And inside the heat insulating material 2,
A heating element 3 for heating the inside of the furnace body 1 is provided, and a closed container 4 is installed at a position surrounded by the heating element 3. The hermetic container 4 can have a porous glass body 5 installed therein. Further, an additive gas introducing pipe 6 for supplying an additive (or a compound containing the additive) into the closed container 4 is provided on the upper part of the furnace body 1, and the additive gas introducing pipe 6 is the additive. Gas pressure regulator 7
The additive gas can be introduced into the closed container 4 via the. The gas introducing pipe 6 communicates with the atmospheric gas introducing pipe 8, and the atmospheric gas introducing pipe 8 is connected to the atmospheric gas regulator 10 via the gas introducing pipe 9. Therefore, it becomes possible to introduce the mixed gas of the atmospheric gas and the additive gas, that is, the additive-containing gas into the closed container 4. Further, since the gas introduction pipe 9 is also communicated with the inside of the furnace body 1 around the closed container 4, the furnace body 1 and the closed container 4 have substantially the same pressure.
さらに炉体１の下部および密閉容器４の下部にはそれぞ
れ、リークバルブ１１および１２が備えられている。Further, leak valves 11 and 12 are provided in the lower portion of the furnace body 1 and the lower portion of the closed container 4, respectively.
前記添加剤ガス圧力調整器７および雰囲気ガス圧力調整
器１０は前記密閉管４および炉体１内に導入する添加剤
ガスおよび雰囲気ガスの量および混合比などを制御し、
前記密閉容器４内および炉体１内の圧力を調整可能にな
っている。また、この圧力の制御の微調整は前記リーク
バルブ１１および１２によって行われる。The additive gas pressure regulator 7 and the atmospheric gas pressure regulator 10 control the amounts and mixing ratios of the additive gas and the atmospheric gas introduced into the closed tube 4 and the furnace body 1,
The pressure inside the closed container 4 and inside the furnace body 1 can be adjusted. The leak valves 11 and 12 finely adjust the pressure control.
このような本発明による石英ガラスの製造装置によれ
ば、まず、密閉容器４内に、たとえばＶＡＤ法で製造し
た多孔質ガラス体５を設置し、該炉体１内および該密閉
容器４内に、たとえばHeガス、およびSF6ガスを、それ
ぞれ圧力調整器１０、７によって圧力を調整しながら導
入する。この際、密閉容器４内および炉体１内の圧力
は、リークバルブ１２および１１によってガスを排出す
るもとにより微調整される。また、密閉容器４と炉体１
内の圧力は、ガス導入管８によって連通しているので、
つねに等しい圧力になっている。According to such a quartz glass manufacturing apparatus of the present invention, first, the porous glass body 5 manufactured by, for example, the VAD method is installed in the closed container 4, and the inside of the furnace body 1 and the closed container 4 are installed. , He gas, and SF 6 gas, for example, are introduced while adjusting the pressure with the pressure regulators 10 and 7, respectively. At this time, the pressures inside the closed container 4 and the furnace body 1 are finely adjusted by discharging gas through the leak valves 12 and 11. Further, the closed container 4 and the furnace body 1
Since the internal pressure is communicated by the gas introduction pipe 8,
The pressure is always equal.
このような状態において、この密閉容器４の廻りに設け
られた発熱体３に電力を供給し、1500〜1600℃に加熱し
て、前記多孔質ガス体５を焼結・透明ガラス化するもの
である。In such a state, electric power is supplied to the heating element 3 provided around the closed container 4 to heat it to 1500 to 1600 ° C. to sinter the porous gas body 5 into transparent glass. is there.
実施例１ 第１図に示す製造装置を用いて、石英ガラスを製造し
た。Example 1 Quartz glass was manufactured using the manufacturing apparatus shown in FIG.
Heガスを圧力調整器１０によって、2.0Kg/cm2の圧力に
調整し、ガス導入管８および９より炉体１内および密閉
容器４内にそれぞれ、前記Heガスを導入した。またSF6
ガスを圧力調整器７によって、2.1Kg/cm2の圧力に調整
し、ガス導入管６より密閉容器４内に導入した。多孔質
ガラス体５としてはＶＡＤ法によって製造したSiO2ガラ
スのみよりなる多孔質ガラス体５（嵩密度0.2g/cm3）を
使用した。The He gas was adjusted to a pressure of 2.0 Kg / cm 2 by the pressure adjuster 10, and the He gas was introduced into the furnace body 1 and the closed container 4 through the gas introduction pipes 8 and 9, respectively. Also SF 6
The gas was adjusted to a pressure of 2.1 Kg / cm 2 by the pressure adjuster 7 and introduced into the closed container 4 through the gas introduction pipe 6. As the porous glass body 5, a porous glass body 5 (bulk density 0.2 g / cm 3 ) made of only SiO 2 glass manufactured by the VAD method was used.
