JPH0692255B2 - Plate-like BaO.6Fe (2) (2) O (3) - Google Patents
Plate-like BaO.6Fe (2) (2) O (3)Info
- Publication number
- JPH0692255B2 JPH0692255B2 JP60191248A JP19124885A JPH0692255B2 JP H0692255 B2 JPH0692255 B2 JP H0692255B2 JP 60191248 A JP60191248 A JP 60191248A JP 19124885 A JP19124885 A JP 19124885A JP H0692255 B2 JPH0692255 B2 JP H0692255B2
- Authority
- JP
- Japan
- Prior art keywords
- bao
- particles
- plate
- powder
- flux
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 claims description 44
- 239000010419 fine particle Substances 0.000 claims description 27
- 230000004907 flux Effects 0.000 claims description 15
- 239000013081 microcrystal Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910001422 barium ion Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 230000005415 magnetization Effects 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 239000000696 magnetic material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000005291 magnetic effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000005294 ferromagnetic effect Effects 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 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 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、板状BaO・6Fe2O3微粒子粉末の製造方法に関
するものであり、詳しくは、粒度が均斉な微細粒子であ
って、粒子が１個１個バラバラであり、且つ、大きな磁
化値を有する板状BaO・6Fe2O3微粒子粉末のみをオート
クレーブ等の特殊な装置を用いることなく工業的、経済
的に有利に得ることを目的とする。TECHNICAL FIELD The present invention relates to a method for producing plate-like BaO.6Fe 2 O 3 fine particle powder, and more specifically, it is a fine particle having a uniform particle size. The purpose is to industrially and economically obtain only plate-like BaO.6Fe 2 O 3 fine particle powders that have a large magnetization value, without using special equipment such as an autoclave. And
本発明に係る板状BaO・6Fe2O3微粒子粉末の主な用途
は、焼結磁石及びゴム、プラスチック磁石用磁性材料粉
末、磁気記録用磁性材料粒子粉末、防食、防錆塗料用顔
料粉末等である。The main uses of the plate-like BaO · 6Fe 2 O 3 fine particle powder according to the present invention are sintered magnets and rubber, magnetic material powder for plastic magnets, magnetic material particle powder for magnetic recording, anticorrosion, pigment powder for anticorrosive paints, etc. Is.
BaO・6Fe2O3粒子粉末は、焼結磁石及びゴム、プラスチ
ック磁石用材料粒子粉末として現在広く使用されてい
る。BaO.6Fe 2 O 3 particle powder is currently widely used as a material particle powder for sintered magnets, rubbers, and plastic magnets.
焼成磁石は、BaO・6Fe2O3粒子粉末等の磁性材料粉末を
加圧、成型した後、本焼成を行うことにより製造され
る。The fired magnet is manufactured by pressurizing and molding magnetic material powder such as BaO.6Fe 2 O 3 particle powder, and then performing main firing.
また、ゴム、プラスチック磁石はBaO・6Fe2O3粒子粉末
等の磁性材料粉末をゴム、プラスチックと混練、成型す
ることにより製造される。Rubber and plastic magnets are manufactured by kneading and molding magnetic material powder such as BaO.6Fe 2 O 3 particle powder with rubber and plastic.
次に、近年、磁気記録分野における記録密度の高密度化
に伴い、従来方式に比べ、約３倍以上の高密度記録がで
きる垂直磁化方式の実用化が進められているが、板状Ba
O・6Fe2O3粒子粉末はこれら磁気記録用材料粒子粉末と
しても期待される。Next, in recent years, along with the increase in recording density in the magnetic recording field, the practical application of the perpendicular magnetization method capable of performing high-density recording about three times or more compared with the conventional method is progressing.
O.6Fe 2 O 3 particle powder is also expected as a material particle powder for magnetic recording.
更に、近代工業の発展と共に各種の金属材料の使用量が
急速に増大し、その使用条件も多様化し、より一層過酷
な環境下で使用されるようになった結果、金属製品の腐
食の問題がクローズアップされ、防食、防錆塗料用の需
要が激増しているが、板状BaO・6Fe2O3粒子粉末は、こ
れら防食、防錆塗料用顔料粉末としても期待される。Furthermore, with the development of modern industry, the amount of various metal materials used has rapidly increased, and the usage conditions have diversified, and as a result of being used in an even more severe environment, the problem of corrosion of metal products has been raised. The demand for anti-corrosion and anti-corrosion paints has been drastically increased, and plate-like BaO.6Fe 2 O 3 particle powder is also expected as a pigment powder for these anti-corrosion and anti-corrosion paints.
