JPS63233017A - Magnetic powder of barium ferrite and its production - Google Patents
Magnetic powder of barium ferrite and its productionInfo
- Publication number
- JPS63233017A JPS63233017A JP2173887A JP2173887A JPS63233017A JP S63233017 A JPS63233017 A JP S63233017A JP 2173887 A JP2173887 A JP 2173887A JP 2173887 A JP2173887 A JP 2173887A JP S63233017 A JPS63233017 A JP S63233017A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic powder
- barium ferrite
- precipitate
- gram atom
- ferrite magnetic
- 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
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000006247 magnetic powder Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 16
- 230000004907 flux Effects 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 10
- 229910052725 zinc Inorganic materials 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000005415 magnetization Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 150000001553 barium compounds Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- -1 Si and Ca Chemical class 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、六角板状のマグネトプランバイＩ・型バリウ
ムフェライト磁性粉およびそ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 hexagonal plate-shaped magnetoplumbai type I barium ferrite magnetic powder and a method for producing the same.
さらに詳しくは、本発明は高密度記録用の磁気記録媒体
に用いるのに適した、比表面積が２０〜７０ｒｄ／Ｑ、
保磁力が２００〜１５０００ｅであり、飽和磁化が従来
の水熱合成法により得られるものと比較して飛躍的に向
上したマグネトブランバイト型バリウムフェライト磁性
粉およびその製造方法に間するものである。More specifically, the present invention is suitable for use in magnetic recording media for high-density recording, and has a specific surface area of 20 to 70rd/Q.
The present invention is related to a magnetoblanbite barium ferrite magnetic powder having a coercive force of 200 to 15,000 e and a saturation magnetization dramatically improved compared to that obtained by conventional hydrothermal synthesis, and a method for producing the same.
近年、磁気記録の高密度化の要求に伴い、バリウムフェ
ライト磁性粉を磁気記録媒体として用いる垂直磁気記録
方式の開発が進められている。In recent years, with the demand for higher density magnetic recording, development of perpendicular magnetic recording systems using barium ferrite magnetic powder as a magnetic recording medium has been progressing.
垂直磁気記録方式に用いられるバリウムフェライト磁性
粉としては、保磁力が適当な値（２００〜１５０００ｅ
）で、飽和磁化ができるだけ高く、しかも各粒子の磁気
特性が均一で、また粒子が小さく均一で、粒子の凝集、
焼結などがなく、分散性のよいものが望まれている。The barium ferrite magnetic powder used in the perpendicular magnetic recording system has a coercive force of an appropriate value (200 to 15,000e).
), the saturation magnetization is as high as possible, the magnetic properties of each particle are uniform, the particles are small and uniform, and particle aggregation,
A material that does not require sintering and has good dispersibility is desired.
特に、他の記録媒体用磁性粉と比べてバリウムフェライ
ト磁性粉は飽和磁化が低いため、できるだけ高い飽和磁
化をもつ微細粒子が望まれている。In particular, since barium ferrite magnetic powder has a lower saturation magnetization than other magnetic powders for recording media, fine particles with as high a saturation magnetization as possible are desired.
（従来の技術）
従来、バリウムフェライト磁性粉の製造方法としては、
例えば共沈法、ガラス結晶化法、水熱合成法等種々の方
法が知られており、ガラス結晶化法については特公昭６
０−１５５７４号公報、水熱合成法については、例えば
特開昭５９−１７５７０７号公報、特公昭５ｏ−１２ｑ
７３号公報、特公昭６０−１５５７６号公報、特開昭６
０−１３７００２号公報等で提案されている。(Conventional technology) Conventionally, the method for producing barium ferrite magnetic powder is as follows:
For example, various methods are known, such as coprecipitation, glass crystallization, and hydrothermal synthesis.
Regarding the hydrothermal synthesis method, see Japanese Patent Application Laid-Open No. 59-175707, Japanese Patent Publication No. 5o-12q.
Publication No. 73, Japanese Patent Publication No. 60-15576, Japanese Patent Publication No. 60-15576
This method has been proposed in JP 0-137002 and the like.
前記従来の方法で製造されるバリウムフェライト磁性粉
はいずれも次式Ｂａ Ｏ−ｎ Ｆｅ２Ｏ３で示されるＦ
ｅ原子の一部をＣｏ、Ｔｉ、Ｎｉ、Ｍｎ、Ｃｕ、Ｚｎ。All of the barium ferrite magnetic powders produced by the conventional method have F represented by the following formula Ba O-n Fe2O3.
Some of the e atoms are Co, Ti, Ni, Mn, Cu, and Zn.
Ｉｎ、Ｇｅ、Ｎｂ、Ｚｒ等の金属元素単独、またはそれ
らの組合わせを用いて、かつ置換原子の価数の合計が置
換されるＦｅ原子のそれと等しくなるように置換したも
のである。Metal elements such as In, Ge, Nb, and Zr are used alone or in combination, and the total valence of the substituted atoms is equal to that of the substituted Fe atom.
また特開昭６１−２３６１９４号公報には、ＦｅＪＩＸ
子をＡｆＪ、Ｃｄ 、Ｚｎから選ばれる一種以上の原子
で置換することにより、飽和磁化を向上させることが開
示されている。Also, in Japanese Patent Application Laid-Open No. 61-236194, FeJIX
It has been disclosed that the saturation magnetization can be improved by replacing the atoms with one or more atoms selected from AfJ, Cd, and Zn.
