JP2011035006A - Magnetic material, magnet, and method of manufacturing magnetic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a nano composite magnet without using a rare-earth element. <P>SOLUTION: A magnetic particle 10 includes a hard-magnetic-phase core part 11 containing ε-Fe<SB>2</SB>O<SB>3</SB>and a soft-magnetic-phase shell part 12 containing Fe and covering at least a part of the core part 11. The magnetic particle 10 is manufactured by reducing surfaces of powder of ε-Fe<SB>2</SB>O<SB>3</SB>. Thus, the magnetic particle 10 can be manufactured by reducing an oxide of Fe without using a rare-earth element. When a sintered magnet or a bond magnet is manufactured using the magnetic particles 10, a nano composite magnet without using a rare-earth element can be manufactured. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a so-called nanocomposite magnet.

Magnets are used in a wide range of fields. At present, neodymium magnets (Nd ₂ Fe ₁₄ B compounds) are widely used as high-performance magnets, but in recent years, higher performance has been demanded. One means of achieving such high performance is a nano-structure in which a soft magnetic phase with high magnetization and a hard magnetic phase with high coercive force are uniformly distributed in the same structure and both are magnetically coupled by exchange interaction. Composite magnets are attracting attention.

For example, Patent Document 1 discloses a nanocomposite magnet having a core-shell structure in which a hard magnetic phase of an Nd ₂ Fe ₁₄ B compound is a core and an Fe soft magnetic phase is a shell. In Patent Document 1, Nd ₂ Fe ₁₄ B compound particles are added and dispersed in a solvent containing a surfactant, and then an Fe precursor is added to the surface of the Nd ₂ Fe ₁₄ B compound particles. A nanocomposite magnet having a core-shell structure in which the hard magnetic phase of the Nd ₂ Fe ₁₄ B compound is used as a core and the soft magnetic phase of Fe is used as a shell is produced by precipitating Fe particles on the substrate, drying, and sintering. A method is disclosed.

JP 2008-117855 A

  By the way, the technique disclosed in Patent Document 1 uses Nd, which is a rare earth element, in the hard magnetic phase. However, since rare earth elements are expensive and their supply may become unstable, there is a demand to suppress the amount of rare earth elements used as much as possible. The present invention has been made in view of the above, and an object thereof is to produce a nanocomposite magnet without using rare earth elements.

In order to solve the above-described problems and achieve the object, a magnetic material according to the present invention includes a core portion of a hard magnetic phase containing ε-Fe ₂ O ₃ , Fe, and at least a part of the core portion. And a magnetic particle having a shell portion of a soft magnetic phase covering the surface.

As a desirable mode of the present invention, in the magnetic material, it is preferable that a part of Fe of ε-Fe ₂ O ₃ constituting the core portion is substituted with at least one of Co and Ni.

  As a desirable mode of the present invention, in the magnetic material, it is preferable that a part of Fe constituting the shell portion is substituted with at least one of Co and Ni.

As a desirable aspect of the present invention, in the magnetic material, the core portion preferably contains a metal oxide other than ε-Fe ₂ O ₃ .

As a desirable mode of the present invention, in the magnetic material, it is preferable that an SiO ₂ layer is provided on at least a part of the surface of the shell portion.

  In order to solve the above-described problems and achieve the object, a magnet according to the present invention includes the magnetic material.

In order to solve the above-described problems and achieve the object, a method for producing a magnetic material according to the present invention includes a powder production process for producing ε-Fe ₂ O ₃ powder, and the ε-Fe ₂ O ₃ powder. And a reduction step for reducing the surface of the substrate.

As a desirable mode of the present invention, in the method for manufacturing a magnetic material, at least a part of the surface of the ε-Fe ₂ O ₃ powder manufactured in the powder manufacturing process is covered with SiO _2. preferable.

As a desirable aspect of the present invention, in the method for producing the magnetic material, the step of removing the SiO ₂ from the surface of the ε-Fe ₂ O ₃ powder after the reduction step or before the reduction step. It is preferable to include.

