JPH04305026A - Production of fluoride glass - Google Patents
Production of fluoride glassInfo
- Publication number
- JPH04305026A JPH04305026A JP6853991A JP6853991A JPH04305026A JP H04305026 A JPH04305026 A JP H04305026A JP 6853991 A JP6853991 A JP 6853991A JP 6853991 A JP6853991 A JP 6853991A JP H04305026 A JPH04305026 A JP H04305026A
- Authority
- JP
- Japan
- Prior art keywords
- fluoride glass
- glass
- fluoride
- hydrofluoric acid
- raw material
- 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.)
- Withdrawn
Links
- 239000005383 fluoride glass Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910001632 barium fluoride Inorganic materials 0.000 description 10
- 229910007998 ZrF4 Inorganic materials 0.000 description 5
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910002319 LaF3 Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000000516 activation analysis Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910009527 YF3 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はフッ化物ガラス原料もし
くはフッ化物ガラス中の酸化物を除去するフッ化物ガラ
スの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing fluoride glass by removing oxides from fluoride glass raw materials or fluoride glass.
【０００２】0002
【従来の技術】フッ化物ガラスを素材とし、ＺｒＦ４
−ＢａＦ２を主成分とする光ファイバはその伝送損失が
１０−２ｄＢ／ｋｍ 程度となることが予想されている
。しかしながら、これまで達成されている損失値は０．
７ｄＢ／ｋｍ であるとされており、この原因としてＦ
ｅ、Ｃｕなどの遷移金属不純物イオン、または水酸基な
どによる光吸収損失、及びフッ化物ガラス固有の不安定
性によって生じる結晶化や酸化物により形成される散乱
体などによる散乱損失が挙げられる。[Prior art] Made of fluoride glass, ZrF4
It is expected that an optical fiber whose main component is -BaF2 will have a transmission loss of about 10-2 dB/km. However, the loss values achieved so far are 0.
7dB/km, and the cause of this is F.
Examples include light absorption loss due to transition metal impurity ions such as e, Cu, or hydroxyl groups, and scattering loss due to crystallization caused by the inherent instability of fluoride glass and scatterers formed by oxides.
【０００３】これまで、原料精製による遷移金属不純物
の除去、ガラス溶融を乾燥雰囲気とする水酸基の除去、
ガラス組成の検討に基づくガラス安定性の向上による結
晶化の抑制等によって上述した損失値が達成されている
。[0003] Up until now, the removal of transition metal impurities by refining raw materials, the removal of hydroxyl groups by creating a dry atmosphere for glass melting,
The above-mentioned loss value is achieved by suppressing crystallization by improving glass stability based on examination of glass composition.
【０００４】0004
【発明が解決しようとする課題】ところが、ここにおい
て、残る重要な損失要因である酸化物による散乱体の除
去については、ガラス原料にフッ化アンモニウムを加え
て溶融することによりその低減を図ってきたところであ
るが、現状ではその成果は十分に得られていないもので
ある。[Problem to be solved by the invention] However, the removal of scatterers caused by oxides, which remains an important loss factor, has been attempted to be reduced by adding ammonium fluoride to the glass raw material and melting it. However, at present, sufficient results have not been obtained.
【０００５】この酸化物の散乱体については、従来より
、ジルコニア、ＺｒＯ２ であることが示されており、
ＺｒＯ２ の生成はもう一つの主成分であるＢａＦ２
の原料中に含まれるＢａＯに起因することが明らかにさ
れている。即ち、
ＺｒＦ４ ＋２ＢａＯ→ＺｒＯ２ ＋２ＢａＦ２ なる
反応により安定したＺｒＯ２ が生成され、ガラス内部
に散乱体として存在することとなる。[0005] Regarding this oxide scatterer, it has been shown that zirconia and ZrO2 are conventionally used.
The production of ZrO2 is caused by another main component, BaF2.
It has been revealed that this is caused by BaO contained in the raw materials. That is, stable ZrO2 is generated by the reaction ZrF4 +2BaO→ZrO2 +2BaF2 and exists as a scatterer inside the glass.
