JPH09142848A - Production of magnetic oxide powder - Google Patents
Production of magnetic oxide powderInfo
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- JPH09142848A JPH09142848A JP7295635A JP29563595A JPH09142848A JP H09142848 A JPH09142848 A JP H09142848A JP 7295635 A JP7295635 A JP 7295635A JP 29563595 A JP29563595 A JP 29563595A JP H09142848 A JPH09142848 A JP H09142848A
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- magnetic oxide
- oxide powder
- peroxide
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低温焼結に適した
表面活性の高い磁性酸化物粉体を製造する方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a magnetic oxide powder having high surface activity, which is suitable for low temperature sintering.
【０００２】[0002]
【従来の技術】従来、磁性酸化物粉体、例えばＭｎ−Ｚ
ｎ系フェライト粉体の製造方法としては、次のような種
々の方法が提案されている。2. Description of the Related Art Conventionally, magnetic oxide powders such as Mn-Z are used.
The following various methods have been proposed as a method for producing the n-type ferrite powder.
【０００３】（ａ）フェライトを構成する元素の酸化物
あるいは炭酸塩の粉体を混合した後、この混合粉体を高
温で仮焼してＭｎ−Ｚｎフェライト粉体を得る方法。(A) A method of obtaining powder of Mn-Zn ferrite by mixing powders of oxides or carbonates of elements constituting ferrite and then calcining the mixed powder at high temperature.
【０００４】（ｂ）Ｍｎ，Ｚｎ及びＦｅの水溶性化合物
の混合溶液に蓚酸塩を添加してそれらの蓚酸塩化合物を
沈殿させた後、この蓚酸塩化合物を仮焼してＭｎ−Ｚｎ
フェライト粉体を得る方法。(B) Oxalates are added to a mixed solution of water-soluble compounds of Mn, Zn and Fe to precipitate the oxalate compounds, and the oxalate compounds are calcined to obtain Mn-Zn.
Method for obtaining ferrite powder.
【０００５】（ｃ）ＦｅのアルコキシドとＭｎ及びＺｎ
のアセチルアセトネート化合物を有機溶剤に溶解して混
合溶液を作製し、この混合溶液に水を加えて加水分解を
行ないゲルを生成させ、そのゲルを仮焼してＭｎ−Ｚｎ
フェライト粉体を得る方法。(C) Alkoxide of Fe and Mn and Zn
Of the acetylacetonate compound is dissolved in an organic solvent to prepare a mixed solution, water is added to the mixed solution to cause hydrolysis to form a gel, and the gel is calcined to prepare Mn-Zn
Method for obtaining ferrite powder.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
製造方法それぞれにおいて、以下に示すような問題点を
有していた。However, each of the above-described manufacturing methods has the following problems.
【０００７】（ａ）の方法においては、出発原料が酸化
物又は炭酸塩の粉体であるため、各々の粉体を原子レベ
ルで均一に分散させることができず、得られたフェライ
ト粉体に部分的な組成ずれが生じた。又、出発原料粉体
の表面活性が低いので、スピネル化合物を得るためには
高温で仮焼しなければならなかった。In the method (a), since the starting material is an oxide or carbonate powder, it is impossible to uniformly disperse each powder at the atomic level, and the obtained ferrite powder is added. A partial composition shift occurred. Further, since the starting material powder has a low surface activity, it was necessary to perform calcination at a high temperature in order to obtain a spinel compound.
【０００８】なお、出発原料の各粉体は、湿式反応によ
り合成した微細な沈殿物を仮焼して得ることが可能であ
る。しかしながら、合成段階での沈殿物が微細であって
も乾燥、仮焼後はやはり凝集して粒径が大きくなり、表
面活性が低下した状態になっている。したがって、この
場合においても各々の粉体を原子レベルで均一に混合分
散させることができず、均一なスピネル化合物を得るた
めには高温で仮焼する必要があった。Each powder of the starting material can be obtained by calcining a fine precipitate synthesized by a wet reaction. However, even if the precipitate in the synthesis stage is fine, after drying and calcination, it still aggregates and the particle size becomes large, and the surface activity is reduced. Therefore, even in this case, the respective powders could not be uniformly mixed and dispersed at the atomic level, and it was necessary to perform calcination at a high temperature in order to obtain a uniform spinel compound.
【０００９】又、以上のように高温で仮焼して得られる
磁性酸化物粉体は、強固な凝集体となって表面活性が低
下するので、焼成温度を一段と高くする必要があった。
この問題を解決するために、焼結助材を添加することに
よって焼結温度を下げる方法が提唱されている。しかし
ながら、焼結助材を添加することで焼結温度を低下させ
ることはできるが、一方では磁気特性を劣化させるため
根本的な解決策とはなっていない。Further, since the magnetic oxide powder obtained by calcination at high temperature as described above becomes a strong agglomerate and its surface activity is lowered, it is necessary to further raise the firing temperature.
