JP4760811B2 - Rare earth magnet and manufacturing method thereof - Google Patents

Description

  The present invention relates to a rare earth magnet and a method for manufacturing the same.

  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. In recent years, in rare earth magnets, when the corrosion resistance of the magnet body itself has been improved, or when it is used for applications that do not require the corrosion resistance as in the past, it is easier and less expensive than before, to a certain extent In some cases, it is required to be able to form a protective layer capable of exhibiting the above corrosion resistance.

As an example of a rare earth magnet having such a protective layer, Patent Document 1 listed below contains aluminum fine particles and at least one component selected from chromium, molybdenum, tungsten, and phosphorus on the surface of the rare earth permanent magnet. A permanent magnet having a coating is disclosed.
JP 2002-75767 A

  By the way, although the rare earth magnet is mounted and used in various devices, the size of the rare earth magnet is inevitably limited depending on the space in which the rare earth magnet is mounted. In a rare earth magnet having a protective layer as described above, when a rare earth magnet of the same size is formed, the thinner the protective layer, the larger the size of the magnet element that actually exhibits magnetic properties. Therefore, higher magnetic characteristics can be obtained. Therefore, it is desirable that the protective layer be as thin as possible as long as the required corrosion resistance is obtained.

  However, although the rare earth magnet having a coating containing aluminum fine particles as described above can be formed at a low cost, the aluminum fine particles themselves have a size larger than a certain extent, so that they are thinned. There was a limit. For this reason, when trying to obtain a certain level of corrosion resistance, the thickness of the protective layer tends to be large, and the magnetic properties often decrease even if the corrosion resistance is sufficient.

  Therefore, the present invention has been made in view of such circumstances, and an object thereof is to provide a rare earth magnet having a protective layer that can provide sufficient corrosion resistance even when it is thin, and a method for manufacturing the same.

In order to achieve the above object, a rare earth magnet of the present invention is a rare earth magnet having a magnet body containing a rare earth element and a protective layer formed on the surface of the magnet body, wherein the protective layer is xAl. ₂ O ₃ · yP ₂ O ₅ · zH ₂ O formed from an aluminum phosphate condensation film having a composition represented by ₂ O ₃ · yP ₂ O ₅ · zH ₂ O , the protective layer being the same metal as at least one of the metal elements contained in the magnet The concentration of at least one of the metal elements further including an element and contained in the protective layer is increased from the surface side of the protective layer toward the magnet body side .

  The aluminum phosphate condensation film, which is a protective layer for the rare earth magnet of the present invention, is a film formed by condensation of aluminum phosphate, so it has a uniform and dense structure, and against contact with moisture, etc. The film shape can be sufficiently maintained even if the thickness is reduced. For this reason, the rare earth magnet of the present invention can maintain sufficient corrosion resistance, even when a thin protective layer is formed, which hardly causes intrusion of moisture or the like in the atmosphere and deterioration of the protective layer itself.

  Further, the rare earth magnet is generally mounted on various devices by being bonded to a predetermined member using an adhesive or the like, but the aluminum phosphate condensation forming the protective layer in the present invention. Since the film has a uniform and dense structure as described above, it can exhibit excellent adhesion when such adhesion is performed. Moreover, there is little decrease in adhesion due to moisture absorption or the like. Therefore, the rare earth magnet of the present invention can be very well bonded to other members.

  In the rare earth magnet of the present invention, it is preferable that the protective layer further includes the same metal element as at least one of the metal elements contained in the magnet body. If it carries out like this, a magnet element | base_body and a protective layer will contain the same metal element, and these adhesiveness will become favorable. As a result, the protective layer is very rarely peeled off from the magnet body, and it becomes easier to obtain a rare earth magnet having sufficient corrosion resistance even if the protective layer is thin.

