JP2001189204A - Magnetic material, method of manufacturing the same, and bonded magnet - Google Patents
Magnetic material, method of manufacturing the same, and bonded magnetInfo
- Publication number
- JP2001189204A JP2001189204A JP37503799A JP37503799A JP2001189204A JP 2001189204 A JP2001189204 A JP 2001189204A JP 37503799 A JP37503799 A JP 37503799A JP 37503799 A JP37503799 A JP 37503799A JP 2001189204 A JP2001189204 A JP 2001189204A
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- magnet
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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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、永久磁石として有
用な磁石材料、その製造方法、およびそのような磁石材
料を用いて得たボンド磁石に関する。[0001] The present invention relates to a magnet material useful as a permanent magnet, a method for producing the same, and a bonded magnet obtained by using such a magnet material.
【０００２】[0002]
【従来の技術】高性能希土類磁石としては、従来からＳ
ｍＣｏ系磁石、ＮｄＦｅＢ磁石などが知られており、各
種用途に用いられている。これらの磁石にはＦｅ、Ｃｏ
が多量に含まれているが、Ｆｅ、Ｃｏは飽和磁束密度の
増大に寄与している。また、これらの磁石にはＮｄ、Ｓ
ｍなどの希土類元素が含まれており、希土類元素は結晶
場中における４ｆ電子の挙動に由来して、非常に大きな
磁気異方性をもたらす。これにより保磁力の増大が図ら
れ、高性能な磁石が実現されている。2. Description of the Related Art As a high performance rare earth magnet, S
mCo-based magnets, NdFeB magnets, and the like are known and used for various applications. These magnets include Fe, Co
Is contained in a large amount, but Fe and Co contribute to an increase in the saturation magnetic flux density. In addition, these magnets have Nd, S
m and the like, and the rare earth element brings about a very large magnetic anisotropy due to the behavior of 4f electrons in the crystal field. Thereby, the coercive force is increased, and a high-performance magnet is realized.
【０００３】このような高性能磁石は、主としてモー
タ、計測器、スピーカーなどの電子機器、電気機器に使
用されている。特に、ハードディスクドライブ用にはＮ
ｄＦｅＢ急冷粉を用いたボンド磁石が多用されている。[0003] Such high-performance magnets are mainly used in electronic equipment such as motors, measuring instruments, and speakers, and electrical equipment. In particular, N for hard disk drives
Bond magnets using dFeB quenched powder are frequently used.
【０００４】近年、各種電子機器の小型軽量化の要求が
高まり、これに対応できる大きな最大磁気エネルギー積
をもつ永久磁石の出現が求められている。[0004] In recent years, there has been an increasing demand for smaller and lighter electronic devices, and there has been a demand for a permanent magnet having a large maximum magnetic energy product to cope with the demand.
【０００５】これに対して、最近、ＳｍＦｅを主体とす
る合金が開発されている。例えば、特開平６−１７２９
３６号公報には、ＴｂＣｕ７相からなる磁性材料が、特
開平７−６６０２１号公報にはＴｂＣｕ７相とＦｅＣｏ
相からなる磁性材料が、特開平８−３１６０１８号公報
にはＴｂＣｕ７相、Ｔｈ2 Ｚｎ１７相、Ｔｈ2 Ｎｉ１ ７
相のいずれかとｂｃｃ相１０〜６０体積％からなる磁石
材料がそれぞれ開示されている。On the other hand, recently, alloys mainly composed of SmFe have been developed. For example, JP-A-6-1729
No. 36 discloses a magnetic material comprising a TbCu 7 phase, and JP-A-7-66021 discloses a TbCu 7 phase and a FeCo
Magnetic material consisting of phases, Japanese Patent Laid-Open No. 8-316018 TbCu 7 phase, Th 2 Zn 17 phase, Th 2 Ni 1 7
Disclosed are magnet materials consisting of any one of the phases and 10 to 60% by volume of the bcc phase.
【０００６】[0006]
【発明が解決しようとする課題】上述のように、ＳｍＦ
ｅを主体とする磁性材料、磁石材料は、ＮｄＦｅＢ急冷
粉を上回る高エネルギー積をもつ新しい磁石材料とし
て、特にボンド磁石に適したものとして開発されてき
た。しかしながら、最近の電子機器では、高密度実装に
よる熱対策が要求されており、また、車搭載用の磁石は
特に使用環境温度が高く、これらの用途には高エネルギ
ー積化に加え、磁石特性の高耐熱性、すなわち高保磁力
化が重要となっているが、上述の磁石材料は、これらの
特性をすべて満たすものではない。As described above, SmF
Magnetic materials and magnet materials mainly composed of e have been developed as new magnet materials having a higher energy product than NdFeB quenched powder, particularly suitable for bonded magnets. However, recent electronic devices are required to take measures against heat by high-density mounting. In addition, magnets mounted on vehicles have a particularly high usage environment temperature. Although high heat resistance, that is, high coercive force is important, the above-described magnet materials do not satisfy all of these characteristics.
【０００７】即ち、上記特許公報に記載されている磁性
材料は、いずれも高保磁力化および耐熱性に問題があ
る。本発明は、このような課題に対処するためになされ
たもので、高エネルギー積と高耐熱性を併せ有する磁石
材料、その製造方法、およびボンド磁石を提供すること
を目的とする。[0007] That is, all of the magnetic materials described in the above-mentioned patent publications have problems in high coercive force and heat resistance. The present invention has been made to address such a problem, and an object of the present invention is to provide a magnet material having both high energy product and high heat resistance, a method for manufacturing the same, and a bonded magnet.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するた
め、本発明は、下記一般式で表され、主相がＴｂＣｕ７
相と、Ｔｈ2 Ｎｉ１７相おとを含むことを特徴とする磁
石材料を提供する。In order to solve the above problems, the present invention is represented by the following general formula, wherein the main phase is TbCu 7
The invention provides a magnetic material comprising a phase and a Th 2 Ni 17 phase.
