JPS6311296B2 - - Google Patents
Info
- Publication number
- JPS6311296B2 JPS6311296B2 JP58110081A JP11008183A JPS6311296B2 JP S6311296 B2 JPS6311296 B2 JP S6311296B2 JP 58110081 A JP58110081 A JP 58110081A JP 11008183 A JP11008183 A JP 11008183A JP S6311296 B2 JPS6311296 B2 JP S6311296B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- mol
- glass
- fluorosulfate
- infrared
- 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 24
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 238000000149 argon plasma sintering Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 2
- TZPLJBLDIVEZCK-UHFFFAOYSA-I aluminum sodium barium(2+) lanthanum(3+) zirconium(4+) pentafluoride Chemical compound [F-].[Na+].[F-].[Al+3].[F-].[La+3].[F-].[Ba+2].[F-].[Zr+4] TZPLJBLDIVEZCK-UHFFFAOYSA-I 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000005383 fluoride glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XCXLEIPEAAEYTF-UHFFFAOYSA-M sodium fluorosulfate Chemical compound [Na+].[O-]S(F)(=O)=O XCXLEIPEAAEYTF-UHFFFAOYSA-M 0.000 description 2
- OCKJAMWMDSEBOY-UHFFFAOYSA-L FS(=O)(=O)[O-].[Ba+2].FS(=O)(=O)[O-] Chemical compound FS(=O)(=O)[O-].[Ba+2].FS(=O)(=O)[O-] OCKJAMWMDSEBOY-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- XIZLNMKPMZIAID-UHFFFAOYSA-M [Cs+].[O-]S(F)(=O)=O Chemical compound [Cs+].[O-]S(F)(=O)=O XIZLNMKPMZIAID-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- 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
- C03C13/042—Fluoride glass compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
本発明は、光学的特性の優れた赤外線透過ガラ
スに関する。
弗化ジルコニウム系のガラスは、赤外線透過性
に優れていることから赤外線光学用材料として有
望視されているが、この系のガラスは一般に熱的
に不安定で結晶化しやすい問題があり、そのため
熱的安定性をもたらす弗化ジルコニウム−弗化バ
リウム−弗化ナトリウム−弗化ランタン−弗化ア
ルミニウム系のガラスが提案されている。
例えば弗化ジルコニウム48〜70モル％、弗化バ
リウム14〜30モル％、弗化ナトリウム７〜26モル
％、弗化ランタン２〜７モル％、弗化アルミニウ
ム２〜６モル％とした組成のものは熱的に充分安
定したガラスとなり、大型のガラス塊が得られる
とか、光フアイバへの紡糸加工が行ないやすいと
いつた効果を発揮する。
もちろん、こうした提案例でも各組成の割合が
上記の範囲から外れると結晶化が起こりやすくな
る。
ところで、上記の組成からなるガラスの場合、
赤外線透過性、熱的安定性を有するのでこの点に
限つてよいといえるが、光の散乱に関してはこれ
が大きく、従つて当該ガラスの場合、光学系ガラ
スとしてまだ不充分であるといえる。
つぎに光散乱現象の抑制に関し、これを検討し
たところ、上記組成のガラス中に硫酸イオンを添
加するのが有効であると判明したが、この硫酸イ
オンの添加は光散乱の抑制には有効であつても波
長４〜5μｍ域において大きな吸収があらわれ、
赤外線透過性が阻害されるといつた結果を新たに
惹き起こすこととなつた。
本発明は上記の問題点に鑑みこの種の赤外線透
過ガラスにおいて、赤外線透過性、熱的安定性、
光散乱の現象など、これら諸特性を満足に確保す
べく改善したものであり、その特徴とする構成は
下記の通りである。
すなわち本発明に係る赤外線透過ガラスは、弗
化ジルコニウム48〜70モル％と、弗化バリウム14
〜30モル％と、弗化ナトリウム７〜26モル％と、
弗化ランタン２〜７モル％と、弗化アルミニウム
２〜６モル％と、フルオロ硫酸塩0.1〜５モル％
とからなることを特徴としている。
かかる本発明の場合、弗化ジルコニウム−弗化
バリウム−弗化ナトリウム−弗化ランタン−弗化
アルミニウム系において既述のごとく赤外線透過
性、熱的安定性を具備しているのであり、これに
フルオロ硫酸塩が添加されていることにより、弗
化ジルコニウムガラスと対比して光散乱強度が約
100分の１程度にまで減じられている。
本発明において、フルオロ硫酸塩による光散乱
抑制効果は前記における硫酸イオンの場合とほぼ
同じであるが、硫酸イオンの添加が赤外線透過性
を阻害するのに対し、フルオロ硫酸塩の添加はこ
うした弊害を全く惹き起こさない。
図は本発明における３mm厚のガラス（ただしフ
ルオロ硫酸塩５モル％）と、該ガラスにおいてそ
のフルオロ硫酸塩を硫酸イオン（２モル％）に代
えた比較例のガラスにつき、これらの赤外線吸収
特性を測定した結果であり、この図で明らかなよ
うに本発明のガラスイは比較例ロのガラスよりも
赤外線透過性が優れている。
本発明の場合、所定のガラスを作成する際、そ