  Furthermore, when the protective layer contains the same metal element as the magnet body, the concentration of at least one of the metal elements contained in the protective layer increases from the surface side of the protective layer toward the magnet body side. Further preferred. In this case, the content ratio of the metal element at the interface portion between the protective layer and the magnet body becomes the highest, thereby further increasing the adhesion between the two, and it becomes difficult for stress to occur in the protective layer, and the protective layer Occurrence of cracks is greatly suppressed. As a result, even a thin protective layer can provide better corrosion resistance.

The method for producing a rare earth magnet of the present invention is a method for suitably producing the rare earth magnet of the present invention, comprising a magnet element containing a rare earth element and a protective layer formed on the surface of the magnet element. A magnet body is a sintered body, a process of attaching a treatment solution made of an aqueous solution in which aluminum phosphate is dissolved in water, and a magnet body to the magnet body. deposited by condensing aluminum phosphate in the treating solution on the surface of the magnet body is formed from aluminum phosphate condensation film having a composition represented by _{xAl 2 O 3 · yP 2 O} 5 · zH 2 O A protective layer further comprising the same metal element as at least one of the metal elements contained in the magnet body, and the concentration of at least one of the metal elements contained in the protective layer is Magnetism from the surface side of the layer Characterized by a step of forming a protective layer that is larger towards the prime side.

  According to such a manufacturing method, since aluminum phosphate is adhered to the magnet body and then condensed on the surface of the magnet body to form an aluminum phosphate film, a thin but dense structure can be obtained. The aluminum phosphate condensed film can be easily formed.

  According to the present invention, it is possible to provide a rare earth magnet that has a protective layer that can provide sufficient corrosion resistance even when it is thin, and that can be satisfactorily adhered to other members, and a method for manufacturing the same.

  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.

  FIG. 1 is a perspective view showing a rare earth magnet according to a preferred embodiment of the present invention. Moreover, FIG. 2 is a figure which shows typically the cross-sectional structure which follows the II-II line | wire of the rare earth magnet shown in FIG. As shown in the figure, the rare earth magnet 1 includes a magnet body 2 and a protective layer 4 formed so as to cover the surface thereof, and has a substantially rectangular parallelepiped shape as a whole.

  First, the magnet body 2 is a permanent magnet containing a rare earth element, and a composition known as a rare earth magnet can be applied without particular limitation. The rare earth elements contained in the magnet body 2 refer to scandium (Sc), yttrium (Y), and lanthanoid elements belonging to Group 3 of the long-period periodic table. Examples of lanthanoid elements include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), and dysprosium. (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) and the like are included.

  Examples of the constituent material of the magnet body 2 include a material containing the rare earth element and a transition element other than the rare earth element in combination. In this case, the rare earth element is preferably at least one element selected from the group consisting of Nd, Sm, Dy, Pr, Ho, and Tb. These elements include La, Ce, Gd, Er, Eu, Tm, Yb, and More preferably, it further contains at least one element selected from the group consisting of Y.

  As transition elements other than rare earth elements, iron (Fe), cobalt (Co), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu) At least one element selected from the group consisting of zirconium (Zr), niobium (Nb), molybdenum (Mo), hafnium (Hf), tantalum (Ta) and tungsten (W) is preferable, and Fe and / or Co are more preferable. preferable.

  More specifically, examples of the constituent material of the magnet body 2 include R—Fe—B and R—Co materials. In the former constituent material, R is preferably a rare earth element mainly composed of Nd. In the latter constituent material, R is preferably a rare earth element mainly composed of Sm.

  As a constituent material of the magnet body 2, an R—Fe—B constituent material is particularly preferable. When the magnet body 2 is of the R—Fe—B type, excellent magnet characteristics can be obtained, and the effect of improving the corrosion resistance due to the formation of the protective layer 4 can be obtained more favorably.

