JPH02229726A - Production of glass - Google Patents
Production of glassInfo
- Publication number
- JPH02229726A JPH02229726A JP5011689A JP5011689A JPH02229726A JP H02229726 A JPH02229726 A JP H02229726A JP 5011689 A JP5011689 A JP 5011689A JP 5011689 A JP5011689 A JP 5011689A JP H02229726 A JPH02229726 A JP H02229726A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- porous body
- ions
- bulk density
- solvent
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000012808 vapor phase Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000000567 combustion gas Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 14
- 230000000996 additive effect Effects 0.000 abstract description 8
- 239000005373 porous glass Substances 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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]
- C03B37/01413—Reactant delivery systems
- C03B37/01433—Reactant delivery systems for delivering and depositing additional reactants as liquids or solutions, e.g. for solution doping of the porous glass preform
-
- 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
- C03B19/1415—Reactant delivery systems
- C03B19/1438—Reactant delivery systems for delivering and depositing additional reactants as liquids or solutions, e.g. solution doping of the article or deposit
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
- C03B2201/10—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/28—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/32—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は各種添加物を含む石英ガラスの製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing quartz glass containing various additives.
現在、光ファイバのブリフォームを作成する方法として
は、ＶＡＤ法を始めとする、Ｓｉ Ｃ １４等のガラス
原料ガスを火炎中に通して生成するガラス微粒子をター
ゲット上に堆積させ、得られたガラス多孔質体を焼結し
ガラス塊を得る、という方法が主流になっている。これ
は高純度の多孔質ガラスを比較的安価に得られる優れた
方法である。Currently, methods for creating optical fiber preforms include the VAD method, in which a glass raw material gas such as SiC 14 is passed through a flame and glass fine particles are deposited on a target. The mainstream method is to sinter a porous body to obtain a glass lump. This is an excellent method for obtaining high-purity porous glass at a relatively low cost.
従来のこの種の気相合成法では、添加物として使える物
質がガス化できるものに限られる。また、気相反応にお
いて酸化物粒子が生成する反応は、元素の種類によって
限られている。さらにその添加量も気相反応の化学平衡
によって限定されているため、大量に添加しようとして
も、反応により不可能な場合が多い。そのため、特定の
元素を所望の添加量含ませたガラスを合成することがで
きないという欠点があった。In this type of conventional gas phase synthesis method, substances that can be used as additives are limited to those that can be gasified. In addition, reactions that produce oxide particles in gas phase reactions are limited depending on the type of element. Furthermore, the amount of addition is limited by the chemical equilibrium of the gas phase reaction, so even if you try to add a large amount, it is often impossible due to the reaction. Therefore, there was a drawback that it was not possible to synthesize a glass containing a desired amount of a specific element.
本発明の目的は、このような従来法の欠点を解消し、希
望の添加物を大量にガラス内に添加できるガラスの製造
方法を提供することにある。An object of the present invention is to provide a method for producing glass that eliminates the drawbacks of the conventional methods and allows a large amount of desired additives to be added into the glass.
本発明は、気相合成法によりガラスを製造する方法にお
いて、気相法により得られたガラス多孔質体にＢ． Ｇ
ｅ， Ｐ， Ｓｂ， Ｉｖ及びＴｉよりなる群から選
ばれる元素のイオン又は該元素の酸化物イオンのｌ以上
と溶媒からなる溶液を含浸させ、しかる後に乾燥せしめ
、次いで焼結することを特徴とするガラスの製造方法で
ある。The present invention provides a method for producing glass by vapor phase synthesis, in which a glass porous body obtained by vapor phase synthesis contains B. G
It is characterized by impregnating it with a solution consisting of a solvent and ions of an element selected from the group consisting of e, P, Sb, Iv, and Ti or at least 1 oxide ion of the element, followed by drying, and then sintering. This is a method for manufacturing glass.