【０００９】（Ｒ１）ｘ（Ｒ２）ｙＴ
１００−ｘ−ｙ−ｚ−α−βＭｚＸαＡβ （式中、Ｒ１は、少なくとも１種以上の希土類元素（Ｙ
を含む）、Ｒ２は、Ｔｉ、Ｚｒ、ＨｆおよびＮｂからな
る群から選ばれる少なくとも１種、Ｔは、Ｆｅ、Ｃｏお
よびＮｉからなる群から選ばれる少なくとも１種、Ｍ
は、Ｖ、Ｃｒ、Ｍｎ、Ｔａ、Ｍｏ、Ｗ、Ｓｎ、Ｇａ、Ａ
ｌ、ＧｅおよびＳｉからなる群から選ばれる少なくとも
１種、Ｘは、Ｃ、Ｎ、Ｈ、ＯおよびＦからなる群から選
ばれる少なくとも１種、Ａは、ＢおよびＰからなる群か
ら選ばれる少なくとも１種であり、ｘ、ｙ、ｚ、α、β
は、式２≦ｘ≦２０、０．１≦ｙ≦２０、０≦ｚ≦１
０、０．１≦α≦２０、０≦β≦５（原子％）を満たす
正の数である。） また、本発明は、下記一般式で表され、主相がＴｂＣｕ
７相と、Ｔｈ2 Ｎｉ１ ７相とを含み、更に副相としてＦ
ｅまたはＦｅＣｏ相を１０体積％まで含むことを特徴と
する磁石材料を提供する。(R 1 ) x (R 2 ) y T
100-x-y-z- α-β M z X α A β ( wherein, R 1 is at least one or more rare earth elements (Y
R 2 is at least one selected from the group consisting of Ti, Zr, Hf and Nb; T is at least one selected from the group consisting of Fe, Co and Ni;
Is V, Cr, Mn, Ta, Mo, W, Sn, Ga, A
1, at least one selected from the group consisting of Ge and Si, X is at least one selected from the group consisting of C, N, H, O and F, and A is at least one selected from the group consisting of B and P X, y, z, α, β
Is represented by the formula 2 ≦ x ≦ 20, 0.1 ≦ y ≦ 20, 0 ≦ z ≦ 1
0, a positive number satisfying 0.1 ≦ α ≦ 20 and 0 ≦ β ≦ 5 (atomic%). The present invention is represented by the following general formula, wherein the main phase is TbCu.
Includes 7 and phase, the Th 2 Ni 1 7 phase, F as further subphase
Provided is a magnet material characterized by containing up to 10% by volume of an e or FeCo phase.
【００１０】（Ｒ１）ｘ（Ｒ２）ｙＴ
１００−ｘ−ｙ−ｚ−α−βＭｚＸαＡβ （式中、Ｒ１は、少なくとも１種以上の希土類元素（Ｙ
を含む）、Ｒ２は、Ｔｉ、Ｚｒ、ＨｆおよびＮｂからな
る群から選ばれる少なくとも１種、Ｔは、Ｆｅ、Ｃｏお
よびＮｉからなる群から選ばれる少なくとも１種、Ｍ
は、Ｖ、Ｃｒ、Ｍｎ、Ｔａ、Ｍｏ、Ｗ、Ｓｎ、Ｇａ、Ａ
ｌ、ＧｅおよびＳｉからなる群から選ばれる少なくとも
１種、Ｘは、Ｃ、Ｎ、Ｈ、ＯおよびＦからなる群から選
ばれる少なくとも１種、Ａは、ＢおよびＰからなる群か
ら選ばれた少なくとも１種であり、ｘ、ｙ、ｚ、α、β
は、式２≦ｘ≦２０、０．１≦ｙ≦２０、０≦ｚ≦１
０、０．１≦α≦２０、０≦β≦５（原子％）を満たす
正の数である。） 更に、本発明は、上述の磁石材料の粉末と樹脂との混合
物を成形してなることを特徴とするボンド磁石を提供す
る。(R 1 ) x (R 2 ) y T
100-x-y-z- α-β M z X α A β ( wherein, R 1 is at least one or more rare earth elements (Y
R 2 is at least one selected from the group consisting of Ti, Zr, Hf and Nb; T is at least one selected from the group consisting of Fe, Co and Ni;
Is V, Cr, Mn, Ta, Mo, W, Sn, Ga, A
at least one selected from the group consisting of l, Ge and Si, X is at least one selected from the group consisting of C, N, H, O and F, and A is selected from the group consisting of B and P X, y, z, α, β
Is represented by the formula 2 ≦ x ≦ 20, 0.1 ≦ y ≦ 20, 0 ≦ z ≦ 1
0, a positive number satisfying 0.1 ≦ α ≦ 20 and 0 ≦ β ≦ 5 (atomic%). Further, the present invention provides a bonded magnet obtained by molding a mixture of the above-mentioned powder of the magnetic material and a resin.
【００１１】本発明の磁石材料において、上記式中、Ｒ
１は、磁性材料に大きな磁気異方性をもたらし、ひいて
は高い保磁力を与えるのに有効な元素である。Ｌａ、Ｃ
ｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈ
ｏ、Ｅｒ、Ｔｍ、Ｌｕ、およびＹからなる群から選ばれ
る希土類元素である。In the magnetic material of the present invention, in the above formula, R
Numeral 1 is an element effective to bring a large magnetic anisotropy to a magnetic material and to give a high coercive force. La, C
e, Pr, Nd, Sm, Eu, Gd, Tb, Dy, H
It is a rare earth element selected from the group consisting of o, Er, Tm, Lu, and Y.
【００１２】Ｒ１は、高飽和磁束密度の観点からはＬ
ａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍが好ましく、特に高保磁力
の点からはＳｍが好ましい。その量は、２原子％未満で
は磁気異方性が小さくなりすぎ、高保磁力が得られな
い。一方、２０原子％を越えると飽和磁束密度が小さく
なり、高エネルギー積化が困難である。好ましくは３〜
１８原子％であり、さらに好ましくは４〜１６原子％で
ある。R 1 is L from the viewpoint of high saturation magnetic flux density.
a, Ce, Pr, Nd, and Sm are preferred, and Sm is particularly preferred from the viewpoint of high coercive force. If the amount is less than 2 atomic%, the magnetic anisotropy becomes too small and a high coercive force cannot be obtained. On the other hand, if it exceeds 20 atomic%, the saturation magnetic flux density becomes small, and it is difficult to increase the energy product. Preferably 3 to
It is 18 atomic%, and more preferably 4 to 16 atomic%.