上述した通り、BaO・6Fe2O3粒子粉末は、様々の分野で
の使用が期待されているが、いずれの分野においても共
通して要求されるBaO・6Fe2O3粒子粉末の特性は優れた
分散性と大きな磁化値である。即ち、高性能、高特性の
製品を得ようとすれば、磁性材料粉末である板状BaO・6
Fe2O3粒子粉末が大きな磁化値を有していることはもち
ろん、焼結磁石においては加圧、成型に際して磁性材料
粉末を一定方向に高密度に整列、配向させることが必要
であり、また、ゴム、プラスチック磁石の製造において
は混練に際して、磁気記録媒体及び防食、防錆塗料の製
造においては塗料化に際して磁性材料粉末を均一、且
つ、高密度に分散させる必要があり、優れた分散性と大
きな磁化値を有するBaO・6Fe2O3粒子粉末は最も要求さ
れるところである。As described above, the BaO · 6Fe 2 O 3 particles, although the use of a variety of fields are expected, excellent characteristics of the BaO · 6Fe 2 O 3 particles are commonly required in any of the areas It has excellent dispersibility and a large magnetization value. That is, in order to obtain a product with high performance and characteristics, plate-like BaO.
Not only does the Fe 2 O 3 particle powder have a large magnetization value, but in a sintered magnet, it is necessary to align and orient the magnetic material powder in a certain direction at a high density during pressing and molding. In the production of rubber and plastic magnets, it is necessary to disperse the magnetic material powder uniformly and at high density during kneading in the production of magnetic recording media and anticorrosion and rust-preventive paints in the case of kneading in the production of magnets. BaO.6Fe 2 O 3 particle powder having a large magnetization value is the most demanded.
分散性の優れたBaO・6Fe2O3粒子粉末としては、粒度が
均斉な微細粒子であって、且つ、粒子が１個１個バラバ
ラであることが必要である。The BaO.6Fe 2 O 3 particle powder having excellent dispersibility needs to be fine particles having a uniform particle size, and the particles should be scattered one by one.
従来、BaO・6Fe2O3粒子粉末を製造する代表的な方法と
して、鉄原料とBa原料との混合物を1000℃以上の高温で
加熱焼成する、所謂乾式法、Fe（III）とBaイオンとを
含むアルカリ性懸濁液を150〜330℃の温度範囲において
水熱処理する、所謂水熱処理法、及びBaO・9/2Fe2O3微
結晶粉末を空気中で加熱焼成する方法等が知られてい
る。Conventionally, as a typical method for producing BaO · 6Fe 2 O 3 particle powder, a so-called dry method of heating and firing a mixture of an iron raw material and a Ba raw material at a high temperature of 1000 ° C. or higher, Fe (III) and Ba ions A hydrothermal treatment of an alkaline suspension containing OH in a temperature range of 150 to 330 ° C., a so-called hydrothermal treatment method, and a method of heating and firing BaO.9 / 2Fe 2 O 3 microcrystalline powder in air are known. .
優れた分散性と大きな磁化値を有するBaO・6Fe2O3粒子
粉末は、現在最も要求されているところであるが、上述
した通りの乾式法による場合には、焼結によって平均径
が数μｍの多結晶よりなり、粉砕によってもせいぜい１
μｍ程度である為に、分散性が悪いものである。BaO.6Fe 2 O 3 particle powder having excellent dispersibility and large magnetization value is currently the most demanded, but in the case of the dry method as described above, the average diameter of several μm is obtained by sintering. Consists of polycrystals and at most 1 even when crushed
Since it is about μm, the dispersibility is poor.
また、上述した通りの水熱処理法による場合には、粒子
が１個１個バラバラであるBaO・6Fe2O3粒子粉末が得ら
れるが、生成するBaO・6Fe2O3粒子粉末の磁化値は高々4
0emu/g程度であり、しかも、オートクレーブという特殊
な装置が必要であり、工業的、経済的ではない。In addition, when the hydrothermal treatment method as described above is used, BaO.6Fe 2 O 3 particle powders in which the particles are scattered one by one are obtained, but the magnetization value of the generated BaO.6Fe 2 O 3 particle powder is At most 4
It is about 0emu / g, and it requires a special device called an autoclave, which is not industrial or economical.