【０００６】一方、原料精製は、一般に、昇華精製によ
ってなされるが、ＺｒＦ４ 、ＢａＦ２ 、ＬａＦ３
、ＡｌＦ３ 、ＹＦ３ 、ＬｉＦ、ＮａＦなどのガラス
原料のうち、アルカリフッ化物としてのＺｒＦ４ 、Ａ
ｌＦ３ は蒸気圧が高いため精製原料中に酸化物が残留
する可能性は極めて低い。一方、このアルカリフッ化物
を除いた他のフッ化物は蒸気圧が低く、酸化物が残留す
る可能性が高い。即ち、フッ化物ガラスから酸化物散乱
体を除去するにはＢａＦ２ などの非昇華性フッ化物原
料中に残留する酸化物を除去することが不可欠となって
いる。On the other hand, raw material purification is generally carried out by sublimation purification, but ZrF4, BaF2, LaF3
, AlF3, YF3, LiF, NaF, etc., ZrF4, A as alkali fluoride
Since lF3 has a high vapor pressure, it is extremely unlikely that oxides will remain in the refined raw material. On the other hand, other fluorides other than this alkali fluoride have low vapor pressures and are likely to remain as oxides. That is, in order to remove oxide scatterers from fluoride glass, it is essential to remove oxides remaining in non-sublimable fluoride raw materials such as BaF2.
【０００７】このように酸化物の散乱体については、そ
の生体と起源が明確にされ、フッ化物ガラス原料にもと
もと原因があることが示されている。ところが、その有
効な除去手段が示されていないのが現状である。[0007] As described above, the origin of the oxide scatterers has been clarified, and it has been shown that the fluoride glass raw material is the original cause. However, at present, no effective means for removing it has been proposed.
【０００８】本発明はこのような問題点を解決するもの
であって、フッ化物ガラス原料中に含まれる酸化物不純
物を効果的に除去することのできるフッ化物ガラスの製
造方法を提供することを目的としている。The present invention is intended to solve these problems, and aims to provide a method for producing fluoride glass that can effectively remove oxide impurities contained in raw materials for fluoride glass. The purpose is
【０００９】[0009]
【課題を解決するための手段】上述の目的を達成するた
めの本発明のフッ化物ガラスの製造方法は、粉末状のフ
ッ化物ガラス原料もしくはこのフッ化物ガラス原料を所
定のガラス組成比となるように調合されたガラス原料混
合体にフッ酸を加えてフッ酸水溶液またはコロイド溶液
を形成し、この溶液にフッ素ガスを反応させることで水
分を除去することを特徴とするものである。[Means for Solving the Problems] A method for producing fluoride glass of the present invention to achieve the above-mentioned object is to use a powdered fluoride glass raw material or the fluoride glass raw material in a predetermined glass composition ratio. The method is characterized in that hydrofluoric acid is added to the glass raw material mixture prepared in 1 to form an aqueous hydrofluoric acid solution or a colloidal solution, and water is removed by reacting this solution with fluorine gas.
【００１０】0010
【作用】フッ化物ガラス原料段階もしくはそのガラス原
料混合体、即ち、溶融に先立つ前処理として酸化物に対
して高い溶融性をもつフッ酸による処理とその溶液から
酸化物の再形成の原因となる水分がフッ素ガスを用いて
非可逆的に除去することで、この処理を経て作成される
フッ化物ガラス中の酸素濃度が極めて低減される。[Action] At the fluoride glass raw material stage or its glass raw material mixture, treatment with hydrofluoric acid which has high melting properties for oxides as a pretreatment prior to melting and the re-formation of oxides from the solution. By irreversibly removing moisture using fluorine gas, the oxygen concentration in the fluoride glass created through this treatment is extremely reduced.
【００１１】[0011]
【実施例】以下、図面に基づいて本発明の実施例を詳細
に説明する。Embodiments Hereinafter, embodiments of the present invention will be described in detail based on the drawings.
【００１２】（第１実施例）図１に本発明の第１実施例
に係るフッ化物ガラスの製造方法を表すフローチャート
を示す。(First Embodiment) FIG. 1 is a flowchart showing a method for manufacturing fluoride glass according to a first embodiment of the present invention.