（発明が解決しようとする問題点）
水熱合成法により得られるバリウムフェライト磁性粉は
、一般に粒子の凝集が少なく、比較的分散性は良く、微
粒子であるが、飽和磁化が５５ｃｍＵ／ａ程度かそれよ
りも低いものしか得られなかった。これは、バリウムフ
ェライト磁性粉の表面積が２０ ｄ／Ｑ以上、特に超微
粒子の磁性粉では５０ｒｒ？／Ｑ以上になると粒子表面
の非磁性層の部分が無視できなくなるため、および保磁
力調整のために添加する各種金属元素のためと考えられ
ている。(Problems to be Solved by the Invention) Barium ferrite magnetic powder obtained by hydrothermal synthesis generally has little particle aggregation, relatively good dispersibility, and fine particles, but the saturation magnetization is about 55 cmU/a. I could only get something lower than that. This means that the surface area of barium ferrite magnetic powder is 20 d/Q or more, especially for ultrafine particle magnetic powder of 50rr? This is thought to be due to the fact that the non-magnetic layer on the grain surface cannot be ignored when the value exceeds /Q, and the various metal elements added to adjust the coercive force.
また特開昭６１−２３６１０４号公報に記載されている
バリウムフェライト磁性粉はガラス結晶化法により得ら
れたものであるが、該公報の明細書には、Ｚｎ、＠独の
場合の効果についての具体的な記載がなく、またバリウ
ムフェライト磁性粉の結晶構造、粒径、比表面積、保磁
力および保磁力コントロールについても同等記載がない
。Furthermore, the barium ferrite magnetic powder described in JP-A No. 61-236104 was obtained by a glass crystallization method, but the specification of the publication does not mention the effect in the case of Zn, @Germany. There is no specific description, and there is no equivalent description regarding the crystal structure, particle size, specific surface area, coercive force, and coercive force control of the barium ferrite magnetic powder.
（発明の目的）
本発明の目的は、水熱合成法における前記難点を解決し
、高い飽和磁化を有し、かつ微粒子で比表面積が２０〜
７０ｒｒｒ１０、保磁力が２００〜１５０００ｅであり
、高密度記録用の磁気記録媒体に用いるのに適したバリ
ウムフェライト磁性粉およびその製造方法を提供するこ
とにある。(Objective of the invention) The object of the present invention is to solve the above-mentioned difficulties in the hydrothermal synthesis method, to have high saturation magnetization, and to have fine particles with a specific surface area of 20 to 20.
70rrr10, coercive force of 200 to 15000e, and is suitable for use in magnetic recording media for high-density recording, and a method for producing the barium ferrite magnetic powder.
（問題点を解決するための手段）
本発明者等は、鋭意検討の結果、バリウムフェライト磁
性粉のＦｅ原子の一部をｚｎ単独で置換した場合は、は
とんど効果が認められないが、前述の一最式に示したよ
うに、Ｚｎと特定の置換元素の組合わせで置換すること
により、飽和磁化が著しく向上することを見出した。(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that when some of the Fe atoms in barium ferrite magnetic powder are replaced with zn alone, no effect is observed in most cases. As shown in the above-mentioned equation, it has been found that the saturation magnetization can be significantly improved by substituting Zn with a combination of a specific substituting element.
すなわち、本発明は、−服代
％式％））
（ただし、ＭｌはＮｉ、Ｃｏ、Ｃｕ、ＭｇおよびＭｎか
らなる群から選ばれた一種または二種以上の金属を示し
、Ｍ２はＳｉ、Ｔａ、Ｓｂ、Ｎｂ、Ｚｒ、およびＴｉか
らなる群から選ばれた一種または二種以上の金属を示し
、ｎ＝０．８〜１．０、ｘ ＝ ０．５− １．５、ｙ
＝０．Ｏ１〜ｘ、ｚ＝０．１〜１．５の数値である。）
で表される六角板状マグネトブランバイト型バリウムフ
ェライト磁性粉およびその製造方法に関する。That is, in the present invention, - clothing cost % formula %)) (However, Ml represents one or more metals selected from the group consisting of Ni, Co, Cu, Mg and Mn, and M2 represents Si, Ta. , represents one or more metals selected from the group consisting of Sb, Nb, Zr, and Ti, n = 0.8 to 1.0, x = 0.5-1.5, y
=0. O1~x, z=values of 0.1~1.5. )
The present invention relates to a hexagonal plate-shaped magnetoblanbite type barium ferrite magnetic powder represented by and a method for producing the same.
本発明においては、出発原料として、バリウム１グラム
原子に対して鉄１〜１２グラム原子、鉄１２−ｘ−ｙ−
ｚグラム原子に対して、ＭｌがＸグラム原子、Ｍ２がＸ
グラム原子および亜鉛がＺグラム原子の割合のそれぞれ
の元素の化合物を用い、該出発原料を水に溶解し、これ
に混合後の溶液中の水酸化アルカリ濃度が３モル／１以
上となるように水酸化アルカリを加えて沈澱物を生成さ
せ、該沈澱物を倉むスラリを１３０〜３００℃で水熱処
理した後、生成した沈澱物に融剤を混合し、混合物乞７
００〜９５０℃で焼成し、得られた焼成物を洗浄するこ
とにより、前記六角板状マグネトブランバイト型バリウ
ムフェライト磁性粉が得られる。In the present invention, as a starting material, 1 to 12 gram atoms of iron per 1 gram atom of barium, iron 12-x-y-
For z gram atom, Ml is X gram atom, M2 is
Using a compound of each element in a ratio of gram atom and zinc to Z gram atom, the starting material is dissolved in water, and the alkali hydroxide concentration in the solution after mixing is 3 mol/1 or more. After adding an alkali hydroxide to form a precipitate and hydrothermally treating the slurry containing the precipitate at 130 to 300°C, a fluxing agent is mixed with the precipitate produced, and the mixture
By firing at 00 to 950°C and washing the fired product, the hexagonal plate-shaped magnetoblanbite type barium ferrite magnetic powder is obtained.
