JPH10297933A - Glass for Faraday rotating element - Google Patents
Glass for Faraday rotating elementInfo
- Publication number
- JPH10297933A JPH10297933A JP9109089A JP10908997A JPH10297933A JP H10297933 A JPH10297933 A JP H10297933A JP 9109089 A JP9109089 A JP 9109089A JP 10908997 A JP10908997 A JP 10908997A JP H10297933 A JPH10297933 A JP H10297933A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- verdet constant
- present
- sio
- faraday
- 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.)
- Granted
Links
- 239000011521 glass Substances 0.000 title abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 6
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 14
- 229910052771 Terbium Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical group [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 7
- 238000004017 vitrification Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005291 magnetic effect Effects 0.000 description 5
- -1 terbium ions Chemical class 0.000 description 5
- 238000007496 glass forming Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000005383 fluoride glass Substances 0.000 description 1
- 239000005303 fluorophosphate glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
- Glass Compositions (AREA)
Abstract
(57)【要約】
【課題】 大きなベルデ定数を与えるため高濃度のTb
2 O3 を含ませた実用上十分に安定なガラス組成物を提
供すること。
【解決手段】 モル%でTb2 O3 が25〜50%、S
iO2 が5〜40%、B 2 O3 が5〜45%、Ga2 O
3 が5〜35%、さらにP2 O5 が0〜7%、GeO2
が0〜20%、またMgO、CaO、SrOおよびBa
Oがそれぞれ0〜6%で、(MgO+CaO+SrO+
BaO)が0〜6%、La2 O3 が0〜6%、Gd2 O
3 が0〜6%、Yb2 O3 が0〜6%、Dy2 O3 が0
〜15%、〔Tb2 O3 +La2 O3 +Gd2 O3 +Y
b2 O3 +Dy2 O3 〕が25〜60%及びZrO2 が
0〜8%からなる組成のファラデー回転素子用ガラス。(57) [Summary]
PROBLEM TO BE SOLVED: To provide a high concentration Tb for giving a large Verdet constant
TwoOThreeTo provide a practically sufficiently stable glass composition containing
To offer.
SOLUTION: Tb in mol%TwoOThreeIs 25-50%, S
iOTwoIs 5 to 40%, B TwoOThreeIs 5 to 45%, GaTwoO
ThreeIs 5 to 35%, and PTwoOFiveIs 0-7%, GeOTwo
Is 0 to 20%, and MgO, CaO, SrO and Ba
O is 0 to 6% each, and (MgO + CaO + SrO +
BaO) 0-6%, LaTwoOThreeIs 0-6%, GdTwoO
ThreeIs 0-6%, YbTwoOThreeIs 0-6%, DyTwoOThreeIs 0
~ 15%, [TbTwoOThree+ LaTwoOThree+ GdTwoOThree+ Y
bTwoOThree+ DyTwoOThreeIs 25-60% and ZrOTwoBut
A glass for a Faraday rotator having a composition of 0 to 8%.
Description
【0001】[0001]
【発明の属する技術分野】本発明は大きなベルデ定数を
与えるテルビウムイオンを大量に含み、実用上十分な安
定性を持つファラデー回転素子用ガラス組成物に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass composition for a Faraday rotator containing a large amount of terbium ions giving a large Verdet constant and having sufficient stability for practical use.
【0002】[0002]
【従来の技術】常磁性化合物の酸化テルビウムを含むガ
ラスは大きなベルデ定数を持つことが知られている。こ
のような材料は光磁気効果の一つであるファラデー効果
を示す。ファラデー効果とは磁場中におかれたそのよう
な透明な材料を通過する直線偏光した光の偏光面を回転
させる効果である。このような効果は光アイソレータや
磁界センサなどに利用されている。これまでによく知ら
れているファラデー回転素子用ガラスは特公昭51−4
6524号公報に記載されているSiO2 −B2O3 −
Al2 O3 −Tb2 O3 系ガラス、特公昭52−328
81号公報に記載のP2 O5 −B2 O3 −Tb2 O3 系
ガラスあるいは特公昭55−42942号公報に記載の
P2 O5 −TbF3 −アルカリ土類フッ化物系ガラスな
どである。2. Description of the Related Art It is known that glass containing terbium oxide as a paramagnetic compound has a large Verdet constant. Such a material exhibits the Faraday effect, which is one of the magneto-optical effects. The Faraday effect is the effect of rotating the plane of polarization of linearly polarized light passing through such a transparent material placed in a magnetic field. Such effects are used in optical isolators, magnetic field sensors, and the like. The glass for the Faraday rotating element which has been well known so far is Japanese Patent Publication No. 51-4.
