JP3749276B2 - Infrared transmission glass - Google Patents
Infrared transmission glass Download PDFInfo
- Publication number
- JP3749276B2 JP3749276B2 JP29223894A JP29223894A JP3749276B2 JP 3749276 B2 JP3749276 B2 JP 3749276B2 JP 29223894 A JP29223894 A JP 29223894A JP 29223894 A JP29223894 A JP 29223894A JP 3749276 B2 JP3749276 B2 JP 3749276B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- infrared
- present
- mol
- wavelength
- 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 32
- 230000005540 biological transmission Effects 0.000 title 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 8
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000087 laser glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 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
- 238000004433 infrared transmission spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000126 substance 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７．５μｍの赤外域まで高い光線透過性を有するため、可視、近赤外、赤外域において使用される各種光学機器に用いる窓、レンズ、プリズム、フィルター、光計測ファイバー、レーザガラスおよび非線形光学材料などに利用される。
【０００２】
【従来の技術】
波長７．５μｍ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。酸化物ガラスにおいて赤外線透過ガラスとしてアルミネトガラス、ゲルマネトガラス、テルライト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。波長７μｍの赤外域まで良好な透過率を示すガラスとして米国特許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すると同時に熱的に安定で、波長７．５μｍの赤外域まで高い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、従来の技料資料に具体的に示されていないＢｉ2Ｏ3−ＺｎＯ−Ｒ2Ｏ（Ｒ’Ｏ）（Ｒ＝Ｌｉ、Ｎａ、Ｋ Ｒ’＝Ｃａ、Ｓｒ、Ｂａ）各三成分系において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、ガラスの成分を多成分化にすることによって、どの三成分系よりも熱的に安定で、しかも大きくて均一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、本発明の赤外線透過ガラスは、ｍｏｌ％で、Ｂｉ2Ｏ3 ４０〜７５％、ＺｎＯ ５〜２０％、Ｒ2Ｏ（ただし、Ｒ＝Ｌｉ、Ｎａ、Ｋ）５〜３５％、Ｒ’Ｏ（ただし、Ｒ’＝Ｃａ、Ｓｒ、Ｂａ）５〜３０％、Ｂ ２ Ｏ ３ ０〜２％およびＳｉＯ ２ ０〜２％を含有し、ＰｂＯ、Ｇａ２Ｏ３及びＣｄＯを含有しないことを特徴とするものである。
好ましい組成は、ｍｏｌ％で、Ｂｉ2Ｏ3 ４０〜６０％、ＺｎＯ ５〜２０％、Ｒ2Ｏ（ただし、Ｒ＝Ｌｉ、Ｎａ、Ｋ） ５〜３５％、Ｒ’Ｏ（ただし、Ｒ’＝Ｃａ、Ｓｒ、Ｂａ） ５〜３０％、Ｂ ２ Ｏ ３ ０〜２％およびＳｉＯ ２ ０〜２％を含有し、ＰｂＯ、Ｇａ２Ｏ３及びＣｄＯ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。これらの好ましい組成から従来のガラス溶融および成形技術を使用し、５０×５０×１０ｍｍのサイズの均一なガラスが得られた。
【０００６】
尚、Ｒには１０ｍｏｌ％以下のＣｓおよびＲｂを添加することができる。Ｒ’には各々５ｍｏｌ％以下のＭｇＯ、ＣｄＯおよびＰｂＯを添加することもできるが、ＣｄＯ、ＰｂＯは環境に有害なので添加するのは好ましくない。
さらにガラスの安定性および耐久性の改善等のためにＧｅＯ2、ＳｉＯ2、Ｂ2Ｏ3、Ｐ2Ｏ5、Ｔｌ2Ｏ、ＴｅＯ2、ＷＯ3、Ａｌ2Ｏ3、Ａｓ2Ｏ3、Ｓｂ2Ｏ3等を添加することができるが、赤外透過性が悪化するために各々２ｍｏｌ％以下にすべきである。尚、レーザガラスとしてはＴｍ、ＥｒおよびＰｒ等の希土類酸化物を５ｍｏｌ％以下添加しても差しつかえない。
【０００７】
ＲＦ、ＲＣＩまたはＲ’Ｆ2、Ｒ’ＣＩ2の添加は３μｍ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５ｍｏｌ％を超えるとガラスの安定性が悪くなるので５ｍｏｌ％以下とすべきである。
【０００８】
本発明ガラスは波長７．５μｍの赤外域まで高い光線透過率を示すと同時に、２．２以上という非常に高い屈折率を持つため光学レンズや非線形光学材料としても利用できる。
【０００９】
本発明のガラスは通常の方法により容易に製造できる。すなわち、所定のガラス原料を調合し、よく混合した後１０００〜１２００℃の白金坩堝に投入し、溶融、攪拌後、冷却することによって均一なガラスが容易に製造できる。
【００１０】
【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屈折率（Ｎｄ）、可視吸収端波長、赤外吸収端波長および厚さ１ｍｍガラスの光線透過率の５０％での波長を示す。表に示すように本発明のガラスは屈折率が高くて、可視域から波長９μｍの赤外域まで透明で７．５μｍまで５０％以上の透過率を有することがわかる。
【００１１】
【表１】
【発明の効果】
以上述べたとおり、本発明の赤外線透過ガラスはＢｉ2Ｏ3−ＺｎＯ−Ｒ2Ｏ−Ｒ’Ｏ系ガラスであり、熱的に安定で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は本発明のガラスＮｏ．３の赤外透過スペクトルである（厚さ１ｍｍ）。[0001]
[Industrial application fields]
