JPH0986915A - Production of iron-carbon complex ferromagnetic fine particle - Google Patents
Production of iron-carbon complex ferromagnetic fine particleInfo
- Publication number
- JPH0986915A JPH0986915A JP7245857A JP24585795A JPH0986915A JP H0986915 A JPH0986915 A JP H0986915A JP 7245857 A JP7245857 A JP 7245857A JP 24585795 A JP24585795 A JP 24585795A JP H0986915 A JPH0986915 A JP H0986915A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- fine particles
- carbon
- fine particle
- ferromagnetic fine
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉄−炭素複合強磁
性微粒子の新規な製造方法に関するものである。さらに
詳しくいえば、本発明は、耐酸化性に優れた強磁性鉄微
粒子として各種用途に有用であるのみならず、導電性材
料、触媒材料、磁性流体や電気粘性流体の材料などとし
ても応用が期待できる炭素質によって表面が被覆されて
成る強磁性鉄微粒子を、簡便な操作で効率よく製造する
方法に関するものである。TECHNICAL FIELD The present invention relates to a novel method for producing iron-carbon composite ferromagnetic fine particles. More specifically, the present invention is not only useful for various applications as ferromagnetic iron fine particles having excellent oxidation resistance, but also applicable as a conductive material, a catalyst material, a magnetic fluid or an electrorheological fluid material, etc. The present invention relates to a method for efficiently producing ferromagnetic iron fine particles whose surface is coated with a promising carbonaceous substance by a simple operation.
【０００２】[0002]
【従来の技術】炭素質によって表面が被覆された強磁性
鉄微粒子（鉄−炭素複合強磁性微粒子）は、耐酸化性に
優れた強磁性鉄微粒子として各種用途に有用であるのみ
ならず、例えば導電性材料、触媒材料、磁性流体や電気
粘性流体の材料などとしても、その応用が期待されてい
る。2. Description of the Related Art Ferromagnetic iron fine particles whose surface is coated with carbonaceous material (iron-carbon composite ferromagnetic fine particles) are not only useful for various applications as ferromagnetic iron fine particles having excellent oxidation resistance, Its application is also expected as a conductive material, a catalyst material, a magnetic fluid or an electrorheological fluid material.
【０００３】従来、鉄−炭素複合材料の製造方法として
は、鉄を含有する金属錯体を原料とする方法、例えば
（１）フェロセニル残基を有するポリマーを不活性ガス
雰囲気下又は真空中にて熱分解する方法、（２）ピッチ
などの炭素源とフェロセン誘導体や鉄を中心金属とする
配位化合物との混合物を、不活性ガス雰囲気下において
熱分解する方法、（３）フェロセン誘導体を直接熱分解
する方法などが知られている。Conventionally, as a method for producing an iron-carbon composite material, a method using a metal complex containing iron as a raw material, for example, (1) a polymer having a ferrocenyl residue is heated in an inert gas atmosphere or in a vacuum. Decomposition method (2) Pyrolysis of a mixture of a carbon source such as pitch and a ferrocene derivative or a coordination compound having iron as a central metal in an inert gas atmosphere, (3) Direct thermal decomposition of a ferrocene derivative It is known how to do it.
