JP2012146789A - Rare-earth magnet - Google Patents

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JP2012146789A
JP2012146789A JP2011003372A JP2011003372A JP2012146789A JP 2012146789 A JP2012146789 A JP 2012146789A JP 2011003372 A JP2011003372 A JP 2011003372A JP 2011003372 A JP2011003372 A JP 2011003372A JP 2012146789 A JP2012146789 A JP 2012146789A
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rare earth
earth magnet
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crystal structure
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JP5752425B2 (en
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Akira Nanbu
英 南部
Hiroyuki Suzuki
啓幸 鈴木
Matahiro Komuro
又洋 小室
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Hitachi Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a magnetic material for a rare-earth magnet in which the magnetic characteristics of the rare-earth magnet are enhanced without increasing the usage of rare elements.SOLUTION: In the magnetic material for a rare-earth magnet, a peak corresponding to Sm-Fe bond is given to the position of 0.295-0.325 nm on a radial distribution function, as a result of EXAFS measurement and analysis, by making an F element intrude substantially to the middle of the longer bond distance out of an Fe-Fe bond or an Fe-Z bond of a binary system Re-Fe or a ternary system R-Fe-Z. Consequently, magnetic moment is increased, or magnetic anisotropy is modified.

Description

本発明は、希土類磁石に係り、例えば、４ｆ遷移金属−３ｄ遷移金属合金−非金属元素の組み合わせからなる高性能永久磁石材料の構造に関する。   The present invention relates to a rare earth magnet, for example, a structure of a high-performance permanent magnet material made of a combination of a 4f transition metal-3d transition metal alloy-nonmetallic element.

４ｆ遷移金属−３ｄ遷移金属合金は高性能永久磁石材料として知られている。これら高性能永久磁石の指標には、キュリー温度、磁化、磁気異方性の３要素が挙げられる。これら３要素を飛躍的に向上させる方法の１つに母相の結晶に非磁性原子を挿入させる方法が知られている。例えば、現状で最高性能を持つ永久磁石材料として４ｆ遷移金属のＮｄと３ｄ遷移金属のＦｅからなるＮｄ２Ｆｅ１４合金と非磁性元素であるホウ素の組み合わせであるＮｄ２Ｆｅ１４Ｂが知られており（非特許文献１）、その他に４ｆ遷移金属のＳｍと３ｄ遷移金属のＦｅからなるＳｍ２Ｆｅ１７に非磁性元素Ｎを侵入させたＳｍ２Ｆｅ１７Ｎ３（特許文献１、非特許文献４）等も知られている。 4f transition metal-3d transition metal alloys are known as high performance permanent magnet materials. These high performance permanent magnet indicators include three elements of Curie temperature, magnetization, and magnetic anisotropy. As one of the methods for dramatically improving these three elements, a method of inserting a nonmagnetic atom into a parent phase crystal is known. For example, Nd 2 Fe 14 B, which is a combination of Nd 2 Fe 14 alloy composed of 4d transition metal Nd and 3d transition metal Fe and boron, which is a nonmagnetic element, is known as a permanent magnet material having the highest performance at present. In addition, Sm 2 Fe 17 N 3 in which a nonmagnetic element N is penetrated into Sm 2 Fe 17 composed of Sm of 4f transition metal and Fe of 3d transition metal (Non-patent Document 1) 4) etc. are also known.