The present invention relates to a new infrared transmitting glass. Since the glass of the present invention has high light transmittance from the visible region to the infrared region having a wavelength of 7.5 μm, windows, lenses, prisms, filters, light used in various optical devices used in the visible, near infrared, and infrared regions. Used for measuring fiber, laser glass and nonlinear optical material.
[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 7.5 μm. However, both have drawbacks that the manufacturing process is complicated and thermally unstable. Among oxide glasses, aluminate glass, germanate glass, tellurite glass, and the like are known as infrared transmissive glasses, but all of them have very poor light transmittance in the infrared region having a wavelength of 5.0 μm or more. Bi 2 O 3 —PbO—BaO—ZnO glass disclosed in US Pat. No. 3,723,141 as a glass exhibiting good transmittance up to an infrared region of a wavelength of 7 μm and disclosed in JP-A-5-132333 Ga 2 O 3 —Bi 2 O 3 —R 2 O (R: alkali metal) glass is known, but these glasses contain a large amount of PbO harmful to the environment and expensive Ga 2 O 3. include.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an infrared transmitting glass which eliminates the above-mentioned drawbacks and is thermally stable and has a high light transmittance up to an infrared region having a wavelength of 7.5 μm.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has conducted intensive research, and as a result, Bi 2 O 3 —ZnO—R 2 O (R′O) (not specifically shown in conventional technical materials) R = Li, Na, K R ′ = Ca, Sr, Ba) It was discovered that there is a vitrification range in each ternary system, and based on these findings, the above substances were combined to increase the glass components. By making it into a component, it was found that a glass which is more thermally stable than any ternary system and which is large and uniform can be obtained, and the present invention has been made.
[0005]
That is, the infrared transmitting glass of the present invention is mol%, Bi 2 O 3 40 to 75%,
Preferred compositions are mol%, Bi 2 O 3 40-60%, ZnO 5-20%, R 2 O (where R = Li, Na, K) 5-35%, R′O (where R ′ = Ca, Sr, Ba) 5~30 %, infrared transmitting glass which contains 2
[0006]
In addition, 10 mol% or less of Cs and Rb can be added to R. Each of R ′ may contain 5 mol% or less of MgO, CdO and PbO, but it is not preferable to add CdO and PbO because they are harmful to the environment.
GeO 2, SiO 2, B 2
[0007]
The addition of RF, RCI or R′F 2 , R′CI 2 is effective to reduce absorption by OH in the vicinity of 3 μm, but if the amount exceeds 5 mol%, the stability of the glass deteriorates, so that 5 mol. % Or less.
[0008]
The glass of the present invention exhibits a high light transmittance up to an infrared region having a wavelength of 7.5 μm, and at the same time has a very high refractive index of 2.2 or more, so that it can be used as an optical lens or a nonlinear optical material.
[0009]
The glass of the present invention can be easily produced by a usual method. That is, a predetermined glass raw material is prepared, mixed well, put into a platinum crucible at 1000 to 1200 ° C., melted, stirred, and then cooled, whereby uniform glass can be easily produced.
[0010]
【Example】
Next, examples will be described.
