JP3073807B2 - Iron-rare earth permanent magnet material and method for producing the same - Google Patents

Iron-rare earth permanent magnet material and method for producing the same

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Publication number
JP3073807B2
JP3073807B2 JP03257932A JP25793291A JP3073807B2 JP 3073807 B2 JP3073807 B2 JP 3073807B2 JP 03257932 A JP03257932 A JP 03257932A JP 25793291 A JP25793291 A JP 25793291A JP 3073807 B2 JP3073807 B2 JP 3073807B2
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Japan
Prior art keywords
powder
iron
rare earth
alloy
permanent magnet
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JP03257932A
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Japanese (ja)
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JPH0565603A (en
Inventor
雅夫 岩田
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Hitachi Metals Ltd
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Hitachi Metals Ltd
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/058—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • H01F1/0593—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2 of tetragonal ThMn12-structure

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、すぐれた磁気特性を有
する鉄−希土類系永久磁石材料およびその製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an iron-rare earth permanent magnet material having excellent magnetic properties and a method for producing the same.

【０００２】[0002]

【従来の技術】Ｆｅ，Ｃｏ等の３ｄ遷移金属とＲ（Ｙ，
Ｔｈおよびすべてのランタノイド元素からなる群の中か
ら選ばれた１種または２種以上の元素の組合せ）とから
なる金属間化合物の中には高い結晶磁気異方性と大きな
飽和磁化とを示すものがあり、高保磁力、高エネルギ−
積を有する永久磁石材料として有望である。しかし、Ｆ
ｅ−Ｒのみの２元系からなる合金では、高いキュリー点
や一軸の結晶磁気異方性を得ることは難しい場合が多
い。このために、第３の元素としてＮ(窒素)を添加する
ことによりその点を改良した材料が、先に本発明者によ
り提供されている（特開昭６０−１３１９４４号）。ま
た、Ｓｍ−Ｆｅの２元系合金もキュリー点・結晶磁気異
方性の両面から見て永久磁石材料としては適さないが、
近年、これに第３の元素としてＴｉ，Ｖ，Ｃｒ，Ａｌ，
Ｓｉ，Ｍｏ，Ｗを添加することにより特性の改善を計る
試みが行われている（ K.H.J.Buschow: Journal of App
lied Physics, 63巻, 3130頁, 1988年発行）。 すなわ
ち、ＧをＴｉ，Ｖ，Ｃｒ，Ａｌ，Ｓｉ，Ｍｏ，Ｗとする
とき、Ｓｍ（Ｆｅ1-xＧx）12なる組成の合金では体心正
方晶構造が安定化され、これが優れた永久磁石特性を示
す、というものである。中でも、ＳｍＦｅ11Ｔｉが優れ
ている、とされる。2. Description of the Related Art 3d transition metals such as Fe and Co and R (Y,
And one or more elements selected from the group consisting of Th and all of the lanthanoid elements) which exhibit high magnetocrystalline anisotropy and large saturation magnetization. With high coercive force and high energy
It is promising as a permanent magnet material having a product. But F
It is often difficult to obtain a high Curie point or uniaxial crystal magnetic anisotropy with a binary alloy composed of only e-R. To this end, a material improved in this respect by adding N (nitrogen) as a third element has been previously provided by the present inventor (JP-A-60-131944). Also, a binary alloy of Sm-Fe is not suitable as a permanent magnet material in terms of both Curie point and crystal magnetic anisotropy,
In recent years, Ti, V, Cr, Al,
Attempts have been made to improve characteristics by adding Si, Mo, and W (KHJ Buschow: Journal of App.
lied Physics, 63, 3130, 1988). That is, when G is Ti, V, Cr, Al, Si, Mo, and W, the alloy having the composition of Sm (Fe 1-x G x ) 12 stabilizes the body-centered tetragonal structure, which is an excellent permanent material. It shows magnet properties. Among them, SmFe 11 Ti is said to be excellent.

【０００３】[0003]

【発明が解決しようとする課題】しかし、Ｓｍ（Ｆｅ
1-xＧx）12なる組成の合金において、体心正方晶構造を
生成させ所望の特性を得るためには超急冷法やメカニカ
ルアロイング法，等の特殊な製法を必要としているのが
現状である。しかも、その場合でも所期の特性が必ずし
も安定的には得られにくい、すなわち、同じ組成の合金
を同じように処理しても所期の特性は得られない場合が
あったりする、といった問題もある。However, Sm (Fe
In 1-x G x) 12 comprising an alloy of composition, current situation is in order to obtain the desired properties to produce a body-centered tetragonal structure in need rapid quenching method or the mechanical alloying method, a special production method etc. It is. Moreover, even in such a case, the desired characteristics are not always obtained stably, that is, even if the alloys having the same composition are treated in the same manner, the desired characteristics may not be obtained in some cases. is there.

【０００４】[0004]

【課題を解決するための手段】上記のように、Ｓｍ（Ｆ
ｅ1-xＧx）12なる合金において体心正方晶構造を生成さ
せ所望の特性を得るためには超急冷法やメカニカルアロ
イング法等の特殊な製法を必要とすること、また、その
場合でも所期の特性が必ずしも安定的には得られにくい
こと、の理由につき、本発明者は鋭意検討を重ねた結
果、これらの問題の解決のためには、いわゆる「準安定
・非平衡な状態」の関与に着目することが重要であるら
しいことがわかった。すなわち、超急冷法においてはそ
の急速なる冷却により原子拡散が抑制されることから、
また、メカニカルアロイング法では処理そのものの特質
から、いずれも「準安定・非平衡な状態」が出現しやす
い状況にあるが、目的とする体心正方晶構造が形成され
るためには、その生成過程においてこのような「準安定
・非平衡な状態」の出現することが必須要件であるらし
いことがわかった。As described above, Sm (F
In order to generate a body-centered tetragonal structure and obtain desired characteristics in an alloy of e 1-x G x ) 12, a special manufacturing method such as a super-quenching method or a mechanical alloying method is required. However, the present inventor has conducted intensive studies on the reason that the desired characteristics are not always obtained stably, and as a result of solving these problems, a so-called “metastable and non-equilibrium state” was found. It seems that it is important to focus on the involvement of "." In other words, in the rapid quenching method, atom diffusion is suppressed by rapid cooling,
In addition, in the mechanical alloying method, the “metastable and non-equilibrium state” is likely to appear due to the nature of the treatment itself, but in order for the desired body-centered tetragonal structure to be formed, It has been found that the appearance of such a “metastable and non-equilibrium state” appears to be an essential requirement in the generation process.

【０００５】しかし、これらのいわゆる「準安定・非平
衡な状態」は、元来が安定ではないところの "準安定・
非平衡" な状態のものなのであるから、わずかな微妙な
条件の違いにより、該相が生成されたり生成されなかっ
たりする場合があることは、むしろ当然とも言える。そ
こで、上記問題を解決して、体心正方晶構造が安定的に
生成されるようにするためには、合金中に格子間侵入型
原子であるＮ(窒素)もしくはＢ(硼素)もしくはＣ(炭素)
またはこれらの元素の組合せを含有させるようにすれ
ば、局所的な格子の乱れ、すなわち、本来の熱力学的完
全安定な状態とは異なったいわば準安定・非平衡な状態
がより容易に惹起されやすくなるようになり、効果的で
あるのではないかと考えて、この面からの検討を進めた
結果、本発明を完成するに到ったものである。However, these so-called "metastable and non-equilibrium states" are originally "metastable and non-equilibrium".
It is rather natural that the phase may or may not be produced by subtle differences in conditions, since it is in a "non-equilibrium" state. In order to stably generate a body-centered tetragonal structure, interstitial atoms such as N (nitrogen) or B (boron) or C (carbon) are required in the alloy.
Alternatively, when a combination of these elements is contained, local lattice disorder, that is, a metastable / non-equilibrium state which is different from the original thermodynamically completely stable state is more easily caused. As a result, the present invention has been completed, and as a result of studying from this aspect, the present invention has been completed.

【０００６】すなわち、本発明は、ＲをＹ，Ｔｈおよび
すべてのランタノイド元素からなる群の中から選ばれた
１種または２種以上の元素の組合せ、ＸをＮ(窒素)、Ｃ
(炭素)もしくはＢ(硼素)またはこれらの元素の組合せと
するとき、原子百分率で 、Ｒ：３〜３０％、Ｘ：０．
３〜５０％を含み、残部が実質的にＦｅから成り、主相
が体心正方晶ＴｈＭｎ１２型構造を有することを特徴と
する鉄−希土類系永久磁石材料である。また本発明は、
予め、実質的にＮを含有しないかまたはＮ含有量が所望
の量よりは少ない鉄−希土類系合金を作製した後、これ
をＮを含む気体中で処理して前記合金中にＮを侵入させ
ることにより所望のＮ含有量にする前記鉄−希土類系永
久磁石材料の製造方法である。That is, according to the present invention, R represents a combination of one or more elements selected from the group consisting of Y, Th and all lanthanoid elements, and X represents N (nitrogen), C
When (carbon) or B (boron) or a combination of these elements is used, R: 3 to 30%, X: 0.
An iron-rare earth permanent magnet material containing 3 to 50%, the balance substantially consisting of Fe, and a main phase having a body-centered tetragonal ThMn 12 type structure. The present invention also provides
After previously preparing an iron-rare earth alloy containing substantially no N or having a N content smaller than a desired amount, the alloy is treated in a gas containing N to allow N to enter the alloy. This is a method for producing the iron-rare earth permanent magnet material having a desired N content.