【０００４】前記（１）の方法としては、例えば（イ）
アルゴン気流中において、フェロセン−メチルエチルケ
トンのコポリマーを約５００℃で、あるいはポリ（β‐
フェロセニルクロロアクロレイン）を約４００℃で熱分
解する方法［「Ｄｏｋｌ．Ａｋａｄ．Ｎａｕｋ ＳＳＳ
Ｒ」第１９４巻，第８４３ページ（１９７０年）］、
（ロ）アセチルフェロセンとフルフラールとを硫酸触媒
の存在下に重縮合させて得られたポリマーを、真空中に
おいて、３５０〜４００℃で加熱する方法［「ネイチャ
ー（Ｎａｔｕｒｅ）」第２６７巻，第８２３ページ（１
９７７年）］、（ハ）１‐フェロセニルエタノール‐ホ
ルムアルデヒド‐フェノールのコポリマーを、真空中に
おいて、３５０〜４００℃で熱分解する方法［「Ｂｕｌ
ｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．」第５０巻，第１１５
７〜１１６０ページ（１９７７年）］などが報告されて
いる。これらの方法で得られた鉄−炭素複合材料は、
鉄、酸化鉄あるいは鉄イオンの微粒子がカーボンマトリ
ックス中に高分散したものである。しかしながら、これ
らの方法においては、熱分解処理する前に、固定化や重
合といった煩雑な処理が必要であるため、簡便な製造方
法とはいえない。また、熱分解処理温度が比較的低いた
め、原料中に含まれる酸素が酸化鉄を形成し、その結
果、複合材料中の金属鉄の含有量が低くなるのを免れな
いという問題がある。As the method (1), for example, (a)
The ferrocene-methyl ethyl ketone copolymer was heated at about 500 ° C. in an argon stream, or poly (β-
Ferrocenyl chloroacrolein) at a temperature of about 400 ° C. [“Dokl. Acad. Nauk SSS
R ", Volume 194, 843 (1970)],
(B) A method in which a polymer obtained by polycondensing acetylferrocene and furfural in the presence of a sulfuric acid catalyst is heated at 350 to 400 ° C. in vacuum [“Nature”, Vol. 267, Vol. 823]. Page (1
977)], (C) a method of thermally decomposing a 1-ferrocenylethanol-formaldehyde-phenol copolymer at 350 to 400 ° C. in a vacuum [“Bul
l. Chem. Soc. Jpn. Volume 50, 115
7 to 1160 (1977)] and the like are reported. The iron-carbon composite material obtained by these methods is
Fine particles of iron, iron oxide or iron ions are highly dispersed in a carbon matrix. However, these methods cannot be said to be a simple production method because a complicated treatment such as immobilization and polymerization is required before the thermal decomposition treatment. Further, since the thermal decomposition treatment temperature is relatively low, there is a problem that oxygen contained in the raw material forms iron oxide, and as a result, the content of metallic iron in the composite material becomes low.
【０００５】また、前記（２）の方法としては、（イ）
水素気流中において、飽和ベンゼン蒸気と共にフェロセ
ンを約１１００℃で熱分解する方法［「応用物理」第５
４巻，第５０７〜５１０ページ（１９８５年）］、
（ロ）溶媒可溶性メソフェーズピッチとトリス（アセチ
ルアセトナト）鉄（ＩＩＩ）錯体とを、不活性ガス雰囲
気下に４００〜１０００℃で熱処理する方法［「学振第
１１７委員会資料」（１９９３年）］、（ハ）ポリスチ
レンを核とするシード重合により得られたポリアクリロ
ニトリル系高分子微粒子と２種類の金属塩とを反応させ
て、２種類の金属が固定された高分子錯体微粒子を製造
し、このものを４００〜１０００℃で焼成する方法
［「ポリマー・プレプリンツ（Ｐｏｌｙｍｅｒ Ｐｒｅ
ｐｒｉｎｔｓ）」第４２巻，第３６６０〜３６６２ペー
ジ（１９９３年）］などが報告されている。これらの方
法で得られた鉄−炭素複合材料は、鉄や酸化鉄の微粒子
がカーボンマトリックス中に高分散したものである。し
かしながら、これらの方法においては、原料の炭素／鉄
比が大きいため、得られた複合材料中の鉄含有量が最大
でも約１５重量％と少なく、その結果複合材料の磁性も
飽和磁化で最高２３．０ｅｍｕＧ／ｇ程度であり、決し
て大きな値とはいえず、十分な機能が期待できないとい
う問題がある。As the method (2), (a)
A method of thermally decomposing ferrocene with saturated benzene vapor at about 1100 ° C. in a hydrogen stream [“Applied Physics” No. 5
Volume 4, pp. 507-510 (1985)],
(B) A method of heat-treating a solvent-soluble mesophase pitch and a tris (acetylacetonato) iron (III) complex at 400 to 1000 ° C. under an inert gas atmosphere [“Gakshin 117 Committee Material” (1993). ] (C) Polyacrylonitrile-based polymer fine particles obtained by seed polymerization using polystyrene as a nucleus are reacted with two kinds of metal salts to produce polymer complex fine particles to which two kinds of metals are fixed, A method of baking this at 400 to 1000 ° C. [“Polymer Preprints (Polymer Pre
"Prints)" Vol. 42, pp. 3660-3662 (1993)] and the like. The iron-carbon composite material obtained by these methods is obtained by highly dispersing fine particles of iron or iron oxide in a carbon matrix. However, in these methods, since the carbon / iron ratio of the raw material is large, the iron content in the obtained composite material is as low as about 15% by weight at the maximum, and as a result, the magnetism of the composite material is 23 at the maximum in saturation magnetization. It is about 0.0 emuG / g, which is not a large value, and there is a problem that a sufficient function cannot be expected.