No. 6524, SiO 2 —B 2 O 3 —
Al 2 O 3 -Tb 2 O 3 based glass, JP-B 52-328
81 No. P 2 O 5 -B 2 O 3 according to -Tb 2 O according to 3 based glass or Sho 55-42942 JP P 2 O 5 -TbF 3 - such as an alkaline earth fluoride glass is there.
【0003】ファラデー回転ガラスの性能をあらわすベ
ルデ定数は含まれるテルビウム原子の割合に依存するこ
とが、"Journal of Applied Physics", Volume 35, Num
ber8,2338などによって明らかにされている。つまり、
高性能なファラデー回転ガラスを得るためには、高濃度
のテルビウムを含ませることが必要である。このような
高濃度に希土類化合物を含むガラスは溶融温度が高く、
一般的なガラス(ソーダシリケートガラスなど)に比べ
るとガラス化しにくく、光学的に均質なガラスを作製す
るのが大変難しい。P2 O5 を母体とするフツリン酸塩
ガラスは希土類元素の含量を高められず、結果的に大き
なベルデ定数を持つことができない。また、ガラスの成
分であるフッ化物が高い溶融温度下で揮発し、組成の変
動やガラスの安定性に影響を及ぼす可能性も高い。同様
にP2 O5 とB2 O3 を母体としたガラスでは溶融温度
が高くなると、溶融容器である白金が浸食され、ガラス
が着色したり異物が混入するおそれがある。SiO2 −
B2 O3 −Al2 O3 −Tb2 O3 系ガラスは最も基本
的なファラデー回転ガラスであると考えられるが、高濃
度のテルビウムを含む場合にはガラス化しにくく、得ら
れるベルデ定数は−0.31min/Oe・cm程度で
ある。The Verdet constant, which represents the performance of a Faraday rotating glass, depends on the proportion of terbium atoms contained therein, as described in "Journal of Applied Physics", Volume 35, Num.
ber8,2338 and so on. That is,
In order to obtain a high-performance Faraday rotating glass, it is necessary to contain a high concentration of terbium. Glass containing a rare earth compound in such a high concentration has a high melting temperature,
Compared with general glass (soda silicate glass, etc.), it is difficult to vitrify, and it is very difficult to produce optically homogeneous glass. The fluorophosphate glass containing P 2 O 5 as a base cannot increase the content of rare earth elements, and consequently cannot have a large Verdet constant. Further, the fluoride which is a component of the glass is likely to volatilize under a high melting temperature, which may cause a change in the composition and affect the stability of the glass. Similarly, when the melting temperature of the glass mainly composed of P 2 O 5 and B 2 O 3 is increased, the platinum which is the melting container is eroded, and the glass may be colored or foreign matter may be mixed. SiO 2 −
The B 2 O 3 —Al 2 O 3 —Tb 2 O 3 system glass is considered to be the most basic Faraday rotating glass. However, when high-concentration terbium is contained, vitrification is difficult, and the obtained Verdet constant is − It is about 0.31 min / Oe · cm.