更に、上述した通りのBaO・9/2Fe2O3を空気中で加熱焼
成する方法による場合には、BaO・9/2Fe2O3が粒度が均
斉な微細粒子であることに起因して得られる板状BaO・6
Fe2O3粒子粉末も粒度が均斉な微細粒子であるが、BaO・
6Fe2O3粒子粉末中に非磁性のBaO・Fe2O3が混在し磁化値
が低下する原因となる。Further, when the BaO · 9 / 2Fe 2 O 3 of as described above by way of heating and firing in air, the BaO · 9 / 2Fe 2 O 3 due to the particle size is uniformity fine particles obtained Plated BaO ・ 6
Fe 2 O 3 particle powder is also a fine particle with a uniform particle size.
6Fe 2 O 3 magnetization BaO · Fe 2 O 3 nonmagnetic mixed in the particles in the powder causes a decrease.
そこで、粒度が均斉な微細粒子であって、粒子が１個１
個バラバラであり、且つ、大きな磁化値を有する板状Ba
O・6Fe2O3粒子のみを工業的、経済的に量産する為の技
術手段の確立が強く要望されている。Therefore, each particle is a fine particle with a uniform particle size.
Plate-like Ba that has individual and large magnetization values
There is a strong demand for establishment of technical means for mass-producing only O · 6Fe 2 O 3 particles industrially and economically.
本発明者は、粒度が均斉な微細粒子であって、粒子が１
個１個バラバラであり、且つ、大きな磁化値を有する板
状BaO・6Fe2O3粒子粉末のみをオートクレーブ等の特殊
な装置を用いることなく工業的、経済的に容易に得るべ
く種々検討を重ねた結果、本発明に到達したのである。The present inventors have found that fine particles having a uniform particle size are
Various studies have been repeated to obtain industrially and economically only plate-like BaO.6Fe 2 O 3 particle powders that have a large magnetization value and are individually separated without using a special device such as an autoclave. As a result, the present invention has been reached.
即ち、本発明は、BaO・9/2Fe2O3微結晶、又は、必要に
より、Baイオンを含むアルカリ性Fe（OH）２懸濁液中
に、35〜95℃の温度範囲に於て酸化性ガスを通じて液の
撹拌と同時にFe（II）を酸化することにより生成させた
BaO・9/2Fe2O3微結晶と融剤との混合物を700〜900℃の
温度範囲で加熱焼成した後、該加熱焼成物を洗浄して融
剤を除去することにより板状BaO・6Fe2O3微粒子を生成
させることからなる板状BaO・6Fe2O3微粒子粉末の製造
方法である。That is, according to the present invention, BaO.9 / 2Fe 2 O 3 microcrystals, or, if necessary, in an alkaline Fe (OH) 2 suspension containing Ba ions, is oxidized in a temperature range of 35 to 95 ° C. It was generated by oxidizing Fe (II) at the same time as stirring the liquid through gas.
After the firing of the BaO · 9 / 2Fe 2 O 3 mixture of microcrystalline and flux in the temperature range of 700 to 900 ° C., the plate BaO · 6Fe by removing the flux by washing the heating fired product a 2 O 3 fine particles consists in generating a plate BaO · 6Fe 2 O 3 production method of fine powder.
先ず、本発明において最も重要な点は、原料であるBaO
・9/2Fe2O3微結晶を融剤の存在下、700〜900℃の温度範
囲で加熱焼成した場合には、粒度が均斉な微細粒子であ
って、粒子１個１個バラバラであり、且つ、大きな磁化
値を有する板状BaO・6Fe2O3微粒子粉末のみが得られる
点である。First, the most important point in the present invention is the raw material BaO.
When 9 / 2Fe 2 O 3 microcrystals are heated and fired in the temperature range of 700 to 900 ° C. in the presence of a flux, they are fine particles having a uniform particle size, and the particles are scattered one by one. Moreover, it is a point that only tabular BaO.6Fe 2 O 3 fine particle powder having a large magnetization value can be obtained.
