The present invention relates to a rare-earth magnet.
An Nd—Fe—B sintered magnet was invented in 1982, has been served as a permanent magnet material having the highest performance in the world up until now and employed in a number of products including voice coil motors (VCMs) for hard disc drives (HDDs), nuclear magnetic resonance imaging (MRI) apparatuses, and power generators. The production of the Nd—Fe—B sintered magnet has been on an upward trend particularly in applications for motors and power generators because of measures for energy-saving. Moreover, the Nd—Fe—B sintered magnet is the most promising magnetic material for large-sized driving motors in Hybrid Electric Vehicles (HEVs) which have been developed with consideration for environmental pollution, and therefore, further expanding production has been expected.
A Maximum energy product and a coercivity are indexes indicating magnetic material performance. The maximum energy product refers to a maximal energy which a magnet can generate. The coercivity refers to a magnetic field which, when a reverse magnetic field is applied to a magnetized magnet, cancels the magnetization.
The Nd—Fe—B magnet has been improved since its invention in 1982, whereby it currently possesses a maximum energy product approximately twice as larger as that of an Sm—Co magnet which had had the highest performance until then. On the other hand, the Nd—Fe—B magnet possesses a coercivity that is only around a half of that of the Sm—Co magnet.
In general, it is required to possess a large saturation magnetization and a large coercivity in order to enhance the maximum energy product as a performance index for permanent magnets. As a basic technology for improving the Nd—Fe—B sintered magnet so as to possess an enhanced coercivity, a method in which Nd is partially replaced with Dy, a heavy rare earth, to enhance magnetocrystalline anisotropy has been currently known. Patent Literature 1, for example, discloses a permanent magnet which is prepared by wet-mixing a Dy compound and a magnet raw material to coat the raw material surface with the Dy compound, mixing the coated raw material with a resin binder and forming a green sheet, and sintering the green sheet. Also Patent Literature 2 discloses a rare earth sintered magnet comprising a plurality of crystal grains of R2T14B (R is a rare earth element such as Nd or Dy, and T is a transition metal element such as Fe) and crystal grain boundaries which exist between the neighboring crystal grains and have larger amounts of Nd and Cu and a smaller amount of Dy than the surface of the crystal grains.
Magnetic moment of Dy, however, has a nature to be combined with those of Nd and Fe in antiparallel. Therefore, there exists a problem that although coercivity of the Nd—Fe—B sintered magnet increases by addition of Dy, magnetization decreases and consequently the maximum energy product decreases as the amount of Dy added increases. In the products having low operating temperatures upon use of the magnets, such as MRI or speakers, since a high coercivity is not required at an elevated temperature, almost no Dy is added to the magnet and the Nd—Fe—B magnet having a maximum energy product up to about 50 MGOe is also employed. On the other hand, in the motors employed in HEVs, the Nd—Fe—B magnet having a coercivity as high as 30 kOe at room temperature is required in consideration of the temperature dependence of the coercivity since the operating temperature is 200° C. or higher. In this case, it is necessary to add about 10% of Dy and this results in a reduction in maximum energy product down to about 30 MGOe. That is, addition of Dy to the Nd—Fe—B magnet enhances the coercivity, while sacrificing the large maximum energy product which is a characteristic of the Nd—Fe—B magnet.
In addition, since a Dy content in a rare earth ore is low and its places of origin is unevenly distributed in China, there is a concern that when the Nd—Fe—B magnets are supplied in a large amount for HEV uses, Dy market price may jump up and actually result in impossibility of HEV production in near future. Based on such a background, it is currently highly required to develop a high-performance permanent magnet having both a high maximum energy product and a high heat durability in a manner to obtain a high coercivity, while adding no or reduced Dy in amount.
Patent Literature 1: JP Patent Publication (Kokai) No. 2009-224671A (2009)
Patent Literature 2: JP Patent Publication (Kokai) No. 2011-187734A (2011)
Accordingly, the present invention is intended to provide a rare-earth magnet structure exhibiting a high coercivity.
In order to solve the problem described above, the present inventor has intensively researched and consequently found that a high coercivity can be obtained by arranging a rare earth element within a two-dimensional plane of a sheet having strong covalent bonds and laminating the sheet with a layer comprising a transition metal element to complete the present invention.