【０００６】さらに、上記（３）のフェロセン誘導体を
直接熱分解する方法（特願平６−６８０２０号）は、簡
便であるが、フェロセンの配位子であるシクロペンタジ
エン環が炭素源であるために、原料の炭素／鉄モル比は
１０又はそれ以上と大きく、したがって、得られる複合
材料中の鉄含有量は、５０重量％以下であり、その結
果、複合材料の飽和磁化も５０ｅｍｕＧ／ｇ以下と小さ
い。Further, the method (3) of directly pyrolyzing the ferrocene derivative (Japanese Patent Application No. 6-68020) is simple, but the cyclopentadiene ring which is a ferrocene ligand is a carbon source. In addition, the carbon / iron molar ratio of the raw material is as large as 10 or more, and therefore the iron content in the obtained composite material is 50% by weight or less, and as a result, the saturation magnetization of the composite material is 50 emuG / g or less. And small.
【０００７】なお、鉄ペンタカルボニル単独の熱分解に
よる鉄超微粒子の製造法は知られているが［「材料」第
４３巻，第１６０９〜１６１４ページ（１９９４
年）］、この方法で得られたものは炭素で被覆されたも
のではなく、本発明に係る鉄−炭素複合強磁性微粒子と
は異なる。Although a method for producing ultrafine iron particles by thermal decomposition of iron pentacarbonyl alone is known [[Materials] Vol. 43, pp. 1609-1614 (1994).
)], The one obtained by this method is not coated with carbon, and is different from the iron-carbon composite ferromagnetic fine particles according to the present invention.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、鉄含有量が多く、高い飽和磁化を有する
鉄−炭素複合強磁性微粒子を、簡便なプロセスで効率よ
く製造する方法を提供することを目的としてなされたも
のである。Under these circumstances, the present invention efficiently manufactures iron-carbon composite ferromagnetic fine particles having a high iron content and a high saturation magnetization by a simple process. The purpose is to provide a method.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、鉄カルボニル
化合物は熱分解処理で、鉄の配位子であるカルボニルが
一酸化炭素ガスとして飛散し生成する微粒子の炭素源と
して寄与しないために、原料としてこの鉄カルボニル化
合物と有機物との混合物を用いることにより、炭素／鉄
比を小さくすることができ、その目的を達成しうること
を見出し、この知見に基づいて本発明を完成するに至っ
た。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that iron carbonyl compounds are thermally decomposed and that carbonyl, which is an iron ligand, is carbon monoxide. Use of a mixture of this iron carbonyl compound and an organic substance as a raw material because it does not contribute to the carbon source of the fine particles generated by scattering as a gas, and the carbon / iron ratio can be reduced, and the object can be achieved. The present invention has been completed based on this finding.
【００１０】すなわち、本発明は、有機物と鉄カルボニ
ル化合物との混合物を熱分解処理することを特徴とする
鉄−炭素複合強磁性微粒子の製造方法を提供するもので
ある。また、本発明は、上記有機物として有機低分子化
合物を用いる鉄−炭素複合強磁性微粒子の製造方法、有
機物と鉄カルボニル化合物とを、有機物の炭素／鉄モル
比が０．０１〜１０になるように混合したものを熱分解
処理する鉄−炭素複合強磁性微粒子の製造方法、及び熱
分解処理を減圧下又は不活性ガス存在下に５００〜２０
００℃の範囲の温度において行う鉄−炭素複合強磁性微
粒子の製造方法を提供する。That is, the present invention provides a method for producing iron-carbon composite ferromagnetic fine particles, which comprises subjecting a mixture of an organic substance and an iron carbonyl compound to thermal decomposition treatment. Further, the present invention provides a method for producing iron-carbon composite ferromagnetic fine particles using an organic low molecular weight compound as the organic substance, wherein the organic substance and the iron carbonyl compound are added such that the carbon / iron molar ratio of the organic substance is 0.01 to 10. The method for producing iron-carbon composite ferromagnetic fine particles, which comprises subjecting a mixture of the above to pyrolysis treatment, and the pyrolysis treatment to 500 to 20 under reduced pressure or in the presence of an inert gas.