【０００７】[0007]

【作用】以下、本発明の鉄−希土類系永久磁石材料につ
き詳細に説明する。本発明において、Ｒは、磁気異方性
を生み保磁力を発生させる上で本質的な役割を担う、極
めて重要な構成元素である。Ｒとしては、Ｙ，Ｔｈおよ
びすべてのランタノイド元素、すなわち、Ｙ，Ｌａ，Ｃ
ｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，ＬｕおよびＴｈが含ま
れ、これらからなる群の中から選ばれた１種または２種
以上の元素の組合せとして用いればよい。Ｒは、原子百
分率で３〜３０％、好ましくは５〜１８％、さらに好ま
しくは６〜１２％の範囲にあることが必要である。Ｒが
３％未満では保磁力が得られないので、Ｒの下限は３％
とする。一方、Ｒが３０％を超えると飽和磁化が小さく
なりすぎるとともに、材料の酸化が激しく耐食性がきわ
めて悪くなるので、Ｒの上限は３０％とする。安定した
磁気特性を得るためには、Ｒの量は通常５〜１８％の範
囲に選ぶことが望ましい。とりわけＲの量を６〜１２％
とするときは体心正方晶構造が安定に得られやすい。な
お、特に高い磁束密度と大きなエネルギ−積とを得たい
時には、Ｒを７〜９％に選択することが有効である。Hereinafter, the iron-rare earth permanent magnet material of the present invention will be described in detail. In the present invention, R is a very important constituent element that plays an essential role in generating magnetic anisotropy and generating coercive force. R represents Y, Th and all lanthanoid elements, ie, Y, La, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
y, Ho, Er, Tm, Yb, Lu, and Th are included and may be used as a combination of one or more elements selected from the group consisting of these. R needs to be in the range of 3 to 30%, preferably 5 to 18%, more preferably 6 to 12% in atomic percentage. If R is less than 3%, a coercive force cannot be obtained, so the lower limit of R is 3%.
And On the other hand, if R exceeds 30%, the saturation magnetization becomes too small, and the material is oxidized severely, resulting in extremely poor corrosion resistance. Therefore, the upper limit of R is set to 30%. In order to obtain stable magnetic characteristics, it is desirable that the amount of R is usually selected in the range of 5 to 18%. Especially the amount of R is 6-12%
In this case, a body-centered tetragonal structure is easily obtained in a stable manner. In particular, when it is desired to obtain a high magnetic flux density and a large energy product, it is effective to select R to be 7 to 9%.

【０００８】Ｍは、体心正方晶構造を生成する上で大き
な効果を持つ元素である。Ｍとしては、Ｔｉ，Ｃｒ，
Ｖ，Ｚｒ，Ｎｂ，Ａｌ，Ｍｏ，Ｍｎ，Ｈｆ，Ｔａ，Ｗ，
Ｍｇ，Ｓｉ，Ｓｎ，Ｇｅが含まれ、これらからなる群の
中から選ばれた１種または２種以上の元素の組合せとし
て用いればよい。Ｍの中の多くの元素は、また一方、本
発明構成元素の中のＸとの親和力が強い元素でもあるの
で、本発明においては、特に比較的不安定なＮを合金中
で安定化させる上でもＭがまた大きな効果を有してい
る。そして、後述のようにＸ自体もまた体心正方晶構造
を安定化させる効果を有しているので、結局、ＭとＸと
は相乗的に作用して体心正方晶構造を安定化する上に大
いに効果がある。これらの効果を発揮させるためには、
Ｍの量は原子百分率で０．５〜３０％であればよいが、
通常は１〜１５％であることが好ましい。Ｍが０．５％
未満では上記した効果が得られないので、Ｍの下限は
０．５％とする。一方、Ｍが３０％を超えると飽和磁化
が小さくなりすぎるので、Ｍの上限は３０％とする。こ
の内でも、安定した磁気特性を得るためには、Ｍの量は
通常１〜１５％の範囲に選ぶことが望ましい。特にＭが
Ｔｉの場合には、その含有量が重量百分率で１０％を超
えるように選ぶことにより、いっそう安定なＴｈＭｎ12
型体心正方晶構造を生成させることができ、材料の熱的
安定性をも増すことができる。上記したＭは、いずれも
保磁力Ｈｃを発生させる上で効果があるが、それらの中
でＡｌ，Ｓｉ，Ｓｎ，Ｇｅには飽和磁化を低下させやす
い欠点がある。[0008] M is an element having a great effect in generating a body-centered tetragonal structure. As M, Ti, Cr,
V, Zr, Nb, Al, Mo, Mn, Hf, Ta, W,
Mg, Si, Sn, and Ge are included, and may be used as a combination of one or more elements selected from the group consisting of these. Many of the elements in M are also elements having a strong affinity for X in the constituent elements of the present invention. Therefore, in the present invention, particularly, the relatively unstable N is stabilized in the alloy. But M also has a great effect. Since X itself also has the effect of stabilizing the body-centered tetragonal structure as described later, M and X eventually act synergistically to stabilize the body-centered tetragonal structure. Is very effective. To achieve these effects,
The amount of M may be 0.5 to 30% in atomic percentage,
Usually, it is preferably 1 to 15%. M is 0.5%
If it is less than the above, the above-mentioned effects cannot be obtained, so the lower limit of M is set to 0.5%. On the other hand, if M exceeds 30%, the saturation magnetization becomes too small, so the upper limit of M is set to 30%. Among them, in order to obtain stable magnetic properties, it is desirable that the amount of M is usually selected in the range of 1 to 15%. In particular, when M is Ti, the content is selected to be more than 10% by weight, so that the more stable ThMn 12
A type-centered tetragonal structure can be generated and the thermal stability of the material can be increased. All of the above M are effective in generating the coercive force Hc, but among them, Al, Si, Sn, and Ge have a disadvantage that the saturation magnetization is easily reduced.

【０００９】Ｘ，即ちＮ(窒素)もしくはＢ(硼素)もしく
はＣ(炭素)またはこれらの元素の組合せ，は、本発明に
おいて、合金中に準安定・非平衡な状態を惹起すること
により体心正方晶構造を生成する上でのいわば一種の駆
動力としての作用を発揮するとともに、磁気特性面から
いうと飽和磁化を増すとともに高保磁力を発生させる本
質的に重要な役割を果たしているところの必須構成成分
であるが、その含有量は、原子百分率で０．３〜５０
％、好ましくは２〜２０％、さらに好ましくは５〜１５
％の範囲にあることが必要である。Ｘが０．３％未満で
はＸの添加効果が認められず飽和磁化が小さいので、Ｘ
の下限は０．３％とする。一方、Ｘが５０％を超えると
飽和磁化がかえって小さくなりすぎるので、Ｘの上限は
５０％とする。体心正方晶構造を安定的に生成させるた
めには、Ｘの量は通常２〜２０％、とりわけ５〜１５％
の範囲に選ぶことが望ましい。X, that is, N (nitrogen) or B (boron) or C (carbon) or a combination of these elements, is used in the present invention to induce a metastable and non-equilibrium state in the alloy, thereby achieving a body-centered state. Indispensable in that it acts as a kind of driving force in generating a tetragonal structure, and plays an essentially important role in increasing saturation magnetization and generating high coercive force in terms of magnetic properties. Although it is a constituent component, its content is from 0.3 to 50 in atomic percentage.
%, Preferably 2 to 20%, more preferably 5 to 15%
%. When X is less than 0.3%, the effect of addition of X is not recognized and the saturation magnetization is small.
Is 0.3%. On the other hand, when X exceeds 50%, the saturation magnetization is rather too small, so the upper limit of X is set to 50%. In order to stably form a body-centered tetragonal structure, the amount of X is usually 2 to 20%, particularly 5 to 15%.
It is desirable to select within the range.

【００１０】Ｘは材料中において、少なくとも一時期
は、格子間侵入型の原子として存在する必要がある。そ
うすることによって、Ｘは合金中に局所的な格子の乱れ
を生じ一種の準安定・非平衡な状態を惹起し、これが体
心正方晶構造を生成する上でのいわば「活性化された状
態」として作用し得る。X must exist as interstitial atoms in the material for at least one time. By doing so, X causes a local lattice disorder in the alloy, causing a kind of metastable and non-equilibrium state, which is a so-called "activated state" in forming a body-centered tetragonal structure. "

【００１１】このためには、特にＮについて言えば、こ
れを材料中に含有させる方法としては、Ｎをもともと含
むようなものを原材料として用いるという方法によって
もよいが、むしろ、後の工程において、適宜な気体中も
しくは液体中において処理することによりＮを材料の中
へ侵入させる方法が推奨される。Ｎを侵入させるために
用いる気体としては、Ｎ2ガス、Ｎ2＋Ｈ2混合ガス、Ｎ
Ｈ3ガス、およびこれらの混合ガス等（Ｈ2ガスもしくは
その他の不活性ガス等で希釈する場合を含む）を用いる
ことが出来る。また、その場合の処理温度としては通常
２００〜１０００℃、特に４００〜７００℃とすればよ
い。また、その場合の処理時間としては通常０．２〜５
０時間程度でよいが、材料の所望特性に応じて適宜選択
すればよい。[0011] For this purpose, particularly with respect to N, the method of incorporating N into the material may be a method of using a material that originally contains N as a raw material, but rather, in a later step, It is recommended that N be introduced into the material by treating in an appropriate gas or liquid. Examples of the gas used for infiltrating N include N 2 gas, N 2 + H 2 mixed gas, and N 2 gas.
H 3 gas and a mixed gas thereof (including a case of dilution with H 2 gas or another inert gas) can be used. In this case, the processing temperature may be generally 200 to 1000 ° C, particularly 400 to 700 ° C. The processing time in that case is usually 0.2 to 5
The time may be about 0 hours, but may be appropriately selected according to the desired characteristics of the material.

