JPH06279008A - Production of spherical iron nitride fine particle by sintering - Google Patents
Production of spherical iron nitride fine particle by sinteringInfo
- Publication number
- JPH06279008A JPH06279008A JP7042893A JP7042893A JPH06279008A JP H06279008 A JPH06279008 A JP H06279008A JP 7042893 A JP7042893 A JP 7042893A JP 7042893 A JP7042893 A JP 7042893A JP H06279008 A JPH06279008 A JP H06279008A
- Authority
- JP
- Japan
- Prior art keywords
- iron nitride
- particles
- iron
- sintering
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば、磁性塗料や、
磁性トナー或いは磁性キャリア等の粉末磁性材料に利用
可能な窒化鉄微粒子を製造する方法に関するものであ
る。BACKGROUND OF THE INVENTION The present invention relates to a magnetic paint,
The present invention relates to a method for producing iron nitride fine particles that can be used as a powder magnetic material such as a magnetic toner or a magnetic carrier.
【０００２】[0002]
【従来の技術】従来より、新しい機能性材料としての磁
性流体が注目されてきている。2. Description of the Related Art Conventionally, magnetic fluid as a new functional material has been attracting attention.
【０００３】例えば、磁性塗料、或いは画像形成装置用
の磁性トナー或いは磁性キャリア等、粉末磁性材料とし
ては、磁化の値が大きく、等方的な形状（針状、棒状、
板状、偏平状等、異方的形状以外の形状を指し、長径と
短径があまり違わない回転楕円体、長辺と短辺があまり
違わない直方体や多面体、又はそれに類する不定形等）
を有し、且つ均一なサイズ、特に、粒径が２０ｎｍ〜１
００μｍ程度の微粒子が必要とされる。For example, as a powder magnetic material such as a magnetic paint, a magnetic toner or a magnetic carrier for an image forming apparatus, the value of magnetization is large, and an isotropic shape (needle shape, rod shape,
It refers to a shape other than an anisotropic shape, such as a plate shape or flat shape, and has a spheroid whose major axis and minor axis do not differ much, a rectangular parallelepiped or polyhedron whose major side and minor side do not differ much, and similar irregular shapes.)
And have a uniform size, especially a particle size of 20 nm to 1
Fine particles of about 00 μm are required.
【０００４】そのため、従来は、球状に焼結させたフェ
ライト粒子、あるいはカルボニル鉄粉が用いられてい
た。Therefore, conventionally, spherically sintered ferrite particles or carbonyl iron powder has been used.
【０００５】しかしながら、フェライトは磁化が小さ
く、画像形成装置に用いられる磁性トナー等としてはあ
まり適さない。However, since ferrite has small magnetization, it is not very suitable as a magnetic toner used in an image forming apparatus.
【０００６】一方、カルボニル鉄粉は、そのままで球状
性がよく、その磁化も大きいが、酸化に対して安定でな
い。しかも磁性トナーや磁性キャリアとして好適な１μ
ｍ以下のサイズの粉体を得にくい等の欠点を有してい
る。On the other hand, carbonyl iron powder has a good spherical property as it is, and its magnetization is large, but it is not stable against oxidation. Moreover, it is suitable for magnetic toner and magnetic carrier.
It has a defect that it is difficult to obtain a powder having a size of m or less.
【０００７】そのため、化学的に安定で大きな磁化を有
する磁性材料として、窒化鉄が注目されている。Therefore, iron nitride has been attracting attention as a magnetic material that is chemically stable and has a large magnetization.
【０００８】現在、窒化鉄微粒子の製造方法としては、
次のものが公知である。即ち、 特公昭５９−３４１２５号公報等で開示されている、
アンモニアガス雰囲気中で鉄粉末を５００℃以上の温度
で加熱窒化する方法（アンモニア窒化法）、 特開平２−１６４４４３号公報等で開示されている、
鉄カルボニルＦｅ（ＣＯ）5 と窒素Ｎ2 ガスを原料とし
て、グロー放電プラズマ中で分解反応させる方法（プラ
ズマＣＶＤ法）、 特開平３−１８７９０７号公報で開示されている、鉄
カルボニルの炭化水素の油溶液とアンモニアガスとを約
２００℃で反応させる方法（気相- 液相反応法）、及び 減圧したアンモニアガス雰囲気中で鉄を加熱蒸発させ
る方法（ガス中蒸発法）が知られている。At present, as a method for producing iron nitride fine particles,
The following are known. That is, as disclosed in Japanese Patent Publication No. 59-34125,
A method of heating and nitriding iron powder at a temperature of 500 ° C. or higher in an ammonia gas atmosphere (ammonia nitriding method) is disclosed in JP-A-2-164443.