In order to solve this problem, a method of lowering the sintering temperature by adding a sintering aid has been proposed. However, although it is possible to lower the sintering temperature by adding a sintering aid, this is not a fundamental solution because it deteriorates the magnetic properties.
【００１０】さらに、仮焼後の凝集した粉体を微細化す
るために粉砕が必要であるが、このときに粉砕装置の内
壁あるいはメディアの磨耗物が不純物として混入した。Further, it is necessary to pulverize the agglomerated powder after calcination to make it fine, but at this time, the abrasion material of the inner wall of the pulverizing device or the medium is mixed as an impurity.
【００１１】（ｂ）の製造方法においては、フェライト
を構成する元素間で，蓚酸塩を生成する最適ｐＨが互い
に異なる場合があり、このようなときには目的とする分
子化合物を生成できず、組成の異なる分子化合物と未反
応の金属イオン各々の蓚酸塩の混合物が得られることに
なる。したがって、構成元素の均一分散性は、（ａ）の
方法と比べると改善されているもののまだ不十分であっ
た。In the manufacturing method (b), the optimum pH for producing oxalate may differ between the elements constituting the ferrite, and in such a case, the desired molecular compound cannot be produced and the composition of the composition is A mixture of different molecular compounds and oxalates of each unreacted metal ion will be obtained. Therefore, although the uniform dispersibility of the constituent elements was improved as compared with the method (a), it was still insufficient.
【００１２】又、これら沈殿物の溶解度がそれぞれ異な
るため、洗浄時の溶出量に差が生じ、仕込み時の組成と
得られる沈殿物の組成との間にずれが生じた。Further, since the solubilities of these precipitates are different from each other, there is a difference in the elution amount at the time of washing, which causes a difference between the composition at the time of charging and the composition of the obtained precipitate.
【００１３】さらに、得られた蓚酸塩化合物を仮焼して
スピネル化するときの反応メカニズムは、まず蓚酸塩化
合物が脱ＣＯ2 や脱ＣＯにより炭酸塩を経て酸化物に分
解した後、生成した酸化物同志が固相反応するものであ
る。したがって、この製造方法においても（ａ）と同様
に、高温で仮焼する必要があった。このため、仮焼後の
凝集したフェライト粉体の粉砕が必要であり、この粉砕
時に不純物の混入を避けることができなかった。Further, the reaction mechanism when the obtained oxalate compound is calcined to form a spinel is that the oxalate compound is produced by decomposing the oxalate compound into an oxide through a carbonate by de-CO 2 and de-CO. The oxides are solid-phase reacted. Therefore, also in this manufacturing method, similarly to (a), it was necessary to perform calcination at a high temperature. For this reason, it is necessary to pulverize the agglomerated ferrite powder after calcination, and it is impossible to avoid mixing of impurities during the pulverization.
【００１４】さらに又、蓚酸塩化合物を生成させた後の
廃液処理として、未反応の蓚酸イオンに起因するＢＯＤ
を下げる曝気処理や、酸性廃液の中和処理を必要とし
た。Furthermore, as a waste liquid treatment after the formation of the oxalate compound, BOD resulting from unreacted oxalate ion
It required aeration treatment to lower the temperature and neutralization treatment of acidic waste liquid.
【００１５】（ｃ）の製造方法においては、仮焼温度が
低く、表面活性及び純度が高いフェライト粉体が得られ
る。しかしながら、使用する出発原料の価格が非常に高
価であって、実験室規模では最適であるが量産には適さ
なかった。In the manufacturing method of (c), a calcination temperature is low and a ferrite powder having high surface activity and high purity can be obtained. However, the price of the starting material used was very high, and although it was optimal on a laboratory scale, it was not suitable for mass production.
【００１６】そこで、本発明の目的は、上記の問題点を
解決して、粒径が小さく表面活性が高く易焼結性であっ
て、安価な磁性酸化物粉体の製造方法を提供することに
ある。Therefore, an object of the present invention is to solve the above problems and provide a method for producing an inexpensive magnetic oxide powder having a small particle size, high surface activity, easy sinterability. It is in.
【００１７】[0017]
【課題を解決するための手段】上記目的を達成するた
め、本発明の磁性酸化物粉体の製造方法は、一般式Ｍｅ
Ｆｅ2 Ｏ4 （但し、ＭｅはＭｎ、Ｎｉ、Ｚｎ、Ｃｕ、Ｃ
ｏのうち少なくとも１種類の２価の金属元素）で示され
る磁性酸化物粉体の製造において、α−ＦｅＯＯＨ粉体
表面に前記Ｍｅ金属元素の過酸化物を担持固定した後、
熱処理することを特徴とする。In order to achieve the above object, the method for producing a magnetic oxide powder according to the present invention is carried out according to the general formula Me.
