JP5682416B2 - Rare earth magnet, manufacturing method thereof, and rotating machine - Google Patents

Description

  The present invention relates to a rare earth magnet, a manufacturing method thereof, and a rotating machine including the rare earth magnet.

  Although a rare earth magnet containing a rare earth element has an excellent magnetic force, it contains a rare earth element that is easily oxidized as a main component, and therefore tends to have low corrosion resistance. Therefore, rare earth magnets are often configured such that a protective layer made of resin, plating, or the like is provided on the surface of a magnet body containing a rare earth element.

  By the way, in recent years, a protective layer capable of imparting a certain degree of corrosion resistance has been provided for the reason that the corrosion resistance of the magnet body itself has been improved and that the corrosion resistance of the conventional magnet magnet is not required depending on the use of the rare earth magnet. The number of cases where it is required to be easily formed at low cost is increasing.

For example, as a method of forming a protective layer on the surface of the magnet body relatively easily, a method of coating the surface of the magnet body with a colloidal solution composed of inorganic fine particles (SiO ₂ ) and solidifying by heating (patent) Document 1) or a method of forming a protective layer containing inorganic particles and a compound of a metal element contained in the magnet body on the surface of the magnet body by bringing the magnet body into contact with an acidic solution containing inorganic particles ( Patent document 2) is known. According to such a method, it is possible to obtain a rare earth magnet having a protective layer on the surface thereof at a relatively simple and low cost.

JP-A 63-301506 Japanese Patent Laid-Open No. 2007-251061

  However, although the protective layer formed by the above prior art method can be formed by a simple method, there are many cases where the protective layer does not have sufficient characteristics to suppress the occurrence of rust of the rare earth magnet. This is because, as a result of investigations by the present inventors, in a protective layer formed by a conventional simple method, it is inevitable that some defects are generated, and in an environment where water adheres. It has been found that when a rare earth magnet is used, moisture reaches the magnet body through defects in the protective layer, thereby causing corrosion of the magnet body.

  Therefore, the present invention has been made in view of such circumstances, and a rare earth magnet that can be manufactured by a simple method and that can sufficiently suppress the generation of rust even in an environment where water adheres, and the manufacture thereof It aims to provide a method. Moreover, an object of this invention is to provide a rotary machine provided with such a rare earth magnet.

In order to achieve the above object, a rare earth magnet of the present invention includes a light element (hereinafter, sometimes referred to as “ ^RL ”), Fe and B containing a magnet element, and a surface of the magnet element. The protective layer includes R ^L , Fe, and M (M is Si, Al, Zn, Mn, Ge, Sn, Bi, Pb, Ga, Cu, Ni, and And an alloy containing at least one element selected from the group consisting of Co.).

The rare earth magnet of the present invention having such a configuration can be easily manufactured by the manufacturing method of the present invention described later. The rare earth magnet of the present invention, the surface of the magnet body containing ^{R L,} alloys containing R L, Fe and M (hereinafter, referred to as ^"R L -Fe-M alloy".) Protection containing Since it is provided with a layer, even if it is used in an environment where water adheres, it is difficult to generate rust and has excellent corrosion resistance. Although the cause is not necessarily clear, the present inventors presume as follows.

That is, the R ^L —Fe—M alloy contained in the protective layer has a lower corrosion potential than an alloy containing R ^L , Fe, and B mainly constituting the main phase of the magnet body. For this reason, when the rare earth magnet is used in an environment that is susceptible to corrosion, such as adhesion of water, the R ^L —Fe—M alloy in the protective layer is more easily corroded than the magnet body. As a result, in the rare earth magnet of the present invention provided with a protective layer containing an R ^L -Fe-M alloy, even if water adheres, the magnet body is electrochemically protected and thus is not easily corroded. Occurrence is considered to be suppressed. In addition, the ^RL- Fe-M alloy in the protective layer often produces a corrosion product when corroded by adhesion of water or the like. The defect of the protective layer is blocked by the object. Also by such an effect | action, it is thought that water etc. adhere to a magnet element body through a protective layer, and as a result, it becomes difficult to generate | occur | produce rust. In addition, an effect | action is not necessarily limited to these.

The rare earth magnet of the present invention preferably further comprises an external protective layer containing an ^RL oxide on the surface of the protective layer. Since the ^RL oxide contained in the external protective layer is already an oxide, it is difficult to cause corrosion due to oxidation by water or the like. Therefore, by further providing such an external protective layer on the surface of the protective layer described above, it is possible to suppress the intrusion of corrosive substances such as water into the inside of the external protective layer, and even in the case of intrusion. Since corrosion of the magnet body can be prevented by the layer, a further excellent corrosion resistance can be obtained by the synergistic effect of the protective layer and the external protective layer.

Furthermore, in the rare earth magnet of the present invention, it is preferable that the protective layer further contains an oxide of ^RL . In this manner, the protective layer contains a combination of oxides of R ^L with R ^L -Fe-M alloy, the corrosion of the protective layer itself becomes to be effectively suppressed, as described above R ^L - In addition to the corrosion prevention effect of the magnet body by the Fe-M alloy, further excellent corrosion resistance can be obtained. In particular, when the above-mentioned external protective layer is provided on the surface of the protective layer, both the protective layer and the external protective layer contain an ^RL oxide, so that the adhesion between these layers is also improved. Corrosion resistance tends to be further improved.