【００１２】一方、Ｂ，Ｃを含有させる方法について
は、Ｂ，Ｃをもともと含むようなものを原材料として用
いることが通常に可能である。ただし、この場合でも、
もしＢ，Ｃの化合物の形のものを用いる場合には、極め
て安定な化合物，例えばＭ元素との硼化物，Ｒ元素との
硼化物，Ｍ元素との炭化物，Ｒ元素との炭化物，等は合
金中においてＢ，Ｃ原子単体の形に解離せず、従って格
子間侵入型の原子として存在させることが困難な場合が
多いので、あまり好ましくない。Ｂ，Ｃの原材料として
は、金属ボロン，黒鉛等の純元素，または比較的安定度
の低い化合物，例えばフェロボロン，Ｆｅ3Ｃ等Ｆｅと
の炭化物，等が推奨される。本発明において、Ｂは他の
２つの格子間侵入型元素Ｎ，Ｃに比較して、原材料から
合金中に添加することは最も容易である点が特長であ
る。Ｂ，Ｃは、本発明の鉄−希土類系永久磁石材料の中
でＭを含有しないような鉄−希土類系永久磁石材料に対
しては特に効果的である。これは、Ｂ，ＣはＮと異なり
最初から材料中に存在させておくことが容易に可能であ
るためであると考えられる。On the other hand, as for the method of containing B and C, it is usually possible to use those containing B and C as raw materials. However, in this case,
If the compounds in the form of compounds B and C are used, extremely stable compounds such as borides with element M, borides with element R, carbides with element M, carbides with element R, etc. It is not preferable because it does not dissociate into B and C atoms alone in the alloy, and it is often difficult to make them exist as interstitial atoms. As raw materials for B and C, pure elements such as metal boron and graphite, or compounds having relatively low stability, for example, ferroboron, carbides with Fe such as Fe 3 C, etc. are recommended. In the present invention, B is characterized in that it is easiest to add B from a raw material into an alloy as compared with the other two interstitial elements N and C. B and C are particularly effective for the iron-rare earth permanent magnet material containing no M in the iron-rare earth permanent magnet material of the present invention. This is presumably because B and C, unlike N, can be easily present in the material from the beginning.

【００１３】なお、ＮもしくはＢ，Ｃを材料中に存在さ
せることにより体心正方晶構造が安定化される理由につ
いては、正確なところは未だ不明であり鋭意検討中の段
階であるが、一応次のように推定される。例えばＳｍＦ
ｅ12では体心正方晶構造が生成されないが、これはＴｈ
（＋４価のイオン半径＝1.02 ）対 Ｍｎ（＋２価のイ
オン半径＝0.80 ），Ｓｍ（＋３価のイオン半径＝1.00
）対 Ｆｅ（＋３価のイオン半径＝0.60 ）で比較し
た場合、Ｆｅの大きさがＳｍに比べて小さすぎるためで
あると考えられる。そして、この中のＦｅの一部を例え
ばＴｉ（＋３価のイオン半径＝0.69 ）等で置換して前
記ＳｍＦｅ11Ｔｉ等とすることにより体心正方晶ＴｈＭ
ｎ12型構造が生成されるようになるのであるが、Ｔｉ等
は図１に示す体心正方晶ＴｈＭｎ12型構造において８ｉ
サイトに存在するといわれている。従って、このときの
Ｔｉ等の役割は、その原子径がＦｅよりも大きいこと等
に由来して８ｉサイトにおいて格子を拡張している点に
あると考えられ、このことからＳｍ原子径に見合うよう
な格子の整合が実現され体心正方晶構造の生成が可能に
なってくるものと考えられる。そうであるとするなら
ば、格子を伸長する上で大いに効果のある格子間侵入型
原子のＸを上記Ｔｉに代えて，あるいは上記Ｔｉと併せ
用いることにより、いっそう安定的にＴｈＭｎ12型構造
の生成を実現することが可能になる。The exact reason why the body-centered tetragonal crystal structure is stabilized by the presence of N or B, C in the material is not yet clear and is under intensive study. It is estimated as follows. For example, SmF
body-centered tetragonal structure at e 12 is not generated, but this is Th
(+4 ion radius = 1.02) vs. Mn (+2 ion radius = 0.80), Sm (+3 ion radius = 1.00)
This is considered to be because the size of Fe is too small compared to Sm when compared with Fe (+ trivalent ion radius = 0.60). Then, a part of Fe therein is replaced with, for example, Ti (+3 valent ion radius = 0.69) or the like to obtain the above-mentioned SmFe 11 Ti or the like, thereby obtaining a body-centered tetragonal ThM
An n 12 type structure is generated, and Ti and the like are 8i in the body-centered tetragonal ThMn 12 type structure shown in FIG.
It is said that it exists on the site. Therefore, the role of Ti or the like at this time is considered to be that the lattice is expanded at the 8i site due to the fact that its atomic diameter is larger than that of Fe. It is considered that a proper lattice matching is realized and a body-centered tetragonal structure can be generated. If so, X of the interstitial interpenetrating atom, which is very effective in elongating the lattice, can be used more stably for the ThMn 12 type structure by using the above-mentioned Ti instead of or in combination with the above-mentioned Ti. Generation can be realized.

【００１４】格子間侵入型原子Ｘとしては、Ｎ(窒素)も
しくはＢ(硼素)もしくはＣ(炭素)の各々を単独で用いて
もよいが、それらを組み合わせて用いるといっそう効果
的である場合もある。合金が元素Ｍを含まない場合に
は、特にＮとＢ，ならびにＣとＢの組み合わせが効果的
である。Ｎ，Ｃが占める格子間位置サイトとＢが占める
格子間位置サイトとはおそらく異なると思われる点にそ
の理由があるものと考えられる。また、ＮならびにＢ，
Ｃはいずれも格子間侵入型に存在し得る原子であるとい
う点では共通点を有するのであるが、前記のように、Ｎ
は気体から、Ｂ，Ｃは原材料から、というふうに敢えて
異なった機構を通じて合金中に含有させるようにすれ
ば、それらの各々の機構で占めやすい格子間位置を各々
に占めさせ得ることから、性格の異なる両機構をともに
利用することにより格子間侵入型構造の形成をより確実
なものとするようにできることが期待される。また、そ
のような機構の違いに由来して、ＮとＢ，Ｃとの間には
メカニズム細部については当然差異があることが予想さ
れ、また、ＢとＣとの間にも原子径・原子価（即ち，電
子構造）等の違いに由来して当然差異があることも予想
される。As the interstitial atom X, N (nitrogen), B (boron) or C (carbon) may be used alone, but it may be more effective to use them in combination. is there. When the alloy does not contain the element M, a combination of N and B and a combination of C and B are particularly effective. The reason is that the interstitial position site occupied by N and C is probably different from the interstitial position site occupied by B. Also, N and B,
C has a common feature in that C is an atom that can exist in an interstitial manner.
If the alloys are intentionally included in the alloy through different mechanisms, such as from gases and B and C from raw materials, they can occupy interstitial positions easily occupied by each of these mechanisms. It is expected that the formation of the interstitial interstitial structure can be made more reliable by using both different mechanisms. Also, it is expected that there is a difference in the details of the mechanism between N and B and C due to such a difference in the mechanism. It is also expected that there will naturally be differences due to differences in valence (ie, electronic structure).

【００１５】なお、体心正方晶構造の生成をいっそう確
実なものとし、所望の特性を得るために、本発明と超急
冷法やメカニカルアロイング法等の処理を組み合わせて
もよいことは言うまでもない。It is needless to say that the present invention may be combined with a process such as a super-quenching method or a mechanical alloying method in order to further secure the formation of the body-centered tetragonal structure and obtain desired characteristics. .

【００１６】本発明の鉄−希土類系永久磁石材料におい
て、Ｆｅの一部をＣｏで置換することにより、保磁力を
向上させると共に材料磁気特性の温度特性を向上させる
ことができる。このためにはＣｏの量は原子百分率で１
〜５０％、好ましくは５〜３０％の範囲にあることが望
ましい。Ｃｏ含有量が１％未満では保磁力を向上する効
果が小さく、また５０％を越えると飽和磁束密度が次第
に低下してくる。Ｃｏの量を５〜３０％に選ぶことによ
り材料磁気特性の温度特性が向上する。In the iron-rare earth permanent magnet material of the present invention, by substituting a part of Fe with Co, the coercive force can be improved and the temperature characteristics of the material magnetic characteristics can be improved. For this purpose, the amount of Co is 1 atomic percent.
It is desirably in the range of ~ 50%, preferably 5-30%. If the Co content is less than 1%, the effect of improving the coercive force is small, and if it exceeds 50%, the saturation magnetic flux density gradually decreases. By selecting the amount of Co from 5 to 30%, the temperature characteristics of the magnetic properties of the material are improved.