Fe 2 O 4 (However, Me is Mn, Ni, Zn, Cu, C
In the production of the magnetic oxide powder represented by at least one kind of divalent metal element of o), after the peroxide of the Me metal element is supported and fixed on the surface of the α-FeOOH powder,
Characterized by heat treatment.
【００１８】又、前記熱処理温度は、磁性酸化物粉体が
Ｍｎ−Ｚｎ系フェライトであるときは７００〜９００℃
であり、磁性酸化物粉体がＮｉ−Ｚｎ系フェライトであ
るときは４５０〜７００℃であることを特徴とする。The heat treatment temperature is 700 to 900 ° C. when the magnetic oxide powder is Mn-Zn ferrite.
And when the magnetic oxide powder is a Ni—Zn ferrite, the temperature is 450 to 700 ° C.
【００１９】又、Ｍｅ金属イオンを含む溶液にα−Ｆｅ
ＯＯＨ粉体を分散させたスラリー中に、アルカリ及び過
酸化水素を加えて前記Ｍｅ金属の過酸化物を生成させ、
該過酸化物を前記α−ＦｅＯＯＨ粉体表面に担持固定さ
せることを特徴とする。Further, α-Fe is added to a solution containing Me metal ions.
To the slurry in which the OOH powder is dispersed, alkali and hydrogen peroxide are added to generate the Me metal peroxide,
The peroxide is supported and fixed on the surface of the α-FeOOH powder.
【００２０】さらに、前記Ｍｅ金属イオン源は、水溶性
のＭｅ金属化合物又は硝酸、塩酸、硫酸及び酢酸のうち
いずれかに可溶なＭｅ金属化合物であることを特徴とす
る。そして、前記アルカリ源は、ＮａＯＨ、ＫＯＨ及び
ＬｉＯＨのうち少なくとも１種類であることを特徴とす
る。Further, the Me metal ion source is characterized by being a water-soluble Me metal compound or a Me metal compound soluble in any of nitric acid, hydrochloric acid, sulfuric acid and acetic acid. The alkali source is at least one of NaOH, KOH, and LiOH.
【００２１】本発明の、α−ＦｅＯＯＨ粉体表面にＦｅ
以外の磁性酸化物を構成する金属元素の過酸化物を担持
固定した前駆体を熱処理する方法によれば、α−ＦｅＯ
ＯＨ及び過酸化物が３００℃付近でそれぞれ熱分解しな
がら互いに反応を開始する。即ち、低熱処理温度でスピ
ネル化反応が起きる。このため、反応物の凝集が抑えら
れて従来のように機械的強制粉砕を必要とせず、粉砕に
より不純物が混入することもない。Fe on the surface of the α-FeOOH powder of the present invention
According to the method of heat-treating the precursor carrying and fixing the peroxide of the metal element constituting the magnetic oxide other than α-FeO
OH and peroxide start to react with each other while thermally decomposing at around 300 ° C. That is, the spinelization reaction occurs at a low heat treatment temperature. Therefore, agglomeration of the reaction product is suppressed and mechanical forced pulverization is not required unlike in the conventional case, and impurities are not mixed by pulverization.
【００２２】又、本発明によれば、α−ＦｅＯＯＨ粉体
の懸濁液中でＦｅ以外の磁性酸化物を構成する金属の過
酸化物を生成させ、α−ＦｅＯＯＨ粉体表面に沈着させ
る。したがって、α−ＦｅＯＯＨ粉体各々の表面をＦｅ
以外の磁性酸化物を構成する過酸化物で均一に被覆する
ことが可能である。Further, according to the present invention, a peroxide of a metal constituting a magnetic oxide other than Fe is produced in a suspension of α-FeOOH powder and deposited on the surface of the α-FeOOH powder. Therefore, the surface of each α-FeOOH powder is
It is possible to uniformly coat with a peroxide constituting a magnetic oxide other than.
【００２３】又、本発明で得られる過酸化物の溶解度積
は１０-11 と、蓚酸塩法で得られる蓚酸塩化合物の溶解
度積１０-7〜１０-8と比較して３〜４桁も小さく、生成
沈殿物の溶出が大幅に抑えられる。Further, the solubility product of the peroxide obtained in the present invention is 10 -11 , which is 3 to 4 digits as compared with the solubility product 10 -7 to 10 -8 of the oxalate compound obtained by the oxalate method. It is small and the elution of the produced precipitate is greatly suppressed.
【００２４】[0024]
【発明の実施の形態】以下、本発明の磁性酸化物粉体の
製造方法について、まずＭｎ−Ｚｎ系フェライトを例と
してその実施の形態を説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of the method for producing a magnetic oxide powder of the present invention will be described by taking Mn-Zn ferrite as an example.