  The present invention can produce a nanocomposite magnet without using rare earth elements.

FIG. 1 is a schematic diagram showing a structure of a magnet configured using the magnetic material according to the present embodiment. FIG. 2 is a schematic view showing magnetic particles constituting the magnetic material according to the present embodiment. FIG. 3A is a schematic diagram illustrating adjacent magnetic particles in a magnet composed of the magnetic particles according to the present embodiment. FIG. 3-2 is a schematic diagram showing adjacent magnetic particles in a magnet composed of magnetic particles having Fe as a core portion and ε-Fe ₂ O ₃ as a shell portion. FIG. 4 is a flowchart showing the steps of the magnetic material manufacturing method according to this embodiment. FIGS. 5-1 is a figure which shows the process of the manufacturing method of the magnetic material which concerns on this embodiment. FIGS. 5-2 is a figure which shows the process of the manufacturing method of the magnetic material which concerns on this embodiment.

  Hereinafter, the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by the form (henceforth embodiment) for implementing the following invention. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range.

The magnetic material according to the present embodiment has a hard magnetic phase core portion containing ε-Fe ₂ O ₃ and a soft magnetic phase shell portion containing Fe and covering at least a part of the core portion. It is characterized in that it contains particles. In addition, the magnet according to the present embodiment is characterized in that it includes the magnetic material according to the present embodiment. For example, the magnetic material according to the present embodiment can be sintered or the magnet according to the present embodiment can be sintered. It is obtained by hardening the material with a binder.

FIG. 1 is a schematic diagram showing a structure of a magnet configured using the magnetic material according to the present embodiment. A magnet 1 shown in FIG. 1 is made of a magnetic material according to this embodiment, and includes a core portion 11 including ε-Fe ₂ O ₃ and a shell that includes Fe and covers at least a part of the core portion 11. The nanocomposite magnet is formed by densifying the magnetic particles composed of the portion 12. A nanocomposite magnet is composed of a two-phase composite structure of a hard magnetic phase with a large coercive force on the order of nm (nanometers) and a soft magnetic phase with high magnetization. It is a magnet that acts as if it were a uniform and uniform magnet due to the exchange coupling action. Since it exhibits a magnetization behavior in which a hard magnetic phase and a soft magnetic phase are coupled by a magnetic spring, it is also called an exchange spring magnet.

In nanocomposite magnets, when the composite structure of a hard magnetic phase and a soft magnetic phase is refined to the order of nanometers, an exchange coupling action works between the soft magnetic phase and the hard magnetic phase, so that a soft magnetic field can be softened even when an inversion magnetic field is applied. The magnetization reversal of the magnetic phase is prevented by the exchange coupling action to the magnetization of the hard magnetic phase. At this time, the magnetization curve behaves as if the soft magnetic phase and the hard magnetic phase are single-phase magnets due to the exchange coupling action. As a result, a magnetization curve having a high magnetization from the soft magnetic phase and a coercive force from the hard magnetic phase is realized, and as a result, a magnetic material having a high energy product (BH) _max can be obtained. . As described above, the magnet 1 is made of the magnetic material according to the present embodiment. Next, the magnetic particles constituting the magnetic material according to the present embodiment will be described.

FIG. 2 is a schematic view showing magnetic particles constituting the magnetic material according to the present embodiment. The magnetic particle 10 includes a hard magnetic phase core portion 11 containing ε-Fe ₂ O ₃ and a soft magnetic phase shell portion 12 containing Fe and covering at least a part of the core portion 11. ε-Fe ₂ O ₃ is a hard magnetic material and is an oxide magnet and has the largest coercive force. The magnetic particle 10 is configured by combining such a hard magnetic material and a highly magnetized Fe (soft magnetic material). More specifically, in the magnetic particle 10, a hard magnetic phase containing ε-Fe ₂ O ₃ is used as the core portion 11, and at least a part, preferably all, of the core portion 11 is covered with the shell portion 12 containing Fe. It becomes a core-shell structure.