本発明においては、まず出発原料であるバリウム、鉄、
Ｍｌ 、Ｍ２および亜鉛のそれぞれの化合物を水に溶解
し、これに水酸化アルカリを加えて沈澱物を生成させる
。In the present invention, the starting materials barium, iron,
The respective compounds of M1, M2 and zinc are dissolved in water and alkali hydroxide is added thereto to form a precipitate.
バリウム化合物としては、硝酸バリウム、塩化バリウム
、水酸化バリウム等が用いられる。バリウムの使用量は
、バリウム濃度が０．０３〜０．５０モル／Ｉｌｌの範
囲になるようにするのが六角板状の形状のよい粒子を得
るうえで望ましい。As the barium compound, barium nitrate, barium chloride, barium hydroxide, etc. are used. The amount of barium used is preferably such that the barium concentration is in the range of 0.03 to 0.50 mol/Ill in order to obtain particles with a good hexagonal plate shape.
鉄化合物としては、硝酸第二鉄、塩化第二鉄等が用いら
れる。鉄の使用量はバリウム１グラム原子に対して１〜
１２グラム原子である。鉄の量が少なすぎると、マグネ
トブランバイト型バリウムフェライトの生成量が少なく
、形状も六角板状でなくなる。また鉄の量が多すぎると
ベマタイトが副生したり、またバリウムフェライトの粒
子が大きくなり、磁気特性も劣ってくる。As the iron compound, ferric nitrate, ferric chloride, etc. are used. The amount of iron used is 1 to 1 gram atom of barium.
It is a 12 gram atom. If the amount of iron is too small, the amount of magnetobrambite barium ferrite produced will be small and the shape will not be hexagonal plate-like. Furthermore, if the amount of iron is too large, bematite may be produced as a by-product, and barium ferrite particles may become large, resulting in poor magnetic properties.
Ｍｌの化合物としては、Ｎｉ、Ｃｏ、Ｃｕ、Ｍ（ｌおよ
びＭｎからなる群から選ばれた一種または二種以上の金
属の塩化物、硝酸塩等が用いられる０Ｍｌの使用量は、
鉄１°２−ｘ−ｙ−ｚグラム原子に対してＸグラム原子
（ｘ ＝ ０．５〜１．５）になるようにするのが好適
であり、Ｘの値によって磁気特性、主に保磁力を制御で
きる。As the compound of Ml, chlorides, nitrates, etc. of one or more metals selected from the group consisting of Ni, Co, Cu, M(l and Mn) are used.The amount of 0Ml used is:
It is preferable to set X gram atoms (x = 0.5 to 1.5) for 1°2-xy-z gram atoms of iron, and the value of X determines the magnetic properties, mainly the retention. Can control magnetic force.
Ｍ２の化合物としては、Ｓｉ、”ｒ’ａ、Ｓｂ、Ｎｂ、
Ｚｒ。As the compound of M2, Si, "r'a, Sb, Nb,
Zr.
およびＴｉからなる群から選ばれた一種または二種以上
の金属の塩化物、硝酸塩等が用いられる。A chloride, nitrate, etc. of one or more metals selected from the group consisting of Ti and Ti are used.
Ｍ２の使用量は、鉄１２−ｘ−ｙ−ｚグラム原子に対し
てＸグラム原子（ｙ＝ｏ、０１〜Ｘ）になるようにする
のが好適である。Ｍ２の使用量がＭｌの使用量より多く
なると（ｙ＞ｘの場合〉、飽和磁化の向上効果が得られ
ないので、好ましくない。The amount of M2 used is preferably X gram atoms (y=o, 01 to X) for every 12-xyz gram atom of iron. If the amount of M2 used is greater than the amount of Ml used (if y>x), the effect of improving saturation magnetization cannot be obtained, which is not preferable.
亜鉛化合物としては、塩化亜鉛、硝酸亜鉛等が用いられ
る。亜鉛の使用量は鉄１２−ｘ−ｙ−ｚグラム原子に対
してＺグラム原子（ｚ＝ｏ、０１〜１゜５、好ましくは
０．１〜１．０）になるようにするのが好適である。亜
鉛と前記の置換元素の特定の組合わせで、Ｆｅ原子の一
部を置換することにより、得られるバリウムフエライＩ
・磁性粉の飽和磁化が飛躍的に向上する。As the zinc compound, zinc chloride, zinc nitrate, etc. are used. The amount of zinc used is preferably Z gram atoms (z=o, 01 to 1°5, preferably 0.1 to 1.0) per 12-xyz gram atoms of iron. It is. Barium ferrite I obtained by substituting a part of Fe atoms with a specific combination of zinc and the above-mentioned substituting elements
・The saturation magnetization of magnetic powder is dramatically improved.
水酸化アルカリとしては、水酸化ナトリウム、水酸化カ
リウム等が用いられる。水酸化アルカリ、の使用量は水
酸化アルカリを混合した後の溶液中の水酸化アルカリ濃
度が３モル／ｐ以上となる量が必要であり、４〜８モル
／ｌの範囲が好ましい。As the alkali hydroxide, sodium hydroxide, potassium hydroxide, etc. are used. The amount of alkali hydroxide used must be such that the alkali hydroxide concentration in the solution after mixing the alkali hydroxide is 3 mol/p or more, and is preferably in the range of 4 to 8 mol/l.
水酸化アルカリの量が少なずぎると粒子が大きくなった
り、粒度分布が広くなったり、またへマタイトが生成す
る。また水酸化アルカリを過度に多くするのは経済的で
ない。If the amount of alkali hydroxide is too small, the particles become large, the particle size distribution becomes wide, and hematite is generated. Further, it is not economical to increase the amount of alkali hydroxide excessively.
