JPS6090828A - Manufacture of needlelike spinel ferrite powder - Google Patents

Abstract

PURPOSE:To form the titled powder giving a high density sintered ferrite body with crystal anisotropy by mixing needlelike gamma-Fe2O3 powder or the like with the hydroxide or oxide of Mn or the like and sintering the mixture. CONSTITUTION:An alkali such as NaOH is added to an aqueous soln. of a salt of Mn, Zn or Ni such as zinc sulfate to precipitate the hydroxide or oxide of Mn, Zn or Ni such as basic zinc hydroxide. Needlelike gamma-Fe2O3, alpha-Fe2O3 or alpha-FeOOH is mixed with said hydroxide or oxide, and the mixture is sintered at <=700 deg.C in an inert gaseous atmosphere to manufacture needlelike spinel ferrite powder. A precipitate produced by suspending gamma-Fe2O3 or the like in said aqueous salt soln. and adding an alkali to the suspension may be sintered.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、電子工業用フェライト多結晶体もしくは単結
晶体作成用に用いる針状スピネルフェライト粉体の製造
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing acicular spinel ferrite powder used for producing ferrite polycrystals or single crystals for the electronic industry.

従来例の構成とその問題点 従来、フェライト用原料粉体としては、Ｆｅ２Ｏ３、Ｍ
ｎ３０＜　、　Ｚ−ｎ　ＯｌＮｉＯｌＭ　ｎ　Ｃ０３な
ど金属酸化物または金属炭酸塩や、各種異種金属の硫酸
塩水溶液をアルカリで中和沈澱させた共沈原料粉体があ
る。しかし、前者の金属酸化物や金属炭酸塩を用いた場
合、粒径が不ぞろいであったり、粒形状も一定でなく、
又加熱時に炭酸城をうた。又、後者の共沈原料は、比較
的純度も高く、粒度分布も良いが、粉体形状がヌピネ、
レフエライトが立方晶系の結晶構造をしているため立方
体をしておシ、そのため結晶異方性を有するフェライト
焼結体の作成ができなかったと共に、その原料粉体の表
面活性が高いため、焼結体作成のため加熱する途中で過
度に酸化したシするため、高密度フェライト焼結体の製
造が回灯な不利益があった。Structure of conventional example and its problems Conventionally, raw material powder for ferrite has been Fe2O3, M
There are coprecipitation raw material powders prepared by neutralizing and precipitating aqueous solutions of metal oxides or metal carbonates such as n30<, Z-nOlNiOlMnC03, and sulfates of various metals with alkali. However, when the former metal oxides and metal carbonates are used, the particle sizes are uneven and the particle shape is not constant.
Also, it sings carbonated castle when heated. In addition, the latter coprecipitation raw material has relatively high purity and good particle size distribution, but the powder shape is
Because leferite has a cubic crystal structure, it is cubic, so it was not possible to create a ferrite sintered body with crystal anisotropy, and the raw material powder had high surface activity. Excessive oxidation occurs during heating to create a sintered body, which has the disadvantage of making it difficult to produce a high-density ferrite sintered body.

発明の目的 本発明の目的は結晶異方性を有するフェライト焼結体、
又は、この焼結体を出発材料とするフェライト単結晶体
作成に用いるゑ状異方性を有スルスピネル原料粉体を提
供することであシ、さらには高密度焼結体作成用の原料
粉体を提供することである。Object of the invention The object of the invention is to provide a ferrite sintered body having crystal anisotropy,
Alternatively, it is possible to provide a spinel raw material powder with anisotropy for use in producing a ferrite single crystal using this sintered body as a starting material, and furthermore, to provide a raw material powder for producing a high-density sintered body. The goal is to provide the following.