  The magnetic material according to the present embodiment includes the magnetic particles 10. The magnetic material according to the present embodiment may be an aggregate of only a plurality of magnetic particles 10 having a core-shell structure. The magnetic particles 10 are made of Fe oxide and Fe and do not contain rare earth elements. If a magnet is produced using the magnetic material according to this embodiment including such magnetic particles 10, a nanocomposite magnet can be produced without using rare earth elements.

Here, the core part 11 of the magnetic particle 10 contains ε-Fe ₂ O ₃ and has it as a main component. This is because the ratio of ε-Fe ₂ O _{3 in} the total volume of the core part 11 is the same. It means larger than 50 vol%. In the magnetic particle 10, a part of ε-Fe ₂ O ₃ Fe constituting the core portion 11 may be substituted with at least one of Co and Ni. Furthermore, the core part 11 of the magnetic particle 10 may contain a metal oxide other than ε-Fe ₂ O _{3 in} the remainder of ε-Fe ₂ O ₃ . Thus, by including a metal oxide other than ε-Fe ₂ O ₃ as a different phase in the remainder of ε-Fe ₂ O ₃ in the core portion 11, Magnetic characteristics can also be improved.

  Further, the shell portion 12 of the magnetic particle 10 contains Fe as a main component, which means that the proportion of Fe in the total volume of the shell portion 12 is larger than 50 vol%. In addition, the shell part 12 of the magnetic particle 10 may contain a different phase other than Fe, for example, a metal oxide, an intermetallic compound, or the like in the remaining part of Fe. As described above, by including a phase different from Fe as a different phase in the remaining part of Fe in the shell portion 12, the magnetic characteristics of the magnet 1 manufactured including the magnetic particles 10 can be improved.

  Here, in the magnetic particle 10, a part of Fe constituting the shell portion 12 may be replaced with at least one of Co and Ni. In this way, since the residual magnetic flux density Br of the shell portion 12 can be improved, the magnetic characteristics of the magnet 1 manufactured including the magnetic particles 10 can be improved. The crystal structure of Fe constituting the shell portion 12 is not limited and may be amorphous. However, α-Fe is more preferable because it has a larger magnetization than amorphous.

FIG. 3A is a schematic diagram illustrating adjacent magnetic particles in a magnet composed of the magnetic particles according to the present embodiment. When the core part 11 and the shell part 12 of the magnetic particle 10 shown in FIG. 3A are spherical, the diameter (core diameter) of the core part 11 including ε-Fe ₂ O ₃ is D. To do. The hard magnetic phase containing ε-Fe ₂ O ₃ cannot secure a sufficient coercive force if the size is too small. The core diameter D is preferably 10 nm or more. In this way, since the coercive force of ε-Fe ₂ O ₃ constituting the core portion 11 can be ensured, the core portion 11 can be reliably operated as a hard magnetic phase.

  In the magnetic particle 10, the region where the shell portion 12, which is a soft magnetic phase, exists is a distance at which the exchange coupling action works from the interface between the hard magnetic phase and the soft magnetic phase, that is, the interface 13 between the core portion 11 and the shell portion 12. It is preferable that the region is a or less (hereinafter referred to as exchange coupling distance). In the magnetic particle 10, since the shell portion 12 is a soft magnetic phase, the thickness (shell thickness) t of the shell portion 12 is preferably equal to or less than the exchange coupling distance a (t ≦ a). In this way, since the exchange coupling action acts reliably between the soft magnetic phase and the hard magnetic phase, the magnet composed of the magnetic particles 10 has improved magnetic properties and improved performance as a magnet.

  When a magnet is manufactured using the magnetic material according to the present embodiment, the performance of the magnet is improved when the volume fraction Vc1 of the soft magnetic phase is larger than the total volume of the magnet. Therefore, the magnetic particles 10 constituting the magnetic material according to the present embodiment are not less than the lower limit value of the core diameter D described above, and the manufactured magnets satisfy the condition that the shell thickness t is the exchange coupling distance a or less. The core diameter D and the shell thickness t are determined so that the volume fraction Vc1 of the soft magnetic phase becomes larger with respect to the total volume.

