JPS6259066B2 - - Google Patents
Info
- Publication number
- JPS6259066B2 JPS6259066B2 JP55108202A JP10820280A JPS6259066B2 JP S6259066 B2 JPS6259066 B2 JP S6259066B2 JP 55108202 A JP55108202 A JP 55108202A JP 10820280 A JP10820280 A JP 10820280A JP S6259066 B2 JPS6259066 B2 JP S6259066B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- mgf
- glass
- fluoride
- component
- 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
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
-
- 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
- C03C3/325—Fluoride glasses
Landscapes
- Chemical & Material Sciences (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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Description
本発明は波長２μｍ以上の赤外線波長領域にお
いても透過性を有する光学フアイバ用ガラスに関
する。
従来、光学フアイバには一般に石英系
（SiO2）ガラスが使用されてきた。しかし、この
種のガラスでは、Si−Ｏ結合の振動に起因する赤
外吸収があり、これとレーリ散乱のため、伝送損
失の小さい波長領域が波長0.6〜1.7μｍの可視域
から近赤外域に限られ、それにより長波長の波長
域においては、光学フアイバの低損失化は実現で
きなかつた。
一方、ハライドガラスは、その赤外吸収が石英
系ガラスより長波長側にあるので、石英系ガラス
と比べてより長波長まで光を透過し、波長２μｍ
以上の光学フアイバ素材として有望であることが
知られていた。しかしながら、従来のBeF2系ガ
ラス、ZnCl2系ガラス及びZrF4−ThF4−BaF2ガ
ラス等のハライドガラスは、その構成成分とし
て、潮解性及び毒性を有するBeF2、潮解性を有
するZnCl2、又は有毒なThF4を使用しているの
で、湿気による経時変化、すなわち水のＯ−Ｈ結
合に起因する赤外吸収の増大が予測され、光学フ
アイバ用素材としては信頼性の面で問題があるば
かりでなく、製造過程及び使用に際しての安全性
の面でも問題がある。
本発明はこのような現状に鑑みてなされたもの
であり、その目的は、波長２μｍ以上の赤外領域
においても低損失であり、かつ毒性及び吸湿性の
ない光学フアイバ用ガラスを提供することであ
る。
本発明につき概説すれば、本発明の光学フアイ
バ用ガラスは(a)MgF2又はMgF2の一部をCaF2，
SrF2及びBaF2よりなる群から選ばれた少なくと
も１種のフツ化物で置換した混合物20〜55モル
％、(b)YF3及びランタノイド元素のフツ化物より
なる群から選ばれた少なくとも１種のフツ化物５
〜50モル％及び(c)AlF320〜65モル％よりなるこ
とを特徴とするものである。
本発明においては、(a)成分としてMgF2又は
MgF2の一部をCaF2，SrF2及びBaF2よりなる群
から選ばれた少なくとも１種のフツ化物で置換し
た混合物、(b)成分としてYF3及びランタノイド元
素のフツ化物（例えばLaF3，GdF3，LuF3，
CeF3及びNdF3等が一般的）よりなる群から選ば
れた少なくとも１種のフツ化物及び(c)成分として
AlF3を使用する。
これらの基本的なガラス構成成分は、いずれも
潮解性及び毒性がなく、従来のハライドガラスに
おけるような吸湿性及び毒性の問題を同時に解決
すると共に、(b)成分を用いることにより、ガラス
化範囲を拡大し、又結晶化に対する安定性を増大
することができる。
上記各成分の混合割合すなわち組成は、(a)成分
20〜55モル％、(b)成分５〜50モル％、そして(c)成
分20〜65モル％とすることが適当であり、(a)成分
及び(b)成分の割合が、この範囲を外れると、自濁
して結晶化して望ましくない。又、(c)成分の割合
が上記範囲未満では同様に白濁結晶化が起り、
又、上記範囲を越えるとガラス質にはなるが乳白
化して透明にならないので望ましくない。
又、本発明においては、前記したように、(a)成
分としてMgF2の一部をCaF2，SrF2及びBaF2よ
りなる群から選ばれた少なくとも１種のフツ化物
で置換した混合物を適用することができるが、そ
の置換量は(a)成分全体のモル％の約20〜90％程度
の広範囲とすることができ、特に限定されない。
本発明の光学フアイバ用ガラスの作製に当つて
は、前記組成の各フツ化物粉末を白金るつぼ等の
耐熱性容器中に入れて混合し、アルゴンガス等の
不活性ガス雰囲気下において1050℃程度の温度に
加熱して溶融し、次いで水等により容器底部を冷
却して容易にガラス化することができる。
次に、本発明を実施例により説明するが、本発
明はこれらによりなんら限定されるものではな
い。
実施例 １
下記第１表に示す所定の組成を有するフツ化物
の混合粉末（試料番号１〜８はMgF2，YF3及び
AlF3よりなるもの、同９〜11はMgF2、ランタノ
イド元素のフツ化物及びAlF3よりなるもの、そ
して同12はMgF2，YF3、ランタノイド元素のフ
ツ化物及びAlF3よりなるものの場合を示す）約
１ｇを白金るつぼに入れ、アルゴンガス雰囲気下
において1050℃で溶融した。次いで、これらのる
つぼの底を水に浸して冷却することにより、厚さ
約0.4mmのガラス化した12種の光学フアイバ用素
材を得た。