Provided is a method for producing iron-carbon composite ferromagnetic fine particles, which is performed at a temperature in the range of 00 ° C.
【００１１】[0011]
【発明の実施の形態】本発明方法においては、原料とし
て有機物と鉄カルボニル化合物との混合物が用いられ
る。ここで、鉄カルボニル化合物としては、例えばペン
タカルボニル鉄（０）、テトラカルボニルビス（シクロ
ペンタジエニル）鉄（Ｉ）、トリカルボニルシクロオク
タテトラエン鉄（Ｉ）、ドデカカルボニル鉄（０）など
を挙げることができる。これらの鉄カルボニル化合物は
単独で用いてもよいし、２種以上を混合して用いてもよ
い。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, a mixture of an organic substance and an iron carbonyl compound is used as a raw material. Here, as the iron carbonyl compound, for example, pentacarbonyl iron (0), tetracarbonylbis (cyclopentadienyl) iron (I), tricarbonylcyclooctatetraene iron (I), dodecacarbonyl iron (0), etc. Can be mentioned. These iron carbonyl compounds may be used alone or in combination of two or more.
【００１２】一方、有機物については特に制限はない
が、有機低分子化合物が好ましく、また分子中に窒素、
酸素、リン、硫黄、ホウ素、セレンなどのヘテロ元素が
含まれていてもよい。この有機物は、鉄カルボニル化合
物と混合し、同時に気化、熱分解される必要があるた
め、併用する鉄カルボニル化合物と著しく沸点の異なる
ものは適さない。この有機物としては、例えば炭化水素
化合物、塩化炭化水素化合物、含窒素有機化合物、含酸
素有機化合物、含リン有機化合物、含硫黄有機化合物、
含ホウ素有機化合物、含セレン有機化合物などを用いる
ことができる。On the other hand, the organic substance is not particularly limited, but an organic low molecular compound is preferable, and nitrogen in the molecule,
Hetero elements such as oxygen, phosphorus, sulfur, boron and selenium may be contained. Since this organic substance needs to be mixed with the iron carbonyl compound and vaporized and thermally decomposed at the same time, it is not suitable to use a substance having a boiling point significantly different from that of the iron carbonyl compound used in combination. Examples of the organic matter include hydrocarbon compounds, chlorinated hydrocarbon compounds, nitrogen-containing organic compounds, oxygen-containing organic compounds, phosphorus-containing organic compounds, sulfur-containing organic compounds,
A boron-containing organic compound, a selenium-containing organic compound or the like can be used.
【００１３】炭化水素化合物としては、例えばペンタ
ン、オクタン、ドデカン、ジメチルプロパン、ジメチル
ブタン、シクロヘキサン、シクロドデカン、アダマンタ
ン、ノルボルナン、ベンゼン、トルエンなどが、塩化炭
化水素化合物としては、例えば塩化プロピルやクロロシ
クロヘキサンなどが挙げられる。含窒素有機化合物とし
ては、例えばエチルアミン、ジエチルアミン、トリエチ
ルアミン、ジプロピルアミン、ｎ‐ブチルアミン、エチ
レンジアミンなどの脂肪族アミン類などが挙げられる。Hydrocarbon compounds include, for example, pentane, octane, dodecane, dimethylpropane, dimethylbutane, cyclohexane, cyclododecane, adamantane, norbornane, benzene and toluene, and examples of chlorinated hydrocarbon compounds include propyl chloride and chlorocyclohexane. And so on. Examples of the nitrogen-containing organic compound include aliphatic amines such as ethylamine, diethylamine, triethylamine, dipropylamine, n-butylamine and ethylenediamine.
【００１４】含酸素有機化合物としては、例えばエタノ
ールやプロパノールなどの脂肪族アルコール類、シクロ
ヘキサノールやシクロドデカノールなどの脂肪族環状ア
ルコール類、アダマンタノールなどの架橋脂肪族アルコ
ール類、フェノールやビスフェノールなどのフェノール
類、脂肪族及び芳香族ケトン類、脂肪族及び芳香族アル
デヒド類、脂肪族及び芳香族エステル類、脂肪族及び芳
香族エーテル類、脂肪族カルボン酸類などが挙げられ
る。Examples of the oxygen-containing organic compound include aliphatic alcohols such as ethanol and propanol, aliphatic cyclic alcohols such as cyclohexanol and cyclododecanol, crosslinked aliphatic alcohols such as adamantanol, and phenol and bisphenol. Examples include phenols, aliphatic and aromatic ketones, aliphatic and aromatic aldehydes, aliphatic and aromatic esters, aliphatic and aromatic ethers, and aliphatic carboxylic acids.