【００２５】（実施例１）表１に示す組成になるよう
に、水溶性の金属化合物である硝酸マンガン及び硝酸亜
鉛を正確に秤量分取して純水に溶解し、ＮａＯＨを加え
て溶液のｐＨを５〜６に調整した後、正確に秤量分取し
たα−ＦｅＯＯＨ粉体を高速攪拌しながら加えて懸濁液
を作製した。その後、ＮａＯＨを加え懸濁液のｐＨを９
以上に保ちながら、過酸化物を生成させるのに必要な過
酸化水素水をゆっくりと加えてＭｎ及びＺｎを構成金属
元素とする過酸化物をα−ＦｅＯＯＨ粉体表面に沈着さ
せて前駆体沈殿物を作製した。Example 1 Manganese nitrate and zinc nitrate, which are water-soluble metal compounds, were accurately weighed out and dissolved in pure water so that the composition shown in Table 1 was obtained, and NaOH was added to form a solution. After adjusting the pH to 5 to 6, accurately weighed and collected α-FeOOH powder was added with high-speed stirring to prepare a suspension. Then add NaOH to adjust the pH of the suspension to 9
While keeping the above, the hydrogen peroxide solution necessary for generating the peroxide is slowly added to deposit the peroxide having Mn and Zn as the constituent metal elements on the surface of the α-FeOOH powder, thereby precipitating the precursor. The thing was made.
【００２６】その後、得られた前駆体沈殿物の洗浄を繰
り返してＮａ+ を除去し、熱風乾燥器内で乾燥させた
後、６５０〜９００℃で熱処理を行ないＭｎ−Ｚｎフェ
ライトの粉体を得た。Thereafter, the obtained precursor precipitate was repeatedly washed to remove Na + and dried in a hot air drier, and then heat-treated at 650 to 900 ° C. to obtain Mn-Zn ferrite powder. It was
【００２７】[0027]
【表１】 [Table 1]
【００２８】次に、これら熱処理済み粉体について、Ｘ
線回折（ＸＲＤ）分析、マグネットによる磁性化の有無
の定性確認を行なった。その結果を表２に示す。Next, regarding these heat-treated powders, X
Line diffraction (XRD) analysis and qualitative confirmation of the presence or absence of magnetization by a magnet were performed. Table 2 shows the results.
【００２９】（比較例１）表１に示す組成になるよう
に、酸化鉄（Ｆｅ2 Ｏ3 ）、酸化マンガン及び酸化亜鉛
の粉体を正確に秤量分取し、混合粉砕した後７００〜９
５０℃で熱処理を行ないＭｎ−Ｚｎフェライトの粉体を
得た。以下、実施例１と同様にＸ線回折（ＸＲＤ）分
析、マグネットによる磁性化の有無の定性確認を行なっ
た。その結果を表２に示す。Comparative Example 1 Iron oxide (Fe 2 O 3 ), manganese oxide and zinc oxide powders were accurately weighed out so as to have the composition shown in Table 1, mixed and ground, and then 700 to 9
Heat treatment was performed at 50 ° C. to obtain Mn—Zn ferrite powder. Thereafter, as in Example 1, X-ray diffraction (XRD) analysis and qualitative confirmation of the presence or absence of magnetization by a magnet were performed. Table 2 shows the results.
【００３０】（比較例２）表１に示す組成になるよう
に、硝酸マンガン及び硝酸亜鉛を正確に秤量分取して純
水に溶解し、ＮａＯＨを加えて溶液のｐＨを５〜６に調
整した後、正確に秤量分取した酸化鉄（Ｆｅ2 Ｏ3 ）粉
体を高速攪拌しながら加えて懸濁液を作製した。その
後、ＮａＯＨを加え懸濁液のｐＨを９以上に保ちなが
ら、過酸化物を生成させるのに必要な過酸化水素水をゆ
っくりと加えてＭｎ及びＺｎを構成金属元素とする過酸
化物をＦｅ2 Ｏ3 粉体表面に沈着させて前駆体沈殿物を
作製した。Comparative Example 2 Manganese nitrate and zinc nitrate were accurately weighed out and dissolved in pure water so that the composition shown in Table 1 was obtained, and NaOH was added to adjust the pH of the solution to 5-6. After that, an iron oxide (Fe 2 O 3 ) powder that was accurately weighed out was added with high speed stirring to prepare a suspension. Thereafter, while adding NaOH to maintain the pH of the suspension at 9 or more, the hydrogen peroxide solution necessary for generating peroxide is slowly added to convert the peroxide containing Mn and Zn as constituent metal elements to Fe. A precursor precipitate was prepared by depositing it on the surface of 2 O 3 powder.