発明の構成 本発明は、針状γ−Ｆｅ２０３、同形状α−Ｆｅ２０３
　および針状α−ＦｅＯＯＨの少くとも一種類の粉体と
、Ｍｎ、ＺｎまたはＮｉの塩の水溶液からアルカリで沈
澱させて得たＭｎ、ＺｎまたはＮｉの水酸化物または酸
化物の少くとも１種類との混合物を、７００℃以下の温
度で焼結せしめることにより針状スピネルフェライト粉
体を得ることを特徴とする針状スピネルフェライト粉体
の製造法に係るものである。Structure of the Invention The present invention provides acicular γ-Fe203, same-shaped α-Fe203
and at least one kind of powder of acicular α-FeOOH and at least one kind of hydroxide or oxide of Mn, Zn or Ni obtained by precipitation with alkali from an aqueous solution of a salt of Mn, Zn or Ni. This invention relates to a method for producing acicular spinel ferrite powder, characterized in that acicular spinel ferrite powder is obtained by sintering a mixture of

本発明に従って針状γ−Ｆｅ２０３、同形状α−Ｆｅｚ
０３　またはａ−ＦｅＯＯＨの粉体とＭ　ｎ　。According to the present invention, acicular γ-Fe203, the same shape α-Fez
03 or a-FeOOH powder and M n .

ＺｎまたはＮｉの水酸化物または酸化物との混合物を得
るには、（１）予めＭｎ、ＺｎまたはＮｉの塩の水溶液
からアルカリで沈澱させて得たＭｎ、ＺｎまたはＮｉの
水酸化物または酸化物を調製しておき、これに針状γ−
Ｆ　ｅ２０３　等を混合させてもよいし、または、（２
）針状ｒ−Ｆｅ２０３　等を、Ｍｎ、ＺｎまたはＮｉの
水溶性塩の水溶液中に混合し、この水溶液にアルカリを
添加して、Ｍｎ、Ｚｎ４たはＮｉの水酸化物または酸化
物の沈澱物を生成せしめ、この系を水洗、乾燥すること
によっても同様な混合物を得ることができる。To obtain a mixture with a hydroxide or oxide of Zn or Ni, (1) a hydroxide or oxide of Mn, Zn or Ni obtained by precipitating with alkali from an aqueous solution of a salt of Mn, Zn or Ni; A needle-shaped γ-
Fe203 etc. may be mixed, or (2
) Acicular r-Fe203 etc. are mixed into an aqueous solution of a water-soluble salt of Mn, Zn or Ni, and an alkali is added to this aqueous solution to precipitate the hydroxide or oxide of Mn, Zn4 or Ni. A similar mixture can also be obtained by generating, washing this system with water, and drying it.

三元以上の金属の針状ヌピネルフエライト粉体を製造す
るには、Ｍｎ、ＺｎおよびＮｉのうち２種以上の金属の
水酸化物または酸化物を同時に使用するか、あるいは、
Ｍｎ、ＺｎおよびＮｉのうちの一つの金属の水酸化物ま
たは酸化物と針状γ−Ｆｅ２０３　等とを本発明方法に
従って焼結させた後、かくして得られた焼結体の粉末を
更に他の金属（Ｍｎ、、ＺｎおよびＮｉのうち）の水酸
化物または酸化物と共に焼結させること、あるいは更に
同様の操作を繰返すととによってこれを製造することが
できる。To produce acicular Nupinell ferrite powder of ternary or more metals, hydroxides or oxides of two or more metals among Mn, Zn, and Ni may be used simultaneously, or
After sintering the hydroxide or oxide of one of the metals Mn, Zn and Ni and acicular γ-Fe203 etc. according to the method of the present invention, the powder of the sintered body thus obtained is further sintered with other metals. This can be produced by sintering with hydroxides or oxides of metals (among Mn, Zn and Ni) or by further repeating the same operation.

実施例の説明 以下、本発明の内容を実施例に基いて詳細に説明する。Description of examples Hereinafter, the content of the present invention will be explained in detail based on examples.

