JPH08245295A - Rare earth element-iron-cobalt-boron tetragonal compound - Google Patents
Rare earth element-iron-cobalt-boron tetragonal compoundInfo
- Publication number
- JPH08245295A JPH08245295A JP7348303A JP34830395A JPH08245295A JP H08245295 A JPH08245295 A JP H08245295A JP 7348303 A JP7348303 A JP 7348303A JP 34830395 A JP34830395 A JP 34830395A JP H08245295 A JPH08245295 A JP H08245295A
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- Prior art keywords
- compound
- tetragonal
- permanent magnet
- phase
- magnetic
- Prior art date
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Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、希土類・鉄・ボロンを
必須成分とする希土類・鉄・ボロン系正方晶化合物を基
礎とした置換・修飾型正方晶化合物、特に希土類・鉄・
コバルト・ボロン系正方晶化合物に関する。この正方晶
化合物は、磁性材料等特に永久磁石の構成化合物として
も有用な物質発明の対象である。BACKGROUND OF THE INVENTION The present invention relates to a substitution / modification type tetragonal compound based on a rare earth / iron / boron tetragonal compound containing rare earth / iron / boron as an essential component, particularly a rare earth / iron / tetragonal compound.
The present invention relates to a cobalt-boron tetragonal compound. This tetragonal compound is a subject of the invention of a substance useful as a constituent compound of a magnetic material or the like, particularly a permanent magnet.
【０００２】Ｒ（希土類元素）とＣｏは種々の安定な化
合物を形成する。なかでもＳｍＣｏ5やＳｍ2Ｃｏ17は高
い飽和磁化、高いキュリー点、大きい磁気異方性定数を
有しており、これらの化合物をベースとして超高性能永
久磁石材料が開発された。現在ＲＣｏ磁石は小型モータ
や小型スピーカなど様々な用途に広く利用されている。
しかしながら、これらのＳｍＣｏ系磁石は資源が稀少な
ＳｍやＣｏを多量に含んでいるので高価である。そのた
めＳｍやＣｏをあまり含まないか、あるいは全く含まな
い材料の開発が望まれている。R (rare earth element) and Co form various stable compounds. Among them, SmCo 5 and Sm 2 Co 17 have high saturation magnetization, high Curie point, and large magnetic anisotropy constant, and an ultrahigh performance permanent magnet material was developed based on these compounds. Currently, RCo magnets are widely used in various applications such as small motors and small speakers.
However, these SmCo-based magnets are expensive because they contain a large amount of Sm and Co, which are scarce resources. Therefore, it is desired to develop a material containing little or no Sm or Co.
【０００３】この目的に沿った永久磁石材料とする上で
の観点からＲＣｏ化合物と同様に巨大な異方性定数をも
っているＲＦｅ系化合物が注目された。しかしＲＦｅ系
ではＲＣｏ系ほど多種類の化合物は存在しない。特にＲ
元素の中では資源的に豊富なＣｅ、Ｌａ、Ｎｄなど軽希
土類でＲ2Ｆｅ17型化合物とほんの少数の他の化合物
（例Ｎｄ6Ｆｅ23、ＰｒＦｅ2）が見出されているにすぎ
ない。これらの化合物はキュリー点も低く、異方性定数
も小さいため、実用的な永久磁石とするのに必要な特性
を示さない。From the viewpoint of making a permanent magnet material for this purpose, an RFe compound having a huge anisotropy constant like an RCo compound has been noted. However, in the RFe system, there are not as many kinds of compounds as in the RCo system. Especially R
Among the elements, light rare earths such as Ce, La, and Nd, which are abundant in resources, have been found as R 2 Fe 17 type compounds and only a few other compounds (eg Nd 6 Fe 23 , PrFe 2 ). . Since these compounds have a low Curie point and a small anisotropy constant, they do not exhibit the properties required for a practical permanent magnet.
【０００４】最近、ＲＦｅ系合金の超急冷リボンが高保
磁力を示すことが見出され、永久磁石材料としての関心
が高まっている。しかし、ＲＦｅ超急冷リボンでは実用
形状、寸法の磁石が得られず、まだ実用永久磁石とはい
えない。また、磁気特性の上でも超急冷リボンは従来の
磁石に比べて低い値しか示さない。Recently, it has been found that an ultra-quenched ribbon of an RFe alloy exhibits a high coercive force, and the interest as a permanent magnet material is increasing. However, the RFe ultra-quenching ribbon cannot provide a magnet having a practical shape and size, and cannot be said to be a practical permanent magnet. Also, in terms of magnetic properties, the ultra-quenched ribbon shows a lower value than the conventional magnet.
【０００５】本発明は、上述の従来技術で達成されてい
ないＲ、Ｆｅ、Ｃｏ及び第４成分を少くとも必須成分と
し室温以上で安定な新規な化合物を提供することを基本
的目的とする。本発明は、特にＲ、Ｆｅ、Ｃｏ、Ｂを必
須の成分とする新規な化合物に基づきさらに置換ないし
修飾成分を含む新規な化合物であって磁性材料及び永久
磁石の構成化合物として有用なものを提供することを基
本目的とする。本発明はまた、従来必要とされているＳ
ｍやＣｏを実用上は必ずしも多量に用いることなく、優
れた実用的磁気特性を備えた或いは発現可能な磁性材料
及び永久磁石の構成化合物として有用なものを提供せん
とするものである。The basic object of the present invention is to provide a novel compound which contains at least essential components of R, Fe, Co and the fourth component, which have not been achieved by the above-mentioned prior art, and which is stable at room temperature or higher. The present invention provides a novel compound which further contains a substitution or modification component based on a novel compound containing R, Fe, Co and B as essential components and which is useful as a constituent compound of a magnetic material and a permanent magnet. The basic purpose is to do. The present invention also provides the previously required S
It is an object of the present invention to provide a useful material as a constituent compound of a magnetic material and a permanent magnet having excellent practical magnetic properties or capable of exhibiting them without necessarily using a large amount of m and Co in practical use.
【０００６】即ち、本願発明の基礎を成す出願（特願昭
５８−９４８７６）の開示によれば、Ｒ（ＲはＹを含む
希土類元素の一種以上）、Ｆｅ、Ｂを必須成分とし、格
子定数のｃ0が約１２Åである正方晶系の結晶構造を有
するＲＦｅＢ正方晶化合物が得られる。このＲＦｅＢ正
方晶化合物は本願発明の基礎をなす。That is, according to the disclosure of the application forming the basis of the present invention (Japanese Patent Application No. 58-94876), R (R is one or more rare earth elements including Y), Fe and B are essential components, and the lattice constant is An RFeB tetragonal compound having a tetragonal crystal structure with c 0 of about 12Å is obtained. This RFeB tetragonal compound forms the basis of the present invention.
【０００７】本発明は第１に、上記ＲＦｅＢ系正方晶化
合物において、ＦｅをＣｏにて置換したもの即ち、Ｒ
（Ｆｅ、Ｃｏ）Ｂ正方晶化合物（好ましくは原子比にて
Ｃｏ５０％以下 −以下明記ないときは％は原子比を示
す−）を提供する。ＣｏによるＦｅの置換は正方晶化合
物のキュリー点の増大の効果がある。The present invention firstly relates to the above-mentioned RFeB type tetragonal compound in which Fe is replaced by Co, that is, R
Provide a (Fe, Co) B tetragonal compound (preferably not more than 50% Co by atomic ratio-% means atomic ratio unless otherwise specified). Substitution of Fe with Co has the effect of increasing the Curie point of a tetragonal compound.
【０００８】好ましくは、かかる化合物が非磁性相によ
り互いに隔離されていることにより、優れた磁石特性を
発現できる構成化合物を与える。なお、好ましくはこの
場合（特に焼結体の場合）、正方晶化合物の平均結晶粒
径は１〜１００μｍである。Preferably, such compounds are separated from each other by a non-magnetic phase to provide a constituent compound capable of exhibiting excellent magnet characteristics. In this case (particularly in the case of a sintered body), the average crystal grain size of the tetragonal compound is preferably 1 to 100 μm.