【００３１】その後、得られた前駆体沈殿物の洗浄を繰
り返してＮａ+ を除去し、熱風乾燥器内で乾燥させた
後、６００〜９５０℃で熱処理を行ないＭｎ−Ｚｎフェ
ライトの粉体を得た。以下、実施例１と同様にＸ線回折
（ＸＲＤ）分析、マグネットによる磁性化の有無の定性
確認を行なった。その結果を表２に示す。Thereafter, the obtained precursor precipitate was repeatedly washed to remove Na + and dried in a hot air drier, and then heat-treated at 600 to 950 ° C. to obtain Mn-Zn ferrite powder. It was Thereafter, as in Example 1, X-ray diffraction (XRD) analysis and qualitative confirmation of the presence or absence of magnetization by a magnet were performed. Table 2 shows the results.
【００３２】[0032]
【表２】 [Table 2]
【００３３】表２に示す通り、Ｘ線回折（ＸＲＤ）分析
結果では、実施例１、比較例１、２の粉体とも、７００
℃以上の熱処理で、スピネル化合物の回折ピークが検出
されている。一方、マグネットによる磁性の発現の有無
のチェックの結果では、実施例１の粉体の場合には７０
０℃以上の熱処理で磁性の発現が認められているのに対
して、比較例１、２の粉体は熱処理が８００℃以上にな
らないと磁性の発現が認められない。As shown in Table 2, the X-ray diffraction (XRD) analysis results show that the powders of Example 1 and Comparative Examples 1 and 2 were 700
The diffraction peak of the spinel compound is detected by the heat treatment at ℃ or above. On the other hand, the result of checking the presence or absence of magnetism by the magnet shows 70 in the case of the powder of Example 1.
While the magnetism is exhibited by the heat treatment at 0 ° C. or higher, the powders of Comparative Examples 1 and 2 do not exhibit the magnetism unless the heat treatment is performed at 800 ° C. or higher.
【００３４】これは比較例１、２の粉体は、７００℃の
熱処理ではスピネル化合物の生成割合が少なく、磁性が
発現しないことを示しており、比較例１、２の粉体の表
面活性が実施例１の粉体と比較して低いことを示すもの
である。This shows that the powders of Comparative Examples 1 and 2 have a small spinel compound production rate by the heat treatment at 700 ° C. and do not exhibit magnetism, and the powders of Comparative Examples 1 and 2 have surface activity. It is shown to be lower than that of the powder of Example 1.
【００３５】又、α−ＦｅＯＯＨ粉体表面に過酸化物を
担持固定した実施例１と、酸化鉄（Ｆｅ2 Ｏ3 ）粉体表
面に過酸化物を担持固定した比較例２とを比較すると、
比較例２の場合は、酸化鉄の反応性が悪いためスピネル
化反応が起こりにくく、磁性の発現温度が実施例１の場
合よりも１００℃高い８００℃以上となっている。Further, comparing Example 1 in which a peroxide is carried and fixed on the surface of α-FeOOH powder and Comparative Example 2 in which a peroxide is carried and fixed on the surface of iron oxide (Fe 2 O 3 ) powder, are compared. ,
In the case of Comparative Example 2, the reactivity of iron oxide is poor, so that the spinelization reaction is unlikely to occur, and the temperature for developing magnetism is 800 ° C. or higher, which is 100 ° C. higher than in the case of Example 1.
【００３６】以上の実施例１及び比較例１、２から明ら
かなように、α−ＦｅＯＯＨ粉体表面上に、Ｆｅ以外の
磁性酸化物を構成するＭｎ及びＺｎ金属の過酸化物を担
持固定した前駆体を用いることで、スピネル化温度の低
温化を図ることができる。As is clear from Example 1 and Comparative Examples 1 and 2 described above, the Mn and Zn metal peroxides constituting the magnetic oxide other than Fe are supported and fixed on the surface of the α-FeOOH powder. By using the precursor, the spinelization temperature can be lowered.
【００３７】次に、本発明の磁性酸化物粉体の製造方法
について、Ｎｉ−Ｚｎ系フェライトを例としてその実施
の形態を説明する。Next, an embodiment of the method for producing the magnetic oxide powder of the present invention will be described by taking Ni-Zn ferrite as an example.
