JPH0474722A - Production of garnet fine powder - Google Patents
Production of garnet fine powderInfo
- Publication number
- JPH0474722A JPH0474722A JP18410190A JP18410190A JPH0474722A JP H0474722 A JPH0474722 A JP H0474722A JP 18410190 A JP18410190 A JP 18410190A JP 18410190 A JP18410190 A JP 18410190A JP H0474722 A JPH0474722 A JP H0474722A
- Authority
- JP
- Japan
- Prior art keywords
- garnet
- elements
- fine particles
- rare earth
- optical
- 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.)
- Pending
Links
- 239000002223 garnet Substances 0.000 title claims abstract description 58
- 239000000843 powder Substances 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010419 fine particle Substances 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- -1 M n Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 34
- 239000000203 mixture Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 22
- 239000000758 substrate Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000012159 carrier gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000015654 memory Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 230000005374 Kerr effect Effects 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 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
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229910000982 rare earth metal group alloy Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910000687 transition metal group alloy Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、磁気光学特性に優れ、光アイソレータ、光サ
ーキュレータ、光スィッチ、光導波路、光メモリ等の用
途に好適なガーネット微粒子粉末の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing fine garnet powder having excellent magneto-optical properties and suitable for use in optical isolators, optical circulators, optical switches, optical waveguides, optical memories, etc. .
（従来の技術およびその問題点）
従来、磁気光学効果の優れた材料としては、希土類金属
と遷移金属との非晶質合金からなるものが知られている
。(Prior Art and its Problems) Conventionally, materials made of amorphous alloys of rare earth metals and transition metals are known as materials with excellent magneto-optical effects.
しかし、このような非晶質合金材料は、酸化腐食を受け
やすく、磁気光学特性が劣化するという欠点があった。However, such amorphous alloy materials have the drawback of being susceptible to oxidative corrosion and deteriorating magneto-optical properties.
また、非晶質合金は光透過性が低いので、表面での反射
による磁気光学効果（カー効果）を利用するが、非晶質
合金は一般にカー回転角が小さいため、感度が低いとい
う問題があった。In addition, since amorphous alloys have low light transmittance, the magneto-optical effect (Kerr effect) due to reflection on the surface is used, but since amorphous alloys generally have a small Kerr rotation angle, there is a problem of low sensitivity. there were.
これに対し、特公昭５６−１５１２５号公報には、ガー
ネットの多結晶質酸化物薄膜を用いた磁気光学材料が提
案されている。この酸化物を用いた磁性体は、耐蝕性に
優れており、また磁性膜の透過光による磁気光学効果（
ファラデー効果）を利用するため、感度が高いという利
点がある。しかしながら、多結晶質であるために、結晶
粒界での光散乱、複屈折や磁壁移動によって雑音が大き
くなるという欠点がある。On the other hand, Japanese Patent Publication No. 56-15125 proposes a magneto-optical material using a thin film of garnet polycrystalline oxide. Magnetic materials using this oxide have excellent corrosion resistance, and the magneto-optical effect (
Since it utilizes the Faraday effect), it has the advantage of high sensitivity. However, since it is polycrystalline, it has the disadvantage that noise increases due to light scattering, birefringence, and domain wall movement at crystal grain boundaries.
また、前記した磁性薄膜を基板上に作製する場合には、
作製温度が５００°Ｃ以上と高いために、耐熱性のある
基板しか使用できないという問題があった。In addition, when producing the above-described magnetic thin film on a substrate,
Since the manufacturing temperature is as high as 500° C. or higher, there is a problem in that only heat-resistant substrates can be used.
一方、特開昭６２−１１９７５８号公報には、イツトリ
ウム鉄ガーネツト粒子を用いた塗布型光磁気記録材料が
開示されている。このような塗布型媒体では、前記多結
晶質酸化物薄膜のような結晶粒界の悪影響はないが、該
公報に記載されているガーネット粒子は、粒子径が１．
５μｍと大きく、このような粒子を用いた場合には、光
の散乱が起こるため、サブミクロン波長の光を利用する
用途には通していない。On the other hand, JP-A-62-119758 discloses a coated magneto-optical recording material using yttrium iron garnet particles. In such a coating type medium, there is no adverse effect of grain boundaries as in the polycrystalline oxide thin film, but the garnet particles described in this publication have a particle size of 1.
When such particles are used, which are as large as 5 μm, light scattering occurs, making them impractical for applications that utilize submicron wavelength light.
（発明の目的）
本発明は、前記問題点を解決し、耐蝕性に優れ、磁気光
学効果が大きく、光透過性にも優れ、光アイソレータ、
光サーキュレータ、光スィッチ、光導波路、光メモリ等
の用途に好適なガーネット微粒子粉末の製造法を提供す
ることにある。(Objective of the Invention) The present invention solves the above problems, has excellent corrosion resistance, a large magneto-optic effect, excellent optical transparency, and is an optical isolator.
