JPH03164491A - Production of garnet type ferrite single crystal - Google Patents
Production of garnet type ferrite single crystalInfo
- Publication number
- JPH03164491A JPH03164491A JP10319590A JP10319590A JPH03164491A JP H03164491 A JPH03164491 A JP H03164491A JP 10319590 A JP10319590 A JP 10319590A JP 10319590 A JP10319590 A JP 10319590A JP H03164491 A JPH03164491 A JP H03164491A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- garnet
- type ferrite
- mol
- polycrystalline body
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 61
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 32
- 239000002223 garnet Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000000843 powder Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 238000005304 joining Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000012071 phase Substances 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910052727 yttrium Inorganic materials 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- 238000003746 solid phase reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 206010022971 Iron Deficiencies Diseases 0.000 description 2
- 206010022979 Iron excess Diseases 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000005381 magnetic domain Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/342—Oxides
- H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
- H01F1/346—[(TO4) 3] with T= Si, Al, Fe, Ga
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、多結晶体に種単結晶を接合して熱処理するこ
とにより多結晶体を単結晶化するガーネット型フェライ
ト単結晶の製造方法に関し、特に光アイソレークなどの
磁気光学素子として使用するガーネット型フェライト単
結晶の製造方法に関するものである。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a method for manufacturing a garnet-type ferrite single crystal in which a polycrystalline body is made into a single crystal by bonding a seed single crystal to the polycrystalline body and heat-treating the polycrystalline body. In particular, the present invention relates to a method for manufacturing a garnet-type ferrite single crystal used as a magneto-optical element such as an optical isolake.
（従来の技術）
ガーネット型フェライトは、Ｙ：３７゜５モル％、Ｆｅ
：６２．５モル％を主な組成とし、必要に応じてＹの
一部およびＦｅの一部を置換した組成として知られてい
る。磁気光学素子として使用するガーネット型フェライ
ト結晶としては、多結晶体は粒界に気孔等が残存し光を
通しにくいため、単結晶体を使用していた。(Prior art) Garnet type ferrite has Y: 37°5 mol%, Fe
:62.5 mol % is the main composition, and it is known as a composition in which part of Y and part of Fe are substituted as necessary. As a garnet-type ferrite crystal used as a magneto-optical element, a single crystal has been used because polycrystals have pores and the like remaining in the grain boundaries, making it difficult for light to pass through.
従来、ガーネット型フェライト単結晶体を得る方法とし
て、多結晶体に種単結晶を接合して熱処理することによ
り、同相反応を利用して多結晶体を単結晶化し、ガーネ
ット型フェライト単結晶体を製造する方法が、特公昭６
１−１３９１号公報および特開昭６３−３５４９０号公
報において知られている。Conventionally, the method for obtaining a garnet-type ferrite single crystal is to bond a seed single crystal to a polycrystalline body and heat treat it to make the polycrystalline into a single crystal using an in-phase reaction. The manufacturing method was developed in 1977.
It is known from Japanese Patent Publication No. 1-1391 and Japanese Patent Application Laid-Open No. 63-35490.
（発明が解決しようとする課題）
しかしながら、上述した単結晶の製造方法においては、
鉄の含有量（一部鉄以外の組成と置換したときは鉄に換
算した値）が目標値である６２．５モル％より多い組成
では、単結晶中に酸化鉄の第２相が残留してしまう問題
があった。また、イツトリウムの含有量（一部イットリ
ウム以外の組成と置換したときはイツトリウムに換算し
た値）が目標値である３７．５モル％より多い組成では
、単結晶が成長しないという問題もあった。そのため、
このような場合は、安定した単結晶の育成を実施するこ
とができなかった。(Problem to be solved by the invention) However, in the method for manufacturing a single crystal described above,
If the iron content (value converted to iron when partially replaced with a composition other than iron) is higher than the target value of 62.5 mol%, the second phase of iron oxide will remain in the single crystal. There was a problem. In addition, there was also the problem that single crystals did not grow if the yttrium content (value converted to yttrium when a part of the composition was replaced with a composition other than yttrium) was higher than the target value of 37.5 mol%. Therefore,
In such cases, stable single crystal growth could not be achieved.