【００３８】（実施例２）表３に示す組成になるよう
に、水溶性の金属化合物である硝酸ニッケル及び硝酸亜
鉛を正確に秤量分取して純水に溶解し、ＮａＯＨを加え
て溶液のｐＨを５〜６に調整した後、正確に秤量分取し
たα−ＦｅＯＯＨ粉体を高速攪拌しながら加えて懸濁液
を作製した。その後、ＮａＯＨを加え懸濁液のｐＨを９
以上に保ちながら、過酸化物を生成させるのに必要な過
酸化水素水をゆっくりと加えてＮｉ及びＺｎを構成金属
元素とする過酸化物をα−ＦｅＯＯＨ粉体表面に沈着さ
せて前駆体沈殿物を作製した。Example 2 Water-soluble metallic compounds, nickel nitrate and zinc nitrate, were accurately weighed out and dissolved in pure water so that the composition shown in Table 3 was obtained, and NaOH was added to the solution. After adjusting the pH to 5 to 6, accurately weighed and collected α-FeOOH powder was added with high-speed stirring to prepare a suspension. Then add NaOH to adjust the pH of the suspension to 9
While keeping the above, the hydrogen peroxide solution necessary to generate the peroxide is slowly added to deposit a peroxide containing Ni and Zn as constituent metal elements on the α-FeOOH powder surface to form a precursor precipitate. The thing was made.
【００３９】その後、得られた前駆体沈殿物の洗浄を繰
り返してＮａ+ を除去し、熱風乾燥器内で乾燥させた
後、３１０〜７００℃で熱処理を行ないＮｉ−Ｚｎフェ
ライトの粉体を得た。Thereafter, the obtained precursor precipitate was repeatedly washed to remove Na + , dried in a hot air drier, and then heat-treated at 310 to 700 ° C. to obtain Ni—Zn ferrite powder. It was
【００４０】[0040]
【表３】 [Table 3]
【００４１】次に、これら熱処理済み粉体について、Ｘ
線回折（ＸＲＤ）分析、マグネットによる磁性化の有無
の定性確認を行なった。その結果を表４に示す。Next, regarding these heat-treated powders, X
Line diffraction (XRD) analysis and qualitative confirmation of the presence or absence of magnetization by a magnet were performed. Table 4 shows the results.
【００４２】（比較例３）表３に示す組成になるよう
に、酸化鉄（Ｆｅ2 Ｏ3 ）、酸化ニッケル及び酸化亜鉛
の粉体を正確に秤量分取し、混合粉砕した後６００〜７
００℃で熱処理を行ないＮｉ−Ｚｎフェライトの粉体を
得た。以下、実施例２と同様にＸ線回折（ＸＲＤ）分
析、マグネットによる磁性化の有無の定性確認を行なっ
た。その結果を表４に示す。COMPARATIVE EXAMPLE 3 Iron oxide (Fe 2 O 3 ), nickel oxide and zinc oxide powders were accurately weighed out so as to have the composition shown in Table 3, mixed and pulverized, and then 600 to 7
Heat treatment was performed at 00 ° C. to obtain Ni—Zn ferrite powder. Thereafter, as in Example 2, X-ray diffraction (XRD) analysis and qualitative confirmation of the presence or absence of magnetization by a magnet were performed. Table 4 shows the results.
【００４３】（比較例４）表３に示す組成になるよう
に、硝酸ニッケル及び硝酸亜鉛を正確に秤量分取して純
水に溶解し、ＮａＯＨを加えて溶液のｐＨを５〜６に調
整した後、正確に秤量分取した酸化鉄（Ｆｅ2 Ｏ3 ）粉
体を高速攪拌しながら加えて懸濁液を作製した。その
後、ＮａＯＨを加え懸濁液のｐＨを９以上に保ちなが
ら、過酸化物を生成させるのに必要な過酸化水素水をゆ
っくりと加えてＮｉ及びＺｎを構成金属元素とする過酸
化物をＦｅ2 Ｏ3 粉体表面に沈着させて前駆体沈殿物を
作製した。Comparative Example 4 Nickel nitrate and zinc nitrate were accurately weighed out and dissolved in pure water so that the composition shown in Table 3 was obtained, and NaOH was added to adjust the pH of the solution to 5-6. After that, an iron oxide (Fe 2 O 3 ) powder that was accurately weighed out was added with high speed stirring to prepare a suspension. Thereafter, while adding NaOH to maintain the pH of the suspension at 9 or more, the hydrogen peroxide solution necessary for producing peroxide is slowly added to convert the peroxide containing Ni and Zn as constituent metal elements to Fe. A precursor precipitate was prepared by depositing it on the surface of 2 O 3 powder.
【００４４】その後、得られた前駆体沈殿物の洗浄を繰
り返してＮａ+ を除去し、熱風乾燥器内で乾燥させた
後、３１０〜７００℃で熱処理を行ないＮｉ−Ｚｎフェ
ライトの粉体を得た。以下、実施例２と同様にＸ線回折
（ＸＲＤ）分析、マグネットによる磁性化の有無の定性
確認を行なった。その結果を表４に示す。Thereafter, the obtained precursor precipitate was repeatedly washed to remove Na + , dried in a hot air drier, and then heat-treated at 310 to 700 ° C. to obtain Ni—Zn ferrite powder. It was Thereafter, as in Example 2, X-ray diffraction (XRD) analysis and qualitative confirmation of the presence or absence of magnetization by a magnet were performed. Table 4 shows the results.