The object of the present invention is to provide a method for producing garnet fine particles suitable for use in optical circulators, optical switches, optical waveguides, optical memories, and the like.
（問題点を解決するための手段）
本発明は、 一般式 ＲａＢ＋ｂＦｅｃＭａ Ｏ＊（た
だし、ＲはＹ及びランタン系列元素からなる群より選ば
れる一種以上の希土類元素を示し、Ｍは＾ｌ、Ｇａ、Ｃ
ｒ、Ｍｎ、Ｓｃ、 Ｉｎ、Ｒｕ、Ｒｈ、Ｃｏ、Ｆｅ（Ｉ
Ｉ ）、Ｃｕ、Ｎｉ、Ｚｎ。(Means for Solving the Problems) The present invention has the general formula RaB+bFecMa O* (where R represents one or more rare earth elements selected from the group consisting of Y and lanthanum series elements, and M represents ^l, Ga, C
r, Mn, Sc, In, Ru, Rh, Co, Fe(I
I), Cu, Ni, Zn.
Ｌ ｉ＋ Ｓ ｌ ｌ Ｇ ｅ ＋ Ｚ ｒ ＋ Ｔ
ｉ＋ Ｈｆ ＋ Ｓ ｎ ＋ Ｐ ｂ ＋ Ｍ ｏ 、
■及びＮｂからなる群より選ばれる一種以上の元素を示
し、ａ＋ｂ士ｃ ＋ ｄ ＝ ７．０〜８． Ｏｌａ
＋ ｂ ＝ ２．０〜３．５、ｃ士ｄ ＝ ４．０〜６
． Ｏｌａ ＝ ０．５〜３．５、ｂ−０〜２．５、ｃ
＝ ３．０〜６．０、ｄ＝０〜２．０であり、ｅは他
の元素の原子価を満足する酸素の原子数である。）で表
される希土類鉄ガーネットを構成する割合で選ばれた各
元素イオンを含む溶液を、微小の液滴とし、これを加熱
することにより、前記一般式で表され、かつ平均粒子径
が３０〜３０００人である希土類鉄ガーネット微粒子を
得ることを特徴とするガーネット微粒子粉末の製造法に
関する。L i + S l l G e + Z r + T
i+Hf+Sn+Pb+Mo,
(1) Indicates one or more elements selected from the group consisting of Nb and a + b + c + d = 7.0 to 8. Ola
+ b = 2.0 ~ 3.5, c = 4.0 ~ 6
．． Ola = 0.5~3.5, b-0~2.5, c
= 3.0 to 6.0, d = 0 to 2.0, and e is the number of oxygen atoms satisfying the valences of other elements. ) A solution containing ions of each element selected in the ratio constituting the rare earth iron garnet represented by The present invention relates to a method for producing fine garnet powder, which is characterized in that fine particles of rare earth iron garnet having a particle size of 3,000 to 3,000 are obtained.
本発明における希土類鉄ガーネット微粒子は、ＲＪｅｓ
Ｏ＋□で表されるガーネット又は該ガーネットの希土類
元素の一部が旧で置換されたもの、及び／又はＦｅの一
部がＭで置換されたものである。The rare earth iron garnet fine particles in the present invention are RJes
A garnet represented by O+□ or a garnet in which a part of the rare earth element is replaced with old, and/or a part of Fe is replaced with M.
前記一般式におけるＲは、Ｙ 、Ｌ ａ ＋ Ｃｅ ＋
Ｐ ｒ ＋ Ｎ ｄ ＋ Ｐ ｍＳ ｍ ＋ Ｅ ｕ
、Ｇ ｄ 、Ｔ ｂ ＋ Ｄ ｙ ＋ Ｈｏ 、Ｅ
ｒ ＋ Ｔｒａ ＋ Ｙ ｂ及びＬｕからなる群より選
ばれる一種以上の希土類元素を示す。R in the general formula is Y, L a + Ce +
P r + N d + P mS m + E u
, G d , T b + D y + Ho , E
Indicates one or more rare earth elements selected from the group consisting of r + Tra + Y b and Lu.
また、Ｍは鉄と置換可能な元素であり、ＡＩ、Ｇａ。Further, M is an element that can be substituted for iron, such as AI and Ga.