本発明の特に好ましい実施態様としては、上記ガラス多
孔質体のカサ密度が０．３〜ｌ． Ｏ ｇ／ｃｉであり
、該ガラス多孔質体に表面張力が１ ０ ０ ｄｙｎ／
ｃｍ以下で、沸点が３０〜１５０℃である上記元素のイ
オン又は該元素の酸化物イオンの１以上を含有する溶液
を含浸させることを特徴とする上記ガラスの製造方法が
挙げられ、さらには上記ガラス多孔質体としてカサ密度
の分布が、その最大と最小の差が０． ２ ｇ／ｃｍ３
より小さいものを用いること、上記乾燥を４０〜１６０
℃の温度範囲で行なうことが好ましい。In a particularly preferred embodiment of the present invention, the glass porous body has a bulk density of 0.3 to 1.0 l. O g/ci, and the surface tension of the glass porous body is 100 dyn/
cm or less and a boiling point of 30 to 150° C. A method for manufacturing the above-mentioned glass is mentioned, which is characterized by impregnating the glass with a solution containing one or more of the ions of the above-mentioned elements or the oxide ions of the above-mentioned elements having a boiling point of 30 to 150° C. As a glass porous material, the bulk density distribution has a difference between the maximum and minimum of 0. 2 g/cm3
Use a smaller one, dry above 40~160
Preferably, the reaction is carried out in the temperature range of .degree.
本発明の上記ガラス多孔質体としては、ガラス原料ガス
及び燃焼ガスをガラス合成用バーナに投入し、生成した
ガラス粒子を出発材の周囲に堆積させたものを用いるこ
とが、高純度でかつカサ密度分布が均一な点で特に好ま
しい。As the above-mentioned glass porous body of the present invention, it is preferable to use one obtained by introducing frit gas and combustion gas into a glass synthesis burner and depositing the generated glass particles around the starting material. Particularly preferred in terms of uniform density distribution.
本発明者等は、気相法により合成したガラス多孔質体が
大量の液体を吸収できることに着目し、該ガラス多孔質
体に吸収される液体（溶媒）に添加物を加えておくこと
により、該添加物を容易にガラス多孔質体内に導入する
ことができると考えついた。その後の乾燥工程において
、上記溶媒はガラス多孔質体よ−り気化し、添加物元素
のみが多孔質体内に均一に残留する。このとき、気相法
により作製したガラス多孔質体の細孔はほぼ均一に分布
しているため、該ガラス多孔質内に均一に添加物、を導
入することができる。このようにして得た含浸多孔質体
を焼結する工程において、ガラス粒子が融合することに
よりガラス体となるが、このとき添加物はそのままガラ
ス体内に導入される。The present inventors focused on the fact that a glass porous body synthesized by a gas phase method can absorb a large amount of liquid, and by adding additives to the liquid (solvent) absorbed by the glass porous body, The inventors have come up with the idea that the additive can be easily introduced into a porous glass body. In the subsequent drying step, the solvent is vaporized from the glass porous body, and only the additive elements remain uniformly within the porous body. At this time, since the pores of the glass porous body produced by the vapor phase method are distributed almost uniformly, the additive can be uniformly introduced into the glass porous body. In the step of sintering the impregnated porous body thus obtained, the glass particles are fused to form a glass body, and at this time, the additives are directly introduced into the glass body.
本発明に用いる多孔質体としては、ガラス原料ガスを燃
焼ガス．助燃性ガス等とともにバーナーに導入して、該
バーナーの火炎中で酸化反応または火炎加水分解反応さ
せることにより生成するガラス微粒子を出発材先端また
は外周に堆積させてガラス微粒子堆積体（多孔質体）を
製造する、所謂気相法により合成さたものを用いる。ガ
ラス原料ガスとしては、例えばＳｉ Ｃ ｅ＊． Ｓｉ
Ｈ Ｃ ｌ２． Ｓｉ ｘｃｌ等を、燃焼ガスとして
は例えば市，炭化水素等を、助燃性ガスとしては缶等を
用いることができる。As the porous body used in the present invention, frit gas is used as combustion gas. A glass particle deposit (porous body) is produced by introducing glass particles into a burner together with a combustion supporting gas and causing an oxidation reaction or flame hydrolysis reaction in the flame of the burner, and depositing them on the tip or outer periphery of the starting material. A product synthesized by the so-called gas phase method is used. As the glass raw material gas, for example, SiC e*. Si
HCl2. For example, Si xcl or the like can be used as the combustion gas, carbon dioxide, hydrocarbons, etc. can be used as the combustion gas, and cans or the like can be used as the combustion auxiliary gas.
