JPS6054895B2 - Fluorophosphate glass with almost no bubbles and its manufacturing method - Google Patents
Fluorophosphate glass with almost no bubbles and its manufacturing methodInfo
- Publication number
- JPS6054895B2 JPS6054895B2 JP1405379A JP1405379A JPS6054895B2 JP S6054895 B2 JPS6054895 B2 JP S6054895B2 JP 1405379 A JP1405379 A JP 1405379A JP 1405379 A JP1405379 A JP 1405379A JP S6054895 B2 JPS6054895 B2 JP S6054895B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- fluorophosphate glass
- bubbles
- manufacturing
- bromine
- 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
- 239000005303 fluorophosphate glass Substances 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 238000002834 transmittance Methods 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- -1 platinum ions Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007670 refining Methods 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
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)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
従来、燐酸を硝子形成材とし、これに多量の各種金属弗
化物を加えた、いわゆる弗燐酸塩硝子は、低屈折高分散
の光学特性を有する極めて有用な硝子として知られてい
る。[Detailed Description of the Invention] Conventionally, so-called fluorophosphate glass, which is made by using phosphoric acid as a glass forming material and adding a large amount of various metal fluorides to it, has been known as an extremely useful glass having optical properties of low refraction and high dispersion. It is being
他方、近来、原子の核分裂に代わる次のエネルギー源と
して核融合が注目され、これを行うレーザー発振材料と
して、大口径のレーザーロッドやディスクが多量に使用
され、このレーザーガラスの特性として非線形光学常数
の小さいものが要求されるが、それには弗燐酸塩硝子が
最適とされている。しかし、この硝子は溶融中に小泡を
多く発生し、これが浮上消失し難いため、製品中に多数
の小泡が残留して品質を著しく低下する。On the other hand, in recent years, nuclear fusion has attracted attention as the next energy source to replace nuclear fission, and large diameter laser rods and disks are widely used as laser oscillation materials for this purpose.The characteristics of this laser glass include nonlinear optical constants. A small one is required, and fluorophosphate glass is said to be optimal for this purpose. However, this glass generates many small bubbles during melting, and since these bubbles are difficult to float and disappear, many small bubbles remain in the product, significantly degrading the quality.
またレーザーに使用した場合、発振効率を高くするため
、透過率の著しく良い硝子が要求されるが、これまで原
料の純度を上げても、一定の限度以上には良くすること
ができなかつた。一般に、硝子の清澄剤としてＡＳ２Ｏ
３やＳｂ、Ｏｓが使用されるが、弗燐酸塩硝子の場合に
は１０００℃以下の低い溶解温度て処理されるため殆ん
ど効果がない。Furthermore, when used in lasers, glass with extremely high transmittance is required to increase oscillation efficiency, but until now it has not been possible to improve the transmittance beyond a certain limit even by increasing the purity of the raw materials. Generally, AS2O is used as a glass refining agent.
3, Sb, and Os are used, but in the case of fluorophosphate glass, they are hardly effective because they are processed at a low melting temperature of 1000° C. or less.
即ちこの硝子では１０００℃以上の高温度で溶解すると
、弗素の揮発が増大し、所期の光学特性が得られず、甚
だしいときは、硝子が先送する等の欠点がある。本発明
者等は、これらの難点を解決するため種々研究した結果
、前記の小泡発生の原因を知ると共に、本発明を得たの
である。That is, when this glass is melted at a high temperature of 1000° C. or higher, the volatilization of fluorine increases, making it impossible to obtain the desired optical properties, and in extreme cases, there are disadvantages such as the glass being delayed. As a result of various studies to solve these difficulties, the present inventors learned the cause of the generation of small bubbles and obtained the present invention.
弗燐酸塩硝子は多量の弗素を含有するので、溶融性硝子
中のガスの過飽和度が極めて高く、かつ極低粘度のため
、溶融るつぼとして使用した白金と硝子との接触面に多
数の小泡が発生し、これが該面から離れて硝子中に多数
存在することになる。Since fluorophosphate glass contains a large amount of fluorine, the degree of supersaturation of the gas in the meltable glass is extremely high, and because it has an extremely low viscosity, many small bubbles form on the contact surface between the platinum and the glass used as a melting crucible. is generated, and a large number of these particles are present in the glass away from the surface.
ところが、弗燐酸塩硝子に、アニオニツク％で０．１以
上の沃素及び／又は臭素を添加すれば、前記の小泡発生
の防止に極めて有効であり、また溶解を行う場合、Ｎｏ
等の中性ガスの雰囲気ですると、短波長域の透過率を良
くすることを見出し’た。However, if iodine and/or bromine is added to fluorophosphate glass in an anionic percentage of 0.1 or more, it is extremely effective in preventing the formation of small bubbles, and when dissolving it,
We have discovered that the transmittance in the short wavelength range can be improved by using a neutral gas atmosphere such as .
即ち、弗燐酸塩硝子に沃素及び／又は臭素を添加すれば
、白金と硝子との濡れが極めて悪くなり、白金るつぼの
接触面における小泡の発生が殆んど防止され、従つて硝
子中の泡が極めて少く、良質の光学製品を得ることがで
きる。That is, if iodine and/or bromine are added to fluorophosphate glass, the wetting between platinum and glass becomes extremely poor, the generation of small bubbles on the contact surface of the platinum crucible is almost prevented, and the There are very few bubbles and high quality optical products can be obtained.