特開２００８−７８６１０号公報JP 2008-78610 A

M. Sagawa, S. Fujimura, N. Togawa, H. Yamamoto and Y. Matsuura, J. Appl. Phys. 55, 2083 (1984)M. Sagawa, S. Fujimura, N. Togawa, H. Yamamoto and Y. Matsuura, J. Appl. Phys. 55, 2083 (1984) P. Ueble, K. Hummler and M. Fahnle, Phys. Rev. B53, 3296 (1996).P. Ueble, K. Hummler and M. Fahnle, Phys. Rev. B53, 3296 (1996). J. D. Ardisson，A. I. C. Persiano, L. O. Ladeira and F. A. Batista, J. Mat Sci. Lett. 16, 1658 (1997)J. D. Ardisson, A. I. C. Persiano, L. O. Ladeira and F. A. Batista, J. Mat Sci. Lett. 16, 1658 (1997) J. M. D Coey, J. F. Lawler, H. Sun, J. E. M. Allan, J. Appl. Phys. 69, 307 (1991)J. M. D Coey, J. F. Lawler, H. Sun, J. E. M. Allan, J. Appl. Phys. 69, 307 (1991) T. W. Capehart, R. K. Mishra and F. E. Pinkerton, Appl. Phys. Lett. 58, 1395 (1991)T. W. Capehart, R. K. Mishra and F. E. Pinkerton, Appl. Phys. Lett. 58, 1395 (1991) K. Kobayashi, M. Ohmura, Y. Uoshida, M. Sagawa, J. Magn. Magn. Mater 247, 42(2002)K. Kobayashi, M. Ohmura, Y. Uoshida, M. Sagawa, J. Magn. Magn. Mater 247, 42 (2002)

既存の永久磁石材料の母相としてはＮｄ２Ｆｅ１４Ｂが最高性能を持つものとして知られているが、希少資源である希土類元素（Ｎｄ）の使用量が依然として多い。よって、これよりも希土類元素が少ない組成で、磁気特性の高い材料の開発が課題となる。母材としてＮｄ２Ｆｅ１４を用いるとＦｅに対する希土類（Ｎｄ）の組成比は原子数比で１２．５％であるが、Ｓｍ２Ｆｅ１７を母材に用いると、Ｆｅに対する希土類（Ｓｍ）の組成比を１０．５％にまで減ずることができる。質量比で考えた場合組成式Ｎｄ２Ｆｅ１４中のＮｄが２７％に対し、組成式Ｓｍ２Ｆｅ１７中のＳｍでは２４％となる。 Nd 2 Fe 14 B is known to have the highest performance as the parent phase of existing permanent magnet materials, but the amount of rare earth element (Nd) that is a rare resource is still large. Therefore, the development of a material with less rare earth elements and higher magnetic properties is a challenge. When Nd 2 Fe 14 is used as a base material, the composition ratio of rare earth (Nd) to Fe is 12.5% in terms of atomic ratio, but when Sm 2 Fe 17 is used as a base material, the composition ratio of rare earth (Sm) to Fe is increased. The composition ratio can be reduced to 10.5%. When considered in terms of mass ratio, Nd in the composition formula Nd 2 Fe 14 is 27%, whereas Sm in the composition formula Sm 2 Fe 17 is 24%.

非特許文献２ではＧｄ２Ｆｅ１７Ｆ３について計算から磁気モーメント、磁気異方性エネルギーの増加を予想しているが、キュリー点については議論していない。更に、結晶構造の安定性も議論されておらず実際に安定物質として存在できるかは不明である。 Non-Patent Document 2 predicts an increase in magnetic moment and magnetic anisotropy energy from calculation for Gd 2 Fe 17 F 3 , but does not discuss the Curie point. Furthermore, the stability of the crystal structure is not discussed, and it is unclear whether it can actually exist as a stable substance.

非特許文献３ではＲ２Ｆｅ１７Ｆｘを測定しているが、Ｆ元素の元素分析等は行われておらず、Ｆ元素の効果であるか否かは不明であり、キュリー点の上昇が最大でも約４０°と低いことが課題である。 In Non-Patent Document 3, R 2 Fe 17 Fx is measured, but elemental analysis of the F element is not performed, and it is unclear whether or not it is an effect of the F element, and the rise of the Curie point is maximum. However, the problem is that it is as low as about 40 °.

そこで、本発明の目的は、希少元素の使用量を増加させることなく、希土類磁石の磁気特性を高めることである。   Accordingly, an object of the present invention is to enhance the magnetic properties of rare earth magnets without increasing the amount of rare elements used.

４ｆ遷移金属−３ｄ遷移金属−非磁性元素の組み合わせからなる磁性材料では、これまで非磁性元素として、ホウ素（Ｂ）、窒素（Ｎ）、炭素（Ｃ）等が使われることが多かったが、本発明では非磁性元素として、フッ素（Ｆ）を用いることを特徴とする新規強磁性材料を用いる。   In a magnetic material comprising a combination of 4f transition metal-3d transition metal-nonmagnetic element, boron (B), nitrogen (N), carbon (C), etc. have been often used as nonmagnetic elements. In the present invention, a novel ferromagnetic material characterized by using fluorine (F) as a nonmagnetic element is used.