【００１３】この第１実施例では、ＺｒＦ４ −ＢａＦ
２ 系ガラスの主成分であるＢａＦ２ について、図１
に示すフローチャートに基づきフッ化物ガラスの製造方
法を実施したものである。図１に示すように、ステップ
Ｓ１にて、昇華精製したＢａＦ２ を粉体状にして１０
０ｇを５００ｍｌのテフロン性バブラー型密閉容器に入
れる。そして、ステップＳ２にて、粉体状のＢａＦ２
にＥＬ級４９％のフッ酸を２００ｍｌ加え、ステップＳ
３にて、マグネティックスターラで約５時間攪拌する。
次に、ステップＳ４にて、Ｆ２ ／Ｈｅの混合ガス（混
合比１：１）を毎分０．１リットル水溶液中にバブルさ
せる。このバブリングは２０℃に保たれたドライボック
ス内で約１０時間行う。そして、ステップＳ５にて、Ｆ
２ ガスをバブルせずに液面上をフローさせながら容器
を８０℃に加熱する。この状態で１０時間保持し、粉末
状のＢａＦ２ を得る。これを原料として、ＺｒＦ４
−ＢａＦ２ −ＬａＦ３ −ＹＦ３ −ＡｌＦ３ −Ｎ
ａＦ（組成比 ４７．５−２３．５−２．５−２．０
−４．５−２０モル％）のフッ化物ガラスを作製した。In this first embodiment, ZrF4-BaF
Regarding BaF2, which is the main component of 2-based glass, Figure 1
This is a method for producing fluoride glass based on the flowchart shown in FIG. As shown in FIG. 1, in step S1, sublimation-purified BaF2 is powdered for 10
0g into a 500ml Teflon bubbler-type airtight container. Then, in step S2, powdered BaF2
Add 200ml of EL grade 49% hydrofluoric acid to Step S.
At step 3, stir using a magnetic stirrer for about 5 hours. Next, in step S4, a mixed gas of F2/He (mixing ratio 1:1) is bubbled into the aqueous solution at 0.1 liter per minute. This bubbling is performed for about 10 hours in a dry box maintained at 20°C. Then, in step S5, F
2. Heat the container to 80°C while allowing the gas to flow on the liquid surface without bubbles. This state is maintained for 10 hours to obtain powdered BaF2. Using this as a raw material, ZrF4
-BaF2 -LaF3 -YF3 -AlF3 -N
aF (composition ratio 47.5-23.5-2.5-2.0
-4.5-20 mol%) fluoride glass was produced.
【００１４】このように作製したフッ化物ガラスから円
板状の試料を切り出し、サイクロトロン放射化分析によ
って酸素濃度を測定した。すると、この試料の酸素濃度
の測定値２８ｐｐｍが得られた。一方、上記のような処
理をしていない従来のＢａＦ２ を使用したフッ化物ガ
ラスの酸素濃度は１９２ｐｐｍであり、これに比べて本
実施例のフッ化物ガラスの製造方法によって作製された
フッ化物ガラスは著しく酸素濃度が低減されていること
が解った。A disk-shaped sample was cut out from the fluoride glass thus produced, and the oxygen concentration was measured by cyclotron activation analysis. Then, a measured value of 28 ppm was obtained for the oxygen concentration of this sample. On the other hand, the oxygen concentration of conventional fluoride glass using BaF2, which has not been subjected to the above-mentioned treatment, is 192 ppm, and compared to this, the fluoride glass produced by the fluoride glass production method of this example has an oxygen concentration of 192 ppm. It was found that the oxygen concentration was significantly reduced.
【００１５】（第２実施例）この第２実施例では、上述
した実施例と同様の組成に調合したガラス原料混合体に
てフッ化物ガラスの製造方法を実施した。まず、５０ｇ
の調合原料を２５０ｍｌのテフロン性バブラー型密閉容
器に入れる。そして、１００ｍｌのＥＬ級４９％のフッ
酸を加える。そして、マグネティックスターラで約３時
間攪拌する。次に、Ｆ２ ガスをこの水溶液中にバブル
させ、更に、Ｆ２ ガスをバブルせずに液面上をフロー
させながら容器を８０℃に加熱する。この状態で８時間
保持し、その後、粉末原料混合体を金るつぼに移す。そ
して、これを原料として、溶融装置内に入れてフッ化物
ガラスを作製した。(Second Example) In this second example, a method for producing fluoride glass was carried out using a glass raw material mixture prepared to have the same composition as in the above-mentioned example. First, 50g
Place the blended raw materials in a 250 ml Teflon bubbler-type airtight container. Then, 100 ml of EL grade 49% hydrofluoric acid is added. Then, stir with a magnetic stirrer for about 3 hours. Next, F2 gas is bubbled into this aqueous solution, and the container is heated to 80° C. while the F2 gas is allowed to flow on the liquid surface without bubbling. This state is maintained for 8 hours, and then the powder raw material mixture is transferred to a metal crucible. Then, this was used as a raw material and put into a melting device to produce fluoride glass.