Moreover, the method for producing a rare earth magnet of the present invention includes a magnet body containing R ^L , Fe and B, and M (M is Si, Al, Zn, Mn, And a film comprising an oxide or hydroxide of at least one element selected from the group consisting of Ge, Sn, Bi, Pb, Ga, Cu, Ni and Co. And a method for producing a rare earth magnet having a heat treatment step of forming a protective layer containing an alloy containing ^RL , Fe, and at least one element of M on the surface of the magnet body. .

In the method for producing a rare earth magnet of the present invention, a composite in which a film containing an oxide or hydroxide of M is formed on the surface of a magnet body is heat-treated, and a reaction occurs between the magnet body and the film. Thus, a protective layer containing an alloy containing R ^L , Fe and M is formed on the surface of the magnet body. Thus, according to the method for producing a rare earth magnet of the present invention, a protective layer can be formed simply by subjecting the composite to a heat treatment. Therefore, a protective layer can be easily formed on the surface of the magnet body. it can. Moreover, since the rare earth magnet obtained by the manufacturing method of this invention is equipped with the protective layer containing ^RL- Fe-M alloy on the surface of the magnet element body containing ^RL , it is an environment where water adheres. Even if it is used, it does not easily generate rust and can exhibit excellent corrosion resistance. The reason is considered to be due to the same reason as described for the rare earth magnet of the present invention.

In the method for producing a rare earth magnet of the present invention, it is preferable that the heat treatment is performed at a temperature of 500 ° C. or higher and lower than the sintering temperature of the magnet body. By performing the heat treatment in such a temperature range, the R ^L —Fe—M alloy is sufficiently contained, thereby forming a protective layer that can exhibit the above-described effects satisfactorily, and having a high magnetic property A magnet is obtained.

  In addition, before the heat treatment step, the composite body forming step for forming the composite body is performed by bringing the magnet body into contact with an acidic aqueous solution containing M oxide or hydroxide particles. Is preferred. According to such a composite formation step, it is possible to easily obtain a composite that is advantageous for forming a rare earth magnet having excellent corrosion resistance.

  The present invention further provides a rotating machine comprising the rare earth magnet of the present invention. Since the rotating machine of the present invention includes the rare earth magnet of the present invention, even when used under severe conditions such as high humidity, the rare earth magnet has little corrosion due to the occurrence of rust, etc., and therefore has excellent performance over a long period of time. Can be demonstrated.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the rare earth magnet which can fully suppress generation | occurrence | production of rust also in the environment where water adheres, and its manufacturing method. In addition, according to the present invention, by providing such a rare earth magnet, it is possible to provide a rotating machine capable of maintaining excellent performance over a long period of time even in an environment where water easily adheres. .

It is a perspective view of the rare earth magnet concerning one embodiment of the present invention. It is the II-II sectional view taken on the line of the rare earth magnet shown in FIG. It is explanatory drawing which shows the internal structure of the rotary machine which concerns on one Embodiment of this invention. 2 is a scanning electron microscope (SEM) photograph of a cut surface of the rare earth magnet of Example 1. FIG. It is an analysis result in the X-ray diffraction (XRD) of the rare earth magnet surface of Example 1.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.

  First, a rare earth magnet according to a preferred embodiment will be described.

  FIG. 1 is a perspective view of a rare earth magnet according to an embodiment of the present invention. 2 is a cross-sectional view of the rare earth magnet shown in FIG. 1 taken along the line II-II. As shown in FIGS. 1 and 2, a rare earth magnet 100 according to the present embodiment includes a magnet body 10, a protective layer 20 that covers the surface of the magnet body 10, and an external protective layer 22 that covers the surface of the protective layer 20. With.

  The protective layer 20 does not necessarily have to cover the entire surface of the magnet body 10, and may cover at least a part of the surface, but the entire surface of the magnet body 10 is covered. The effect of suppressing the occurrence of rust can be obtained better. Further, the outer protective layer 22 need not necessarily cover the entire surface of the protective layer 20, but more preferably covers the entire surface. Thereby, the effect of preventing the generation of rust by the rare earth magnet 100 is further easily obtained.

The magnet body 10 is a rare earth magnet including rare earth elements (R), iron (Fe), and boron (B), and is mainly composed of an R—Fe—B alloy. The magnet body 10 includes at least a light rare earth element (R ^L ) as R. Here, ^RL includes scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), and europium (Eu). It is.

The magnet body 10 contains at least ^RL as R, but may further contain a heavy rare earth element (hereinafter, referred to as “ ^RD ” in some cases) in addition to ^RL . ^RD includes gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). If the magnet body 10 containing both ^{R L} and ^{R D,} in their sum, preferably when more than 70 mol% is in ^{R L,} and more preferably 85 mol% or more is in the ^{R L.} Hereinafter, in the case where both R ^L and R ^D are collectively shown, only “rare earth element (R)” is described.

The magnet body 10 preferably includes at least one selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, and Eu as ^RL . In particular, it is preferable that ^RL includes at least one of Nd and Pr. Thereby, the residual magnetic flux density (Br) and the coercive force (iHc) of the rare earth magnet 100 are remarkably improved.

  The magnet body 10 has a main phase having a substantially tetragonal crystal structure, and a R-rich phase having a high mixing ratio of rare earth elements (R) and a mixing ratio of boron atoms in the grain boundary portion of the main phase. Has a structure having a high boron-rich phase. These R-rich phase and boron-rich phase are non-magnetic phases that do not have magnetism. Such a nonmagnetic phase is contained in the magnet body 10 in an amount of 0.5 to 50% by volume, for example. Moreover, the particle size of the main phase is, for example, about 1 to 100 μm.