Ｃｒ ＋ Ｍ ｎ ＋ Ｓ ｃ ＋ Ｉ ｎ ＋ Ｒｕ
＋ Ｒｈ 、Ｃｏ ＋ Ｆ ｅ （Ｉｆ ） ＋ Ｃ
ｕ ＋ Ｎ ｉ ＋ Ｚ ｎ ＋ Ｌ ｉ＋ Ｓ ｉＧ
ｅ、Ｚｒ、Ｔｉ、Ｈｆ、Ｓｎ、Ｐｂ、Ｍｏ、 Ｖ及びＮ
ｂからなる群より遺ばれる一種以上の元素を示す。Ｍの
元素の中、３価元素のＡＩ、Ｇａ、Ｃｒ、Ｍｎ、Ｓｃ、
Ｉｎ、Ｒｕ、Ｒｈ及びＣＯは単独で、２価元素のＣｏ
＋ Ｆ ｅ 、Ｃｕ ＋ Ｎ ｉ及びＺｎ、又は１価
元素のＬｉは、４価元素のＳｉ、Ｇｅ、Ｚｒ、Ｔｉ、Ｈ
ｆ、Ｓｎ、Ｐｂ及びＭｏ、又は５価元素の■及びＮｂと
の組み合わせで３価と等価な元素として置換されること
が好ましい。Cr + M n + S c + I n + Ru
+ Rh, Co + Fe (If) + C
u + N i + Z n + L i+ S iG
e, Zr, Ti, Hf, Sn, Pb, Mo, V and N
Indicates one or more elements remaining from the group consisting of b. Among the elements of M, trivalent elements AI, Ga, Cr, Mn, Sc,
In, Ru, Rh and CO alone are divalent elements Co
+ Fe, Cu + Ni and Zn, or the monovalent element Li is the tetravalent element Si, Ge, Zr, Ti, H
It is preferable to substitute elements equivalent to trivalent elements in combination with f, Sn, Pb, and Mo, or pentavalent elements (■) and Nb.
前記一般式におけるそれぞれの元素の割合は、ａ ＋
ｂ ＋ ｃ ＋ ｄ ＝ ７．０〜８． Ｏｌａ ＋
ｂ ＝ ２．０〜３゜５ ｃ＋ｄ＝４．０〜６．０
、ａ ＝ ０．５〜３．５、ｂ−〇〜２．５、ｃ ＝
３．０〜６．０．ｄ＝０〜２．０であり、ｅは他の元素
の原子価を満足する酸素の原子数である。The proportion of each element in the general formula is a +
b + c + d = 7.0~8. Ola +
b = 2.0~3゜5 c+d=4.0~6.0
, a = 0.5~3.5, b-〇~2.5, c =
3.0-6.0. d=0 to 2.0, and e is the number of oxygen atoms satisfying the valences of other elements.
本発明において、ガーネットの希土類元素の一部を好ま
しくは０．２５〜２．５のＢｉで置換することにより、
ファラデー回転角を大きくすることができる。また、鉄
の一部を好ましくは０，３〜２．０のＭで置換すること
により、キュリー温度を下げ、飽和磁化を小さくするこ
とができる。In the present invention, by replacing a part of the rare earth element of garnet with preferably 0.25 to 2.5 Bi,
The Faraday rotation angle can be increased. Moreover, by replacing a part of iron with M, preferably 0.3 to 2.0, the Curie temperature can be lowered and the saturation magnetization can be reduced.
また、本発明においては、前記希土類鉄ガーネット微粒
子のＲの一部がさらに、Ｐｂ、Ｃａ、Ｍｇ等の２価元素
で置換されてもよく、その場合に、Ｍの４価又は５価元
素で電荷補償してもよい。Further, in the present invention, a part of R in the rare earth iron garnet fine particles may be further substituted with a divalent element such as Pb, Ca, Mg, etc. In that case, M is substituted with a tetravalent or pentavalent element. Charge compensation may be performed.
本発明における希土類鉄ガーネット微粒子の平均粒子径
は３０〜３０００人、好ましくは１００〜１０００人で
ある。平均粒子径が３０人よりも小さくなると熱攪乱の
ために超常磁性となってしまう。また、３０００人より
も大きくなると光の散乱が起こるので好ましくない。ま
た、粒子形状は光学的に対称であることが好ましく、球
状が望ましいが、多面体状、板状でもよい。The average particle diameter of the rare earth iron garnet fine particles in the present invention is 30 to 3,000 particles, preferably 100 to 1,000 particles. When the average particle size is smaller than 30 particles, it becomes superparamagnetic due to thermal disturbance. Moreover, if the number of people exceeds 3,000, light scattering will occur, which is not preferable. Further, the particle shape is preferably optically symmetrical, preferably spherical, but may be polyhedral or plate-like.