Method of decomposing and reacting iron carbonyl Fe (CO) 5 and nitrogen N 2 gas in glow discharge plasma (plasma CVD method), of hydrocarbons of iron carbonyl disclosed in JP-A-3-187907. There are known a method of reacting an oil solution and ammonia gas at about 200 ° C (gas phase-liquid phase reaction method), and a method of heating and evaporating iron in a reduced pressure ammonia gas atmosphere (gas evaporation method).
【０００９】アンモニア窒化法では、形成させる窒化鉄
粒子の大きさが、原料となる鉄粒子の大きさによって決
まり、現在のところ、最低粒径は１μｍであって、それ
以下にできない。ガス中蒸発法では、いくつかの粒子が
鎖状に連結しているので、単一の粒子を得ることは困難
であり、更に製造過程でのエネルギー効率も悪く、また
生産性において乏しい。プラズマＣＶＤ法や気相−液相
反応法は、窒化鉄磁性流体の製造のために開発された方
法であり、磁性流体に最適な１０ｎｍ程度の超微粒子が
得られる。In the ammonia nitriding method, the size of iron nitride particles to be formed is determined by the size of iron particles as a raw material, and the minimum particle size is 1 μm at present, and it cannot be made smaller than that. In the gas evaporation method, it is difficult to obtain a single particle because several particles are linked in a chain, and further, energy efficiency in the manufacturing process is poor, and productivity is poor. The plasma CVD method and the gas phase-liquid phase reaction method are methods developed for the production of iron nitride magnetic fluid, and ultrafine particles of about 10 nm, which are optimal for magnetic fluid, can be obtained.
【００１０】しかしながら、過去においてこれらの方法
から、２０ｎｍ以上の粒子は得られておらず、また、プ
ラズマＣＶＤ法は、広い適用範囲を有する方法ではある
ものの、当該方法を行なうための反応装置は複雑で高価
なものであり、且つその操業には高度なテクニックが要
求されるため、技術的経済的に必ずしも効率の良い方法
とはいえない。そのため気相−液相反応法を基礎とし、
これから、所望粒径の窒化鉄粒子を合成することが期待
される。However, particles of 20 nm or more have not been obtained from these methods in the past, and although the plasma CVD method has a wide range of application, the reaction apparatus for carrying out the method is complicated. However, it is not necessarily an efficient method in terms of technology and economy because it is expensive and requires high technique for its operation. Therefore, based on the gas-liquid reaction method,
From this, it is expected to synthesize iron nitride particles having a desired particle size.
【００１１】[0011]
【発明が解決しようとする課題】既に述べたように、磁
性塗料、あるいは画像形成装置用の磁性トナーや磁性キ
ャリア等、粉末磁性材料としては、２０ｎｍ〜１００μ
ｍ程度の微粒子が必要とされるのに対して、従来の気相
−液相反応法では、２０ｎｍ以上の粒径で等方的形状の
窒化鉄粒子を製造することができなかった。As described above, the powder magnetic material such as the magnetic paint, the magnetic toner or the magnetic carrier for the image forming apparatus is 20 nm to 100 .mu.m.
While fine particles of about m are required, the conventional vapor-liquid reaction method cannot produce isotropic iron nitride particles having a particle size of 20 nm or more.
【００１２】そこで本発明者らが、窒化鉄微粒子形成過
程を鋭意研究した結果、鉄カルボニルとアンモニアガス
との反応による当該窒化鉄の前駆物質である鉄アンミン
カルボニル錯体Ｆｅ2 （ＣＯ） 5（ＮＨ2 ） 2、Ｆｅ3
（ＣＯ） 9（ＮＨ）2 がその臨界濃度以上の濃度を維持
するように継続される限り、窒化鉄の形成が、窒化鉄の
微粒子核の表面において、優先的に且つ、以前よりも容
易に成されることをつかみ、一旦生成した窒化鉄の微粒
子核を消滅させることなく、その表面において一層ずつ
増大させ、当該窒化鉄を成長させることに成功した（特
願平４−９１１２４号）。The inventors of the present invention have made extensive studies on the formation process of iron nitride fine particles. As a result, the iron ammine carbonyl complex Fe 2 (CO) 5 (NH) which is a precursor of the iron nitride by the reaction of iron carbonyl and ammonia gas has been found. 2 ) 2 , Fe 3
As long as (CO) 9 (NH) 2 is maintained to maintain its concentration above its critical concentration, the formation of iron nitride is preferentially and easier than before at the surface of the iron nitride particulate nuclei. By taking advantage of the fact that the iron nitride is formed, it has succeeded in growing the iron nitride by gradually increasing it on the surface thereof without extinguishing the fine iron oxide nuclei that have been formed once (Japanese Patent Application No. 4-91124).
