JP3732545B2 - Infrared transmission glass - Google Patents
Infrared transmission glass Download PDFInfo
- Publication number
- JP3732545B2 JP3732545B2 JP03001695A JP3001695A JP3732545B2 JP 3732545 B2 JP3732545 B2 JP 3732545B2 JP 03001695 A JP03001695 A JP 03001695A JP 3001695 A JP3001695 A JP 3001695A JP 3732545 B2 JP3732545 B2 JP 3732545B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- wavelength
- present
- infrared
- infrared transmission
- 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 - Lifetime
Links
- 239000011521 glass Substances 0.000 title claims description 25
- 230000005540 biological transmission Effects 0.000 title 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 6
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000003287 optical effect Effects 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
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000005387 chalcogenide glass Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005383 fluoride glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- 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
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
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
【０００１】
【産業上の利用分野】
本発明は新しい赤外線透過ガラスに関する。本発明のガラスは可視域から波長７．８μｍの赤外域まで高い光線透過性を有するため、近赤外、赤外域において使用される各種光学機器に用いられる窓、レンズ、プリズム、フィルター、光計測ファイバーなどに利用される。
【０００２】
【従来の技術】
波長７．８μｍの赤外域まで高い光線透過性を有する赤外透過ガラスとしてはフッ化物ガラスとカルコゲン化物ガラスが知られている。しかし、どちらも製造過程が繁雑で、かつ、熱的に不安定であるという欠点がある。酸化物系ガラスとしてはアルミン酸塩ガラス、ゲルマン酸塩ガラス、亜テルル酸塩ガラスなどが知られているが、いずれも波長５．０μｍ以上の赤外域での光線透過性が非常に悪い。より長い波長の赤外域まで良好な透過率を示す酸化物ガラスとしては米国特許３，７２３，１４１号に示されているＢｉ2Ｏ3−ＰｂＯ−ＢａＯ−ＺｎＯ系のガラスと特開平５−１３２３３３号公報に開示されているＧａ2Ｏ3−Ｂｉ2Ｏ3−Ｒ2Ｏ（Ｒ＝アルカリ金属）系のガラスが知られているが、これらのガラスには環境に有害なＰｂＯと高価なＧａ2Ｏ3が大量に含まれている。
【０００３】
【発明が解決しようとする課題】
本発明の課題は上記の欠点を除去し、波長７．８μｍの赤外域まで良好な光線透過性を有する赤外線透過ガラスを提供することにある。
【０００４】
【課題を解決するための手段】
上記の問題点を解決するために、本発明者は鋭意研究を重ねた結果、従来の技術資料に具体的に示されていないＢｉ2Ｏ3−ＲＯ（Ｒ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）−Ｌｉ2Ｏ各三成分系において大きなガラス化範囲が存在することを発見し、さらにこれらの発見に基づいて上述の物質を組み合わせることによって、どの三成分系よりも熱的に安定なガラスが得られることを見いだし、本発明をなすに至った。
【０００５】
すなわち、本発明は、モル％で、Ｂｉ２Ｏ３ １０〜４０％（ただし４０％を除く）、ＲＯ（ただし、Ｒ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）５〜５０％、Ｌｉ２Ｏ ２０〜７０％を含有し、ＰｂＯ、ＣｄＯおよびＧａ２Ｏ３を含有しないことを特徴とする赤外線透過ガラスである。
【０００６】
Ｂｉ2Ｏ3、ＲＯ、Ｌｉ2Ｏ成分は通常の酸化物、炭酸塩、および硝酸塩原料からとることが可能である。これらの三成分系以外には、ＺｎＯは熱的に安定性が向上するために添加し得るが、その量が１０モル％を超えるとガラスの安定性がかえって低下するので１０モル％以下とすべきである。さらに、Ｐ2Ｏ5、ＳｉＯ2、ＧｅＯ2、ＴｅＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、Ｆｅ2Ｏ3、Ｓｂ2Ｏ3、Ａｓ2Ｏ3はガラスの安定性および化学的耐久性改善のために添加できるが、赤外透過性を悪化させるために各々２モル％以下とすべきである。
【０００７】
フッ化物または塩化物の添加（例えば、ＡｌＦ3、ＺｎＦ2、ＬｉＣｌ、ＫＣｌ、ＢａＣｌ2などの成分）は３．０μｍ付近にあるＯＨによる吸収を小さくするのに有効であるが、その量が５モル％を超えるとガラスの安定性が悪くなるので、５モル％以下とすべきである。
【０００８】
本発明のガラスは所定のガラス原料を調合し、よく混合した後、白金坩堝に投入し、９００〜１２００℃で３０分間溶融し、その後溶融ガラスをステンレス板上にキャストすることで容易に得られる。
【０００９】
【実施例】
次に実施例について説明する。
表１に本発明の実施例について、これらのガラスの可視吸収端波長、赤外吸収端波長および光線透過率の５０％での波長を示す（厚さ１ｍｍ）。表に示すように本発明のガラスは可視域から波長９．５μｍの赤外域まで透明で７．８μｍまで５０％以上の高い光線透過率を有することがわかる。
【００１０】
【表１】
【発明の効果】
以上述べたとおり、本発明のの赤外線透過ガラスは、Ｂｉ2Ｏ3−ＲＯ−Ｌｉ2Ｏ系ガラスであり、波長７．８μｍまでの赤外域に優れた光線透過性を有するものである。
【図面の簡単な説明】
図１に本発明の１例として、Ｂｉ2Ｏ3−ＳｒＯ−Ｌｉ2Ｏ系のガラス形成範囲を示す。白丸はガラス、白半分の丸は部分的に結晶したもの、黒丸は結晶化したものを表している。[0001]
[Industrial application fields]
The present invention relates to a new infrared transmitting glass. Since the glass of the present invention has a high light transmittance from the visible region to the infrared region with a wavelength of 7.8 μm, windows, lenses, prisms, filters, optical measurement used in various optical devices used in the near infrared region and the infrared region. Used for fiber etc.