  In the magnet body 10, the content of R with respect to the entire magnet body 10 is preferably 8 to 40 atomic%. When the content of R is less than 8 atomic%, the crystal structure of the main phase becomes almost the same as that of α iron, and the coercive force (iHc) tends to be small. On the other hand, if it exceeds 40 atomic%, the R-rich phase is excessively formed, and the residual magnetic flux density (Br) tends to decrease.

  Further, the Fe content is preferably 42 to 90 atomic% with respect to the entire magnet body 10. When the Fe content is less than 42 atomic%, Br decreases, and when it exceeds 90 atomic%, iHc tends to decrease. Furthermore, the B content is preferably 2 to 28 atomic%. If the B content is less than 2 atomic%, a rhombohedral structure is likely to be formed, and this tends to reduce iHc. On the other hand, if it exceeds 28 atomic%, a boron-rich phase is excessively formed, and this tends to decrease Br.

  In the magnet body 10, a part of Fe may be substituted with cobalt (Co). Thus, if a part of Fe is replaced by Co, the temperature characteristics can be improved without deteriorating the magnetic characteristics. In this case, it is desirable that the amount of substitution of Co not be larger than the content of Fe. If the Co content exceeds the Fe content, the magnetic properties of the magnet body 10 tend to deteriorate.

  A part of B in the magnet body 10 may be substituted with an element such as carbon (C), phosphorus (P), sulfur (S), or copper (Cu). Thus, by replacing a part of B, the magnet body 10 can be easily manufactured and the manufacturing cost can be reduced. At this time, the substitution amount of these elements is desirably an amount that does not substantially affect the magnetic properties, and is preferably 4 atomic% or less with respect to the total amount of constituent atoms.

  Furthermore, from the viewpoint of improving iHc and reducing manufacturing costs, the magnet body 10 includes, in addition to the above elements, aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), Manganese (Mn), bismuth (Bi), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), antimony (Sb), germanium (Ge), tin (Sn), zirconium (Zr), Elements such as nickel (Ni), silicon (Si), gallium (Ga), copper (Cu), and hafnium (Hf) may be included. These addition amounts are also preferably in a range that does not affect the magnetic properties, and are preferably 10 atomic% or less with respect to the total amount of constituent atoms. In addition, oxygen (O), nitrogen (N), carbon (C), calcium (Ca), etc. are conceivable as components inevitably mixed, and these are about 3 atomic% with respect to the total amount of constituent atoms. It may be contained in the following amounts.

The protective layer 20 is a layer containing an alloy containing R ^L , Fe, and M (R ^L —Fe—M alloy). The ^{R L} contained in R ^L -Fe-M alloy, include the same elements as ^{R L} that may be included in the magnet body 10. ^{R L} contained in R ^L -Fe-M alloy is preferably a same element with at least one ^{R L} contained in the magnet body 10. ^Furthermore, when the R L -Fe-M alloy containing a plurality of types of ^{R L,} all of those ^{R L} is more preferably a ^{R L} the same type included in the magnet body 10. Increased ^{R L} contained in ^R L -Fe-M alloy in the protective layer 20, if the same as ^{R L} contained in the magnet body 10, the adhesion between the protective layer 20 and the magnet body 10 is Thus, the corrosion resistance is improved, and the rare earth magnet 100 can be easily manufactured by a manufacturing method described later.

M in the R ^L —Fe—M alloy contained in the protective layer 20 is silicon (Si), aluminum (Al), zinc (Zn), manganese (Mn), germanium (Ge), tin (Sn), bismuth (Bi ), Lead (Pb), gallium (Ga), copper (Cu), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), tungsten (W), vanadium (V), niobium (Nb) ), Tantalum (Ta), titanium (Ti), hafnium (Hf), and zirconium (Zr). In this specification, Si is included in the metal.

  M is preferably an element whose standard free energy of formation of an oxide at 500 ° C. is higher than that of the rare earth element (R). By including an element having such properties as M, the effect of preventing the generation of rust by the protective layer 20 can be obtained particularly well, and the rare earth magnet 100 can be easily manufactured by a manufacturing method as described later. It becomes. Specifically, as M, a standard free energy of formation of an oxide at 500 ° C. is preferably −250 kcal or more, and more preferably −230 kcal or more.

Among them, M is preferably at least one element selected from the group consisting of Si, Al, Zn, Mn, Ge, Sn, Bi, Pb, Ga, Cu, Ni and Co, and includes Si, Al, Zn and At least one element selected from the group consisting of Mn is more preferable, and at least one element selected from the group consisting of Si, Al, and Zn is more preferable. By including these elements as M, the corrosion potential of the R ^L -Fe-M alloy becomes extremely low as compared with an alloy containing R ^L , Fe and B which mainly constitutes the main phase of the magnet body. Therefore, when the R ^L —Fe—M alloy is preferentially corroded over the magnet body, an effect of suppressing the corrosion of the magnet body (sacrificial anticorrosive effect) is further easily obtained. As a result, the corrosion resistance of the rare earth magnet 100 is further improved. Further, when M is particularly Si, the stability of the corrosion products generated by the corrosion of the R ^L -Fe-M alloy tends to be high, and the effect of improving the corrosion resistance due to the generation of such corrosion products is further increased. Get higher.

The R ^L —Fe—M alloy in the protective layer 20 is made of, for example, an intermetallic compound having a composition represented by R ^L ₆ Fe _14-x M _x (x ≧ 1). The protective layer preferably has a phase having a tetragonal crystal structure constituted by such an R ^L —Fe—M alloy. By having such a phase, the sacrificial anticorrosive effect as described above by the protective layer 30 can be easily obtained, and high corrosion resistance can be obtained.