【０００９】さらに本発明において、第２に、Ｒ（Ｆ
ｅ、Ｃｏ）Ｂ系の正方晶化合物に下記特定のＡ元素を含
有したものも同様の正方晶系を示し、磁性材料及び永久
磁石の構成化合物として有用かつ優れたものである。但
しＡ元素はＴｉ、Ｎｉ、Ｂｉ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、
Ｍｏ、Ｗ、Ｍｎ、Ａｌ、Ｓｂ、Ｇｅ、Ｓｎ、Ｚｒ、Ｈ
ｆ、Ｃｕ、Ｓ、Ｃ、Ｃａ、Ｍｇ、Ｓｉ、Ｏ及びＰの一種
以上である。Further, in the present invention, secondly, R (F
e, Co) B-type tetragonal compounds containing the following specific A element also show the same tetragonal system and are useful and excellent as constituent compounds of magnetic materials and permanent magnets. However, the A element is Ti, Ni, Bi, V, Nb, Ta, Cr,
Mo, W, Mn, Al, Sb, Ge, Sn, Zr, H
It is one or more of f, Cu, S, C, Ca, Mg, Si, O and P.
【００１０】好ましくは、このＲ（Ｆｅ、Ｃｏ）ＢＡ正
方晶化合物が非磁性相で互いに隔離されている状態のと
き、永久磁石の構成化合物として最も優れている。なお
この場合（特に焼結体の場合）、このＲ（Ｆｅ、Ｃｏ）
ＢＡ正方晶化合物の平均結晶粒径が１〜１００μｍであ
ることが好ましい。Preferably, when the R (Fe, Co) BA tetragonal compound is in a state in which it is isolated from each other in the non-magnetic phase, it is the most excellent as a constituent compound of the permanent magnet. In this case (especially in the case of a sintered body), this R (Fe, Co)
The average crystal grain size of the BA tetragonal compound is preferably 1 to 100 μm.
【００１１】有用な磁気特性を得るため、本発明におい
て、高性能の磁性材料、永久磁石とするためには、正方
晶系（後述参照）の結晶構造を有する化合物を主相とす
る必要がある。ここで主相とは材料中に含まれているい
くつかの相のうち、体積比で５０％以上を占める相をい
う。即ち、この主相としては、Ｒ（Ｆｅ、Ｃｏ）Ｂ化合
物、Ｒ（Ｆｅ、Ｃｏ）ＢＡ化合物の一種以上が構成化合
物となる。In order to obtain useful magnetic properties, in the present invention, a compound having a tetragonal (see later) crystal structure must be the main phase in order to obtain a high-performance magnetic material or permanent magnet. . Here, the main phase means a phase that occupies 50% or more in volume ratio among some phases contained in the material. That is, as the main phase, one or more of R (Fe, Co) B compounds and R (Fe, Co) BA compounds are constituent compounds.
【００１２】第１及び第２の発明（特定発明、併合発
明）においてかつ正方晶化合物に基づいて磁性材料又は
永久磁石を製造する場合、その組成を好ましくはＢ２〜
２８％、Ｒ８〜３０％、残部実質上Ｆｅとすることによ
って優れた磁気特性が得られ、より好ましくはＦｅ４０
〜９０％とし、これを基本系としてＣｏ置換あるいはＡ
元素添加を行う。In the first and second inventions (specific invention, combined invention) and when a magnetic material or a permanent magnet is produced based on a tetragonal compound, the composition is preferably B2 to.
28%, R8-30%, and the balance substantially Fe to obtain excellent magnetic properties, and more preferably Fe40
~ 90%, with this as the basic system, Co substitution or A
Element addition is performed.
【００１３】なお磁性材料又は永久磁石とする場合、Ａ
元素の量は好ましくは次の通りである：Ｔｉ 4.5％以
下、 Ｎｉ 8.0％以下、Ｂｉ 5.0％以下、
Ｖ 9.5％以下、Ｎｂ 12.5％以下、 Ｔａ
10.5％以下、Ｃｒ 8.5％以下、 Ｍｏ 9.5％
以下、Ｗ 9.5％以下、 Ｍｎ 8.0％以下、Ａ
ｌ 9.5％以下、 Ｓｂ 2.5％以下、Ｇｅ 7.0
％以下、 Ｓｎ 3.5％以下、Ｚｒ 5.5％以下、
Ｈｆ 5.5％以下、Ｃｕ 3.5％以下、
Ｓ 2.0％以下、Ｃ 4.0％以下、 Ｃａ 8.
0％以下、Ｍｇ 8.0％以下、 Ｓｉ 8.0％以
下、Ｏ 1.0％以下、および Ｐ 3.5％以下（但し
Ａ元素は２以上含むこともでき、その場合、Ａ元素の合
量は、当該含有Ａ元素のうち最大値を有するものの値以
下含有できる）。When a magnetic material or a permanent magnet is used, A
The amount of elements is preferably as follows: Ti 4.5% or less, Ni 8.0% or less, Bi 5.0% or less,
V 9.5% or less, Nb 12.5% or less, Ta
10.5% or less, Cr 8.5% or less, Mo 9.5%
Below, W 9.5% or less, Mn 8.0% or less, A
l 9.5% or less, Sb 2.5% or less, Ge 7.0
%, Sn 3.5% or less, Zr 5.5% or less,
Hf 5.5% or less, Cu 3.5% or less,
S 2.0% or less, C 4.0% or less, Ca 8.
0% or less, Mg 8.0% or less, Si 8.0% or less, O 1.0% or less, and P 3.5% or less (however, the A element can also be contained in 2 or more, in which case, the total amount of the A element is the contained A element. Of these, the maximum value can be contained below the value).
【００１４】以下、本発明について詳述する。The present invention will be described in detail below.
【００１５】本発明者らはＲＦｅ系化合物の磁気的性質
と構造の関係について従来の研究結果をもとに考察し
た。その結果次のことが明らかになった。The present inventors have discussed the relationship between the magnetic properties and the structure of RFe compounds based on the results of conventional studies. As a result, the following became clear.
【００１６】（１）ＲＦｅ系化合物の磁気的性質には、
Ｆｅどうしの原子間距離や、Ｆｅ原子の周囲の環境（最
近核原子の数、種類など）がきわめて大きい役割を果し
ている。(1) The magnetic properties of the RFe compound include:
The interatomic distance between Fe atoms and the environment around Fe atoms (such as the number and type of nuclear atoms recently) play an extremely large role.
【００１７】（２）ＲとＦｅの組合せだけでは結晶状態
で永久磁石として適した化合物は存在しない。(2) There is no compound suitable for a permanent magnet in the crystalline state only by the combination of R and Fe.
【００１８】本発明者らは、ＲＦｅ化合物において、Ｆ
ｅ原子の周囲の環境を変え、永久磁石として適した特性
を与えるためには第三の元素の存在が不可欠であるると
判断した。そこで第三の元素Ｘとして、種々の元素を加
えたＲＦｅＸ三元化合物について、磁気的性質を詳細に
調べた。その結果ＸとしてＢを含むＲＦｅＢ基本化合物
を見出した。ＲＦｅＢ基本化合物は未知の化合物であり
従来のＲＦｅ化合物よりキュリー点も高く、異方性定数
も大きいため優れた永久磁石材料の構成化合物となりう
ることが明らかとなった。The present inventors have found that in RFe compounds, F
It was judged that the presence of the third element is indispensable in order to change the environment around the e-atom and give the characteristics suitable as a permanent magnet. Therefore, the magnetic properties of the RFeX ternary compound containing various elements as the third element X were examined in detail. As a result, an RFeB basic compound containing B as X was found. It has been revealed that the RFeB basic compound is an unknown compound, has a higher Curie point and a larger anisotropy constant than the conventional RFe compound, and thus can be an excellent constituent compound of a permanent magnet material.
【００１９】以下実施例に従いさらに詳細に述べる。Further details will be described below with reference to examples.
【００２０】実験方法 （１）原料（純度は重量％） Ｆｅ： 電解鉄 99.9％ Ｂ： フェロボロンまたは99％の純度のＢ Ｒ： 99％ Ｔｉ、Ｍｏ、Ｍｎ、Ｓｂ、Ｎｉ、Ｔａ： ９８％ Ａｌ、Ｃｕ： 99.9％ Ｈｆ： 95％ Ｖ： フェロバナジウム（81.2％Ｖ） Ｎｂ： フェロニオブ（67.6％Ｎｂ） Ｃｒ： フェロクロム（61.9％Ｃｒ） Ｚｒ： フェロジルコニウム（75.5％Ｚｒ）Experimental method (1) Raw material (purity is% by weight) Fe: electrolytic iron 99.9% B: ferroboron or 99% pure BR: 99% Ti, Mo, Mn, Sb, Ni, Ta: 98% Al , Cu: 99.9% Hf: 95% V: Ferrovanadium (81.2% V) Nb: Ferroniobium (67.6% Nb) Cr: Ferrochrome (61.9% Cr) Zr: Ferrozirconium (75.5% Zr)
【００２１】（２）実験手順は図２に図示の通りであ
る。実験結果は次の通りであった。なお、手順（Ａ）は
化合物の同定のための実験手順を示し、手順（Ｂ）は永
久磁石にした場合の実験手順を示す。(2) The experimental procedure is as shown in FIG. The experimental results were as follows. The procedure (A) shows an experimental procedure for identifying a compound, and the procedure (B) shows an experimental procedure when a permanent magnet is used.