FIG. 3-2 is a schematic diagram showing adjacent magnetic particles in a magnet composed of magnetic particles having Fe as a core portion and ε-Fe ₂ O ₃ as a shell portion. Magnetic particles 10a shown in Figure 3-2, unlike the magnetic particles 10 shown in Figure 3-1, a soft magnetic phase core portion 11a has a main component Fe, shell portion 12a is the _ε-Fe 2 _{O 3} main It is a hard magnetic phase as a component. In the magnetic particle 10a, since the shell portion 12a has a hard magnetic phase, the shell thickness t is preferably 10 nm or more. Moreover, since the core part 11a has the soft magnetic phase in the magnetic particle 10a, the core part 11a has an exchange coupling distance a from the interface between the hard magnetic phase and the soft magnetic phase, that is, the interface 13a between the core part 11a and the shell part 12a. It is preferable to exist in the following areas. That is, the distance from the interface 13a to the center of the core portion 11a is preferably equal to or less than the exchange coupling distance a. When the core portion 11a is spherical, the core diameter D ≦ 2 × a.

The volume fraction Vc1 and the volume fraction Vc2 described above are compared with the volume V1 of the magnetic particle 10 shown in FIG. 3-1 and the volume V2 of the magnetic particle 10a shown in FIG. 3-2 having the same size. The magnetic particle 10a shown in FIG. 3-2 has a shell thickness t = b of the hard magnetic phase shell portion 12a and a core diameter D of the soft magnetic phase core portion 11a of 2 × a. Here, if the core diameter D of the core portion 11a exceeds 2 × a, the exchange coupling action becomes insufficient, so the core diameter D of the core portion 11a does not exceed 2 × a. Here, the dimension b that defines the shell thickness t is a dimension that can secure a coercive force to the extent that ε-Fe ₂ O ₃ can function as a hard magnetic phase.

  As described above, from the viewpoint of improving the performance of the magnet, there is a demand for increasing the volume fraction of the soft magnetic phase as much as possible. For this reason, the magnetic particle 10a shown in FIG. 3-2 has a soft magnetic phase core 11a in consideration of the exchange coupling distance a and the limitation on the size of the hard magnetic phase (the shell thickness t is set to the above-described size b). The maximum value of the core diameter D is 2 × a. In this case, the diameter of the magnetic particle 10a is 2 × (a + b).

  In the magnetic particle 10 shown in FIG. 3A, the shell thickness t of the shell portion 12 of the soft magnetic phase is set to a, and the core diameter D of the core portion 11 of the hard magnetic phase is set to b or more. Then, the diameter of the magnetic particle 10 is 2 × a + b, which is smaller than the diameter of the magnetic particle 10a illustrated in FIG. In order to make the diameter of the magnetic particle 10 shown in FIG. 3-1 the same as the diameter of the magnetic particle 10a shown in FIG. 3-2, the shell thickness t of the shell portion 12a of the soft magnetic phase is determined from the exchange coupling distance a. Therefore, the core diameter D of the core portion 11 of the hard magnetic phase is set to 2 × b. Accordingly, the diameter of the magnetic particle 10 shown in FIG. 3A is 2 × (a + b), which is the same size as the diameter of the magnetic particle 10a shown in FIG. 3-2.

  Since the volume V1 of the magnetic particle 10 shown in FIG. 3-1 and the volume V2 of the magnetic particle 10a shown in FIG. 3-2 have the same size, V1 = V2 = V. The volume fraction Vc1 of the soft magnetic phase in the magnetic particle 10 shown in FIG. 3A is obtained by the equation (1), and the volume fraction V2 of the soft magnetic phase in the magnetic particle 10a shown in FIG. 3-2 is obtained by the equation (2). be able to. Equation (3) shows the difference ΔVc between Vc1 and Vc2. From equation (3), ΔVc> 0, so Vc1> Vc2.