本発明においては、粒度が均斉な微細粒子であるBaO・9
/2Fe2O3微結晶を原料として用い、次いで、該原料を融
剤の存在下700〜900℃の温度範囲で加熱焼成して、粒子
並びに粒子相互間で焼結を生起することなく、また、非
磁性であるBaO・Fe2O3の生成を防止することによって、
粒度が均斉な微細粒子であって、粒子１個１個バラバラ
であり、且つ、大きな磁化値を有する板状BaO・6Fe2O3
微粒子粉末のみを得ている。In the present invention, BaO 9 which is a fine particle having a uniform particle size
/ 2Fe 2 O 3 microcrystals are used as a raw material, and then the raw material is heated and fired in the temperature range of 700 to 900 ° C. in the presence of a flux, without causing sintering between particles and each other, and By preventing the formation of BaO.Fe 2 O 3 which is non-magnetic,
Plate-like BaO ・ 6Fe 2 O 3 that is a fine particle with a uniform particle size, which is scattered one by one and has a large magnetization value
Only fine particle powder is obtained.
本発明における他の重要な点は、オートクレーブ等の特
殊な装置を用いることなく、優れた分散性と大きな磁化
値を有する板状BaO・6Fe2O3微粒子粉末が得られる為、
工業的、経済的な量産が可能な点である。Another important point in the present invention is that, without using a special device such as an autoclave, a plate-like BaO.6Fe 2 O 3 fine particle powder having excellent dispersibility and a large magnetization value can be obtained,
The point is that industrial and economical mass production is possible.
次に、本発明方法実施にあたっての諸条件について述べ
る。Next, various conditions for carrying out the method of the present invention will be described.
本発明におけるBaO・9/2Fe2O3微結晶は、例えば、Fe（I
II）とBaイオンとを含むアルカリ性懸濁液を110〜190℃
の温度範囲で水熱処理する方法、Baイオンを含むアルカ
リ性Fe（OH）２懸濁液中に、35〜95℃の温度範囲におい
て酸化性ガスを通じて液の撹拌と同時にFe（II）を酸化
する常圧下の水溶液反応による方法のいずれの方法によ
っても得ることができるが、工業的、経済的な量産を考
慮すれば、後者の方法によって得ることが望ましい。The BaO.9 / 2Fe 2 O 3 microcrystals in the present invention are, for example, Fe (I
II) and Ba ions at 110-190 ℃
The method of hydrothermal treatment in the temperature range of 1), the Fe (II) 2 suspension containing Ba ions in the temperature range of 35 ~ 95 ℃, and the oxidation of Fe (II) at the same time as the stirring of the liquid is carried out. Although it can be obtained by any method of the aqueous solution reaction under reduced pressure, the latter method is preferable in view of industrial and economical mass production.
前者のBaO・9/2Fe2O3微結晶の生成におけるFe（III）塩
としては、塩化第２鉄及び硝酸第２鉄を用いることがで
きる。Baイオンとしては、水酸化バリウム、塩化バリウ
ム、硝酸バリウム等を使用することができる。Ferric chloride and ferric nitrate can be used as the Fe (III) salt in the former formation of BaO.9 / 2Fe 2 O 3 microcrystals. As the Ba ions, barium hydroxide, barium chloride, barium nitrate or the like can be used.
後者のBaO・9/2Fe2O3微結晶の生成におけるアルカリ性F
e（OH）２懸濁液は、Fe（II）塩と沈澱剤としてのアル
カリとを反応させることにより得られる。Fe（II）塩と
しては、ピックリング廃液としての塩化鉄を使用するこ
とが経済的である。Baイオンとしては、水酸化バリウ
ム、塩化バリウム、硝酸バリウム等を使用することがで
きる。Alkaline F in the formation of the latter BaO ・ 9 / 2Fe 2 O 3 crystallites
The e (OH) 2 suspension is obtained by reacting a Fe (II) salt with an alkali as a precipitating agent. As the Fe (II) salt, it is economical to use iron chloride as a pickling waste liquid. As the Ba ions, barium hydroxide, barium chloride, barium nitrate or the like can be used.
沈澱剤としてはNaOHやKOHが使用できる。NaOH or KOH can be used as a precipitant.
酸化反応の温度は、35℃〜95℃である。BaO・9/2Fe2O3
の生成する酸化温度は、沈澱剤の種類や濃度等によって
左右される。The temperature of the oxidation reaction is 35 ° C to 95 ° C. BaO ・ 9 / 2Fe 2 O 3
The oxidation temperature produced by the is dependent on the type and concentration of the precipitating agent.
35℃未満である場合には、酸化速度が著しく小さくな
り、生成BaO・9/2Fe2O3微結晶の成長が遅くなる。If the temperature is lower than 35 ° C, the oxidation rate will be remarkably low, and the growth of the BaO.9 / 2Fe 2 O 3 microcrystals formed will be slow.