【００１３】Ｒ２は、ＴｂＣｕ７相を容易に形成させる
元素であるとともに、結晶構造の希土類サイトに入り、
Ｔｈ2 Ｎｉ１７相の安定化に寄与する。更に、磁気異方
性の調整を行い、特に等方性ボンド磁石材料の実現に有
効である。Ｒ２は、Ｚｒ、Ｈｆ、Ｔｉ、Ｎｂから選ばれ
る少なくとも１種であり、特にＺｒが好ましい。その量
は、０．１原子％未満ではＴｂＣｕ７相、あるいはＴｈ
2 Ｎｉ１７相の形成が困難であり、一方２０原子％を越
えると飽和磁束密度が低下してしまい、高エネルギー積
が得られにくくなる。好ましくは０．５〜１８原子％で
あり、さらに好ましくは１〜１６原子％である。R 2 is an element that easily forms the TbCu 7 phase, and enters the rare earth site of the crystal structure.
It contributes to the stabilization of the Th 2 Ni 17 phase. Further, the magnetic anisotropy is adjusted, which is particularly effective for realizing an isotropic bonded magnet material. R 2 is at least one selected from Zr, Hf, Ti, and Nb, and Zr is particularly preferable. If the amount is less than 0.1 atomic%, TbCu 7 phase or Th
2 formed of Ni 17 phase is difficult, whereas causes decreases the saturation magnetic flux density exceeds 20 atomic%, it is difficult to obtain a high energy product. Preferably it is 0.5-18 atomic%, More preferably, it is 1-16 atomic%.
【００１４】Ｔは、磁性材料の大きな飽和磁束密度を実
現するための基本元素であり、Ｆｅ、Ｃｏから選ばれる
少なくとも１種である。特に、Ｆｅを主体にすることが
好ましく、Ｔの中で５０％以上がＦｅからなるのが基本
である。Ｃｏは、Ｆｅの４０％までを置換することが可
能である。T is a basic element for realizing a large saturation magnetic flux density of the magnetic material, and is at least one selected from Fe and Co. In particular, it is preferable to mainly use Fe, and basically, 50% or more of T is made of Fe. Co can replace up to 40% of Fe.
【００１５】Ｍは、磁気特性改善に有効な元素であり、
Ｖ、Ｃｒ、Ｍｎ、Ｔａ、Ｍｏ、Ｗ、Ｓｎ、Ｇａ、Ａｌ、
Ｇｅ、およびＳｉからなる群から選ばれる少なくとも１
種である。その量が増えると飽和磁束密度が低下するた
め、１０原子％以下が好ましい。さらに好ましくは８原
子％以下である。M is an element effective for improving magnetic properties.
V, Cr, Mn, Ta, Mo, W, Sn, Ga, Al,
At least one selected from the group consisting of Ge and Si
Is a seed. If the amount increases, the saturation magnetic flux density decreases, so that it is preferably 10 atomic% or less. More preferably, it is 8 atomic% or less.
【００１６】Ｘは、Ｃ、Ｎ、Ｈ、Ｆ、Ｏから選ばれる１
種以上であり、主として主相の格子間位置に存在し、主
相のキュリー温度、磁化、磁気異方性を向上させる働き
を有する。その量は、０．１原子％未満では上記効果が
十分には得られず、一方、２０原子％を超えると保磁力
が低下してしまう。なお、より好ましくは１原子％以上
である。X is 1 selected from C, N, H, F and O
Or more, and mainly exists at the interstitial position of the main phase, and has a function of improving the Curie temperature, magnetization, and magnetic anisotropy of the main phase. If the amount is less than 0.1 atomic%, the above effect cannot be sufficiently obtained, while if it exceeds 20 atomic%, the coercive force decreases. It is more preferably at least 1 atomic%.
【００１７】これらの元素の中では、特にＮ（窒素）が
好ましく、窒素の導入にあたりＨ（水素）も同時に格子
間に侵入することが多い。また、Ａは、急冷時のアモル
ファス化、熱処理時の微細な結晶粒析出に有効な元素で
あり、特にＢが好ましい。その量は、５原子％以下であ
る。Of these elements, N (nitrogen) is particularly preferred, and H (hydrogen) often enters the lattice at the same time as nitrogen is introduced. A is an element that is effective for amorphizing during quenching and precipitating fine crystal grains during heat treatment, and B is particularly preferable. Its amount is not more than 5 atomic%.
【００１８】なお、上記式により実質的に表される磁石
材料は、酸化物などの不可避不純物を含有することを許
容する。また、Ｆｅの析出もその量によって許容され
る。その量は、Ｘ線回折で主相の主回折線の強度に対し
て２０％までのＦｅの主回折線である。The magnet material substantially represented by the above formula is allowed to contain unavoidable impurities such as oxides. Further, the precipitation of Fe is also permitted depending on the amount. The amount is the main diffraction line of Fe up to 20% of the intensity of the main diffraction line of the main phase in X-ray diffraction.
【００１９】上記式で表される磁石材料の主相は、Ｔｂ
Ｃｕ７相と、Ｔｈ2 Ｎｉ１７相とを含む。その割合は、
Ｔｈ2 Ｎｉ１７相が、０を含まず１００％未満の範囲で
ある。Ｔｈ2 Ｎｉ１７相の割合が増えると、高い保磁力
が実現しやすくなり、耐熱性が改善される。The main phase of the magnet material represented by the above formula is Tb
It contains a Cu 7 phase and a Th 2 Ni 17 phase. The percentage is
The Th 2 Ni17 phase is in a range of less than 100% without including 0. When the proportion of the Th 2 Ni 17 phase increases, a high coercive force is easily realized, and the heat resistance is improved.