上記の強磁性材料は、図１に示すような、Ｔｈ２Ｚｎ１７型結晶構造を有し、Ｒ‐Ｆｅの２元系またはＲ−Ｆｅ−Ｚの３元系の結晶構造内にＦ元素を侵入させる。ＥＸＡＦＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）の解析結果から、Ｆ元素の侵入位置は、図１に示した９ｅ位置であり、その位置に全てのＦが入った場合の組成式はＲ２Ｆｅ１７Ｚ３になる。 The above-mentioned ferromagnetic material has a Th 2 Zn 17 type crystal structure as shown in FIG. 1, and an F element is included in the R—Fe binary system or the R—Fe—Z ternary crystal structure. Invade. From the analysis result of EXAFS (X-ray Absorption Fine Structure), the intrusion position of the F element is the 9e position shown in FIG. 1, and the composition formula when all F is contained in the position is R 2 Fe 17 Z It becomes 3 .

本発明の構造の磁性材料を用いることにより、主相の磁性が飛躍的に改善され、磁化の増加、更に磁気異方性が改質することを特徴とする、強磁性フッ素化合物磁性材料を提供することができる。   By using a magnetic material having the structure of the present invention, there is provided a ferromagnetic fluorine compound magnetic material characterized in that the magnetism of the main phase is dramatically improved, the magnetization is increased, and the magnetic anisotropy is further modified. can do.

Ｔｈ２Ｚｎ１７型結晶構造（侵入原子ありの場合）を示す図。It shows the Th 2 Zn 17 type crystal structure (With intrusion atoms). 侵入原子無しでの４ｆ遷移金属（Ｓｍ）と３ｄ遷移金属（Ｆｅ）の位置関係を示す図。The figure which shows the positional relationship of 4f transition metal (Sm) and 3d transition metal (Fe) without an intrusion atom. 侵入したＦ原子と４ｆ遷移金属と３ｄ遷移金属の位置関係を示す図。The figure which shows the positional relationship of the penetrated F atom, 4f transition metal, and 3d transition metal. ＥＸＡＦＳ測定結果を示す図。The figure which shows an EXAFS measurement result. ＥＸＡＦＳ解析結果に基づいて算出された動径分布関数を示す図。The figure which shows the radial distribution function calculated based on the EXAFS analysis result. Ｓｍ２Ｆｅ１７とフッ素侵入Ｓｍ２Ｆｅ１７のそれぞれの磁化の磁場依存性を示す図。It shows the magnetic field dependence of the respective magnetizations of Sm 2 Fe 17 and fluorine penetration Sm 2 Fe 17.

物質の磁気的性質は結晶構造、結晶内の原子位置によって決まる。本発明においては、基本結晶構造は母材のＳｍ２Ｆｅ１７によって決まり、それは図１に示すようなＴｈ２Ｚｎ１７型であり、ＳｍとＦｅからなる層とＦｅだけからなる層が交互に積み重なった構造をしている。この基本結晶格子内にＦ原子が侵入している。よって、このＦ原子の侵入位置が決めることが重要となる。結晶構造内に侵入した原子位置を決める方法としては、単結晶Ｘ線回折が優れた方法であるが、侵入型希土類磁石においては大きな単結晶を作ることが難しく、単結晶Ｘ線回折法の適応が難しい。 The magnetic properties of a substance are determined by the crystal structure and atomic position within the crystal. In the present invention, the basic crystal structure is determined by the base material Sm 2 Fe 17 , which is a Th 2 Zn 17 type as shown in FIG. 1, in which layers composed of Sm and Fe and layers composed only of Fe are alternately stacked. Have a structure. F atoms enter the basic crystal lattice. Therefore, it is important to determine the entry position of this F atom. Single crystal X-ray diffraction is an excellent method for determining the position of an atom that has penetrated into a crystal structure. However, it is difficult to form a large single crystal in an intrusion-type rare earth magnet. Is difficult.