本発明において、より低い保磁力を有した板状BaO・6Fe
2O3微粒子粉末を得る場合には、当然のことながら、Co
（II）又はCo（II）及びMn、Zn等の２価金属イオンＭ
（II）とTi（IV）とを含むBaO・9/2Fe2O3微結晶を原料
として用いればよく、このような微結晶は、水熱処理反
応におけるFe（III）とBaイオンとを含むアルカリ性懸
濁液中又は常圧下の水溶液反応におけるアルカリ性Fe
（OH）２懸濁液中にあらかじめCo（II）又はCo（II）及
びMn、Zn等の２価金属イオンＭ（II）とTi（IV）とを存
在させることにより得ることができる。In the present invention, plate-like BaO · 6Fe having a lower coercive force
As a matter of course, when obtaining 2 O 3 fine particle powder, Co
(II) or Co (II) and divalent metal ion M such as Mn and Zn
BaO.9 / 2Fe 2 O 3 microcrystals containing (II) and Ti (IV) may be used as a raw material, and such microcrystals are alkaline containing Fe (III) and Ba ions in the hydrothermal treatment reaction. Alkaline Fe in suspension or in aqueous reaction under atmospheric pressure
It can be obtained by previously allowing Co (II) or Co (II) and a divalent metal ion M (II) such as Mn and Zn and Ti (IV) to exist in the (OH) 2 suspension.
本発明における融剤は、Na、Ｋ或いはLiの硫酸塩、Na、
Ｋ或いはCaの塩化物、臭化的、沃化物若しくは弗化物、
Ba或いはSrの塩化物若しくは弗化物から選ばれた一種又
は二種以上の融剤を使用することができるが、NaClの使
用が経済的である。BaO・9/2Fe2O3に対する混合比は少
なくとも4wt％が必要である。The flux in the present invention is a sulfate of Na, K or Li, Na,
Chloride, bromide, iodide or fluoride of K or Ca,
One or more fluxes selected from chlorides or fluorides of Ba or Sr can be used, but the use of NaCl is economical. The mixing ratio for BaO · 9 / 2Fe 2 O 3 should be at least 4 wt%.
本発明における加熱焼成温度は、700〜900℃の温度範囲
である。The heating and firing temperature in the present invention is in the temperature range of 700 to 900 ° C.
本発明における加熱焼成は、融剤の存在下で行われる
為、BaO・6Fe2O3への変化温度が低くなると共にBaO・Fe
2O3の生成が防止される。変化温度は融剤の種類、混合
度合や原料BaO・9/2Fe2O3粒子の大きさによって左右さ
れる。加熱焼成温度が900℃以上である場合には、粒子
及び粒子相互間の焼結が著しい。Since the heating and firing in the present invention is carried out in the presence of the flux, the change temperature to BaO · 6Fe 2 O 3 becomes low and BaO · Fe
Generation of 2 O 3 is prevented. The change temperature depends on the type of flux, the degree of mixing and the size of the raw material BaO.9 / 2Fe 2 O 3 particles. When the heating / baking temperature is 900 ° C. or higher, the particles and the sintering between the particles are remarkable.
本発明における洗浄は、通常は水を用いればよく、必要
により、酢酸水溶液、塩酸水溶液を用いることができ
る。For washing in the present invention, water may be usually used, and if necessary, an acetic acid aqueous solution or a hydrochloric acid aqueous solution may be used.
次に、実施例により本発明を説明する。 Next, the present invention will be described with reference to examples.
尚、以下の実施例における粒子の平均径は電子顕微鏡写
真から測定した数値、また、磁化値及び抗磁力は粉末状
態で10KOeの磁場においてVSMで測定したものである。In addition, the average diameter of the particles in the following examples is a value measured from an electron micrograph, and the magnetization value and the coercive force are measured by VSM in a powder state in a magnetic field of 10 KOe.
実施例１ 1.25mol/のFeCl2を含む240ml溶液に11.82gのBa（OH）
28H2Oを溶解し、これに60gのNaOHを添加し、水にて全容
１とした。このアルカリ性Fe（OH）２懸濁液を加熱
し、BaCO3の生成を防ぐ為、CO2を除去した空気を40℃に
於て毎時250の速度で吹込んだ。５時間後、懸濁液中
のFe（II）は完全にFe（III）に変化していた。茶色非
強磁性沈澱を別、水洗後80℃で乾燥した。Example 1 11.82 g Ba (OH) 2 in a 240 ml solution containing 1.25 mol / FeCl 2.