そこで、発熱体３に電力を供給し、毎時100℃の割合で
昇温し、前記多孔質ガラス体５を圧力2.0Kg/cm2のHe−S
F6混合ガス（組成比；He：25％、SF6：75％）雰囲気下
で焼結・透明ガラス下した。Therefore, electric power is supplied to the heating element 3 to raise the temperature at a rate of 100 ° C./hour, and the porous glass body 5 is heated to a pressure of 2.0 kg / cm 2 of He—S.
Sintering and transparent glass were performed in an atmosphere of F 6 mixed gas (composition ratio; He: 25%, SF 6 : 75%).
このようにして製造された透明ガラス体の屈折率ｎ１を
純粋なSiO2ガラスの屈折率ｎｏとの比で測定した結果、
比屈折率差（Δｎ＝ｎ１／ｎｏ−１）は−1.0％であっ
た。また、上記条件において、混合ガスの圧力を3.0Kg/
cm3としたときは、Δｎは−1.5％となった。しかしなが
ら、上記条件において、混合ガラスの圧力を1.0Kg/cm2
としたときの透明ガラス体の屈折率はΔｎ＝0.6％であ
り、本発明の方法によって良好にFが添加されているこ
とが確認された。As a result of measuring the refractive index n 1 of the transparent glass body manufactured in this way with the refractive index n o of pure SiO 2 glass,
The relative refractive index difference (Δn = n 1 / n o −1) was −1.0%. Further, under the above conditions, the pressure of the mixed gas is 3.0 kg /
When it was defined as cm 3 , Δn was −1.5%. However, under the above conditions, the pressure of the mixed glass was 1.0 kg / cm 2
The refractive index of the transparent glass body was Δn = 0.6%, and it was confirmed that F was satisfactorily added by the method of the present invention.
また前述のように作製された本発明による石英ガラスを
クラッド材として用いて光ファイバを製造したところ、
良好な特性の光ファイバが得られた。Further, when an optical fiber was manufactured by using the silica glass according to the present invention manufactured as described above as a clad material,
An optical fiber with good characteristics was obtained.
実施例２ 前記第１図に示した装置において、雰囲気ガスの添加剤
ガスとしてSF6の変わりにNH3を使用し、さらに混合ガス
圧力を3.0Kg/cm3としたとき、Δｎは1.0％となった。さ
らに、、このように製造したNドープガラスをコアガラ
スとし、SiO2ガラスをクラッドガラスとして光ファイバ
を作製した結果、良好な光伝送特性を示した。Example 2 In the apparatus shown in FIG. 1, when NH 3 was used instead of SF 6 as the additive gas of the atmosphere gas and the mixed gas pressure was 3.0 Kg / cm 3 , Δn was 1.0%. became. Furthermore, as a result of producing an optical fiber using the N-doped glass thus produced as a core glass and SiO 2 glass as a clad glass, good optical transmission characteristics were shown.
また、加水分解反応によってゾル・ゲル法で作製した多
孔質ガラス体を使用した場合も同様な結果が期待でき
る。この場合F等の添加量は、使用する多孔質ガラス体
の嵩密度に多く依存し、嵩密度が小さい程添加量が多く
なる傾向を示した。Similar results can be expected when a porous glass body produced by a sol-gel method by a hydrolysis reaction is used. In this case, the addition amount of F or the like depends largely on the bulk density of the porous glass body used, and the addition amount tends to increase as the bulk density decreases.
また、Ｎ、Ｆのほか、Nb、Euなどのハロゲン化物を雰囲
気ガス中に混合し、実施例１と同様の操作によってNb、
Euなどを含む透明ガラス体が得られた。In addition to N and F, halides such as Nb and Eu were mixed in the atmosphere gas, and Nb and Eu were mixed by the same operation as in Example 1.
A transparent glass body containing Eu etc. was obtained.
以上説明したように本発明による石英ガラスの製造方法
によれは、多孔質ガラスを１気圧を超える圧力下におい
て、添加剤を含む雰囲気ガスに曝し、焼結・透明ガラス
化するので、従来においては微小量しか添加できなかっ
たF、Nなどの添加剤の添加量を高濃度に添加できるとい
う利点がある。As described above, according to the method for producing quartz glass according to the present invention, the porous glass is exposed to the atmospheric gas containing the additive under a pressure exceeding 1 atm to sinter and become transparent vitrification. There is an advantage that the additive amount of F, N, etc., which can be added only in a minute amount, can be added at a high concentration.
特に、Fなどを高濃度に添加した透明ガラス体の場合、
光ファイバクラッド層として使用すれば、良好な特性の
光ファイバを得られるという利点もある。Especially in the case of a transparent glass body with a high concentration of F etc. added,
When used as an optical fiber clad layer, there is also an advantage that an optical fiber having good characteristics can be obtained.
さらに本発明による製造装置によれば、前記方法を容易
に、かつ簡便に実施できるばかりでなく、多孔質ガラス
体を、たとえば石英ガラス製の密閉容器内に密閉してい
るため、意図したに不純物の混入を防止できるととも
に、前記石英ガラス製の密閉容器の内外が同圧に保持さ
れているため、加熱によって石英ガラスが軟化しても前
記ガラスが変形することがなく、良好に１気圧以上の雰
囲気ガスを導入できるという利点がある。Further, according to the manufacturing apparatus of the present invention, not only can the method be carried out easily and simply, but also the porous glass body is sealed in a sealed container made of, for example, quartz glass. And the inside and outside of the quartz glass closed container are kept at the same pressure, the quartz glass is not deformed even if it is softened by heating. There is an advantage that atmospheric gas can be introduced.