それに対し、Ｘ線吸収微細構造法（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ；ＸＡＦＳ）法は大きな結晶が必要なく、粉末しか得られないような材料にでも適応出来る利点がある。特に、元素固有の吸収端エネルギーから数１００〜１０００ｅＶにわたって現れるＥＸＡＦＳ（Ｅｘｔｅｎｄｅｄ Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）と呼ばれる構造を解析することで目的元素近傍の原子間距離を与えることが出来る。
＜測定＞
ＸＡＦＳの測定は、広いエネルギー領域に渡って明るいＸ線を試料に照射する必要があり、殆どの場合放射光施設と呼ばれる大型の加速器を光源とする測定を必要とし、日本国内では大型放射光施設ＳＰｒｉｎｇ８等がこれに相当する。 On the other hand, the X-ray absorption fine structure method (XAFS) method has an advantage that it can be applied to a material in which only a powder is obtained without requiring a large crystal. In particular, an interatomic distance near the target element can be given by analyzing a structure called EXAFS (Extended X-ray Absorption Fine Structure) that appears over several hundred to 1000 eV from the absorption edge energy unique to the element.
<Measurement>
XAFS measurement requires that the sample be irradiated with bright X-rays over a wide energy range, and in most cases, requires measurement using a large accelerator called a synchrotron radiation facility as a light source. SPring8 or the like corresponds to this.

図４に、上記ＳＰｒｉｎｇ８を光源に用いてＳｍ２Ｆｅ１７Ｆ３を測定したＸＡＦＳ測定結果を示す。比較のために、母材となるＦ導入の無いＳｍ２Ｆｅ１７の測定結果も同時に図４に示す。
＜解析＞
ＥＸＡＦＳの解析は、図４に示した生スペクトルからバックグラウンドを取り除き、現れる周期振動構造をフーリエ変換することで行われる。更に子細な解析には、モデルを用いて計算した結果とフィッティングすることを行う。 FIG. 4 shows the XAFS measurement result of measuring Sm 2 Fe 17 F 3 using the above SPring 8 as a light source. For comparison, the measurement result of Sm 2 Fe 17 without F introduction as a base material is also shown in FIG.
<Analysis>
The analysis of EXAFS is performed by removing the background from the raw spectrum shown in FIG. 4 and Fourier transforming the appearing periodic vibration structure. For further detailed analysis, fitting with the result calculated using the model is performed.

図５に、図４に示す生スペクトルを基にしてフーリエ変換の結果得られた動径分布関数を示す。比較のために、母材となるＦの侵入の無いＳｍ２Ｆｅ１７の測定結果も示す。フーリエ変換の結果の横軸が目的元素原子からの距離であり、ピーク位置に目的原子近傍の原子が存在すると考えられる。
＜結果＞
母材となるＳｍ２Ｆｅ１７の動径分布関数には、３Å付近に大きなピークが一本観測されている。これが、Ｓｍに一番近接したＦｅに由来すると考えられる。よって、このピークについては、非特許文献４、非特許文献６等で、図１に示した、結晶構造の９ｄ位置のＦｅと６ｃ位置のＳｍ間距離に由来すると一般に了解されている。 FIG. 5 shows a radial distribution function obtained as a result of Fourier transform based on the raw spectrum shown in FIG. For comparison, a measurement result of Sm 2 Fe 17 without intrusion of F as a base material is also shown. The horizontal axis of the result of the Fourier transform is the distance from the target element atom, and it is considered that an atom near the target atom exists at the peak position.
<Result>
In the radial distribution function of Sm 2 Fe 17 as a base material, one large peak is observed near 3 °. This is considered to be derived from Fe closest to Sm. Therefore, it is generally understood that this peak is derived from the distance between the Fe at the 9d position and the Sm at the 6c position shown in FIG. 1 in Non-Patent Document 4, Non-Patent Document 6, and the like.