  Next, the volume fraction Vc1 of the soft magnetic phase in the magnetic particle 10 shown in FIG. 3A is compared with the volume fraction Vc2 of the soft magnetic phase in the magnetic particle 10a shown in FIG. 3-2. In this comparison, the volume fraction of the volume of the magnetic particles 10 shown in FIG. 3A and the volume of the magnetic particles 10a shown in FIG. Vc1 and volume fraction Vc2 are compared.

  Here, in the magnetic particle 10 shown in FIG. 3A, the core diameter D of the core portion 11 of the hard magnetic phase is b, and the shell thickness t of the shell portion 12 of the soft magnetic phase is the exchange coupling distance a. In the magnetic particle 10 shown in FIG. 3-2, the core diameter D of the core portion 11 of the soft magnetic phase is twice the exchange coupling distance a (2 × a), and the shell thickness t of the shell portion 12 of the hard magnetic phase. Is b.

  The volume fraction Vc1 of the soft magnetic phase in the magnetic particle 10 shown in FIG. 3A is the equation (4), and the volume fraction Vc2 of the soft magnetic phase in the magnetic particle 10a shown in FIG. 3-2 is the equation (2) described above. Can be obtained. Equation (5) shows the difference ΔVc between Vc1 and Vc2. From equation (5), since ΔVc> 0, Vc1> Vc2.

Thus, in any case, better volume fraction Vc1 of the soft magnetic phase in the magnetic particles 10 shown in Figure 3-1, the volume fraction V c of the soft magnetic phase in the magnetic particles 10a shown in Figure 3-2 Greater than 2. Therefore, in order to increase the volume fraction of the soft magnetic phase in the core-shell structure magnetic particles combining the soft magnetic phase and the hard magnetic phase, the soft magnetic phase is disposed outside the hard magnetic phase. The configuration of the magnetic particles 10 is suitable. Further, by using ε-Fe ₂ O ₃ , which is a hard magnetic phase, as the core part 11 as in the magnetic particle 10, the easy axis of magnetization in the magnetic particle 10 becomes one direction, and an anisotropic magnet can be easily formed. Become. When the denominator and numerator of formula (4) are multiplied by b / a ⁴ and arranged by b / a, the volume fraction Vc1 of the soft magnetic phase decreases as b / a decreases when both a and b are positive. (Ie, as b decreases) it increases. Here, the diameter of the core portion 11 corresponds to b. Therefore, the magnetic particle 10 having the hard magnetic phase as the core portion 11 and the soft magnetic phase as the shell portion 12 can increase the volume fraction Vc1 of the soft magnetic phase as the diameter of the core portion 11 is reduced. .

  In the above description, the magnetic particles 10, the core portion 11, and the shell portion 12 have a spherical shape, but the shapes of the magnetic particles 10, the core portion 11, and the shell portion 12 are not limited thereto. Next, the manufacturing method of the magnetic particle 10 which comprises the magnetic material which concerns on this embodiment, ie, the manufacturing method of the magnetic material which concerns on this embodiment, is demonstrated.

FIG. 4 is a flowchart showing the steps of the magnetic material manufacturing method according to this embodiment. FIGS. 5A and 5B are diagrams illustrating the steps of the magnetic material manufacturing method according to the present embodiment. In producing magnetic particles constituting the magnetic material according to the present embodiment, first, a powder of ε-Fe ₂ O ₃ is produced (step S101: powder production process). powder _ε-Fe 2 _{O 3,} for example, are made from iron (III) nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H 2 O), for example, by using a reversed micelle method, a sol-gel method, etc. .

In this embodiment, the production method of the ε-Fe ₂ O ₃ powder is not particularly limited, but a chemical process such as a reverse micelle method or a sol-gel method is used for the production of the ε-Fe ₂ O ₃ powder. By using, ε-Fe ₂ O ₃ powder of about several tens of nanometers can be produced relatively easily as compared with the case of using a physical and mechanical process. Incidentally, in fabricating a powder of _ε-Fe 2 _{O 3,} it may be added a step of coating the surface of the powder of the _ε-Fe 2 _{O 3} in SiO _2. Thereby, in the step of preparing a powder of _ε-Fe 2 _{O 3,} it is possible to suppress grain growth of the powder of the _ε-Fe 2 _{O 3} preferred.