That is, a rare-earth magnet according to the present invention comprises a sheet of an element bonded with each other through a covalent bond and a layer comprising a transition metal element laminated with the sheet, wherein a rare earth element is arranged within a plane of the sheet.
According to the present invention, since a rare earth element is arranged within a sheet having strong covalent bonds, crystal structures are difficult to be disturbed in the vicinity of the grain boundary faces and the magnetic anisotropy is high in the vicinity of the grain boundary faces, and a rare-earth magnet having a high coercivity can be obtained. Technical problems, configurations and effects other than those described above will be shown by the illustration of the embodiments below.
The present invention will be illustrated in detail below referring to the drawings.
The element constituting the sheets 100 are at least one selected from the group consisting of, for example, C, Si and Ge. The rare earth element is, for example, at least one selected from the group consisting of Nd, Tb and Dy. Furthermore the element constituting the layers consisting of transition metal element 200 is, for example, at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni and Cu.
An anisotropic magnetic energy is an index which determines a magnitude of the coercivity. When a magnetization is rotated in an angle α to the easy axis of magnetization, magnetocrystalline anisotropic energy EA is represented by the following expression:
E
A
=K
1 sin2 α+K2 sin4 α+K3 sin6 α+ . . . [Expression 1]
where, K1, K2 and K3 are magnetocrystalline anisotropy constants which are the indexes indicating magnitudes of the anisotropy.
In a simplified case, using the first term only, EA is represented by the following expression:
E
A
=K
1 sin2 α [Expression 2]
This magnetocrystalline anisotropy constant K1 is calculated by the following expression:
K
1=−3J(J−½)αJr2A20 [Expression 3]
where, J represents a total angular momentum of a rare earth ion and <r2> represents an expected value for r2 concerning a radial wave function of the 4f electrons (expected squared value for the position coordinate of the 4f electrons). αJ is a parameter depending upon the spatial distribution geometry of the 4f electrons, which is referred to as Stevens factor. These J, <r2> and αJ take fixed values depending upon the type of the rare earth ion, respectively, and in the case of an Nd ion, for example, J=9/2, αJ=−7/(32×112), and <r2>=1.001a0 (where, a0 is the Bohr radius 0.5291772108×10−10 m). In addition, A20 is a principal term of the crystal field parameters and the correlation between K1 and A20 for Nd ion is represented by K1=0.347A20<r2> when the values are substituted for J and αJ in the above expression. That is, the conditions for obtaining large anisotropy are that A20 takes a positive value and A20 takes a large value. It is noted that the crystal field parameters are amounts depending upon the electronic states. That is, if a crystal structure of a rare-earth magnet having a large anisotropic magnetic energy could be found through determining the crystal field parameters by the electronic state calculation using, for example, the first-principles calculation, then it would be possible to obtain a rare-earth magnet having a large coercivity.
Accordingly, a calculation example of the crystal field parameters for an Nd2Fe14B magnet, as a conventional structure, by the electronic state calculation using the first-principles calculation will be shown, and subsequently, based on the results, a guideline for enhancing the anisotropic magnetic energy of the rare-earth magnet and increasing the coercivity thereof will be presented.
The electronic state calculation for Nd2Fe14B was analyzed by the Full-potential Linearized Augmented Plane Wave (FLAPW) method based on the Density Functional Theory (DFT). In an ordinary electronic state calculation, it is usual to assume spherical symmetry for electron density or one-electron potential within a sphere around each atom (Muffin-tin sphere). It is, however, necessary to calculate the state of the localized 4f electrons in an Nd ion accurately for derivation of the crystal field parameters relating to the magnetic anisotropy of the Nd ion. It is not appropriate to assume spherical symmetry for the electron density or the one-electron potential in order to determine the electron state accurately in the solid. Accordingly, the present inventor performed the first-principles calculation using Full-potential. Full-potential refers to a method taking aspherical surface effects into consideration for the one-electron potential, charge, and spherical harmonics of the core electrons. In addition the Linearized Augmented Plane Wave (LAPW) method linearizes the radial wave function concerning energy and employs the augmented plane wave as the basis function, thereby being able to reduce the calculation load without deterioration of calculating accuracy for both within and outside of the Muffin-tin spheres. In the pseudopotential method which is most commonly used in the first-principles calculation, only valence electrons are treated in the calculation while calculating the core electrons by means of substitution as the pseudopotential. On the other hand the FLAPW method treats all the electrons, and therefore, it can be one of the methods having the highest accuracy among the current first-principles calculation techniques. In the present embodiment, the FLAPW method was employed in the electronic state calculation for Nd2Fe14B. The first-principles calculation program used was WIEN2k, which is a general purpose code developed by Professor K. Schwartz (Vienna University of Technology) et al.