  The R-Fe-B-based magnet element body 2 has a main phase with a substantially tetragonal crystal structure, and a rare earth-rich phase having a high rare earth element content in the grain boundary portion of the main phase, and boron It has a structure having a boron-rich phase with a high proportion of atoms. These rare earth-rich phase and boron-rich phase are nonmagnetic phases that do not have magnetism. Such a nonmagnetic phase is usually contained in an amount of 0.5 to 50% by volume in the magnet constituting material. Moreover, the particle size of the main phase is usually about 1 to 100 μm.

  In such R—Fe—B-based constituent materials, the rare earth element content is preferably 8 to 40 atomic%. When the rare earth element content 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 decrease. On the other hand, if it exceeds 40 atomic%, a rare earth-rich phase is excessively formed, and the residual magnetic flux density (Br) tends to be small.

  The Fe content is preferably 42 to 90 atomic%. 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 constituent materials described above, a part of Fe in the R—Fe—B system may be substituted with 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 2 tend to deteriorate.

  A part of B in the constituent material may be substituted with an element such as carbon (C), phosphorus (P), sulfur (S) or copper (Cu). By replacing a part of B in this way, the magnet body 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.

  Further, from the viewpoint of improving iHc and reducing manufacturing costs, in addition to the above-described structure, 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), Nickel (Ni), Silicon (Si) Further, elements such as gallium (Ga), copper (Cu), and hafnium (Hf) may be added. 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), and the like are conceivable as components inevitably mixed, and these are about 3 atomic% or less with respect to the total amount of constituent atoms. It may be contained in an amount of.

The protective layer 4 is composed of an aluminum phosphate condensed film. The aluminum phosphate condensed film is preferably composed of a so-called condensed phosphate obtained by dehydration condensation of aluminum phosphate as a raw material. Mainly, aluminum phosphate is bonded to phosphorus atoms. It has a high molecular weight structure that shares oxygen. Aluminum phosphate condensation coating, for example, has a _xAl 2 _O 3 _· yP composition represented by ₂ O 5 · zH ₂ O as chemical formulas. In this composition, the preferable range of x / y is 0.25 to 0.6, and more preferably 0.35 to 0.5.

  The protective layer 4 may contain metal elements such as Na, K, Mg, Ca, Sr, Ba, Zn, and Mn in addition to Al. The amount of the element contained in the protective layer 4 is, for example, XRF (X-ray fluorescence analysis), EPMA (X-ray microanalyzer method), XPS (X-ray photoelectron spectroscopy), AES (Auger electron spectroscopy) or EDS. It can be measured using a known composition analysis method such as (energy dispersive X-ray fluorescence spectroscopy).

  The thickness of the protective layer 4 formed from this aluminum phosphate condensation film is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. According to the protective layer 4 having such a thickness, excellent corrosion resistance can be obtained, and high magnetic properties can be obtained by sufficiently maintaining the size of the magnet body. If this thickness is less than 0.1 μm, sufficient corrosion resistance may not be obtained. On the other hand, when the thickness exceeds 5 μm, the ratio of the protective layer 4 in the rare earth magnet 1 becomes too large, and there is a tendency that the magnetic properties when the size is constant are lowered, and the protective layer 4 is likely to be cracked. . In applications where corrosion resistance is required rather than magnetic properties, the protective layer 4 may be thicker than the above range.

  The protective layer 4 is composed of an aluminum phosphate condensed film, and more preferably contains the same metal element as at least one of the metal elements contained in the magnet body 2. For example, the protective layer 4 preferably contains one or more of rare earth elements and transition elements contained in the magnet body 2. These metal elements may be included in the protective layer 4 in a compound state.

  In particular, the protective layer 4 preferably contains a rare earth element contained in the magnet body 2, and when the magnet body 2 is of Nd-Fe-B type, the protective layer 4 contains at least Nd, preferably It is more preferable that Nd and Fe are included. These metal elements contained in the protective layer 4 are particularly preferably metal elements derived from the magnet body 2, for example, elements that have moved from the magnet body 2 to the protective layer 4 when the rare earth magnet 1 is manufactured. .

