JPH0280349A - Fluoride glass for fiber - Google Patents
Fluoride glass for fiberInfo
- Publication number
- JPH0280349A JPH0280349A JP63142898A JP14289888A JPH0280349A JP H0280349 A JPH0280349 A JP H0280349A JP 63142898 A JP63142898 A JP 63142898A JP 14289888 A JP14289888 A JP 14289888A JP H0280349 A JPH0280349 A JP H0280349A
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- glass
- fluoride glass
- baf2
- zrf4
- 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
- 239000005383 fluoride glass Substances 0.000 title claims abstract description 63
- 239000000835 fiber Substances 0.000 title claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 abstract description 20
- 230000008025 crystallization Effects 0.000 abstract description 20
- 229910001632 barium fluoride Inorganic materials 0.000 abstract description 16
- 229910007998 ZrF4 Inorganic materials 0.000 abstract description 14
- 238000000149 argon plasma sintering Methods 0.000 abstract description 14
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 abstract description 14
- 229910004504 HfF4 Inorganic materials 0.000 abstract description 7
- 229910001637 strontium fluoride Inorganic materials 0.000 abstract description 7
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 abstract description 7
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract description 4
- 239000013307 optical fiber Substances 0.000 abstract 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910002319 LaF3 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910009527 YF3 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012808 vapor phase Substances 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
- 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
-
- 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)
- 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)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はファイバー用フッ化物ガラスに関する。[Detailed description of the invention] [Industrial application field] The present invention relates to fluoride glasses for fibers.
本発明のファイバー用フッ化物ガラスは、光通信用ファ
イバー、医療用ファイバー、工業用ファイバー等に好ま
しく用いられる。The fluoride glass for fibers of the present invention is preferably used for optical communication fibers, medical fibers, industrial fibers, and the like.
［従来の技術およびその問題点］
光通信用ファイバーとしては、気相合成法（ＣＶＤ法）
等により作製される光の損失の少ない石英ガラスファイ
バーが用いられている。しかしながら、石英ガラスファ
イバーは、波長１．５μ■の光を伝送するものである。[Conventional technology and its problems] As fiber for optical communication, vapor phase synthesis method (CVD method)
A quartz glass fiber with low optical loss, which is manufactured by the above method, is used. However, the quartz glass fiber transmits light with a wavelength of 1.5 μι.
光の損失はレーリー散乱と赤外吸収により決まり、石英
ガラスの場合は理論損失値に近いところまで光の損失レ
ベルは到達している。Light loss is determined by Rayleigh scattering and infrared absorption, and in the case of silica glass, the light loss level has reached a level close to the theoretical loss value.
そこで光の損失が少なくなる２゜５５μｍの光を伝送で
きるファイバーとしてフッ化物ガラスが注目されている
。Therefore, fluoride glass is attracting attention as a fiber that can transmit light of 2°55 μm and reduces optical loss.
フッ化物ガラスとしては、ＺｒＦ４及び／又はＨｆＦａ
を必須成分として含むフッ化物ガラスがあり、このよう
なフッ化物ガラスとしては、特開昭５７−９２５４５号
公報に−ＺｒＦａ 、ＢａＦ２、ＮａＦ１ＹＦ３から成
るガラスが記載されている。As the fluoride glass, ZrF4 and/or HfFa
There is a fluoride glass containing as an essential component, and as such a fluoride glass, a glass consisting of -ZrFa, BaF2, and NaF1YF3 is described in JP-A-57-92545.
またＺｒＦａ及び／又はＨｆＦａを必須成分とする他の
フッ化物ガラスとしては、特開昭６２−２７５０３９＠
公報に、ＺｒＦ４及び／又はＨｆＦ４と、ＡＪ！Ｆ３と
、ＣａＦ＋ 、ＳｒＦ２及びＢａＦ２のうちの少なくと
も１種とから成るフッ化物ガラスが記載されている。Other fluoride glasses containing ZrFa and/or HfFa as essential components include JP-A-62-275039@
In the publication, ZrF4 and/or HfF4 and AJ! A fluoride glass consisting of F3 and at least one of CaF+, SrF2 and BaF2 is described.
しかしながら、これらのフッ化物ガラスは、ガラスの結
晶化に対する安定性がある程度改善されているが、充分
なものではなかった。However, although the stability of these fluoride glasses against glass crystallization has been improved to some extent, it has not been sufficient.