なお、上記の侵入位置を示す記号９ｄは、結晶学上で用いられるＷｙｃｋｏｆｆ記号と称するものであり、数字は単位格子内にある等価点の数を意味し、アルファベットはその位置における対称性の順序を示すものとする。また、６ｃや後述する９ｄなどの記号も同様な扱いをするものとする。   The symbol 9d indicating the intrusion position is referred to as a Wyckoff symbol used in crystallography, the number means the number of equivalent points in the unit cell, and the alphabet is the order of symmetry at that position. It shall be shown. Further, symbols such as 6c and 9d described later are handled in the same manner.

Ｆ侵入試料では３Å付近に加えて、２Å付近にもピークが現れている。３Å付近のピークはＳｍ−Ｆｅ間距離に相当し、Ｆ侵入試料にのみ現れた２ÅのピークがＳｍ−Ｆの結合距離に相当すると考えられる。   In the F intrusion sample, a peak appears in the vicinity of 2 て in addition to the vicinity of 3 Å. The peak near 3 ピ ー ク corresponds to the Sm-Fe distance, and the 2Å peak that appears only in the F intrusion sample is considered to correspond to the Sm-F bond distance.

ＥＸＡＦＳの生データのフーリエ変換では各元素の後方散乱振幅係数の違いから、結合距離は若干短めに現れることが知られており、正確な結合距離を求めるにはモデルとの逆フーリエ変換を用いたフィッティング解析が不可欠となる。フィッティング解析を行うことで正確な結合距離だけでなく、配位数、配位子の種類等も求めることが出来る。   In the Fourier transform of the raw data of EXAFS, it is known that the coupling distance appears slightly shorter due to the difference in the backscattering amplitude coefficient of each element, and in order to obtain the accurate coupling distance, the inverse Fourier transform with the model was used. Fitting analysis is essential. By performing the fitting analysis, not only the accurate bond distance but also the coordination number, the type of ligand, and the like can be obtained.

モデルを構築し、フィッティングした結果から正確に求めた結合距離は母材のＳｍ２Ｆｅ１７におけるＳｍ−Ｆｅ距離が３．０２Åであり、これは過去に（非特許文献４）（非特許文献５）で報告された値３．１０〜３．０７Åとよく一致する。同じくフィッティングによって求めたＦ侵入材料のＳｍ‐Ｆｅ距離は３．１１Åであり約３％ほど広がっている。 The bond distance accurately obtained from the result of constructing and fitting the model was 3.02 mm in the Sm-Fe distance in the base material Sm 2 Fe 17 , which was previously (Non-Patent Document 4) (Non-Patent Document 5) ) Is in good agreement with the value reported in 3.10 to 3.07cm. Similarly, the Sm-Fe distance of the F intrusion material obtained by fitting is 3.11 mm, which is about 3% wider.

Ｆ侵入試料のＳｍ−Ｆ距離はフィッティングの結果から２．２４５Åであると求められ、同時に配位数が約３であることも分った。なお、本測定における測定精度は±５％程度であるので、Ｓｍ−Ｆ距離が０．２１３〜０．２３６ｎｍの範囲とみなせる。従って、比較例として下記の表１に列挙した非特許文献１−３で示されたＳｍ−Ｒ距離に対して、有意差が十分に認められる。   The Sm-F distance of the F intrusion sample was determined to be 2.245 mm from the result of fitting, and at the same time, it was found that the coordination number was about 3. Since the measurement accuracy in this measurement is about ± 5%, the Sm-F distance can be regarded as a range of 0.213 to 0.236 nm. Therefore, a significant difference is sufficiently recognized with respect to the Sm-R distance shown in Non-Patent Documents 1-3 listed in Table 1 below as a comparative example.

以上の結合距離の一覧を表１に示す。   Table 1 shows a list of the above coupling distances.

Figure 2012146789
Figure 2012146789

以上の結果、また非特許文献６に示されたＳｍ２Ｆｅ１７Ｎ３−ｘの解析結果からの類推から、Ｆの侵入位置は図１の９ｅ位置に近いと類推される。つまり、ＦはＳｍを含む層にのみ含まれ、Ｆ侵入後の結晶格子はＳｍとＦｅとＦを含む層とＦｅのみを含む層が交互に積み上がった構造をしている。 From the above results and the analogy from the analysis results of Sm 2 Fe 17 N 3-x shown in Non-Patent Document 6, it can be inferred that the intrusion position of F is close to the 9e position in FIG. That is, F is contained only in the layer containing Sm, and the crystal lattice after the penetration of F has a structure in which layers containing Sm, Fe and F and layers containing only Fe are alternately stacked.