実施例〔１〕 試薬特級の硫酸亜鉛ＺｎＳ０４７Ｈ２０２８７５５ｇを
溶解した１モル／４溶液に試薬特級のＮａＯＨから作成
しｆｃ−１モ）ｖ／　ｌ　ＮａＯＨ溶液を滴加し、７１
）Ｎ７にて沈澱させた塩基性水酸化亜鉛３Ｚｎ（ＱＨ）
２−ＺｎＳＯ４−４Ｈ２０５３１，５ｇを調製する。こ
の沈澱物をよく水洗後、乾燥し、これと市販の長さ０．
５μｍ％　ｉｏ。Example [1] To a 1 mol/4 solution in which 2028755 g of reagent-grade zinc sulfate ZnS047H was dissolved, a fc-1 mo) v/l NaOH solution prepared from reagent-grade NaOH was added dropwise, and 71
) Basic zinc hydroxide 3Zn (QH) precipitated in N7
Prepare 1.5 g of 2-ZnSO4-4H2053. This precipitate was thoroughly washed with water and dried, and this was combined with a commercially available length of 0.
5 μm% io.

０５　μｍ程度の針状ｒ　−Ｆ　ｅ２０３１５９．異を
ボールミルにて湿式混合し、十分混合後、乾燥し、これ
を９９．９９％以上の高純度Ｎ２　ガス気流中で、６０
０　”Ｃで２時間熱処理を行って焼結物を得た。比較の
ため、熱処理温度だけを７００”Ｃと８００℃で行って
得た焼結物も作成した。それぞれの熱処理後の焼結物の
粉体はＸ線回折法によりＺ　ｎ　Ｆ　ｅ　２０４である
事が確認された。へ処理温度を３００〜４００”０位に
下げると未反応部分の存在が認められた。更に透過電子
顕微鏡により、その粉体形状を観察すると、６００″Ｃ
及び７００”Ｃで熱処理したものでは、針状であったが
、８００゛Ｃで熱処理したものでは粒状に変化していた
。Acicular r -F e203159.05 μm. The different materials were wet mixed in a ball mill, thoroughly mixed, dried, and mixed in a stream of high purity N2 gas of 99.99% or higher for 60 min.
A sintered product was obtained by performing heat treatment at 0"C for 2 hours. For comparison, sintered products obtained by performing heat treatment only at 700"C and 800"C were also created. The powder of the sintered product after each heat treatment was confirmed to be Z n Fe 204 by X-ray diffraction method. When the treatment temperature was lowered to 300-400"C, the presence of unreacted portions was observed. Furthermore, when the powder shape was observed using a transmission electron microscope, it was found that the temperature at 600"C
Those heat-treated at 700"C were acicular, but those heat-treated at 800"C were granular.

上記の実施例では、硫酸亜鉛を用いた例を示し念が、硫
酸亜鉛以外の酢酸亜鉛、塩化亜鉛、硝酸亜鉛等の塩を用
いて作成された水酸化物、又は酸化物を利用することも
できる。但し、残留陰イオンの影響を考慮して使用する
亜鉛水酸化物または酸化物を選択する必要がある。The above example uses zinc sulfate, but hydroxides or oxides prepared using salts other than zinc sulfate such as zinc acetate, zinc chloride, and zinc nitrate may also be used. can. However, it is necessary to select the zinc hydroxide or oxide to be used in consideration of the influence of residual anions.

出発原料についても針状のα−Ｆｅ２０３　又は針状α
−Ｆｅ００Ｈを用いても、針状スピネルフェライト粉体
が合成できるが、完全な単−相からなる原料粉体を得る
には針状γ−Ｆｅ２０３を用いた方が好ましい。The starting material is also acicular α-Fe203 or acicular α
Although acicular spinel ferrite powder can be synthesized using -Fe00H, it is preferable to use acicular γ-Fe203 in order to obtain a completely single-phase raw material powder.