そして、ガラスの結晶化に対する安定性が充分でないと
、ガラス作製中やファイバー化するときに微結晶を生じ
易く、この微結晶が光を散乱するために得られたファイ
バーにおいて光の損失が多くなるという欠点がある。If the glass does not have sufficient stability against crystallization, microcrystals are likely to form during glass production or fiberization, and these microcrystals scatter light, resulting in a large loss of light in the resulting fiber. There is a drawback.
従って本発明の目的は、上記フッ化物ガラスの欠点を解
消し、結晶化に対する安定性に優れているので・、ガラ
ス中に生成する微結晶を減少させることができ、結果と
して光の散乱を少なくすることが可能なファイバー用フ
ッ化物ガラスを提供することにある。Therefore, the purpose of the present invention is to eliminate the above-mentioned drawbacks of fluoride glass, and because it has excellent stability against crystallization, it is possible to reduce microcrystals generated in the glass, and as a result, to reduce light scattering. The object of the present invention is to provide a fluoride glass for fibers that can be used for fibers.
１問題点を解決するための手段］
本発明は上述の問題点を解決するためになされたもので
あり、本発明のファイバー用フッ化物ガラスは、下記の
２つの態様のファイバー用フッ化物ガラスからなるもの
である。[Means for Solving Problem 1] The present invention has been made to solve the above-mentioned problems, and the fluoride glass for fiber of the present invention is obtained from the following two embodiments of fluoride glass for fiber. It is what it is.
態様（Ａ）：
フッ化物成分として、ＺｒＦ４及び／又はＨｆＦａと、
ＢａＦ２とを含有し、更にＰ２０５を全フッ化物成分に
対して０．１モル％以上含有することを特徴とするフッ
化物ガラス。Embodiment (A): ZrF4 and/or HfFa as a fluoride component,
A fluoride glass characterized by containing BaF2 and P205 in an amount of 0.1 mol% or more based on the total fluoride components.
態様（Ｂ）：
フッ化物成分として、ＺｒＦ４及び／又はＨｆＦａと、
Ａｊ！Ｆ３と、ＭｇＦ２ 、ＣａＦ２、ＳｒＦ２及びＢ
ａＦ２からなる群から選択される少なくとも１種とを含
有し、更にＰ２０５を全フッ化物成分に対して０．１モ
ル％以上含有することを特徴とするフッ化物ガラス。Embodiment (B): ZrF4 and/or HfFa as a fluoride component,
Aj! F3, MgF2, CaF2, SrF2 and B
A fluoride glass characterized by containing at least one member selected from the group consisting of aF2, and further containing 0.1 mol% or more of P205 based on the total fluoride components.
上記態様（Ａ）及び（Ｂ）のファイバー用フッ化物ガラ
スにおいて、Ｐ２０５の含有量は０．１モル％以上に限
定されるが、特に０．１〜１５モル％であるのが好まし
い。In the above embodiments (A) and (B) of the fluoride glass for fibers, the content of P205 is limited to 0.1 mol% or more, and is particularly preferably 0.1 to 15 mol%.
態様（Ａ）のフッ化物ガラスは、フッ化物成分としＴＺ
ｒＦａ及び／又はＨｆＦ４と、ＢａＦ２とを必須成分と
して含有するものである。The fluoride glass of embodiment (A) has TZ as a fluoride component.
It contains rFa and/or HfF4 and BaF2 as essential components.
このようなフッ化物ガラスとしては、上記必須成分（Ｚ
ｒＦ４及び／又はＨｆＦ４と、３ａＦ２）のみからなる
ものや、５７〜６９モル％のＺｒＦ４．２６〜３９モル
％のＢａＦ２及び２〜７モル％のＹＦ３を含むものく特
開昭５７−９２５４５号公報参照）が用いられる。Such fluoride glass contains the above essential component (Z
JP-A No. 57-92545 contains only rF4 and/or HfF4 and 3aF2), 57-69 mol% ZrF, 26-39 mol% BaF2 and 2-7 mol% YF3. ) is used.
また態様（Ｂ）のフッ化物ガラスは、フッ化物成分とし
てＺｒＦ４及び／又はＨｆＦａと、ＡｌＦ３と、ＭｇＦ
２ 、ＣａＦ２．５ｒＦｚ及びＢａＦ２からなる群から
選択される少なくとも１種とを必須成分として含有する
ものである。このようなフッ化物ガラスとしては、特開
昭６２−２７５０３９号公報に開示された下記の２種の
フッ化物ガラス（ｂｌ）及び（ｂ２）が挙げられる。Further, the fluoride glass of aspect (B) contains ZrF4 and/or HfFa, AlF3, and MgF as fluoride components.