本発明の目的は上述した課題を解消して、安定した単結
晶育成が可能なガーネット型フェライト単結晶の製造方
法を提供しようとするものである。An object of the present invention is to solve the above-mentioned problems and provide a method for manufacturing a garnet-type ferrite single crystal that allows stable single crystal growth.
（課題を解決するための手段）
本発明のガーネット型フェライト単結晶の製造方法は、
多結晶体に種単結晶を接合して熱処理することにより、
多結晶体を単結晶化するガーネット型フェライト単結晶
の製造方法において、多結晶体の組成を目標値に対して
±０．１モル％以下に制御することを特徴とするもので
ある。(Means for Solving the Problems) The method for producing a garnet-type ferrite single crystal of the present invention includes:
By joining a seed single crystal to a polycrystalline body and heat-treating it,
A method for manufacturing a garnet-type ferrite single crystal in which a polycrystalline body is made into a single crystal is characterized in that the composition of the polycrystalline body is controlled to be within ±0.1 mol % with respect to a target value.
ここで、ガーネット型フェライトとは、一般式Ａ３Ｂ６
０１２で表され、ＡとしてはＹ、希土類元素（Ｌａ、
Ｃｅ、 Ｐｒ、 Ｎｄ、 Ｐｍ、 Ｓｍ、 Ｅｕ、 Ｇ
ｄ、 Ｔｂ、 Ｄｙ、 Ｈｏ。Here, garnet type ferrite is of the general formula A3B6
012, where A is Y, rare earth elements (La,
Ce, Pr, Nd, Pm, Sm, Eu, G
d, Tb, Dy, Ho.
Ｅｒ、 Ｔｍ、 Ｙｂ、 Ｌｕ）、 Ｂｉ、 Ｃａ、
Ｐｂ等を、ＢとしてはＦｅを基本元素として、ＡＡ、
Ｇａ、 Ｉｎ、 Ｓｎ、 Ｚｒ、 Ｔｉ。Er, Tm, Yb, Lu), Bi, Ca,
Pb etc., B is Fe as the basic element, AA,
Ga, In, Sn, Zr, Ti.
Ｇｅ＋ Ｖｔ Ｓｂ、Ｓｃ等を含むものである。It includes Ge+Vt Sb, Sc, etc.
また、ここでいう目標値とは、ガーネットの結晶構造（
組成）のＡ３Ｂ５Ｏ□２におけるＡ：Ｂ＝３７．５０：
６２．５０を示すものである。Ａに含まれる元素のモル
数の和とＢに含まれる元素のモル数の和が、この目標値
に近い場合のみガーネット単一相のものが得られ、それ
以外では第２相が存在する。即ち、固溶範囲が非常に狭
い。Also, the target value here refers to the crystal structure of garnet (
A:B=37.50 in A3B5O□2 of composition):
62.50. A garnet single phase is obtained only when the sum of the moles of elements contained in A and the sum of the moles of elements contained in B are close to this target value, and in other cases, a second phase is present. That is, the solid solution range is very narrow.
（作 用）
上述した構成において、多結晶体の組成を、それぞれ目
標値に対して±０．１モル％以下好ましくは±０．０５
モル％以下に制御することにより、多結晶体に種単結晶
を接合して熱処理することによる固相反応により単結晶
を得る・場合に、酸化鉄の第２相の残留もなく、単結晶
の育成の成長距離が良好なガーネット型フェライト単結
晶を得ることができることを見出したことによる。(Function) In the above-mentioned configuration, the composition of the polycrystalline body is adjusted to ±0.1 mol% or less, preferably ±0.05 mol%, with respect to each target value.
By controlling the mol% or less, when a single crystal is obtained by a solid phase reaction by joining a seed single crystal to a polycrystal and heat treating it, there is no residual iron oxide second phase and the single crystal is This is due to the discovery that it is possible to obtain a garnet-type ferrite single crystal with a good growth distance.
その際、組成制御の方法として、２種類の組成の近似し
て異なるガーネット型フェライト粉末、すなわちある元
素の含有量が多い粉末と少ない粉末を、そのうちの一方
は目標とする組成より高く他の一方が低いフェライト粉
末を所定比で混合すると、本発明で目標とする±０．１
０％程度の精度をより簡単に達成できるため好ましい。At that time, as a composition control method, two types of garnet-type ferrite powders with approximately different compositions, one with a high content of a certain element and one with a low content, are used, one of which is higher than the target composition and the other with a lower content. When ferrite powder with low
This is preferable because accuracy of about 0% can be achieved more easily.