前記出発原料の水溶液に水酸化アルカリを混合する方法
については、特に制限はないが、例えば出発原料の水溶
液に、直接水酸化アルカリを添加するか、あるいは水酸
化アルカリの水溶液を添加する方法がある。あるいはバ
リウム化合物を水酸化アルカリの水溶液側に加えて、こ
れと鉄を含む水溶液を混合する方法がある。There is no particular restriction on the method of mixing the alkali hydroxide into the aqueous solution of the starting material, but for example, there are methods of directly adding the alkali hydroxide or adding an aqueous solution of the alkali hydroxide to the aqueous solution of the starting material. . Alternatively, there is a method of adding a barium compound to the aqueous solution of alkali hydroxide and mixing this with an aqueous solution containing iron.
さらに、予め出発原料の水溶液あるいは水酸化アルカリ
の水溶液にＳｉ 、Ｃａなどの水に可溶性の化合物、例
えばケイ酸、ケイ酸ナトリウム、硝酸カルシウム、塩化
カルシウム等を若干添加することができる。これらの添
加物は粒子形状を制御するうえで好ましい。Furthermore, a small amount of water-soluble compounds such as Si and Ca, such as silicic acid, sodium silicate, calcium nitrate, and calcium chloride, can be added in advance to the aqueous solution of the starting material or the aqueous solution of alkali hydroxide. These additives are preferred for controlling particle shape.
次に、沈澱物を含むスラリを水熱処理することにより、
バリウムフェライトの微細な結晶が生成、沈澱する。水
熱処理の温度は１３０〜３００℃、好ましくは１４０〜
２８０℃である。温度が低すぎると結晶の生成が充分で
なく、また温度が高すぎると最終的に得られるバリウム
フェライト粉末の粒径が大きくなるので好ましくない、
水熱処理時間は普通、０．５〜２０時間程度であり、水
熱処理には通常、オートクレーブが採用される。Next, by hydrothermally treating the slurry containing the precipitate,
Fine crystals of barium ferrite are formed and precipitated. The temperature of hydrothermal treatment is 130-300℃, preferably 140-300℃
The temperature is 280°C. If the temperature is too low, crystal formation will not be sufficient, and if the temperature is too high, the particle size of the final barium ferrite powder will become large, which is undesirable.
The hydrothermal treatment time is usually about 0.5 to 20 hours, and an autoclave is usually employed for the hydrothermal treatment.
次いで、水熱処理により生成した微細な結晶の沈澱物を
水洗して、遊離のアルカリ分を除去した後、得られた沈
澱物に融剤を混合する。融剤としては、塩化ナトリウム
、塩化カリウム、塩化バリウム、塩化ストロンチウムお
よびフッ化ナトリウムのうち少なくとも一種が用いられ
る。融剤の使用量は沈澱物（乾燥物基準）に対して、１
０〜１８０重１％、好ましくは３０〜１２０重量％が適
当である。融剤の量が少なすぎると粒子の焼結が起り、
また多すぎても多くしたことによる利点はなく、経済的
でない、沈澱物と融剤の混合方法は特に制限はなく、例
えば沈澱物のスラリに融剤を加えて湿式混合した後゛、
スラリを乾燥してもよく、あるいは沈澱物を乾燥した後
、融剤を加えて乾式混合してもよい。Next, the fine crystal precipitate produced by the hydrothermal treatment is washed with water to remove free alkali, and then a flux is mixed with the obtained precipitate. As the flux, at least one of sodium chloride, potassium chloride, barium chloride, strontium chloride, and sodium fluoride is used. The amount of flux used is 1 for the precipitate (dry basis).
A suitable amount is 0 to 180% by weight, preferably 30 to 120% by weight. If the amount of flux is too small, sintering of the particles will occur,
Also, even if the amount is too large, there is no advantage and it is not economical. There are no particular restrictions on the method of mixing the precipitate and the flux. For example, after adding the flux to the slurry of the precipitate and wet-mixing,
The slurry may be dried, or the precipitate may be dried and then a flux may be added and dry mixed.
次いで、得られた混合物を焼成することにより、バリウ
ムフェライトの結晶化が完全に行われる。Next, the resulting mixture is fired to completely crystallize the barium ferrite.
焼成温度は７００〜９５０℃、好ましくは８００〜９３
０℃である。温度が低すぎると結晶化が進まず、飽和磁
化が低くなる。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、焼成時間は１０
分〜３０時間程度が適当である。焼成雰囲気は特に制限
されないが、一般に空気雰囲気が便利である。Firing temperature is 700-950℃, preferably 800-93℃
It is 0°C. If the temperature is too low, crystallization will not proceed and the saturation magnetization will become low. Also, if the temperature is too high, the particles will become large or sintering will occur, which is undesirable.
Approximately 30 minutes to 30 hours is appropriate. The firing atmosphere is not particularly limited, but an air atmosphere is generally convenient.
得られた焼成物を洗浄後、濾過、乾燥することにより、
バリウムフェライト磁性粉が得られる。By washing, filtering and drying the obtained baked product,
Barium ferrite magnetic powder is obtained.
洗浄は焼成物中の融剤、過剰のバリウムなどの不純物を
十分に除去できればよとのような方法で行ってもよい、
洗浄液としては水や硝酸、塩酸などの無機酸、酢酸、プ
ロピオン酸などの有機酸などを用いることができる。Cleaning may be carried out by any method as long as impurities such as flux and excess barium in the fired product can be sufficiently removed.
As the cleaning liquid, water, inorganic acids such as nitric acid and hydrochloric acid, and organic acids such as acetic acid and propionic acid can be used.