【００２０】主相の平均結晶粒径は、１０〜１００ｎｍ
の範囲にあることが望ましい。主相の平均結晶粒径が１
０ｎｍ未満では高保磁力が得られにくく、１００ｎｍを
超えると残留磁束密度が低下し、最大エネルギー積が低
くなる。ここで、ＴｂＣｕ７相とＴｈ2 Ｎｉ１７相の割
合は、ＴＥＭ写真から得られる結晶粒１０個以上に対し
て、個別に回折パターンをとり、区別する方法、あるい
は粉末Ｘ線回折をとり、ＴｂＣｕ７相のみのパターンに
対してその強度比から算出する方法のいずれでもよい。The average crystal grain size of the main phase is 10 to 100 nm.
Is desirably within the range. Average grain size of main phase is 1
If it is less than 0 nm, it is difficult to obtain a high coercive force, and if it exceeds 100 nm, the residual magnetic flux density decreases, and the maximum energy product decreases. The ratio of TbCu7 phase and Th 2 Ni 17 phase to the crystal grains 10 or more obtained from TEM photographs, taken individually diffraction pattern, taking a method or powder X-ray diffraction, distinguish, TbCu 7 Any of the methods of calculating from the intensity ratio for the pattern of only the phase may be used.
【００２１】また、平均結晶粒径は、ＴＥＭ写真で得ら
れた主相粒について最も大きい径と小さい径の平均をそ
の粒の粒径とし、これを１０個以上とり、平均した値で
代表するか、あるいはＳｃｈｅｅｒｅｒの式を用いて粉
末Ｘ線パターンの半値幅から求めてもよい。The average crystal grain size is represented by the average of the largest and smallest diameters of the main phase grains obtained in the TEM photograph as the grain size, and 10 or more of the averaged grain sizes are represented by the average value. Alternatively, it may be determined from the half width of the powder X-ray pattern using the Scherer equation.
【００２２】本発明はまた、主として希土類元素（Ｙを
含む）と遷移金属とを含む合金溶湯を、高速移動する冷
却体上に射出して冷却し、アモルファス相を含む金属体
を形成する工程、前記金属体を熱処理することにより、
平均結晶粒径が１０〜１００ｎｍである、ＴｂＣｕ７相
と、Ｔｈ2 Ｎｉ１７相とを含む金属組織体を形成する工
程、および前記金属組織体に、窒素、水素、炭素、フッ
素及び炭素からなる群から選ばれた少なくとも１種を導
入する工程を具備することを特徴とする磁石材料の製造
方法を提供する。ここで、高速移動とは、典型的には、
１０ｍ／ｓ以上の速さを意味する。The present invention also provides a step of injecting a molten alloy mainly containing a rare earth element (including Y) and a transition metal onto a high-speed moving cooling body and cooling it to form a metal body containing an amorphous phase. By heat-treating the metal body,
A step of forming a metal structure including a TbCu 7 phase and a Th 2 Ni 17 phase having an average crystal grain size of 10 to 100 nm, and forming the metal structure from nitrogen, hydrogen, carbon, fluorine, and carbon. A method for producing a magnet material, comprising a step of introducing at least one member selected from the group. Here, high-speed movement typically means
It means a speed of 10 m / s or more.
【００２３】かかる本発明の磁石材料の製造方法につい
て、以下、より詳細に説明する。上記式でＸを除く（た
だしＣは含んでいてもよい）合金を溶解した後、図１に
示す装置を用いて、液体急冷法（たとえば単ロール法）
により急冷し、薄帯状あるいはフレーク状の試料を作製
する。The method for producing the magnet material of the present invention will be described below in more detail. After dissolving the alloy except X in the above formula (C may be included), a liquid quenching method (for example, a single roll method) is performed using the apparatus shown in FIG.
To produce a strip-shaped or flake-shaped sample.
【００２４】即ち、誘導加熱コイル３を備えた容器２内
に合金を導入して、誘導加熱コイル３により合金を溶解
した後、容器２の下端のノズル４から、回転するロール
１上に溶解した合金を供給し急冷し、合金薄帯５を得
る。この際、５０％以上をアモルファス相にするのが好
ましいが、急冷時点で５０％以上微細結晶が析出してい
てもよい。That is, the alloy was introduced into the container 2 provided with the induction heating coil 3, and the alloy was melted by the induction heating coil 3. Then, the alloy was melted from the nozzle 4 at the lower end of the container 2 onto the rotating roll 1. The alloy is supplied and quenched to obtain an alloy ribbon 5. At this time, it is preferable that 50% or more of the amorphous phase is formed, but 50% or more of fine crystals may be precipitated at the time of quenching.
【００２５】図１に示す装置による単ロール法以外に
も、アトマイズ法、回転ディスク法、メカニカルアロイ
ング法、メカニカルグライディング法により、アモルフ
ァス相を含む合金組織を作製することも可能である。な
お、急速冷却の雰囲気は、不活性雰囲気または真空中で
ある。In addition to the single roll method using the apparatus shown in FIG. 1, an alloy structure containing an amorphous phase can be produced by an atomizing method, a rotating disk method, a mechanical alloying method, or a mechanical grinding method. The rapid cooling atmosphere is an inert atmosphere or a vacuum.
【００２６】次いで、この合金薄帯を熱処理し、ＴｂＣ
ｕ７相とＴｈ2 Ｎｉ１７相との混相組織にする。その熱
処理温度は、組成、あるいは急冷状態の結晶相の析出状
態にもよるが、７００〜１０００℃で１０分〜１０時間
程度が好ましい。Next, this alloy ribbon is heat-treated, and TbC
to mixed-phase organization of the u 7 phase and the Th 2 Ni 17 phase. The heat treatment temperature depends on the composition or the state of precipitation of the rapidly cooled crystal phase, but is preferably from 700 to 1000 ° C. for about 10 minutes to 10 hours.