In
Then, the method for analyzing the crystal field parameters will be illustrated. The crystal field parameters are obtained using the following expression:
A
2
0
r
2
=4πa20∫0∞drr2V20(r)ρ4f(r) [Expression 4]
wherein, V20(r) is a one-electron potential energy component, which is a component when Vcry, a crystal electric field potential acting on the rare earth ion, is expanded using the following real spherical harmonics:
Z
L
M({circumflex over (r)}) [Expression 5]
as shown in the following expression:
In addition, ρ4f(r) is a density of the 4f electrons. a20 is a numerical factor of Z20 and satisfies the following expression:
a
20=√{square root over (5/4π)}/2 [Expression 7]
Further, <r1> is an average of the squared radial coordinate r2 for the 4f electrons, which is obtained by the following expression:
r
1
=4π∫drr2r1ρ4f(r). [Expression 8]
The results of the calculation and literature data of the experimental results for the crystal field parameter, A20<r2>, are shown in Table 1. According to the literature (Motohiko Yamada, Hiroaki Kato, Hisao Yamamoto, and Yasuaki Nakagawa: Crystal-field analysis of the magnetization process in a series of Nd2Fe14B-type compounds, Phys. Rev. B 38, 620 (1988)), the crystal field parameter, A20<r2>, which reproduces the magnetization curve determined by the experiment, is estimated to be about 300K, translating into the result close to those obtained in the calculation in the present embodiment. Particularly, A20<r2> values are positive for both the Nd (f) site and Nd (g) site. In order that Nd2Fe14B bulk has uniaxial anisotropy and the c axis becomes the easy axis of magnetization, A20<r2> values are required to be positive. The calculation results for the crystal field parameters of the present embodiment satisfied the conditions, whereby suitability of the calculation method was confirmed.
Then, factors affecting the magnitude of the crystal field parameters will be investigated.
Low coercivity regions are considered to exist in the vicinity of the grain boundary faces in the Nd—Fe—B magnet, and it is therefore thought to be effective to clarify the correlation between the crystal structures and the magnetic properties in the vicinity of the Nd2Fe14B grain boundary faces of from an electron theory in order to obtain a guiding principle for enhancing the coercivity performance. The structures at the crystal grain boundaries in the Nd—Fe—B magnet are complicated, however, and it is difficult to treat the actual system in a manner of first-principles.
Accordingly, in the present embodiment, crystal field parameters in a Nd2Fe14B surface model are analyzed to evaluate the presence of a difference from the Nd2Fe14B bulk model, whereby the correlation between the crystal structures and the magnetic properties in the vicinity of the grain boundary faces will be studied. It is noted that there exists arbitrariness in respect of surface orientation and surface formation upon creating a surface model. Thus, in the present embodiment, effects of the surface formation on the Nd ion crystal field parameters were investigated employing five cases, i.e., Nd ion-exposed and unexposed Nd2Fe14B (001) surface models, Nd ion-exposed and unexposed Nd2Fe14B (100) surface models, and Nd ion-exposed Nd2Fe14B (110) surface model, as the objects to be analyzed, the results obtained were summarized, and then a study was carried out concerning how the surface formation affects the magnetocrystalline anisotropy.
