JPS6319451B2 - - Google Patents
Info
- Publication number
- JPS6319451B2 JPS6319451B2 JP18440583A JP18440583A JPS6319451B2 JP S6319451 B2 JPS6319451 B2 JP S6319451B2 JP 18440583 A JP18440583 A JP 18440583A JP 18440583 A JP18440583 A JP 18440583A JP S6319451 B2 JPS6319451 B2 JP S6319451B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- coefficient
- section
- stimulated emission
- thermal expansion
- 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
- 239000000087 laser glass Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 239000011521 glass Substances 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 230000035939 shock Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000005365 phosphate glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004017 vitrification 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
Description
本発明はガラス形成成分としてP2O5とSiO2を
併有したレーザーガラスに関する。
比較的多量のアルカリ成分を含有する燐酸塩レ
ーザーガラスは、誘導放出断面積が大きいという
長所を具えているものの、機械的強度及び化学的
耐久性が貧弱であることに加えて、熱膨張係数が
大きい故に耐熱衝撃性が小さいことが欠点として
指摘されている。燐酸塩レーザーガラスのこうし
た欠点は、そのガラス組成にR″2O3（R″はＹ、
La、Ｂ、Alを示す）やR′O（R′はMg、Ca、Sr、
Ba、Zn、Pbを示す。以下同じ）を配合すること
で改善することができる。しかし、R″2O3やR′O
の配合はレーザーガラスの誘導放出断面積を低下
させる不都合がある。一方、珪酸塩レーザーガラ
スは一般に機械的強度と耐熱衝撃性が大きい反
面、誘導放出断面積が小さい。
本発明は燐酸塩レーザーガラスと珪酸塩レーザ
ーガラスのそれぞれの長所を兼ね備えた、具体的
には誘導放出断面積が大きいうえに耐熱衝撃性も
大きい、従つて熱膨張係数が小さいレーザーガラ
スを提供するものである。
本発明者等が得た知見によれば、従来燐酸塩レ
ーザーガラスの欠点を改善する目的でガラス組成
に配合されていたAl2O3とR′Oの一部又は全部を
SiO2で置換することにより、燐酸塩レーザーガ
ラス本来の誘導放出断面積を実質的に損うことな
く熱膨張係数を小さく、従つて耐熱衝撃性を大き
くすることができる。しかも燐酸塩ガラスへの
SiO2の多量添加は、一般に分相乃至結晶化を招
くとされているにも拘らず、本発明のガラス組成
にはそうした傾向が認められないばかりか、螢光
の濃度消光が小さいガラスが得られることを本発
明者等は確認した。
而して本発明の珪燐酸塩レーザーガラスは、
P2O5−SiO2−R2O（ＲはLi、Na、Ｋを示す）−
Nd2O3を基本組成とし、モル％表示でP2O545〜
70、SiO28〜30、P2O5＋SiO265〜95、Li2O＋
Na2O＋K2O4〜20、Nd2O30.01〜12、Al2O30〜
10、La2O3＋Y2O3＋B2O30〜５、R′O0〜10、
Nb2O5＋CeO20〜１の組成を有することを特徴と
する。そしてこのガラスのレーザーガラスとして
の特長点は、螢光の濃度消光が小さく、誘導放出
断面積が大で熱膨張係数が小さいことにある。
本発明のガラス組成（モル％表示）に於て、
P2O5は45〜70％存在していることが必要であつ
て、この範囲を逸脱した場合にはガラスの安定性
が悪化する。SiO2は８〜30％の範囲で誘導放出
断面積を大幅に低下させることなく、熱膨張係数
を小さくするが、30％を越えると誘導放出断面積
が所望値より低下する。また、誘導放出断面積を
高水準に保持したまま、熱膨張係数を小さくする
ためには、P2O5＋SiO2の合量は65〜95％の範囲
になければならない。
Li2O＋Na2O＋K2Oの合量が４％未満ではガラ
ス化が困難になり、20％を越えると熱膨張係数が
大きくなるので、本発明では４〜20％の範囲が選
ばれている。ちなみに、熱膨張係数を小さくする
うえではLi2Oが有利であるが、誘導放出断面積
を大きくする点ではK2Oが有利である。Nd2O3は
レーザーガラスの必須成分であつて、レーザーガ
ラスとしての特性を発揮させるには、少なくとも
0.01％のNd2O3が必要であり、本発明のガラス組
成では12％（Nd3+イオンとして30×1020イオ
ン／c.c.）まで導入可能である。
任意成分について言えば、Al2O3は０〜10％の
範囲で誘導放出断面積に著しい悪影響を及ぼすこ
となく、熱膨張係数を小さくする。そして化学的
耐久性を向上させるためには５％以上含まれてい
ることが望ましい。La2O3＋Y2O3＋B2O3は０〜
５％の範囲でAl2O3に置換して使用することがで
きる。R′O（Ｒ＝Mg、Ca、Sr、Ba、Zn、Pb）は
０〜10％の範囲でLi2O、Na2O、K2Oに置換して
用いることができ、熱膨張係数の低下、化学的耐
久性の向上に有効である。また、Nb2O5＋CeO2
は０〜１％の範囲でソーラリゼーシヨン防止剤と
して有効に働く成分である。
本発明の珪燐酸塩レーザーガラスは、上記した
ガラス組成が得られるようガラス原料を配合して
溶融し、常法通り乾燥ガスによるバブリング等の
方法により充分に脱水してから所望の形状に成形
される。
次に実施例を示して本発明に係るレーザーガラ
スの性状を具体的に説明する。
実施例 １
The present invention relates to a laser glass containing both P 2 O 5 and SiO 2 as glass forming components. Phosphate laser glass, which contains a relatively large amount of alkaline components, has the advantage of a large stimulated emission cross section, but has poor mechanical strength and chemical durability, as well as a low coefficient of thermal expansion. Due to its large size, it has been pointed out that its low thermal shock resistance is a drawback. These drawbacks of phosphate laser glass are due to its glass composition, R″ 2 O 3 (R″ is Y,