【００２７】その後、熱処理された合金薄帯を、所定の
雰囲気中３５０〜６００℃で、１０分から５時間処理
し、Ｘ元素を導入する。なお、Ｂ、Ｏ、Ｃ、Ｐについて
は、予め合金溶解時点で導入することが可能である。Thereafter, the heat-treated alloy ribbon is treated in a predetermined atmosphere at 350 to 600 ° C. for 10 minutes to 5 hours to introduce the element X. Note that B, O, C, and P can be introduced before melting the alloy.
【００２８】Ｘの導入方法は、次の通りである。即ち、
得られた薄帯状あるいはフレーク状試料を粉砕し、数十
μｍ〜数ｍｍの大きさの粉末とする。窒素を導入する場
合、この粉末を窒素雰囲気中、あるいはアンモニアと水
素の混合ガス中で３００〜６００℃の範囲で１０分から
５時間、処理を行う。また、炭素を導入する場合には、
メタン、エタン、プロパンガスなどの炭素を含むガス雰
囲気中で処理する。この時、Ａｒ或いは窒素雰囲気中で
〜５時間熱処理を追加してもよい。The method of introducing X is as follows. That is,
The obtained ribbon-like or flake-like sample is pulverized to obtain a powder having a size of several tens μm to several mm. When introducing nitrogen, this powder is treated in a nitrogen atmosphere or a mixed gas of ammonia and hydrogen at a temperature of 300 to 600 ° C. for 10 minutes to 5 hours. Also, when introducing carbon,
The treatment is performed in a gas atmosphere containing carbon such as methane, ethane, and propane gas. At this time, heat treatment may be additionally performed in an Ar or nitrogen atmosphere for up to 5 hours.
【００２９】以上のようにして得た、本発明の磁石材料
の粉末を、エポキシ系、ナイロン系などの樹脂と混合
し、成形することにより、ボンド磁石を製造することが
出来る。樹脂としてエポキシ系のような熱硬化性樹脂を
用いる場合には、圧縮成形したあとに、３７３〜４７３
Ｋ程度の温度でキュア処理をすることが望ましく、また
樹脂としてナイロン系のような熱可塑性樹脂を用いる場
合は、射出成形法を用いることが好ましい。The powder of the magnetic material of the present invention obtained as described above is mixed with an epoxy-based or nylon-based resin and molded to produce a bonded magnet. When a thermosetting resin such as an epoxy resin is used as the resin, 373 to 473 after compression molding.
It is desirable to perform the curing treatment at a temperature of about K, and when a thermoplastic resin such as a nylon resin is used as the resin, it is preferable to use an injection molding method.
【００３０】また、圧縮成形ボンド磁石を製造する場合
には、加圧時に磁場を印加して結晶方位を揃えることに
より、高磁束密度を有する永久磁石を製造することがで
きる。When a compression-molded bonded magnet is manufactured, a permanent magnet having a high magnetic flux density can be manufactured by applying a magnetic field at the time of pressurization and aligning the crystal orientation.
【００３１】[0031]
【発明の実施の形態】以下、本発明の実施の形態として
の種々の実施例および比較例を示し、本発明について、
より具体的に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, various examples and comparative examples as embodiments of the present invention will be shown.
This will be described more specifically.
【００３２】実施例１、比較例１ 図１に示す装置（ロール材質：Ｃｕ）を用い、単ロール
法により薄帯状試料を得た。即ち、高純度のＳｍ、Ｚ
ｒ、Ｃｏ、Ｆｅ、Ｂの各原料を、誘導加熱コイル３を備
えた容器２内に導入して、 Ａｒ雰囲気中で誘導加熱コ
イル３により溶解した後、容器２の下端のノズル４か
ら、４０ｍ／ｓのロール周速で回転するロール１上に溶
解した合金を供給して超急冷し、合金薄帯５を得た。Example 1, Comparative Example 1 Using the apparatus shown in FIG. 1 (roll material: Cu), a ribbon-shaped sample was obtained by a single roll method. That is, high purity Sm, Z
The raw materials of r, Co, Fe, and B are introduced into the container 2 provided with the induction heating coil 3 and melted by the induction heating coil 3 in an Ar atmosphere. The melted alloy was supplied onto the roll 1 rotating at a roll peripheral speed of / s and was rapidly quenched to obtain an alloy ribbon 5.
【００３３】次いで、この合金薄帯５をＸ線回折により
分析したところ、アモルファス相のみであることを確認
した。得られた合金薄帯５を８５０℃、３０分間熱処理
し、ＴｂＣｕ７相とＴｈ2 Ｎｉ１７相の両者を析出させ
た。Ｘ線回折強度から、Ｔｈ 2 Ｎｉ１７相の割合は５０
％であった。Next, this alloy ribbon 5 is subjected to X-ray diffraction.
Analysis confirmed that only amorphous phase
did. Heat treatment of the obtained alloy ribbon 5 at 850 ° C. for 30 minutes
And TbCu7Phase and ThTwoNi17Deposit both phases
Was. From the X-ray diffraction intensity, Th TwoNi17The proportion of the phase is 50
%Met.
【００３４】また、比較例として、Ｓｍ、Ｚｒ、Ｆｅ、
Ｃｏの各原料を、１ｍ／ｓのロール周速を用いたことを
除いて、実施例１と同様の単ロール法を用い、溶解し、
冷却し、合金薄帯を得た。この合金薄帯をＸ線回折によ
り分析したところ、Ｔｈ2 Ｎｉ１７相単相であることを
確認した。As comparative examples, Sm, Zr, Fe,
Co raw materials were melted using the same single-roll method as in Example 1 except that a roll peripheral speed of 1 m / s was used.
After cooling, an alloy ribbon was obtained. When this alloy ribbon was analyzed by X-ray diffraction, it was confirmed that the alloy ribbon was a single phase of Th 2 Ni 17 phase.