【００１７】本発明の鉄−希土類系永久磁石材料におい
て、Ｆｅの一部をＮｉで置換することにより、材料の耐
食性を改善させることができる。このためにはＮｉの量
は原子百分率で０．５〜３０％、好ましくは２〜１０％
の範囲にあることが望ましい。０．５％未満では耐食性
の向上効果が少なく、また３０％を越えると飽和磁束密
度が低下する。In the iron-rare earth permanent magnet material of the present invention, the corrosion resistance of the material can be improved by substituting a part of Fe with Ni. For this purpose, the amount of Ni is 0.5 to 30% by atom, preferably 2 to 10%.
Is desirably within the range. If it is less than 0.5%, the effect of improving the corrosion resistance is small, and if it exceeds 30%, the saturation magnetic flux density decreases.

【００１８】[0018]

【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明は特にこれらに限定されるものではな
い。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

【００１９】（実施例１） 重量比でＦｅ６７．１％，Ｎｄ２１．５％，Ｔｉ５．４
８％，Ｃｒ５．９５％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ７６．１％，Ｎｄ９．４２％，Ｔｉ７．２５％，Ｃｒ
７．２５％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらにデ
ィスクミルで粉砕して、約３０μm径の粉体とした。こ
の粉体にＮを含有させるために、これをＮ2ガス中ほぼ
５００℃付近の温度において処理した。この処理により
材料中にＮが１．３１重量％含有された。したがって材
料全体としての組成は、重量％でＦｅ６６．２％，Ｎｄ
２１．２％，Ｔｉ５．４１％，Ｃｒ５．８７％，Ｎ
１．３１％、すなわち原子％ではＦｅ７１．８％，Ｎｄ
８．８９％，Ｔｉ６．８４％，Ｃｒ６．８４％，Ｎ
５．６７％に相当する。この粉体をジェットミルでさら
に微粉砕した後、２０kOeの磁場中において配向させワ
ックスで固化して磁気特性を測定したところ、飽和磁化
（４πＩｓ）は１３７emu/g，保磁力（ｉＨｃ）は５３
００ Oeであった。また、得られた粉体をＣｕＫα線を
用いてＸ線回折したところ、その多くが体心正方晶Ｔｈ
Ｍｎ12型の結晶構造であると認められた。Example 1 67.1% Fe, 21.5% Nd, 5.4% Ti by weight
The raw materials were weighed so as to be 8% and Cr 5.95%, and were melted in an argon atmosphere. This alloy is F
e76.1%, Nd9.42%, Ti 7.25%, Cr
Equivalent to 7.25%. 900 ° C of the obtained ingot
For 7 days, and then roughly pulverized in an iron mortar and further pulverized with a disc mill to obtain a powder having a diameter of about 30 μm. This powder was treated at a temperature of about 500 ° C. in N 2 gas so as to contain N. As a result of this treatment, 1.31% by weight of N was contained in the material. Therefore, the composition of the whole material is Fe 66.2% by weight%, Nd
21.2%, Ti 5.41%, Cr 5.87%, N
1.31%, that is, 71.8% Fe and Nd in atomic%
8.89%, Ti 6.84%, Cr 6.84%, N
This corresponds to 5.67%. This powder was further pulverized by a jet mill, and then oriented in a magnetic field of 20 kOe, solidified with wax, and measured for magnetic properties. The saturation magnetization (4πIs) was 137 emu / g, and the coercive force (iHc) was 53.
00 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, most of the powder was found to have a body-centered tetragonal Th.
The crystal structure was confirmed to be of Mn 12 type.

【００２０】（実施例２） 重量比でＦｅ６７．４％，Ｎｄ２１．６％，Ｔｉ１１．
０％となるように原料を秤量し、これをアルゴン雰囲気
中で溶製した。この合金は原子％でＦｅ７６．１％，Ｎ
ｄ９．４２％，Ｔｉ１４．５％に相当する。得られたイ
ンゴットを９００℃で７日間焼鈍した後、鉄製乳鉢中で
粗粉砕し、さらにディスクミルで粉砕して、約３０μm
径の粉体とした。この粉体にＮを含有させるために、こ
れをＮ2ガス中ほぼ５００℃付近の温度において処理し
た。この処理により材料中にＮが１．２６重量％含有さ
れた。したがって材料全体としての組成は、重量％でＦ
ｅ６６．６％，Ｎｄ２１．３％，Ｔｉ１０．９％，Ｎ
１．２６％、すなわち原子％ではＦｅ７２．０％，Ｎｄ
８．９１％，Ｔｉ１３．７％，Ｎ ５．４２％に相当す
る。この粉体をジェットミルでさらに微粉砕した後、２
０kOeの磁場中において配向させワックスで固化して磁
気特性を測定したところ、飽和磁化（４πＩｓ）は１４
３emu/g，保磁力（ｉＨｃ）は７８００ Oeであった。ま
た、得られた粉体をＣｕＫα線を用いてＸ線回折したと
ころ、その多くが体心正方晶ＴｈＭｎ12型の結晶構造で
あると認められた。(Example 2) Fe67.4%, Nd21.6%, Ti11.
The raw materials were weighed so as to be 0%, and were melted in an argon atmosphere. This alloy contains 76.1% Fe in atomic%, N
d corresponds to 9.42% and Ti corresponds to 14.5%. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar and further pulverized by a disc mill to obtain about 30 μm.
It was a powder of a diameter. This powder was treated at a temperature of about 500 ° C. in N 2 gas so as to contain N. As a result of this treatment, 1.26% by weight of N was contained in the material. Therefore, the composition of the material as a whole is expressed as F% by weight.
e66.6%, Nd21.3%, Ti10.9%, N
1.26%, that is, 72.0% of Fe in atomic%, Nd
It corresponds to 8.91%, Ti 13.7% and N 5.42%. After further pulverizing this powder with a jet mill,
When the magnetic properties were measured by orientation in a magnetic field of 0 kOe and solidification with wax, the saturation magnetization (4πIs) was 14
3 emu / g and coercive force (iHc) were 7800 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００２１】（実施例３） 重量比でＦｅ７１．１％，Ｎｄ２１．７％，Ｔｉ７．２
０％となるように原料を秤量し、これをアルゴン雰囲気
中で溶製した。この合金は原子％でＦｅ８０．９％，Ｎ
ｄ９．５６％，Ｔｉ９．５６％に相当する。得られたイ
ンゴットを９００℃で７日間焼鈍した後、鉄製乳鉢中で
粗粉砕し、さらにディスクミルで粉砕して、約３０μm
径の粉体とした。この粉体にＮを含有させるために、こ
れをＮ2ガス中ほぼ５００℃付近の温度において処理し
た。この処理により材料中にＮが１．１５重量％含有さ
れた。したがって材料全体としての組成は、重量％でＦ
ｅ７０．３％，Ｎｄ２１．５％，Ｔｉ７．１２％，Ｎ
１．１５％、すなわち原子％ではＦｅ７６．８％，Ｎｄ
９．０８％，Ｔｉ９．０８％，Ｎ ５．０３％に相当す
る。この粉体をジェットミルでさらに微粉砕した後、２
０kOeの磁場中において配向させワックスで固化して磁
気特性を測定したところ、飽和磁化（４πＩｓ）は９８
emu/g，保磁力（ｉＨｃ）は３１００ Oeであった。ま
た、得られた粉体をＣｕＫα線を用いてＸ線回折したと
ころ、その多くが体心正方晶ＴｈＭｎ12型の結晶構造で
あると認められた。Example 3 Fe 71.1%, Nd 21.7%, Ti 7.2 by weight
The raw materials were weighed so as to be 0%, and were melted in an argon atmosphere. This alloy is 80.9% Fe in atomic%, N
This corresponds to d 9.56% and Ti 9.56%. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar and further pulverized by a disc mill to obtain about 30 μm.
It was a powder of a diameter. This powder was treated at a temperature of about 500 ° C. in N 2 gas so as to contain N. As a result of the treatment, 1.15% by weight of N was contained in the material. Therefore, the composition of the material as a whole is expressed by weight% of F
e 70.3%, Nd 21.5%, Ti 7.12%, N
1.15%, that is, 76.8% Fe in atomic%, Nd
It corresponds to 9.08%, Ti 9.08%, and N 5.03%. After further pulverizing this powder with a jet mill,
When the magnetic properties were measured by orientation in a magnetic field of 0 kOe and solidification with wax, the saturation magnetization (4πIs) was 98%.
emu / g and coercive force (iHc) were 3100 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００２２】（実施例４） 重量比でＦｅ７３．９％，Ｓｍ２３．５％，Ｂ ２．６
０％となるように原料を秤量し、これをアルゴン雰囲気
中で溶製した。この合金は原子％でＦｅ７６．９％，Ｓ
ｍ９．０９％，Ｂ １４．０％に相当する。得られたイ
ンゴットを９００℃で７日間焼鈍した後、鉄製乳鉢中で
粗粉砕し、さらにディスクミルで粉砕して、約３０μm
径の粉体とした。この粉体にＮを含有させるために、こ
れをＮ2＋Ｈ2ガス中ほぼ５００℃付近の温度において処
理した。この処理により材料中にＮが１．５８重量％含
有された。したがって材料全体としての組成は、重量％
でＦｅ７２．７％，Ｓｍ２３．１％，Ｂ ２．５６％，
Ｎ １．５８％、すなわち原子％ではＦｅ７２．１％，
Ｓｍ８．５３％，Ｂ １３．１％，Ｎ ６．２３％に相当
する。この粉体をジェットミルでさらに微粉砕した後、
２０kOeの磁場中において配向させワックスで固化して
磁気特性を測定したところ、飽和磁化（４πＩｓ）は１
１５emu/g，保磁力（ｉＨｃ）は３１００ Oeであった。
また、得られた粉体をＣｕＫα線を用いてＸ線回折した
ところ、その多くが体心正方晶ＴｈＭｎ12型の結晶構造
であると認められた。Example 4 Fe 73.9%, Sm 23.5%, B 2.6 by weight
The raw materials were weighed so as to be 0%, and were melted in an argon atmosphere. This alloy contains 76.9% Fe in atomic%, S
m 9.09% and B 14.0%. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar and further pulverized by a disc mill to obtain about 30 μm.
It was a powder of a diameter. In order to make this powder contain N, it was treated in N 2 + H 2 gas at a temperature of about 500 ° C. As a result of this treatment, 1.58% by weight of N was contained in the material. Therefore, the composition of the whole material is
With Fe 72.7%, Sm 23.1%, B 2.56%,
N 1.58%, that is, 72.1% Fe in atomic%,
This corresponds to 8.53% of Sm, 13.1% of B, and 6.23% of N. After further pulverizing this powder with a jet mill,
When the magnetic properties were measured after orientation in a magnetic field of 20 kOe and solidification with wax, the saturation magnetization (4πIs) was 1
15 emu / g and coercive force (iHc) were 3100 Oe.
Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００２３】（実施例５） 重量比でＦｅ７３．９％，Ｎｄ２２．５％，Ｃ １．０
１％，Ｂ ２．６０％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ７３．３％，Ｎｄ８．６７％，Ｃ ４．６７％，Ｂ １
３．３％に相当する。得られたインゴットを９００℃で
７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらにディ
スクミルで粉砕して、約３０μm径の粉体とした。この
粉体をジェットミルでさらに微粉砕した後、２０kOeの
磁場中において配向させワックスで固化して磁気特性を
測定したところ、飽和磁化（４πＩｓ）は１１０emu/
g，保磁力（ｉＨｃ）は２５００ Oeであった。また、得
られた粉体をＣｕＫα線を用いてＸ線回折したところ、
その多くが体心正方晶ＴｈＭｎ12型の結晶構造であると
認められた。Example 5 73.9% Fe, 22.5% Nd, 1.0 C by weight
The raw materials were weighed so as to be 1% and B 2.60%, and were melted in an argon atmosphere. This alloy is F
e 73.3%, Nd 8.67%, C 4.67%, B1
It corresponds to 3.3%. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar and further pulverized by a disk mill to obtain a powder having a diameter of about 30 μm. After further pulverizing the powder with a jet mill, orienting it in a magnetic field of 20 kOe, solidifying it with wax, and measuring its magnetic properties, the saturation magnetization (4πIs) was 110 emu /
g, the coercive force (iHc) was 2500 Oe. When the obtained powder was subjected to X-ray diffraction using CuKα radiation,
Most of them were recognized as having a body-centered tetragonal ThMn 12 type crystal structure.