【００１３】このように新しい製造方法によって、従
来、特にアンモニア窒化法を用いても製造することので
きなかった２０ｎｍ〜１μｍ程度の粒径で等方的形状の
窒化鉄粒子を製造することが可能になったが、このよう
な方法では、一旦生成した窒化鉄の微粒子核の表面にお
いて一層ずつ増大させるので、成長速度がその層厚みに
制限を受けるという宿命を伴っている。As described above, according to the new production method, it is possible to produce isotropic iron nitride particles having a particle size of about 20 nm to 1 μm which could not be produced by the conventional ammonia nitriding method. However, in such a method, the growth rate is limited by the layer thickness because the surface is gradually increased on the surface of the iron nitride fine particle nuclei that have been formed.
【００１４】したがって、磁性塗料や画像形成装置用の
磁性トナーや磁性キャリア等として必要とされる微粒子
に成長させるために、更に一段と効率の良い方法が求め
られる。Therefore, a more efficient method is required to grow fine particles required for magnetic paints, magnetic toners for image forming apparatuses, magnetic carriers and the like.
【００１５】特願平４−９１１２４号に開示された製造
方法では、一旦生成した窒化鉄の微粒子の表面において
徐々に窒化鉄粒子を成長させるとしているので、この成
長段階を飛躍的に早めるか、その代替措置を講じること
が考えられる。In the production method disclosed in Japanese Patent Application No. 4-91124, the iron nitride particles are gradually grown on the surface of the iron nitride fine particles that have been once formed. It is possible to take alternative measures.
【００１６】そこで発明者は種々検討した結果、例え
ば、等方状の型枠のようなものに微粒子を詰め込んで焼
き固めることで等方状粒子を所望の粒子径で得ることが
できるが、この考え方を応用して造粒することに着目し
た。Then, as a result of various studies, the inventor can obtain isotropic particles with a desired particle size by, for example, packing fine particles in an isotropic mold frame and baking the mixture. We focused on granulation by applying the idea.
【００１７】本発明は、磁性材料としても優れた特性を
有する２０ｎｍ〜１００μｍ程度の粒径で等方的形状の
窒化鉄粒子を効率良く製造する新しい方法を提供するこ
とを課題としている。An object of the present invention is to provide a new method for efficiently producing isotropic iron nitride particles having a particle size of about 20 nm to 100 μm, which is excellent as a magnetic material.
【００１８】[0018]
【課題を解決するための手段】本発明は上記課題を、窒
化鉄コロイドの形成段階を経て窒化鉄微粒子を製造する
方法において、窒化鉄コロイドを所定程度に希釈化した
上で、噴霧乾燥し、得られた窒化鉄の乾燥粉末をアンモ
ニアガス、窒素ガス又は不活性ガス雰囲気中で焼結させ
ることによって、解決した。Means for Solving the Problems The present invention addresses the above problems by, in a method for producing iron nitride fine particles through a step of forming an iron nitride colloid, diluting the iron nitride colloid to a predetermined degree, and then spray-drying it. This was solved by sintering the obtained dry powder of iron nitride in an atmosphere of ammonia gas, nitrogen gas or an inert gas.