（実施例）
実施例１
脱イオン水１３００ｍＮに、硝酸第二鉄［Ｆｅ（ＮＯ３
）３・９Ｈ２０］ １２８７．６ｇ、硝酸コバルト［Ｃ
０（Ｎｏ３）２−６Ｈ２０コロ４．７ｇ、四塩化チタン
（Ｔ＋ ＣＪ ４） ｌ ９．’７ ｇおよび硝酸亜鉛
［Ｚｎ（ＮＯ３）２ ・６Ｈ２０コ３５．２ｇを溶解し
、別に脱イオン水１３００ｍＪに、水酸化バリウム［Ｂ
ａ（ＯＨ）２・８Ｈ２０］ １４０．２ｇ、カセイソー
ダ（ＮａＯＨ）１４８０ｇを溶解し、両溶液を混合して
沈澱物を生成させた。(Example) Example 1 Ferric nitrate [Fe(NO3
)3.9H20] 1287.6g, cobalt nitrate [C
0 (No 3) 2-6H20 roller 4.7 g, titanium tetrachloride (T+ CJ 4) l 9. '7 g and 35.2 g of zinc nitrate [Zn(NO3)2 6H20] were dissolved, and barium hydroxide [B
a(OH)2.8H20] and 1480 g of caustic soda (NaOH) were dissolved, and both solutions were mixed to form a precipitate.
得られた沈澱物を含むスラリをオートクレーブに入れ、
１４５℃で８時間水熱処理を行った０次いで得られた沈
澱物を十分に水洗した後、濾過、乾燥し、これに融剤と
してＮａ ＣｊとＢａ ＣＪＩ ２・２Ｈ，、Ｏめ重量
比が１：１の混合物を沈澱物に対して１００重量％加え
て混合した。この混合物を空気雰囲気下で８６０℃で２
時間焼成した。得られた焼成物を水で十分水洗した後、
濾過、乾燥してバリウムフェライト磁性粉を得た。The resulting slurry containing the precipitate was placed in an autoclave;
After hydrothermal treatment at 145°C for 8 hours, the resulting precipitate was thoroughly washed with water, filtered and dried, and mixed with Na CJ and Ba CJI 2.2H, 2H, O in a weight ratio of 1 as a fluxing agent. :100% by weight of the mixture was added to the precipitate and mixed. This mixture was heated at 860°C for 2 hours under air atmosphere.
Baked for an hour. After washing the obtained fired product thoroughly with water,
It was filtered and dried to obtain barium ferrite magnetic powder.
得られたバリウムフェライト磁性粉は、Ｘ線粉末回折ス
ペクトルおよび組成分析の結果、Ｂａ○’ ”９８（Ｆ
ｅ１０．５Ｃ００，７５” ０．３５Ｚｎ０．４０ｏ＋
７．６）であり、マグネトブランバイト型であった。As a result of X-ray powder diffraction spectrum and composition analysis, the obtained barium ferrite magnetic powder has a Ba○' 98 (F
e10.5C00,75” 0.35Zn0.40o+
7.6), and was of the magnetobrambite type.
またこのバリウムフェライト磁性粉について透過型電子
顕ｒ１ｆｉ（Ｔ Ｆ、 Ｍ ）で粒子形状（粒子径、粒
子厚、分布）を測定した結果（粒子１００個の平均値）
および振動試料式磁力計で磁気特性を測定した結果を第
１表に示す。In addition, the particle shape (particle diameter, particle thickness, distribution) of this barium ferrite magnetic powder was measured using a transmission electron microscope r1fi (TF, M) (average value of 100 particles).
Table 1 shows the results of measuring the magnetic properties using a vibrating sample magnetometer.
実施例２
脱イオン水１３００ｒｔ＋ｊ）に、硝酸第二鉄１２７０
．２ｇ、硝酸コバルト６９．０ｇ、四塩化チタン１６．
９ｇ、硝酸亜鉛７０．６ｇを溶解し、別に脱イオン水１
３００ｍｊ！に、水酸化バリウム１４０．２ｇおよびカ
セイソーダ１４８０ｇを溶解し、両溶液を混合して沈澱
物を生成させた。Example 2 Ferric nitrate 1270 ml of deionized water 1300 rt+j)
．． 2g, cobalt nitrate 69.0g, titanium tetrachloride 16.
Dissolve 9g of zinc nitrate and 70.6g of zinc nitrate, and separately add 11g of deionized water.
300mj! 140.2 g of barium hydroxide and 1480 g of caustic soda were dissolved in the solution, and both solutions were mixed to form a precipitate.
得られた沈澱物を含むスラリをオートクレーブに入れ、
１７０℃で８時間水熱処理を行った１次いで得られた沈
澱物を十分に水洗した後、濾過、乾燥し、これに融剤と
してＮａ ＣｆＪとＢａ ｃ Ｊ ２・２Ｆ１２０との
重量比で１：１の混合物を沈澱物に対して１００重量％
加えて混合した。この混合を空気雰囲気下で８９０℃で
２時間焼成した。得られた焼成物を水で十分水洗した後
、濾過、乾燥してバリウムフェライト磁性粉を得た。The resulting slurry containing the precipitate was placed in an autoclave;
Hydrothermal treatment was carried out at 170° C. for 8 hours.The resulting precipitate was thoroughly washed with water, filtered and dried, and a flux of Na CfJ and Bac J 2.2F120 was added to this in a weight ratio of 1:1. 1 mixture at 100% by weight based on the precipitate
Add and mix. This mixture was baked at 890° C. for 2 hours under an air atmosphere. The obtained fired product was thoroughly washed with water, filtered and dried to obtain barium ferrite magnetic powder.
得られたバリウムフェライト磁性粉は、Ｘ線粉末回折ス
ペクトルおよび組成分析の結果、ＢａＯ゛０°９７（Ｆ
”１０．１０Ｃ００，８０ＴｉＯ，３０Ｚｌｏ、８０°
１７．３５ ）であり、マグネトプランバイ１〜型であ
った。As a result of X-ray powder diffraction spectrum and composition analysis, the obtained barium ferrite magnetic powder has a BaO゛0°97 (F
”10.10C00, 80TiO, 30Zlo, 80°
17.35), and was a magnetopranby type 1~.