The calculation results of the crystal field parameter, A20<r2>, are summarized for the various analyzed surface models in
The difference between the Nd ion-exposed (001) surface model where the crystal field parameter, A20<r2>, has a negative value and other models where the A20<r2> has a positive value is the existence of the Fe ions along the direction of the c axis (easy axis of magnetization, z axis) of the Nd ion of interest (
Based on the results described above, the guideline for enhancing the coercivity of the rare-earth magnet will be investigated. Low coercivity regions are considered to exist in the vicinity of the grain boundary faces in the Nd—Fe—B magnet. In
Based on the mechanism described above, the present inventor has attained an idea described below. That is, in order to enhance the coercivity of the rare-earth magnet, it is desirable to strengthen the two-dimensional structure of the layers containing the rare earth element so as to give a structure in which there exists less disturbance of the two-dimensional structure even in the vicinity of the grain boundaries and the transition metal element is located above and below the rare earth ions in the c axis direction. The element constituting the two-dimensional structure may be bonded through covalent bonds in order to strengthen the two-dimensional structure.
Whether an element constituting the two-dimensional structure forms a covalent bond or not is determined by the most closely neighboring interatomic distance for atoms thereof. When C, Si and Ge have a diamond structure, the most closely neighboring interatomic distances are 0.154 nm, 0.235 nm and 0.245 nm, respectively. Therefore when C, Si and Ge have a two-dimensional structure, they are thought to form covalent bonds in the case of having interatomic distances of approximately above-described distances ±10%. That is, when the element is C and the most closely neighboring distance is 0.13 nm or more and 0.16 nm or less, the element will form covalent bond, when the element is Si and the most closely neighboring distance is 0.21 nm or more and 0.26 nm or less, the element will form covalent bond, and when the element is Ge and the most closely neighboring distance is 0.22 nm or more and 0.27 nm or less, the element will form covalent bond.
Then a method for manufacturing the rare-earth magnet shown in
As the substrate on which the film of the transition metal or 3C—SiC, a material which is nonmagnetic and excellent in flat smoothness is preferred. Surface roughness of the substrate is defined by JIS B0601 or ISO468. Desirably a arithmetic mean roughness Ra is 1.0 μm or less, preferably 0.5 μm or less, and more preferably 0.1 μm or less. With regard to flatness of the substrate, the more flat, the more desirable. Commercially a monocrystal Si wafer for semiconductor device manufacturing is preferably employed as the substrate because of extremely excellent surface roughness and flatness thereof. In addition to the monocrystal Si wafer, a polycrystal Si wafer, a cleavage plane of RB2C2 (R is a rare earth element) in which a rare earth element is arranged within the same plane in the crystal, or the like is also applicable.
The coercivity can be further enhanced by heat-treating the laminate after film formation in vacuo or an inert gas atmosphere as necessary so as to remove point defects and lattice strain which may be generated at, for example, a junction of the sheet and the layer comprising a transition metal element. The temperature of the heat-treating varies depending upon the composition or film thickness, but is preferably 600 K-900 K. When the heat-treating is performed at a lower temperature for a longer time, mutual diffusion of the rare earth element and the transition metal element can be inhibited, and therefore, the material having higher magnetic properties can be easily obtained as a result.
Furthermore the rare-earth magnet of the present invention may be surface-treated to form a protective film for preventing oxidation in the atmosphere as necessary. As the protective film resin films can be applied in addition to metallic films excellent in corrosion resistance and strength and polyimide film or the like may be employed. As the surface-treating method Al coating using the vapor phase growth method or Ni plating using a known plating method is preferred and a relatively thinner thickness of the protective film is desirable not to decrease the volume magnetic properties. It may be suitably selected whether to surface treat before processing into the final product or to surface treat after the processing depending upon product forms or uses.
It should be noted that the present invention is not limited to the embodiment described above but may include various modifications. It is possible, for example, to replace a part of a constitution of a certain embodiment with a constitution of other embodiment, or alternatively, it is possible to add a constitution of other embodiment to a constitution of a certain embodiment. Also, with respect to a part of a constitution of each embodiment it is possible to add other constitution thereto, eliminate it, or substitute it.
All the publications, Patents and Patent applications cited herein are incorporated herein in their entirety by reference.
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/JP2012/057805 | 3/26/2012 | WO | 00 | 8/19/2014 |