Was dissolved 2 8H 2 O, was added thereto 60g of NaOH, and the total volume 1 with water. This alkaline Fe (OH) 2 suspension was heated and CO 2 -free air was blown into it at a rate of 250 per hour at 40 ° C. to prevent the formation of BaCO 3 . After 5 hours, Fe (II) in the suspension had completely changed to Fe (III). The brown non-ferromagnetic precipitate was separated, washed with water and dried at 80 ° C.
図１に示すＸ−線分析によれば、乾燥試料はBaO・9/2Fe
2O3相のみより成立っており、図２に示す電子顕微鏡写
真（×100000）によれば、平均径0.02μｍの粒度が均斉
な粒状粒子から成立っていた。According to the X-ray analysis shown in FIG. 1, the dry sample is BaO.9 / 2Fe.
It is composed of only the 2 O 3 phase, and according to the electron micrograph (× 100000) shown in FIG. 2, it was composed of granular particles having an average particle size of 0.02 μm and having a uniform size.
得られたBaO・9/2Fe2O3微結晶2gに0.12gのNaClを含む水
溶液を添加（融剤の添加量はBaO・9/2Fe2O3に対し6wt％
に該当する。）し、水分を蒸発後800℃にて大気中で２
時間焼成した。焼成分中のNaCl分を水洗して得られた茶
色強磁性粉末は３図のＸ−線回折図から明らかな通り、
BaO・6Fe2O3微粒子粉末のみから成り、その磁性は磁化
値Ｍ＝56emu/g、抗磁力Hcは2.7KOeであった。An aqueous solution containing 0.12 g of NaCl was added to 2 g of the obtained BaO ・ 9 / 2Fe 2 O 3 microcrystals (the amount of flux added was 6 wt% based on BaO ・ 9 / 2Fe 2 O 3).
Corresponds to. ), And after evaporation of the water, in the air at 800 ° C for 2
Burned for hours. The brown ferromagnetic powder obtained by washing the NaCl component in the baked component with water, as is clear from the X-ray diffraction diagram of FIG.
It consisted only of BaO.6Fe 2 O 3 fine particle powder, and its magnetism had a magnetization value M = 56 emu / g and a coercive force Hc of 2.7 KOe.
また、電子顕微鏡観察の結果、粒度が均斉であって平均
径0.5μｍの微細な板状粒子であり、且つ、粒子が１個
１個バラバラな粒子であった。In addition, as a result of electron microscopic observation, it was found that the particles were fine plate-like particles having a uniform particle size and an average diameter of 0.5 μm, and the particles were scattered one by one.
実施例２ 2.50mol/のFeCl2を含む240ml溶液に23.6gのBa（OH）2
8H2Oを溶解し、これに337gのKOHを添加し、水にて全容
１とした。このFe（OH）２懸濁液を加熱し、85℃の温
度に於てCO2を除去した空気を毎時450の速度で吹込ん
だ。８時間後、Fe（II）は殆どFe（III）に変化してい
た。別、水洗、乾燥して得られた茶色非強磁性試料
は、電子顕微鏡観察の結果、平均径0.05μｍの粒度が均
斉な粒状粒子から成立っており、Ｘ−線分析によればBa
O・9/2Fe2O3構造を有していた。EXAMPLE 2 2.50 mol / of 23.6g in 240ml solution containing FeCl 2 of Ba (OH) 2
8H 2 O was dissolved, 337 g of KOH was added, and the total volume was adjusted to 1 with water. The Fe (OH) 2 suspension was heated and CO 2 -free air was blown into it at a rate of 450 / h at a temperature of 85 ° C. After 8 hours, most of Fe (II) was changed to Fe (III). Separately, the brown non-ferromagnetic sample obtained by washing with water and drying was observed by an electron microscope, and as a result, it consisted of granular particles having an average diameter of 0.05 μm and having a uniform particle size.
It had an O.9 / 2Fe 2 O 3 structure.
得られたBaO・9/2Fe2O3微結晶に、NaClの代わりにKClを
用いた以外は実施例１と同様にして融剤を添加して水分
を蒸発した後850℃の温度で２時間焼成した。焼成後の
水洗物は、Ｘ−線回折の結果、BaO・6Fe2O3微粒子のみ
から成り、Ｍ値は55emu/g、Hc値は1.6KOeであった。A flux was added to the obtained BaO.9 / 2Fe 2 O 3 microcrystals in the same manner as in Example 1 except that KCl was used instead of NaCl, and water was evaporated, followed by heating at a temperature of 850 ° C. for 2 hours. Baked. Washed product after firing, the results of X- ray diffraction, consisting solely BaO · 6Fe 2 O 3 fine particles, M value 55 emu / g, Hc value was 1.6KOe.