When the powder of ε-Fe ₂ O ₃ is prepared, the surface of the powder of ε-Fe ₂ O ₃ is reduced (step S102: reduction step), whereby a layer of Fe is formed outside the powder of ε-Fe ₂ O _3. Form. Thus, the core portion 11 of the hard magnetic phase mainly composed of ε-Fe ₂ O ₃ is formed, and at least a part of the surface of the core portion 11 is formed by the shell portion 12 of the soft magnetic phase mainly composed of Fe. The coated magnetic particle 10 is completed (step S103, FIG. 5-1). The magnetic particles 10 are molded into a desired shape and sintered, or bonded with a binder such as a resin to obtain the magnet 1 shown in FIG. The magnet 1 is manufactured as follows, for example.

(Sintered magnet)
The magnetic particles 10 are molded into a desired shape, and the obtained molded body is heat-treated in an inert atmosphere or vacuum to obtain a sintered magnet. Moreover, a sintered magnet can be obtained also by sintering a molded object by plasma activated sintering (PAS: Plasma Activated Sintering) or discharge plasma sintering (SPS: Spark Plasma Sintering). Moreover, an anisotropic sintered magnet is obtained by shaping in a magnetic field.

(Bonded magnet)
A bonded magnet is obtained by blending and molding the magnetic particles 10 and a binder (binder). As the binder, a resin material such as a thermoplastic resin or a thermosetting resin, a low melting point metal such as Al, Pb, Sn, Zn, or Mg, or an alloy made of these low melting point metals can be used. The magnetic particles 10 can be formed into a desired shape by compression molding or injection molding a mixture of the magnetic particles 10 and the binder. Moreover, an anisotropic bonded magnet is obtained by shaping the magnetic particles 10 in a magnetic field.

Incidentally, after the manufacturing method of the above-mentioned magnetic material, but not to remove the SiO ₂ covering the surface of the powder of _ε-Fe 2 _{O 3,} which was reduced surface of the powder of the _ε-Fe 2 _{O 3,} or ε- SiO ₂ may be removed either before reducing the surface of the Fe ₂ O ₃ powder (FIG. 5-2), that is, either before or after the reduction step. As a result, the proportion of SiO ₂ , which does not contribute to the improvement of the magnetic properties in the magnetic particles 10, can be reduced, so that the magnetic properties of the magnet produced including the magnetic particles 10 can be further improved. it can.

Here, from the viewpoint of magnetic properties, it is preferable to remove the SiO ₂ from the magnetic particles 10, but the SiO ₂ may be left on the surface of the magnetic particles 10, that is, the surface of the shell portion 12. When a magnet is produced by sintering the magnetic particles 10, the magnetic particles 10 tend to be bonded to each other by heating to coarsen the structure, but SiO ₂ is left on the surface of the shell portion 12 of the magnetic particles 10. Thus, the coarsening of the structure can be suppressed. The magnetic particles 10, since the shell portion 12 is constituted by Fe, by providing the SiO ₂ layer on the surface of the shell portion 12, since the oxide of the shell portion 12 is suppressed preferred. Note that when leaving the SiO ₂ on the surface of the shell portion 12 of the magnetic particles 10, SiO ₂ is left on at least part of the surface of the shell portion 12, SiO ₂ layers may be provided.

The magnetic particle 10 produced by the method for producing a magnetic material according to the present embodiment includes a hard magnetic phase core portion 11 mainly composed of ε-Fe ₂ O ₃ , Fe as a main component, and the core portion 11. A core-shell structure having a soft magnetic phase shell portion 12 covering at least a part thereof is obtained. Since the magnetic particles 10 are produced by reducing the surface of the powder of ε-Fe ₂ O ₃ , the core portion 11 that is a hard magnetic phase and the shell portion 12 that is a soft magnetic phase are interposed via an interface. And an exchange coupling action works between them. As a result, a magnetic characteristic that the magnetization is large and the coercive force is large can be obtained.