【００１５】含リン有機化合物としては、例えばトリメ
チルホスフィン、トリエチルホスフィンなどのアルキル
ホスフィン類などが挙げられる。含硫黄有機化合物とし
ては、例えばエチルメルカプタンやプロピルメルカプタ
ンなどのメルカプタン類、エチレンチオグリコール、
１，２‐プロパンジチオールなどのジチオール類、ジプ
ロピルスルフィドなどのジアルキルスルフィド類、ジプ
ロピルジスルフィドなどのジアルキルジスルフィド類、
チオフェンなどのチオフェン類などが挙げられる。ま
た、含ホウ素有機化合物としては、例えばトリエチルボ
ラン、トリブチルボラン、クロロジエチルボランなど
が、含セレン有機化合物としては、例えばジメチルセレ
ナイドやジエチルセレナイドなどが挙げられる。本発明
においては、これらの有機物は単独で用いてもよいし、
２種以上を組み合わせて用いてもよい。Examples of the phosphorus-containing organic compound include alkylphosphines such as trimethylphosphine and triethylphosphine. Examples of the sulfur-containing organic compound include mercaptans such as ethyl mercaptan and propyl mercaptan, ethylene thioglycol,
Dithiols such as 1,2-propanedithiol, dialkyl sulfides such as dipropyl sulfide, dialkyl disulfides such as dipropyl disulfide,
Examples thereof include thiophenes such as thiophene. Examples of the boron-containing organic compound include triethylborane, tributylborane, and chlorodiethylborane, and examples of the selenium-containing organic compound include dimethyl selenide and diethyl selenide. In the present invention, these organic substances may be used alone,
Two or more kinds may be used in combination.
【００１６】本発明においては、まず、前記有機物と鉄
カルボニル化合物とを、有機物中の炭素と鉄とのモル比
が、好ましくは０．０１〜１０、より好ましくは１〜６
の範囲になるよう混合して、原料を調製する。In the present invention, first, the organic substance and the iron carbonyl compound have a molar ratio of carbon to iron in the organic substance of preferably 0.01 to 10, and more preferably 1 to 6.
The raw materials are prepared by mixing so as to be within the range.
【００１７】次に、この原料混合物を減圧下又は不活性
ガス存在下において、好ましくは５００〜２０００℃の
範囲の温度で熱分解処理する。この温度が前記範囲を逸
脱すると、所望の性状を有する鉄−炭素複合強磁性微粒
子が収率よく得られない。所望の性状を有する鉄−炭素
複合強磁性微粒子を収率よく得るには、熱分解温度は特
に８００〜１３００℃の範囲が好ましい。Next, the raw material mixture is pyrolyzed under reduced pressure or in the presence of an inert gas, preferably at a temperature in the range of 500 to 2000 ° C. If the temperature deviates from the above range, iron-carbon composite ferromagnetic fine particles having desired properties cannot be obtained in good yield. In order to obtain iron-carbon composite ferromagnetic fine particles having desired properties in good yield, the thermal decomposition temperature is preferably in the range of 800 to 1300 ° C.
【００１８】この熱分解処理を減圧下で行う場合は、圧
力は１〜５０，０００Ｐａの範囲が好ましく、特に１０
〜５，０００Ｐａの範囲が好ましい。一方、不活性ガス
存在下で行う場合は、アルゴンや窒素などの不活性ガス
を、好ましくは５〜１，０００ｃｍ3／分、より好まし
くは１０〜３００ｃｍ3／分の速度で反応系に流通させ
るのが有利である。熱分解時間は、原料の種類や熱分解
温度などにより左右され、一概に定めることはできない
が、通常は３０〜１２０分間程度で十分である。When the thermal decomposition treatment is carried out under reduced pressure, the pressure is preferably in the range of 1 to 50,000 Pa, particularly 10
The range of up to 5,000 Pa is preferable. On the other hand, when the reaction is carried out in the presence of an inert gas, an inert gas such as argon or nitrogen is passed through the reaction system at a rate of preferably 5 to 1,000 cm 3 / min, more preferably 10 to 300 cm 3 / min. Is advantageous. The thermal decomposition time depends on the type of raw material, the thermal decomposition temperature, and the like, and cannot be determined unconditionally, but 30 to 120 minutes is usually sufficient.