【００２４】（実施例６） 重量比でＦｅ５５．６％，Ｎｄ２０．８％，Ｔｉ１０．
６％，Ｃｏ１３．０％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ６２．９％，Ｎｄ９．０９％，Ｔｉ１４．０％，Ｃｏ
１４．０％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらにデ
ィスクミルで粉砕して、約３０μm径の粉体とした。こ
の粉体にＮを含有させるために、これをＮＨ3ガス中ほ
ぼ４５０℃付近の温度において処理した。この処理によ
り材料中にＮが１．６３重量％含有された。したがって
材料全体としての組成は、重量％でＦｅ５４．７％，Ｎ
ｄ２０．４％，Ｔｉ１０．４％，Ｃｏ１２．８％，Ｎ
１．６３％、すなわち原子％ではＦｅ５８．６％，Ｎｄ
８．４６％，Ｔｉ１３．０％，Ｃｏ１３．０％，Ｎ
６．９６％に相当する。この粉体をジェットミルでさら
に微粉砕した後、２０kOeの磁場中において配向させワ
ックスで固化して磁気特性を測定したところ、飽和磁化
（４πＩｓ）は１１７emu/g，保磁力（ｉＨｃ）は４３
００ Oeであった。また、得られた粉体をＣｕＫα線を
用いてＸ線回折したところ、その多くが体心正方晶Ｔｈ
Ｍｎ12型の結晶構造であると認められた。Example 6 By weight ratio, 55.6% of Fe, 20.8% of Nd, 10% of Ti10.
The raw materials were weighed so as to be 6% and 13.0% Co, and were melted in an argon atmosphere. This alloy is F
e 62.9%, Nd 9.09%, Ti 14.0%, Co
This corresponds to 14.0%. 900 ° C of the obtained ingot
For 7 days, and then roughly pulverized in an iron mortar and further pulverized with a disc mill to obtain a powder having a diameter of about 30 μm. This powder was treated at approximately 450 ° C. in NH 3 gas in order to make the powder contain N. As a result of this treatment, 1.63% by weight of N was contained in the material. Therefore, the composition of the whole material is 54.7% Fe,
d 20.4%, Ti 10.4%, Co 12.8%, N
1.63%, that is, 58.6% Fe in atomic%, Nd
8.46%, Ti 13.0%, Co 13.0%, N
This corresponds to 6.96%. This powder was further finely pulverized by a jet mill, then oriented in a magnetic field of 20 kOe, solidified with wax, and measured for magnetic properties. The saturation magnetization (4πIs) was 117 emu / g and the coercive force (iHc) was 43
00 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, most of the powder was found to have a body-centered tetragonal Th.
The crystal structure was confirmed to be of Mn 12 type.

【００２５】（実施例７） 重量比でＦｅ６１．５％，Ｓｍ２１．５％，Ｔｉ１０．
５％，Ｎｉ６．４６％から成る合金をアルゴン雰囲気中
で溶製した。この合金は原子％でＦｅ６９．９％，Ｓｍ
９．０９％，Ｔｉ１４．０％，Ｎｉ６．９９％に相当す
る。得られたインゴットを９００℃で７日間焼鈍した
後、鉄製乳鉢中で粗粉砕し、さらにディスクミルで粉砕
して、約３０μm径の粉体とした。この粉体にＮを含有
させるために、これをＮ2ガス中ほぼ４５０℃付近の温
度において処理した。この処理により材料中にＮが０．
２９２重量％含有された。したがって材料全体としての
組成は、重量％でＦｅ６１．３％，Ｓｍ２１．５％，Ｔ
ｉ１０．５％，Ｎｉ６．４４％，Ｎ ０．２９２％、す
なわち原子％ではＦｅ６９．０％，Ｓｍ８．９７％，Ｔ
ｉ１３．８％，Ｎｉ６．９０％，Ｎ １．３１％に相当
する。この粉体をジェットミルでさらに微粉砕した後、
２０kOeの磁場中において配向させワックスで固化して
磁気特性を測定したところ、飽和磁化（４πＩｓ）は１
０５emu/g，保磁力（ｉＨｃ）は２９００ Oeであった。
また、得られた粉体をＣｕＫα線を用いてＸ線回折した
ところ、その多くが体心正方晶ＴｈＭｎ12型の結晶構造
であると認められた。(Example 7) Fe61.5%, Sm21.5%, Ti10.
An alloy composed of 5% and Ni 6.46% was melted in an argon atmosphere. This alloy contains 69.9% Fe in atomic%, Sm
It corresponds to 9.09%, Ti 14.0% and Ni 6.99%. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar and further pulverized by a disk mill to obtain a powder having a diameter of about 30 μm. This powder was treated at a temperature of about 450 ° C. in N 2 gas in order to contain N. By this processing, N in the material is reduced to 0.
292% by weight. Therefore, the composition of the material as a whole is 61.3% Fe, 21.5% Sm,
i 10.5%, Ni 6.44%, N 0.292%, that is, in atomic%, 69.0% of Fe, 8.97% of Sm, T
It corresponds to i 13.8%, Ni 6.90%, and N 1.31%. After further pulverizing this powder with a jet mill,
When the magnetic properties were measured after orientation in a magnetic field of 20 kOe and solidification with wax, the saturation magnetization (4πIs) was 1
05 emu / g and coercive force (iHc) were 2900 Oe.
Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００２６】（実施例８） 重量比でＦｅ６５．６％，Ｓｍ２１．９％，Ｔｉ１０．
７％，Ｂ １．８１％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ６８．６％，Ｓｍ８．５０％，Ｔｉ１３．１％，Ｂ
９．８０％に相当する。この粉体をジェットミルでさら
に微粉砕した後、２０kOeの磁場中において配向させワ
ックスで固化して磁気特性を測定したところ、飽和磁化
（４πＩｓ）は１１４emu/g，保磁力（ｉＨｃ）は５９
００ Oeであった。また、得られた粉体をＣｕＫα線を
用いてＸ線回折したところ、その多くが体心正方晶Ｔｈ
Ｍｎ12型の結晶構造であると認められた。(Example 8) Fe65.6%, Sm21.9%, Ti10.
The raw materials were weighed so as to be 7% and B 1.81%, and were melted in an argon atmosphere. This alloy is F
e68.6%, Sm8.50%, Ti13.1%, B
This corresponds to 9.80%. This powder was further finely pulverized by a jet mill, then oriented in a magnetic field of 20 kOe, solidified with wax, and measured for magnetic properties. The saturation magnetization (4πIs) was 114 emu / g, and the coercive force (iHc) was 59.
00 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, most of the powder was found to have a body-centered tetragonal Th.
The crystal structure was confirmed to be of Mn 12 type.