本発明においては、前記一般式で表される希土類鉄ガー
ネットを構成する割合で選ばれた各元素イオンを含む溶
液を、微小の液滴とし、これを加熱することにより希土
類鉄ガーネット微粒子が得られる。In the present invention, rare earth iron garnet fine particles are obtained by forming minute droplets of a solution containing ions of each element selected in proportions constituting the rare earth iron garnet represented by the general formula above, and heating the droplets. .
本発明においては、まず前記一般式で表される希土類鉄
ガーネットを構成する割合で選ばれた各元素イオンを含
む溶液を調製する。In the present invention, first, a solution containing ions of each element selected in proportions constituting the rare earth iron garnet represented by the above general formula is prepared.
前記各元素イオンを含む溶液は、各元素の化合物、例え
ば、硝酸塩、硫酸塩、塩化物、アルコキシド等を溶媒に
溶解して得られる。The solution containing ions of each element is obtained by dissolving compounds of each element, such as nitrates, sulfates, chlorides, alkoxides, etc., in a solvent.
溶媒としては、前記各元素の化合物が溶解するものであ
ればよく、通常、水、アルコール類、エーテル類やそれ
らの混合溶媒が用いられる。The solvent may be any solvent as long as it can dissolve the compounds of the above-mentioned elements, and water, alcohols, ethers, and mixed solvents thereof are usually used.
前記各元素イオンを含む溶液の濃度は、０．１〜１０重
量％が好ましい。The concentration of the solution containing each element ion is preferably 0.1 to 10% by weight.
濃度が高すぎると、生成するガーネット微粒子の粒径が
大きくなり、また濃度が低すぎると微粒子の生産性が悪
くなるので好ましくない。If the concentration is too high, the particle size of the produced garnet fine particles will increase, and if the concentration is too low, the productivity of fine particles will deteriorate, which is not preferable.
次に、前記各元素イオンを含む溶液を、物理的な方法、
例えば超音波発振等により微細な霧状の液滴にする。Next, the solution containing each of the elemental ions is prepared by a physical method,
For example, it is made into fine mist-like droplets by ultrasonic oscillation or the like.
液滴の大きさは、１０μｍ以下が好ましい。大きくなる
と、得られるガーネット粒子が粗大なものとなるので好
ましくない。The size of the droplet is preferably 10 μm or less. If it is too large, the resulting garnet particles will become coarse, which is not preferable.
次いで、この液滴をキャリアーガスとともに直接、プラ
ズマ又は加熱炉に導入し、加熱処理することにより、ガ
ーネット粒子が得られる。Garnet particles are then obtained by directly introducing the droplets together with a carrier gas into a plasma or heating furnace and heat-treating them.
キャリアーガスとしては、酸化物が生じる条件であれば
、特に限定されないが、例えば、空気、酸素等が挙げら
れる。The carrier gas is not particularly limited as long as it is under conditions that produce oxides, and examples thereof include air, oxygen, and the like.
加熱温度は、希土類鉄ガーネットの組成により異なるが
、６００〜９００°Ｃが好ましい温度が低すぎると結晶
化が十分でなく、また温度が高すぎると粒子が大きくな
ったり、焼結が起こるので好ましくない。The heating temperature varies depending on the composition of the rare earth iron garnet, but is preferably 600 to 900°C. If the temperature is too low, crystallization will not be sufficient, and if the temperature is too high, the particles will become large or sintering will occur, so it is preferable. do not have.
本発明によれば、前記各元素イオンを含む溶液を微細な
霧状の液滴とし、これを高温で象、激に焼結することに
より、微細で粒子径の揃った均一組成の希土類鉄ガーネ
ット粒子が得られる。According to the present invention, a solution containing ions of each of the above elements is made into fine atomized droplets, which are heated to a high temperature and intensely sintered to produce rare earth iron garnet with a uniform composition and fine particle size. particles are obtained.
本発明により得られるガーネット微粒子粉末は、光アイ
ソレータ、光サーキュレータ、光スインチ、光導波路、
光メモリ等の用途に用いられる。The garnet fine particles obtained by the present invention can be used for optical isolators, optical circulators, optical spinches, optical waveguides,
Used for applications such as optical memory.
例えば、基板上に、ガーネット微粒子粉末とバインダー
からなる磁性層を設けることにより光磁気記録媒体が得
られる。For example, a magneto-optical recording medium can be obtained by providing a magnetic layer made of fine garnet particles and a binder on a substrate.
バインダーとしては、無機酸化物の非晶質バインダーや
有機バインダーが用いられる。As the binder, an amorphous binder of an inorganic oxide or an organic binder is used.
磁性層の厚みは、０．０５〜２．０μｍ、特に０．２〜
１．０μｍの範囲が記録ビットの安定性の上で好ましい
。The thickness of the magnetic layer is 0.05 to 2.0 μm, particularly 0.2 to 2.0 μm.