In addition, since the magnetic particles 10 are made of an oxide of Fe and do not need to use rare earth elements, a nanocomposite magnet that does not use rare earth elements can be obtained by making a magnet using a magnetic material containing the magnetic particles 10. Can be made. Further, magnets made of a magnetic material containing magnetic particles 10 created by the manufacturing method described above, as described later, it can be determined that those having a magnet equivalent magnetic properties using a rare earth element .

  As mentioned above, since the magnetic material which concerns on this embodiment, and the magnet produced from this magnetic material do not use expensive rare earth elements, these manufacturing costs can be reduced. Although rare earth elements may be unstable in supply, the magnetic material according to the present embodiment uses an Fe-based material (Fe or Fe oxide) that is stably supplied. Can be realized. Furthermore, the process for reducing rare earth elements is special, and the energy required for reduction increases. For this reason, magnets using rare earth elements require labor to recycle. However, since the magnetic material according to the present embodiment and the magnet made from this magnetic material can be made from an Fe-based material without using rare earth elements, there is an advantage that recycling is easy.

The nanocomposite magnet disclosed in Patent Document 1 described above has a hard magnetic phase core dimension on the order of microns, and forms a shell by generating soft magnetic phase nanoparticles on the surface of such a core. . As a result, since the core dimension is larger than the shell thickness, the volume fraction (Vc1) of the soft magnetic phase cannot be increased. On the other hand, since the magnetic particles constituting the magnetic material according to the present embodiment have a particle size of several tens of nanometers as will be described later, the volume fraction Vc1 of the soft magnetic phase is increased. Further, in Patent Document 1 described above, the core is manufactured by physical pulverization. However, in this embodiment, the core is manufactured using a chemical process as described above, and SiO 2 is used to suppress grain growth. _Two layers are coated. Thereby, in this embodiment, the system of the core part of a hard magnetic phase can be made small compared with the cited reference 1. As a result, the magnet produced from the magnetic material according to the present embodiment has the same magnetic characteristics as a magnet using rare earth elements.

(Production example)
Next, an example in which the magnetic material according to this embodiment is produced will be described. This magnetic material is a magnetic particle having a core-shell structure having a core portion of a hard magnetic phase mainly composed of ε-Fe ₂ O ₃ and a shell portion of a soft magnetic phase mainly composed of Fe. The magnetic particles were produced by the following procedure.
(1) The surface of the particles of ε-Fe ₂ O ₃ was reduced by leaving the particles of ε-Fe ₂ O ₃ in a hydrogen stream at an atmospheric temperature of 200 ° C. to 600 ° C. for 1 hour to 100 hours.
(2) Thereafter, the atmospheric temperature is lowered to 20 ° C. to 100 ° C., the oxygen concentration is changed to an atmosphere of 0.5% or less, and in a constant temperature between 20 ° C. and 100 ° C. and in a constant atmosphere, The protective layer was formed on the surface by allowing the particles of ε-Fe ₂ O ₃ after reduction to stand for a predetermined time. The time for leaving the reduced ε-Fe ₂ O ₃ particles was within 24 hours. As a result, magnetic particles having a core-shell structure having a core portion of a hard magnetic phase mainly composed of ε-Fe ₂ O ₃ and a shell portion of a soft magnetic phase mainly composed of Fe were produced.