2, CaF2.5rFz, and at least one selected from the group consisting of BaF2 as an essential component. Examples of such fluoride glasses include the following two types of fluoride glasses (bl) and (b2) disclosed in JP-A-62-275039.
フッ化物ガラス（ｂｌ）・・・ＺｒＦ４及び／又はＨｆ
Ｆａと、ＡｌＦ３と、ＭｇＦ２ 、ＣａＦ２、ＳｒＦ２
及びＢａＦ、＋からなる群から選択される少なくとも１
種とを、下記組成
ＺｒＦ４及び／又はＨｆ Ｆ ａ Ｏ，５〜２５％
Ａ１．Ｆ３ ２０〜４５ＭＯＦ２
０〜１５ＣａＦ２
０〜４２ＳｒＦ２ ０
〜２５ＢａＦ２ ０〜２５ＭｇＦ
２、ＣａＦ２、ＳｒＦ２
及びＢａＦ２の合間２０〜７０
で含有するフッ化物ガラス。Fluoride glass (bl)...ZrF4 and/or Hf
Fa, AlF3, MgF2, CaF2, SrF2
and at least one selected from the group consisting of BaF, +
seeds with the following composition ZrF4 and/or Hf F a O, 5 to 25%
A1. F3 20~45MOF2
0-15CaF2
0~42SrF2 0
~25BaF2 0~25MgF
2. Fluoride glass containing between 20 and 70% of CaF2, SrF2 and BaF2.
フッ化物ガラス（ｂ２）・・・上記フッ化物（ｂｌ）に
さらに下記成分
ＹＦ３及び／又は
ランタノイド元素
のフッ化物
ＺｎＦ＋
ＣａＦ２
ｎＦ３
ａＦ３
ｂＦ２
θ〜２５
０〜２０
０〜２０
０〜１０
０〜１０
０〜２５
アルカリ金属の
フッ化物 ０〜２０をこれらの
追加成分の合間が１〜５５％となるように加えたフッ化
物ガラス。Fluoride glass (b2)...The above fluoride (bl) further contains the following components YF3 and/or fluoride of lanthanide element ZnF+ CaF2 nF3 aF3 bF2 θ~25 0~20 0~20 0~10 0~10 0~ 25 Fluoride glass containing 0 to 20 alkali metal fluorides such that the content of these additional components is 1 to 55%.
又、態様（Ｂ）のフッ化物ガラスとして、ＺｒＦ４及び
／又はＨｆＦａと、ＡｊＦ３と、ＢａＦ２と、ＬａＦａ
と、ＮａＦとから成るもの（特開昭６１−６３５４４号
公報参照）を用いることもできる。Further, as the fluoride glass of aspect (B), ZrF4 and/or HfFa, AjF3, BaF2, LaFa
and NaF (see Japanese Patent Laid-Open No. 61-63544).
上記態様（Ａ）及び（Ｂ）のフッ化物ガラスは必須成分
としてＲ２０５を含有するものである。The fluoride glasses of embodiments (A) and (B) above contain R205 as an essential component.
フッ化物ガラスの結晶化に対づる安定性の低下は、ガラ
スの溶融条件、例えば溶融雰囲気中の酸素や水分の存在
や、フッ化物原料中の酸化物等にも依存するが、本質的
には、フッ化物ガラスはイオン結合性が強く、低粘性で
あるためにイオンの拡散が起り易いことに依存する。本
発明においてフッ化物ガラス中に含有させたＰ２Ｏ５は
修飾酸化物を溶解する能力、従って酸化物などの不純物
を溶解する能力が大きく、かつ網目形成酸化物であるた
め、粘性を大ぎくしイオンの拡散をおさえることにより
、フッ化物ガラスの結晶化に対する安定性を高めるもの
と考えられる。The decrease in stability of fluoride glass due to crystallization depends on the glass melting conditions, such as the presence of oxygen and moisture in the melting atmosphere, and the presence of oxides in the fluoride raw material, but essentially This depends on the fact that fluoride glass has strong ionic bonding properties and low viscosity, which facilitates ion diffusion. In the present invention, the P2O5 contained in the fluoride glass has a great ability to dissolve modified oxides, and therefore impurities such as oxides, and is a network-forming oxide, so it greatly reduces the viscosity and ions. It is thought that by suppressing diffusion, the stability of the fluoride glass against crystallization is increased.