Note that the R ^L -Fe-M alloy may be an alloy mainly containing R ^L , Fe, and M, and some of these elements may be substituted with other elements. However, in order to obtain the effect of preventing rust by the protective layer 20 satisfactorily, the substitution amount of each element is preferably 50 atomic% or less. For example, in the case of R ^L ₆ Fe _14-x M _x , part of Fe may be substituted with Co. Moreover, although a part of ^RL may be substituted with heavy rare earth elements ( ^RD ), from the viewpoint of the corrosion potential of the ^RL- Fe-M alloy, the protective layer 20 does not contain ^RD. Is preferred.

The protective layer 20 may contain other compounds in addition to the above R ^L —Fe—M alloy. For example, it is preferable that the protective layer 20 further includes an ^RL oxide in addition to the ^RL- Fe-M alloy. The oxide of R ^L, include _R L 2 _{O 3.} The R ^L in the oxide of R ^L contained in the protective layer 20, include the same elements as R ^L that may be included in the magnet body 10, at least one R ^L contained in the magnet body 10 The same element is preferable. If R ^L constituting the oxide of R ^L contains multiple types, if it is the same element as R ^L all of which are included in the magnet body 10 preferably.

When the protective layer 20 contains the same ^RL oxide as that contained in the magnet body 10, the adhesion between the magnet body 10 and the protective layer 20 is improved, and the protective layer 20 and the external protection are protected. The adhesion with the layer 22 is also improved, and the corrosion resistance tends to be further improved. However, in order to sufficiently obtain the sacrificial anticorrosive effect of the R—Fe—M alloy, the content ratio of the R—Fe—M alloy in the protective layer 20 is preferably 10% by mass or more.

  The thickness of the protective layer 20 (indicated by D1 in FIG. 2) is preferably 0.1 to 50 μm. When the thickness D1 of the protective layer 20 is within such a range, the corrosion resistance and magnet characteristics of the rare earth magnet 100 are likely to be good.

Outer protective layer 22 includes an oxide of R ^L, when it is formed of only an oxide of R ^L preferred. An example of such an oxide is R ^L ₂ O ₃ . As ^{R L} is the ^R _L 2 _{O 3} in the outer protective layer 22, include the same elements as ^{R L} that may be included in the magnet body 10, at least one ^{R L} contained in the magnet body 10 The same element is preferable. In the external protective layer 22, if R ^L constituting the oxide of R ^L contains multiple types, if it is the same element as R ^L all of which are included in the magnet body 10 preferably. Thus, when the external protective layer 22 contains the same ^RL as that contained in the magnet body 10, the adhesion with the protective layer 20 is improved and the corrosion resistance tends to be further improved.

  The thickness of the external protective layer 22 (indicated by D2 in FIG. 2) is preferably 0.1 to 5 μm. When the thickness D2 of the external protective layer 22 is within such a range, the corrosion resistance and magnet characteristics of the rare earth magnet 100 are likely to be good.

  In the rare earth magnet 100, the interface between the magnet body 10 and the protective layer 20 and the interface between the protective layer 20 and the external protective layer 22 are elemental compositions between the magnet body 10, the protective layer 20, and the external protective layer 22. Therefore, it can be determined by visual observation of an electron micrograph.

  Further, the inclusion of the above-described alloys and oxides in the protective layer 20 and the external protective layer 22 means that, for example, an electron probe microanalyzer (EPMA), an X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy). : XPS), known compositional analysis methods such as Auger Electron Spectroscopy (AES) or energy dispersive X-ray Spectroscopy (EDS), and X-ray diffraction (X-ray Diffra) : XRD) or confirmed by performing analysis by a known structural analysis method such as electron diffraction (Electron Diffraction). Rukoto is possible.

  Although the dimension of the rare earth magnet 100 is not specifically limited, For example, vertical length is 1-200 mm, horizontal length is 1-200 mm, and height is about 1-30 mm. In addition, the shape of the rare earth magnet 100 is not limited to the rectangular parallelepiped shown in FIGS. 1 and 2, and may be a ring shape or a disk shape.

  The rare earth magnet of the present invention is not limited to the structure of the rare earth magnet 100 described above, and can be changed as appropriate. For example, the rare earth magnet may further include another layer for protecting the rare earth magnet 100 on the surface of the outer protective layer 22. Examples of such a layer include a resin layer and a plating layer.

Moreover, the rare earth magnet does not necessarily have to include the above-described external protective layer 22. Even if the external protective layer 22 is not provided, by providing the protective layer 20 on the surface of the magnet body 10, the sacrificial anticorrosive effect by the ^RL- Fe-M alloy in the protective layer 20, and further R ^Since the rare earth magnet 100 does not easily generate rust due to the effect of repairing the defects of the protective layer 20 by the corrosion product generated from the ^L— Fe—M alloy, high corrosion resistance can be exhibited.

  Next, a preferred embodiment of the method for manufacturing the rare earth magnet 100 described above will be described.

The method for producing a rare earth magnet according to the present embodiment includes performing heat treatment on a composite body including a magnet body including R ^L , Fe, and B and a film including an oxide or hydroxide of M to obtain a magnet body. A heat treatment step of forming a protective layer containing an alloy containing R ^L , Fe, and M on the surface of

In the method for producing a rare earth magnet of the present embodiment, first, a magnet body 10 including R ^L , Fe, and B is prepared.