またこのバリウムフェライト磁性粉について透過型電子
顕微鏡（ＴＥＭ）で粒子形状（粒子径２粒子厚、分布）
を測定した結果（粒子１００個の平均値）および振動試
料式磁力計で磁気特性を測定した結果を第１表に示す。In addition, the particle shape (particle size 2 particle thickness, distribution) of this barium ferrite magnetic powder was measured using a transmission electron microscope (TEM).
Table 1 shows the results of measuring (average value of 100 particles) and the results of measuring magnetic properties using a vibrating sample magnetometer.
比較例１
脱イオン水１３００ｒｒ＋Ｊに、硝酸第二鉄１２６３．
１ｇ、硝酸コバルト６４．７ｇおよび四塩化チタン４２
．２ｇを溶解し、別に脱イオン水１３００ｍＱに、水酸
化バリウＪｘ１４０．２ｇおよびカセイソーダ１４８０
ｇを溶解し、両溶液を混合して沈澱物を生成させた。Comparative Example 1 Add 1263 ml of ferric nitrate to 1300 rr+J of deionized water.
1g, cobalt nitrate 64.7g and titanium tetrachloride 42
．． Separately in 1300 mQ of deionized water, dissolve 140.2 g of barium hydroxide Jx and 1480 caustic soda.
g was dissolved and both solutions were mixed to form a precipitate.
得られた沈澱物を含むスラリをオートクレーブに入れ、
１９０℃で６時間水熱処理を行った０次いで得られた沈
澱物を十分に水洗した後、濾過、乾燥し、これに融剤と
してＮａ ＣｆＪとＢａ ＣＤ ２・２Ｈ２０との重量
比で１＝１の混合物を沈澱物に対して１００重量％加え
て混合した。この混合を空気雰囲気下で８６０℃で２時
間焼成した。得られた焼成物を水で十分水洗した後、濾
過、乾燥してバリウムフェライト磁性粉を得た。The resulting slurry containing the precipitate was placed in an autoclave;
After hydrothermal treatment at 190°C for 6 hours, the resulting precipitate was thoroughly washed with water, filtered and dried, and mixed with NaCfJ and BaCD2.2H20 as a flux in a weight ratio of 1=1. 100% by weight of the mixture was added to the precipitate and mixed. This mixture was baked at 860° C. for 2 hours under an air atmosphere. The obtained fired product was thoroughly washed with water, filtered and dried to obtain barium ferrite magnetic powder.
得られたバリウムフェライト磁性粉は、Ｘ線粉末回折ス
ペクトルおよび組成分析の結果、Ｂａ０・０．９８ （
Ｆｅ １ｏ、５Ｃｏ Ｏ，−ｔ５Ｔ Ｉ ｏ、７５０１
８．ｏ ）であり、マグネトブランバイト型であった。As a result of X-ray powder diffraction spectrum and composition analysis, the obtained barium ferrite magnetic powder has a Ba0.0.98 (
Fe 1o, 5CoO, -t5T Io, 7501
8. o) and was of the magnetobrambite type.
またこのバリウムフェライト磁性粉について透過型電子
顕微鏡（ＴＥＭ）で粒子形状（粒子径、粒子厚、分布）
を測定した結果（粒子１００個の平均値）および振動試
料式磁力計で磁気特性を測定した結果と第１表に示す。The barium ferrite magnetic powder was also examined using a transmission electron microscope (TEM) to determine its particle shape (particle diameter, particle thickness, and distribution).
Table 1 shows the results of measuring (average value of 100 particles) and the results of measuring magnetic properties using a vibrating sample magnetometer.
比較例２
脱イオン水１３００ｍＮに、硝酸第二鉄１２６３．１ｇ
、四塩化チタン４２２ｇ、ｆＡ酸亜鉛７０．０ｇを溶解
し、別に脱イオン水１３００ｍｊｌに、水酸化バリウｊ
、１４０．２ ｇおよびカセイソーダ１４８０ｇを溶解
し、両溶液を混合して沈澱物を生成させた。Comparative Example 2 1263.1 g of ferric nitrate in 1300 mN of deionized water
, dissolve 422 g of titanium tetrachloride and 70.0 g of zinc fA acid, and separately add barium hydroxide to 1300 mjl of deionized water.
, 140.2 g and 1480 g of caustic soda were dissolved, and both solutions were mixed to form a precipitate.
得られた沈澱物を含むスラリをオートクレーブに入れ、
１９０℃で６時間水熱処理を行った０次いで得られた沈
澱物を十分に水洗した後、濾過、乾燥し、これに融剤と
してＮａ ＣｊｌとＢａ Ｃｊ ２・２Ｈ２０との重量
比で１＝１の混合物を沈澱物に対して１００重量％加え
て混合した。この混合を空気雰囲気下で８６０℃で２時
間焼成した。得られた焼成物を水で十分水洗した後、濾
過、乾燥してバリウムフェライト磁性粉を得た。The resulting slurry containing the precipitate was placed in an autoclave;
After hydrothermal treatment at 190°C for 6 hours, the resulting precipitate was thoroughly washed with water, filtered and dried, and added as a flux with Na Cjl and Ba Cj 2.2H20 in a weight ratio of 1=1. 100% by weight of the mixture was added to the precipitate and mixed. This mixture was baked at 860° C. for 2 hours under an air atmosphere. The obtained fired product was thoroughly washed with water, filtered and dried to obtain barium ferrite magnetic powder.