The powder of ε-Fe ₂ O ₃ was prepared by the following procedure using a reverse micelle method.
(1) First, two kinds of micelle solutions (micelle solution A and micelle solution B) were prepared.
(1-1) The micelle solution A was prepared as follows. Mix 54 ml of ion-exchanged water, 164.7 ml of n-octane and 33.3 ml of 1-butanol. Thereto, 0.0135 mol of iron (III) nitrate nonahydrate is added and dissolved with good stirring at room temperature. Further, cetyltrimethylammonium bromide as a surfactant is added in such an amount that the molar ratio of ion-exchanged water / surfactant is 30, and dissolved by stirring. Thereby, micelle solution A was obtained.
(1-2) The micelle solution B was prepared as follows. Mix 16.2 ml of 28% ammonia water in 36 ml of ion-exchanged water and stir. Then, add 164.7 ml of n-octane and 33.3 ml of 1-butanol and stir well. To the solution, cetyltrimethylammonium bromide as a surfactant, was added in an amount such that the molar ratio becomes 30 (water deionized water + ammonia in water) / surfactant is dissolved. Thereby, the micelle solution B was obtained.
(2) When the micelle solution A and the micelle solution B are prepared, the micelle solution B is added dropwise to the micelle solution A while stirring the micelle solution A well. After the dropping is completed, the mixed solution of the micelle solution A and the micelle solution B is continuously stirred for 60 minutes.
(3) While stirring the obtained mixed solution, 15 ml of tetraethoxysilane (TEOS) is added to the mixed solution. The stirring is continued for about 1 day. By this step, a layer of SiO ₂ is formed on the surface of the iron compound powder.
(4) The obtained solution is centrifuged by a centrifuge. The precipitate obtained by this treatment is recovered. The collected precipitate is washed several times with ethanol.
(5) After drying the obtained precipitate, it heat-processes in the furnace in an atmospheric condition. The heat treatment condition is 1050 ° C. for 4 hours. The heat-treated powder is stirred in a 10 mol / l NaOH aqueous solution for 24 hours to remove SiO ₂ present on the powder surface.
(6) The powder from which SiO ₂ was removed was filtered, washed with water, and dried to obtain ε-Fe ₂ O ₃ powder.

The powder of ε-Fe ₂ O ₃ obtained by the above procedure had a particle size (determined from a TEM image) of 10 nm to 40 nm. In the magnetic particles after the reduction, the core diameter of the core portion of ε-Fe ₂ O ₃ was 5 nm to 35 nm, and the shell thickness of the shell portion of Fe (α-Fe) was 3 nm to 10 nm. The magnetic properties of the magnetic particles were measured with a VSM (sample vibration magnetometer). As a result, the residual magnetic flux density Br was 85 (emu / g), and the coercive force HcJ was 10700 (Oe). From this result, it may be determined that a magnet produced using the magnetic particles produced in this production example has the same magnetic properties as a magnet using a rare earth element.

  As described above, the magnetic material and magnet according to the present invention and the method for producing the magnetic material are useful for producing a magnet without using a rare earth element, and are particularly suitable for a nanocomposite magnet.

1 Magnet 10, 10a Magnetic particle 11, 11a Core portion 12, 12a Shell portion 13, 13a Interface

Claims (9)

a core portion of a hard magnetic phase containing ε-Fe ₂ O ₃ ;
A soft magnetic phase shell portion containing Fe and covering at least a part of the core portion;
Magnetic material comprising magnetic particles having _2. The magnetic material according to claim 1, wherein a part of Fe of ε-Fe ₂ O ₃ constituting the core portion is substituted with at least one of Co and Ni.   The magnetic material according to claim 1 or 2, wherein a part of Fe constituting the shell portion is substituted with at least one of Co and Ni. The magnetic material according to claim 1, wherein the core portion includes a metal oxide other than ε-Fe ₂ O ₃ . 5. The magnetic material according to claim 1, wherein an SiO ₂ layer is provided on at least a part of the surface of the shell portion.   A magnet comprising the magnetic material according to claim 1. a powder production process for producing a powder of ε-Fe ₂ O ₃ ;
A reduction step of reducing the surface of the ε-Fe ₂ O ₃ powder;
The manufacturing method of the magnetic material characterized by including. The method for producing a magnetic material according to claim 7, wherein at least a part of the surface of the ε-Fe ₂ O ₃ powder produced in the powder production step is covered with SiO ₂ . The magnetic material manufacturing method according to claim 8, further comprising a step of removing the SiO ₂ from a surface of the ε-Fe ₂ O ₃ powder after the reduction step or before the reduction step. Method.

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