なお、上記調合補正のほかに、工程の安定化等により上
記精度に組成を制御できる場合はその方法でも組成制御
できる。In addition to the above-mentioned formulation correction, if the composition can be controlled to the above-mentioned accuracy by stabilizing the process, the composition can also be controlled by that method.
また、熱処理を熱間静水圧プレス処理（以下、ＨＩＰ又
はＨＩＰ処理と記す）で行うと、さらに安定した単結晶
育成が可能になるため好ましいとともに、酸素を含む雰
囲気ガス好ましくは酸素を０．１％以上２０％以下含有
する雰囲気ガス中で熱処理すると、ガーネットの分解溶
融温度が上昇するためより焼結温度も高くでき焼結しや
すくなり、さらに各組成が分解しにく（なり他の相の発
生を防止できるため好ましい。In addition, it is preferable to perform the heat treatment by hot isostatic pressing (hereinafter referred to as HIP or HIP treatment) because it enables more stable single crystal growth. When heat-treated in an atmospheric gas containing garnet % to 20%, the decomposition and melting temperature of garnet increases, making the sintering temperature higher and sintering easier. This is preferable because it can prevent occurrence.
なお、ここで光吸収係数αは、以下の式より得ることが
できる。Note that the light absorption coefficient α can be obtained from the following formula.
■０
ここで Ｉｏ：入射光の強度（反射を除く）■ ＝出射
光の強度
ｌ ：多結晶体の厚さ（ｃｍ）
である。■0 Here, Io: Intensity of incident light (excluding reflection)■ =Intensity of outgoing light l: Thickness of polycrystal (cm).
（実施例） 以下、本発明について詳細に説明する。(Example) The present invention will be explained in detail below.
まず、原料となるガーネット型フェライト粉末の製造法
について説明する。本発明においては所定組成のガーネ
ット型フェライト粉末が得られればどのような製造法で
あっても問題はないが、特に以下に述べる共沈法による
２方法が好ましい。First, a method for producing garnet-type ferrite powder, which is a raw material, will be explained. In the present invention, any manufacturing method may be used as long as a garnet-type ferrite powder having a predetermined composition can be obtained, but the two methods using the coprecipitation method described below are particularly preferred.
すなわち、（１）少なくとも２価の鉄イオンとイツトリ
ウムまたは希土類金属イオンを含む混合水溶液から、塩
基により水酸化物を共沈させ、次いで鉄を３価に酸化し
つつ共沈物を合成した後、分離・乾燥・仮焼する方法、
および（２）少なくとも３価の硝酸鉄とイツトリウムま
たは希土類金属の硝酸塩を含む混合水溶液を原料とし、
この金属塩混合水溶液を塩基の水溶液中に滴下すること
により水酸化物を共沈させた後、分離・乾燥・仮焼する
方法が好ましい。That is, (1) from a mixed aqueous solution containing at least divalent iron ions and yttrium or rare earth metal ions, a hydroxide is coprecipitated with a base, and then a coprecipitate is synthesized while oxidizing the iron to trivalent, and then Separation, drying, and calcining methods;
and (2) using a mixed aqueous solution containing at least trivalent iron nitrate and yttrium or rare earth metal nitrate as a raw material,
A preferred method is to drop the metal salt mixed aqueous solution into an aqueous base solution to coprecipitate the hydroxide, followed by separation, drying, and calcining.