【００１９】噴霧乾燥することで、液滴の表面張力が粒
子を球状とし、更に窒化鉄コロイドは窒化鉄超微粒子が
均一に分散しているので均一の粒径を有する窒化鉄乾燥
粉末を得ることができる。By spray-drying, the surface tension of the liquid droplets makes the particles spherical, and further, the iron nitride colloid has ultrafine iron nitride particles uniformly dispersed, so that an iron nitride dry powder having a uniform particle diameter can be obtained. You can
【００２０】磁性塗料、あるいは磁性トナーや磁性キャ
リア等に必要とされる２０ｎｍ〜１００μｍ程度の粒径
を得るにあたっては、コロイド形成段階で窒化鉄コロイ
ドの濃度を調整したり、焼結段階でその条件を制御する
ことによっって、所定粒径の窒化鉄を得ることができ
る。In order to obtain the particle size of about 20 nm to 100 μm required for the magnetic paint, the magnetic toner, the magnetic carrier, etc., the concentration of the iron nitride colloid is adjusted in the colloid formation step, and the conditions are set in the sintering step. It is possible to obtain iron nitride having a predetermined grain size by controlling
【００２１】本発明においては、窒化鉄の原料物質とし
て鉄カルボニルを、原料ガスとしてアンモニアを用いる
が、アンモニアに代えて、アミン類等の液状あるいは固
体として反応系に導入できる任意の窒素化合物を用いる
こともできる。有機溶媒としては、例えば、炭化水素
類、あるいはその混合物、ケトン類、エーテル類、エス
テル類、アミン類等が好適で、当該溶媒に添加される界
面活性剤としては、アミン類が好適であるが、これらに
限定されない。In the present invention, iron carbonyl is used as a raw material of iron nitride and ammonia is used as a raw material gas. Instead of ammonia, any nitrogen compound that can be introduced into the reaction system as a liquid or solid such as amines is used. You can also As the organic solvent, for example, hydrocarbons, or a mixture thereof, ketones, ethers, esters, amines and the like are preferable, and as the surfactant added to the solvent, amines are preferable. , But not limited to these.
【００２２】種結晶として得られた窒化鉄コロイドを、
有機溶媒用クローズドタイプの公知の噴霧乾燥機等を用
いて、乾燥粉末とする。噴霧乾燥機で使用するにあた
り、適切な程度に希釈化するため、ケロシン等の有機溶
媒を用いる。噴霧乾燥は、窒素、アンモニア、不活性ガ
スあるいはこれらの混合ガス雰囲気中で行う。The iron nitride colloid obtained as a seed crystal,
It is made into a dry powder using a known spray dryer of a closed type for organic solvents. When using in a spray dryer, an organic solvent such as kerosene is used in order to dilute to an appropriate degree. The spray drying is performed in an atmosphere of nitrogen, ammonia, an inert gas or a mixed gas thereof.
【００２３】得られた乾燥窒化鉄粉末は、そのままでは
微粒子が集合した多結晶体であり、空隙が多い。そこで
単結晶の球状微粒子を得るために、加熱処理を施すこと
により、当該粉末を焼結させる。乾燥段階と同じく、窒
素、アンモニア、不活性ガスあるいはこれらの混合ガス
雰囲気で焼結する。焼結温度は、２００〜３００℃が好
ましい。The obtained dry iron nitride powder is a polycrystalline body in which fine particles are aggregated as it is, and has many voids. Therefore, in order to obtain single crystal spherical fine particles, the powder is sintered by performing a heat treatment. Similar to the drying step, sintering is performed in an atmosphere of nitrogen, ammonia, an inert gas or a mixed gas thereof. The sintering temperature is preferably 200 to 300 ° C.
【００２４】得られた単結晶の窒化鉄粒子の表面に付着
している界面活性剤が不必要な場合には、アセトン、キ
シレン、ベンゼン、石油ベンジン、シクロヘキサン等の
溶媒を用いて取り除けばよい。When the surfactant attached to the surface of the obtained single crystal iron nitride particles is unnecessary, it may be removed by using a solvent such as acetone, xylene, benzene, petroleum benzine, cyclohexane and the like.
【００２５】[0025]
【実施例】以下に、本発明の実施例を挙げて更に具体的
に説明する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００２６】（１）コロイド形成段階 図１に示される窒化金属磁性流体の合成装置は、底部に
加熱装置２を取り付けた耐熱性熱分解反応槽１に、複数
の気密性導入フランジを有する蓋３を気密に接続するこ
とで形成されている。反応槽１内の溶液４を攪拌できる
ように、一つの導入フランジ５に攪拌装置６が取り付け
られている。導入管７を通して、原料気体が溶液４に導
入されるようになっている。別の導入フランジ８に設け
られた管路を介して原料物質９が、導入口１０を介し
て、例えば界面活性剤１１が導入される。別の導入口１
２に配置された管路が分岐され、一方には、窒化金属微
粒子の生成反応を行う際の還流冷却装置１３が接続さ
れ、他方の管路には、蒸留冷却装置としてのコンデンサ
ー１４が接続されている。(1) Colloid Formation Stage In the metal nitride magnetic fluid synthesizing apparatus shown in FIG. 1, a lid 3 having a plurality of airtight introduction flanges is provided in a heat-resistant pyrolysis reaction tank 1 having a heating device 2 attached to the bottom thereof. It is formed by connecting airtightly. A stirring device 6 is attached to one introduction flange 5 so that the solution 4 in the reaction tank 1 can be stirred. The raw material gas is introduced into the solution 4 through the introduction pipe 7. The raw material 9 is introduced through a conduit provided in another introduction flange 8 and, for example, a surfactant 11 is introduced through an introduction port 10. Another inlet 1
The pipe line arranged in 2 is branched, one side is connected to a reflux cooling device 13 for carrying out a reaction for producing metal nitride fine particles, and the other pipe line is connected to a condenser 14 as a distillation cooling device. ing.