【００１９】このようにして得られた鉄−炭素複合強磁
性微粒子は、鉄粒子の表面が炭素質により被覆された構
造を有している。該鉄粒子は、粉末Ｘ線回折及び透過型
電子顕微鏡観察により、粒径が数〜数１０ｎｍ程度のα
‐鉄であることが確認された。The iron-carbon composite ferromagnetic fine particles thus obtained have a structure in which the surface of the iron particles is covered with carbonaceous material. According to powder X-ray diffraction and transmission electron microscope observation, the iron particles have an α value of about several to several tens nm.
-Is confirmed to be iron.
【００２０】本発明方法においては、鉄カルボニル化合
物を原料として用いることにより、鉄の配位子であるカ
ルボニルが、フェロセンのシクロペンタジエニル環と異
なり、熱分解処理で一酸化炭素ガスとして飛散し、生成
する複合微粒子中の炭素源として寄与しないため、有機
物と鉄カルボニル化合物とのモル比を適当に調節するこ
とによって、複合微粒子中に含まれる鉄粒子の割合を５
０重量％以上と高くすることができ、その結果飽和磁化
を向上させることが可能である。In the method of the present invention, by using an iron carbonyl compound as a raw material, carbonyl, which is an iron ligand, scatters as carbon monoxide gas in the thermal decomposition treatment unlike cyclopentadienyl ring of ferrocene. Since it does not contribute as a carbon source in the produced composite fine particles, the ratio of the iron particles contained in the composite fine particles is adjusted to 5 by appropriately adjusting the molar ratio of the organic substance and the iron carbonyl compound.
It can be as high as 0% by weight or more, and as a result, the saturation magnetization can be improved.
【００２１】[0021]
【発明の効果】本発明によると、炭素質によって表面が
被覆された強磁性鉄微粒子（鉄−炭素複合強磁性微粒
子）を、簡便な操作によって効率よく製造することがで
きる。この複合強磁性微粒子は、耐酸化性に優れた強磁
性鉄微粒子として各種用途に有用であるのみならず、導
電性材料、触媒材料、磁性流体や電気粘性流体の材料な
どとしても応用が期待できる。According to the present invention, ferromagnetic iron fine particles (iron-carbon composite ferromagnetic fine particles) whose surface is coated with carbonaceous matter can be efficiently produced by a simple operation. The composite ferromagnetic fine particles are not only useful for various applications as ferromagnetic iron fine particles having excellent oxidation resistance, but also expected to be applied as a conductive material, a catalyst material, a magnetic fluid or an electrorheological fluid material, etc. .
【００２２】[0022]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２３】実施例１ 鉄ペンタカルボニル４ｍｍｏｌ（０．７８３ｇ）とジ‐
ｎ‐プロピルアミン２ｍｍｏｌ（０．２０２ｇ）を混合
し［炭素／鉄＝６／４（モル比）］、石英製の反応管の
左端に入れ、液体窒素で冷却した。約３時間系内を真空
排気後、同反応管の右側を９００℃に加熱し、反応温度
に達したのち、左端の原料混合物を加熱蒸発させ蒸気を
右側の加熱部に導いた。９００℃で４５分反応した後、
同温度で３０分排気後冷却し、反応管の内壁に付着した
生成物０．１５９５ｇを得た。得られた鉄−炭素複合強
磁性微粒子の収率、磁気測定から求めた常温１５ｋＧで
の飽和磁化、元素分析の炭素・窒素・水素などの含有量
から求めた鉄の含量、粉末Ｘ線から求めたα‐鉄（２θ
＝４５°）の結晶子の大きさ（Ｌ）及び熱分解温度をそ
れぞれ表２に示す。また、原料の使用条件を表１に示
す。なお、炭素／鉄モル比における炭素はジ‐ｎ‐プロ
ピルアミンの炭素である。また、複合微粒子の収率は、
鉄ペンタカルボニルとジ‐ｎ‐プロピルアミンとの合計
量に対する重量％である。Example 1 4 mmol (0.783 g) of iron pentacarbonyl and di-
2 mmol (0.202 g) of n-propylamine was mixed [carbon / iron = 6/4 (molar ratio)], placed in the left end of a quartz reaction tube, and cooled with liquid nitrogen. After evacuation of the system for about 3 hours, the right side of the reaction tube was heated to 900 ° C., and after reaching the reaction temperature, the raw material mixture at the left end was heated and evaporated, and the vapor was led to the heating section on the right side. After reacting at 900 ° C for 45 minutes,