フッ化物ガラス中に含有されるＰ２Ｏ５の量は０．１モ
ル％未満ではガラスの結晶化に対する安定性を高くする
効果を得ることができないが、０゜１モル％以上ならば
、上記効果を得ることができる。好ましいＲ２０５の含
有量は０．１〜１５モル％である。Ｒ２０５が１５モル
％を超えると、Ｒ２０ｓに由来するＰとＯの結合による
吸収が短波長に拡がり波長２．５５μｍにまで吸収によ
る光の損失が影響するようになるので、好ましくない。If the amount of P2O5 contained in the fluoride glass is less than 0.1 mol%, the effect of increasing the stability against crystallization of the glass cannot be obtained, but if it is 0.1 mol% or more, the above effect can be obtained. be able to. The preferred content of R205 is 0.1 to 15 mol%. If R205 exceeds 15 mol %, the absorption due to the bond between P and O originating from R20s will spread to shorter wavelengths, and the loss of light due to absorption will affect wavelengths up to 2.55 μm, which is not preferable.
このように本発明のフッ化物ガラスはＲ２０ｓの量が少
１ｔ（０，１モル％以上、好ましくは０゜１〜１５モル
％）でもガラスの結晶化に対する安定性を高めることが
でき、また多量のＲ２０ｓを添加したことによる上記悪
影響を排除できる点で優れている。As described above, the fluoride glass of the present invention can improve the stability against crystallization of the glass even with a small amount of R20s of 1 t (0.1 mol% or more, preferably 0.1 to 15 mol%), and even with a large amount of R20s. It is excellent in that it can eliminate the above-mentioned adverse effects caused by the addition of R20s.
（実施例）
以下、本発明の実施例について説明するが、本発明はこ
れらの実施例に限定されるものではない。(Examples) Examples of the present invention will be described below, but the present invention is not limited to these Examples.
なお％は特記しない限りモル％を示すものとする。Note that % indicates mol% unless otherwise specified.
実施例−１
出発原料として、ＺｒＦ４、ＢａＦ２、ＬａＦ３、Ｎａ
Ｆ、、Ｂａ （ＰＯａ ）２を用いた。Example-1 ZrF4, BaF2, LaF3, Na as starting materials
F,,Ba(POa)2 was used.
これらをＺｒＦ４ ：５３．０％、ＢａＦ２ ：２３
゜０％、ＬａＦ３ ：４．０％、ＮａＦ：２０．０％
（全フッ化物で１００％）およびＰ２Ｏ５：１゜５％と
なるように混合した。得られた混合物を白金ルツボに入
れたのち、アルゴン雰囲気とした約８５０℃の電気炉中
で約２時間加熱溶融した。溶融後、電気炉内から白金ル
ツボを取り出し、約２７０℃まで放冷した。その後、約
２７０℃のアニール炉に入れ徐冷して５０ｊｗφ、厚さ
１１ｍの無色透明のガラスを得た。These were ZrF4: 53.0%, BaF2: 23%
゜0%, LaF3: 4.0%, NaF: 20.0%
(total fluoride: 100%) and P2O5:1.5%. The resulting mixture was placed in a platinum crucible and then heated and melted for about 2 hours in an electric furnace at about 850° C. in an argon atmosphere. After melting, the platinum crucible was taken out from the electric furnace and allowed to cool to about 270°C. Thereafter, it was placed in an annealing furnace at about 270° C. and slowly cooled to obtain a colorless and transparent glass having a diameter of 50 jw and a thickness of 11 m.
ガラスの結晶化に対づる安定性は、示差走査熱量計（Ｄ
ＳＣ）を用いて、約２０ａｙのガラスを室温から１０℃
／Ｓｉｎの剪温速度で５５０℃まで昇温したときの結晶
化による発熱量を測定することにより行った。第１図に
ＤＳＧ曲線を示す。その結果、本実施例のガラスは発熱
量が５．３９ｃａｌ／ｇと少なく、結晶化に対する安定
性が高いことが明らかとなった。The stability of glass against crystallization can be measured using differential scanning calorimetry (D
About 20 ay of glass was heated from room temperature to 10℃ using SC).