本発明に係るガラス多孔質体は、そのカサ密度が０．３
〜１． ０ ｇ／ｃｊ （［気孔率；１−カサ密度／１
２］であるから、気孔率では８６．４〜５４．５％）の
範囲にあるものが好ましい。カサ密度が小さい方が吸収
される液体量が多《なるが、０． ３ ｇ／ｃｒｊ未満
では小さすぎて割れ易く不都合であり、Ｉ． Ｄ ｇ／
ａｄを越えると液体が吸収されず、本発明の目的を達成
するには不適である。さらに、該ガラス多孔質体のカサ
密度の分布は均一性の点で、その最大と最小の差が０．
２ ｇ／ｃｒｌ以下であることが望ましい。カサ密度
が不均一な場合には溶液吸収量が不均一となり添加物１
度にムラが生じる。そのためにカサ密度は均一なものほ
ど好ましい。気相法によるガラス多孔質体は他の方法に
よるものよりも均一ではあるが、その均一性の許容範囲
として上下限値の差が０． ２ ｇ／ｃｔｌ以下が好ま
しいのである。The glass porous body according to the present invention has a bulk density of 0.3
~1. 0 g/cj ([porosity; 1-bulk density/1
2], the porosity is preferably in the range of 86.4 to 54.5%). The smaller the bulk density, the more liquid will be absorbed, but 0. If it is less than 3 g/crj, it is too small and easily breaks, which is inconvenient. D g/
If it exceeds ad, liquid will not be absorbed and it will be unsuitable for achieving the purpose of the present invention. Furthermore, in terms of uniformity, the bulk density distribution of the glass porous body has a difference between the maximum and minimum of 0.
It is desirable that it be 2 g/crl or less. If the bulk density is uneven, the amount of solution absorbed will be uneven and additive 1
Unevenness occurs from time to time. For this reason, it is preferable that the bulk density be uniform. Although the glass porous material produced by the vapor phase method is more uniform than those produced by other methods, the difference between the upper and lower limits is 0.000% as an acceptable range for uniformity. 2 g/ctl or less is preferable.
本発明において該ガラス多孔質体に添加可能な元素とし
ては、ガラス化の際にそれを妨げたり、結晶化するもの
であってはならず、Ｂ．Ｇｅ，Ｐ，Ｓｂ． Ａ７！及び
Ｔｉよりなる群から選ばれる１以上である。これらの元
素は、そのイオン又は該元素の酸化物のイオンを溶媒で
ある液体中に含ませた溶液として上記ガラス多孔質体に
含浸させる。これらの元素イオン又は該元素の酸化物イ
オンは、その後の焼結によりすべて当該元素の酸化物と
なってガラス中に存在するが、Ｂ． Ｇｅ． Ｐ，
Ｓｂはいずれもガラス構造を形成できる酸化物となり、
またＭ及びＴｉはガラス構造を形成するための中間酸化
物となることができる。In the present invention, the elements that can be added to the glass porous body must not interfere with vitrification or cause crystallization, and B. Ge, P, Sb. A7! and one or more selected from the group consisting of Ti. These elements are impregnated into the glass porous body as a solution in which ions or ions of oxides of the elements are contained in a liquid that is a solvent. All of these element ions or oxide ions of the elements become oxides of the elements through subsequent sintering and are present in the glass. Ge. P,
Sb becomes an oxide that can form a glass structure,
Furthermore, M and Ti can serve as intermediate oxides for forming a glass structure.
溶媒としての液体は、添加元素の溶解度の大きいものが
好ましく、また、容易に気化するように沸点が低いもの
がよい。このような液体としては、例えばメタノール，
エタノール，プロパノール等のアルコールやアセトン、
水等が挙げられる。上記の元素のイオン又は該元素の酸
化物のイオンを含む溶液の沸点範囲は３０〜１５０℃の
ものが特に好ましい。The liquid used as the solvent preferably has a high solubility for the added element, and has a low boiling point so that it can be easily vaporized. Examples of such liquids include methanol,
Alcohols such as ethanol and propanol, acetone,
Examples include water. The boiling point range of the solution containing ions of the above elements or ions of oxides of the elements is particularly preferably from 30 to 150°C.