【0004】[0004]
【発明が解決しようとする課題】大きなベルデ定数を持
たせるためにはより多くのテルビウム原子をガラス中に
導入しなければならない。例えば、特公昭51−465
24号公報においては、Tb2 O3 が10〜30モル%
のガラス組成物が開示されている。しかし、さらに高濃
度のTb2 O3 を含む安定なガラスについては十分な情
報がない。Tb2O3 の含有量が多ければ多いほどガラ
ス形成能が低下し、製造上十分安定に得られるガラス組
成物はほとんど存在していない。本発明の目的はより高
濃度のTb2 O3 を含む実用上十分に安定なガラス組成
物を提供することにある。In order to have a large Verdet constant, more terbium atoms must be introduced into the glass. For example, Japanese Patent Publication No. 51-465
No. 24, Tb 2 O 3 contains 10 to 30 mol%
Are disclosed. However, there is not enough information on stable glasses containing even higher concentrations of Tb 2 O 3 . The higher the content of Tb 2 O 3, the lower the glass forming ability, and almost no glass composition can be obtained with sufficient stability in production. An object of the present invention is to provide a practically sufficiently stable glass composition containing a higher concentration of Tb 2 O 3 .
【0005】[0005]
【課題を解決するための手段】SiO2 −B2 O3 を基
礎とするガラスは一般的なガラス、たとえば理化学用ガ
ラスや光学ガラスにおいて使用され、あらゆる点におい
て信頼性が高い。そこで本発明者らはSiO 2−B2 O
3 系において、よりTb2 O3 含有量の多いガラス組成
系を探索することがもっと適切であると判断して鋭意研
究した結果、Ga2 O3 の使用が予想外の効果を奏する
ことを発見して本発明に到達した。SUMMARY OF THE INVENTION Glasses based on SiO 2 -B 2 O 3 are used in general glasses, for example in physics and chemistry glasses and optical glasses, and are highly reliable in every respect. Therefore, the present inventors have developed SiO 2 -B 2 O
In the 3 systems, we determined that it was more appropriate to search for a glass composition system with a higher Tb 2 O 3 content, and as a result of intensive research, we found that the use of Ga 2 O 3 had unexpected effects. As a result, the present invention has been reached.
【0006】本発明者らは以下に示すSiO2 −B2 O
3 −Ga2 O3 −Tb2 O3 系においてTb2 O3 の含
有量が多いガラス形成領域を見いだした。すなわち、本
発明は、下記組成を有するファラデー回転素子用ガラス
に関する。 (好ましい範囲) Tb2 O3 25〜50% 30〜45% SiO2 5〜40% 10〜35% B2 O3 5〜45% 10〜40% Ga2 O3 5〜35% 7〜30% P2 O5 0〜 7% 1〜 7% GeO2 0〜20% 1〜20% RO 0〜 6%(R=Mg、Ca、Sr、Ba) ここでMgO+CaO+SrO+BaO= 0〜 6% 0〜 5% La2 O3 0〜 6% 0〜 5% Gd2 O3 0〜 6% 0〜 5% Yb2 O3 0〜 6% 0〜 5% Dy2 O3 0〜15% 0〜10% Tb2 O3 +La2 O3 +Gd2 O3 +Yb2 O3 +Dy2 O3 = 25〜60% 30〜50% ZrO2 0〜 8% 0〜 7%The present inventors have found that the following SiO 2 -B 2 O
It found a glass forming region high content of Tb 2 O 3 in 3 -Ga 2 O 3 -Tb 2 O 3 system. That is, the present invention relates to a glass for a Faraday rotator having the following composition. (Preferred range) Tb 2 O 3 25~50% 30~45 % SiO 2 5~40% 10~35% B 2 O 3 5~45% 10~40% Ga 2 O 3 5~35% 7~30% P 2 O 5 0-7% 1-7% GeO 2 0-20% 1-20% RO 0-6% (R = Mg, Ca, Sr, Ba) where MgO + CaO + SrO + BaO = 0-6% 0-5% la 2 O 3 0~ 6% 0~ 5% Gd 2 O 3 0~ 6% 0~ 5% Yb 2 O 3 0~ 6% 0~ 5% Dy 2 O 3 0~15% 0~10% Tb 2 O 3 + La 2 O 3 + Gd 2 O 3 + Yb 2 O 3 + Dy 2 O 3 = 25 to 60% 30 to 50% ZrO 2 0 to 8% 0 to 7%
【0007】本発明のファラデー回転素子用ガラスの好
ましい組成範囲は下記のとおりである。モル%でTb2
O3 が25〜50%、SiO2 が10〜35%、B2 O
3 が10〜40%、Ga2 O3 が5〜35%、さらにP
2 O5 が1〜7%、GeO2が1〜20%、またMg
O、CaO、SrOおよびBaOがそれぞれ0〜6%
で、(MgO+CaO+SrO+BaO)が0〜6%、
La2 O3 が0〜6%、Gd2 O3 が0〜6%、Yb2
O3 が0〜6%、Dy2 O3 が0〜15%、〔Tb 2 O
3 +La2 O3 +Gd2 O3 +Yb2 O3 +Dy
2 O3 〕が25〜60%からなり、ZrO2 が0〜8%
となるファラデー回転素子用ガラス。The glass for a Faraday rotator of the present invention is preferably used.