Table 1 shows the refractive index (Nd), the visible absorption edge wavelength, the infrared absorption edge wavelength, and the wavelength at 50% of the light transmittance of the glass having a thickness of 1 mm for the examples of the present invention. As shown in the table, it can be seen that the glass of the present invention has a high refractive index, is transparent from the visible region to the infrared region having a wavelength of 9 μm, and has a transmittance of 50% or more from 7.5 μm.
[0011]
[Table 1]
【The invention's effect】
As described above, the infrared transmitting glass of the present invention is a Bi 2 O 3 —ZnO—R 2 O—R′O-based glass, which is thermally stable and has light transmittance excellent in the infrared region.
[Brief description of the drawings]
1 shows the glass No. 1 of the present invention. 3 is an infrared transmission spectrum (thickness 1 mm).
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29223894A JP3749276B2 (en) | 1994-11-01 | 1994-11-01 | Infrared transmission glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29223894A JP3749276B2 (en) | 1994-11-01 | 1994-11-01 | Infrared transmission glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08133779A JPH08133779A (en) | 1996-05-28 |
| JP3749276B2 true JP3749276B2 (en) | 2006-02-22 |
Family
ID=17779262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29223894A Expired - Lifetime JP3749276B2 (en) | 1994-11-01 | 1994-11-01 | Infrared transmission glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3749276B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3732545B2 (en) * | 1995-01-26 | 2006-01-05 | 株式会社オハラ | Infrared transmission glass |
| JPH1155205A (en) * | 1997-07-31 | 1999-02-26 | Anritsu Corp | Digital signal demodulation device |
| JP4240720B2 (en) * | 2000-01-26 | 2009-03-18 | 旭硝子株式会社 | Light amplification glass |
| JP4862233B2 (en) * | 2000-11-17 | 2012-01-25 | 旭硝子株式会社 | Light amplification glass |
| JP6631775B2 (en) * | 2014-08-11 | 2020-01-15 | 日本電気硝子株式会社 | Infrared transmission glass |
| JP6537806B2 (en) * | 2014-10-29 | 2019-07-03 | 株式会社オハラ | Infrared transmitting glass, optical element and preform |
| JP2017151408A (en) * | 2016-02-22 | 2017-08-31 | 株式会社タムロン | Infrared transmission film, optical film, antireflection film, optical component, optical system and imaging device |
-
1994
- 1994-11-01 JP JP29223894A patent/JP3749276B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08133779A (en) | 1996-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2700512B2 (en) | High dispersion optical glass | |
| JP6207242B2 (en) | Optical glass | |
| US4526874A (en) | Optical light weight glass with a refractive index of >1.70, an Abbe index of >22 and a density of <3.5 G/CM3 | |
| JP4351730B2 (en) | Optical glass | |
| JP2565813B2 (en) | Optical glass | |
| JPH0149649B2 (en) | ||
| JPH10265238A (en) | Optical glass having negative anomalous dispensability | |
| JP2006327926A (en) | Optical glass | |
| JPH09188540A (en) | Optical glass free from solarization | |
| JP5271483B2 (en) | Optical glass | |
| JPS6112856B2 (en) | ||
| GB2378700A (en) | Tellurite glass | |
| JPS6411581B2 (en) | ||
| JPS58151347A (en) | Phototropism glass having not less than 1.59 refractive index, not less than 44 abbe number and not more than 3.0g/cm3 density | |
| JPH04104918A (en) | Near infrared absorbing glass | |
| WO2019142936A1 (en) | Ultraviolet ray-transmitting glass and molded article | |
| JPS6325245A (en) | Filter glass for cutting near-infrared rays | |
| JP3749276B2 (en) | Infrared transmission glass | |
| JPH0455136B2 (en) | ||
| JPH10167753A (en) | Lead-free crown glass | |
| JP2024019356A (en) | Optical glass and optical element | |
| JP2021050125A (en) | Optical glass and optical element | |
| JP3034427B2 (en) | Low temperature softening optical glass for mold press | |
| JP6812148B2 (en) | Optical glass, optics blank, and optics | |
| US3826661A (en) | High index optical glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040701 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050111 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050307 Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20050307 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20050307 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050707 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050802 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051129 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20051201 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111209 Year of fee payment: 6 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111209 Year of fee payment: 6 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121209 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121209 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121209 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121209 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131209 Year of fee payment: 8 |
|
| EXPY | Cancellation because of completion of term |