【００２７】原料としてアルドリッヒ(Aldrich) 社製で
純度９６．５％の鉄カルボニルを、溶媒として和光純薬
製のケロシン（軽油等でもよい）を、界面活性剤として
花王製のＮ- ジエチレンイソブテニルサクシンイミド
（アミン）を、並びに日本酸素製で純度９９．９９％の
アンモニアガスを用いた。Iron carbonyl manufactured by Aldrich and having a purity of 96.5% is used as a raw material, kerosene (light oil etc.) manufactured by Wako Pure Chemical Co., Ltd. is used as a solvent, and N-diethyleneisobutene manufactured by Kao is used as a surfactant. Tenylsuccinimide (amine) was used, as well as ammonia gas manufactured by Nippon Oxygen and having a purity of 99.99%.
【００２８】先ず、図１の合成装置の反応槽１におい
て、鉄カルボニル２００ｇ、アミン１１．３ｇ、ケロシ
ン５３．１ｇからなる混合溶液４中に、導入管７を介し
てアンモニアガスを流量３９０ｍｌ／ｍｉｎでバブリン
グしながら十分混合し、加熱装置２によって９０℃まで
加熱し、当該温度で混合溶液４を１時間保持し、その
後、更に１８５℃に昇温し、再び１時間保持する。この
２段階の加熱操作を、反応槽１中の鉄カルボニルが全て
消費されるまで周期的に繰り返した。結局、当該合成操
作を１０回繰り返し、種結晶として、窒化鉄コロイド
０．６リットルを得た。得られた磁性窒化鉄粒子の平均
粒径を透過型電子顕微鏡の高倍率写真から求めた平均粒
径は１０．４ｎｍであった。First, in the reaction tank 1 of the synthesizer shown in FIG. 1, ammonia gas is introduced into the mixed solution 4 consisting of 200 g of iron carbonyl, 11.3 g of amine and 53.1 g of kerosene through the introduction pipe 7 and a flow rate of 390 ml / min. While bubbling in, the mixture is thoroughly mixed, heated to 90 ° C. by the heating device 2, the mixed solution 4 is held at that temperature for 1 hour, then further heated to 185 ° C., and held again for 1 hour. The two-step heating operation was periodically repeated until all the iron carbonyl in the reaction tank 1 was consumed. Eventually, the synthesis operation was repeated 10 times to obtain 0.6 liter of iron nitride colloid as a seed crystal. The average particle size of the obtained magnetic iron nitride particles was 10.4 nm as determined from a high magnification photograph of a transmission electron microscope.
【００２９】（２）噴霧乾燥段階 このようにして得られた窒化鉄コロイドに希釈用のベン
ジンを、重量比で窒化鉄コロイド：ベンジン＝１：３０
の割合で添加し、攪拌した後、当該溶液を有機溶媒用ク
ローズドタイプの噴霧乾燥機（スプレードライヤ）を用
いて乾燥した。乾燥には坂本技研ＤＡ−１６００型を用
い、２流体ノズルで窒素雰囲気中に窒素ガスと希釈原料
溶液を噴霧した。乾燥温度は出口温度６０℃であった。
噴霧乾燥した窒化鉄粒子は多孔質の球状であり、平均粒
径は２．９ミクロンであった。窒化鉄乾燥粉末６３ｇを
得た。(2) Spray-drying step The iron nitride colloid thus obtained is diluted with benzine for dilution in a weight ratio of iron nitride colloid: benzine = 1: 30.
After adding and stirring, the solution was dried using a closed type spray dryer for organic solvents (spray dryer). A Sakamoto Giken DA-1600 type was used for drying, and nitrogen gas and a diluted raw material solution were sprayed in a nitrogen atmosphere with a two-fluid nozzle. The drying temperature was an outlet temperature of 60 ° C.
The spray-dried iron nitride particles were porous, spherical and had an average particle size of 2.9 microns. 63 g of iron nitride dry powder was obtained.