A range of 1.0 μm is preferable in terms of stability of recording bits.
磁性層は、希土類鉄ガーネット微粒子及びバインダーを
水又は有機溶媒中に分散又は溶解させ、基板上に塗布し
た後、加熱処理等によりバインダーを硬化させることに
より形成される。この際、希土類鉄ガーネット微粒子に
、バインダーの硬化による応力がかかることにより基板
に対して垂直方向に磁化が揃う。また、磁場を基板に対
して垂直方向にかけることにより、配向処理を行っても
よい。The magnetic layer is formed by dispersing or dissolving rare earth iron garnet fine particles and a binder in water or an organic solvent, applying the solution onto a substrate, and then hardening the binder by heat treatment or the like. At this time, the rare earth iron garnet fine particles are subjected to stress due to hardening of the binder, so that their magnetization is aligned in the direction perpendicular to the substrate. Alternatively, the alignment process may be performed by applying a magnetic field in a direction perpendicular to the substrate.
基板としては、特に制限はなく、単結晶基板、多結晶基
板、ガラス等の非晶質基板、その他複合基板等の無機材
料基板、またはアクリル樹脂、ポリカーボネート樹脂、
ポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂等
の有機材料基板を用いることができる。The substrate is not particularly limited, and may be a single crystal substrate, a polycrystalline substrate, an amorphous substrate such as glass, another inorganic material substrate such as a composite substrate, or acrylic resin, polycarbonate resin,
An organic material substrate such as polyester resin, polyamide resin, polyimide resin, etc. can be used.
また、基板と磁性層の間又は磁性層の上に光反射層を設
けることもできる。光反射層としては、Ｃｕ、Ｃｒ、Ａ
Ｉ、Ａｇ、Ａｕ、ＴｉＮ等が用いられる。この光反射層
は、塗布法、めっき法、蒸着法等により基板上又は磁性
層上に形成される。Furthermore, a light reflecting layer can be provided between the substrate and the magnetic layer or on the magnetic layer. As the light reflecting layer, Cu, Cr, A
I, Ag, Au, TiN, etc. are used. This light-reflecting layer is formed on the substrate or magnetic layer by a coating method, plating method, vapor deposition method, or the like.
（実施例）
以下に実施例および比較例を示し、さらに詳しく本発明
について説明する。(Example) The present invention will be explained in more detail by showing Examples and Comparative Examples below.
実施例１
硝酸インドリウム［Ｙ（ＮＯりｘ・６Ｈ，Ｏ］及び硝酸
鉄［Ｆｅ（ＮＯｘ） ｚ・９ＨｚＯ］をＹ：Ｆｅ＝３：
５のモル比で含有する水溶液（４重量％濃度）を調製し
た。Example 1 Indium nitrate [Y(NOx・6H,O]) and iron nitrate [Fe(NOx)z・9HzO] were mixed into Y:Fe=3:
An aqueous solution (4% concentration by weight) containing a molar ratio of 5 was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（空気、流量
５０ ｄ／５ｉｎ）とともに、８５０℃に加熱された管
状電気炉（内径３０ｍ、長さ６００ｍ）に導き、焼成す
ることにより、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
Fine garnet particles are obtained by making micro droplets of approximately μm size, introducing them into a tubular electric furnace (inner diameter 30 m, length 600 m) heated to 850°C (inner diameter 30 m, length 600 m) together with a carrier gas (air, flow rate 50 d/5 in), and firing them. Ta.
得られたガーネット微粒子は、平均粒子径１０００人で
あり、Ｘ線粉末回折スペクトルおよび組成分析の結果、
Ｙ ３． ｏＦｅｓ、 ｏ Ｏ＋ ｚ
であり、ガーネット単相であった。The obtained garnet fine particles had an average particle size of 1,000 particles, and as a result of X-ray powder diffraction spectrum and composition analysis, Y3. oFes, oO+z, and had a garnet single phase.
実施例２
硝酸ジスプロシウム［口ｙ （ＮＯ＋） ｓ・５Ｈ，Ｏ
］ 、硝酸ビスマス［旧（Ｎ（ｈ） ｘ・５８ｚＯ］及
び硝酸鉄をＤｙ：旧：Ｆｅ＝２：１：５のモル比で含有
する水溶液（５重量％濃度）を調製した。Example 2 Dysprosium nitrate [NO+) s・5H,O
], an aqueous solution (5 weight % concentration) containing bismuth nitrate [former (N(h) x ·58zO]) and iron nitrate in a molar ratio of Dy:former:Fe=2:1:5 was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（空気、流量
５０ ｍｌ！ ／ ｗｉｎ）とともに、９００℃に加熱
された管状電気炉（内径３０■、長さ６００ａｅ）に導
き、焼成することにより、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
Garnet fine particles are made into micro droplets of about μm size and guided into a tubular electric furnace (inner diameter 30 mm, length 600 ae) heated to 900°C with a carrier gas (air, flow rate 50 ml!/win) and fired. I got it.