次に、このようにして得られた粉末を目標値に対して±
０．１０モル％以下好ましくは±０．０５モル％以下と
なるよう制御する。本発明においては、その精度が目標
値の±０．ｌＯモル％以下となるよう調合できればどの
ような方法でもよいが、以下に述べる調合補正方法が好
ましい。すなわち、例えばＹ３Ｆ２５０１ｚの結晶でＹ
３７．５モル％、 Ｆｅ６２．５モル％の組成を目標と
した場合について説明する。この場合は、粉末Ａ （Ｙ
３８モル％＋ Ｆｅ６２モル％）と粉末Ｂ （Ｙ３７モ
ル％、 Ｆｅ６３モル％）を準備し、この粉末Ａと粉末
Ｂを割合を変えて混合することにより、目標値（Ｙ３７
．５モル％、 Ｆｅ６２．５モル％）に対してそれぞれ
の値のずれが±０．０５モル％の範囲に入るように制御
している。粉末Ａと粉末Ｂとのモル％の差は出来るだけ
小さい方が望ましい。差が大きいと粉末特性が大きく異
なり成形性、焼結性が良くないことが考えられる。調合
補正のような工程をとらない場合、工程中の組成変動要
因、特に粉砕工程での鉄分の混合やビスマス置換体では
仮焼によるビスマス成分の揮発のため±０．１０モル％
以下での組成制御は難しい。Next, the powder obtained in this way is ±
It is controlled to be 0.10 mol% or less, preferably ±0.05 mol% or less. In the present invention, the accuracy is ±0.0 of the target value. Any method may be used as long as it can be formulated so that the concentration is 10 mol % or less, but the formulation correction method described below is preferred. That is, for example, in a Y3F2501z crystal, Y
A case where the target composition is 37.5 mol % and Fe62.5 mol % will be explained. In this case, powder A (Y
38 mol% + Fe62 mol%) and powder B (Y37 mol%, Fe63 mol%), and by mixing powder A and powder B in different proportions, the target value (Y37
．． 5 mol% and Fe62.5 mol%), the deviation of each value is controlled to be within the range of ±0.05 mol%. It is desirable that the difference in mol% between powder A and powder B is as small as possible. If the difference is large, the powder properties will be greatly different and the moldability and sinterability may be poor. If a process such as formulation correction is not taken, composition fluctuation factors during the process, especially the mixing of iron in the pulverization process and the volatilization of bismuth components due to calcination in the case of bismuth substitutes, will result in ±0.10 mol%.
It is difficult to control the composition below.
次に、調合補正の終了したガーネット型フェライト粉末
を所定形状に成形した後、焼成し、ガーネット型フェラ
イト多結晶体を得ることができる。Next, the garnet-type ferrite powder that has been subjected to blending correction is molded into a predetermined shape and then fired to obtain a garnet-type ferrite polycrystal.
その後、得られたガーネット型フェライト多結晶体から
単結晶体を得るには、固相反応による方法、その−例と
して例えば本願人による特開昭６３−３５４９０号公報
に開示された単結晶ガーネット体の製造法が好適に使用
できる。Thereafter, in order to obtain a single crystal from the obtained garnet type ferrite polycrystal, a solid phase reaction method is used. The manufacturing method can be suitably used.
以下、実際の例について説明する。An actual example will be explained below.
実施例１
硫酸鉄、硝酸イツトリウムを出発原料とする共沈法によ
り、２種類の合成粉末Ａ（モル比でＦｅ ： Ｙ＝６２
．Ｏ： ３８．０）およびＢ（モル比でＦｅ：Ｙ＝
６３． Ｏ二３７． Ｏ）を製造し、これらの粉末を以
下に述べるように混合比を変えて調合補正することによ
りＹ３ＦｅｓＯ＋２を目標組成とした。Example 1 Two types of synthetic powder A (molar ratio of Fe:Y=62) were prepared by a coprecipitation method using iron sulfate and yttrium nitrate as starting materials.
．． O: 38.0) and B (Fe:Y= in molar ratio
63. O237. Y3FesO+2 was set as the target composition by manufacturing Y3FesO+2 and correcting the formulation by changing the mixing ratio of these powders as described below.