そして白金と硝子との濡れが悪くなるため、両者の直接
の反応が進行しにくくなり、該溶融を中性ガス雰囲気で
行うと、白金イオンの硝子中への溶け込みが極めて少く
なり、白金イオンによる光の吸収が少くなるので、短波
長域での透過率が良くなる。Since the wetting of platinum and glass becomes poor, direct reaction between the two becomes difficult to proceed.If the melting is performed in a neutral gas atmosphere, the dissolution of platinum ions into the glass becomes extremely small, and the platinum ions Since light absorption is reduced, transmittance in the short wavelength range is improved.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
カチオニツク％で、 なる組成の弗燐酸塩硝子を基礎硝子として次表を得た。In cationic%, The following table was obtained using fluorophosphate glass with the following composition as the basic glass.
各成分はカチオニツク％又はアニオニツク％で示し、Ｈ
Ｎｄ２Ｏ３，Ｉ，Ｂｒは弗燐酸塩硝子を１００％とし、
外割添加したものであり、またＭＯＯ３はソーラリゼー
シヨン防止剤として入れたものである。上記組成の原料
を約１０００℃で溶融し、８００〜９００℃で攪拌清澄
し、さらに７００℃で攪拌して鋳込み成形し、泡数を測
定した。上表の示すように、沃素及び／又は臭素を添加
しない場合は、泡数が３５０〜５０柵／Ｋ９あつたが、
これらを添加した場合はＯ〜１個／Ｋ９に減少した。Each component is expressed as cationic % or anionic %, H
Nd2O3, I, Br is 100% fluorophosphate glass,
MOO3 was added as a solarization inhibitor. The raw material having the above composition was melted at about 1000°C, stirred and clarified at 800 to 900°C, and further stirred and cast at 700°C, and the number of bubbles was measured. As shown in the table above, when iodine and/or bromine is not added, the number of bubbles is 350 to 50 bars/K9, but
When these were added, the number decreased to 0 to 1 piece/K9.
また、添付の図面は、参考例１，２及び実施例３，４を
窒素ガス雰囲気で溶融成形し、その各透過率曲線をそれ
ぞれの番号を付けて示したもので、弗燐酸塩硝子に沃素
及び／又は臭素を添加し、中性ガス雰囲気で溶融成形し
たものは短波長域の透過率が著しく良くなつたことが分
る。In addition, the attached drawings show the transmittance curves of Reference Examples 1 and 2 and Examples 3 and 4 melted and molded in a nitrogen gas atmosphere with respective numbers attached. It can be seen that the transmittance in the short wavelength region was significantly improved when bromine was added and/or bromine was added and melt-molded in a neutral gas atmosphere.
図は本発明実施例及び参考例の透過率曲線図である。
１，２，３，４・・・参考例１，２及び実施例３，４の
それぞれの透過率曲線。The figure is a transmittance curve diagram of an example of the present invention and a reference example. 1, 2, 3, 4...Transmittance curves of Reference Examples 1 and 2 and Examples 3 and 4.
Claims (1)
ニツク％以上添加してなる弗燐酸塩硝子。 ２ 弗燐酸塩硝子に沃素及び／又は臭素を０．１アニオ
ニツク％以上添加し、かつ中性ガス雰囲気で溶融成形す
ることを特徴とする泡が殆んどなく、短波長域の透過率
が良い弗燐酸塩硝子の製造法。[Scope of Claims] 1. A fluorophosphate glass obtained by adding 0.1% or more of anionic iodine and/or bromine to a fluorophosphate glass. 2. It is characterized by adding 0.1% or more anionic % of iodine and/or bromine to fluorophosphate glass and melting and forming it in a neutral gas atmosphere.It has almost no bubbles and has good transmittance in the short wavelength range. Method for producing fluorophosphate glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1405379A JPS6054895B2 (en) | 1979-02-09 | 1979-02-09 | Fluorophosphate glass with almost no bubbles and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1405379A JPS6054895B2 (en) | 1979-02-09 | 1979-02-09 | Fluorophosphate glass with almost no bubbles and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55109242A JPS55109242A (en) | 1980-08-22 |
| JPS6054895B2 true JPS6054895B2 (en) | 1985-12-02 |
Family
ID=11850337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1405379A Expired JPS6054895B2 (en) | 1979-02-09 | 1979-02-09 | Fluorophosphate glass with almost no bubbles and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6054895B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3634676A1 (en) * | 1985-10-19 | 1987-04-23 | Leitz Ernst Gmbh | OPTICAL FLUORPHOSPHATE GLASSES WITH POSITIVE ANOMAL PARTIAL DISPERSION AND IMPROVED PHYSICO-CHEMICAL PROPERTIES AND METHOD FOR THE PRODUCTION THEREOF |
| JP4469589B2 (en) * | 2003-08-28 | 2010-05-26 | オーエムジー株式会社 | Light transmissive phosphate glass |
-
1979
- 1979-02-09 JP JP1405379A patent/JPS6054895B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55109242A (en) | 1980-08-22 |
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