) and R′O (R′ is Mg, Ca, Sr,
Indicates Ba, Zn, and Pb. This can be improved by adding (the same applies hereinafter). However, R″ 2 O 3 and R′O
This combination has the disadvantage of lowering the stimulated emission cross section of the laser glass. On the other hand, silicate laser glasses generally have high mechanical strength and thermal shock resistance, but have a small stimulated emission cross section. The present invention combines the respective advantages of phosphate laser glass and silicate laser glass, and specifically provides a laser glass with a large stimulated emission cross section, high thermal shock resistance, and therefore a small coefficient of thermal expansion. It is something. According to the knowledge obtained by the present inventors, some or all of Al 2 O 3 and R′O, which were added to the glass composition in order to improve the drawbacks of conventional phosphate laser glasses, can be removed.
By substituting with SiO 2 , the coefficient of thermal expansion can be reduced without substantially impairing the stimulated emission cross section inherent to phosphate laser glass, and therefore the thermal shock resistance can be increased. Moreover, to phosphate glass
Although it is generally believed that the addition of a large amount of SiO 2 causes phase separation or crystallization, the glass composition of the present invention does not exhibit such a tendency, and it is also possible to obtain a glass with low concentration quenching of fluorescence. The present inventors have confirmed that. Therefore, the silicate phosphate laser glass of the present invention is
P 2 O 5 −SiO 2 −R 2 O (R represents Li, Na, K) −
The basic composition is Nd 2 O 3 , and P 2 O 5 45 ~ in mol%
70, SiO2 8 ~ 30, P2O5 + SiO2 65~95, Li2O +
Na 2 O + K 2 O 4 ~ 20, Nd 2 O 3 0.01 ~ 12, Al 2 O 3 0 ~
10, La 2 O 3 + Y 2 O 3 + B 2 O 3 0~5, R′O0~10,
It is characterized by having a composition of Nb 2 O 5 +CeO 2 0-1. The advantages of this glass as a laser glass are that the concentration quenching of fluorescent light is small, the stimulated emission cross section is large, and the coefficient of thermal expansion is small. In the glass composition (expressed in mol%) of the present invention,
It is necessary that P 2 O 5 be present in an amount of 45 to 70%, and if it deviates from this range, the stability of the glass will deteriorate. In the range of 8 to 30%, SiO 2 reduces the coefficient of thermal expansion without significantly reducing the stimulated emission cross section, but if it exceeds 30%, the stimulated emission cross section decreases below the desired value. Further, in order to reduce the coefficient of thermal expansion while maintaining the stimulated emission cross section at a high level, the total amount of P 2 O 5 +SiO 2 must be in the range