The present invention relates to a glass for optical fibers that is transparent even in the infrared wavelength range of 2 μm or more. Traditionally, optical fibers have generally been made of silica-based (SiO 2 ) glass. However, in this type of glass, there is infrared absorption caused by the vibration of Si-O bonds, and due to this and Rayleigh scattering, the wavelength range with small transmission loss shifts from the visible range of wavelengths of 0.6 to 1.7 μm to the near-infrared range. As a result, it has not been possible to reduce the loss of optical fibers in the long wavelength range. On the other hand, halide glass has infrared absorption on the longer wavelength side than silica glass, so it transmits light up to longer wavelengths than silica glass, and has a wavelength of 2 μm.
It was known to be a promising optical fiber material for the above. However, conventional halide glasses such as BeF 2 -based glass, ZnCl 2 -based glass, and ZrF 4 -ThF 4 -BaF 2 glass include BeF 2 which has deliquescent and toxic properties, ZnCl 2 which has deliquescent property, Also, since toxic ThF 4 is used, it is expected that infrared absorption will increase due to changes over time due to moisture, that is, O-H bonds in water, and there is a problem in terms of reliability as a material for optical fibers. In addition, there are problems in terms of safety in the manufacturing process and in use. The present invention was made in view of the current situation, and its purpose is to provide a glass for optical fibers that has low loss even in the infrared region with a wavelength of 2 μm or more and is non-toxic and non-hygroscopic. be. To summarize the present invention, the glass for optical fiber of the present invention includes (a) MgF 2 or a part of MgF 2 with CaF 2 ,
20 to 55 mol% mixture substituted with at least one fluoride selected from the group consisting of SrF 2 and BaF 2 ; (b) at least one fluoride selected from the group consisting of YF 3 and fluorides of lanthanoid elements; Fluoride 5
50 mol% and (c) AlF 3 20 to 65 mol%. In the present invention, MgF 2 or
A mixture in which a portion of MgF 2 is replaced with at least one fluoride selected from the group consisting of CaF 2 , SrF 2 and BaF 2 , component (b) containing YF 3 and a fluoride of a lanthanoid element (e.g. LaF 3 , GdF 3 , LuF 3 ,
At least one fluoride selected from the group consisting of (generally CeF 3 , NdF 3 , etc.) and (c)
Use AlF3 . All of these basic glass constituents are non-deliquescent and non-toxic, and simultaneously solve the problems of hygroscopicity and toxicity of conventional halide glasses, while also increasing the vitrification range by using component (b). can be expanded and the stability against crystallization can be increased. The mixing ratio or composition of each of the above components is (a) component
20 to 55 mol% of component (b), 5 to 50 mol% of component (b), and 20 to 65 mol% of component (c), and the ratio of component (a) and component (b) falls within this range. If it comes off, it becomes cloudy and crystallizes, which is not desirable. In addition, if the ratio of component (c) is less than the above range, cloudy crystallization will occur as well.