Ｆの侵入の無いＳｍ２Ｆｅ１７の場合、６ｃ位置のＳｍと９ｄ位置のＦｅは図２のように６ｃを中心に、六角形を形成している。ＥＸＡＦＳの結果から得られたＳｍ−Ｆｅ距離、Ｓｍ−Ｆ距離と配位数３を満足するような位置関係としては、図３に示すように９ｅと呼ばれる位置をＦが占める構造が考えられる。
＜磁化曲線（磁気異方性と磁力の改善）＞
図６に２５℃における母相のＳｍ２Ｆｅ１７とフッ素侵入Ｓｍ２Ｆｅ１７Ｆ３の磁化曲線の比較を示す．母相Ｓｍ２Ｆｅ１７では磁化曲線に履歴は生じておらず、磁化容易軸がａｂ面内であることを反映している。一方、フッ素侵入Ｓｍ２Ｆｅ１７Ｆ３では磁化曲線に履歴が生じており、磁化容易軸がｃ軸方向であることが示唆されている．試料の粒径が最適化されておらず、観測された保持力は僅かであるが粒径を最適化することで顕著に保持力が増大すると考えられる。 In the case of Sm 2 Fe 17 without intrusion of F, Sm at the 6c position and Fe at the 9d position form a hexagon around 6c as shown in FIG. As a positional relationship satisfying the Sm-Fe distance, Sm-F distance and coordination number 3 obtained from the EXAFS result, a structure in which F occupies a position called 9e as shown in FIG. 3 can be considered.
<Magnetic curve (improvement of magnetic anisotropy and magnetic force)>
FIG. 6 shows a comparison of the magnetization curves of the parent phase Sm 2 Fe 17 and the fluorine-invaded Sm 2 Fe 17 F 3 at 25 ° C. In the parent phase Sm 2 Fe 17 , no history occurs in the magnetization curve, which reflects that the easy axis of magnetization is in the ab plane. On the other hand, in the fluorine intrusion Sm 2 Fe 17 F 3 , there is a history in the magnetization curve, suggesting that the easy magnetization axis is the c-axis direction. The particle size of the sample is not optimized, and the observed holding force is slight, but it is considered that the holding force is remarkably increased by optimizing the particle size.

このように、Ｓｍ２Ｆｅ１７格子にＦが侵入することにより、面内異方性から１軸異方性へと磁気異方性が変化し、永久磁石材料としての可能性を示すことが確認出来た。 Thus, it is confirmed that the penetration of F into the Sm 2 Fe 17 lattice changes the magnetic anisotropy from the in-plane anisotropy to the uniaxial anisotropy and shows the possibility as a permanent magnet material. done.

なお、上述の実施の形態の説明においては、４ｆ遷移金属としてＳｍを代表金属として選定したが、他の４ｆ遷移金属についても上記母相の構成要素として適用が可能であり、また希土類であるＹ（イットリウム）も適用できる。   In the description of the above-described embodiment, Sm is selected as the representative metal as the 4f transition metal. However, other 4f transition metals can also be applied as the constituent elements of the parent phase, and are Y, which is a rare earth. (Yttrium) is also applicable.

また、上記実施の形態においては、Ｒ−Ｆｅの２元系を主としたが、Ｒ−Ｆｅ−Ｚの３元系にも適用が可能である。ここで、Ｒは４ｆ遷移金属またはＹ（イットリウム）であり、Ｚは、３ｄ遷移金属（Ｆｅを除く）またはＭｏ、Ｎｂ、Ｗとする。   In the above embodiment, the R—Fe binary system is mainly used, but the present invention can also be applied to an R—Fe—Z ternary system. Here, R is a 4f transition metal or Y (yttrium), and Z is a 3d transition metal (excluding Fe) or Mo, Nb, and W.