得られたガーネット微粒子は、平均粒子径１０００人で
あり、Ｘ線粉末回折スペクトルおよび組成分析の結果、
ＤｙＪｉ＋Ｆｅ５０ ＋！
であり、ガーネット単相であった。The obtained garnet fine particles had an average particle diameter of 1000 mm, and as a result of X-ray powder diffraction spectrum and composition analysis, DyJi+Fe50+! It was a single phase of garnet.
実施例３
硝酸ジスプロシウム、硝酸ビスマス及び硝酸鉄をＤｙ：
Ｂｉ：Ｆｅ＝１．５ ： １．５ ： ５のモル比で含
有する水溶液（３重量％濃度）を調製した。Example 3 Dysprosium nitrate, bismuth nitrate and iron nitrate as Dy:
An aqueous solution (3% by weight concentration) containing Bi:Fe in a molar ratio of 1.5:1.5:5 was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（酸素、流量
５０ ｄ／５ｉｎ）とともに、９５０°Ｃに加熱された
管状電気炉（内径３０■、長さ６００ｍ）に導き、焼成
することにより、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
Garnet fine particles are formed into minute droplets of about μm size, guided into a tubular electric furnace (inner diameter 30 mm, length 600 m) heated to 950°C with carrier gas (oxygen, flow rate 50 d/5 in), and fired. I got it.
得られたガーネット微粒子は、平均粒子径８００人であ
り、Ｘ線粉末回折スペクトルおよび組成分析の結果、
ＤＶ＋、ｓＢｉ＋、 ５ＦｅｓＯＩｚであり、ガーネ
ット単相であった。The obtained garnet fine particles had an average particle size of 800 mm, and as a result of X-ray powder diffraction spectrum and composition analysis, they were DV+, sBi+, 5FesOIz, and had a single garnet phase.
実施例４
硝酸ジスプロシウム、硝酸ビスマス、硝酸鉄及び硝酸ア
ルミニウム［Ａｌ（ＮＯ３）３・９Ｈ，Ｏ］ をＤｙ
： Ｂｉ ：Ｆｅ：Ａ１＝１．５ ： １．５ ： ４
．２ ： ０．８のモル比で含有する水溶液（５重量％
濃度）を調製した。Example 4 Dysprosium nitrate, bismuth nitrate, iron nitrate and aluminum nitrate [Al(NO3)3.9H,O]
: Bi : Fe: A1=1.5 : 1.5 : 4
．． 2: Aqueous solution containing at a molar ratio of 0.8 (5% by weight)
concentration) was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（酸素、流量
５０ ｄ／−１ｎ）とともに、８５０℃に加熱された管
状電気炉（内径３０ｍ、長さ６００ｍ）に導き、焼成す
ることにより、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
The garnet fine particles are made into micro droplets of about μm size, introduced into a tubular electric furnace (inner diameter 30 m, length 600 m) heated to 850 °C together with a carrier gas (oxygen, flow rate 50 d/-1 n), and fired. Obtained.
得られたガーネット微粒子は、平均粒子径１０００人で
あり、Ｘ線粉末回折スペクトルおよび組成分析の結果、
ＤｙＩ、５Ｂｉ＋、５Ｆｅ４．ｔＡｌｏ、ｓＯ＋ｚであ
り、ガーネット単相であった。The obtained garnet fine particles had an average particle size of 1,000 particles, and as a result of X-ray powder diffraction spectrum and composition analysis, they contained DyI, 5Bi+, 5Fe4. tAlo, sO+z, and a garnet single phase.
実施例５
硝酸ジスプロシウム、硝酸ビスマス及び硝酸鉄をＤｙ：
Ｂｉ：Ｆｅ＝２ ： １ ： ５のモル比で含有する水
溶液（５重量％濃度）を調製した。Example 5 Dysprosium nitrate, bismuth nitrate and iron nitrate as Dy:
An aqueous solution containing Bi:Fe in a molar ratio of 2:1:5 (5% concentration by weight) was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（酸素）とと
もに、減圧下（５０Ｔｏｒｒ） 、マイクロウェーブプ
ラズマ中（電力３００Ｗ）に導き、焼成することにより
、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
Garnet fine particles were obtained by making micro droplets of about μm size, guiding them together with a carrier gas (oxygen) into microwave plasma (power: 300 W) under reduced pressure (50 Torr), and firing them.