After exhausting at the same temperature for 30 minutes and cooling, 0.1595 g of a product adhered to the inner wall of the reaction tube was obtained. The yield of the obtained iron-carbon composite ferromagnetic fine particles, the saturation magnetization at room temperature of 15 kG determined by magnetic measurement, the iron content determined from the content of carbon, nitrogen, hydrogen, etc. in elemental analysis, and the powder X-ray Α-iron (2θ
Table 2 shows the crystallite size (L) at 45 °) and the thermal decomposition temperature. Table 1 shows the usage conditions of the raw materials. The carbon in the carbon / iron molar ratio is carbon of di-n-propylamine. Further, the yield of the composite fine particles is
It is a weight% with respect to the total amount of iron pentacarbonyl and di-n-propylamine.
【００２４】実施例２〜４ 実施例１において、ジ‐ｎ‐プロピルアミンの代わりに
シクロヘキサン、ジエチルアミン及びジ‐ｎ‐ブチルア
ミン２ｍｍｏｌをそれぞれ用いた以外は、実施例１と同
様にして実施した。原料の使用条件を表１に、得られた
鉄−炭素複合強磁性微粒子の収率、飽和磁化、鉄の含
量、結晶子の大きさ及び熱分解温度を表２に示す。Examples 2 to 4 The procedure of Example 1 was repeated, except that cyclohexane, diethylamine and di-n-butylamine (2 mmol) were used instead of di-n-propylamine. Table 1 shows the use conditions of the raw materials, and Table 2 shows the yield, saturation magnetization, iron content, crystallite size, and thermal decomposition temperature of the obtained iron-carbon composite ferromagnetic fine particles.
【００２５】実施例５、６ 実施例１において、ジ‐ｎ‐プロピルアミンの使用量を
それぞれ１ｍｍｏｌ及び４ｍｍｏｌに変えた以外は、実
施例１と同様にして実施した。原料の使用条件を表１
に、得られた鉄−炭素複合強磁性微粒子の収率、飽和磁
化、鉄の含量、結晶子の大きさ及び熱分解温度を表２に
示す。Examples 5 and 6 The procedure of Example 1 was repeated, except that the amounts of di-n-propylamine used were changed to 1 mmol and 4 mmol, respectively. Table 1 shows the usage conditions of raw materials
Table 2 shows the yield, saturation magnetization, iron content, crystallite size and thermal decomposition temperature of the obtained iron-carbon composite ferromagnetic fine particles.
【００２６】実施例７〜９ 実施例１において、熱分解温度をそれぞれ８００℃、９
５０℃及び１０００℃に変えた以外は、実施例１と同様
にして実施した。原料の使用条件を表１に、得られた鉄
−炭素複合強磁性微粒子の収率、飽和磁化、鉄の含量、
結晶子の大きさ及び熱分解温度を表２に示す。Examples 7 to 9 In Example 1, the thermal decomposition temperatures were 800 ° C. and 9 respectively.
It carried out like Example 1 except having changed into 50 ° C and 1000 ° C. The usage conditions of the raw materials are shown in Table 1, yield of the obtained iron-carbon composite ferromagnetic fine particles, saturation magnetization, iron content,
Table 2 shows the crystallite size and the thermal decomposition temperature.
【００２７】比較例 実施例１において、鉄ペンタカルボニルとジ‐ｎ‐プロ
ピルアミンの代わりにフェロセン５．４ｍｍｏｌ（１
ｇ）を用いた以外は、実施例１と同様にして実施した。
原料の使用条件を表１に、得られた鉄−炭素複合強磁性
微粒子の飽和磁化、鉄の含量、結晶子の大きさ及び熱分
解温度を表２に示す。表２から分かるように、飽和磁化
は４７．７ｅｍｕＧ／ｇで、実施例の値の半分以下であ
り、また鉄の結晶子の大きさは１９．６８ｎｍで、実施
例の値の倍以上であった。Comparative Example In Example 1, instead of iron pentacarbonyl and di-n-propylamine, ferrocene 5.4 mmol (1
It carried out like Example 1 except having used g).