【００２２】（１）高特性を示すＦｅ−Ｂ−Ｎｄ基本焼
結体（原子百分比で７７Ｆｅ−１５Ｎｄ−８Ｂ）につい
て測定した典型的な粉末Ｘ線ディフラクトメータのパタ
ーンを図１に示す。このパターンはきわめて複雑で、こ
れまで知られているどのようなＲＦｅ系化合物、ＦｅＢ
化合物、あるいはＲＢ系化合物によっても説明できな
い。(1) A pattern of a typical powder X-ray diffractometer measured on an Fe-B-Nd basic sintered body (77Fe-15Nd-8B in atomic percentage ratio) showing high characteristics is shown in FIG. This pattern is extremely complex, and any RFe compound known so far, FeB
It cannot be explained by the compound or RB compound.
【００２３】（２）（１）の試料のＸＭＡ測定による
と、焼結体は三つまたは四つの相からなっている。主相
はＦｅ、Ｂ、Ｒを同時に含んでおり、第二相はＲが重量
比で７０％以上のＲ濃縮相、第三相は主相よりもＢの富
んだ相である。第四相は酸化物の相である。(2) According to the XMA measurement of the sample of (1), the sintered body is composed of three or four phases. The main phase contains Fe, B, and R at the same time, the second phase is an R-enriched phase in which R is 70% by weight or more, and the third phase is a phase richer in B than the main phase. The fourth phase is the oxide phase.
【００２４】（３）図１の粉末Ｘ線ディフラクトメータ
のパターンを解析した結果、このパターンに含まれる強
いピークは全部ａ0＝8.80Å、ｃ0＝12.23Å の正方晶と
して説明できる。図１各Ｘ線ピークのところに指数を示
す。ＸＭＡ測定において観察された、Ｆｅ、Ｂ、Ｒを同
時に含む主相が、この構造をもっていることが判明し
た。この構造の特徴は、格子定数が大変大きいことであ
る。このように巨大な格子定数をもった正方晶の化合物
は、ＲＦｅ、ＦｅＢ、ＢＲいずれの二元系化合物におい
ても知られていない。(3) As a result of analyzing the pattern of the powder X-ray diffractometer shown in FIG. 1, all the strong peaks contained in this pattern can be explained as tetragonal crystals with a 0 = 8.80Å and c 0 = 12.23Å. Figure 1 shows the index at each X-ray peak. It was found that the main phase containing Fe, B, and R simultaneously, which was observed in XMA measurement, had this structure. The feature of this structure is that the lattice constant is very large. A tetragonal compound having such a huge lattice constant is not known as a binary compound of any of RFe, FeB and BR.
【００２５】（４）種々の組成をもち、かつ前記方法を
含む種々の製造方法によって作成されたＦｅＢＲ系およ
びＦｅＣｏＢＲ系永久磁石について、Ｘ線ディフラクト
メータの測定およびＸＭＡ測定、光学顕微鏡観察を行っ
た結果、つぎのことが明らかになった。(4) X-ray diffractometer measurement, XMA measurement, and optical microscope observation were carried out on FeBR-based and FeCoBR-based permanent magnets having various compositions and produced by various manufacturing methods including the above-mentioned method. As a result, the following became clear.
【００２６】（ｉ）（３）で述べたＲ、Ｆｅ、Ｂを基本
成分とし格子定数ａ0約９Å、ｃ0約１２Åの巨大ユニッ
トセルを有する正方晶の化合物が存在する場合に、永久
磁石として良好な特性を持つ。代表的なＦｅＢＲおよび
ＦｅＣｏＢＲ系磁石について得られた主相の正方晶化合
物の格子定数は表１の通りである。(I) In the presence of a tetragonal compound having a giant unit cell having R, Fe, and B as basic components described in (3) and having lattice constants a 0 about 9Å and c 0 about 12Å, a permanent magnet is used. With good characteristics. Table 1 shows the lattice constants of tetragonal compounds of the main phase obtained for typical FeBR and FeCoBR magnets.
【００２７】ＲＦｅ、ＦｅＢ、ＢＲなど従来ある二元系
化合物を基本とする化合物では、良好な永久磁石特性は
得られない。Good permanent magnet characteristics cannot be obtained with compounds based on conventional binary compounds such as RFe, FeB and BR.
【００２８】（ii）上記正方晶化合物が適度の結晶粒径
をもち、かつこの化合物がＲが多量に含まれた非磁性相
が混在する微細組織の場合に正方晶化合物は、永久磁石
の構成化合物として特に良好な特性を示す。(Ii) In the case where the tetragonal compound has a proper crystal grain size and the compound has a fine structure in which a nonmagnetic phase containing a large amount of R is mixed, the tetragonal compound has a structure of a permanent magnet. It exhibits particularly good properties as a compound.
【００２９】本正方晶化合物に基づく永久磁石（例えば
焼結磁石の一実施例の場合）では上述の正方晶の化合物
の平均結晶粒径が１〜１００μｍ（好ましくは1.5〜９
０μｍ、さらに好ましくは1.5〜８０μｍ）の範囲にあ
ることが望ましく、１μｍより小さいか１００μｍより
大ではＨｃが１ｋＯｅ以下となり、それを構成化合物と
する材料の工業材料としての価値が低下する。In a permanent magnet based on the present tetragonal compound (for example, in the case of one embodiment of a sintered magnet), the above-mentioned tetragonal compound has an average crystal grain size of 1 to 100 μm (preferably 1.5 to 9).
0 μm, more preferably 1.5 to 80 μm) is desirable, and if it is smaller than 1 μm or larger than 100 μm, Hc becomes 1 kOe or less, and the value of the material containing it as an industrial material decreases.
【００３０】また正方晶化合物の存在形態としては、高
い異方性定数をもつ微粒子が１つ１つ非磁性の相によっ
て隔離されていることが理想であり、このようなときに
高いＨｃを発現することが判明した。本願発明の正方晶
化合物は、この隔離微粒子を成すことによって理想的組
織を形成でき、この組織形態に基づいて焼結磁石に限ら
ず、或いはその構成元素の置換の有無に拘らず理論的永
久磁石ないし永久磁石材料の設計ができる。そのため非
磁性の相が１体積％以上あることが好ましい。焼結磁石
の一実施例において、Ｈｃが１ｋＯｅ以上であるために
非磁性の相が少なくとも体積比で１％以上とすることが
好ましいが、４５％をこえるのは好ましくない。より好
ましい範囲は２〜１０％である。非磁性の相は主として
Ｒを多量に含む金属間化合物相によって構成される。非
磁性の相としては酸化物の相も一部有効に働きうるがこ
れらに必ずしも限定されず、また上述の体積比の範囲も
必ずしもそれらに限定されない。Further, as the existence form of the tetragonal compound, it is ideal that each fine particle having a high anisotropy constant is separated by a non-magnetic phase, and at such a time, a high Hc is expressed. It turned out to be. The tetragonal compound of the present invention can form an ideal structure by forming the isolated fine particles, and is not limited to a sintered magnet based on this structure morphology, or a theoretical permanent magnet regardless of the substitution of constituent elements thereof. Or the design of permanent magnet material is possible. Therefore, it is preferable that the nonmagnetic phase is 1% by volume or more. In one embodiment of the sintered magnet, since Hc is 1 kOe or more, it is preferable that the nonmagnetic phase is at least 1% by volume, but it is not preferable that it exceeds 45%. A more preferable range is 2 to 10%. The nonmagnetic phase is mainly composed of an intermetallic compound phase containing a large amount of R. As the non-magnetic phase, an oxide phase may partly work effectively, but the non-magnetic phase is not necessarily limited to these, and the above range of the volume ratio is not necessarily limited thereto.
【００３１】（iii） 上記ＲＦｅＢ正方晶化合物及びＲ
（Ｆｅ、Ｃｏ）Ｂ正方晶化合物は広い組成範囲で生成し
うる。またＲ、Ｆｅ、Ｂ以外の元素を添加又は置換して
も安定に存在しうる。(Iii) The above-mentioned RFeB tetragonal compound and R
The (Fe, Co) B tetragonal compound can be produced in a wide composition range. Further, even if an element other than R, Fe and B is added or substituted, it can exist stably.