また、電子顕微鏡観察の結果、粒度が均斉であって平均
径0.3μｍの微細な板状粒子であり、且つ、粒子が１個
１個バラバラな粒子であった。In addition, as a result of electron microscopic observation, the particles were fine, plate-like particles having a uniform particle size and an average diameter of 0.3 μm, and the particles were scattered one by one.
実施例３ 1.25mol/のFeCl2、0.208mol/のCoCl2及び0.208mol/
のTiCl4を含む240ml溶液に11.82gのBa（OH）28H2Oを
溶解し、これに60gのNaOHを添加し、水にて全容１と
した。このアルカリ性懸濁液を加熱し、40℃に於てCO2
を除去した空気を毎時250の速度で吹込んだ。５時間
後、懸濁液中のFe（II）は完全にFe（III）に変化して
いた。茶色非強磁性沈澱を別、水洗後80℃で乾燥し
た。Ｘ−線分析によれば乾燥試料は、BaO・9/2Fe2O3相
のみより成立っており、電子顕微鏡観察の結果、粒度が
均斉な平均径0.02μｍの粒状粒子より成立っていた。Example 3 1.25 mol / FeCl 2 , 0.208 mol / CoCl 2 and 0.208 mol /
11.82 g of Ba (OH) 2 8H 2 O was dissolved in a 240 ml solution containing TiCl 4 of, and 60 g of NaOH was added thereto, and the total volume was adjusted to 1 with water. This alkaline suspension is heated to CO 2 at 40 ° C.
The removed air was blown at a speed of 250 per hour. After 5 hours, Fe (II) in the suspension had completely changed to Fe (III). The brown non-ferromagnetic precipitate was separated, washed with water and dried at 80 ° C. Dried sample according to X- ray analysis is, BaO · 9 / 2Fe have Seiritsu' of only 2 O 3 phase, as a result of electron microscopic observation, the particle size had Seiritsu' than granular particles having an average diameter of 0.02μm of symmetry.
得られたCo及びTiを含有するBaO・9/2Fe2O3微結晶2gに
0.12gのNaClを含む水溶液を添加（融剤の添加量はBaO・
9/2Fe2O3に対し6wt％に該当する。）し、水分を蒸発後8
00℃にて大気中で２時間焼成した。焼成分中のNaCl分を
水洗して得られた茶色強磁性粉末はＸ−線回折の結果、
BaO・6Fe2O3微粒子粉末のみから成り、その磁性は磁化
値Ｍ＝54.1emu/g、抗磁力Hcは0.89KOeであった。2 g of BaO ・ 9 / 2Fe 2 O 3 microcrystals containing Co and Ti obtained
An aqueous solution containing 0.12 g of NaCl was added (the amount of flux added was BaO.
This corresponds to 6 wt% with respect to 9 / 2Fe 2 O 3 . ) And after evaporation of water 8
Firing was performed in the air at 00 ° C for 2 hours. The brown ferromagnetic powder obtained by washing the NaCl component in the baked component with water was the result of X-ray diffraction,
It consisted only of BaO.6Fe 2 O 3 fine particle powder, and its magnetism had a magnetization value M = 54.1 emu / g and a coercive force Hc of 0.89 KOe.
また、電子顕微鏡観察の結果、粒度が均斉であって平均
径0.5μｍの微細な板状粒子であり、且つ、粒子が１個
１個バラバラな粒子であった。In addition, as a result of electron microscopic observation, it was found that the particles were fine plate-like particles having a uniform particle size and an average diameter of 0.5 μm, and the particles were scattered one by one.
本発明におけるBaO・6Fe2O3微粒子粉末の製造方法によ
れば、前出実施例に示した通り、粒度が均斉な微細粒子
であって、粒子１個１個がバラバラであり、且つ、大き
な磁化値を有する板状BaO・6Fe2O3微粒子粉末を得るこ
とができるので、焼結磁石及びゴム、プラスチック磁石
用磁性材料粉末、磁気記録用磁性材料粉末、防食、防錆
塗料用顔料粉末として好適である。According to the method for producing a BaO.6Fe 2 O 3 fine particle powder according to the present invention, as shown in the above-mentioned examples, the particles are fine particles having a uniform particle size, and each particle is scattered and large. Since it is possible to obtain plate-like BaO ・ 6Fe 2 O 3 fine particle powder having a magnetization value, it can be used as a magnetic powder for magnetic materials for sintered magnets and rubbers, plastic magnets, magnetic material powder for magnetic recording, pigment powder for anticorrosion and anticorrosive paints It is suitable.