  Thus, when the protective layer 4 contains the same kind of metal element as the magnet body 2, when the protective layer 4 is viewed in the thickness direction (thickness direction from the magnet body 2 to the surface), this metal element is It is preferable that the protective layer 4 is contained at least from the magnet element body 2 side to the region on the surface side from the middle, and to the surface of the protective layer 4 (that is, the whole of the protective layer 4 in the thickness direction). More preferably. In this case, in the protective layer 4, it is more preferable that the concentration of at least one of the above metal elements increases from the surface side toward the magnet body 2 side.

  When the protective layer 4 has such a configuration, the adhesion between the protective layer 4 and the magnet body 2 is further improved. Moreover, it becomes difficult to generate stress in the protective layer 4 and the generation of cracks is reduced. As a result, the corrosion resistance of the rare earth magnet 1 is further improved. The concentration of the metal element in the protective layer 4 can be measured by, for example, Auger electron spectroscopy. The concentration in this case refers to the ratio of the corresponding metal element to the total amount of metal element measured by such a measuring method.

  Next, a preferred embodiment of a method for manufacturing the rare earth magnet 1 having the above-described configuration will be described.

In manufacturing the rare earth magnet 1, first, the magnet body 2 is formed. The magnet body 2 can be manufactured by powder metallurgy. 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.

  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 10 hours. After firing, the obtained sintered body may be quenched. Furthermore, this sintered body is subjected to heat treatment at 500 to 900 ° C. for 1 to 5 hours in an inert gas atmosphere or in a vacuum, if necessary, or by cutting or polishing the sintered body. The magnet element body 2 is obtained by processing into a (practical shape).

  The magnet body 2 obtained in this way is appropriately washed in order to remove surface irregularities and impurities adhering to the surface. The cleaning is preferably, for example, acid cleaning using an acid solution. According to the acid cleaning, it becomes easy to obtain the magnet body 2 having a smooth surface by dissolving and removing the irregularities and impurities on the surface of the magnet body 2.

  Nitric acid is preferred as the acid used in this acid cleaning. When plating a general steel material, non-oxidizing acids such as hydrochloric acid and sulfuric acid are often used. However, when the rare earth element is contained like the magnet body 2, if these acids are used for the treatment, hydrogen generated by the acid is occluded on the surface of the magnet body 2 and the occlusion site becomes brittle. A large amount of powdery undissolved material may be generated. This powdery undissolved material is not desirable because it may cause surface roughness, defects, poor adhesion and the like after the surface treatment. Therefore, it is preferable not to include the non-oxidizing acid described above in the treatment liquid used for the acid cleaning. Therefore, in this embodiment, it is preferable to use nitric acid, which is an oxidizing acid that generates little hydrogen.

  When nitric acid is used for the acid cleaning, the nitric acid concentration in the treatment liquid is preferably 1 N or less, particularly preferably 0.5 N or less. If the concentration of nitric acid is too high, the dissolution rate of the magnet body 2 becomes too fast and it becomes difficult to control the amount of dissolution, especially in large-scale processing such as barrel processing, and it is difficult to maintain the dimensional accuracy of the product. Tend to be. On the other hand, if the nitric acid concentration is too low, the amount of dissolution tends to be insufficient. For this reason, the nitric acid concentration is preferably 1 N or less, and particularly preferably 0.5 to 0.05 N. The amount of Fe dissolved at the end of the treatment is preferably about 1 to 10 g / l.

  The amount of dissolution of the surface of the magnet body 2 by such acid cleaning is preferably 5 μm or more, preferably 10 to 15 μm in average thickness from the surface. By doing so, the altered layer and the oxide layer due to the processing of the surface of the magnet body 2 can be almost completely removed, and the desired protective layer 4 can be formed more accurately in the protective layer 4 forming step described later. Can do.