実　施　例　〔２〕 試薬特級の硫酸マンガンを溶解した１モル／ｌ溶液に、
試薬特級のＮａＯＨから作成した１モｌ　／　ｌ　Ｎ　
ａ　ＯＨ溶液を滴加し、ｐＨｓで沈澱させて得た酸化マ
ンガンＭｎ３０３の沈澱物をよく水洗、乾燥し、これと
実施例〔１〕に記載の方法で得た塩基性水酸化亜鉛（水
洗、乾燥後のもの）および針状γ−Ｆｅ２０３とを混合
し、実施例〔ｌ〕と同様にしてＮ２ガス気流中で６００
°Ｃで熱処理して粉末焼結物を得た。なお、酸化マンガ
ン：塩基性水酸化亜鉛：針状γ−Ｆｅ２０３の配合比率
は　：であった。かくして得られた焼結物 は針状のＭｎ−Ｚ’ｎ−フェライト粉末であった。Example [2] In a 1 mol/l solution of reagent-grade manganese sulfate,
1 mol/l N made from reagent grade NaOH
a The precipitate of manganese oxide Mn303 obtained by adding dropwise an OH solution and precipitating at pHs was thoroughly washed with water and dried, and this and the basic zinc hydroxide obtained by the method described in Example [1] (washed with water, After drying) and acicular γ-Fe203 were mixed and heated in a N2 gas stream for 600 min in the same manner as in Example [l].
A powder sintered product was obtained by heat treatment at °C. The blending ratio of manganese oxide: basic zinc hydroxide: acicular γ-Fe203 was as follows. The sintered product thus obtained was an acicular Mn-Z'n-ferrite powder.

同様に、Ｎ１とＺｎの沈澱物と針状γ−Ｆｅ２０３　と
の混合物を７００”Ｃ以下で熱処理すると、針状２〆Ｐ
ｉｌｌのＮｉ−Ｚｎフェライトの原料粉体が合成さ扛た
。Similarly, when a mixture of N1 and Zn precipitates and acicular γ-Fe203 is heat-treated at 700"C or less, acicular 2〆P
A raw material powder of Ni-Zn ferrite was synthesized.

実施例〔３〕 実施例〔１〕で用いた針状γ−Ｆｅ２０３　１５０ｇを
濃度１モルの硫酸亜鉛液ｌｌ中に投入し、よく混合攪拌
を行ない、これに１モル濃度のＮａＯＨ溶液を滴下し、
ｐＨを７前後になるまで加えた。滴下後、沈澱物をよく
水洗し、乾燥後Ｎ２ガス気流中で６００°Ｃ２時間熱処
理を行った。得られた焼結原料粉体は、Ｘ線回析により
Ｚ　ｎ　Ｆ　ｅ２０４である事が確認され、更に、透過
電子顕微鏡観察によシ、針状粉体である事が確認された
。上記の実施例〔３〕ではγ−Ｆｅ２０ｓ−Ｚｎ　化合
物の組み合せについて述べたが、実施例〔１〕および〔
２〕の説明に関して述べたのと同様に、ＭｎＦｅ２Ｏ４
、Ｍｎ　−Ｚｎ　−７−ｔ−ライト、Ｎ　ｉ　Ｆ　ｅ２
０４、Ｎｉ−Ｚｎ−フェライトの各針状粉体が、実施例
〔３〕と同様な方法で合成できる。Example [3] 150 g of the acicular γ-Fe203 used in Example [1] was put into 1 molar zinc sulfate solution, mixed well and stirred, and a 1 molar NaOH solution was added dropwise thereto. ,
The pH was added until the pH was around 7. After dropping, the precipitate was thoroughly washed with water, dried, and then heat-treated at 600° C. for 2 hours in a N2 gas stream. The obtained sintering raw material powder was confirmed to be Z n Fe204 by X-ray diffraction, and was further confirmed to be needle-shaped powder by transmission electron microscopy observation. In Example [3] above, the combination of γ-Fe20s-Zn compounds was described, but in Example [1] and [
2], MnFe2O4
, Mn-Zn-7-t-lite, N i Fe2
Each needle-like powder of 04 and Ni-Zn-ferrite can be synthesized in the same manner as in Example [3].