【００３２】永久磁石として良好な特性を示すための、
材料としての組成範囲はつぎの通りである。原子百分比
で２〜２８％のＢ、８〜３０％のＲおよび４０〜９０％
のＦｅを必須成分とする合金系（I）。In order to exhibit good characteristics as a permanent magnet,
The composition range of the material is as follows. Atomic percentage of 2-28% B, 8-30% R and 40-90%
Alloy system (I) containing Fe as an essential component.
【００３３】また２〜２８％のＢ、８〜３０％のＲ、４
０〜９０％のＦｅおよび５０％以下のＣｏを必須成分と
する合金系（II）。Also, 2 to 28% of B, 8 to 30% of R,
An alloy system (II) containing 0 to 90% Fe and 50% or less Co as essential components.
【００３４】合金系（I）、（II）においてＢ２％以
下、Ｒ８％以下ではＨｃが１ｋＯｅ以下となり、永久磁
石とした場合の工業的価値が低下する。Ｂ２８％以上、
Ｒ３０％以上ではＢｒが４ｋＧ以下となり、ハードフェ
ライトよりも低下してしまう。合金系（II）においては
Ｆｅに対する置換Ｃｏ量の増大にともなって正方晶化合
物のキュリー点が上昇し（３００〜７５０℃）、温度特
性が向上するが、Ｃｏが５０％以上となると、Ｈｃが１
ｋＯｅ以下となり永久磁石とした場合の価値は低くな
る。しかし、永久磁石以外の磁性材料としての用途に
は、それでも構わない。In the alloy systems (I) and (II), when B2% or less and R8% or less, Hc becomes 1 kOe or less, and the industrial value of a permanent magnet decreases. B28% or more,
When R is 30% or more, Br becomes 4 kG or less, which is lower than that of hard ferrite. In the alloy system (II), the Curie point of the tetragonal compound rises (300 to 750 ° C.) with an increase in the amount of Co substituted with Fe (300 to 750 ° C.), and the temperature characteristics are improved, but when Co is 50% or more, Hc is 1
The value becomes less than kOe, and the value of the permanent magnet becomes low. However, it may be used as a magnetic material other than the permanent magnet.
【００３５】上記必須成分に加えて各種の添加元素およ
び原料や製造工程から混入する不純物元素を含む合金も
前記範囲内において主相を正方晶化合物とすることがで
き、その場合に良好な永久磁石特性を示す。In addition to the above essential components, an alloy containing various additive elements and impurity elements mixed in from raw materials and manufacturing processes can have a tetragonal compound as the main phase within the above range, and in such a case, a good permanent magnet is obtained. Show the characteristics.
【００３６】また１％以下のＨ、Ｌｉ、Ｎａ、Ｋ、Ｂ
ｅ、Ｓｒ、Ｂａ、Ａｇ、Ｚｎ、Ｎ、Ｆ、Ｓｅ、Ｔｅ、Ｐ
ｂを含んでも上記基本ないしＣｏ置換正方晶化合物は安
定であり良好な永久磁石が得られる。Further, 1% or less of H, Li, Na, K, B
e, Sr, Ba, Ag, Zn, N, F, Se, Te, P
Even if b is included, the basic or Co-substituted tetragonal compound is stable and a good permanent magnet can be obtained.
【００３７】上述のように、ＲＦｅＢ系あるいはＲ（Ｆ
ｅ、Ｃｏ）Ｂ系正方晶化合物は従来全く知られていない
化合物であり、この化合物を主相とすることにより永久
磁石として高い特性が得られることは、新規の事実であ
る。ＲＦｅＢ基本化合物に基づく合金のキュリー点はＲ
ＦｅＢ基本化合物に基づき凡そ３００〜３７０℃の範囲
にあり、このような化合物に基づく合金は従来知られて
いない。As described above, the RFeB system or R (F
The (e, Co) B-type tetragonal compound is a compound that has not been known at all, and it is a novel fact that high characteristics as a permanent magnet can be obtained by using this compound as the main phase. The Curie point of an alloy based on the RFeB basic compound is R
It is in the range of about 300 to 370 ° C. based on the FeB basic compound, and an alloy based on such a compound has not been heretofore known.
【００３８】従来、ＲＦｅ系合金において超急冷法によ
るリボン磁石の報告がいくつかあるが、本発明は以下の
点でこれらの公知例とは異なる。すなわち、リボン磁石
は非晶質または凖安定結晶状態から安定な結晶状態に移
行する中途段階において永久磁石としての特性が得られ
る。従来の報告によると、これらの磁石材料が高保磁力
を示すのは非晶質状態が残留した状態または準安定なＦ
ｅ3ＢやＲ6Ｆｅ23が主相として存在する状態である。本
発明の正方晶化合物に基づく磁石では非晶質状態の合金
相の残留は検出されず、Ｆｅ3ＢやＲ6Ｆｅ23相は主相で
はない。Conventionally, there have been some reports of ribbon magnets in the RFe alloy by the ultra-quenching method, but the present invention is different from these known examples in the following points. That is, the ribbon magnet has the characteristics of a permanent magnet in the middle of the transition from the amorphous or stable crystalline state to the stable crystalline state. According to previous reports, these magnet materials have a high coercive force because the amorphous state remains or the metastable F
This is a state in which e 3 B and R 6 Fe 23 exist as the main phase. In the magnet based on the tetragonal compound of the present invention, no residual alloy phase in the amorphous state is detected, and the Fe 3 B or R 6 Fe 23 phase is not the main phase.
【００３９】本発明の正方晶化合物において希土類元素
ＲはＹを包含し、軽希土類及び重希土類を包含する希土
類元素であり、そのうち一種以上を用いる。即ちこのＲ
としては、Ｎｄ、Ｐｒ、Ｌａ、Ｃｅ、Ｔｂ、Ｄｙ、Ｈ
ｏ、Ｅｒ、Ｅｕ、Ｓｍ、Ｇｄ、Ｐｍ、Ｔｍ、Ｙｂ、Ｌｕ
及びＹが包含される。Ｒとしては軽希土類をもって足
り、特にＮｄ、Ｐｒが好ましい。また通例Ｒのうち一種
をもって足りるが、実用上は二種以上の混合物（ミッシ
ュメタル、ジジム等）を入手上の便宜等理由により用い
ることができ、Ｓｍ、Ｙ、Ｅｒ、Ｔｍ、Ｃｅ、Ｇｄ等は
Ｎｄ、Ｐｒを主体とする他のＲ（Ｎｄ、Ｐｒ、Ｔｂ、Ｄ
ｙ、Ｈｏ）との混合物として用いることができる。Ｌａ
はＮｄ、Ｐｒを主体とする他のＲとの混合物として用い
る必要がある。なお、このＲは純希土類元素でなくとも
よく、工業上入手可能な範囲で製造上不可避な不純物を
含有するもので差支えない。In the tetragonal compound of the present invention, the rare earth element R includes Y and is a rare earth element including light rare earth and heavy rare earth, and at least one of them is used. That is, this R
As Nd, Pr, La, Ce, Tb, Dy, H
o, Er, Eu, Sm, Gd, Pm, Tm, Yb, Lu
And Y are included. A light rare earth element is sufficient as R, and Nd and Pr are particularly preferable. Usually, one of R is sufficient, but in practice, a mixture of two or more kinds (Misch metal, didymium, etc.) can be used for reasons such as convenience of availability, and Sm, Y, Er, Tm, Ce, Gd, etc. Is another R (Nd, Pr, Tb, D) mainly composed of Nd and Pr.
y, Ho). La
Must be used as a mixture with other R mainly composed of Nd and Pr. It should be noted that R does not have to be a pure rare earth element, and may contain impurities that are unavoidable in production within a range that is industrially available.
【００４０】Ｂ（ホウ素）としては、純ボロン又はフェ
ロボロンを用いることができ、不純物としてＡｌ、Ｓ
ｉ、Ｃ等を含むものも用いることができる。As B (boron), pure boron or ferroboron can be used, and Al and S as impurities.
Those containing i, C, etc. can also be used.
【００４１】以下に本発明の正方晶化合物及びこれを構
成化合物とする永久磁石ないし永久磁石材料について実
施例をもって更に詳説する。The tetragonal compound of the present invention and the permanent magnet or permanent magnet material containing the tetragonal compound will be described in more detail with reference to examples.