の原材料中にフルオロ硫酸塩を添加するが、この
フルオロ硫酸塩を形成するカチオンの種類はあま
り重要でなく、添加に際しては赤外線透過性を妨
げることのないよう、しかもガラス中に可溶な塩
の形とする。
フルオロ硫酸塩としては、フルオロ硫酸塩ナト
リウム（NaSO3F）、フルオロ硫酸セシウムなど
のアルカリ金属塩やフルオロ硫酸バリウムなどの
アルカリ土類金属塩などがあげられる。
本発明においてフルオロ硫酸塩の量を0.1〜５
モル％とした理由は、0.1モル％を下回るフルオ
ロ硫酸塩では光散乱現象に対する抑制効果が不充
分となり、５モル％を上回るフルオロ硫酸塩では
ガラスの熱的安定性に低下傾向がみられるからで
ある。
次に実施例について説明する。
実施例
弗化ジルコニウム、弗化バリウム、弗化ランタ
ン、弗化アルミニウム、フルオロ硫酸ナトリウム
を原料とし、白金ルツボを用いて別表のごとき組
成の各種ガラスを作製した。
これら実施例での各ガラスは熱的に安定してい
て大きな塊のガラスが作成でき、結晶化を来たす
ことなる光フアイバに加工することができた。
もちろん光散乱の傾向はみられず、赤外線吸収
のピークもみられなかつた。
以上説明した通り、本発明に係る赤外線透過ガ
ラスは赤外線透過性、熱的安定性、光散乱の現象
などにつき、優れた光学的特性を有し、したがつ
て赤外線用光学部品、赤外線伝送用材料として好
適なものとなる。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an infrared transmitting glass with excellent optical properties. Zirconium fluoride glasses are seen as promising materials for infrared optics due to their excellent infrared transmittance; however, this type of glass is generally thermally unstable and prone to crystallization, so Glasses based on zirconium fluoride-barium fluoride-sodium fluoride-lanthanum fluoride-aluminum fluoride have been proposed, which provide mechanical stability. For example, a composition containing 48 to 70 mol% of zirconium fluoride, 14 to 30 mol% of barium fluoride, 7 to 26 mol% of sodium fluoride, 2 to 7 mol% of lanthanum fluoride, and 2 to 6 mol% of aluminum fluoride. The resulting glass is sufficiently thermally stable, and has the advantage of being able to obtain large glass lumps and making it easier to spin into optical fibers. Of course, even in such a proposed example, crystallization is likely to occur if the ratio of each composition deviates from the above range. By the way, in the case of glass with the above composition,
Since it has infrared transmittance and thermal stability, it can be said to be good only in this respect, but in terms of light scattering, this is large, and therefore, in the case of this glass, it can be said that it is still insufficient as an optical system glass. Next, we investigated the suppression of light scattering phenomena and found that it is effective to add sulfate ions to the glass with the above composition; however, the addition of sulfate ions is not effective in suppressing light scattering. Even if there is a large absorption in the wavelength range of 4 to 5 μm,
This resulted in a new result in which infrared transmittance was inhibited. In view of the above-mentioned problems, the present invention provides an infrared transmitting glass of this kind that has excellent infrared transmittance, thermal stability,
It has been improved to satisfactorily ensure these various properties such as the phenomenon of light scattering, and its characteristic structure is as follows. That is, the infrared transmitting glass according to the present invention contains 48 to 70 mol% of zirconium fluoride and 14% of barium fluoride.