得られたバリウムフエライＩ・磁性粉は、Ｘ線粉末回折
スペクトルおよび組成分析の結果、ｓａ ｏ ・０．９
ｓ （ＦＣｌｏ、５Ｚｎ ０．７ｓＴＩ Ｏ，ｒｂｏ
１８．ｏ）であり、マグオ司ヘブランバ・イ１−型であ
った。As a result of X-ray powder diffraction spectrum and composition analysis, the obtained barium ferrite I magnetic powder had sa o 0.9.
s (FClo, 5Zn 0.7sTI O, rbo
18. o), and it was a type 1 of Maguoshi Heburamba I.
またこのバリウムフェライト磁性粉について透過型電子
顕微鏡（ＴＥＭ）で粒子形状（粒子径。In addition, the particle shape (particle diameter) of this barium ferrite magnetic powder was determined using a transmission electron microscope (TEM).
粒子厚、分布）を測定した結果（粒子１００個の平均値
）および振動試料式磁力計で磁気特性を測定した結果を
第１表に示す。Table 1 shows the results of measuring the particle thickness and distribution (average value of 100 particles) and the results of measuring the magnetic properties using a vibrating sample magnetometer.
第１表
（発明の効果）
本発明によれば、一般式
％式％））
（ただし、ＭｌはＮｉ、Ｃｏ、Ｃｕ、ＭｇおよびＭｎか
らなる群からＡばれる一種または二種以上の金属含水し
、Ｍ２はＳｉ、Ｔａ、Ｓｂ、Ｎｂ、ＺｒおよびＴｉから
なる群から選ばれる一種または二種以上の金属を示し、
ｎ＝０．８〜１．０、ｘ ＝ ０．５〜１．５、ｙ＝０
．０１〜ｘ、ｚ−０，１〜１．５の数値である。）で表
される六角板状マグネトブランバイト型バリウムフェラ
イト磁性粉が得られる。このバリウノ、フェライト磁性
粉は前記一般式に示すように、従来の水熱合成法で製造
された一般式
Ｂａ Ｏ−ｎＦｅ２Ｏ３で示されるＦｅ原子の一部をｃ
ｏ’、Ｔ ｉ、 Ｎ ｉ、Ｍｎ、 Ｃｕ、 Ｚｎ、 Ｉ
ｎ、 Ｇｅ、 Ｎ ｂ等の金属単独、またはそれらの
組合わせを用いて、かつ置換原子の価数の合計が置換さ
れるＦｅ原子のそれと等しくなるように置換したバリウ
ムフェライト磁性粉とは異なった組成である。Table 1 (Effects of the Invention) According to the present invention, Ml is a hydrated metal containing one or more metals A from the group consisting of Ni, Co, Cu, Mg and Mn. , M2 represents one or more metals selected from the group consisting of Si, Ta, Sb, Nb, Zr and Ti,
n=0.8~1.0, x=0.5~1.5, y=0
．． They are numerical values of 01 to x, z-0, 1 to 1.5. ) A hexagonal plate-shaped magnetoblanbite-type barium ferrite magnetic powder is obtained. As shown in the general formula above, this bariuno ferrite magnetic powder is produced by converting some of the Fe atoms, which are produced by the conventional hydrothermal synthesis method and has the general formula BaO-nFe2O3, into C.
o', T i, N i, Mn, Cu, Zn, I
Barium ferrite magnetic powder is different from barium ferrite magnetic powder, which is substituted using metals such as n, Ge, Nb, etc., or a combination thereof, and the total valence of the substituted atoms is equal to that of the substituted Fe atom. It is the composition.
さらには、本発明で得られるマグネトプランバイｌ−型
バリウムフェライト磁性粉は平均粒子径が１００ｎｍ以
下、粒度分布がシャープで標準偏差３０ ｎ ｒｎ以下
の粉末であり、ＥｌＥＴ法による比表面積が３０ｒｒｒ
／ｌ程度のときに、飽和磁化は６５ｅｌｌｕ／ｌ以上、
５０耐／Ｑ程度のときに、飽和磁化は５８ ｅｍｕ／ｌ
以上と従来の水熱合成法により得られたものと比較して
飛躍的に高い値を示す、またこのバリウムフェライト磁
性粉の板状比は２〜１５の範囲である。さらに保磁力に
ついてはＭｌの添加量を変えることにより、自由に制御
することができる。Furthermore, the magnetopranby l-type barium ferrite magnetic powder obtained by the present invention is a powder with an average particle diameter of 100 nm or less, a sharp particle size distribution, and a standard deviation of 30 nrn or less, and a specific surface area of 30 rrr by the ElET method.
/l, the saturation magnetization is 65elu/l or more,
When the resistance is about 50/Q, the saturation magnetization is 58 emu/l
This barium ferrite magnetic powder exhibits a significantly higher value than that obtained by the conventional hydrothermal synthesis method, and the plate ratio of this barium ferrite magnetic powder is in the range of 2 to 15. Furthermore, the coercive force can be freely controlled by changing the amount of Ml added.
Claims (2)
１＿ｘＭ２＿ｙＺｎ＿ｚＯ＿１＿８＿−＿（＿ｘ＿−＿
ｙ＿＋＿ｚ＿）＿／＿２） （ただし、Ｍ１はＮｉ、Ｃｏ、Ｃｕ、ＭｇおよびＭｎか
らなる群から選ばれた一種または二種以上の金属を示し
、Ｍ２はＳｉ、Ｔａ、Ｓｂ、Ｎｂ、Ｚｒ、およびＴｉか
らなる群から選ばれた一種または二種以上の金属を示し
、ｎ＝０．８〜１．０、ｘ＝０．５〜１．５、ｙ＝０．
０１〜ｘ、ｚ＝０．１〜１．５の数値である。）で表さ
れる六角板状マグネトプランバイト型バリウムフェライ
ト磁性粉。(1) General formula BaO・n(Fe_1_2_-_x_-_y_-_zM
1_xM2_yZn_zO_1_8_-_(_x_-_
y_+_z_)_/_2) (However, M1 represents one or more metals selected from the group consisting of Ni, Co, Cu, Mg and Mn, and M2 represents Si, Ta, Sb, Nb, Zr, and Indicates one or more metals selected from the group consisting of Ti, n=0.8 to 1.0, x=0.5 to 1.5, y=0.