第１図は本発明による石英ガラスの製造装置の一実施例
の断面図である。 １…炉体、２…断熱材、３…発熱体、４…密閉容器、５
…多孔質ガラス体、６…添加物ガス導入管、７…添加物
ガス圧力調整器、８、９…雰囲気ガス導入管、１０…雰
囲気ガス圧力調整器、１１、１２…リークバルブ。FIG. 1 is a sectional view of an embodiment of a quartz glass manufacturing apparatus according to the present invention. 1 ... Furnace body, 2 ... Insulating material, 3 ... Heating element, 4 ... Closed container, 5
... Porous glass body, 6 ... Additive gas introduction pipe, 7 ... Additive gas pressure regulator, 8, 9 ... Atmosphere gas introduction pipe, 10 ... Atmosphere gas pressure regulator, 11, 12 ... Leak valve.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 塙 文明 茨城県那珂郡東海村大字白方字白根162番 地 日本電信電話株式会社茨城電気通信研 究所内 (72)発明者 大森 保治 茨城県那珂郡東海村大字白方字白根162番 地 日本電信電話株式会社茨城電気通信研 究所内 (56)参考文献 特開 昭62−27342（ＪＰ，Ａ) 特開 昭60−255638（ＪＰ，Ａ) 特開 昭59−3032（ＪＰ，Ａ) 実開 昭57−116733（ＪＰ，Ｕ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Fumiaki Hanawa Tokai-mura, Naka-gun, Ibaraki Prefecture 162 Shirahoji, Shirane, Nippon Telegraph and Telephone Corporation, Ibaraki Telecommunications Research Institute (72) Inventor Houji Omori Naka-gun, Ibaraki Prefecture Tokai-mura, Oita, Shirahoji 162, Shirane, Nippon Telegraph and Telephone Corporation, Ibaraki Research Institute of Telecommunications (56) Reference JP-A-62-27342 (JP, A) JP-A-60-255638 (JP, A) JP Sho 59-3032 (JP, A) Actually opened Sho 57-116733 (JP, U)
Claims (2)
焼結し透明ガラス化する石英ガラスの製造方法におい
て、前記焼結・透明ガラス化は、１気圧を超える添加剤
含有雰囲気ガス中で行うことを特徴とする石英ガラスの
製造方法。1. A porous glass body is heated to a high temperature in an electric furnace.
A method for producing quartz glass, which comprises sintering and vitrifying into transparent vitreous, wherein the sintering and vitrifying is performed in an atmosphere gas containing an additive exceeding 1 atm.
をその内部に設置可能な密閉容器と、この密閉容器を加
熱するための発熱体と、前記電気炉内と密閉容器内の圧
力をほぼ等しくなるように調整でき、かつ前記容器内の
添加物含有雰囲気ガスを１気圧を超えた圧力に加圧可能
な圧力調整装置とを有することを特徴とする石英ガラス
の製造装置。2. An airtight container provided in an electric furnace, in which a porous glass body can be installed, a heating element for heating the airtight container, and pressures in the electric furnace and the airtight container. And a pressure adjusting device capable of pressurizing the additive-containing atmosphere gas in the container to a pressure exceeding 1 atm, the apparatus for producing quartz glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19576485A JPH0667765B2 (en) | 1985-09-06 | 1985-09-06 | Quartz glass manufacturing method and manufacturing apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19576485A JPH0667765B2 (en) | 1985-09-06 | 1985-09-06 | Quartz glass manufacturing method and manufacturing apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6259535A JPS6259535A (en) | 1987-03-16 |
| JPH0667765B2 true JPH0667765B2 (en) | 1994-08-31 |
Family
ID=16346568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19576485A Expired - Lifetime JPH0667765B2 (en) | 1985-09-06 | 1985-09-06 | Quartz glass manufacturing method and manufacturing apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0667765B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2582592B2 (en) * | 1987-10-06 | 1997-02-19 | 三菱電線工業株式会社 | Method for manufacturing base material for optical functional element |
| JP2830617B2 (en) * | 1992-06-17 | 1998-12-02 | 日立電線株式会社 | Rare earth element-doped multi-core fiber and method for producing the same |
| EP3205630B1 (en) * | 2016-02-12 | 2020-01-01 | Heraeus Quarzglas GmbH & Co. KG | Diffuser material made of synthetically produced quartz glass, method for preparing a shaped body made fully or partially from same |
| US11554981B2 (en) | 2019-06-11 | 2023-01-17 | Corning Incorporated | Apparatuses and methods for processing optical fiber preforms |
-
1985
- 1985-09-06 JP JP19576485A patent/JPH0667765B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6259535A (en) | 1987-03-16 |
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