得られたガーネット微粒子は、平均粒子径１０００人で
あり、Ｘ線粉末回折スペクトルおよび組成分析の結果、
ＤｙｚＢｉ＋Ｆｅ、Ｏ、ｚ
であり、ガーネット単相であった。The obtained garnet fine particles had an average particle diameter of 1,000 particles, and the results of X-ray powder diffraction spectrum and composition analysis showed that they were DyzBi+Fe, O, z, and had a single garnet phase.
実施例６
硝酸ガドリニウム［Ｇｄ（ＮＯ３）ｚ・６Ｈ２０］ 、
硝酸ジスプロシウム、硝酸ビスマス、硝酸鉄及び硝酸ア
ルミニウムをＧｄ：Ｄｙ：Ｂｉ ：Ｆｅ：ＡＩ＝０．３
５ ： １．１５ ： １．５ ： ４．２ ： ０．
８のモル比で含有する水溶液（５重量％濃度）を調製し
た。Example 6 Gadolinium nitrate [Gd(NO3)z・6H20],
Dysprosium nitrate, bismuth nitrate, iron nitrate and aluminum nitrate as Gd:Dy:Bi :Fe:AI=0.3
5: 1.15: 1.5: 4.2: 0.
An aqueous solution (5% by weight concentration) containing a molar ratio of 8 was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（酸素、流量
５０ｄ／ａ＋ｉｎ）とともに、９００°Ｃに加熱された
管状電気炉（内径３０ｍｎ、長さ６００ｍａ）に導き、
焼成することにより、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
It is made into micro droplets of about μm size and introduced into a tubular electric furnace (inner diameter 30 mm, length 600 ma) heated to 900 °C together with a carrier gas (oxygen, flow rate 50 d/a+in).
Garnet fine particles were obtained by firing.
得られたガーネット微粒子は、平均粒子径１０００人で
あり、Ｘ線粉末回折スペクトルおよび組成分析の結果、
Ｇｄｏ、 ｚｓＤＶ＋、 ＋ｓＢｉ＋、 ５Ｆｅ４．
ｚＡＩｏ、 ｓｏ ＋ｚであり、ガーネット単相であっ
た。The obtained garnet fine particles had an average particle diameter of 1,000 mm, and as a result of X-ray powder diffraction spectrum and composition analysis, they contained the following: Gdo, zsDV+, +sBi+, 5Fe4.
zAIo, so +z, and it was a garnet single phase.
実施例７
硝酸ジスプロシウム、硝酸ビスマス、硝酸鉄及び硝酸ガ
リウム［Ｇａ （ＮＯ：ｌ） ：＋−９Ｈ２０１をＤｙ
： Ｂｉ ： Ｆｅ ：Ｇａ＝１．５ ： １．５
： ４．２ ： ０．８のモル比で含有する水溶液（５
重量％濃度）を調製した。Example 7 Dysprosium nitrate, bismuth nitrate, iron nitrate and gallium nitrate [Ga (NO:l):+-9H201
: Bi : Fe : Ga=1.5 : 1.5
: 4.2 : Aqueous solution containing in a molar ratio of 0.8 (5
(wt% concentration) was prepared.
この水溶液を超音波振動子（１，７ＭＨｚ）により、３
μｍ程度の微小液滴にし、キャリアーガス（酸素、流量
５０ｄ／ｓ＋ｉｎ）とともに、８００°Ｃに加熱された
管状電気炉（内径３０Ｉｌ！ｌ！ｌ、長さ６００閣）に
導き、焼成することにより、ガーネット微粒子を得た。This aqueous solution was heated using an ultrasonic vibrator (1.7 MHz) for 3
By making micro droplets of about μm size and introducing them together with a carrier gas (oxygen, flow rate 50 d/s+in) into a tubular electric furnace (inner diameter 30 l! l! l, length 600 mm) heated to 800 °C, and firing. , garnet fine particles were obtained.
得られたガーネット微粒子は、平均粒子径１０００人で
あり、Ｘ線粉末回折スペクトルおよび組成分析の結果、
Ｄｙ＋、 ｓＢｉ＋、 ５Ｆｅ４． ｚＧａｏ、 ｓｏ
＋ｚであり、ガーネット単相であった。The obtained garnet fine particles had an average particle size of 1,000 yen, and as a result of X-ray powder diffraction spectrum and composition analysis, they contained Dy+, sBi+, 5Fe4. zGao, so
+z, and was a garnet single phase.