The preferred composition range is as follows. Tb in mole%Two
OThreeIs 25-50%, SiOTwoIs 10 to 35%, BTwoO
ThreeIs 10 to 40%, GaTwoOThreeIs 5 to 35%, and P
TwoOFiveIs 1-7%, GeOTwoIs 1-20%, and Mg
O, CaO, SrO and BaO are each 0 to 6%
(MgO + CaO + SrO + BaO) is 0 to 6%,
LaTwoOThreeIs 0-6%, GdTwoOThreeIs 0-6%, YbTwo
OThreeIs 0-6%, DyTwoOThreeIs 0 to 15%, [Tb TwoO
Three+ LaTwoOThree+ GdTwoOThree+ YbTwoOThree+ Dy
TwoOThree] Of 25-60%, and ZrOTwoIs 0-8%
Glass for Faraday rotation elements.
【0008】ここで、Tb2 O3 は25%よりも少ない
と十分なベルデ定数が得られない。50%を超えるとガ
ラス化が困難になる。好ましい範囲は30〜45%であ
る。SiO2 は5%よりも少ないとガラス化が困難で、
40%を超えると溶融温度が高くなり、作業が困難にな
る。好ましくは10〜35%の範囲である。B2 O3は
5%よりも少ないと溶融温度が高くなり、結果としてガ
ラス化が困難になる。45%を超えるとガラスとしての
安定性が低下する。好ましい範囲は10〜40%であ
る。Ga2 O3 は5%よりも少ないとガラス形成能にほ
とんど寄与しない。35%を超えると溶融温度が高くな
り好ましくない。好ましくは7〜30%の範囲である。
また、P2 O5 をこのガラス系に導入するとガラス形成
能力はより高められる。しかし、7%を超えるとガラス
化が困難になる。より好ましくは1〜7%の範囲であ
る。GeO2 も同様にガラスの形成能力を高める働きを
するが、20%を超えるとガラスが得られない。より好
ましいのは1〜20%の範囲で使用することである。Here, if Tb 2 O 3 is less than 25%, a sufficient Verdet constant cannot be obtained. If it exceeds 50%, vitrification becomes difficult. The preferred range is 30-45%. If the content of SiO 2 is less than 5%, vitrification is difficult,
If it exceeds 40%, the melting temperature becomes high, and the work becomes difficult. Preferably it is in the range of 10 to 35%. When the content of B 2 O 3 is less than 5%, the melting temperature becomes high, and as a result, vitrification becomes difficult. If it exceeds 45%, the stability as glass decreases. The preferred range is 10 to 40%. If the content of Ga 2 O 3 is less than 5%, it hardly contributes to the glass forming ability. If it exceeds 35%, the melting temperature increases, which is not preferable. Preferably it is in the range of 7 to 30%.
Further, when P 2 O 5 is introduced into this glass system, the glass forming ability is further enhanced. However, if it exceeds 7%, vitrification becomes difficult. More preferably, it is in the range of 1 to 7%. GeO 2 also functions to enhance the ability to form glass, but if it exceeds 20%, glass cannot be obtained. More preferably, it is used in the range of 1 to 20%.