The magnet body 10 including R ^L , Fe, and B can be manufactured by, for example, a powder metallurgy method. In this method, first, an alloy having a desired composition is manufactured by a known alloy manufacturing process such as a casting method or a strip casting method. Next, this alloy is pulverized (coarse pulverization) to a particle size of 10 to 100 μm using a coarse pulverizer such as a jaw crusher, a brown mill, a stamp mill, and then finely pulverized using a jet mill, an attritor or the like. Finely pulverize to a particle size of 0.5-5 μm with a machine. Then, the powder thus obtained is molded at a pressure of 0.5 to ⁵ t / cm ² in a magnetic field having a magnetic field strength of preferably 600 kA / m or more to obtain a molded body. As the molding method, either a uniaxial pressing method or an isotropic pressing method such as CIP may be used.

  Thereafter, the obtained molded body is preferably fired in an inert gas atmosphere or in a vacuum at 1000 to 1200 ° C. for 0.5 to 100 hours. Firing may be performed a plurality of times. After firing, the obtained sintered body may be quenched.

  Furthermore, it is preferable to apply an aging treatment to the sintered body. In the aging treatment, the sintered body may be heated at about 450 to 950 ° C. In the aging treatment, the sintered body may be heated for about 0.1 to 100 hours. The aging treatment may be performed in an inert gas atmosphere. By performing such an aging treatment, the coercive force of the rare earth magnet is further improved. The aging treatment may be performed by multi-stage heating. For example, in an aging treatment comprising two stages of heating, the sintered body may be heated at a temperature of 700 ° C. or higher and lower than the firing temperature for 0.1 to 50 hours in the first stage. What is necessary is just to heat a sintered compact at 450-700 degreeC for 0.1 to 100 hours at the 2nd step.

  The sintered body (magnet body 10) obtained by the above processing may be processed into a desired shape as necessary. Examples of the processing method include shape processing such as cutting and grinding, and chamfering processing such as barrel polishing.

  The magnet body 10 obtained in this way may be appropriately subjected to pretreatment in order to remove surface irregularities and impurities attached to the surface. The pretreatment may be performed on the sintered body before processing or may be performed on the sintered body after processing. Examples of the pretreatment include acid cleaning (etching) using an acid solution, cleaning using an alkaline solution, shot blasting, and the like, and acid cleaning is particularly preferable. According to the acid cleaning, it is easy to obtain the magnet body 10 having a smooth surface by dissolving and removing the irregularities and impurities on the surface of the magnet body 10, and it is possible to efficiently form a protective layer and an external protective layer described later. .

  The amount of dissolution of the surface of the sintered body (magnet body 10) by such acid cleaning is preferably 5 μm or more, preferably 10 to 15 μm in average thickness from the surface. In this way, the altered layer and the oxide layer due to the processing of the surface of the magnet body can be almost completely removed, and in the formation process of the protective layer and the external protective layer described later, the desired protective layer and the external protective layer are more It can be formed with high accuracy.

  In addition, after removing the treatment solution used for the acid washing by washing with water after the above acid washing, the magnet body 10 has an ultra-thin body in order to completely remove a small amount of undissolved substances and residual acid components remaining on the surface. It is preferable to perform cleaning using sonic waves. This ultrasonic cleaning can be performed, for example, in pure water or an alkaline solution with very little chlorine ions that generate rust on the surface of the magnet body 10. After the ultrasonic cleaning, water cleaning may be performed as necessary.

Next, a film containing M oxide or hydroxide is formed on the surface of the magnet body 10 described above to obtain a composite (composite forming step). M is the same as the element M contained in the protective layer 20 of the rare earth magnet 100. Examples of the oxide and hydroxide of M include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), aluminum oxyhydroxide (AlOOH), aluminum hydroxide (Al (OH) ₃ ), and zinc oxide (ZnO). ) And the like.

  As a method of forming a film containing M oxide or hydroxide on the surface of the magnet body 10, a gas phase method such as sputtering or ion plating, a method of applying an M alkoxide solution, Examples thereof include a method of applying a dispersion of oxide or hydroxide particles, and a method of bringing an acidic aqueous solution containing M oxide or hydroxide particles into contact with the magnet body 10.

  Among these, a method in which an acidic aqueous solution containing M oxide or hydroxide particles (hereinafter referred to as “treatment liquid”) is brought into contact with the magnet body 10 is preferable. According to this method, the dissolution of the magnet body 10 caused by bringing the magnet body 10 into contact with the acidic processing liquid as a driving force makes M uniformly in the entire region of the magnet surface 10 in contact with the processing liquid. A film containing oxide or hydroxide particles can be deposited. Therefore, according to this method, it is possible to easily obtain a film having a high film thickness uniformity, and as a result, it is possible to form a protective layer that has a high film thickness uniformity and can exhibit excellent corrosion resistance. Become.

  The treatment liquid is obtained, for example, by mixing M oxide or hydroxide particles, an acid having an oxidizing property such as nitric acid, and water, and preferably has an acidity of pH 0 to 6. According to the treatment liquid having such acidity, the magnet element body 10 is favorably dissolved, so that a film tends to be easily formed. The average particle diameter of the M oxide or hydroxide particles is preferably 1-1000 nm, and more preferably 5-100 nm. By using M oxide or hydroxide particles having such a particle size, the dispersibility of the particles in the treatment liquid becomes good, and it is possible to form a film with higher uniformity of film thickness. Become.

  Examples of the method of bringing the treatment liquid into contact with the magnet body 10 include a method of applying or spraying the treatment liquid on the magnet body 10 or immersing the magnet body 10 in the treatment liquid. Among these, the method of immersing the magnet body 10 in the treatment liquid is more preferable because a film having a uniform film thickness can be easily formed.