【００４２】実施例１（参考例） ６ａｔ％Ｂ、１６ａｔ％Ｐｒ、残部Ｆｅの合金を粉砕し
て平均粒度１５μｍの粉末を作製した。この粉末を２ｔ
／ｃｍ2 の圧力で１９ｋＯｅの磁場中においてプレス
し、２×１０-1ＴｏｒｒのＡｒ中で１０９０℃ 一時間
焼結した。Example 1 (Reference Example) An alloy of 6 at% B, 16 at% Pr and the balance Fe was pulverized to prepare a powder having an average particle size of 15 μm. 2 tons of this powder
It was pressed in a magnetic field of 19 kOe at a pressure of / cm 2 and sintered in Ar at 2 × 10 −1 Torr at 1090 ° C. for 1 hour.
【００４３】Ｘ線回折によると、この焼結体の主相は正
方晶化合物であり、格子定数はａ0＝8.85Å、 ｃ0＝12.
26Åであった。ＸＭＡおよび光学顕微鏡観察の結果、主
相はＦｅ、Ｂ、Ｐｒを同時に含み、体積比で９０％を占
めていた。主相の粒界相を成す、Ｒを８０％以上含む非
磁性化合物相の合計は体積比３％で、残りは酸化物とポ
ア（空孔）であった。この正方晶化合物の平均結晶粒径
は２５μｍであった。According to X-ray diffraction, the main phase of this sintered body is a tetragonal compound, and the lattice constants are a 0 = 8.85Å, c 0 = 12.
It was 26Å. As a result of XMA and optical microscope observation, the main phase simultaneously contained Fe, B, and Pr, and occupied 90% by volume. The total volume of the non-magnetic compound phase containing 80% or more of R forming the grain boundary phase of the main phase was 3% by volume, and the rest was oxides and pores. The average crystal grain size of this tetragonal compound was 25 μm.
【００４４】磁気測定の結果はつぎの通りである。 Ｂｒ＝9.9ｋＧ、Ｈｃ＝6.5ｋＯｅ、（ＢＨ）ｍａｘ＝１
８ＭＧＯｅ これは従来のリボン磁石材料に比べてはるかに高い値で
ある。The results of the magnetic measurement are as follows. Br = 9.9kG, Hc = 6.5kOe, (BH) max = 1
8MGOe This is a much higher value than the conventional ribbon magnet material.
【００４５】実施例２（参考例） ８ａｔ％Ｂ、１５％ａｔＮｄ、残部Ｆｅ合金を粉砕して
平均粒度３μｍの粉末を作製した。この粉末を２ｔ／ｃ
ｍ2 の圧力で１０ｋＯｅの磁場中においてプレスし２×
１０-1ＴｏｒｒのＡｒ中で１１００℃ １時間焼結し
た。Example 2 (Reference Example) 8 at% B, 15% at Nd and the balance Fe alloy were pulverized to prepare a powder having an average particle size of 3 μm. 2 t / c of this powder
Pressed in a magnetic field of 10 kOe at a pressure of m 2 for 2 ×
Sintered in Ar at 10 -1 Torr for 1 hour at 1100 ° C.
【００４６】Ｘ線回折によると、この焼結体の主相は正
方晶化合物であり、格子定数はａ0＝8.80Å、ｃ0＝12.2
3Å であった。ＸＭＡおよび光学顕微鏡観察の結果、主
相は体積比でＦｅ、Ｂ、Ｎｄを同時に含み90.5％を占め
ていた。主相の粒界相を成す、Ｒを８０％以上含む非磁
性の化合物相は体積比４％で、残りはほとんど酸化物と
ポアであった。この正方晶化合物の平均結晶粒径は１５
μｍであった。According to X-ray diffraction, the main phase of this sintered body was a tetragonal compound, and the lattice constants were a 0 = 8.80Å and c 0 = 12.2.
3Å. As a result of observation by XMA and an optical microscope, the main phase contained 90.5% by volume of Fe, B, and Nd at the same time. The nonmagnetic compound phase containing 80% or more of R constituting the grain boundary phase of the main phase had a volume ratio of 4%, and the rest was mostly oxides and pores. The average crystal grain size of this tetragonal compound is 15
μm.
【００４７】磁気特性はＢｒ＝12.1ｋＧ、Ｈｃ＝9.3ｋ
Ｏｅ、（ＢＨ）ｍａｘ＝３４ＭＧＯｅであった。これは
従来のリボン磁石に比べてはるかに高い値である。The magnetic characteristics are as follows: Br = 12.1 kG, Hc = 9.3 k
Oe, (BH) max = 34 MGOe. This is a much higher value than the conventional ribbon magnet.
【００４８】実施例３ １０ａｔ％Ｃｏ、８ａｔ％Ｂ、１５ａｔ％Ｎｄ、残部Ｆ
ｅの合金を粉砕して平均粒径 1.1μｍの粉末を作製し
た。この粉末を２ｔ／ｃｍ2 の圧力で１２ｋＯｅの磁場
中においてプレスし 1.5ＴｏｒｒのＡｒ中、１０８０℃
で１時間焼結した。Example 3 10 at% Co, 8 at% B, 15 at% Nd, balance F
The alloy of e was pulverized to prepare a powder having an average particle size of 1.1 μm. This powder was pressed in a magnetic field of 12 kOe at a pressure of 2 t / cm 2 and then heated in Ar at 1.5 Torr at 1080 ° C.
For 1 hour.
【００４９】Ｘ線回折によると、この焼結体の主相は正
方晶化合物であり、格子定数はａ0＝8.79Å、ｃ0＝12.2
1Å であった。ＸＭＡおよび光学顕微鏡観察の結果、主
相はＦｅ、Ｃｏ、Ｂ、Ｎｄを同時に含み体積比で９０％
を占めていた。According to X-ray diffraction, the main phase of this sintered body was a tetragonal compound, and the lattice constants were a 0 = 8.79Å and c 0 = 12.2.
1Å. As a result of XMA and optical microscope observation, the main phase contains Fe, Co, B, and Nd at the same time, and the volume ratio is 90%.
Was occupied.
【００５０】Ｒを８０％以上含む非磁性化合物相は体積
比 4.5％で残りはほとんど酸化物とポアであり、正方晶
化合物の平均結晶粒径は3.1μｍであった。The nonmagnetic compound phase containing 80% or more of R was 4.5% in volume ratio, the rest was mostly oxides and pores, and the average crystal grain size of the tetragonal compound was 3.1 μm.
【００５１】磁気測定の結果は次の通りである。 Ｂｒ＝12.0ｋＧ、ｉＨｃ＝9.2ｋＯｅ、（ＢＨ）ｍａｘ
＝３４ＭＧＯｅ これは従来のリボン磁石材料に比べてはるかに高い値で
ある。The results of the magnetic measurement are as follows. Br = 12.0 kG, iHc = 9.2 kOe, (BH) max
= 34 MGOe This is a much higher value than the conventional ribbon magnet material.
【００５２】実施例４（参考例） ５ａｔ％Ｂ、７ａｔ％Ｎｄ、３ａｔ％Ｐｒ、２ａｔ％Ｔ
ｂ、残部Ｆｅの合金を粉砕して平均粒径 2.1μｍの粉末
を作製した。この粉末を２ｔ／ｃｍ2 の圧力で１５ｋＯ
ｅの磁場中においてプレスし、１ＴｏｒｒのＡｒ中１１
３０℃で１時間焼結した。Example 4 (reference example) 5 at% B, 7 at% Nd, 3 at% Pr, 2 at% T
b, an alloy of the balance Fe was pulverized to prepare a powder having an average particle size of 2.1 μm. This powder was added at a pressure of 2 t / cm 2 to 15 kO
Pressed in the magnetic field of e, 11 in 1 Torr of Ar
Sintered at 30 ° C. for 1 hour.
【００５３】Ｘ線回折によると、この焼結体の主相は正
方晶化合物であり、格子定数はａ0＝8.80Å、ｃ0＝12.2
4Å であった。ＸＭＡおよび光学顕微鏡観察の結果、主
相はＦｅ、Ｎｄ、Ｐｒ、Ｔｂ、Ｂを含み体積比で９１％
を占めていた。Ｒを８０％以上含む非磁性化合物相は体
積比で 1.5％で、その他にＦｅリッチの強磁性低保磁力
相が体積比で１％含まれ、残りはほとんど酸化物とポア
であり、正方晶化合物の平均結晶粒径は５μｍであっ
た。According to X-ray diffraction, the main phase of this sintered body was a tetragonal compound, and the lattice constants were a 0 = 8.80Å, c 0 = 12.2.
4Å. As a result of XMA and optical microscope observation, the main phase contained Fe, Nd, Pr, Tb, and B, and the volume ratio was 91%.