従って、本実施の形態で示す磁性材料は、図１に示すような、Ｔｈ２Ｚｎ１７型結晶構造を有し、Ｒ‐Ｆｅの２元系またはＲ−Ｆｅ−Ｚの３元系の結晶構造内にＦ元素が侵入した構造になっている。そのＦ元素の侵入位置は、ＥＸＡＦＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｆｉｎｅ Ｓｔｒｕｃｔｕｒｅ）の解析結果から、図１に示した９ｅ位置であり、その位置に全てのＦが入った場合の組成式の一般式はＲ２Ｆｅ１７Ｚ３になる。 Therefore, the magnetic material shown in this embodiment has a Th 2 Zn 17 type crystal structure as shown in FIG. 1, and has an R—Fe binary system or an R—Fe—Z ternary crystal structure. It has a structure in which the F element has entered. The intrusion position of the F element is the 9e position shown in FIG. 1 from the analysis result of EXAFS (X-ray Absorption Fine Structure), and the general formula of the composition formula when all F is contained in the position is R 2 Fe 17 Z 3 .

従って、Ｒ２Ｆｅ１７Ｚｘと置くと、Ｆが侵入していない場合はＸ＝０となるので、０＜Ｘ≦３の範囲とすることができる。 Therefore, when R 2 Fe 17 Z x is set, X = 0 when F does not enter, so that the range of 0 <X ≦ 3 can be obtained.

＜フッ素の導入方法１＞
母材のＳｍ２Ｆｅ１７にフッ素を導入する方法としては、フッ化アンモニウム（ＮＨ４Ｆ）、酸性フッ化アンモニウム（ＮＨ４・ＨＦ）、ケイフッ化アンモニウム（（ＮＨ４Ｆ）２ＳｉＦ６）、ホウフッ化アンモニウム等の熱分解・昇華が利用出来る。
いずれの場合も大気を排気後、上述した物質の熱分解・昇華によって生じるガス中でＳｍ２Ｆｅ１７を１５０〜４００℃にて処理することでフッ化物強磁性体を得る。 <Fluorine introduction method 1>
As a method of introducing fluorine into the base material Sm 2 Fe 17 , ammonium fluoride (NH 4 F), acidic ammonium fluoride (NH 4 · HF), ammonium silicofluoride ((NH 4 F) 2 SiF 6 ), boron fluoride Thermal decomposition and sublimation of ammonium fluoride can be used.
In any case, after evacuating the atmosphere, a fluoride ferromagnetic material is obtained by treating Sm 2 Fe 17 at 150 to 400 ° C. in a gas generated by thermal decomposition and sublimation of the above-described substances.

＜フッ素の導入方法２＞
他のフッ素導入方法としては、三フッ化窒素（ＮＦ３）、三フッ化ホウ素（ＢＦ３）、フッ化水素（ＨＦ）等のガスフローも使用できる。具体的には、例えばフッ化カルシウム（ＣａＦ２）に濃硫酸を滴下することで発生するＨＦガス中でＳｍ２Ｆｅ１７を１５０〜４００℃にて処理することでフッ化物強磁性体を得ることができる。 <Method 2 for introducing fluorine>
As another fluorine introduction method, a gas flow of nitrogen trifluoride (NF 3 ), boron trifluoride (BF 3 ), hydrogen fluoride (HF), or the like can be used. Specifically, for example, a fluoride ferromagnetic material is obtained by treating Sm 2 Fe 17 at 150 to 400 ° C. in HF gas generated by dropping concentrated sulfuric acid onto calcium fluoride (CaF 2 ). Can do.