【0009】アルカリ土類金属酸化物(MgO、Ca
O、SrO、BaO)はガラスの溶融温度を低下させ、
よりガラス化し易くさせる成分であるが、一種または二
種以上の合量は6%を超えると効果がない。好ましい範
囲は5%以下である。La2 O 3 、Gd2 O3 及びYb
2 O3 は本発明のガラス系に適する希土類酸化物でガラ
スを安定にするが、それぞれ6%を超えると結晶化や光
磁気効果が低下する。好ましくは5%以下である。Dy
2 O3 も同様の効果を期待して使用されるが、Dy2 O
3 にはTb2 O3 のようなベルデ定数に寄与する効果が
あり、その上限は15%である。好ましくは10%以下
である。Tb2 O3 、La2 O3 、Gd2O3 、Yb2
O3 、Dy2 O3 の合量が25%よりも少ないと十分な
ベルデ定数が得られず60%を超えるとガラス化が困難
になる。好ましい範囲は30〜50%である。ZrO2
もまたガラスの安定化に寄与する。しかし8%を超える
と溶融温度が高くなり、ガラス化が困難になる。好まし
くは0〜7%の範囲である。Alkaline earth metal oxides (MgO, Ca
O, SrO, BaO) lower the melting temperature of the glass,
It is a component that makes it easier to vitrify.
If the total amount of the seeds exceeds 6%, there is no effect. Preferred range
The box is 5% or less. LaTwoO Three, GdTwoOThreeAnd Yb
TwoOThreeIs a rare earth oxide suitable for the glass system of the present invention.
Stabilization, but when each exceeds 6%, crystallization and light
The magnetic effect decreases. Preferably it is 5% or less. Dy
TwoOThreeIs used with the expectation of a similar effect, but DyTwoO
ThreeHas TbTwoOThreeEffects that contribute to the Verdet constant
And the upper limit is 15%. Preferably 10% or less
It is. TbTwoOThree, LaTwoOThree, GdTwoOThree, YbTwo
OThree, DyTwoOThreeLess than 25% is sufficient
Verdet constant cannot be obtained and vitrification is difficult if it exceeds 60%.
become. The preferred range is 30-50%. ZrOTwo
Also contributes to the stabilization of the glass. But more than 8%
And the melting temperature becomes high, making vitrification difficult. Preferred
In the range of 0 to 7%.
【0010】本発明は大きなベルデ定数を持つガラスに
関するもので、アルカリ金属酸化物やZnOなどの低溶
融化合物の添加は特性に大きな影響を与えない範囲で使
用可能である。また、Tb2 O3 の原料となる酸化物は
おもにTb4 O7 で、磁気特性を示すのはTb3+であ
る。つまり、ガラスを溶融する際にはすべてのテルビウ
ムを3価の状態に還元することが理想である。一般的に
ガラスの溶融時に脱泡剤として使用されるSb2 O3 や
カーボンなどは還元効果があり、これらの還元効果を持
つ添加物の使用が好ましい。また、還元雰囲気中での溶
融も3価のテルビウムの生成に大きな効果がある。The present invention relates to a glass having a large Verdet constant. The addition of a low-melting compound such as an alkali metal oxide or ZnO can be used within a range that does not significantly affect properties. The oxide serving as a raw material of Tb 2 O 3 is mainly Tb 4 O 7 , and Tb 3+ exhibits magnetic properties. That is, when melting glass, it is ideal to reduce all terbium to a trivalent state. Generally, Sb 2 O 3 or carbon used as a defoaming agent at the time of melting glass has a reducing effect, and it is preferable to use an additive having these reducing effects. Further, melting in a reducing atmosphere also has a great effect on the generation of trivalent terbium.