This was done by measuring the amount of heat generated by crystallization when the temperature was raised to 550° C. at a shearing rate of /Sin. FIG. 1 shows the DSG curve. As a result, it was revealed that the glass of this example had a low calorific value of 5.39 cal/g and had high stability against crystallization.
光の散乱の測定は、波長４８８ ｎｍ及び５１４゜５ｓ
ｍのＡｒイオンレーザ−１波長６２３．８ｓｍのＨｅ−
Ｎｅレーザーの光を、１５ｓｖＸ １０ｓｍＸ ２０Ｊ
ＩＭ＋の大きさに大面研摩したガラスに入射させ、上記
３つの波長に対する、９０°方向の散乱（レーリー比：
Ｒ９０°）を測定し、これらをプロットして、波長（ｎ
ｍ）を変動させた場合のレーリー比の直線を求めた。そ
の結果、この直線は石英ガラスのレーリー比の直線に近
いことが判明した。The measurement of light scattering was performed at a wavelength of 488 nm and 514°5 seconds.
m Ar ion laser - 1 wavelength 623.8 sm He -
Ne laser light, 15svX 10smX 20J
Scattering in the 90° direction for the above three wavelengths (Rayleigh ratio:
Measure the wavelength (n
A straight line of Rayleigh ratio was determined when m) was varied. As a result, it was found that this straight line was close to the Rayleigh ratio straight line of silica glass.
実施例−２
Ｒ２０５の聞を２．５モル％にした以外は実施例１と同
様に実施して、ファイバー用フッ化物ガラスを得た。Example 2 A fluoride glass for fibers was obtained in the same manner as in Example 1 except that the content of R205 was 2.5 mol %.
冑られたフッ化物ガラスを実施例−１と同様の方法で、
結晶化による発熱量を測定した。得られたＤＳＣ曲線を
第１図に示す。発熱量は２．０５ｃａｔ／ｇであり、実
施例−１におｔプる発熱量よりも更に少ないものであっ
た。The crushed fluoride glass was treated in the same manner as in Example-1,
The amount of heat generated by crystallization was measured. The obtained DSC curve is shown in FIG. The calorific value was 2.05 cat/g, which was even smaller than the calorific value of Example-1.
さらに、このフッ化物ガラスについて実施例−１と同様
の方法で、光の散乱を測定したところ、そのレーリー比
の直線が実施例−１の場合よりも石英ガラスのレーリー
比の直線にさらに近いことが判明した。Furthermore, when the light scattering of this fluoride glass was measured in the same manner as in Example-1, it was found that the Rayleigh ratio straight line was closer to the Rayleigh ratio straight line of silica glass than in Example-1. There was found.
比較例−１
出発原料として、Ｂａ （ＰＯ３）２を用いなかった以
外は実施例−１と同様にして、フッ化物成分の種類およ
び組成（モル％）が実施例−１と同一で、Ｐ２０５を含
まない無色透明のガラスを得た。Comparative Example-1 The same procedure was used as in Example-1 except that Ba (PO3)2 was not used as the starting material, the type and composition (mol%) of the fluoride component were the same as in Example-1, and P205 was used. A colorless and transparent glass containing no chlorine was obtained.
得られたガラスについて実施例−１と同様の方法で結晶
化による発熱量を測定した。得られた０３０曲線を第１
図に示す。発熱量は１４．２７ｃａｌ／ｇと極めて多い
ものであった。The amount of heat generated by crystallization of the obtained glass was measured in the same manner as in Example-1. The obtained 030 curve is the first
As shown in the figure. The calorific value was extremely high at 14.27 cal/g.
また、実施例−１と同様の方法で、光の散乱を測定した
。得られたレーリー比の直線は石英ガラスのそれと著し
く隔てられており、光の散乱が顕著に認められた。Furthermore, light scattering was measured in the same manner as in Example-1. The obtained Rayleigh ratio straight line was significantly different from that of silica glass, and light scattering was observed significantly.
実施例−３
出発原料として、実施例−１のフッ化物成分とともにＨ
ｆＦ４を用い、ＨｆＦ４ ：３９．８％、ＺｒＦａ
：１３．２％、ＢａＦ２：２３．０％、ＬａＦ３ ：４
．０％、ＮａＦ：２０．０％（全フッ化物で１００％）
およびＰ２０５ ：０．５％となるように混合したの
ち、実施例−１と同様の方法で無色透明のフッ化物ガラ
スを得た。Example-3 As a starting material, along with the fluoride component of Example-1, H
Using fF4, HfF4: 39.8%, ZrFa
: 13.2%, BaF2: 23.0%, LaF3: 4
．． 0%, NaF: 20.0% (100% with total fluoride)
and P205: 0.5%, and then a colorless and transparent fluoride glass was obtained in the same manner as in Example-1.