  The film thickness of the film containing M oxide or hydroxide is preferably in the range of 0.1 μm to 30 μm. If it is 0.1 μm or less, there is a possibility that a protective layer having sufficient corrosion resistance cannot be formed because it is too thin. On the other hand, if the thickness exceeds 30 μm, the protective layer becomes too thick, and it may be difficult to manufacture the rare earth magnet 100 with high dimensional accuracy.

Next, in the heat treatment step, the composite in which the above-described film is formed on the surface of the magnet body 10 is subjected to heat treatment, and an alloy containing R ^L , Fe and M on the surface of the magnet body 10 (R ^The protective layer 20 and the external protective layer 22 containing ( ^L— Fe—M alloy) are formed.

In such heat treatment, it is considered that the R-rich phase of the magnet body 10 is first melted. Here, R (R ^L and R ^D included as necessary) is more easily oxidized than M contained in the film formed on the surface of the composite. Therefore, when the R-rich phase melted by the heat treatment contacts the M oxide or hydroxide in the film, the M oxide or hydroxide undergoes a reduction reaction by the R-rich phase, and as a result, the M oxide Alternatively, it is considered that the R ^L —Fe—M alloy is generated in the portion where the film containing hydroxide is formed, and the protective layer 20 is formed. Then, it is considered that an external protective layer 22 further containing an oxide of ^RL is formed on the surface of the protective layer 20 due to a large amount of oxidation of the R-rich phase caused by such a reaction. In addition, the formation mechanism of the protective layer 20 and the external protective layer 22 is not necessarily limited to this.

  M is preferably an element whose standard free energy of formation of oxide at 500 ° C. is higher than that of the rare earth element (R), more preferably at least one element selected from the group consisting of Si, Al, Zn and Mn. More preferred is at least one element selected from the group consisting of Al and Zn. According to the oxide or hydroxide of M selected from these, the above-described reduction reaction easily occurs, so that the protective layer 20 and the external protective layer 22 are easily formed.

  The temperature of the heat treatment is preferably 500 ° C. or more and not more than the sintering temperature of the magnet body. By performing the heat treatment in this temperature range, the R-rich phase existing at the grain boundary in the magnet body 10 is easily melted, which is advantageous for the formation of the protective layer 20 and the external protective layer 22 by the above-described reduction reaction. . When the heat treatment temperature is too low, the reaction between the R-rich phase and the metal oxide does not sufficiently occur, and the protective layer 20 and the external protective layer 22 having excellent corrosion resistance tend to be hardly formed. Moreover, when the heat treatment temperature is too high, the magnetic properties of the magnet body 10 tend to deteriorate. In order to form the protective layer 20 and the external protective layer 22 having excellent characteristics, the heat treatment temperature is more preferably 500 to 900 ° C.

  The heat treatment time is preferably 10 to 600 minutes. When the heat treatment time is too short, there is a tendency that a sufficient protective layer is hardly formed as compared with the case where the heat treatment time is within the above numerical range. When the heat treatment time is too long, the magnetic properties tend to deteriorate as compared with the case where the heat treatment time is within the above numerical range.

  The heat treatment is preferably performed in an inert gas atmosphere such as argon or in a low-oxygen atmosphere such as vacuum, and specifically, an atmosphere having an oxygen partial pressure of 10 Pa or less is preferable. When the oxygen partial pressure during heat treatment increases, the magnetic properties tend to deteriorate due to oxidation.

  In addition, the rare earth magnet 100 obtained by the manufacturing method of the present embodiment does not necessarily include both the protective layer 20 and the external protective layer 22, and if at least the protective layer 20 is provided, the effect of suppressing the generation of rust. Can be fully demonstrated. In the manufacturing method of the present embodiment, for example, by adjusting the temperature condition and time of the heat treatment or the atmosphere in which the heat treatment is performed, the extent of the reduction reaction caused by the molten R-rich phase as described above can be controlled. Therefore, by appropriately adjusting the above conditions, it is possible to form only the protective layer 20 according to the purpose, or to form both the protective layer 20 and the external protective layer 22.

  The rare earth magnet 100 in which the protective layer 20 and the external protective layer 22 are formed on the surface of the magnet body 10 is obtained by the heat treatment described above. For the rare earth magnet 100, the magnet body 10 described above is manufactured. It is preferable to apply an aging treatment similar to the time. Due to the aging treatment, the coercive force of the rare earth magnet 100 tends to be further improved. The aging treatment temperature is preferably not more than the heat treatment temperature in the heat treatment step. It is preferable that the rare earth magnet 100 heated in such an aging treatment is further rapidly cooled at a cooling rate of 30 ° C./min or more. Thereby, the magnetic characteristics of the rare earth magnet 100 are easily improved.

By the manufacturing method as described above, the magnet body 10 containing R ^L , Fe and B, the protective layer 20 containing the R ^L -Fe-M alloy formed on the surface of the magnet body 10, and the protective layer As a result, the rare earth magnet 100 including the outer protective layer 22 including the ^RL oxide formed on the surface of the ^RL 20 is obtained. The rare earth magnet 100 thus obtained is resistant to corrosion due to the generation of rust and has high corrosion resistance even in an environment where water adheres, and thus maintains excellent magnetic properties over a long period of time. be able to. Therefore, the rare earth magnet having such characteristics is suitably used as a permanent magnet for a rotating machine that requires excellent corrosion resistance, for example.

  Next, a rotating machine according to a preferred embodiment will be described.