比較例１
酸化ジスプロシウム［ＤｙｚＯｓ］ 、酸化ビスマス［
５ｉｚｏｚ］及び酸化鉄［ＦｅｚＯ５］ をＤｙ：Ｂｉ
：Ｆｅ＝２ ：１：５のモル比でＮａＣ１と混合して１
２００°Ｃで焼成することにより、ガーネット粒子を得
た。Comparative Example 1 Dysprosium oxide [DyzOs], bismuth oxide [
5izoz] and iron oxide [FezO5] as Dy:Bi
:Fe=2: Mixed with NaCl in a molar ratio of 1:5 to 1
Garnet particles were obtained by firing at 200°C.
得られたガーネット粒子は、平均粒子径３μｍと大きい
ものであった。The obtained garnet particles had a large average particle diameter of 3 μm.
（発明の効果）
本発明によれば、微細で粒子径の揃った均一組成の希土
類鉄ガーネット粒子が得られる。また、工程が簡略であ
り、生産性も良好である。(Effects of the Invention) According to the present invention, rare earth iron garnet particles that are fine, uniform in particle size, and have a uniform composition can be obtained. Furthermore, the process is simple and the productivity is good.
本発明により得られるガーネット微粒子粉末は、耐蝕性
に優れ、磁気光学効果が大きく、光透過性にも優れてお
り、光アイソレータ、光サーキュレータ、光スィッチ、
光導波路、光メモリ等の用途に好適に用いられる。The garnet fine particles obtained by the present invention have excellent corrosion resistance, a large magneto-optic effect, and excellent optical transparency, and can be used for optical isolators, optical circulators, optical switches, etc.
Suitable for use in optical waveguides, optical memories, etc.
Claims (1)
ＲはＹ及びランタン系列元素からなる群より選ばれる一
種以上の希土類元素を示し、ＭはＡｌ、Ｇａ、Ｃｒ、Ｍ
ｎ、Ｓｃ、Ｉｎ、Ｒｕ、Ｒｈ、Ｃｏ、Ｆｅ（II）、Ｃｕ
、Ｎｉ、Ｚｎ、Ｌｉ、Ｓｉ、Ｇｅ、Ｚｒ、Ｔｉ、Ｈｆ、
Ｓｎ、Ｐｂ、Ｍｏ、Ｖ及びＮｂからなる群より選ばれる
一種以上の元素を示し、ａ＋ｂ＋ｃ＋ｄ＝７．０〜８．
０、ａ＋ｂ＝２．０〜３．５、ｃ＋ｄ＝４．０〜６．０
、ａ＝０．５〜３．５、ｂ＝０〜２．５、ｃ＝３．０〜
６．０、ｄ＝０〜２．０であり、ｅは他の元素の原子価
を満足する酸素の原子数である。）で表される希土類鉄
ガーネットを構成する割合で選ばれた各元素イオンを含
む溶液を、微小の液滴とし、これを加熱することにより
、前記一般式で表され、かつ平均粒子径が３０〜３００
０Åである希土類鉄ガーネット微粒子を得ることを特徴
とするガーネット微粒子粉末の製造法。General formula R_aBi_bFe_cM_dO_e (however,
R represents one or more rare earth elements selected from the group consisting of Y and lanthanum series elements, and M represents Al, Ga, Cr, M
n, Sc, In, Ru, Rh, Co, Fe(II), Cu
, Ni, Zn, Li, Si, Ge, Zr, Ti, Hf,
Indicates one or more elements selected from the group consisting of Sn, Pb, Mo, V and Nb, and a+b+c+d=7.0 to 8.
0, a+b=2.0-3.5, c+d=4.0-6.0
, a=0.5~3.5, b=0~2.5, c=3.0~
6.0, d=0 to 2.0, and e is the number of oxygen atoms satisfying the valences of other elements. ) A solution containing ions of each element selected in the ratio constituting the rare earth iron garnet represented by ~300
A method for producing fine garnet powder, characterized by obtaining rare earth iron garnet fine particles having a diameter of 0 Å.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18410190A JPH0474722A (en) | 1990-07-13 | 1990-07-13 | Production of garnet fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18410190A JPH0474722A (en) | 1990-07-13 | 1990-07-13 | Production of garnet fine powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0474722A true JPH0474722A (en) | 1992-03-10 |
Family
ID=16147415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18410190A Pending JPH0474722A (en) | 1990-07-13 | 1990-07-13 | Production of garnet fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0474722A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004701A1 (en) * | 1993-08-11 | 1995-02-16 | Sumitomo Chemical Company, Limited | Composite metal oxide powder and process for producing the same |
-
1990
- 1990-07-13 JP JP18410190A patent/JPH0474722A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004701A1 (en) * | 1993-08-11 | 1995-02-16 | Sumitomo Chemical Company, Limited | Composite metal oxide powder and process for producing the same |
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