液体がガラス多孔質体の細孔に浸入すると毛細萱力が生
じ、多孔質体の粒子間結合力が弱い場合、ガラス多孔質
体が割れてしまう。この毛細管力は液体の表面張力に比
例するため、表面張力の小さい液体が望ましい。気相合
成法により作製したガラス多孔質体を用いる場合は、含
浸させる上記の元素のイオン又は該元素の酸化物のイオ
ンを含む溶液の表面張力は、ｌ ０ ０ ｄｙｎ／ｃｍ
以下である必要がある。この点で好ましい溶媒はアルコ
ールである。ガラス多孔質体の割れ（クラック発生）は
前記のようにカサ密度に関係するので、上記イオン含有
溶液（含浸溶液）の表面張力が１．０ ０ ｄｙｎ／ｃ
ｍ以下で、しかもガラス多孔質のカサ密度が０．３〜１
． ０ ｇ／ｃｊであるようにすることが好ましい。本
発明等の実験によれば、該ガラス多孔質にはその空孔体
積に対して１００％までの溶液を含浸することができる
。When a liquid enters the pores of a porous glass body, capillary force is generated, and if the bonding force between particles of the porous body is weak, the porous glass body will break. Since this capillary force is proportional to the surface tension of the liquid, a liquid with low surface tension is desirable. When using a glass porous body produced by a vapor phase synthesis method, the surface tension of a solution containing ions of the above elements or ions of oxides of the elements to be impregnated is l 0 0 dyn/cm.
Must be below. A preferred solvent in this regard is an alcohol. As mentioned above, the cracking of the glass porous material is related to the bulk density, so if the surface tension of the ion-containing solution (impregnating solution) is 1.00 dyn/c.
m or less, and the bulk density of the glass porous is 0.3 to 1
．． It is preferable to set it to 0 g/cj. According to the experiments of the present invention, the glass porous material can be impregnated with a solution up to 100% of the pore volume.
該含浸多孔質体を４０〜１６０℃の温度範囲で十分乾燥
させ、該乾燥多孔質体を焼結させることにより、添加物
含有ガラスを得る。発泡のないガラスを得るためは、十
分溶媒を蒸発させた後に焼結することが必要である。焼
結条件は、この種の気相法によるガラス多孔質体を焼結
する通常の条件で行うことができる。The impregnated porous body is sufficiently dried at a temperature range of 40 to 160° C., and the dried porous body is sintered to obtain an additive-containing glass. In order to obtain a glass without foaming, it is necessary to sinter the glass after sufficiently evaporating the solvent. The sintering conditions can be the usual conditions for sintering a glass porous body by this type of vapor phase method.
実施例
本発明によるホウ素添加ンリカガラスの作成について、
実施例に基づき説明する。ガラス多孔質体として、ガラ
ス原料Ｓｉ Ｃ ｅ４を酸水素火炎中で加水分解させ、
生成したシリカ粒子を堆積させたものを用いた。カサ密
度は平均０． ５ ｇ／ａｌである。含浸させる溶液は
メタノールにホウ酸を溶解させたものである゛。メタノ
ールは表面張力が２ ２． ６ ｄｙｎ／ｃｉ＋と小さ
く、沸点も６５℃と低いが、ホウ酸の溶解度は２３［ｒ
／１００ｇメタノール（２９℃）と大きいため、ホウ酸
の溶媒としては、最適である。Example Regarding the preparation of boron-doped phosphor glass according to the present invention,
This will be explained based on an example. As a glass porous body, glass raw material SiC e4 is hydrolyzed in an oxyhydrogen flame,
A deposit of generated silica particles was used. The average bulk density is 0. 5 g/al. The impregnating solution is boric acid dissolved in methanol. Methanol has a surface tension of 2 2. Although it is small at 6 dyn/ci+ and has a low boiling point of 65°C, the solubility of boric acid is 23 [r
/100gmethanol (29°C), making it the most suitable solvent for boric acid.
メタノール１５０ｇにホウ酸３０ｇを溶解させた溶液に
多孔質体１００ｇを漬けた。液の吸収は１０分間ほどで
飽和した。この時の多孔質体の重量は２４６ｇであった
。この多孔質体を２日間室温で放置後、１００℃の雰囲
気で５時間乾燥した。100 g of the porous material was immersed in a solution of 30 g of boric acid dissolved in 150 g of methanol. The liquid absorption reached saturation in about 10 minutes. The weight of the porous body at this time was 246 g. This porous body was left at room temperature for 2 days and then dried in an atmosphere at 100° C. for 5 hours.
乾燥後の重量は１２４ｇであった。この含浸多孔質体を
Ｈｅ雰囲気中１５００℃で３０分間保持したところ、透
明なガラス体を得た。ガラス体の重量は１２０ｇで、化
学分析したところ、ホウ酸ガラスを１７重量％含んだシ
リカガラスであった。The weight after drying was 124 g. When this impregnated porous body was held at 1500° C. for 30 minutes in a He atmosphere, a transparent glass body was obtained. The weight of the glass body was 120 g, and chemical analysis revealed that it was silica glass containing 17% by weight of boric acid glass.