得られたフッ化物ガラスについて実施例−１と同様の方
法で結晶化による発熱量を測定した。得られた０３０曲
線を第２図に示す。発熱量は４゜８５Ｃａｌ／ｇと少な
いものであった。The amount of heat generated by crystallization of the obtained fluoride glass was measured in the same manner as in Example-1. The obtained 030 curve is shown in FIG. The calorific value was as low as 4°85 Cal/g.
さらに、実施例−１と同様の方法で光の散乱を測定した
。その結果、実施例−１と同様の結果が得られた。Furthermore, light scattering was measured in the same manner as in Example-1. As a result, the same results as in Example-1 were obtained.
実施例−４
Ｐ２０ｓの聞を１．０％とした以外は実施例−３と同様
の方法で無色透明のフッ化物ガラスを得た。Example 4 A colorless and transparent fluoride glass was obtained in the same manner as in Example 3 except that the P20s content was 1.0%.
得られたフッ化物ガラスについて実施例−１と同様の方
法で、結晶化による発熱量を測定した。The amount of heat generated by crystallization of the obtained fluoride glass was measured in the same manner as in Example-1.
得られた０３０曲線を第２図に示す。発熱Ｗは２゜１２
ｃａｌ ／ｇであり、実施例−３の場合よりも更に少な
いものであった。The obtained 030 curve is shown in FIG. Heat generation W is 2°12
cal/g, which was even smaller than that in Example-3.
さらに、このフッ化物ガラスについて実施例＝１と同様
の方法で光の散乱を測定したところ、実施例−３と同様
の結果が得られた。Furthermore, when the light scattering of this fluoride glass was measured in the same manner as in Example 1, the same results as in Example 3 were obtained.
比較例−２
出発原ｒ１として、Ｂａ （ＰＯ３）２を用いなかった
以外は実施例−３と同様にして、フッ化物成分の種類お
よび組成（モル％）が実施例−３と同一で、Ｐ２０ｓを
含まない無色透明のフッ化物ガラスを得た。Comparative Example-2 The same procedure was used as in Example-3 except that Ba (PO3)2 was not used as the starting material r1, the type and composition (mol%) of the fluoride component were the same as in Example-3, and P20s A colorless and transparent fluoride glass containing no fluoride was obtained.
得られたフッ化物ガラスについて実施例−１と同様の方
法で、結晶化による発熱−を測定した。The heat generated by crystallization of the obtained fluoride glass was measured in the same manner as in Example 1.
冑られた０３０曲線を第２図に示す。発熱部は１１ 、
１３ｃａｌ ／９と極めて多いものであった。The broken 030 curve is shown in Figure 2. The heat generating part is 11,
The amount was extremely high at 13 cal/9.
さらにこのフッ化物ガラスについて実施例−１と同様の
方法で、光の散乱を測定した。得られたレーり比の直線
は石英ガラスのそれと茗しく隔てられており、光の散乱
が顕著に認められた。Furthermore, light scattering of this fluoride glass was measured in the same manner as in Example-1. The obtained lay ratio straight line was slightly different from that of silica glass, and light scattering was observed significantly.
実施例−５
出発原料として、実施例−１のフッ化物成分とともにＡ
ｊ！Ｆ３、ＹＦ３ 、ＭｇＦ２ 、ＣａＦ２、ＳｒＦ２
、Ａｌ（ＰＯ３）３を用い、ＺｒＦａ：１０．２％、Ａ
ｌＦ３ ：３０．２％、ＹＦ３ ：８゜３％、ＭｇＦ
２ ：３．５％、ＣａＦ＋ ：２０．３％、ＳｒＦ２
１３．２％、ＢａＦ２ ： １０．５％、ＮａＦ：３．
８％（全フッ化物で１００％）およびＰ２Ｏ５ニア、５
％となるように混合した。得られた混合物を白金ルツボ
に入れ、アルゴン雰囲気とした約９００℃の電気炉中で
約２時間加熱溶融した。溶融後、電気炉内から白金ルツ
ボを取り出し、約３８０℃まで放冷した。その後、約３
８０℃のアニール炉に入れ徐冷して５０ｊＩＩφ、厚さ
１３＃ｌＩの無色透明のフッ化物ガラスを得た。Example-5 As a starting material, A along with the fluoride component of Example-1
j! F3, YF3, MgF2, CaF2, SrF2
, using Al(PO3)3, ZrFa: 10.2%, A
lF3: 30.2%, YF3: 8°3%, MgF
2: 3.5%, CaF+: 20.3%, SrF2
13.2%, BaF2: 10.5%, NaF: 3.