Table 1 shows the usage conditions of the raw materials, and Table 2 shows the saturation magnetization, iron content, crystallite size and thermal decomposition temperature of the obtained iron-carbon composite ferromagnetic fine particles. As can be seen from Table 2, the saturation magnetization was 47.7 emuG / g, which was less than half the value of the example, and the size of the iron crystallite was 19.68 nm, which was more than twice the value of the example. It was
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
Claims (4)
を熱分解処理することを特徴とする鉄−炭素複合強磁性
微粒子の製造方法。1. A method for producing iron-carbon composite ferromagnetic fine particles, which comprises subjecting a mixture of an organic substance and an iron carbonyl compound to thermal decomposition treatment.
１記載の製造方法。2. The production method according to claim 1, wherein the organic substance is an organic low-molecular compound.
が、有機物の炭素／鉄モル比０．０１〜１０のものであ
る請求項１又は２記載の製造方法。3. The production method according to claim 1, wherein the mixture of the organic substance and the iron carbonyl compound has an organic substance carbon / iron molar ratio of 0.01 to 10.
在下に５００〜２０００℃の範囲の温度において行う請
求項１、２又は３記載の製造方法。4. The production method according to claim 1, 2 or 3, wherein the thermal decomposition treatment is carried out under reduced pressure or in the presence of an inert gas at a temperature in the range of 500 to 2000 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7245857A JP2782589B2 (en) | 1995-09-25 | 1995-09-25 | Method for producing iron-carbon composite ferromagnetic fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7245857A JP2782589B2 (en) | 1995-09-25 | 1995-09-25 | Method for producing iron-carbon composite ferromagnetic fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0986915A true JPH0986915A (en) | 1997-03-31 |
| JP2782589B2 JP2782589B2 (en) | 1998-08-06 |
Family
ID=17139871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7245857A Expired - Lifetime JP2782589B2 (en) | 1995-09-25 | 1995-09-25 | Method for producing iron-carbon composite ferromagnetic fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2782589B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057626A1 (en) * | 2002-01-07 | 2003-07-17 | The University Of Reading | Microparticles and methods of making them |
| JP2010212580A (en) * | 2009-03-12 | 2010-09-24 | Kurimoto Ltd | Magnetic viscous fluid |
| EP3480340A1 (en) * | 2017-11-03 | 2019-05-08 | The Boeing Company | Iron particle passivation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270406A (en) * | 1987-04-25 | 1988-11-08 | Mitsubishi Petrochem Co Ltd | Production of metal hyperfine powder |
| JPS6483605A (en) * | 1987-09-28 | 1989-03-29 | Mitsubishi Petrochemical Co | Production of superfine metal powder |
| JPH02111804A (en) * | 1988-10-20 | 1990-04-24 | Mitsubishi Petrochem Co Ltd | Manufacture of magnetic metal powder |
-
1995
- 1995-09-25 JP JP7245857A patent/JP2782589B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270406A (en) * | 1987-04-25 | 1988-11-08 | Mitsubishi Petrochem Co Ltd | Production of metal hyperfine powder |
| JPS6483605A (en) * | 1987-09-28 | 1989-03-29 | Mitsubishi Petrochemical Co | Production of superfine metal powder |
| JPH02111804A (en) * | 1988-10-20 | 1990-04-24 | Mitsubishi Petrochem Co Ltd | Manufacture of magnetic metal powder |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057626A1 (en) * | 2002-01-07 | 2003-07-17 | The University Of Reading | Microparticles and methods of making them |
| JP2010212580A (en) * | 2009-03-12 | 2010-09-24 | Kurimoto Ltd | Magnetic viscous fluid |
| EP3480340A1 (en) * | 2017-11-03 | 2019-05-08 | The Boeing Company | Iron particle passivation |
| US10774218B2 (en) | 2017-11-03 | 2020-09-15 | The Boeing Company | Iron particle passivation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2782589B2 (en) | 1998-08-06 |
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