Claims (7)

Ｒ−Ｆｅの２元系（ここで、Ｒは、４ｆ遷移元素またはＹである）からなり、Ｔｈ２Ｚｎ１７型結晶構造を有し、その結晶構造の侵入位置にＦ元素が配置され、化学式Ｒ２Ｆｅ１７Ｆｘ（０＜ｘ≦３）で表記されることを特徴とする希土類磁石。 It consists of a binary system of R—Fe (where R is a 4f transition element or Y), has a Th 2 Zn 17 type crystal structure, and an F element is disposed at the intrusion position of the crystal structure. A rare earth magnet represented by R 2 Fe 17 Fx (0 <x ≦ 3). 請求項１記載の希土類磁石において、
ＥＸＡＦＳ測定（室温）により得られたデータを逆フーリエ変換により求めて得られる動径分布関数において、前記Ｒ−Ｆｅ結合の結合距離に対応するピークと、該ピーク以外にＲ−Ｆに対応するピークとを有することを特徴とする希土類磁石。 The rare earth magnet according to claim 1,
In a radial distribution function obtained by inverse Fourier transform of data obtained by EXAFS measurement (room temperature), a peak corresponding to the bond distance of the R-Fe bond, and a peak corresponding to RF other than the peak And a rare earth magnet. 請求項１または２に記載の希土類磁石において、
ＲがＳｍであり、ＥＸＡＦＳ測定（室温）で求められるＳｍ−Ｆｅ結合距離が０．２９５〜０．３２５ｎｍの範囲内であり、Ｓｍ−Ｆ距離が０．２１３〜０．２３６ｎｍの範囲内にあることを特徴とする希土類磁石。 The rare earth magnet according to claim 1 or 2,
R is Sm, the Sm-Fe bond distance obtained by EXAFS measurement (room temperature) is in the range of 0.295 to 0.325 nm, and the Sm-F distance is in the range of 0.213 to 0.236 nm. Rare earth magnet characterized by that. 請求項１記載の希土類磁石において、
前記Ｒ−Ｆｅ母相に対して、フッ化アンモニウムガス下での高温処理、あるいはフッ化物による溶液処理等を施すことにより、結晶構造の侵入位置にＦ元素を配置させたことを特徴とする希土類磁石。 The rare earth magnet according to claim 1,
A rare earth characterized in that the F element is arranged at the intrusion position of the crystal structure by subjecting the R-Fe matrix to high temperature treatment under ammonium fluoride gas or solution treatment with fluoride. magnet. Ｒ−Ｆｅ−Ｚの３元系（ここで、Ｒは、４ｆ遷移元素またはＹ；Ｚは、Ｆｅを除く３ｄ遷移金属またはＭｏ、Ｎｂ、Ｗである）からなり、Ｔｈ２Ｚｎ１７型結晶構造を有し、その結晶構造の侵入位置にＦ元素が配置され、化学式Ｒ２Ｆｅ１７−ｙＺｙＦｘ（０＜ｘ≦３）（０＜ｙ＜１７）で表記されることを特徴とする希土類磁石。 Th 2 Zn 17 type crystal structure consisting of R—Fe—Z ternary system (where R is a 4f transition element or Y; Z is a 3d transition metal other than Fe or Mo, Nb, W) F element is arranged at the intrusion position of the crystal structure, and is represented by the chemical formula R 2 Fe 17-y Z y Fx (0 <x ≦ 3) (0 <y <17) Rare earth magnet. 請求項５記載の希土類磁石において、
ＥＸＡＦＳ測定（室温）により得られたデータを逆フーリエ変換により求めて得られる動径分布関数において、前記Ｒ−Ｆｅ結合の結合距離に対応するピークと、該ピーク以外にＲ−Ｆに対応するピークとを有することを特徴とする希土類磁石。 The rare earth magnet according to claim 5,
In a radial distribution function obtained by inverse Fourier transform of data obtained by EXAFS measurement (room temperature), a peak corresponding to the bond distance of the R-Fe bond, and a peak corresponding to RF other than the peak And a rare earth magnet. 請求項５に記載の希土類磁石において、
ＲがＳｍであり、ＥＸＡＦＳ測定（室温）で求められるＳｍ−Ｆｅ結合距離が０．２９５〜０．３２５ｎｍの範囲内であり、Ｓｍ−Ｆ距離が０．２１３〜０．２３６ｎｍの範囲内にあることを特徴とする希土類磁石。 The rare earth magnet according to claim 5,
R is Sm, the Sm-Fe bond distance obtained by EXAFS measurement (room temperature) is in the range of 0.295 to 0.325 nm, and the Sm-F distance is in the range of 0.213 to 0.236 nm. Rare earth magnet characterized by that.
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