of 65 to 95%. If the total amount of Li 2 O + Na 2 O + K 2 O is less than 4%, vitrification becomes difficult, and if it exceeds 20%, the coefficient of thermal expansion becomes large. Therefore, in the present invention, a range of 4 to 20% is selected. Incidentally, Li 2 O is advantageous in reducing the coefficient of thermal expansion, but K 2 O is advantageous in increasing the stimulated emission cross section. Nd 2 O 3 is an essential component of laser glass, and in order to exhibit its properties as laser glass, it must be at least
0.01% Nd 2 O 3 is required, and in the glass composition of the present invention, up to 12% (30×10 20 ions/cc as Nd 3+ ions) can be introduced. As for optional ingredients, Al 2 O 3 reduces the coefficient of thermal expansion in the range of 0-10% without significantly adversely affecting the stimulated emission cross section. In order to improve chemical durability, it is desirable that the content be 5% or more. La 2 O 3 + Y 2 O 3 + B 2 O 3 is 0~
It can be used in substitution with Al 2 O 3 in a range of 5%. R′O (R=Mg, Ca, Sr, Ba, Zn, Pb) can be used by replacing with Li 2 O, Na 2 O, K 2 O in the range of 0 to 10%, and the coefficient of thermal expansion It is effective in reducing chemical resistance and improving chemical durability. Also, Nb 2 O 5 + CeO 2
is a component that effectively works as a solarization inhibitor in the range of 0 to 1%. The silicate phosphate laser glass of the present invention is produced by blending and melting glass raw materials to obtain the glass composition described above, sufficiently dehydrating the glass by bubbling with dry gas in a conventional manner, and then forming it into a desired shape. Ru. Next, the properties of the laser glass according to the present invention will be specifically explained with reference to Examples. Example 1
【表】
σｐ：誘導放出断面積 α：熱膨張係数
実施例 ２
Nd3イオン濃度を変化させた以外は実施例１の
No.８の組成で５種の珪燐酸塩ガラスを調製し、各
ガラスの螢光寿命を測定した。結果を表２に示
す。尚、螢光寿命はガラス中に含まれる水の量に
影響されるため、3.3μ付近に生ずるＯ−Ｈ振動に
基づく赤外吸収の吸収係数を水の量の尺度として
表２に併記した。[Table] σ p : Stimulated emission cross section α: Coefficient of thermal expansion Example 2 Same as Example 1 except that the Nd 3 ion concentration was changed.
Five types of silicate phosphate glasses were prepared with composition No. 8, and the fluorescence lifetime of each glass was measured. The results are shown in Table 2. Incidentally, since the fluorescence lifetime is affected by the amount of water contained in the glass, the absorption coefficient of infrared absorption based on O--H vibration occurring around 3.3μ is also shown in Table 2 as a measure of the amount of water.
【表】
表２から明らかな如く、本発明の珪燐酸塩ガラ
スは螢光の濃度消光が小さく、Nd2O3を高濃度域
までドープすることが可能なため、小さなサイズ
で高効率、高出力のガラスレーザーを構成するこ
とが期待できる。[Table] As is clear from Table 2, the silicophosphate glass of the present invention has low concentration quenching of fluorescent light and can be doped with Nd 2 O 3 up to a high concentration range, so it can achieve high efficiency and high performance with a small size. It is expected that it will be possible to construct a high-power glass laser.