【００３５】次に、以上の実施例１および比較例１によ
り得た合金薄帯を粉砕し、粒径（３００μm以下）の合
金粉末とし、これを４６０℃で４時間、アンモニアガス
と水素ガスの流量比を１：１５として窒化を行った。実
施例１の試料を試料振動型磁力計（ＶＳＭ）で測定した
ところ、保磁力は１５ｋＯｅで、（ＢＨ）maxは１７Ｍ
ＧＯｅであった。Next, the alloy ribbon obtained in Example 1 and Comparative Example 1 was pulverized to obtain an alloy powder having a particle size (300 μm or less). The alloy powder was subjected to ammonia gas and hydrogen gas at 460 ° C. for 4 hours. The nitriding was performed at a flow rate ratio of 1:15. When the sample of Example 1 was measured with a sample vibration magnetometer (VSM), the coercive force was 15 kOe and (BH) max was 17 M
GOe.
【００３６】なお、本材料を組成分析したところ、Ｓｍ
6.0Ｚｒ2.6Ｆｅ61.1Ｃｏ15.2Ｂ1.3Ｎ13.8であった。ま
た、比較例１の試料では、保磁力７．０ｋＯｅ、（Ｂ
Ｈ）max１0．８ＭＧＯｅであった。The composition of this material was analyzed to find that Sm
6.0 Zr 2.6 Fe 61.1 Co 15.2 B 1.3 N 13.8 . In the sample of Comparative Example 1, the coercive force was 7.0 kOe, (B
H) The maximum was 10.8 MGOe.
【００３７】実施例１と比較例１をＴＥＭ観察し、平均
粒径を求めたところ、それぞれ３０ｎｍ、４００ｎｍで
あった。また、実施例１のＦｅあるいはＦｅＣｏ相の析
出量は、８体積％であり、比較例１では２５体積％であ
った。Example 1 and Comparative Example 1 were observed with a TEM to determine the average particle diameter, which was 30 nm and 400 nm, respectively. The amount of the Fe or FeCo phase deposited in Example 1 was 8% by volume, and that in Comparative Example 1 was 25% by volume.
【００３８】これらの窒化した試料を平均粒径３μｍま
で微粉砕し、エポキシ樹脂を２重量％添加し、混合した
後、１５０℃で２時間キュアし、ボンド磁石とした。得
られたボンド磁石を室温でＢＨトレーサーにより磁石特
性を評価したところ、実施例１の試料がＨｃ＝１５．４
ｋＯｅ、（ＢＨ）max＝１２．８ＭＧＯｅであり、比較
例１の試料がＨｃ＝６．８ｋＯｅ、（ＢＨ）max＝７．
９ＭＧＯｅであった。These nitrided samples were pulverized to an average particle size of 3 μm, added with 2% by weight of an epoxy resin, mixed, and then cured at 150 ° C. for 2 hours to obtain a bonded magnet. When the magnet properties of the obtained bonded magnet were evaluated at room temperature using a BH tracer, the sample of Example 1 was found to have Hc = 15.4.
kOe, (BH) max = 12.8 MGOe, and the sample of Comparative Example 1 had Hc = 6.8 kOe, (BH) max = 7.
It was 9MGOe.
【００３９】さらに、１５０℃での保磁力を測定したと
ころ、実施例１の試料が７．８ｋＯｅ、比較例１の試料
が３．２ｋＯｅであり、本発明に係るボンド磁石が耐熱
性に優れていることが確認できた。Further, when the coercive force at 150 ° C. was measured, the sample of Example 1 was 7.8 kOe and the sample of Comparative Example 1 was 3.2 kOe, and the bond magnet according to the present invention was excellent in heat resistance. Was confirmed.
【００４０】実施例２〜１８、比較例２，３ 実施例１と同様に高純度の各原料を用い、下記表１に示
す組成の合金を作製した。ただし、Ｂを除くＸの各元素
は、溶解、急冷、熱処理の後に導入した。急冷条件は４
０ｍ／ｓとし、熱処理条件は表に記した通りである。実
施例１と同様に、ボンド磁石を作製し、ＢＨトレーサー
で磁石特性を評価した。Examples 2 to 18 and Comparative Examples 2 and 3 In the same manner as in Example 1, alloys having the compositions shown in Table 1 below were produced using high-purity raw materials. However, each element of X except B was introduced after melting, quenching, and heat treatment. Rapid cooling condition is 4
0 m / s, and the heat treatment conditions are as described in the table. In the same manner as in Example 1, a bonded magnet was prepared, and the magnet properties were evaluated using a BH tracer.
【００４１】得られた室温での磁石特性と１５０℃での
保磁力を測定し、耐熱性の評価を行なったところ、下記
表１に示すような結果を得た。Ｘ線回折結果から得られ
た平均結晶粒径（Ｓｃｈｅｅｒｅｒの式）とＴｈ2 Ｎｉ
１７相の割合、ＦｅあるいはＦｅＣｏ相の析出割合も、
併せて表１に示した。The obtained magnet properties at room temperature and the coercive force at 150 ° C. were measured, and the heat resistance was evaluated. The results shown in Table 1 below were obtained. Average crystal grain size (Schereer's equation) obtained from X-ray diffraction results and Th 2 Ni
The ratio of the 17 phases, the precipitation ratio of the Fe or FeCo phase,
Also shown in Table 1.
【００４２】下記表から明らかなように、本発明の実施
例では高（ＢＨ）max、高保磁力、および高耐熱性のボ
ンド磁石が得られていることがわかる。As is clear from the following table, it is understood that high (BH) max, high coercive force, and high heat resistance bonded magnets are obtained in the examples of the present invention.
【００４３】また、比較として表１にあげた比較例２〜
４に係る合金についても同様の検討を行った。比較例に
ついては１ｍ／ｓのロール周速で急冷し、予めＴｈ2 Ｎ
ｉ１ ７相のみの状態を得た。この合金を粉砕後窒化し、
実施例１と同様にボンド磁石化した。なお、結晶粒径は
ＴＥＭ評価の結果、５００ｎｍであった。For comparison, Comparative Examples 2 to 2 shown in Table 1 were used.