実施例〔４〕 実施例〔１〕で作成した針状Ｚ　ｎ　Ｆ　ｅ　２０４を
出発原料間し、これを濃度１モルの硫酸Ｍｎ溶液に投入
し、混合攪拌しながら、１モルのＮａＯＨを滴下し、ｐ
Ｈａ程度になるようにした。得られた沈澱は、よく水洗
の後、Ｎ２ガヌ気流中で６００℃２時間熱処理した。得
られた原料粉体は、Ｍｎ−Ｚｎ−フェライトであり、か
つ、針状形状を保持したものであった。Example [4] The acicular Z n Fe 204 prepared in Example [1] was used as a starting material, and it was put into a 1 molar Mn sulfate solution, and while stirring, 1 molar NaOH was added dropwise. Shi, p
It was set to about Ha. The obtained precipitate was thoroughly washed with water and then heat-treated at 600° C. for 2 hours in a N2 stream. The obtained raw material powder was Mn-Zn-ferrite and maintained an acicular shape.

発明の効果 実施例〔１〕〜〔４〕で示した針状Ｍｎ−Ｚｎ−フェラ
イト原料粉体を用いて、通常のセラミックスを製造する
のと同様に、バインダーを加えた後、成形体となし、こ
れを５００℃まで空気中でそれ以上の温度ではＮ２中で
１３８０“Ｃまで昇温し、その温度で２時間保持した。Effects of the Invention Using the acicular Mn-Zn-ferrite raw material powders shown in Examples [1] to [4], a binder is added and a molded body is produced in the same way as in the production of ordinary ceramics. This was heated to 500°C in air and above to 1380"C in N2 and held at that temperature for 2 hours.

得られた焼結体は、理論密度の９９．９％の高密度Ｍｎ
−Ｚｎ−フェライトであった。比較のため、従来Ｃ１（
！　−Ｆ　ｅｚＯｓ、ＭｎＣＯ３、ＺｎＯを用いて同じ
条件下で作成した焼結体は、理論密度の９５％のもので
あった。The obtained sintered body has a high density Mn of 99.9% of the theoretical density.
-Zn-ferrite. For comparison, conventional C1 (
! A sintered body made under the same conditions using -F ezOs, MnCO3, and ZnO had a density of 95% of the theoretical density.

Claims (4)