【００４５】[0045]
【表４】 [Table 4]
【００４６】表４に示す通り、実施例２の粉体は、３１
０℃の熱処理でスピネル化合物が生成し、４５０℃の熱
処理で磁性の発現がマグネットにより認められている。
これに対し、比較例３の粉体は、７００℃以上で熱処理
しないとスピネル化合物が生成せず、磁性の発現もマグ
ネットにより認められない。又、比較例４の粉体は、４
５０℃以上で熱処理しないとスピネル化合物が生成せ
ず、６００℃以上で熱処理しないと磁性の発現が認めら
れない。As shown in Table 4, the powder of Example 2 was 31
It is recognized that the spinel compound is generated by the heat treatment at 0 ° C. and the magnetism is expressed by the heat treatment at 450 ° C.
On the other hand, in the powder of Comparative Example 3, a spinel compound is not formed unless heat treatment is performed at 700 ° C. or higher, and magnetism is not recognized by the magnet. Further, the powder of Comparative Example 4 is 4
The spinel compound is not formed unless heat-treated at 50 ° C. or higher, and the magnetism is not recognized unless heat-treated at 600 ° C. or higher.
【００４７】以上の実施例２及び比較例３、４から明ら
かなように、α−ＦｅＯＯＨ粉体表面上に、Ｆｅ以外の
磁性酸化物を構成するＮｉ及びＺｎ金属の過酸化物を担
持固定した前駆体を用いることで、スピネル化温度の低
温化を図ることができる。As is clear from Example 2 and Comparative Examples 3 and 4 described above, the peroxides of Ni and Zn metals constituting the magnetic oxides other than Fe are supported and fixed on the surface of the α-FeOOH powder. By using the precursor, the spinelization temperature can be lowered.
【００４８】なお、上記発明の実施の形態において、Ｍ
ｅ金属イオン源として硝酸マンガン、硝酸ニッケル及び
硝酸亜鉛を用いているが、本発明はこれのみに限定され
るものではない。即ち、ＭｅとしてはＦｅ以外のフェラ
イトを構成する元素であるＭｎ、Ｎｉ、Ｚｎ、Ｃｕ、Ｃ
ｏのうち少なくとも１種類以上を適宜用いることができ
る。又、その化合物の形態としては、硝酸塩などの水溶
性化合物以外に、硝酸、塩酸、硫酸、酢酸などの酸に可
溶なＭｅ化合物を適宜用いることができる。In the embodiment of the invention described above, M
Although manganese nitrate, nickel nitrate and zinc nitrate are used as the metal ion source, the present invention is not limited thereto. That is, as Me, Mn, Ni, Zn, Cu, and C, which are elements other than Fe, which constitute ferrite
At least one kind of o can be appropriately used. Further, as the form of the compound, in addition to water-soluble compounds such as nitrates, Me compounds soluble in acids such as nitric acid, hydrochloric acid, sulfuric acid and acetic acid can be appropriately used.
【００４９】そして、上記発明の実施の形態に示すよう
に、Ｍｎ−Ｚｎ系フェライトの場合には、７００〜９０
０℃で熱処理することにより磁性酸化物粉体を得ること
ができ、Ｎｉ−Ｚｎ系フェライトの場合には、４５０〜
７００℃で磁性酸化物粉体を得ることができる。Then, as shown in the above embodiment of the present invention, in the case of Mn-Zn type ferrite, it is 700 to 90.
Magnetic oxide powder can be obtained by heat treatment at 0 ° C., and in the case of Ni—Zn type ferrite, 450 to
A magnetic oxide powder can be obtained at 700 ° C.
【００５０】又、アルカリ源としてＮａＯＨを用いてい
るが、これのみに限定されるものではない。即ち、ＫＯ
Ｈ又はＬｉＯＨを用いることができる。さらに、Ｍｅ金
属イオンが可溶性アンミン錯体を形成しない場合には、
ＮＨ4 ＯＨを用いることもできる。Although NaOH is used as the alkali source, it is not limited to this. That is, KO
H or LiOH can be used. Further, if the Me metal ion does not form a soluble ammine complex,
NH 4 OH can also be used.
【００５１】[0051]
【発明の効果】以上の説明から明らかなように、本発明
のα−ＦｅＯＯＨ粒子表面にＦｅ以外の磁性酸化物を構
成する金属元素の過酸化物を担持固定した前駆体粉体を
熱処理する方法によれば、従来よりも低い熱処理温度で
スピネル化することができる。As is apparent from the above description, the method of heat-treating the precursor powder in which the peroxide of the metal element constituting the magnetic oxide other than Fe is immobilized on the surface of the α-FeOOH particles of the present invention. According to the method, spinel can be formed at a heat treatment temperature lower than that of the conventional one.