【００２７】（実施例９） 重量比でＦｅ６６．５％，Ｎｄ２１．３％，Ｔｉ１０．
９％，Ｃ １．３６％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ７０．９％，Ｎｄ８．７８％，Ｔｉ１３．５％，Ｃ
６．７６％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらにデ
ィスクミルで粉砕して、約３０μm径の粉体とした。こ
の粉体をジェットミルでさらに微粉砕した後、２０kOe
の磁場中において配向させワックスで固化して磁気特性
を測定したところ、飽和磁化（４πＩｓ）は１１１emu/
g，保磁力（ｉＨｃ）は４２００ Oeであった。また、得
られた粉体をＣｕＫα線を用いてＸ線回折したところ、
その多くが体心正方晶ＴｈＭｎ12型の結晶構造であると
認められた。(Example 9) Fe66.5%, Nd21.3%, Ti10.
The raw materials were weighed so as to be 9% and C 1.36%, and were melted in an argon atmosphere. This alloy is F
e70.9%, Nd8.78%, Ti13.5%, C
This corresponds to 6.76%. 900 ° C of the obtained ingot
For 7 days, and then roughly pulverized in an iron mortar and further pulverized with a disc mill to obtain a powder having a diameter of about 30 μm. After further pulverizing this powder with a jet mill,
When the magnetic properties were measured after being oriented in a magnetic field and solidified with wax, the saturation magnetization (4πIs) was 111 emu /
g, the coercive force (iHc) was 4200 Oe. When the obtained powder was subjected to X-ray diffraction using CuKα radiation,
Most of them were recognized as having a body-centered tetragonal ThMn 12 type crystal structure.

【００２８】（実施例１０） 重量比でＦｅ７４．０％，Ｓｍ１９．９％，Ｔｉ６．０
６％から成る合金をアルゴン雰囲気中で溶製した。この
合金は原子％でＦｅ８３．７％，Ｓｍ８．３７％，Ｔｉ
７．９８％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらに有
機溶媒中でボールミル粉砕し、約１０μｍ径の粉末とし
た。この粉末にＮを含有させるために、これをＮ2ガス
中ほぼ５５０℃付近の温度において処理した。この処理
により材料中にＮが２．２０重量％含有された。したが
って材料全体としての組成は、重量％でＦｅ７２．４
％，Ｓｍ１９．５％，Ｔｉ５．９２％，Ｎ ２．２０
％、すなわち原子％ではＦｅ７６．０％，Ｓｍ７．６０
％，Ｔｉ７．２５％，Ｎ ９．１９％に相当する。この
粉体を２０kOeの磁場中において配向させた後、ワック
スで固化して磁気特性を測定したところ、飽和磁化（４
πＩｓ）は１２２emu/g，保磁力（ｉＨｃ）は５０００
Oeであった。また、得られた粉体をＣｕＫα線を用いて
Ｘ線回折したところ、その多くが体心正方晶ＴｈＭｎ12
型の結晶構造であると認められた。Example 10 74.0% Fe, 19.9% Sm, 6.0% Ti by weight
An alloy consisting of 6% was melted in an argon atmosphere. This alloy contains 83.7% Fe, 8.37% Sm,
It corresponds to 7.98%. 900 ° C of the obtained ingot
For 7 days, and coarsely pulverized in an iron mortar, and further ball-milled in an organic solvent to obtain a powder having a diameter of about 10 μm. This powder was treated at a temperature of about 550 ° C. in N 2 gas in order to contain N. As a result of this treatment, 2.20% by weight of N was contained in the material. Therefore, the composition of the material as a whole is 72.4% by weight of Fe.
%, Sm 19.5%, Ti 5.92%, N 2.20
%, That is, 76.0% of Fe and 7.60 of Sm in atomic%.
%, 7.25% of Ti, and 9.19% of N. After the powder was oriented in a magnetic field of 20 kOe, it was solidified with wax and the magnetic properties were measured.
πIs) is 122 emu / g and coercive force (iHc) is 5000
Oe. When the obtained powder was subjected to X-ray diffraction using CuKα ray, most of the powder was found to have a body-centered tetragonal ThMn 12
The crystal structure was found to be of the type.

【００２９】（実施例１１） 重量比でＦｅ６７．７％，Ｓｍ２０．１％，Ｔｉ６．０
９％，Ｖ ６．１７％から成る合金をアルゴン雰囲気中
で溶製した。この合金は原子％でＦｅ７６．１％，Ｓｍ
８．３７％，Ｔｉ７．９８％，Ｖ ７．６０％に相当す
る。得られたインゴットを９００℃で７日間焼鈍した
後、鉄製乳鉢中で粗粉砕し、さらに有機溶媒中でボール
ミル粉砕し、約１０μｍ径の粉末とした。この粉末にＮ
を含有させるために、これをＮ2ガス中ほぼ５５０℃付
近の温度において処理した。この処理により材料中にＮ
が２．３７重量％含有された。したがって材料全体とし
ての組成は、重量％でＦｅ６６．１％，Ｓｍ１９．６
％，Ｔｉ５．９５％，Ｖ ６．０３％，Ｎ ２．３７％、
すなわち原子％ではＦｅ６８．６％，Ｓｍ７．５５％，
Ｔｉ７．２０％，Ｖ ６．８６％，Ｎ ９．８１％に相当
する。この粉体を２０kOeの磁場中において配向させた
後、ワックスで固化して磁気特性を測定したところ、飽
和磁化（４πＩｓ）は１０６emu/g，保磁力（ｉＨｃ）
は６２００ Oeであった。また、得られた粉体をＣｕＫ
α線を用いてＸ線回折したところ、その多くが体心正方
晶ＴｈＭｎ12型の結晶構造であると認められた。(Example 11) Fe67.7%, Sm20.1%, Ti6.0 by weight ratio
An alloy consisting of 9% and 6.17% V was melted in an argon atmosphere. This alloy contains 76.1% Fe in atomic%, Sm
8.37%, Ti 7.98%, and V 7.60%. The obtained ingot was annealed at 900 ° C. for 7 days, coarsely ground in an iron mortar, and further ball-milled in an organic solvent to obtain a powder having a diameter of about 10 μm. N
Was treated in N 2 gas at a temperature around 550 ° C. By this process, N
Was contained 2.37% by weight. Therefore, the composition of the whole material is Fe 66.1% by weight and Sm 19.6% by weight.
%, 5.95% Ti, 6.03% V, 2.37% N,
That is, in atomic%, Fe is 68.6%, Sm is 7.55%,
This corresponds to 7.20% of Ti, 6.86% of V, and 9.81% of N. This powder was oriented in a magnetic field of 20 kOe, then solidified with wax, and the magnetic properties were measured. The saturation magnetization (4πIs) was 106 emu / g, and the coercive force (iHc).
Was 6200 Oe. Moreover, the obtained powder is CuK
When subjected to X-ray diffraction using α-rays, it was confirmed that most of the crystals had a body-centered tetragonal ThMn 12 type crystal structure.