  In addition, after removing the treatment liquid used for the acid cleaning by washing with water after the above acid cleaning, the magnet body 2 has an ultra-thin structure 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, an alkaline solution, or the like that has very little chlorine ions that generate rust on the surface of the magnet body 2. After the ultrasonic cleaning, water cleaning may be performed as necessary.

After forming the magnet body 2 in this way, a treatment liquid containing aluminum phosphate is adhered to the surface of the magnet body 2. Aluminum phosphate _is a compound represented by _{xAl 2 O 3 · yP 2 O} 5 · zH 2 O, the range of x / y is preferably has a 0.25 to 0.6, 0.35 What is 0.5 is more preferable.

  Examples of the method for attaching the treatment liquid include a method in which the treatment liquid is dropped or sprayed on the surface of the magnet body 2 or the magnet body 2 is immersed in the treatment liquid. From the viewpoint of uniformly attaching the treatment liquid to the entire surface of the magnet body 2, it is preferable to immerse the magnet body 2 in the treatment liquid. Moreover, by immersing in this way, the metal element in the magnet body 2 can easily move into the treatment liquid adhered to the surface, and the same kind of metal element as the magnet body 2 as in the above-described embodiment can be obtained. It becomes easy to obtain the protective layer 4 containing. Specifically, the treatment liquid is attached by a dip spin coating method in which the magnet element body 2 is immersed in the solution and then pulled up, and the magnet element body 2 is further rotated to shake off excess treatment liquid. preferable.

  The treatment liquid is a solution in which aluminum phosphate is dissolved in a solvent, and more preferably an aqueous solution in which aluminum phosphate is dissolved in water. The concentration of aluminum phosphate in the treatment liquid is preferably 0.1 to 50% by mass and more preferably 1 to 40% by mass in terms of anhydride. If this concentration is too low, an aluminum phosphate condensation film having a sufficient molecular weight and excellent corrosion resistance tends to be hardly formed in the condensation described later. On the other hand, when this concentration is too high, the viscosity of the treatment liquid becomes too high and it tends to be difficult to form a uniform film.

  In the treatment liquid, a chelating agent may be further contained in addition to aluminum phosphate. By further containing a chelating agent, a more uniform and dense aluminum phosphate condensed film can be formed. When adding a chelating agent, it is preferable that the quantity is 10-150 mass parts with respect to 100 mass parts of aluminum phosphates.

  As the chelating agent, a phosphonic acid chelating agent or an oxycarboxylic acid chelating agent is suitable. Examples of the phosphonic acid chelating agent include aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and salts thereof. Can be mentioned. Examples of the oxycarboxylic acid chelating agent include oxalic acid, citric acid, malic acid, gluconic acid, malonic acid and salts thereof.

  In addition to the aluminum phosphate and the chelating agent, an additive component suitable for the protective layer 4 may be further contained in the treatment liquid. For example, these metal elements may be contained in the protective layer 4 by separately adding a compound of the same metal element as the magnet body 2 into the treatment liquid.

  After the treatment liquid as described above is attached to the surface of the magnet body 2, the aluminum phosphate in the treatment liquid attached to the surface is condensed. This condensation is dehydration condensation of aluminum phosphate, and can be caused by, for example, heat-treating the magnet body 2 to which the treatment liquid is attached. When condensation is caused by heating, the heat treatment temperature is preferably 150 to 500 ° C, more preferably 150 to 350 ° C. If the temperature is too low, condensation tends not to occur sufficiently, and if it is too high, the magnetic properties tend to deteriorate. The heat treatment time is preferably 1 minute to 6 hours, and more preferably 5 minutes to 2 hours.

  By such condensation, the aluminum phosphate in the treatment liquid adhering to the surface of the magnet body 2 is condensed, and the solvent in the treatment liquid is volatilized and removed. As a result, the protection made of the aluminum phosphate condensation film A layer is formed. As a result, the rare earth magnet 1 having the configuration of the above-described embodiment is obtained.