Was occupied. The volume ratio of the non-magnetic compound phase containing 80% or more of R is 1.5%, the content of Fe-rich ferromagnetic low coercive force phase is 1% by volume, and the balance is mostly oxides and pores. The average crystal grain size of the compound was 5 μm.
【００５４】磁気測定の結果はつぎの通りである。 Ｂｒ＝11.5ｋＧ、ｉＨｃ＝４ｋＯｅ、（ＢＨ）ｍａｘ
＝１７ＭＧＯｅ これは従来のリボン磁石に比べてはるかに高い値であ
る。The results of the magnetic measurement are as follows. Br = 11.5 kG, iHc = 4 kOe, (BH) max
= 17 MGOe This is a much higher value than the conventional ribbon magnet.
【００５５】実施例５（参考例） １７ａｔ％Ｂ、１０ａｔ％Ｎｄ、３ａｔ％Ｌａ、２ａｔ
％Ｇｄ、残部Ｆｅの合金を粉砕して平均粒径 2.7μｍの
粉末を作製した。この粉末を４ｔ／ｃｍ2 の圧力で１２
ｋＯｅの磁場中においてプレスし 1.5ＴｏｒｒのＡｒ中
１０８０℃で１時間焼結した。Example 5 (reference example) 17 at% B, 10 at% Nd, 3 at% La, 2 at
% Gd, the balance Fe was pulverized to prepare a powder having an average particle size of 2.7 μm. This powder was applied at a pressure of 4 t / cm 2 to 12
It was pressed in a magnetic field of kOe and sintered in Ar at 1.5 Torr at 1080 ° C. for 1 hour.
【００５６】Ｘ線回折によると、この焼結体の主相は正
方晶化合物であり、格子定数はａ0＝8.82Å、ｃ0＝12.2
2Å であった。ＸＭＡおよび光学顕微鏡観察の結果、主
相はＦｅ、Ｂ、Ｎｄ、Ｌａ、Ｇｄを含み体積比で82％を
占めていた。Ｒを８０％以上含む非磁性化合物相は体積
比１２％で、残りはほとんどポアであり、正方晶化合物
の平均結晶粒径は７μｍであった。According to X-ray diffraction, the main phase of this sintered body was a tetragonal compound, and the lattice constants were a 0 = 8.82Å and c 0 = 12.2.
2Å. As a result of XMA and optical microscope observation, the main phase contained Fe, B, Nd, La, and Gd, and occupied 82% by volume. The volume ratio of the non-magnetic compound phase containing 80% or more of R was 12%, the rest was almost pores, and the average crystal grain size of the tetragonal compound was 7 μm.
【００５７】磁気測定の結果は次の通りである。 Ｂｒ＝8.2ｋＧ、ｉＨｃ＝5.0ｋＯｅ、（ＢＨ）ｍａｘ＝
１５ＭＧＯｅ これは従来のリボン磁石材料に比べてはるかに高い値で
ある。The results of the magnetic measurement are as follows. Br = 8.2 kG, iHc = 5.0 kOe, (BH) max =
15MGOe This is a much higher value than the conventional ribbon magnet material.
【００５８】実施例６（参考例） １７ａｔ％Ｂ、２８ａｔ％Ｎｄ、残部Ｆｅの合金を粉砕
して平均粒径５μｍの粉末を作製した。この粉末を２ｔ
／ｃｍ2 の圧力で１２ｋＯｅの磁場中においてプレス
し、２×１０-1Ｔｏｒｒ １０５０℃、１時間焼結し
た。焼結後Ａｒ気流で冷却した。Ｘ線回折によると、こ
の焼結体では正方晶化合物のピークが他の相によるピー
クより低く、この化合物は主相ではない。ＸＭＡおよび
光学顕微鏡観察の結果、正方晶化合物は体積比で４８％
でＲを８０％以上含む非磁性化合物相は４７％であっ
た。残りはほとんどポアであり、平均結晶粒径は正方晶
化合物の１６μｍであった。Example 6 (Reference Example) An alloy of 17 at% B, 28 at% Nd and the balance Fe was pulverized to prepare a powder having an average particle size of 5 μm. 2 tons of this powder
It was pressed in a magnetic field of 12 kOe at a pressure of / cm 2 and sintered at 2 × 10 −1 Torr 1050 ° C. for 1 hour. After sintering, it was cooled by an Ar gas flow. According to X-ray diffraction, the peak of the tetragonal compound is lower than the peaks of the other phases in this sintered body, and this compound is not the main phase. As a result of XMA and optical microscope observation, the tetragonal compound is 48% by volume.
The non-magnetic compound phase containing 80% or more of R was 47%. The rest was almost pores, and the average crystal grain size was 16 μm of the tetragonal compound.
【００５９】磁気測定の結果は次の通りである。 Ｂｒ＝4.2ｋＧ、ｉＨｃ＝13.2ｋＯｅ、（ＢＨ）ｍａｘ
＝3.7ＭＧＯｅ これはフェライト系磁石の特性より低い。The results of magnetic measurement are as follows. Br = 4.2 kG, iHc = 13.2 kOe, (BH) max
= 3.7MGOe This is lower than the characteristics of ferrite magnets.
【００６０】焼結後５℃／ｍｉｎで制御冷却したところ
磁気特性はつぎのように上昇した。 Ｂｒ＝4.5ｋＧ、ｉＨｃ＝13.3ｋＯｅ、（ＢＨ）ｍａｘ
＝4.2ＭＧＯｅWhen controlled cooling was carried out at 5 ° C./min after sintering, the magnetic characteristics were increased as follows. Br = 4.5 kG, iHc = 13.3 kOe, (BH) max
= 4.2 MGOe
【００６１】徐冷試料のＸ線回折によると、正方晶化合
物のピークは強くなった。ＸＭＡ測定および光学顕微鏡
観察によると正方晶化合物は体積比５３％になり、Ｒを
８０％以上含む非磁性化合物相は体積比４３％であっ
た。残りはほとんどポアであり、正方晶化合物の平均結
晶粒径は１７μｍであった。According to X-ray diffraction of the slowly cooled sample, the peak of the tetragonal compound became stronger. According to XMA measurement and optical microscope observation, the tetragonal compound had a volume ratio of 53%, and the nonmagnetic compound phase containing 80% or more of R had a volume ratio of 43%. The remainder was mostly pores, and the average crystal grain size of the tetragonal compound was 17 μm.
【００６２】実施例７（参考例を含む） 表１に示す組成の合金を高周波溶解し、図２Ａの工程に
より資料を作製して、Ｘ線回折により主相の構造を決定
した。その結果を表１に示す。これにより正方晶化合物
はＦｅ−Ｂ−Ｎｄ系の広い組成範囲において常温から焼
結温度に至るまで安定であることがわかる。またＦｅ−
Ｃｏ−Ｎｄ−Ｂ系についても同様である。Example 7 (including Reference Example) Alloys having the compositions shown in Table 1 were subjected to high frequency melting, and materials were prepared by the process of FIG. 2A, and the structure of the main phase was determined by X-ray diffraction. Table 1 shows the results. This shows that the tetragonal compound is stable from room temperature to the sintering temperature in a wide composition range of Fe-B-Nd system. Fe-
The same applies to the Co-Nd-B system.
【００６３】これらＲＦｅＢ正方晶化合物、特に、Ｒ
（Ｆｅ、Ｃｏ）Ｂ正方晶化合物は、従来のＲＦｅ、Ｆｅ
Ｂ、ＲＢのどの組合せによっても実現できないユニーク
な特徴を有している磁性材料の構成化合物であり、工業
用材料としての価値が大変大きい。These RFeB tetragonal compounds, in particular, R
The (Fe, Co) B tetragonal compound is a conventional RFe, Fe
It is a constituent compound of a magnetic material having unique characteristics that cannot be realized by any combination of B and RB, and is extremely valuable as an industrial material.
【００６４】なお上記ＲＦｅＢ化合物はほとんどの場
合、ａ軸、ｂ軸、ｃ軸各方向のなす角度は測定誤差の範
囲で９０°であり、かつ、ａ0＝ｂ0≠ｃ0 であるからご
くわずかにずれることもありうる（例えば約１°以
内）。またａ0とｂ0がほんのわずか違う場合も含める。
しかし、この場合にも、実質的な意味で正方晶と呼ぶ。
これは、Ｒ（Ｆｅ、Ｃｏ）Ｂ系化合物についても同様で
ある。In most of the RFeB compounds, the angles formed by the a-axis, b-axis, and c-axis directions are 90 ° within the measurement error range, and a 0 = b 0 ≠ c 0. It may be slightly deviated (for example, within about 1 °). It also includes the case where a 0 and b 0 are slightly different.