On the other hand, if it exceeds the above range, it becomes glassy but becomes opalescent and not transparent, which is not desirable. Further, in the present invention, as described above, a mixture in which part of MgF 2 is replaced with at least one fluoride selected from the group consisting of CaF 2 , SrF 2 and BaF 2 is applied as component (a). However, the amount of substitution can range from about 20 to 90% by mole of the entire component (a), and is not particularly limited. In producing the optical fiber glass of the present invention, fluoride powders having the above compositions are mixed in a heat-resistant container such as a platinum crucible, and heated to about 1050°C in an inert gas atmosphere such as argon gas. It can be easily vitrified by heating to a certain temperature to melt it and then cooling the bottom of the container with water or the like. Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way. Example 1 Fluoride mixed powder having a predetermined composition shown in Table 1 below (sample numbers 1 to 8 are MgF 2 , YF 3 and
9 to 11 are composed of MgF 2 , a fluoride of a lanthanide element, and AlF 3 , and 12 is a composition composed of MgF 2 , YF 3 , a fluoride of a lanthanide element, and AlF 3 ) was placed in a platinum crucible and melted at 1050°C under an argon gas atmosphere. Next, by immersing the bottoms of these crucibles in water and cooling them, 12 types of vitrified optical fiber materials with a thickness of about 0.4 mm were obtained.
【表】
実施例 ２
下記第２表に示す所定の組成を有するフツ化物
の混合粉末（試料番号13〜18、はMgF2の一部を
CaF2，SrF2及びBaF2よりなる群から選ばれた少
なくとも１種のフツ化物で置換した混合物、YF3
及びAlF3よりなるもの、同19〜24はMgF2の一部
をCaF2，SrF2及びBaF2よりなる群から選ばれた
少なくとも１種のフツ化物で置換した混合物、ラ
ンタノイド元素のフツ化物及びAlF3よりなるも
の、そして同25はMgF2の一部をSrF2で置換した
混合物、YF3、ランタノイド元素のフツ化物及び
AlF3よりなるものの場合を示す）約１ｇを白金
るつぼに入れ、アルゴンガス雰囲気下において
1050℃で溶融した。次いで、これらのるつぼの底
を水に浸して冷却することにより、厚さ約0.4mm
のガラス化した13種の光学フアイバ用素材を得
た。[Table] Example 2 Mixed powder of fluoride having the predetermined composition shown in Table 2 below (sample numbers 13 to 18, a part of MgF 2
A mixture substituted with at least one fluoride selected from the group consisting of CaF 2 , SrF 2 and BaF 2 , YF 3
and AlF 3 ; Nos. 19 to 24 are mixtures in which a portion of MgF 2 is replaced with at least one fluoride selected from the group consisting of CaF 2 , SrF 2 and BaF 2 ; fluorides of lanthanide elements; 25 is a mixture of MgF 2 partially replaced with SrF 2 , YF 3 , fluorides of lanthanide elements, and
Approximately 1 g of AlF 3 is placed in a platinum crucible and placed in an argon gas atmosphere.
Melted at 1050℃. The bottoms of these crucibles are then soaked in water and cooled to a thickness of about 0.4 mm.
We obtained 13 types of vitrified optical fiber materials.