8% (100% total fluoride) and P2O5 near, 5
%. The obtained mixture was placed in a platinum crucible and heated and melted for about 2 hours in an electric furnace at about 900° C. in an argon atmosphere. After melting, the platinum crucible was taken out from the electric furnace and allowed to cool to about 380°C. After that, about 3
The glass was placed in an annealing furnace at 80°C and slowly cooled to obtain a colorless and transparent fluoride glass having a diameter of 50jIIφ and a thickness of 13#lI.
得られたフッ化物ガラスを実施例−１と同様の方法で、
結晶化による発熱量を測定した。得られた０３０曲線を
第３図に示す。発熱量は５．０５ｃａｌ／９と少ないも
のであった。The obtained fluoride glass was treated in the same manner as in Example-1,
The amount of heat generated by crystallization was measured. The obtained 030 curve is shown in FIG. The calorific value was as low as 5.05 cal/9.
さらに、実施例−１と同様の方法で光の散乱を測定した
ところ、実施例−１と同様の結果が得られた。Furthermore, when light scattering was measured in the same manner as in Example-1, the same results as in Example-1 were obtained.
比較例−３
出発原料として、Ａｌ （ＰＯａ ）ａとＢａ （ＰＯ
３）２を用いなかった以外は実施例−５と同様にして、
フッ化物成分の種類および組成（モル％）が実施例−５
と同一で、Ｐ２Ｏ５を含まない無色透明のフッ化物ガラ
スを得た。Comparative Example-3 As starting materials, Al (POa)a and Ba (PO
3) Same as Example-5 except that 2 was not used,
The type and composition (mol%) of the fluoride component are as in Example-5.
A colorless and transparent fluoride glass containing no P2O5 was obtained.
得られたフッ化物ガラスについて実施例−１と同様の方
法で、結晶化による発熱量を測定した。The amount of heat generated by crystallization of the obtained fluoride glass was measured in the same manner as in Example-1.
得られたＤＳＣ曲線を第３図に示す。発熱量は３３、１
ｃａｌ ／ｇと多いものであった。The obtained DSC curve is shown in FIG. Calorific value is 33.1
The amount was as high as cal/g.
さらに、実施例−１と同様の方法で、光の散乱を測定し
たところ、得られたレーリー比の直線は石英ガラスのそ
れと著しく隔てられており、光の散乱が顕著に認められ
た。Furthermore, when light scattering was measured in the same manner as in Example 1, the obtained Rayleigh ratio straight line was significantly different from that of quartz glass, and light scattering was clearly observed.
実施例−６〜６６
実施例−１と同様の方法で、表−１の実施例−６〜６６
欄に示したような組成から成る無色透明のフッ化物ガラ
スを得た。Examples-6 to 66 Examples-6 to 66 in Table-1 were prepared in the same manner as in Example-1.
A colorless and transparent fluoride glass having the composition shown in the column was obtained.
得られた実施例−６〜６６のガラスについて実施例−１
と同様な方法で結晶化による発熱量及びレーリー比の測
定を行ったが、すべてのガラスについて、発熱量が少な
くレーリー比の直線が石英ガラスに近いものであった。Example-1 for the obtained glasses of Examples-6 to 66
The calorific value and Rayleigh ratio due to crystallization were measured in the same manner as above, and all of the glasses showed a small calorific value and a straight line of Rayleigh ratio similar to that of quartz glass.
（以下余白）
［発明の効果］
以上述べたように、本発明のフッ化物ガラスは、結晶化
に対する安定性が高く、ガラス中に生成する微結晶を減
少させ、光散乱を少なくできるという効果を有する。従
って光通信用ファイバー母材として極めて有用である。(The following is a blank space) [Effects of the Invention] As described above, the fluoride glass of the present invention has high stability against crystallization, reduces microcrystals generated in the glass, and has the effect of reducing light scattering. have Therefore, it is extremely useful as a fiber base material for optical communications.