01 to x, z=0.1 to 1.5. ) Hexagonal plate-shaped magnetoplumbite-type barium ferrite magnetic powder.
鉄が１〜１２グラム原子、鉄１２−ｘ−ｙ−ｚグラム原
子に対して、Ｍ１がｘグラム原子、Ｍ２がｙグラム原子
および亜鉛がｚグラム原子の割合のそれぞれの元素の化
合物を用い、該出発原料を水に溶解し、これに混合後の
溶液中の水酸化アルカリ濃度が３モル／ｌ以上となるよ
うに水酸化アルカリを加えて沈澱物を生成させ、該沈澱
物を含むスラリを１３０〜３００℃で水熱処理した後、
生成した沈澱物に融剤を混合し、混合物を７００〜９５
０℃で焼成し、得られた焼成物を洗浄することを特徴と
する一般式 ＢａＯ・ｎ（Ｆｅ＿１＿２＿−＿ｘ＿−＿ｙ＿−＿ｚＭ
１＿ｘＭ２＿ｙＺｎ＿ｚＯ＿１＿８＿−＿（＿ｘ＿−＿
ｙ＿＋＿ｚ＿）＿／＿２） （ただし、Ｍ１はＮｉ、Ｃｏ、Ｃｕ、ＭｇおよびＭｎか
らなる群から選ばれた一種または二種以上の金属を示し
、Ｍ２はＳｉ、Ｔａ、Ｓｂ、Ｎｂ、Ｚｒ、およびＴｉか
らなる群から選ばれた一種または二種以上の金属を示し
、ｎ＝０．８〜１．０、ｘ＝０．５〜１．５、ｙ＝０．
０１〜ｘ、ｚ＝０．１〜１．５の数値である。）で表さ
れる六角板状マグネトプランバイト型バリウムフェライ
ト磁性粉の製造方法。(2) As starting materials, 1 to 12 gram atoms of iron for 1 gram atom of barium, x gram atoms of M1, y gram atoms of M2, and y gram atoms of M2 for 12-x-y-z gram atoms of iron; Using a compound of each element in a proportion of z gram atoms, the starting materials are dissolved in water, and alkali hydroxide is added to this so that the alkali hydroxide concentration in the solution after mixing is 3 mol/l or more. After producing a precipitate and hydrothermally treating the slurry containing the precipitate at 130 to 300°C,
A flux is mixed with the generated precipitate, and the mixture is heated to 700 to 95
General formula BaO・n(Fe_1_2_-_x_-_y_-_zM characterized by firing at 0°C and washing the obtained fired product)
1_xM2_yZn_zO_1_8_-_(_x_-_
y_+_z_)_/_2) (However, M1 represents one or more metals selected from the group consisting of Ni, Co, Cu, Mg and Mn, and M2 represents Si, Ta, Sb, Nb, Zr, and Indicates one or more metals selected from the group consisting of Ti, n=0.8 to 1.0, x=0.5 to 1.5, y=0.
01 to x, z=0.1 to 1.5. ) A method for producing hexagonal plate-shaped magnetoplumbite-type barium ferrite magnetic powder.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/151,203 US4778734A (en) | 1987-02-03 | 1988-02-01 | Barium ferrite magnetic powder and magnetic recording medium containing the same |
| KR1019880000982A KR920006822B1 (en) | 1987-02-03 | 1988-02-03 | Ba-ferrite magnetic materials and making method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-281928 | 1986-11-28 | ||
| JP61-281927 | 1986-11-28 | ||
| JP28192786 | 1986-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63233017A true JPS63233017A (en) | 1988-09-28 |
Family
ID=17645880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2173887A Pending JPS63233017A (en) | 1986-11-28 | 1987-02-03 | Magnetic powder of barium ferrite and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63233017A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185829A (en) * | 1986-09-19 | 1988-08-01 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| JPS63260104A (en) * | 1987-04-17 | 1988-10-27 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| JPS63260106A (en) * | 1987-04-17 | 1988-10-27 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| JPS63260110A (en) * | 1987-04-17 | 1988-10-27 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| US5062982A (en) * | 1989-04-07 | 1991-11-05 | Nippon Zeon Co., Ltd. | Magnetic powder for magnetic recording media |
| JP2018110167A (en) * | 2016-12-28 | 2018-07-12 | 国立研究開発法人産業技術総合研究所 | Composite magnetic particle, electromagnetic wave absorber, and method of producing composite magnetic particle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185829A (en) * | 1986-09-19 | 1988-08-01 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
-
1987
- 1987-02-03 JP JP2173887A patent/JPS63233017A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185829A (en) * | 1986-09-19 | 1988-08-01 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185829A (en) * | 1986-09-19 | 1988-08-01 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| JPS63260104A (en) * | 1987-04-17 | 1988-10-27 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| JPS63260106A (en) * | 1987-04-17 | 1988-10-27 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| JPS63260110A (en) * | 1987-04-17 | 1988-10-27 | Nippon Zeon Co Ltd | Magnetic powder for magnetic recording |
| US5062982A (en) * | 1989-04-07 | 1991-11-05 | Nippon Zeon Co., Ltd. | Magnetic powder for magnetic recording media |
| JP2018110167A (en) * | 2016-12-28 | 2018-07-12 | 国立研究開発法人産業技術総合研究所 | Composite magnetic particle, electromagnetic wave absorber, and method of producing composite magnetic particle |
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