【００３０】（３）乾燥粉末焼結段階 次に得られた乾燥粉末を不活性ガス雰囲気中で２２０℃
で１時間加熱し、焼結粒子を得た。(3) Dry Powder Sintering Step Next, the dry powder obtained was heated at 220 ° C. in an inert gas atmosphere.
And heated for 1 hour to obtain sintered particles.
【００３１】得られた窒化鉄粒子の諸物性は表１のとお
りであった。The physical properties of the obtained iron nitride particles are shown in Table 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】本発明の製造方法によって、磁化の値が
大きく且つ粒径の揃った等方的形状の窒化鉄粒子が得ら
れ、このようにして得られた窒化鉄粒子は、粒子表面を
親油性にも親水性にも適宜に変えることができる。得ら
れた粒子は空気中でも安定であるが、更に、水性溶媒
中、又は油溶媒中にそれぞれ懸濁させて、保存、輸送並
びにその他の取り扱いを行なうにあたり、当該粒子が燃
焼することもなく安全で、また取り扱い作業も容易とな
る。According to the production method of the present invention, isotropic iron nitride particles having a large magnetization value and a uniform particle size are obtained, and the iron nitride particles thus obtained are It can be appropriately changed to be lipophilic or hydrophilic. The obtained particles are stable in air, and further suspended in an aqueous solvent or an oil solvent, respectively, and stored, transported, and otherwise handled, the particles are safe without burning. Also, handling work becomes easy.
【図１】公知の窒化鉄粒子の合成装置の概略図である。FIG. 1 is a schematic view of a known apparatus for synthesizing iron nitride particles.
１ 熱分解反応槽 ２ 加熱装置 ６ 攪拌装置 １３ 還流冷却装置 １４ コンデンサー 1 Pyrolysis Reaction Tank 2 Heating Device 6 Stirring Device 13 Reflux Cooling Device 14 Condenser
Claims (1)
微粒子を製造する方法において、窒化鉄コロイドを所定
程度に希釈化した上で、噴霧乾燥し、得られた窒化鉄乾
燥粉末をアンモニアガス、窒素ガス又は不活性ガス雰囲
気中で焼結させてなる窒化鉄微粒子の製造方法。1. A method for producing iron nitride fine particles through a step of forming an iron nitride colloid, which comprises diluting the iron nitride colloid to a predetermined degree and spray-drying the resulting iron nitride dry powder with ammonia gas, A method for producing iron nitride fine particles obtained by sintering in a nitrogen gas or inert gas atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07042893A JP3363938B2 (en) | 1993-03-29 | 1993-03-29 | Method for producing spherical iron nitride fine particles by sintering method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07042893A JP3363938B2 (en) | 1993-03-29 | 1993-03-29 | Method for producing spherical iron nitride fine particles by sintering method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06279008A true JPH06279008A (en) | 1994-10-04 |
| JP3363938B2 JP3363938B2 (en) | 2003-01-08 |
Family
ID=13431206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07042893A Expired - Fee Related JP3363938B2 (en) | 1993-03-29 | 1993-03-29 | Method for producing spherical iron nitride fine particles by sintering method |
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| Country | Link |
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| JP (1) | JP3363938B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006075708A (en) * | 2004-09-09 | 2006-03-23 | Optonix Seimitsu:Kk | Spherical superfine particle and its manufacturing method |
| JP2006077252A (en) * | 2005-09-09 | 2006-03-23 | Optonix Seimitsu:Kk | Ultrafine particle produced by pressurized vibration and injection granulation |
| CN113493895A (en) * | 2020-03-19 | 2021-10-12 | 甘肃省科学院传感技术研究所 | Gamma' -Fe4Preparation method and application of N-shaped magnetic porous membrane |
-
1993
- 1993-03-29 JP JP07042893A patent/JP3363938B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006075708A (en) * | 2004-09-09 | 2006-03-23 | Optonix Seimitsu:Kk | Spherical superfine particle and its manufacturing method |
| US7771788B2 (en) | 2004-09-09 | 2010-08-10 | Optnics Precision Co., Ltd. | Spherical ultrafine particles and process for producing the same |
| JP2006077252A (en) * | 2005-09-09 | 2006-03-23 | Optonix Seimitsu:Kk | Ultrafine particle produced by pressurized vibration and injection granulation |
| CN113493895A (en) * | 2020-03-19 | 2021-10-12 | 甘肃省科学院传感技术研究所 | Gamma' -Fe4Preparation method and application of N-shaped magnetic porous membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3363938B2 (en) | 2003-01-08 |
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