Claims (1)
SiO265〜95、Li2O＋Na2O＋K2O4〜20、
Nd2O30.01〜12、Al2O30〜10、La2O3＋Y2O3＋
B2O30〜５、R′O（但し、R′はMg、Ca、Sr、Ba、
Zn、Pbを示す）０〜10、Nb2O3＋CeO20〜１の
組成を有する珪燐酸塩レーザーガラス。P 2 O 5 45-70, SiO 2 8-30, P 2 O 5 + at 1 mol%
SiO2 65~95, Li2O + Na2O + K2O4 ~20,
Nd 2 O 3 0.01-12, Al 2 O 3 0-10, La 2 O 3 + Y 2 O 3 +
B 2 O 3 0~5, R′O (where R′ is Mg, Ca, Sr, Ba,
Silicophosphate laser glass having a composition of Zn, Pb) 0-10, Nb 2 O 3 +CeO 2 0-1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18440583A JPS6077143A (en) | 1983-10-04 | 1983-10-04 | Silicate laser glass |
| DE19843435133 DE3435133A1 (en) | 1983-10-04 | 1984-09-25 | Silicophosphate laser glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18440583A JPS6077143A (en) | 1983-10-04 | 1983-10-04 | Silicate laser glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6077143A JPS6077143A (en) | 1985-05-01 |
| JPS6319451B2 true JPS6319451B2 (en) | 1988-04-22 |
Family
ID=16152590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18440583A Granted JPS6077143A (en) | 1983-10-04 | 1983-10-04 | Silicate laser glass |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6077143A (en) |
| DE (1) | DE3435133A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61215233A (en) * | 1985-03-19 | 1986-09-25 | Hoya Corp | Silicophosphate laser glass |
| US4661284A (en) * | 1985-09-25 | 1987-04-28 | The United States Of America As Represented By The United States Department Of Energy | Silica and boron-containing ultraphosphate laser glass with low concentration quenching and improved thermal shock resistance |
| US4929387A (en) * | 1988-08-31 | 1990-05-29 | Schott Glass Technologies, Inc. | Phosphate glass useful in high power lasers |
| US5032315A (en) * | 1989-04-03 | 1991-07-16 | Schott Glass Technologies, Inc. | Phosphate glass useful in high power lasers |
| US6636347B1 (en) * | 2000-11-08 | 2003-10-21 | Corning Incorporated | Phosphorus-silicate fibers suitable for extended band amplification |
| US8486850B2 (en) * | 2010-09-13 | 2013-07-16 | Schott Corporation | Aluminophosphate glass composition |
| RU2531958C2 (en) * | 2012-05-02 | 2014-10-27 | Корпорация "Самсунг Электроникс Ко., Лтд" | Electro-optical laser glass and method for production thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075120A (en) * | 1975-05-14 | 1978-02-21 | Kogre, Inc. | Laser phosphate glass compositions |
-
1983
- 1983-10-04 JP JP18440583A patent/JPS6077143A/en active Granted
-
1984
- 1984-09-25 DE DE19843435133 patent/DE3435133A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6077143A (en) | 1985-05-01 |
| DE3435133A1 (en) | 1985-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0917524B1 (en) | Lead and arsenic free borosilicate glass and lamp containing same | |
| US6391810B1 (en) | Lead- and barium-free crystal glass | |
| US4248732A (en) | Laser phosphate glass compositions | |
| US2532386A (en) | Colored phosphate glass | |
| JPH1067536A (en) | Oxyhalide laser glass | |
| US4820662A (en) | Silicophosphate laser glass | |
| US5413971A (en) | Laser absorbing filter glass | |
| US5240885A (en) | Rare earth-doped, stabilized cadmium halide glasses | |
| US3994708A (en) | Method of producing a glass transmissive to ultraviolet radiation | |
| JPH0420858B2 (en) | ||
| JP2525697B2 (en) | Borosilicate glass for electronic flash lamps | |
| US4127415A (en) | Aluminum borophosphate glass compositions | |
| JPS6319451B2 (en) | ||
| US5320985A (en) | Low refractive optical glass of a flint glass type | |
| JPS62216938A (en) | Silica and boron-containing super phosphate laser glass having low concentration quenching and improved thermal shock resistance | |
| RU2500059C1 (en) | Phosphate laser glass | |
| US6831026B2 (en) | Essentially lead free glass and a glass tube made therefrom | |
| DE3346686C2 (en) | Luminescent glasses | |
| JPS6218495B2 (en) | ||
| EP0589198B1 (en) | Rare earth-doped, stabilized cadmium halide glasses | |
| US4257811A (en) | Solarization and irradiation resistant optical glasses | |
| JP2004277252A (en) | Optical amplification glass and optical waveguide | |
| EP0146187B1 (en) | Glass composition suitable for use in a fluorescent lamp | |
| KR100477802B1 (en) | Tm ION-DOPED SILICATE GLASS AND THE USE THEREOF | |
| JP2746716B2 (en) | Rare earth doped multi-component glass fiber |