【００５２】したがって、熱処理による粉体の凝集を抑
えた、粒径が小さく表面活性が高く易焼結性の磁性酸化
物粉体を得ることができる。Therefore, it is possible to obtain a magnetic oxide powder having a small particle size, high surface activity, and easy sinterability, in which agglomeration of the powder due to heat treatment is suppressed.
【００５３】又、本発明の方法は、金属アルコキシドや
アセチルアセトネート化合物のような高価な原料を用い
ないため、安価に磁性酸化物粉体を得ることができる。Further, since the method of the present invention does not use expensive raw materials such as metal alkoxides and acetylacetonate compounds, magnetic oxide powder can be obtained at low cost.
【００５４】さらに、廃液処理として、従来の蓚酸塩法
の場合に必要であったＢＯＤを下げるための曝気処理や
酸性排水の中和処理が必要ない。Further, as the waste liquid treatment, the aeration treatment for lowering the BOD and the neutralization treatment of the acidic waste water which are required in the conventional oxalate method are not required.
Claims (5)
ｎ、Ｎｉ、Ｚｎ、Ｃｕ、Ｃｏのうち少なくとも１種類の
２価の金属元素）で示される磁性酸化物粉体の製造にお
いて、 α−ＦｅＯＯＨ粉体表面に前記Ｍｅ金属元素の過酸化物
を担持固定した後、熱処理することを特徴とする磁性酸
化物粉体の製造方法。1. The general formula MeFe 2 O 4 (where Me is M
In manufacturing a magnetic oxide powder represented by at least one divalent metal element of n, Ni, Zn, Cu, and Co), a peroxide of the Me metal element is supported on the surface of the α-FeOOH powder. A method for producing a magnetic oxide powder, which comprises heat-treating after fixing.
ｎ−Ｚｎ系フェライトであるときは７００〜９００℃で
あり、磁性酸化物粉体がＮｉ−Ｚｎ系フェライトである
ときは４５０〜７００℃であることを特徴とする請求項
１記載の磁性酸化物粉体の製造方法。2. The heat treatment temperature is M for the magnetic oxide powder.
The magnetic oxide according to claim 1, wherein the temperature is 700 to 900 ° C. when it is an n-Zn ferrite, and the temperature is 450 to 700 ° C. when the magnetic oxide powder is a Ni-Zn ferrite. Powder manufacturing method.
ＯＨ粉体を分散させたスラリー中に、アルカリ及び過酸
化水素を加えて前記Ｍｅ金属の過酸化物を生成させ、該
過酸化物を前記α−ＦｅＯＯＨ粉体表面に担持固定させ
ることを特徴とする請求項１記載の磁性酸化物粉体の製
造方法。3. A solution containing Me metal ions is provided with α-FeO 2.
In a slurry in which OH powder is dispersed, alkali and hydrogen peroxide are added to generate a peroxide of the Me metal, and the peroxide is supported and fixed on the surface of the α-FeOOH powder. The method for producing a magnetic oxide powder according to claim 1.
金属化合物又は硝酸、塩酸、硫酸及び酢酸のうちいずれ
かに可溶なＭｅ金属化合物であることを特徴とする請求
項３記載の磁性酸化物粉体の製造方法。4. The Me metal ion source is water-soluble Me.
4. The method for producing magnetic oxide powder according to claim 3, wherein the metal compound is a metal compound soluble in any one of nitric acid, hydrochloric acid, sulfuric acid and acetic acid.
びＬｉＯＨのうち少なくとも１種類であることを特徴と
する請求項３記載の磁性酸化物粉体の製造方法。5. The method for producing a magnetic oxide powder according to claim 3, wherein the alkali source is at least one of NaOH, KOH, and LiOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7295635A JPH09142848A (en) | 1995-11-14 | 1995-11-14 | Production of magnetic oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7295635A JPH09142848A (en) | 1995-11-14 | 1995-11-14 | Production of magnetic oxide powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09142848A true JPH09142848A (en) | 1997-06-03 |
Family
ID=17823207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09142848A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743611A (en) * | 2015-03-20 | 2015-07-01 | 沈阳化工大学 | Method for preparing magnetic magnesium ferrite nanorods by taking basic iron oxide nanorods as templates |
-
1995
- 1995-11-14 JP JP7295635A patent/JPH09142848A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743611A (en) * | 2015-03-20 | 2015-07-01 | 沈阳化工大学 | Method for preparing magnetic magnesium ferrite nanorods by taking basic iron oxide nanorods as templates |
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