However, also in this case, it is called tetragonal in a substantial sense.
The same applies to the R (Fe, Co) B-based compound.
【００６５】[0065]
【表１】 [Table 1]
【００６６】図３は、つぎの工程によって作製した種々
のＲ（Ｆｅ、Ｃｏ）ＢＡ化合物を構成化合物とする永久
磁石体の代表例（１）Ｆｅ−１０Ｃｏ−９Ｂ−１４Ｎｄ
−２Ｍｏ及び（２）Ｆｅ−２０Ｃｏ−８Ｂ−１５Ｐｒ−
２Ｚｒについて正方晶化合物の平均結晶粒径Ｄとの磁気
特性の関係を示す。図４〜図６はさらに種々のＡ元素
（Ｍ）を用いた場合の磁気特性とＭの含有量の関係を示
す。FIG. 3 shows a typical example of a permanent magnet body (1) Fe-10Co-9B-14Nd having various R (Fe, Co) BA compounds as constituent compounds, which were produced by the following steps.
-2Mo and (2) Fe-20Co-8B-15Pr-
The relationship between the magnetic properties of 2Zr and the average crystal grain size D of the tetragonal compound is shown. 4 to 6 show the relationship between the magnetic characteristics and the M content when various A elements (M) are used.
【００６７】（１）合金を高周波溶解し、水冷銅鋳型に
鋳造、出発原料はＦｅとして純度99.9％の電解鉄、Ｂと
してフェロボロン合金（19.38 ％Ｂ、5.32％Ａｌ、0.74
％Ｓｉ、0.03％Ｃ、残部Ｆｅ）、Ｒとして純度99.7％以
上（不純物は主として他の希土類金属）を使用。(1) The alloy was melted by high frequency and cast in a water-cooled copper mold, starting materials were electrolytic iron having a purity of 99.9% as Fe, and ferroboron alloy as B (19.38% B, 5.32% Al, 0.74).
% Si, 0.03% C, balance Fe), and a purity of 99.7% or more as R (impurities are mainly other rare earth metals).
【００６８】Ｃｏは純度99.9％の電解Ｃｏを使用した。As Co, electrolytic Co having a purity of 99.9% was used.
【００６９】Ａ元素（Ｍ）としては純度99％のＴｉ、Ｍ
ｏ、Ｂｉ、Ｍｎ、Ｓｂ、Ｎｉ、Ｔａ、Ｇｅ、９８％の
Ｗ、99.9％のＡｌ、Ｓｎ、９５％のＨｆ、またＶとして
81.2％のＶを含むフェロバハジウム、Ｎｂとして67.6％
のＮｂを含むフェロニオブ、Ｃｒとして61.9％のＣｒを
含むフェロクロムおよびＺｒとして75.5％のＺｒを含む
フェロジルコニウムを使用した。As the A element (M), Ti and M having a purity of 99%
As o, Bi, Mn, Sb, Ni, Ta, Ge, 98% W, 99.9% Al, Sn, 95% Hf, and V
Ferrovadium containing 81.2% V, 67.6% as Nb
Of Nb-containing ferroniobium, Cr of 61.9% Cr of ferrochrome and Zr of 75.5% of Zr of ferrozirconium were used.
【００７０】（２）粉砕 スタンプミルにより３５メッ
シュスルーまでに粗粉砕し、次いでボールミルにより３
時間微粉砕（３〜１０μｍ）。(2) Pulverization Coarse pulverization was performed by a stamp mill to a size of 35 mesh through, and then 3 by a ball mill.
Time milling (3-10 μm).
【００７１】（３）磁界 （１０ｋＯｅ）中配向・成形
（ 1.5ｔ／ｃｍ2にて加圧。）(3) Orientation and molding in a magnetic field (10 kOe) (pressurized at 1.5 t / cm 2 ).
【００７２】（４）焼結 １０００〜１２００℃１時間
Ａｒ中、焼結後放冷。(4) Sintering 1000 to 1200 ° C. for 1 hour in Ar, after sintering, let stand to cool.
【００７３】次に、前記の方法中（２）粉砕をＦｉｓｈ
ｅｒ社製のサブ・シーブ・サイザ（ｓｕｂ−ｓｉｅｖｅ
−ｓｉｚｅｒ）での平均粒度測定値が 0.5〜１００μｍ
の各値をとるよう適当に粉砕時間を変更して行い、各種
組成の試料を作製した。Next, in the above method, (2) crushing is performed by Fish.
er sub-sieve sizer (sub-sieve)
-Size) is 0.5 to 100 μm
Samples of various compositions were prepared by appropriately changing the crushing time so as to take each value of.
【００７４】比較例：１００μｍ以上の結晶粒径とする
ため、焼結後に焼結温度よりも５〜２０℃低い温度でＡ
ｒ雰囲気中にて長時間保持した。Comparative Example: In order to obtain a crystal grain size of 100 μm or more, after the sintering, the temperature A was 5 to 20 ° C. lower than the sintering temperature.
r It was kept in the atmosphere for a long time.
【００７５】このようにして得られた各組成の試料につ
いて磁石化の検討を行い、磁石特性及び正方晶化合物の
平均結晶粒径を測定した。その結果を図３に示す。ここ
で平均結晶粒径とは、試料面を研摩、腐蝕後光学顕微鏡
を用いて×１００〜×１０００の倍率の顕微鏡写真を撮
影し、既知面積の円を描いて円を八等分する直線を描
き、直径上にある平均粒子数を数え、算出した。但し、
境界上（円周上）にて区切られた粒子は１／２個として
数える（この方法はＨｅｙｎの方法として知られてい
る）。空孔の部分は計算より省く。Magnetization was examined for the samples of the respective compositions thus obtained, and the magnet characteristics and the average crystal grain size of the tetragonal compound were measured. The result is shown in FIG. Here, the average crystal grain size means a straight line that divides the circle into eight equal parts by drawing a circle of a known area by taking a photomicrograph of × 100 to × 1000 using an optical microscope after polishing and corroding the sample surface. It was drawn and the average number of particles on the diameter was counted and calculated. However,
The number of particles separated on the boundary (on the circumference) is counted as 1/2 (this method is known as the Heyn method). The holes are omitted from the calculation.
【００７６】組成（１）の試料は平均結晶粒径Ｄ 9.2μ
ｍのときエネルギ積（ＢＨ）ｍａｘ28.5ＭＧＯｅを示
し、組成（２）の試料はＤ 4.6μｍのとき、（ＢＨ）ｍ
ａｘ25.4ＭＧＯｅを示した。The sample of composition (1) had an average crystal grain size of D 9.2 μm.
The energy product (BH) max28.5MGOe is shown at m, and the sample of the composition (2) has (BH) m at D 4.6 μm.
ax25.4MGOe was shown.
【００７７】[0077]
【発明の効果】本願発明は、常温から焼結温度に至るま
で安定に存在する新規なＲＦｅＢ基本系正方晶化合物を
基礎として、さらにＦｅをＣｏにより置換（特に部分的
に）したＲ（Ｆｅ、Ｃｏ）Ｂ系を基礎とし、さらに特定
元素Ａを含む新規なＲ（Ｆｅ、Ｃｏ）ＢＡ系を基礎とし
た新規な正方晶化合物を提供したものである。詳しく
は、Ｃｏの置換によりＦｅＢＲ基本系正方晶化合物のキ
ュリー温度を大きく増大させ、さらに特定元素Ａを含む
ことによってもその基本的磁気特性を失わずに安定に存
在し得ることのみならず、これにより様々な修飾ないし
改良が所望の特性に応じて可能となるという優れた有用
性を備える。正方晶化合物のキュリー温度の増大は、永
久磁石の構成要素の化合物としてとりもなおさず、高温
下にも高い性能を失わない永久磁石の開発の具体的可能
性を担保するものである。EFFECTS OF THE INVENTION The present invention is based on a novel RFeB basic tetragonal compound that exists stably from room temperature to the sintering temperature, and R (Fe, The present invention provides a new tetragonal compound based on a Co) B system and further based on a new R (Fe, Co) BA system containing a specific element A. Specifically, not only does the substitution of Co significantly increase the Curie temperature of the FeBR basic tetragonal compound, and the inclusion of the specific element A not only allows it to exist stably without losing its basic magnetic properties, It has the excellent utility that various modifications or improvements can be made depending on desired properties. The increase in the Curie temperature of the tetragonal compound guarantees the specific possibility of developing a permanent magnet that does not lose its high performance even at high temperatures, as a compound of a constituent element of the permanent magnet.