又、化学的耐久性及び熱的安定性にも優れているため医
療用ファイバー工業用ファイバーとしても有用である。Furthermore, since it has excellent chemical durability and thermal stability, it is also useful as a medical fiber industrial fiber.
さらに適量のＰ２０ｓを含む本発明のフッ化物ガラスは
、ＺｒＦ４とＢａＦ２を主成分とするガラスより熱膨脹
係数が小さくかつ屈折率も低いので、ＺｒＦ４とＢａＦ
２を主成分とするフッ化物ガラスのクラッド用ガラスと
しても極めて適している。Furthermore, the fluoride glass of the present invention containing an appropriate amount of P20s has a smaller coefficient of thermal expansion and a lower refractive index than glass whose main components are ZrF4 and BaF2.
It is also extremely suitable as a cladding glass for fluoride glass containing fluoride glass as the main component.
なお、本発明のフッ化物ガラスは、レンズやプリズム等
の光学ガラスとしても利用可能である。Note that the fluoride glass of the present invention can also be used as optical glass for lenses, prisms, and the like.
第１図は、実施例−１、実施例−２及び比較例−１で得
られたフッ化物ガラスのＤＳＣ曲線図、第２図は、実施
例−３、実施例−４及び比較例−２で得られたフッ化物
ガラスのＤＳＣ曲線図、第３図は、実施例−５及び比較
例−３で得られたＤＳＣ曲線図である。Fig. 1 is a DSC curve diagram of the fluoride glasses obtained in Example-1, Example-2, and Comparative Example-1, and Fig. 2 is a DSC curve diagram of the fluoride glasses obtained in Example-3, Example-4, and Comparative Example-2. FIG. 3 is a DSC curve diagram of the fluoride glass obtained in Example-5 and Comparative Example-3.
Claims (1)
＿４と、ＢａＦ＿２とを含有し、更にＰ＿２Ｏ＿５を全
フッ化物成分に対して０．１モル％以上含有することを
特徴とするファイバー用フッ化物ガラス。 ２、フッ化物成分として、ＺｒＦ＿４及び／又はＨｆＦ
＿４と、ＡｌＦ＿３と、ＭｇＦ＿２、ＣａＦ＿２、Ｓｒ
Ｆ＿２及びＢａＦ＿２からなる群から選択される少なく
とも１種とを含有し、更にＰ＿２Ｏ＿５を全フッ化物成
分に対して０．１モル％以上含有することを特徴とする
ファイバー用フッ化物ガラス。[Claims] 1. ZrF_4 and/or HfF as a fluoride component
_4 and BaF_2, and further contains P_2O_5 in an amount of 0.1 mol% or more based on the total fluoride components. 2. ZrF_4 and/or HfF as a fluoride component
_4, AlF_3, MgF_2, CaF_2, Sr
A fluoride glass for fibers, comprising at least one selected from the group consisting of F_2 and BaF_2, and further containing 0.1 mol% or more of P_2O_5 based on the total fluoride components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63142898A JPH0280349A (en) | 1988-06-10 | 1988-06-10 | Fluoride glass for fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63142898A JPH0280349A (en) | 1988-06-10 | 1988-06-10 | Fluoride glass for fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0280349A true JPH0280349A (en) | 1990-03-20 |
Family
ID=15326165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63142898A Pending JPH0280349A (en) | 1988-06-10 | 1988-06-10 | Fluoride glass for fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0280349A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997007068A1 (en) * | 1995-08-15 | 1997-02-27 | British Technology Group Ltd. | Infrared transmitting optical fibre materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654249A (en) * | 1979-10-04 | 1981-05-14 | Ohara Inc | Fluoride glass |
| JPS59116149A (en) * | 1982-12-23 | 1984-07-04 | Kokusai Denshin Denwa Co Ltd <Kdd> | Optical fiber for infrared rays and its manufacture |
-
1988
- 1988-06-10 JP JP63142898A patent/JPH0280349A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654249A (en) * | 1979-10-04 | 1981-05-14 | Ohara Inc | Fluoride glass |
| JPS59116149A (en) * | 1982-12-23 | 1984-07-04 | Kokusai Denshin Denwa Co Ltd <Kdd> | Optical fiber for infrared rays and its manufacture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997007068A1 (en) * | 1995-08-15 | 1997-02-27 | British Technology Group Ltd. | Infrared transmitting optical fibre materials |
| US6037285A (en) * | 1995-08-15 | 2000-03-14 | Btg International Limited | Infrared transmitting optical fiber materials |
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