【0011】本発明の特徴はSiO 2−B2 O3 −Ga
2 O3 −Tb2 O3 系ガラスを基本としてTb2 O3 を
高濃度で含むことである。ファラデー回転素子用ガラス
としての性能評価の目安であるベルデ定数は633nm
のレーザーを用いた場合、もっとTb2 O3 の含有量が
少ないガラスでも−0.37min/Oe・cm以上で
ある。この値は実用的なファラデー回転素子用ガラスと
しては最も大きな範囲にある。A feature of the present invention is that SiO 2 —B 2 O 3 —Ga
The Tb 2 O 3 a 2 O 3 -Tb 2 O 3 based glass as the base is to contain a high concentration. The Verdet constant, which is a measure of performance as a glass for a Faraday rotating element, is 633 nm.
When the laser is used, the glass content of Tb 2 O 3 is even less than −0.37 min / Oe · cm. This value is in the largest range as a practical glass for a Faraday rotating element.
【0012】本発明のファラデー回転素子用ガラスは、
各成分の原料としてそれぞれ相当する酸化物、水酸化
物、リン酸塩、炭酸塩、硝酸塩等を使用し、所定の割合
で秤量し、充分混合したものをガラス調合原料とし、そ
れを白金製坩堝に投入して、電気炉で1400〜150
0℃で溶融し、白金製攪拌棒で攪拌して清澄、均質化し
てから適当な温度に予熱した金型に鋳込んだ後、徐冷し
て得られる。なお、ガラスの着色を防ぎ脱泡のため還元
効果をもつ添加物、例えば、Sb2 O3 等の添加物を少
量添加するのは好ましく、本発明の効果に影響を与えな
い。なお、本発明のファラデー回転素子用ガラスには、
上記成分のほかに、溶融性の改善、ガラスの安定性拡大
のために、本発明の目的を外れない限り、通常この種の
ガラスで使用されて本明細書に記載されていない他のガ
ラス成分でも、数重量%の範囲内で含有させることが出
来る。The glass for a Faraday rotator of the present invention comprises:
Using the corresponding oxides, hydroxides, phosphates, carbonates, nitrates, etc., as raw materials for each component, weighing them in a predetermined ratio, and mixing them well as glass-blended raw materials, and using them as platinum crucibles And 1400-150 in an electric furnace
It is melted at 0 ° C., stirred with a platinum stirring bar, clarified and homogenized, cast into a mold preheated to an appropriate temperature, and then gradually cooled. It is preferable to add a small amount of an additive having a reducing effect, for example, Sb 2 O 3 , for preventing coloring of the glass and removing bubbles, and does not affect the effects of the present invention. In addition, the glass for a Faraday rotation element of the present invention includes:
In addition to the above components, other glass components that are usually used in this kind of glass and are not described in the present specification, so long as they do not depart from the purpose of the present invention, in order to improve the melting property and expand the stability of the glass. However, it can be contained within a range of several weight%.
【0013】[0013]
【実施例】以下、実施例により本発明を説明するが、本
発明はこれらの実施例に限定されるものではない。 (実施例1)表1に示した実施例1の組成物を通常の方
法でガラス化した。すなわち、それぞれの原料化合物と
して、SiO2 、H3 BO3 、Ga2 O3 、Tb4 O7
をガラス重量100gとなるように所定の割合で秤量
し、それらを混合後、白金製るつぼを用い、1450℃
の電気炉中で約2時間溶融した。溶融中に適時かくはん
を行い、融液を均質化した。その後、鋳型に流し込んで
成形し、さらに650℃の電気炉中でアニールしてガラ
スを得た。ここでSb2 O3 を還元剤として0.5重量
%添加した。得られたガラスの安定性を確認するために
示差熱分析による結晶化温度の測定を行った。また、ベ
ルデ定数の測定も行った。その結果を表2に示した。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 The composition of Example 1 shown in Table 1 was vitrified by an ordinary method. That is, SiO 2 , H 3 BO 3 , Ga 2 O 3 , Tb 4 O 7
Are weighed at a predetermined ratio so that the weight of the glass becomes 100 g, and after mixing them, using a platinum crucible, 1450 ° C.
In an electric furnace for about 2 hours. The melt was homogenized during the melting to homogenize the melt. Thereafter, the mixture was poured into a mold and molded, and further annealed in an electric furnace at 650 ° C. to obtain glass. Here, 0.5% by weight of Sb 2 O 3 was added as a reducing agent. The crystallization temperature was measured by differential thermal analysis to confirm the stability of the obtained glass. The Verdet constant was also measured. The results are shown in Table 2.