  FIG. 3 is an explanatory diagram showing the internal structure of the rotating machine (permanent magnet rotating machine) of the present embodiment. The rotating machine 200 of this embodiment is a permanent magnet synchronous rotating machine (SPM rotating machine), and includes a cylindrical rotor 50 and a stator 30 disposed inside the rotor 50. The rotor 50 is provided with a plurality of rare earth magnets 100 so that the north pole and the south pole are alternately arranged along the inner peripheral surface of the cylindrical core 52 and the cylindrical core 52. The stator 30 has a plurality of coils 32 provided along the inner peripheral surface. The coil 32 and the rare earth magnet 100 are arranged to face each other.

  The rotating machine 200 includes the rare earth magnet 100 according to the above-described embodiment on the rotor 50. Since the rare earth magnet 100 is excellent in corrosion resistance, it is possible to sufficiently suppress a decrease in magnetic characteristics over time. Therefore, the rotating machine 200 can maintain excellent performance for a long time. The rotating machine 200 can be manufactured by a normal method using normal rotating machine parts for parts other than the rare earth magnet 100.

  The rotating machine 200 may be an electric motor (motor) that converts electric energy into mechanical energy by the interaction between the field by the electromagnet generated by energizing the coil 32 and the field by the rare earth magnet 100. The rotating machine 200 may be a generator that converts mechanical energy into electrical energy by electromagnetic induction interaction between the field by the rare earth magnet 100 and the coil 32.

  Examples of the rotating machine 200 that functions as an electric motor (motor) include a permanent magnet DC motor, a linear synchronous motor, a permanent magnet synchronous motor (SPM motor, IPM motor), and a reciprocating motor. Examples of the motor that functions as a reciprocating motor include a voice coil motor and a vibration motor. Examples of the rotating machine 200 that functions as a generator include a permanent magnet synchronous generator, a permanent magnet commutator generator, and a permanent magnet AC generator. The rotating machine described above is used in automobiles, industrial machines, household appliances, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not necessarily limited to these Examples.

(Example 1)
According to the powder metallurgy method, the composition is 22.5 wt% Nd-5.2 wt% Pr-2.7 wt% Dy-0.5 wt% Co-0.3 wt% Al-0.07 wt% Cu-1 An ingot with 0.0 wt% B-balance Fe was prepared. The coarse powder obtained by coarsely pulverizing the ingot was pulverized by a jet mill in an inert gas to obtain a fine powder having an average particle diameter of about 3.5 μm. The fine powder was filled into a mold and pressure molded in a magnetic field to obtain a molded body. After the molded body was fired in vacuum, an aging treatment was performed to obtain a sintered body. The sintered body was cut out and processed to produce a magnet body having dimensions of 13 mm × 8 mm × 2 mm.

The surface of the obtained magnet body is degreased, then immersed in a 2% HNO ₃ aqueous solution for 2 minutes, and then subjected to ultrasonic water washing to etch the surface of the magnet body. It was.

  In addition, after diluting an aqueous silica particle dispersion (Snowtex C: manufactured by Nissan Chemical Industries) to a silica particle concentration of 20% by weight, the pH is adjusted to 2 by adding nitric acid dropwise to adjust the treatment liquid. did.

  The magnet body after the etching was immersed in the treatment liquid for 2 minutes, and then sufficiently washed with water to obtain a composite in which a film containing silica was formed on the surface of the magnet body. When the thickness of the film was confirmed by a scanning electron microscope (SEM), it was about 1 μm.

  The obtained composite was heat-treated at 600 ° C. for 60 minutes in an Ar atmosphere. Furthermore, the heat-treated composite was aged at 550 ° C. for 1 hour in an Ar atmosphere, and then rapidly cooled at 50 ° C./min, thereby producing the rare earth magnet of Example 1.

  The rare earth magnet of Example 1 was cut and the cut surface was polished with a cross section polisher. 4 is a scanning electron microscope (SEM) photograph of a cut surface of the rare earth magnet of Example 1. FIG. As shown in FIG. 4, in the rare earth magnet of Example 1, a protective layer (the layer indicated by “A1” in the figure) that covers the surface of the magnet body and an external protective layer that covers the surface of the protective layer ( In the figure, it was confirmed that a layer indicated by “A2” was formed. Furthermore, when the elemental composition in the protective layer and the external protective layer was confirmed by EPMA, the protective layer contained Nd, Pr, Fe, Si and Al, and the external protective layer contained Nd, Pr and O. It was confirmed.

Moreover, the result of having analyzed the crystal phase contained in the protective layer and the external protective layer of the rare earth magnet of Example 1 from the surface using an X-ray diffractometer (X'pert MPD: manufactured by PANalytical) is shown in FIG. . As shown in FIG. 5, it was found that the protective layer and the external protective layer contain an R ₆ Fe ₁₃ Si phase (tetragonal crystal) and an R ₂ O ₃ phase. From the above analysis, it was confirmed that R ₆ Fe ₁₃ Si was present in the protective layer and R ₂ O ₃ was present in the outer protective layer (R includes Nd and Pr).

(Example 2)
First, in the same manner as in Example 1, a magnet body was prepared, and then the surface was etched. Moreover, the treatment liquid was prepared by dispersing zinc oxide particles having an average particle diameter of 50 nm in 2-propanol and adding polyvinyl butyral as a binder.

  This treatment solution was applied to the surface of the magnet body by dip coating, and then dried at 120 ° C. for 20 minutes to obtain a composite in which a film containing zinc oxide was formed on the surface of the magnet body. When the thickness of the film was confirmed by an electron microscope, it was about 1.4 μm.