The same study was performed for the alloy according to No. 4. For the comparative example, the roll was rapidly cooled at a roll peripheral speed of 1 m / s, and Th 2 N
obtaining the state of i 1 7 phase only. This alloy is pulverized and then nitrided,
A bond magnet was formed in the same manner as in Example 1. The crystal grain size was 500 nm as a result of the TEM evaluation.
【００４４】比較例についても、その結果を表１に示す
が、表１から、比較例に係る合金は、残留磁束密度が低
く、高（ＢＨ）maxが達成されず、また、保磁力も不十
分であることがわかる。The results of the comparative example are also shown in Table 1. From Table 1, it can be seen that the alloy according to the comparative example has a low residual magnetic flux density, cannot achieve a high (BH) max, and has a poor coercive force. It turns out that it is enough.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【発明の効果】以上説明したように、本発明によると、
高エネルギー積と高耐熱性を併せ有する磁石材料、その
製造方法、およびボンド磁石を得ることが可能であり、
工業上極めて有効である。As described above, according to the present invention,
It is possible to obtain a magnet material having both high energy product and high heat resistance, a method for producing the same, and a bonded magnet,
It is extremely effective industrially.
【図１】本発明の方法に用いられる装置の概略を示す
図。FIG. 1 is a diagram schematically showing an apparatus used in a method of the present invention.
１…ロール ２…容器 ３…誘導加熱コイル ４…ノズル ５…合金薄帯 DESCRIPTION OF SYMBOLS 1 ... Roll 2 ... Container 3 ... Induction heating coil 4 ... Nozzle 5 ... Alloy ribbon
───────────────────────────────────────────────────── フロントページの続き (72)発明者 沢 孝雄 神奈川県川崎市幸区小向東芝町１番地 株 式会社東芝研究開発センター内 Ｆターム(参考） 5E040 AA03 AA04 AA19 BB03 BD03 CA01 HB11 NN01 NN06 NN17 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takao Sawa 1-term, Komukai Toshiba-cho, Saiwai-ku, Kawasaki-shi, Kanagawa F-term in the Toshiba R & D Center (reference) 5E040 AA03 AA04 AA19 BB03 BD03 CA01 HB11 NN01 NN06 NN17
Claims (7)
と、Ｔｈ2 Ｎｉ１７相とを含むことを特徴とする磁石材
料。 （Ｒ１）ｘ（Ｒ２）ｙＴ１００−ｘ−ｙ−ｚ−α−βＭ
ｚＸαＡβ （式中、Ｒ１は、少なくとも１種以上の希土類元素（Ｙ
を含む）、Ｒ２は、Ｔｉ、Ｚｒ、ＨｆおよびＮｂからな
る群から選ばれる少なくとも１種、Ｔは、Ｆｅ、Ｃｏお
よびＮｉからなる群から選ばれる少なくとも１種、Ｍ
は、Ｖ、Ｃｒ、Ｍｎ、Ｔａ、Ｍｏ、Ｗ、Ｓｎ、Ｇａ、Ａ
ｌ、ＧｅおよびＳｉからなる群から選ばれる少なくとも
１種、Ｘは、Ｃ、Ｎ、Ｈ、ＯおよびＦからなる群から選
ばれる少なくとも１種、Ａは、ＢおよびＰからなる群か
ら選ばれる少なくとも１種であり、ｘ、ｙ、ｚ、α、β
は、式２≦ｘ≦２０、０．１≦ｙ≦２０、０≦ｚ≦１
０、０．１≦α≦２０、０≦β≦５（原子％）を満たす
正の数である。）1. A magnet material represented by the following general formula, wherein the main phase contains a TbCu 7 phase and a Th 2 Ni 17 phase. (R 1) x (R 2 ) y T 100-x-y-z-α-β M
z X α A β (wherein, R 1 is at least one or more rare earth elements (Y
R 2 is at least one selected from the group consisting of Ti, Zr, Hf and Nb; T is at least one selected from the group consisting of Fe, Co and Ni;
Is V, Cr, Mn, Ta, Mo, W, Sn, Ga, A
1, at least one selected from the group consisting of Ge and Si, X is at least one selected from the group consisting of C, N, H, O and F, and A is at least one selected from the group consisting of B and P X, y, z, α, β
Is represented by the formula 2 ≦ x ≦ 20, 0.1 ≦ y ≦ 20, 0 ≦ z ≦ 1
0, a positive number satisfying 0.1 ≦ α ≦ 20 and 0 ≦ β ≦ 5 (atomic%). )
と、Ｔｈ2 Ｎｉ１７相とを含み、更に副相としてＦｅま
たはＦｅＣｏ相を１０体積％まで含むことを特徴とする
磁石材料。 （Ｒ１）ｘ（Ｒ２）ｙＴ１００−ｘ−ｙ−ｚ−α−βＭ
ｚＸαＡβ （式中、Ｒ１は、少なくとも１種以上の希土類元素（Ｙ
を含む）、Ｒ２は、Ｔｉ、Ｚｒ、ＨｆおよびＮｂからな
る群から選ばれる少なくとも１種、Ｔは、Ｆｅ、Ｃｏお
よびＮｉからなる群から選ばれる少なくとも１種、Ｍ
は、Ｖ、Ｃｒ、Ｍｎ、Ｔａ、Ｍｏ、Ｗ、Ｓｎ、Ｇａ、Ａ
ｌ、ＧｅおよびＳｉからなる群から選ばれる少なくとも
１種、Ｘは、Ｃ、Ｎ、Ｈ、ＯおよびＦからなる群から選
ばれる少なくとも１種、Ａは、ＢおよびＰからなる群か
ら選ばれる少なくとも１種であり、ｘ、ｙ、ｚ、α、β
は、式２≦ｘ≦２０、０．１≦ｙ≦２０、０≦ｚ≦１
０、０．１≦α≦２０、０≦β≦５（原子％）を満たす
正の数である。）2. A magnetic material represented by the following general formula, wherein the main phase contains 7 phases of TbCu and 17 phases of Th 2 Ni and further contains up to 10% by volume of Fe or FeCo phase as a sub phase. . (R 1) x (R 2 ) y T 100-x-y-z-α-β M
z X α A β (wherein, R 1 is at least one or more rare earth elements (Y
R 2 is at least one selected from the group consisting of Ti, Zr, Hf and Nb; T is at least one selected from the group consisting of Fe, Co and Ni;
Is V, Cr, Mn, Ta, Mo, W, Sn, Ga, A
1, at least one selected from the group consisting of Ge and Si, X is at least one selected from the group consisting of C, N, H, O and F, and A is at least one selected from the group consisting of B and P X, y, z, α, β
Is represented by the formula 2 ≦ x ≦ 20, 0.1 ≦ y ≦ 20, 0 ≦ z ≦ 1
0, a positive number satisfying 0.1 ≦ α ≦ 20 and 0 ≦ β ≦ 5 (atomic%). )
あることを特徴とする請求項１または２に記載の磁石材
料。3. The magnetic material according to claim 1, wherein the average crystal grain size is in a range of 10 to 100 nm.