すなわち、合成粉末ＡおよびＢを乾燥弓２００°Ｃで仮
焼・粉砕後、２種の粉末を第１表に示す割合で湿式混合
した後乾燥した。これらの混合粉末を成形し、１４００
℃で８時間焼成した。焼成後の成形体を５ ｍｍ Ｘ
１０＋＋＋ｍ Ｘ １０ｍｍのブロックに切り出し、Ｙ
ａＦｅｓＯ＋□単結晶から作製した種単結晶を接合し、
常圧で酸素雰囲気、１５００ａｔｍのＨＩＰでＡｒ雰囲
気および１５００ａｔｍのＨＩＰで２０％酸素雰囲気で
それぞれ１５００°Ｃにおいて単結晶育成を行った。That is, synthetic powders A and B were calcined and pulverized at 200°C in a drying oven, and then the two types of powders were wet mixed in the proportions shown in Table 1, and then dried. These mixed powders were molded and heated to 1400
It was baked at ℃ for 8 hours. The molded body after firing is 5 mm
Cut into 10+++m x 10mm blocks, Y
A seed single crystal made from aFesO+□ single crystal is joined,
Single crystals were grown at 1500° C. in an oxygen atmosphere at normal pressure, an Ar atmosphere in 1500 atm HIP, and a 20% oxygen atmosphere in 1500 atm HIP.
その後、得られたガーネット型フェライト単結晶の接合
面からの成長距離と第２相が存在するか否かを調べた。Thereafter, the growth distance from the bonding surface of the obtained garnet-type ferrite single crystal and the presence or absence of a second phase were investigated.
結果を第１表に示す。第１表には、あわせて各試料の目
標値に対する制御の結果を示す。The results are shown in Table 1. Table 1 also shows the control results for the target values of each sample.
第１表の結果から、固相反応を利用した単結晶の育成に
おいて、多結晶体の調合補正により組成を目標値に対し
て±０．１モル％以下に制御した場合は、いずれの雰囲
気においても単結晶の育成距離が長（また第２相が存在
せず、安定した単結晶育成が可能なことがわかった。な
お、ＨＩＰにより育成した単結晶は、密度９９．９９％
以上で磁気光学単結晶特有の磁区の迷図パターンの認め
られる結晶性のよいものであった。なおこ・の単結晶は
、１．３．ｃｚｍの波長でファラデー回転角２００ｄｅ
ｇ／ｃｍ ％吸収係数は、Ａｒ雰囲気では１．２ｃｍ’
、０２雰囲気では０．５ｃｍ”−’であった。これに対
し、鉄過剰では、酸化鉄を主成分とする第２相が生成し
、鉄不足では単結晶が成長しなかった。From the results in Table 1, in growing single crystals using solid-phase reactions, if the composition is controlled to within ±0.1 mol% of the target value by correcting the polycrystalline mixture, in any atmosphere It was also found that stable single crystal growth was possible due to the long single crystal growth distance (and no second phase).The single crystal grown by HIP had a density of 99.99%.
As described above, the crystallinity was good and the labyrinthine pattern of magnetic domains peculiar to magneto-optical single crystals was observed. Naoko's single crystal is 1.3. Faraday rotation angle 200 de at wavelength of czm
g/cm % absorption coefficient is 1.2 cm' in Ar atmosphere
, 0.5 cm"-' in the 02 atmosphere. On the other hand, in an iron excess, a second phase containing iron oxide as a main component was formed, and in an iron deficiency, a single crystal did not grow.
実施例２
硝酸ビスマス、硝酸鉄、硝酸イツトリウムを出発原料と
する共沈法により、２種類の合成粉末Ａ（モル比でＢｉ
：Ｆｅ：Ｙ ＝ １２．０：６２．５：２５．０）及び
Ｂ（モル比でＢｉ：Ｆｅ：Ｙ ＝ １３．０：６２．５
：２５．０）を製造し、これらの粉末を以下に述べるよ
うに混合比を変えて調合補正することによりＢｉＹｚＦ
ｅｓＯ＋ｚ（Ｂｉ １２．５モル％、Ｆｅ６２．５モル
％、Ｙ２５．０モル％）を目標組成とした。Example 2 Two types of synthetic powders A (with a molar ratio of Bi
:Fe:Y = 12.0:62.5:25.0) and B (Bi:Fe:Y = 13.0:62.5 in molar ratio
:25.0) and corrected the formulation by changing the mixing ratio of these powders as described below.
The target composition was esO+z (Bi 12.5 mol%, Fe 62.5 mol%, Y 25.0 mol%).
すなわち、合成粉末ＡおよびＢを乾燥８００℃で仮焼・
粉砕後、２種の粉末を第１表に示す割合で湿式混合した
後乾燥した。これらの混合粉末を成形し、９５０℃で１
０時間焼成した。That is, synthetic powders A and B were calcined and dried at 800°C.