[0002]
[Prior art]
Fluoride glass and chalcogenide glass are known as infrared transmitting glasses having high light transmittance up to an infrared region with a wavelength of 7.8 μm. However, both have drawbacks that the manufacturing process is complicated and thermally unstable. As the oxide-based glass, aluminate glass, germanate glass, tellurite glass, and the like are known, but all of them have very poor light transmittance in the infrared region having a wavelength of 5.0 μm or more. Examples of the oxide glass exhibiting good transmittance up to a longer wavelength infrared region include Bi 2 O 3 —PbO—BaO—ZnO glass disclosed in US Pat. No. 3,723,141 and JP-A-5-132333. Ga 2 O 3 —Bi 2 O 3 —R 2 O (R = alkali metal) -based glasses disclosed in Japanese Patent Publication Nos. 1 and 2 are known. These glasses include PbO harmful to the environment and expensive Ga. 2 O 3 is contained in large quantities.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to eliminate the above-mentioned drawbacks and to provide an infrared transmitting glass having good light transmittance up to an infrared region having a wavelength of 7.8 μm.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has conducted intensive studies, and as a result, Bi 2 O 3 —RO (R = Mg, Ca, Sr, Ba) not specifically shown in the conventional technical data. By discovering that there is a large vitrification range in each ternary system of Li 2 O, and further combining the above-mentioned substances based on these findings, a glass that is more thermally stable than any ternary system can be obtained. And the present invention has been made.
[0005]
That is, the present invention is mol%, Bi 2 O 3 10-40% (except 40%), RO (provided that R = Mg, Ca, Sr, Ba) 5-50%, Li 2 O 20- It is an infrared transmitting glass characterized by containing 70% and not containing PbO 2 , CdO, and Ga 2 O 3 .
[0006]
Bi 2 O 3 , RO, and Li 2 O components can be taken from conventional oxide, carbonate, and nitrate raw materials. In addition to these ternary systems, Zn 2 O can be added to improve the thermal stability. However, if the amount exceeds 10 mol%, the stability of the glass is lowered, so that it is 10 mol% or less. Should. Furthermore, P 2 O 5 , SiO 2 , GeO 2 , TeO 2 , B 2 O 3 , Al 2 O 3 , Fe 2 O 3 , Sb 2 O 3 , As 2 O 3 are glass stability and chemical durability. Although it can be added for improvement, it should be 2 mol% or less in order to deteriorate the infrared transmittance.
[0007]
Addition of fluoride or chloride (for example, components such as AlF 3 , ZnF 2 , LiCl, KCl, BaCl 2 ) is effective in reducing absorption by OH in the vicinity of 3.0 μm. If it exceeds mol%, the stability of the glass deteriorates, so it should be 5 mol% or less.
[0008]
The glass of the present invention can be easily obtained by preparing a predetermined glass raw material, mixing it well, putting it in a platinum crucible, melting it at 900 to 1200 ° C. for 30 minutes, and then casting the molten glass on a stainless steel plate. .
[0009]
【Example】
Next, examples will be described.
Table 1 shows the visible absorption edge wavelength, infrared absorption edge wavelength, and wavelength at 50% of the light transmittance of these glasses (thickness 1 mm) for the examples of the present invention. As shown in the table, the glass of the present invention is transparent from the visible region to the infrared region having a wavelength of 9.5 μm and has a high light transmittance of 50% or more from 7.8 μm.
[0010]
[Table 1]
【The invention's effect】
As described above, the infrared transmitting glass of the present invention is a Bi 2 O 3 —RO—Li 2 O glass, and has excellent light transmittance in the infrared region up to a wavelength of 7.8 μm.
[Brief description of the drawings]
FIG. 1 shows a Bi 2 O 3 —SrO—Li 2 O glass forming range as an example of the present invention. White circles represent glass, white half circles are partially crystallized, and black circles are crystallized.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03001695A JP3732545B2 (en) | 1995-01-26 | 1995-01-26 | Infrared transmission glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03001695A JP3732545B2 (en) | 1995-01-26 | 1995-01-26 | Infrared transmission glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08208267A JPH08208267A (en) | 1996-08-13 |
| JP3732545B2 true JP3732545B2 (en) | 2006-01-05 |
Family
ID=12292063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03001695A Expired - Lifetime JP3732545B2 (en) | 1995-01-26 | 1995-01-26 | Infrared transmission glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3732545B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723141A (en) * | 1971-03-22 | 1973-03-27 | W Dumbaugh | Infrared transmissive lead bismuthate glasses |
| US3837868A (en) * | 1973-03-26 | 1974-09-24 | Corning Glass Works | Stabilized bismuthate glasses |
| US5114884A (en) * | 1991-04-26 | 1992-05-19 | Corning Incorporated | Alkali bismuth gallate glasses |
| JP2516531B2 (en) * | 1992-07-06 | 1996-07-24 | 岡谷電機産業株式会社 | Varistor, surge absorber, method for forming protective film, and bismuth borosilicate glass composition |
| JP3749276B2 (en) * | 1994-11-01 | 2006-02-22 | 株式会社オハラ | Infrared transmission glass |
-
1995
- 1995-01-26 JP JP03001695A patent/JP3732545B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08208267A (en) | 1996-08-13 |
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