【0014】[0014]
【表1】 [Table 1]
【0015】[0015]
【表2】 [Table 2]
【0016】[0016]
【表3】 [Table 3]
【0017】(実施例2〜21)表1に示した実施例2
〜21までのガラスを実施例1と同様の方法にて作成し
た。得られたガラスは示差熱分析によって結晶化度を測
定し、実施例1と同様にガラスの安定性を確認した。実
施例2及び3で得られたガラスについてはベルデ定数を
測定した。その結果を表2に示した。(Examples 2 to 21) Example 2 shown in Table 1
Glasses Nos. To 21 were prepared in the same manner as in Example 1. The crystallinity of the obtained glass was measured by differential thermal analysis, and the stability of the glass was confirmed as in Example 1. The Verdet constant was measured for the glasses obtained in Examples 2 and 3. The results are shown in Table 2.
【0018】(比較例1〜2)SiO2 −B2 O3 −A
l2 O3 −Tb2 O3 系ファラデー回転ガラスを作成
し、示差熱分析により本発明のガラスとの比較を行っ
た。その結果を表3に示した。ガラス転移温度Tg、結
晶化温度Tclから得られる(Tcl−Tg)/Tg値
をガラス形成の目安とした。ガラスが安定であればこの
値は大きくなる。例えば、(Tcl−Tg)/Tg値は
実施例10では0.364、比較例1では0.300で
あり実施例10の方が大きく、安定なガラスである。ま
た、テルビウムイオン数も実施例10では1.23×1
022(個/cm3 )、比較例1では1.11×10
22(個/cm3 )と実施例10の方が多い。テルビウム
のイオン数が多いほどベルデ定数は大きくなるので、比
較例1よりも実施例10の方が大きなベルデ定数が得ら
れる。同様に実施例7と比較例2を比べても、実施例7
の方が(Tcl−Tg)/Tg値、テルビウムイオン数
ともに大きい。よって、本発明のSiO2 −B2 O3 −
Ga2 O3 −Tb2 O3 系ガラスはSiO2 −B2 O 3
−Al2 O3 −Tb2 O3 系ガラスよりも安定であり、
大きなベルデ定数が得られることが分かる。(Comparative Examples 1-2) SiOTwo-BTwoOThree-A
lTwoOThree-TbTwoOThreeCreates Faraday rotating glass
And compared with the glass of the present invention by differential thermal analysis.
Was. Table 3 shows the results. Glass transition temperature Tg,
(Tcl-Tg) / Tg value obtained from crystallization temperature Tcl
Was used as a measure of glass formation. If the glass is stable
The value increases. For example, (Tcl−Tg) / Tg value is
0.364 in Example 10 and 0.300 in Comparative Example 1.
Yes, Example 10 is larger and more stable glass. Ma
In Example 10, the number of terbium ions was 1.23 × 1
0twenty two(Pcs / cmThree), 1.11 × 10 in Comparative Example 1.
twenty two(Pcs / cmThree) And Example 10. terbium
Since the Verdet constant increases as the number of ions increases, the ratio
A larger Verdet constant was obtained in Example 10 than in Comparative Example 1.
It is. Similarly, the comparison between Example 7 and Comparative Example 2 reveals that Example 7
Is (Tcl-Tg) / Tg value, number of terbium ions
Both are big. Therefore, the SiO of the present inventionTwo-BTwoOThree−
GaTwoOThree-TbTwoOThreeSystem glass is SiOTwo-BTwoO Three
-AlTwoOThree-TbTwoOThreeMore stable than system glass,
It can be seen that a large Verdet constant is obtained.