【００３０】（実施例１２） 重量比でＦｅ７３．９％，Ｓｍ１９．９％，Ｃｒ６．２
５％から成る合金をアルゴン雰囲気中で溶製した。この
合金は原子％でＦｅ８４．０％，Ｓｍ８．４０％，Ｃｒ
７．６３％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらに有
機溶媒中でボールミル粉砕し、約１０μｍ径の粉末とし
た。この粉末にＮを含有させるために、これをＮ2ガス
中ほぼ５５０℃付近の温度において処理した。この処理
により材料中にＮが１．９７重量％含有された。したが
って材料全体としての組成は重量％でＦｅ７２．４％，
Ｓｍ１９．５％，Ｃｒ６．１３％，Ｎ １．９７％、す
なわち原子％では、Ｆｅ７７．０％，Ｓｍ７．７０％，
Ｃｒ７．００％，Ｎ ８．３３％に相当する。この粉体
を２０kOeの磁場中において配向させた後、ワックスで
固化して磁気特性を測定したところ、飽和磁化（４πＩ
ｓ）は９７emu/g，保磁力（ｉＨｃ）は３０００ Oeであ
った。また、得られた粉体をＣｕＫα線を用いてＸ線回
折したところ、その多くが体心正方晶ＴｈＭｎ12型の結
晶構造であると認められた。(Example 12) 73.9% of Fe, 19.9% of Sm, and 6.2% of Cr by weight ratio
An alloy consisting of 5% was melted in an argon atmosphere. This alloy contains 84.0% Fe, 8.40% Sm,
It corresponds to 7.63%. 900 ° C of the obtained ingot
For 7 days, and coarsely pulverized in an iron mortar, and further ball-milled in an organic solvent to obtain a powder having a diameter of about 10 μm. This powder was treated at a temperature of about 550 ° C. in N 2 gas in order to contain N. As a result of this treatment, 1.97% by weight of N was contained in the material. Therefore, the composition of the whole material is 72.4% by weight of Fe,
Sm 19.5%, Cr 6.13%, N 1.97%, that is, in atomic%, Fe 77.0%, Sm 7.70%,
This corresponds to 7.00% of Cr and 8.33% of N. After the powder was oriented in a magnetic field of 20 kOe, it was solidified with wax and the magnetic properties were measured.
s) was 97 emu / g, and the coercive force (iHc) was 3000 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００３１】（実施例１３） 重量比でＦｅ８０．２％，Ｓｍ１９．８％から成る合金
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ９１．６％，Ｓｍ８．４０％に相当する。得られたイ
ンゴットを９００℃で７日間焼鈍した後、鉄製乳鉢中で
粗粉砕し、さらに有機溶媒中でボールミル粉砕し、約１
０μｍ径の粉末とした。この粉末にＮを含有させるため
に、これをＮＨ3ガス中ほぼ４５０℃付近の温度におい
て処理した。この処理により材料中にＮが２．５２重量
％含有された。したがって材料全体としての組成は、重
量％でＦｅ７８．２％，Ｓｍ１９．３％，Ｎ ２．５２
％、すなわち原子％ではＦｅ８２．０％，Ｓｍ７．５１
％，Ｎ １０．５％に相当する。この粉体を２０kOeの磁
場中において配向させた後、ワックスで固化して磁気特
性を測定したところ、飽和磁化（４πＩｓ）は１２１em
u/g，保磁力（ｉＨｃ）は５７００ Oeであった。また、
得られた粉体をＣｕＫα線を用いてＸ線回折したとこ
ろ、その多くが体心正方晶ＴｈＭｎ12型の結晶構造であ
ると認められた。Example 13 An alloy composed of 80.2% of Fe and 19.8% of Sm by weight was melted in an argon atmosphere. This alloy is F
e91.6% and Sm 8.40%. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar, and further ball-milled in an organic solvent to obtain about 1 kg.
The powder had a diameter of 0 μm. This powder was treated in NH 3 gas at a temperature of about 450 ° C. in order to contain N. As a result of this treatment, 2.52% by weight of N was contained in the material. Therefore, the composition of the entire material is 78.2% Fe, 19.3% Sm, and 2.52% N by weight.
%, That is, 82.0% of Fe and 7.51 of Sm in atomic%.
%, N 10.5%. This powder was oriented in a magnetic field of 20 kOe, then solidified with wax, and the magnetic properties were measured. The saturation magnetization (4πIs) was 121 em.
u / g and coercive force (iHc) were 5700 Oe. Also,
When the obtained powder was subjected to X-ray diffraction using CuKα radiation, it was confirmed that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００３２】（実施例１４） 重量比でＦｅ７３．４％，Ｓｍ１９．８％，Ｔｉ６．０
１％，Ｃ ０．４３％，Ｂ ０．３９％となるように原料
を秤量し、これをアルゴン雰囲気中で溶製した。この合
金は原子％でＦｅ８０．０％，Ｓｍ８．００％，Ｔｉ
７．６４％，Ｃ２．１８％，Ｂ ２．１８％に相当す
る。得られたインゴットを９００℃で７日間焼鈍した
後、鉄製乳鉢中で粗粉砕し、さらに有機溶媒中でボール
ミル粉砕し、約１０μｍ径の粉末とした。この粉末にＮ
を含有させるために、これをＮ2ガス中ほぼ５５０℃付
近の温度において処理した。この処理により材料中にＮ
が１．６８重量％含有された。したがって材料全体とし
ての組成は、重量％でＦｅ７２．２％，Ｓｍ１９．４
％，Ｔｉ５．９１％，Ｃ ０．４２３％，Ｂ ０．３８１
％，Ｎ １．６８％、すなわち原子％ではＦｅ７４．５
％，Ｓｍ７．４５％，Ｔｉ７．１１％，Ｃ ２．０３
％，Ｂ ２．０３％，Ｎ ６．９１％に相当する。この粉
体を２０kOeの磁場中において配向させた後、ワックス
で固化して磁気特性を測定したところ、飽和磁化（４π
Ｉｓ）は１２６emu/g，保磁力（ｉＨｃ）は５６００ Oe
であった。また、得られた粉体をＣｕＫα線を用いてＸ
線回折したところ、その多くが体心正方晶ＴｈＭｎ12型
の結晶構造であると認められた。Example 14 Fe 73.4%, Sm 19.8%, Ti 6.0 by weight ratio
The raw materials were weighed so as to be 1%, C 0.43% and B 0.39%, and were melted in an argon atmosphere. This alloy contains 80.0% Fe, 8.00% Sm,
It corresponds to 7.64%, C 2.18% and B 2.18%. The obtained ingot was annealed at 900 ° C. for 7 days, coarsely ground in an iron mortar, and further ball-milled in an organic solvent to obtain a powder having a diameter of about 10 μm. N
Was treated in N 2 gas at a temperature around 550 ° C. By this process, N
1.68% by weight. Therefore, the composition of the whole material is 72.2% by weight of Fe and 19.4% by weight of Sm.
%, Ti 5.91%, C 0.423%, B 0.381
%, N 1.68%, that is, 74.5 atomic% Fe
%, Sm 7.45%, Ti 7.11%, C 2.03
%, B 2.03% and N 6.91%. After the powder was oriented in a magnetic field of 20 kOe, it was solidified with wax and the magnetic properties were measured.
Is) is 126 emu / g and coercive force (iHc) is 5600 Oe
Met. Further, the obtained powder is converted into X by using CuKα ray.
Line diffraction revealed that most of the crystals had a body-centered tetragonal ThMn 12 type crystal structure.

【００３３】（実施例１５） 重量比でＦｅ６６．４％，Ｓｍ１９．７％，Ｔｉ５．９
７％，Ｖ ６．０５％，Ｃ ０．４２８％，Ｂ １．５４
％となるように原料を秤量し、これをアルゴン雰囲気中
で溶製した。。この合金は原子％でＦｅ６８．３％，Ｓ
ｍ７．５１％，Ｔｉ７．１７％，Ｖ ６．８３％，Ｃ
２．０５％，Ｂ ８．１９％に相当する。得られたイン
ゴットを９００℃で７日間焼鈍した後、鉄製乳鉢中で粗
粉砕し、さらに有機溶媒中でボールミル粉砕し、約１０
μｍ径の粉末とした。この粉末をアルゴンガス中ほぼ５
００℃付近の温度において処理した。この粉体を２０kO
eの磁場中において配向させた後、ワックスで固化して
磁気特性を測定したところ、飽和磁化（４πＩｓ）は９
９emu/g，保磁力（ｉＨｃ）は６７００ Oeであった。ま
た、得られた粉体をＣｕＫα線を用いてＸ線回折したと
ころ、その多くが体心正方晶ＴｈＭｎ12型の結晶構造で
あると認められた。(Example 15) Fe66.4%, Sm19.7%, Ti5.9 by weight ratio
7%, V 6.05%, C 0.428%, B 1.54
% Of the raw material was weighed and melted in an argon atmosphere. . This alloy contains 68.3% Fe in atomic%, S
m 7.51%, Ti 7.17%, V 6.83%, C
2.05% and 8.19% of B. After the obtained ingot was annealed at 900 ° C. for 7 days, it was roughly pulverized in an iron mortar, and further ball-milled in an organic solvent to obtain about 10%.
A powder having a diameter of μm was obtained. This powder is placed in argon gas for approximately 5
The treatment was performed at a temperature around 00 ° C. 20 kO of this powder
After orientation in the magnetic field of e, solidification with wax and measurement of magnetic properties revealed that the saturation magnetization (4πIs) was 9
9 emu / g and coercive force (iHc) were 6700 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００３４】（実施例１６） 重量比でＦｅ７９．１％，Ｓｍ１９．５％，Ｃ ０．７
１％，Ｂ ０．６４％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ８５．１％，Ｓｍ７．８０％，Ｃ ３．５５％，Ｂ
３．５５％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらに有
機溶媒中でボールミル粉砕し、約１０μｍ径の粉末とし
た。この粉末にＮを含有させるために、これをＮ2ガス
中ほぼ５５０℃付近の温度において処理した。この処理
により材料中にＮが１．０３重量％含有された。したが
って材料全体としての組成は、重量％でＦｅ７８．３
％，Ｓｍ１９．３％，Ｃ ０．７０２％，Ｂ ０．６３２
％，Ｎ １．０３％、すなわち原子％ではＦｅ８１．５
％，Ｓｍ７．４７％，Ｃ ３．３９％，Ｂ ３．３９％，
Ｎ ４．２８％に相当する。この粉体を２０kOeの磁場中
において配向させた後、ワックスで固化して磁気特性を
測定したところ、飽和磁化（４πＩｓ）は１２６emu/
g，保磁力（ｉＨｃ）は４９００ Oeであった。また、得
られた粉体をＣｕＫα線を用いてＸ線回折したところ、
その多くが体心正方晶ＴｈＭｎ12型の結晶構造であると
認められた。Example 16 79.1% Fe, 19.5% Sm, C 0.7
The raw materials were weighed so as to be 1% and B 0.64%, and were melted in an argon atmosphere. This alloy is F
e 85.1%, Sm 7.80%, C 3.55%, B
It corresponds to 3.55%. 900 ° C of the obtained ingot
For 7 days, and coarsely pulverized in an iron mortar, and further ball-milled in an organic solvent to obtain a powder having a diameter of about 10 μm. This powder was treated at a temperature of about 550 ° C. in N 2 gas in order to contain N. By this treatment, 1.03% by weight of N was contained in the material. Therefore, the composition of the material as a whole is Fe78.3% by weight.
%, Sm19.3%, C 0.702%, B 0.632
%, N 1.03%, that is, at atomic%, Fe 81.5
%, Sm 7.47%, C 3.39%, B 3.39%,
N corresponds to 4.28%. After the powder was oriented in a magnetic field of 20 kOe, it was solidified with wax and the magnetic properties were measured. The saturation magnetization (4πIs) was 126 emu /
g, the coercive force (iHc) was 4900 Oe. When the obtained powder was subjected to X-ray diffraction using CuKα radiation,
Most of them were recognized as having a body-centered tetragonal ThMn 12 type crystal structure.