【００７８】また、好ましくは所定の非磁性相により互
いに隔離された正方晶化合物は、永久磁石としての理想
的な微細組織を明らかにしたものであり画期的なもので
ある。このような隔離構造によって理想的な永久磁石の
設計の技術的基礎が確立されたものである。Further, preferably, the tetragonal compounds separated from each other by a predetermined non-magnetic phase clarify the ideal microstructure as a permanent magnet and are epoch-making. Such an isolation structure establishes the technical basis for the design of an ideal permanent magnet.
【００７９】かくて、本願発明において、これらの正方
晶化合物は、物質発明としての意義を有し、この知見に
到達する手がかりとなった焼結永久磁石材料とは次元を
異にする基本的な技術思想であり、焼結永久磁石のさら
なる改良及び理論値に近い高性能磁石の開発の指針を与
えると共に、さらに、これらの正方晶化合物を基礎とし
た様々な磁石の設計、開発の科学的、実際的な指針を与
えるものである。即ち、その永久磁石分野における科学
上の意義は言うに及ばず、永久磁石に止まらず様々な磁
性材料関連技術及び産業の発展の一大エポックを画する
ブレークスルーを成すものである。Thus, in the present invention, these tetragonal compounds have a significance as material inventions, and are fundamentally different in dimension from the sintered permanent magnet material that has been the clue to reach this finding. It is a technical idea, and provides guidelines for further improvement of sintered permanent magnets and development of high-performance magnets close to theoretical values, and further, for the design and development of various magnets based on these tetragonal compounds, the scientific, It gives practical guidance. That is, not to mention its scientific significance in the field of permanent magnets, it is a breakthrough that marks a major epoch in the development of various magnetic material-related technologies and industries beyond permanent magnets.
【図１】本発明の参考例たる代表的Ｆｅ−Ｂ−Ｎｄ焼結
体試料の粉末Ｘ線ディフラクトメータの測定結果パター
ンを示す写真である。FIG. 1 is a photograph showing a measurement result pattern of a representative Fe—B—Nd sintered body sample, which is a reference example of the present invention, by a powder X-ray diffractometer.
【図２】実験の手順を示すフローチャートである。
（（Ａ）は化合物の同定、（Ｂ）は永久磁石にした場
合。）FIG. 2 is a flowchart showing the procedure of an experiment.
((A) is the compound identification, (B) is a permanent magnet.)
【図３】平均結晶粒径Ｄ（μｍ）と保磁力ｉＨｃとの関
係を示すグラフである。FIG. 3 is a graph showing the relationship between the average crystal grain size D (μm) and the coercive force iHc.
【図４】ＦｅＣｏＢＲＡ系永久磁石のＡ元素（Ｍ）含有
量とｉＨｃの関係を示すグラフである。FIG. 4 is a graph showing the relationship between the A element (M) content of a FeCoBRA permanent magnet and iHc.
【図５】ＦｅＣｏＢＲＡ系永久磁石のＡ元素（Ｍ）含有
量とｉＨｃの関係を示すグラフである。FIG. 5 is a graph showing the relationship between the content of element A (M) in a FeCoBRA-based permanent magnet and iHc.
【図６】ＦｅＣｏＢＲＡ系永久磁石のＡ元素（Ｍ）含有
量とｉＨｃの関係を示すグラフである。FIG. 6 is a graph showing the relationship between the content of element A (M) in a FeCoBRA-based permanent magnet and iHc.
Claims (2)
上）、Ｆｅ、Ｃｏ、Ｂを必須成分とし、格子定数のｃ0
が約１２Åの正方晶系の結晶構造を有するＲ（Ｆｅ、Ｃ
ｏ）Ｂ正方晶化合物。1. R (where R is one or more rare earth elements including Y), Fe, Co and B are essential components, and the lattice constant c 0 is
Has a tetragonal crystal structure of about 12Å
o) B tetragonal compound.
上）、Ｆｅ、Ｃｏ、Ｂ及びＡ元素（但し、Ａ元素は下記
のＡ元素の１種以上）を必須成分とし、格子定数のｃ0
が約１２Åである正方晶系の結晶構造を有するＲ（Ｆ
ｅ、Ｃｏ）ＢＡ正方晶化合物（Ａ元素：Ｔｉ、Ｎｉ、Ｂ
ｉ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ａｌ、Ｓ
ｂ、Ｇｅ、Ｓｎ、Ｚｒ、Ｈｆ、Ｃｕ、Ｓ、Ｃ、Ｃａ、Ｍ
ｇ、Ｓｉ、Ｏ、およびＰ）。2. A lattice constant, wherein R (where R is one or more rare earth elements including Y), Fe, Co, B and A elements (where A element is one or more of the following A elements) are essential components. C 0
With a tetragonal crystal structure in which R is about 12Å
e, Co) BA tetragonal compound (A element: Ti, Ni, B)
i, V, Nb, Ta, Cr, Mo, W, Mn, Al, S
b, Ge, Sn, Zr, Hf, Cu, S, C, Ca, M
g, Si, O, and P).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7348303A JP2665658B2 (en) | 1995-12-18 | 1995-12-18 | Rare earth / iron / cobalt / boron tetragonal compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7348303A JP2665658B2 (en) | 1995-12-18 | 1995-12-18 | Rare earth / iron / cobalt / boron tetragonal compounds |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4304352A Division JP2684140B2 (en) | 1992-10-19 | 1992-10-19 | Rare earth / iron / cobalt / boron tetragonal compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08245295A true JPH08245295A (en) | 1996-09-24 |
| JP2665658B2 JP2665658B2 (en) | 1997-10-22 |
Family
ID=18396128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7348303A Expired - Lifetime JP2665658B2 (en) | 1995-12-18 | 1995-12-18 | Rare earth / iron / cobalt / boron tetragonal compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2665658B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990081728A (en) * | 1998-04-22 | 1999-11-15 | 히로지 사토 | Composition for permanent magnets |
| JP2008305908A (en) * | 2007-06-06 | 2008-12-18 | Hitachi Metals Ltd | METHOD FOR MANUFACTURING R-Fe-B PERMANENT MAGNET |
| JP2009249232A (en) * | 2008-04-07 | 2009-10-29 | Shinshu Univ | Method and apparatus for growing silicon crystal by applying magnetic field |
| WO2014034390A1 (en) * | 2012-08-31 | 2014-03-06 | Jx日鉱日石金属株式会社 | Fe-BASED MAGNETIC MATERIAL SINTERED BODY |
| CN110880392A (en) * | 2019-11-28 | 2020-03-13 | 厦门钨业股份有限公司 | Neodymium-iron-boron alloy powder, neodymium-iron-boron magnet material, and preparation method and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030185882A1 (en) | 2001-11-06 | 2003-10-02 | Vergez Juan A. | Pharmaceutical compositions containing oxybutynin |
| US6955729B2 (en) | 2002-04-09 | 2005-10-18 | Aichi Steel Corporation | Alloy for bonded magnets, isotropic magnet powder and anisotropic magnet powder and their production method, and bonded magnet |
-
1995
- 1995-12-18 JP JP7348303A patent/JP2665658B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990081728A (en) * | 1998-04-22 | 1999-11-15 | 히로지 사토 | Composition for permanent magnets |
| JP2008305908A (en) * | 2007-06-06 | 2008-12-18 | Hitachi Metals Ltd | METHOD FOR MANUFACTURING R-Fe-B PERMANENT MAGNET |
| JP2009249232A (en) * | 2008-04-07 | 2009-10-29 | Shinshu Univ | Method and apparatus for growing silicon crystal by applying magnetic field |
| WO2014034390A1 (en) * | 2012-08-31 | 2014-03-06 | Jx日鉱日石金属株式会社 | Fe-BASED MAGNETIC MATERIAL SINTERED BODY |
| TWI609368B (en) * | 2012-08-31 | 2017-12-21 | Jx Nippon Mining & Metals Corp | Fe-based magnetic material sintered body |
| US10090012B2 (en) | 2012-08-31 | 2018-10-02 | Jx Nippon Mining & Metals Corporation | Fe-bases magnetic material sintered compact |
| CN110880392A (en) * | 2019-11-28 | 2020-03-13 | 厦门钨业股份有限公司 | Neodymium-iron-boron alloy powder, neodymium-iron-boron magnet material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2665658B2 (en) | 1997-10-22 |
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| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19970513 |