  The preferred embodiments of the present invention have been described above. However, the present invention is not necessarily limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.

  For example, the structure of the rare earth magnet of the present invention is not limited to that of the above-described embodiment, and may further include another protective layer on the surface of the protective layer 4 made of an aluminum phosphate condensed film. Further, the shape of the rare earth magnet is not limited to a rectangular parallelepiped shape, and may have various shapes such as a cubic shape and a cylindrical shape.

  Furthermore, in the method for producing a rare earth magnet, the formation mechanism of the aluminum phosphate condensation film is not necessarily limited to dehydration condensation, and may be other condensation reactions.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Manufacture of rare earth magnets]

Example 1
First, an ingot having a composition of 27.6Nd-4.9Dy-0.5Co-0.4Al-0.07Cu-1.0B-remaining Fe (numbers represent weight percentage) is produced by powder metallurgy. This was coarsely pulverized. Thereafter, jet milling with an inert gas was performed to obtain a fine powder having an average particle size of about 3.5 μm. The obtained fine powder was filled in a mold and molded in a magnetic field. Next, after sintering in vacuum, heat treatment was performed to obtain a sintered body. The obtained sintered body was cut into a size of 20 mm × 10 mm × 2 mm and processed to obtain a magnet body. Next, the obtained magnet body was degreased and then subjected to ultrasonic cleaning.

  Thereafter, an aluminum phosphate aqueous solution (Taki Alpha WR-100 manufactured by Taki Chemical Co., Ltd.) was prepared as a treatment liquid, and this was applied to the surface of the magnet body by the dip spin coating method. Then, the magnet body to which the treatment liquid was adhered was heat-treated at 180 ° C. for 1 hour to obtain a rare earth magnet having a protective layer made of an aluminum phosphate condensed film on the surface of the magnet body. The thickness of this protective layer was about 0.7 μm.

  The thus obtained rare earth magnet of Example 1 was analyzed for the profile in the depth direction of the elements contained in the protective layer by Auger electron spectroscopy (SAM680 manufactured by ULVAC-PHI). As a result, it was confirmed that the protective layer contained Fe and Nd. The analysis result by this Auger spectroscopy is shown in FIG. In FIG. 3, the horizontal axis represents the sputtering time of the rare earth magnet by Ar ions, which is proportional to the depth from the surface. The vertical axis indicates the concentration of each element calculated from the intensity of each element measured at the corresponding sputtering time. However, since the device sensitivity coefficient of each element is used for this calculation, the ratio between different elements may not always be accurate. In this analysis, it is considered that the protective layer is analyzed at a sputtering time of 0 to 22 minutes, and the magnet body is analyzed at a sputtering time of 37 minutes or more. Moreover, it is thought that the time between these is measuring either a protective layer or a magnet body by a place by the influence of surface roughness.

  From FIG. 3, it was confirmed that the concentration of Nd and Fe gradually increased from the surface of the protective layer toward the interface with the magnet body.

(Comparative Example 1)
First, a magnet body was produced in the same manner as in Example 1. Next, No. 3 water glass was prepared as a treatment liquid, and this was applied to the surface of the magnet body by dip spin coating. Then, the magnet body to which the treatment liquid was attached was heat-treated at 150 ° C. for 20 minutes to form a protective layer on the surface of the magnet body, thereby obtaining a rare earth magnet. The thickness of this protective layer was about 0.7 μm.

(Comparative Example 2)
First, a magnet body was produced in the same manner as in Example 1. Next, this magnet body was immersed in a zinc phosphate chemical conversion treatment liquid as a processing liquid, thereby obtaining a rare earth magnet having a protective layer made of a zinc phosphate chemical conversion coating on the surface of the magnet body. The thickness of this protective layer was about 20 μm.