図１及び図２は、それぞれ実施例１で得られたBaO・9/2
Fe2O3微結晶のＸ線回折図と粒子構造を示す電子顕微鏡
写真（×100000）である。 図３は、実施例１で得られたBaO・6Fe2O3微結晶のＸ線
回折図である。1 and 2 show BaO.9 / 2 obtained in Example 1, respectively.
1 is an X-ray diffraction diagram of Fe 2 O 3 microcrystals and an electron micrograph (× 100000) showing a particle structure. FIG. 3 is an X-ray diffraction diagram of the BaO.6Fe 2 O 3 microcrystals obtained in Example 1.
───────────────────────────────────────────────────── フロントページの続き 審査官 米田 健志 (56)参考文献 特開 昭60−90829（ＪＰ，Ａ) 特開 昭59−161002（ＪＰ，Ａ) ─────────────────────────────────────────────────── --Continued from the front page Examiner Takeshi Yoneda (56) References JP-A-60-90829 (JP, A) JP-A-59-161002 (JP, A)
Claims (2)
00〜900℃の温度範囲で加熱焼成した後、該加熱焼成物
を洗浄して融剤を除去することにより板状BaO・6Fe2O3
微粒子を生成させることを特徴とする板状BaO・6Fe2O3
微粒子粉末の製造方法。1. A mixture of BaO.9 / 2Fe 2 O 3 crystallites and a flux is used.
After heating and baking in a temperature range of 00 to 900 ° C., the heating and baking product is washed to remove the flux to obtain plate-shaped BaO.6Fe 2 O 3
Plate-shaped BaO ・ 6Fe 2 O 3 characterized by producing fine particles
Method for producing fine particle powder.
液中に、35〜95℃の温度範囲に於て酸化性ガスを通じて
液の撹拌と同時にFe（II）を酸化することによりBaO・9
/2Fe2O3微結晶を生成させ、次いで、該BaO・9/2Fe2O3微
結晶と融剤との混合物を700〜900℃の温度範囲で加熱焼
成した後、該加熱焼成物を洗浄して融剤を除去すること
により板状BaO・6Fe2O3微粒子を生成させることを特徴
とする板状BaO・6Fe2O3微粒子粉末の製造方法。2. BaO by oxidizing Fe (II) at the same time as stirring the liquid in an alkaline Fe (OH) 2 suspension containing Ba ions in the temperature range of 35 to 95 ° C. through an oxidizing gas.・ 9
/ 2Fe 2 O 3 microcrystals are generated, and then, a mixture of the BaO.9 / 2Fe 2 O 3 microcrystals and the flux is heated and fired in a temperature range of 700 to 900 ° C, and then the heated and fired product is washed. A plate-like BaO · 6Fe 2 O 3 fine particle is produced by removing the flux to remove the plate-like BaO · 6Fe 2 O 3 fine particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60191248A JPH0692255B2 (en) | 1985-08-29 | 1985-08-29 | Plate-like BaO.6Fe (2) (2) O (3) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60191248A JPH0692255B2 (en) | 1985-08-29 | 1985-08-29 | Plate-like BaO.6Fe (2) (2) O (3) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6252134A JPS6252134A (en) | 1987-03-06 |
| JPH0692255B2 true JPH0692255B2 (en) | 1994-11-16 |
Family
ID=16271367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60191248A Expired - Fee Related JPH0692255B2 (en) | 1985-08-29 | 1985-08-29 | Plate-like BaO.6Fe (2) (2) O (3) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692255B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59161002A (en) * | 1983-02-05 | 1984-09-11 | Toda Kogyo Corp | Plate-shaped Ba ferrite fine particle powder for magnetic recording and manufacturing method thereof |
| JPS6090829A (en) * | 1983-10-25 | 1985-05-22 | Ube Ind Ltd | Processing method for barium ferrite |
-
1985
- 1985-08-29 JP JP60191248A patent/JPH0692255B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6252134A (en) | 1987-03-06 |
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