【００１６】このように作製したフッ化物ガラスから円
板状の試料を切り出し、サイクロトロン放射化分析によ
って酸素濃度を測定した。すると、この試料の酸素濃度
の測定値８ｐｐｍが得られ、この実施例によっても作製
されたフッ化物ガラスは著しく酸素濃度が低減されてい
ることが解った。A disk-shaped sample was cut out from the fluoride glass thus produced, and the oxygen concentration was measured by cyclotron activation analysis. As a result, a measured oxygen concentration of 8 ppm was obtained for this sample, and it was found that the fluoride glass produced according to this example also had a significantly reduced oxygen concentration.
【００１７】[0017]
【発明の効果】以上、実施例を挙げて詳細に説明したよ
うに本発明のフッ化物ガラスの製造方法によれば、粉末
状のフッ化物ガラス原料もしくはその原料を所定のガラ
ス組成比となるように調合されたガラス原料混合体にフ
ッ酸を加えてフッ酸水溶液またはコロイド溶液を形成し
、この溶液にフッ素ガスを反応させることで水分を除去
するようにしたので、溶融に先立つ前処理として酸化物
に対して高い溶融性をもつフッ酸による処理とその溶液
から酸化物の再形成の原因となる水分をフッ素ガスを用
いて非可逆的に除去することとなり、この処理を経て作
成されるフッ化物ガラス中の酸素濃度を極めて低減する
ことができる。その結果、光学的に高度に均質なフッ化
物ガラスを製造することができる。Effects of the Invention As described above in detail with reference to Examples, according to the method for producing fluoride glass of the present invention, powdered fluoride glass raw material or its raw material is adjusted to a predetermined glass composition ratio. By adding hydrofluoric acid to the glass raw material mixture prepared in Treatment with hydrofluoric acid, which has a high melting property for substances, and the removal of water that causes the reformation of oxides from the solution using fluorine gas irreversibly. Oxygen concentration in compound glass can be extremely reduced. As a result, optically highly homogeneous fluoride glasses can be produced.
【図１】本発明の一実施例に係るフッ化物ガラスの製造
方法を表すフローチャートである。FIG. 1 is a flowchart showing a method for manufacturing fluoride glass according to an embodiment of the present invention.
Claims (1)
このフッ化物ガラス原料を所定のガラス組成比となるよ
うに調合されたガラス原料混合体にフッ酸を加えてフッ
酸水溶液またはコロイド溶液を形成し、この溶液にフッ
素ガスを反応させることで水分を除去することを特徴と
するフッ化物ガラスの製造方法。Claim 1: A hydrofluoric acid aqueous solution or a colloidal solution is formed by adding hydrofluoric acid to a powdered fluoride glass raw material or a glass raw material mixture prepared by mixing the fluoride glass raw material to a predetermined glass composition ratio. A method for producing fluoride glass, characterized in that water is removed by reacting this solution with fluorine gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6853991A JPH04305026A (en) | 1991-04-01 | 1991-04-01 | Production of fluoride glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6853991A JPH04305026A (en) | 1991-04-01 | 1991-04-01 | Production of fluoride glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04305026A true JPH04305026A (en) | 1992-10-28 |
Family
ID=13376650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6853991A Withdrawn JPH04305026A (en) | 1991-04-01 | 1991-04-01 | Production of fluoride glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04305026A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214946A (en) * | 1988-04-22 | 1990-01-18 | Trw Inc | Method and device for testing air-bag constraint system |
-
1991
- 1991-04-01 JP JP6853991A patent/JPH04305026A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214946A (en) * | 1988-04-22 | 1990-01-18 | Trw Inc | Method and device for testing air-bag constraint system |
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| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980711 |