【００３５】（実施例１７） 重量比でＦｅ７８．７％，Ｓｍ１９．４％，Ｃ ０．９
９％，Ｂ ０．８９％となるように原料を秤量し、これ
をアルゴン雰囲気中で溶製した。この合金は原子％でＦ
ｅ８２．８％，Ｓｍ７．５９％，Ｃ ４．８３％，Ｂ
４．８３％に相当する。得られたインゴットを９００℃
で７日間焼鈍した後、鉄製乳鉢中で粗粉砕し、さらに有
機溶媒中でボールミル粉砕し、約１０μｍ径の粉末とし
た。この粉末をアルゴンガス中ほぼ５００℃付近の温度
において処理した。この粉体を２０kOeの磁場中におい
て配向させた後、ワックスで固化して磁気特性を測定し
たところ、飽和磁化（４πＩｓ）は１２０emu/g，保磁
力（ｉＨｃ）は５０００ Oeであった。また、得られた
粉体をＣｕＫα線を用いてＸ線回折したところ、その多
くが体心正方晶ＴｈＭｎ12型の結晶構造であると認めら
れた。(Example 17) Fe78.7%, Sm19.4%, C0.9 by weight ratio
The raw materials were weighed so as to be 9% and B 0.89%, and were melted in an argon atmosphere. This alloy is F
e 82.8%, Sm 7.59%, C 4.83%, B
This corresponds to 4.83%. 900 ° C of the obtained ingot
For 7 days, and coarsely pulverized in an iron mortar, and further ball-milled in an organic solvent to obtain a powder having a diameter of about 10 μm. This powder was treated in argon gas at a temperature around 500 ° C. After the powder was oriented in a magnetic field of 20 kOe, it was solidified with wax and the magnetic properties were measured. The saturation magnetization (4πIs) was 120 emu / g and the coercive force (iHc) was 5000 Oe. Further, when the obtained powder was subjected to X-ray diffraction using CuKα ray, it was recognized that most of the powder had a body-centered tetragonal ThMn 12 type crystal structure.

【００３６】（実施例１８） 実施例１と同様にして表１〜３に示すような組成の合金
を作製したところ、本発明の効果が得られることが確認
された。Example 18 Alloys having the compositions shown in Tables 1 to 3 were produced in the same manner as in Example 1, and it was confirmed that the effects of the present invention could be obtained.

【００３７】[0037]

【表１】 [Table 1]

【表２】 [Table 2]

【表３】 [Table 3]

【００３８】（実施例１９） 実施例７と同様にして表４に示すような組成の合金を作
製したところ、本発明の効果が得られることが確認され
た。Example 19 An alloy having a composition shown in Table 4 was produced in the same manner as in Example 7, and it was confirmed that the effects of the present invention could be obtained.

【００３９】[0039]

【表４】 [Table 4]

【００４０】[0040]

【発明の効果】以上に説明したように、本発明による鉄
−希土類系永久磁石材料によれば、Ｆｅを主体とする希
土類磁石でありながら、大きな飽和磁化と高い保磁力と
を安定的に得ることができるので、実用上きわめて有用
なものである。また、本発明による鉄−希土類系永久磁
石材料の製造方法によれば、Ｎ(窒素)を含むような本発
明の鉄−希土類系永久磁石材料を安定的に製造し得るの
で、実用上きわめて有用なものである。As described above, according to the iron-rare earth permanent magnet material of the present invention, a large saturation magnetization and a high coercive force can be stably obtained even though the rare earth magnet is mainly composed of Fe. It is very useful in practice. Further, according to the method for producing an iron-rare earth permanent magnet material of the present invention, the iron-rare earth permanent magnet material of the present invention containing N (nitrogen) can be produced stably, which is extremely useful in practical use. It is something.

【図面の簡単な説明】[Brief description of the drawings]

【図１】体心正方晶ＴｈＭｎ12型結晶構造を説明する図
である。FIG. 1 is a diagram illustrating a body-centered tetragonal ThMn 12- type crystal structure.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ２３Ｃ 8/24 Ｃ２３Ｃ 8/24 Ｈ０１Ｆ 1/053 Ｈ０１Ｆ 1/04 Ｈ Ａ (31)優先権主張番号 特願平2−306590 (32)優先日 平成２年11月13日(1990．11．13) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願平2−306591 (32)優先日 平成２年11月13日(1990．11．13) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願平2−306592 (32)優先日 平成２年11月13日(1990．11．13) (33)優先権主張国 日本（ＪＰ） (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 38/00 B22F 1/00,9/04 C01B 21/06 H01F 1/053 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI C23C 8/24 C23C 8/24 H01F 1/053 H01F 1/04 HA (31) Priority claim number Japanese Patent Application No. Hei 2-306590 ( 32) Priority Date November 13, 1990 (November 13, 1990) (33) Priority Country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 2-306591 (32) Priority Date 1990 November 13, 1990 (November 13, 1990) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2-306592 (32) Priority date November 13, 1990 (1990. 11.13) (33) Priority country Japan (JP) (58) Fields investigated (Int. Cl. 7 , DB name) C22C 38/00 B22F 1/00, 9/04 C01B 21/06 H01F 1 / 053

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 ＲをＹ，Ｔｈおよびすべてのランタノイ
ド元素からなる群の中から選ばれた１種または２種以上
の元素の組合せ、ＸをＮ(窒素)、Ｃ(炭素)もしくはＢ
(硼素)またはこれらの元素の組合せとするとき、 原子百分率で 、Ｒ：３〜３０％、Ｘ：０．３〜５０％
を含み、残部が実質的にＦｅから成り、主相が体心正方
晶ＴｈＭｎ １２ 型構造を有することを特徴とする鉄−希
土類系永久磁石材料。1. R is a combination of one or more elements selected from the group consisting of Y, Th and all lanthanoid elements, and X is N (nitrogen), C (carbon) or B
(Boron) or a combination of these elements, R: 3 to 30%, X: 0.3 to 50% in atomic percentage
Wherein the balance substantially consists of Fe, and the main phase has a body-centered tetragonal ThMn 12- type structure. 【請求項２】 ＭをＴｉ，Ｃｒ，Ｖ，Ｚｒ，Ｎｂ，Ａ
ｌ，Ｍｏ，Ｍｎ，Ｈｆ，Ｔａ，Ｗ，Ｍｇ，Ｓｉ，Ｓｎ，
Ｇｅ，Ｇａからなる群の中から選ばれた１種または２種
以上の元素の組合せとするとき、Ｆｅの一部をＭで置換
することにより、原子百分率で、Ｍ：０．５〜３０％を
含むようにしたことを特徴とする請求項１に記載の鉄−
希土類系永久磁石材料。2. M is Ti, Cr, V, Zr, Nb, A
1, Mo, Mn, Hf, Ta, W, Mg, Si, Sn,
When one or a combination of two or more elements selected from the group consisting of Ge and Ga is used, by substituting a part of Fe with M, M: 0.5 to 30% by atomic percentage. 2. The iron according to claim 1, wherein
Rare earth permanent magnet material. 【請求項３】 ＸがＮ、ＮとＣの組み合わせ、ＮとＣと
Ｂの組み合わせ、またはＮとＢの組み合わせであること
を特徴とする請求項１または２に記載の鉄−希土類系永
久磁石材料。3. X is N, a combination of N and C, and N and C are
The iron-rare earth permanent magnet material according to claim 1, wherein the material is a combination of B or a combination of N and B. 4 . 【請求項４】 予め、実質的にＮを含有しないかまたは
Ｎ含有量が所望の量よりは少ない鉄−希土類系合金を作
製した後、これをＮを含む気体中で処理して前記合金中
にＮを侵入させることにより所望のＮ含有量にしたこと
を特徴とする請求項３に記載の鉄−希土類系永久磁石材
料の製造方法。 4. The method according to claim 1, wherein the composition contains substantially no N or
An iron-rare earth alloy with a lower N content than desired is produced.
After being produced, it is treated in a gas containing N to
The desired N content by infiltrating N into the steel
The iron-rare earth permanent magnet material according to claim 3, characterized in that:
Method of manufacturing the ingredients.
JP03257932A 1990-10-05 1991-10-04 Iron-rare earth permanent magnet material and method for producing the same Expired - Lifetime JP3073807B2 (en)

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Application Number Priority Date Filing Date Title
JP2-267736 1990-10-05
JP26773690 1990-10-05
JP27274290 1990-10-11
JP2-272742 1990-10-11
JP2-306589 1990-11-13
JP30658990 1990-11-13
JP2-306591 1990-11-13
JP2-306592 1990-11-13
JP30659290 1990-11-13
JP2-306590 1990-11-13
JP30659090 1990-11-13
JP30659190 1990-11-13
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JP2009249682A (en) * 2008-04-04 2009-10-29 Nec Tokin Corp Hard magnetic alloy and method for producing the same
JP6547141B2 (en) * 2014-08-18 2019-07-24 国立研究開発法人物質・材料研究機構 Rare earth anisotropic magnet material and method of manufacturing the same
CN104724684B (en) * 2015-01-30 2016-07-13 南京邮电大学 A kind of Inxfe4-xn/Fe3n composite material and preparation method thereof
WO2021065254A1 (en) * 2019-10-02 2021-04-08 国立研究開発法人物質・材料研究機構 Magnet, membrane, laminate, motor, generator, and automobile
KR20240030327A (en) * 2022-08-30 2024-03-07 한국재료연구원 METHOD OF PREPARING ThMn12 MAGNETIC MATERIAL POWDER

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