  The obtained composite was heat-treated at 550 ° C. for 180 minutes in an Ar atmosphere, and then rapidly cooled at 50 ° C./minute to produce the rare earth magnet of Example 2.

The rare earth magnet of Example 2 was analyzed for the protective layer and the external protective layer in the same manner as in Example 1. As a result, a protective layer containing R ₆ Fe ₁₃ Zn on the surface of the magnet body, R ₂ O ₃ was confirmed to be formed in this order (R includes Nd and Pr).

(Reference Example 1)
First, in the same manner as in Example 1, a magnet body was prepared, and then the surface was etched. Moreover, the treatment liquid was prepared by dissolving aluminum trisec-butoxide in 2-methoxyethanol.

  This treatment liquid was applied to the surface of the magnet body by dip coating, and then dried at 250 ° C. for 20 minutes to obtain a composite in which a film containing aluminum oxide was formed on the surface of the magnet body. When the thickness of the film was confirmed by an electron microscope, it was about 0.6 μm.

The obtained composite was heat-treated at 620 ° C. for 60 minutes in an Ar atmosphere. Further, the composite after heat treatment was aged at 550 ° C. for 1 hour in an Ar atmosphere, and then rapidly cooled at 50 ° C./minute, whereby the rare earth magnet of Reference Example 1 was produced.

The rare earth magnet of Reference Example 1 was analyzed for the protective layer and the external protective layer in the same manner as in Example 1. As a result, a protective layer containing R ₆ Fe ₁₁ Al ₃ on the surface of the magnet body, R ₂ It was confirmed that the outer protective layer containing O ₃ was formed in this order (R contains Nd and Pr).

(Comparative Example 1)
A rare earth magnet of Comparative Example 1 was produced in the same manner as in Example 1 except that the steps after the etching of the surface of the magnet body were not performed. That is, the rare earth magnet of Comparative Example 1 was produced without forming the protective layer and the external protective layer.

(Comparative Example 2)
First, in the same manner as in Example 1, a composite in which a film containing silica was formed on the surface of the magnet body was obtained. This composite was heat-treated at 400 ° C. for 60 minutes in an Ar atmosphere to produce a rare earth magnet of Comparative Example 2.

The rare earth magnet of Comparative Example 2 was analyzed for the protective layer and the like in the same manner as in Example 1. However, only the silica-containing film was confirmed, and the protective layer containing R ₆ Fe ₁₃ Si as in Example 1 was confirmed. Was not formed.

(Comparative Example 3)
First, a composite in which a film containing zinc oxide was formed on the surface of the magnet body was obtained by the same method as in Example 2. This composite was heat-treated at 400 ° C. for 60 minutes in an Ar atmosphere to prepare a rare earth magnet of Comparative Example 3.

The rare earth magnet of Comparative Example 3 was analyzed for the protective layer and the like in the same manner as in Example 1. However, only the zinc oxide particles were confirmed, and the protective layer containing R ₆ Fe ₁₃ Zn as in Example 2 was used. Was not formed.

(Comparative Example 4)
First, in the same manner as in Reference Example 1 , a composite in which a film containing aluminum oxide was formed on the surface of the magnet body was obtained. This composite was heat-treated at 400 ° C. for 60 minutes in an Ar atmosphere to prepare a rare earth magnet of Comparative Example 4.

With respect to the rare earth magnet of Comparative Example 4, the protective layer and the like were analyzed in the same manner as in Example 1. However, only the film of the aluminum oxide was confirmed, and R ₆ Fe ₁₁ Al ₃ as in Reference Example 1 was changed. The protective layer containing it was not formed.

[Evaluation of corrosion resistance]
The corrosion resistance of the rare earth magnets of each Example and Comparative Example was evaluated by a salt spray test in accordance with JIS K5600-7-1. In the salt spray test, each rare earth magnet was sprayed with 5% salt water for 5 hours in a 35 ° C. environment. And the ratio (rust area ratio) of the area of the part where red rust generate | occur | produced on the surface of each rare earth magnet after a test was computed. The rust area ratio is the ratio (unit:%) of the area where red rust has occurred to the entire surface area of the rare earth magnet. The rust area ratio was calculated by subjecting a photograph of the rare earth magnet after the salt spray test to image processing. Table 1 shows the rust area ratios obtained with the rare earth magnets of the examples and comparative examples.

As shown in Table 1, it was confirmed that the rust area ratio of the rare earth magnets of Examples 1 and 2 was significantly lower than that of the rare earth magnets of Comparative Examples 1 to 4. In particular, in the rare earth magnet of Example 1 provided with a protective layer containing R ₆ Fe ₁₃ Si, no red rust was generated after the salt spray test.

From the above, it was confirmed that the rare earth magnets of Examples 1 and 2 were significantly superior in salt corrosion resistance compared to the rare earth magnets of the comparative examples. In particular, the rare earth magnet of Example 1 was remarkably excellent in salt corrosion resistance.

  DESCRIPTION OF SYMBOLS 10 ... Magnet body, 20 ... Protective layer, 22 ... External protective layer, 30 ... Stator, 32 ... Coil, 50 ... Rotor, 52 ... Core, 100 ... Rare earth magnet, 200 ... Rotating machine.

Claims (2)

A magnet body including a light rare earth element, Fe and B, and a protective layer formed on a surface of the magnet body, wherein the protective layer includes light rare earth element, Fe, and M ( M Represents an element containing at least one element of Si or Zn ), and further includes an external protective layer containing a light rare earth element oxide on the surface of the protective layer. Rare earth magnet. A rotating machine comprising the rare earth magnet according to claim 1 .