ガラス中に発泡はなく、ホウ素の濃度分布も均一であっ
た。There were no bubbles in the glass, and the boron concentration distribution was uniform.
含浸液の飽和量と化学分析から、本発明の方法により、
添加物をガラス内に均一に導入できることが分かる。ま
た、多孔質体の重量変化により、多孔質体の細孔には１
００％液が浸入し、１００℃の乾燥により溶媒成分はほ
ぼ蒸発することが分かる。また、添加物であるホウ素は
、ガラス内で安定な酸化物の状態で存在していた。From the saturation amount of the impregnating liquid and chemical analysis, the method of the present invention shows that
It can be seen that the additive can be uniformly introduced into the glass. In addition, due to the change in the weight of the porous body, the pores of the porous body have a
It can be seen that 00% liquid permeates and the solvent component almost evaporates by drying at 100°C. Furthermore, the additive boron existed in the form of a stable oxide within the glass.
以上説明したように、本発明は従来製造が困難であった
各種添加物を任意の含有量で含んだシリカガラスを製造
することを可能にする、優れた方
法である。As explained above, the present invention is an excellent method that makes it possible to manufacture silica glass containing arbitrary contents of various additives, which have conventionally been difficult to manufacture.
Claims (5)
、気相法により得られたガラス多孔質体にＢ、Ｇｅ、Ｐ
、Ｓｂ、Ａｌ及びＴｉよりなる群から選ばれる元素のイ
オン又は該元素の酸化物イオンの１以上と溶媒からなる
溶液を含浸させ、しかる後に乾燥せしめ、次いで焼結す
ることを特徴とするガラスの製造方法。(1) In a method for manufacturing glass by a vapor phase synthesis method, B, Ge, P
, Sb, Al, and Ti, or an oxide ion of the element, and a solution consisting of a solvent, which is then dried, and then sintered. Production method.
ｇ／ｃｍ＾３であり、該ガラス多孔質体に表面張力が１
００ｄｙｎ／ｃｍ以下で、沸点が３０〜１５０℃である
上記元素のイオン又は該元素の酸化物イオンの１以上を
含有する溶液を含浸させることを特徴とする請求項（１
）に記載のガラスの製造方法。(2) The bulk density of the glass porous body is 0.3 to 1.0
g/cm^3, and the surface tension of the glass porous body is 1
00 dyn/cm or less and a solution containing one or more ions of the above element or oxide ions of the element having a boiling point of 30 to 150°C.
).
大と最小の差が０．２ｇ／ｃｍ＾３より小さいことを特
徴とする請求項（２）に記載のガラスの製造方法。(3) The method for manufacturing glass according to claim 2, wherein the difference between the maximum and minimum bulk density distribution of the glass porous body is smaller than 0.2 g/cm^3.
を特徴とする請求項（１）に記載のガラスの製造方法。(4) The method for producing glass according to claim (1), wherein the drying is performed at a temperature range of 40 to 160°C.
をガラス合成用バーナに投入し、生成したガラス粒子を
出発材の周囲に堆積させたものであることを特徴とする
請求項（１）に記載のガラスの製造方法。(5) Claim (1) characterized in that the glass porous body is obtained by introducing frit gas and combustion gas into a glass synthesis burner and depositing the generated glass particles around the starting material. A method for producing glass as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5011689A JPH02229726A (en) | 1989-03-03 | 1989-03-03 | Production of glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5011689A JPH02229726A (en) | 1989-03-03 | 1989-03-03 | Production of glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02229726A true JPH02229726A (en) | 1990-09-12 |
Family
ID=12850140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5011689A Pending JPH02229726A (en) | 1989-03-03 | 1989-03-03 | Production of glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02229726A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474588A (en) * | 1992-04-07 | 1995-12-12 | Fujikura Ltd | Solution doping of a silica preform with erbium, aluminum and phosphorus to form an optical fiber |
| US9260338B2 (en) | 2014-02-28 | 2016-02-16 | Sumitomo Electric Industries, Ltd. | Porous glass body and method for producing glass preform |
-
1989
- 1989-03-03 JP JP5011689A patent/JPH02229726A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474588A (en) * | 1992-04-07 | 1995-12-12 | Fujikura Ltd | Solution doping of a silica preform with erbium, aluminum and phosphorus to form an optical fiber |
| US9260338B2 (en) | 2014-02-28 | 2016-02-16 | Sumitomo Electric Industries, Ltd. | Porous glass body and method for producing glass preform |
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