After pulverization, the two types of powder were wet mixed in the proportions shown in Table 1 and then dried. These mixed powders were molded and heated at 950°C for 1
It was baked for 0 hours.
焼成後の成形体を５ ｍｍＸ １０ｍｍＸ １０ｍｍの
ブロックに切り出し、Ｂｉ＋ＹｚＦｅｓＯｕ単結晶から
作製した種単結晶を接合し、常圧で酸素雰囲気、１５０
０ａｔｍのＨＩＰでＡ「雰囲気および１５００ａｔｍの
旧Ｐで２０％酸素雰囲気でそれぞれ１０００°Ｃにおい
て単結晶育成を行った。The molded body after firing was cut into blocks of 5 mm x 10 mm x 10 mm, a seed single crystal made from Bi + YzFesOu single crystal was joined, and the blocks were heated in an oxygen atmosphere at normal pressure for 150 mm.
Single crystal growth was performed at 1000°C in an A atmosphere with HIP at 0 atm and a 20% oxygen atmosphere with old P at 1500 atm.
その後、得られたガーネット型フェライト単結晶の接合
面からの成長距離と第２相が存在するか否かを調べた。Thereafter, the growth distance from the bonding surface of the obtained garnet-type ferrite single crystal and the presence or absence of a second phase were investigated.
結果を第２表に示す。第２表には、あわせて各試料の目
標値に対する制御の結果を示す。The results are shown in Table 2. Table 2 also shows the control results for the target values of each sample.
第２表の結果から、実施例１とは組成の異なるガーネッ
ト型フェライト単結晶の製造方法においても、本発明に
よれば実施例１と同様に安定した単結晶育成が可能なこ
とがわかった。この単結晶は、密度が９９．９９％以上
で磁気光学単結晶特有の磁区の迷図パターンの認められ
る結晶性のよいものであった。なおこの単結晶は、ファ
ラデー回転角が２２００ｄｇｅ／ｃｍ、光吸収係数は、
Ａ「雰囲気では１゜３ｃｍ−’、０□雰囲気では０．６
ｃｍ−’であった。なお、鉄過剰では酸化鉄を主成分と
する第２相が生成し、鉄不足ではビスマス酸化物を主成
分とする第２相が生成した。From the results in Table 2, it was found that even in a method for producing a garnet-type ferrite single crystal having a composition different from that in Example 1, stable single crystal growth was possible in the same manner as in Example 1 according to the present invention. This single crystal had a density of 99.99% or more and had good crystallinity with a stray pattern of magnetic domains unique to magneto-optical single crystals. This single crystal has a Faraday rotation angle of 2200 dge/cm and a light absorption coefficient of
A: 1°3cm-' in the atmosphere, 0.6 in the 0□ atmosphere
cm-'. Note that in the case of iron excess, a second phase containing iron oxide as the main component was produced, and in the case of iron deficiency, the second phase containing bismuth oxide as the main component was produced.
（発明の効果）
以上の説明から明らかなように、本発明のガーネット型
フェライト単結晶の製造方法によれば、固相反応を利用
した単結晶の製造において、多結晶体の原料となるフェ
ライト粉末の組成を好ましくは調合補正により所定の範
囲内の誤差にするとともに、好ましくはＨＩＰ処理を酸
化雰囲気内で実施することにより、第２相の残留もなく
十分に育成された単結晶を得ることができる。(Effects of the Invention) As is clear from the above description, according to the method for producing a garnet-type ferrite single crystal of the present invention, ferrite powder, which is a raw material for a polycrystal, is used in the production of a single crystal using a solid phase reaction. It is possible to obtain a sufficiently grown single crystal without any residual second phase by adjusting the composition of the material preferably within a predetermined range by correcting the composition and preferably performing HIP treatment in an oxidizing atmosphere. can.