【特許請求の範囲】[Claims] （１）針状ｒ−Ｆｅ２０３、同形状α−Ｆｅ２０３およ
び針状α−ＦｅＯＯＨの少くとも一種類の粉体と、Ｍｎ
。 ＺｎまたはＮｉの塩の水溶液からアルカリで沈澱させて
得たＭｎ５ＺｎまたはＮｉの水酸化物または酸化物の少
くとも１種類との混合物を、７００℃以下の湿度で焼結
せしめることによシ針状ヌビネルフエライト粉体を得る
ことを特徴とする針状ヌピネルフエライト粉体の製造法
。(1) At least one type of powder of acicular r-Fe203, same-shaped α-Fe203, and acicular α-FeOOH, and Mn
. A acicular shape is obtained by sintering a mixture of Mn and at least one hydroxide or oxide of Zn or Ni obtained by precipitating an aqueous solution of Zn or Ni salt with alkali at a humidity of 700°C or less. A method for producing acicular nupinell ferrite powder, characterized by obtaining nupinell ferrite powder. （２）下記の工程からなることを特徴とする特許請求の
範囲第（１１項記載の針状ヌピネルフエライト粉体の製
造法。 ａ）針状７−Ｆｅ２Ｏ３、同形状α−Ｆｅ２Ｏ３および
針状α−ＦｅＯＯＨの少くとも一種類の粉体を準備する
工程、 ｂ）Ｍｎ、ＺｎまたはＮｉの塩の水溶液からアル沈澱さ
せる工程、 Ｃ）前記ａ）工程で得た粉体と、前記ｂ）工程で得た水
酸化物または酸化物の少くとも一種類とを混合する工程
、および ｄ）前記Ｃ）工程で得た混合物を７００℃以下の温度で
熱処理して針状スピネルフェライト粉体を生成する工程
。(2) A method for producing acicular Nupinell ferrite powder according to Claim 11, characterized by comprising the following steps. a) Acicular 7-Fe2O3, same-shaped α-Fe2O3, and acicular a step of preparing at least one kind of powder of α-FeOOH; b) a step of alkaline precipitation from an aqueous solution of a salt of Mn, Zn or Ni; C) a step of preparing the powder obtained in step a) and step b). and d) heat-treating the mixture obtained in step C) at a temperature of 700°C or less to produce acicular spinel ferrite powder. Process. （３）下記工程からなることを特徴とする特許請求の範
囲第＋１１項記載の針状スピネルフェライト粉体の製造
法。 ａ）針状１−Ｆｅ２Ｏ３、同形状ａ　−Ｆｅ２０３およ
び針状α−ＦｅＯＯＨの少くとも一種類の粉体を準備す
る工程、 ｂ）前記ａ）工程で準備した粉体を、Ｍｎ、Ｚｎまたは
Ｎｉの水溶性塩の少くとも一種類を含む水溶液中に混合
する工程、 Ｃ）前記ｂ）工程で得次混合物にアルカリを添加して、
Ｍｎ、Ｚｎ’ｆたはＮｉの水酸化物または酸化物沈澱物
を生成させる工程、およびｄ）前記Ｃ）工程を終えた系
を、水洗、乾燥し、その残留物を’７００”Ｃ以下の温
度で処理して針状ヌピネルフェライト粉体を生成♀る工
程。(3) A method for producing acicular spinel ferrite powder according to claim 11, which comprises the following steps. a) Step of preparing at least one type of powder of acicular 1-Fe2O3, same-shape a-Fe203, and acicular α-FeOOH, b) The powder prepared in step a) is mixed with Mn, Zn or Ni. C) adding an alkali to the mixture obtained in step b),
The process of generating Mn, Zn'f or Ni hydroxide or oxide precipitates, and d) The system that has completed the above step C) is washed with water and dried, and the residue is heated to a temperature of 700"C or less. Process of producing acicular Nupinell ferrite powder by processing at high temperature. （４）針状ｒ−Ｐｅ２０３、同形状ａ−Ｆｅ２０３　オ
ヨＵ針状α−ＦｅＯＯＨの少くとも一種類の粉体と、Ｍ
ｎ、ＺｎまたはＮｉの塩の水溶液からアルカリで沈澱さ
せて得たＭｎ、ＺｎまたはＮｉの水酸化物または酸化物
の少くとも１種類との混合物を７００″Ｃ以下の温度で
焼結せしめることによシ針状ヌピネルフェライト粉体を
得、更に、かくして得た針状スピネルフェライト粉体と
、Ｍｎ。 ＺｎまたはＮｉの塩の水溶液からアルカリで沈澱させて
得たＭｎ％ＺｎまたはＮｉの水酸化物または酸化物の少
くとも一種との混合物を、７゜○”Ｃ以下の温度で焼結
せしめることにょシ針状スピネルフェライト粉体を得る
ことを特徴とする針状複合ヌピネルフェライト粉体の製
造法。(4) At least one type of powder of acicular r-Pe203, same-shaped a-Fe203 Oyo U acicular α-FeOOH, and M
sintering a mixture with at least one hydroxide or oxide of Mn, Zn or Ni obtained by precipitation with an alkali from an aqueous solution of a salt of Zn, Zn or Ni at a temperature of 700"C or less. A acicular spinel ferrite powder was obtained, and the acicular spinel ferrite powder thus obtained was further hydroxylated with Mn% Zn or Ni obtained by precipitation with an alkali from an aqueous solution of a salt of Mn.Zn or Ni. Acicular spinel ferrite powder is obtained by sintering a mixture with at least one type of compound or oxide at a temperature of 7°○''C or less. Manufacturing method.