脂との混合物を成形してなることを特徴とするボンド磁
石。4. A bonded magnet obtained by molding a mixture of the powder of the magnetic material according to claim 1 and a resin.
む合金溶湯を、高速移動する回転体上に射出して冷却
し、少なくとも一部にアモルファス相を含む金属体を形
成する工程、 前記金属体を熱処理することにより、平均結晶粒径が１
０〜１００ｎｍである、ＴｂＣｕ７相と、Ｔｈ2 Ｎｉ
１７相および／またはＴｈ2 Ｚｎ１７相とを含む金属組
織体を形成する工程、および前記金属組織体に、窒素、
水素、炭素、フッ素及び酸素からなる群から選ばれた少
なくとも１種を導入する工程を具備することを特徴とす
る磁石材料の製造方法。5. A step of injecting a molten alloy containing a rare earth element (including Y) and a transition metal onto a rotating body that moves at a high speed and cooling it to form a metal body containing an amorphous phase at least partially. By heat-treating the metal body, the average crystal grain size becomes 1
TbCu 7 phase and Th 2 Ni of 0-100 nm
Forming a metal structure including a 17 phase and / or a Th 2 Zn 17 phase, and adding nitrogen,
A method for producing a magnet material, comprising a step of introducing at least one selected from the group consisting of hydrogen, carbon, fluorine and oxygen.
とを特徴とする請求項５に記載の磁石材料の製造方法。 （Ｒ１）ｘ（Ｒ２）ｙＴ１００−ｘ−ｙ−ｚ−γＭ
ｚＡ'γ （式中、Ｒ１は、少なくとも１種以上の希土類元素（Ｙ
を含む）、Ｒ２は、Ｔｉ、Ｚｒ、ＨｆおよびＮｂからな
る群から選ばれる少なくとも１種、Ｔは、Ｆｅ、Ｃｏお
よびＮｉからなる群から選ばれる少なくとも１種、Ｍ
は、Ｖ、Ｃｒ、Ｍｎ、Ｔａ、Ｍｏ、Ｗ、Ｓｎ、Ｇａ、Ａ
ｌ、ＧｅおよびＳｉからなる群から選ばれる少なくとも
１種、Ａは、Ｂ、ＣおよびＰからなる群から選ばれる少
なくとも１種であり、ｘ、ｙ、ｚ、γは、式２≦ｘ≦２
０、０．１≦ｙ≦２０、０≦ｚ≦１０、０≦γ≦５（原
子％）を満たす正の数である。）6. The method according to claim 5, wherein the molten alloy is represented by the following general formula. (R 1) x (R 2 ) y T 100-x-y-z-γ M
z A ′ γ (wherein, R 1 is at least one or more rare earth elements (Y
R 2 is at least one selected from the group consisting of Ti, Zr, Hf and Nb; T is at least one selected from the group consisting of Fe, Co and Ni;
Is V, Cr, Mn, Ta, Mo, W, Sn, Ga, A
A is at least one selected from the group consisting of l, Ge and Si, A is at least one selected from the group consisting of B, C and P, and x, y, z and γ are represented by the formula 2 ≦ x ≦ 2
It is a positive number satisfying 0, 0.1 ≦ y ≦ 20, 0 ≦ z ≦ 10, and 0 ≦ γ ≦ 5 (atomic%). )
出して冷却することにより、アモルファス相を５０％以
上含む金属体を得ることを特徴とする請求項５または６
に記載の磁石材料の製造方法。7. A metal body containing at least 50% of an amorphous phase by injecting the molten alloy onto a rotating body that moves at a high speed and cooling it.
3. The method for producing a magnet material according to item 1.
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| JP37503799A JP3735502B2 (en) | 1999-12-28 | 1999-12-28 | Manufacturing method of magnet material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37503799A JP3735502B2 (en) | 1999-12-28 | 1999-12-28 | Manufacturing method of magnet material |
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| JP3735502B2 JP3735502B2 (en) | 2006-01-18 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011014600A (en) * | 2009-06-30 | 2011-01-20 | Hitachi Ltd | Rare earth magnet |
| WO2011068107A1 (en) * | 2009-12-04 | 2011-06-09 | 株式会社日立製作所 | Light rare earth magnet and magnetic device |
| WO2012020617A1 (en) * | 2010-08-11 | 2012-02-16 | 株式会社日立製作所 | Magnetic material, magnetic shaped object, and rotating machine |
-
1999
- 1999-12-28 JP JP37503799A patent/JP3735502B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011014600A (en) * | 2009-06-30 | 2011-01-20 | Hitachi Ltd | Rare earth magnet |
| WO2011068107A1 (en) * | 2009-12-04 | 2011-06-09 | 株式会社日立製作所 | Light rare earth magnet and magnetic device |
| WO2012020617A1 (en) * | 2010-08-11 | 2012-02-16 | 株式会社日立製作所 | Magnetic material, magnetic shaped object, and rotating machine |
| JP2012039017A (en) * | 2010-08-11 | 2012-02-23 | Hitachi Ltd | Magnet material, magnet molding and rotary machine |
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|---|---|
| JP3735502B2 (en) | 2006-01-18 |
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