(Comparative Example 3)
First, a magnet body was produced in the same manner as in Example 1. Further, a treatment liquid in which 800 g of aluminum fine particles were uniformly dispersed in 1 liter of water and 90 g of chromic anhydride, 330 g of phosphoric acid, and 72 g of magnesium oxide were dissolved was prepared. Next, this treatment liquid was applied to the surface of the magnet body by a spray method. Then, the magnet body to which the treatment liquid was attached was heat-treated at 350 ° C. for 1 hour to form a protective layer on the surface of the magnet body to obtain a rare earth magnet. The thickness of this protective layer was about 1 μm.
[Characteristic evaluation]

(Salt spray test)
A salt spray test at 35 ° C. using 5% salt water was performed on the rare earth magnets of Example 1 and Comparative Examples 1 to 3 in accordance with JIS K5600-7-1.

  As a result, in the rare earth magnet of Example 1, no rust was observed even after 24 hours had elapsed from the start of the test. On the other hand, rust was observed after 8 hours for the rare earth magnet of Comparative Example 1, after 3 hours for the rare earth magnet of Comparative Example 2, and after 8 hours for the rare earth magnet of Comparative Example 3.

(Adhesion test)
An aluminum stud pin having a diameter of 4.1 mm was bonded to the rare earth magnets of Example 1 and Comparative Examples 1 to 3 using an epoxy adhesive, and the adhesive was heated and cured. Each of the bonded rare earth magnets was left in an atmosphere of 60 ° C. and 95% RH for 24 hours, and then a tensile test was performed to peel the stud pin from the rare earth magnet.

  As a result, in the rare earth magnets of Example 1 and Comparative Example 2, the stud pin did not peel off even when a force of 500 N was applied, whereas the rare earth magnet of Comparative Example 1 was 270 N, and the rare earth magnet of Comparative Example 3 was 350 N. In each case, peeling occurred.

It is a perspective view which shows the rare earth magnet which concerns on suitable embodiment of this invention. It is a figure which shows typically the cross-sectional structure which follows the II-II line | wire of the rare earth magnet shown in FIG. It is a figure which shows the analysis result by the Auger spectroscopy of the protective layer of the rare earth magnet of Example 1.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Rare earth magnet, 2 ... Magnet base body, 4 ... Protective layer.

Claims (4)

A rare earth magnet having a magnet body containing a rare earth element and a protective layer formed on the surface of the magnet body,
The protective layer _is formed from aluminum phosphate condensation film having a composition represented by _{xAl 2 O 3 · yP 2 O} 5 · zH 2 O,
The protective layer further includes the same metal element as at least one metal element included in the magnet element body, and the concentration of at least one metal element included in the protective layer is the protection element A rare earth magnet , wherein the size increases from the surface side of the layer toward the magnet body side . The magnet body is a sintered body;
The aluminum phosphate condensation film is xAl ₂ O ₃ ・ YP ₂ O ₅ ・ ZH ₂ The rare earth magnet according to claim 1, wherein the rare earth magnet has a composition represented by O and a range of x / y in the range of 0.25 to 0.6. The rare earth magnet according to claim 1, wherein the protective layer contains Nd and Fe as the same metal element as at least one of the metal elements contained in the magnet body. A method for producing a rare earth magnet having a magnet body containing a rare earth element, and a protective layer formed on the surface of the magnet body,
The magnet body is a sintered body,
Attaching a treatment liquid comprising an aqueous solution in which aluminum phosphate is dissolved in water to the magnet body;
Said aluminum phosphate in the treatment solution attached on the magnet body are condensed on the surface of the magnet _body, phosphorus having a composition represented by _{xAl 2 O 3 · yP 2 O} 5 · zH 2 O A protective layer formed from an aluminum oxide condensation film , further comprising at least one metal element of the metal elements contained in the magnet body, and among the metal elements contained in the protective layer A step of forming a protective layer in which at least one concentration of the protective layer increases from the surface side of the protective layer toward the magnet body side ;
A method for producing a rare earth magnet, comprising:

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