~30 mol% and 7-26 mol% sodium fluoride,
2 to 7 mol% of lanthanum fluoride, 2 to 6 mol% of aluminum fluoride, and 0.1 to 5 mol% of fluorosulfate
It is characterized by consisting of. In the case of the present invention, the zirconium fluoride-barium fluoride-sodium fluoride-lanthanum fluoride-aluminum fluoride system has infrared transmittance and thermal stability as described above, and in addition, the fluoride Due to the addition of sulfate, the light scattering intensity is approximately lower than that of zirconium fluoride glass.
It has been reduced to about 1/100th. In the present invention, the light scattering suppressing effect of fluorosulfate is almost the same as that of sulfate ion in the above, but while the addition of sulfate ion inhibits infrared transmittance, the addition of fluorosulfate suppresses this adverse effect. Doesn't cause it at all. The figure shows the infrared absorption properties of a 3 mm thick glass according to the present invention (5 mol% fluorosulfate) and a comparative glass in which the fluorosulfate was replaced with sulfate ions (2 mol%). These are the measurement results, and as is clear from this figure, the glass A of the present invention has better infrared transmittance than the glass of Comparative Example B. In the case of the present invention, when creating a specified glass, fluorosulfate is added to the raw materials, but the type of cation that forms this fluorosulfate is not very important, and when added, it should not interfere with infrared transparency. In addition, it should be in the form of a salt that is soluble in the glass. Examples of the fluorosulfate include alkali metal salts such as sodium fluorosulfate (NaSO 3 F) and cesium fluorosulfate, and alkaline earth metal salts such as barium fluorosulfate. In the present invention, the amount of fluorosulfate is 0.1 to 5.
The reason for the mol% is that if the fluorosulfate is less than 0.1 mol%, the suppressing effect on the light scattering phenomenon will be insufficient, and if the fluorosulfate is more than 5 mol%, the thermal stability of the glass will tend to decrease. be. Next, an example will be described. Examples Using zirconium fluoride, barium fluoride, lanthanum fluoride, aluminum fluoride, and sodium fluorosulfate as raw materials, various glasses having the compositions shown in the attached table were produced using a platinum crucible. Each of the glasses in these examples was thermally stable and large blocks of glass could be made and processed into optical fibers that would undergo crystallization. Of course, no tendency for light scattering was observed, and no infrared absorption peak was observed. As explained above, the infrared transmitting glass according to the present invention has excellent optical properties in terms of infrared transmittance, thermal stability, light scattering phenomenon, etc., and is therefore suitable for use as infrared optical components and infrared transmission materials. It is suitable as 【table】
図面は本発明ガラスとその比較例との赤外線透
過特性を示す説明図である。
The drawing is an explanatory diagram showing the infrared transmission characteristics of the glass of the present invention and its comparative example.
Claims (1)
ウム14〜30モル％と、弗化ナトリウム７〜26モル
％と、弗化ランタン２〜７モル％と、弗化アルミ
ニウム２〜６モル％と、フルオロ硫酸塩0.1〜５
モル％とからなる赤外線透過ガラス。1 48 to 70 mol% of zirconium fluoride, 14 to 30 mol% of barium fluoride, 7 to 26 mol% of sodium fluoride, 2 to 7 mol% of lanthanum fluoride, and 2 to 6 mol% of aluminum fluoride. , fluorosulfate 0.1-5
Infrared transmitting glass consisting of mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58110081A JPS605038A (en) | 1983-06-21 | 1983-06-21 | Infrared transmitting glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58110081A JPS605038A (en) | 1983-06-21 | 1983-06-21 | Infrared transmitting glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS605038A JPS605038A (en) | 1985-01-11 |
| JPS6311296B2 true JPS6311296B2 (en) | 1988-03-14 |
Family
ID=14526548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58110081A Granted JPS605038A (en) | 1983-06-21 | 1983-06-21 | Infrared transmitting glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS605038A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389086C (en) * | 2005-05-11 | 2008-05-21 | 浙江大学 | Rare earth-doped transparent oxyfluoride glass ceramics and preparation method thereof |
-
1983
- 1983-06-21 JP JP58110081A patent/JPS605038A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS605038A (en) | 1985-01-11 |
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