【表】
実施例 ３
MgF220モル％、CaF225モル％、YF310モル
％、CeF35モル％、NdF35モル％及びAlF335モル
％の組成を有するフツ化物の混合粉末約２ｇを白
金るつぼに入れ、アルゴンガス雰囲気下において
1050℃で溶融した。次いで、このるつぼの底を水
に浸して冷却することにより、厚さ0.8mmのガラ
ス化した光学フアイバ用素材を得た。
前記実施例１〜３で得たガラスは、いずれも潮
解性がなく、室温において大気中に５ケ月間放置
しても結晶化せず、湿気による劣化も観察されな
かつた。更に又、これらのガラスはいずれも0.3
〜８μｍの紫外域からの赤外域の広い波長領域に
おいて透明であり、OH基による吸収ピークは観
察されなかつた。
以上説明したように、本発明の光学フアイバ用
ガラスは、従来のSiO2系ガラスと比べてはるか
に長波長である約８μｍという長波長領域まで光
を透過することができ、又、BeF2及びThF4のよ
うな毒性のある成分を含まないので、その製造過
程及び使用に際して安全性が高く、かつ又、
BeF2及びZnCl2のような潮解性がないので、湿気
による特性の劣化もなく、信頼性が高いという利
点を有する。[Table] Example 3 Fluoride mixed powder having a composition of 20 mol% MgF 2 , 25 mol% CaF 2 , 10 mol% YF 3 , 5 mol% CeF 3 , 5 mol% NdF 3 and 35 mol% AlF 3 Approximately 2g was placed in a platinum crucible and placed in an argon gas atmosphere.
Melted at 1050℃. Next, the bottom of this crucible was immersed in water and cooled to obtain a vitrified optical fiber material with a thickness of 0.8 mm. The glasses obtained in Examples 1 to 3 were all non-deliquescent, did not crystallize even when left in the air at room temperature for 5 months, and no deterioration due to moisture was observed. Furthermore, both of these glasses are 0.3
It was transparent in a wide wavelength range from the ultraviolet region to the infrared region of ~8 μm, and no absorption peak due to OH groups was observed. As explained above, the optical fiber glass of the present invention can transmit light up to a long wavelength region of approximately 8 μm, which is a much longer wavelength than conventional SiO 2 glass, and also has BeF 2 and Since it does not contain toxic ingredients such as ThF 4 , it is highly safe in its manufacturing process and use, and
Since it does not have deliquescent properties like BeF 2 and ZnCl 2 , it has the advantage of high reliability without deterioration of properties due to moisture.
Claims (1)
BaF2よりなる群から選ばれた少なくとも１種の
フツ化物で置換した混合物20〜55モル％、(b)YF3
及びランタノイド元素のフツ化物よりなる群から
選ばれた少なくとも１種のフツ化物５〜50モル％
及び(c)AlF320〜65モル％よりなることを特徴と
する光学フアイバ用ガラス。1 (a) MgF 2 or a part of MgF 2 is mixed with CaF 2 , SrF 2 and
20-55 mol% mixture substituted with at least one fluoride selected from the group consisting of BaF 2 , (b) YF 3
and 5 to 50 mol% of at least one fluoride selected from the group consisting of fluorides of lanthanide elements.
and (c) 20 to 65 mol % of AlF 3 . A glass for optical fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10820280A JPS5734045A (en) | 1980-08-08 | 1980-08-08 | Glass for optical fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10820280A JPS5734045A (en) | 1980-08-08 | 1980-08-08 | Glass for optical fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5734045A JPS5734045A (en) | 1982-02-24 |
| JPS6259066B2 true JPS6259066B2 (en) | 1987-12-09 |
Family
ID=14478599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10820280A Granted JPS5734045A (en) | 1980-08-08 | 1980-08-08 | Glass for optical fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5734045A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07136308A (en) * | 1993-11-18 | 1995-05-30 | Masakazu Hayashi | Face protector for kendo |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2688778B1 (en) * | 1992-03-20 | 1994-11-10 | Verre Fluore Sa | FLUORINATED GLASSES. |
-
1980
- 1980-08-08 JP JP10820280A patent/JPS5734045A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07136308A (en) * | 1993-11-18 | 1995-05-30 | Masakazu Hayashi | Face protector for kendo |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5734045A (en) | 1982-02-24 |
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