Claims (1)
り、多結晶体を単結晶化するガーネット型フェライト単
結晶の製造方法において、多結晶体の組成を目標値に対
して±０．１モル％以下に制御することを特徴とするガ
ーネット型フェライト単結晶の製造方法。 ２、前記組成制御の方法として、２種類の組成の異なる
ガーネット型フェライト粉末を所定比で混合した後、成
形し焼成することを特徴とする請求項１記載のガーネッ
ト型フェライト単結晶の製造方法。 ３、前記熱処理を、熱間静水圧プレス処理で行うことを
特徴とする請求項１記載のガーネット型フェライト単結
晶の製造方法。 ４、酸素を含有する雰囲気ガスを用いることを特徴とす
る請求項３記載のガーネット型フェライト単結晶の製造
方法。[Claims] 1. A method for manufacturing a garnet-type ferrite single crystal in which a polycrystalline body is made into a single crystal by bonding a seed single crystal to the polycrystalline body and heat-treating the polycrystalline body, wherein the composition of the polycrystalline body is set to a target value. A method for producing a garnet-type ferrite single crystal, characterized in that the ferrite is controlled to ±0.1 mol% or less. 2. The method for producing a garnet-type ferrite single crystal according to claim 1, wherein the method for controlling the composition comprises mixing two types of garnet-type ferrite powders having different compositions at a predetermined ratio, followed by molding and firing. 3. The method for producing a garnet-type ferrite single crystal according to claim 1, wherein the heat treatment is performed by hot isostatic pressing. 4. The method for producing a garnet type ferrite single crystal according to claim 3, characterized in that an atmospheric gas containing oxygen is used.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2103195A JP2523205B2 (en) | 1989-08-29 | 1990-04-20 | Method for producing garnet-type ferrite single crystal |
| DE69016699T DE69016699T2 (en) | 1989-04-28 | 1990-04-26 | Process for the production of ferrite crystals and process for the production of preferably used ferrite powders. |
| EP90304505A EP0399665B1 (en) | 1989-04-28 | 1990-04-26 | Method of manufacturing ferrite crystals and method of producing ferrite powders preferably used therefor |
| CA002015606A CA2015606C (en) | 1989-04-28 | 1990-04-27 | Method of manufacturing shaped body made of ferrite crystals of garnet polycrystal structure |
| US07/516,907 US5256242A (en) | 1989-04-28 | 1990-04-30 | Method of manufacturing ferrite crystals |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-220178 | 1989-08-29 | ||
| JP22017889 | 1989-08-29 | ||
| JP2103195A JP2523205B2 (en) | 1989-08-29 | 1990-04-20 | Method for producing garnet-type ferrite single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03164491A true JPH03164491A (en) | 1991-07-16 |
| JP2523205B2 JP2523205B2 (en) | 1996-08-07 |
Family
ID=26443844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2103195A Expired - Lifetime JP2523205B2 (en) | 1989-04-28 | 1990-04-20 | Method for producing garnet-type ferrite single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2523205B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0702259A1 (en) | 1994-09-16 | 1996-03-20 | Ngk Insulators, Ltd. | Material for wide-band optical isolators and process for producing the same |
| CN114133235A (en) * | 2021-11-03 | 2022-03-04 | 中国科学院上海硅酸盐研究所 | Axial hot-pressing sintering preparation method of rare earth iron garnet magneto-optical ceramic with good infrared permeability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5926994A (en) * | 1982-08-05 | 1984-02-13 | Matsushita Electric Ind Co Ltd | Preparation of oxide single crystal |
| JPS6335490A (en) * | 1986-07-30 | 1988-02-16 | Ngk Insulators Ltd | Production of single crystal |
-
1990
- 1990-04-20 JP JP2103195A patent/JP2523205B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5926994A (en) * | 1982-08-05 | 1984-02-13 | Matsushita Electric Ind Co Ltd | Preparation of oxide single crystal |
| JPS6335490A (en) * | 1986-07-30 | 1988-02-16 | Ngk Insulators Ltd | Production of single crystal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0702259A1 (en) | 1994-09-16 | 1996-03-20 | Ngk Insulators, Ltd. | Material for wide-band optical isolators and process for producing the same |
| US5584928A (en) * | 1994-09-16 | 1996-12-17 | Ngk Insulators, Ltd. | Material for wide-band optical isolators and process for producing the same |
| CN114133235A (en) * | 2021-11-03 | 2022-03-04 | 中国科学院上海硅酸盐研究所 | Axial hot-pressing sintering preparation method of rare earth iron garnet magneto-optical ceramic with good infrared permeability |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2523205B2 (en) | 1996-08-07 |
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