【0019】[0019]
【表4】 [Table 4]
【0020】[0020]
【発明の効果】このように本発明によれば、高濃度のテ
ルビウムイオンを含有させることができるので、従来の
ファラデー回転ガラスよりも大きなベルデ定数を持つガ
ラスが作成できる。このガラスは実用上十分な安定性を
持ち、小型化が望まれる光アイソレータや磁界センサな
どに好ましく用いることができる。As described above, according to the present invention, a high concentration of terbium ions can be contained, so that a glass having a larger Verdet constant than a conventional Faraday rotating glass can be produced. This glass has practically sufficient stability and can be preferably used for an optical isolator, a magnetic field sensor, and the like for which miniaturization is desired.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成9年5月16日[Submission date] May 16, 1997
【手続補正1】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0007[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【0007】本発明のファラデー回転素子用ガラスの好
ましい組成範囲の一例としては下記のものが挙げられ
る。モル%でTb2 O3 が25〜50%、SiO2 が1
0〜35%、B2 O3 が10〜40%、Ga2 O3 が5
〜35%、さらにP2 O5 が1〜7%、GeO2 が1〜
20%、またMgO、CaO、SrOおよびBaOがそ
れぞれ0〜6%で、(MgO+CaO+SrO+Ba
O)が0〜6%、La2 O 3 が0〜6%、Gd2 O3 が
0〜6%、Yb2 O3 が0〜6%、Dy2 O3 が0〜1
5%、〔Tb2 O3 +La2 O3 +Gd2 O3 +Yb2
O3 +Dy2 O3 〕が25〜60%からなり、ZrO2
が0〜8%となるファラデー回転素子用ガラス。The glass for a Faraday rotator of the present invention is preferably used.
Good composition rangeExamples of the following
You.Tb in mole%TwoOThreeIs 25-50%, SiOTwoIs 1
0-35%, BTwoOThreeIs 10 to 40%, GaTwoOThreeIs 5
~ 35%, plus PTwoOFiveIs 1-7%, GeOTwoIs 1
20%, MgO, CaO, SrO and BaO
In each case from 0 to 6%, (MgO + CaO + SrO + Ba
O) 0-6%, LaTwoO ThreeIs 0-6%, GdTwoOThreeBut
0-6%, YbTwoOThreeIs 0-6%, DyTwoOThreeIs 0-1
5%, [TbTwoOThree+ LaTwoOThree+ GdTwoOThree+ YbTwo
OThree+ DyTwoOThree] Of 25-60%, and ZrOTwo
Is 0 to 8%.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 永濱 忍 埼玉県浦和市針ケ谷4丁目7番25号 株式 会社住田光学ガラス内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shinobu Nagahama 4-7-25 Harigaya, Urawa-shi, Saitama Sumitomo Optical Glass Co., Ltd.
Claims (1)
iO2 が5〜40%、B2 O3 が5〜45%、Ga2 O
3 が5〜35%、さらにP2 O5 が0〜7%、GeO2
が0〜20%、またMgO、CaO、SrOおよびBa
Oがそれぞれ0〜6%で、(MgO+CaO+SrO+
BaO)が0〜6%、La2 O3 が0〜6%、Gd2 O
3 が0〜6%、Yb2 O3 が0〜6%、Dy2 O3 が0
〜15%、〔Tb2 O3 +La2 O3 +Gd2 O3 +Y
b2 O3 +Dy2 O3 〕が25〜60%およびZrO2
が0〜8%からなる組成のファラデー回転素子用ガラ
ス。1. Tb 2 O 3 content of 25 to 50% by mole%, S
iO 2 is 5~40%, B 2 O 3 is 5~45%, Ga 2 O
3 5 to 35%, more P 2 O 5 is 0 to 7% GeO 2
Is 0 to 20%, and MgO, CaO, SrO and Ba
O is 0 to 6% each, and (MgO + CaO + SrO +
BaO) is 0~6%, La 2 O 3 is 0~6%, Gd 2 O
3 0~6%, Yb 2 O 3 is 0~6%, Dy 2 O 3 is 0
1515%, [Tb 2 O 3 + La 2 O 3 + Gd 2 O 3 + Y
b 2 O 3 + Dy 2 O 3 ] is 25% to 60% and ZrO 2
Has a composition of 0 to 8%.
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