Abstract:
Provided is a method for producing an RFeB-based magnet, the method including: disposing a nozzle so as to be opposed to an attachment surface of a base material that is a sintered magnet or hot-plastic worked magnet composed of an RFeB-based magnet containing a light rare earth element R L  that is at least one element selected from the group consisting of Nd and Pr, Fe, and B; ejecting a mixture, from the nozzle, obtained by mixing an organic solvent and an R H -containing powder containing a heavy rare earth element R H  that is at least one element selected from the group consisting of Dy, Tb and Ho so as to attach the mixture to the attachment surface; and heating the base material together with the mixture.

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention relates to a method for producing an RFeB-based magnet that contains R (R is a rare earth element), Fe, and B. More specifically, the present invention relates to a method for producing an RFeB-based magnet which includes a process (grain boundary diffusion process) of diffusing at least one element selected from the group consisting of Dy, Tb and Ho (hereinafter, at least one element selected from the group consisting of Dy, Tb and Ho is referred to as “heavy rare earth element R H ”) to the vicinity of surfaces of main phase grains that contain at least one element selected from the group consisting of Nd and Pr (hereinafter, at least one element selected from the group consisting of Nd and Pr is referred to as “light rare earth element R L ”) as a main rare earth element R through a grain boundary of the main phase grains. 
       BACKGROUND OF THE INVENTION 
       [0002]    A RFeB-based magnet was found by Sagawa et. al in 1982, and has an advantage that many magnetic properties such as residual magnetic flux density are higher than those of permanent magnets in the related art. Accordingly, the RFeB-based magnet has been used in various products such as a drive motor of a hybrid car and an electric car, a motor for electrically-assisted bicycles, an industrial motor, a voice coil motor of a hard disk drive and the like, a high-performance speaker, a headphone, and a permanent magnet-type magnetic resonance diagnostic device. 
         [0003]    Early RFeB-based magnets have a defect that among various magnetic properties, a coercive force H cj  is relatively low. However, it has been found that the coercive force is improved by making the heavy rare earth element R H  be present inside the RFeB-based magnets. The coercive force is a force that resists inversion of magnetization when a magnetic field in a direction opposite to a direction of the magnetization is applied to a magnet, but it is considered that the heavy rare earth element R H  hinders the inversion of magnetization and thus has an effect of increasing the coercive force. 
         [0004]    When examining a magnetization inversion phenomenon in the magnet in detail, there is a characteristic that the magnetization inversion occurs at first in the vicinity of a grain boundary of crystal grains and is diffused to the inside of the crystal grains therefrom. Therefore, in a case where the magnetization inversion at the grain boundary is blocked at first, it is effective for prevention of the magnetization inversion of the entirety of the magnet, that is, an increase in the coercive force. Accordingly, the heavy rare earth element R H  should be present in the vicinity of the grain boundary of the crystal grains. 
         [0005]    On the other hand, when considering the entirety of main phase grains, if an amount of the R H  increases, a residual magnetic flux density B r  decreases, and thus there is a problem that the maximum energy product (BH) max  also decreases. In addition, the R H  is a rare resource and is expensive, and a production area is localized, and thus it is not preferable to increase the amount of R H . Accordingly, it is preferable that the R H  is present in a small amount at the inside of the crystal grains, and be present in a large amount (unevenly distributed) in the vicinity of a surface (in the vicinity of the grain boundary) to increase the coercive force (to prevent a reverse magnetic domain from being formed as much as possible) while suppressing the amount of R H  as much as possible. 
         [0006]    As a method of unevenly distributing the R H  in the vicinity of the surface rather than the inside of the crystal grains, a grain boundary diffusion method is known (for example, refer to Patent Document 1 and Patent Document 2). In the grain boundary diffusion method, a powder, which contains the R H  as an elementary substance, a compound, or an alloy (hereinafter, a powder that contains the R H  is referred to as “R H -containing powder” regardless of the type such as the elementary substance, the compound, and the alloy), and the like is attached to a surface of the RFeB-based magnet, and the RFeB-based magnet is heated. According to this, the R H  penetrates to the inside of the magnet through the grain boundary of the RFeB-based magnet, and thus atoms of the R H  are diffused only in the vicinity of the surface of the crystal grains. Hereinafter, an RFeB-based magnet before performing the grain boundary diffusion process is referred to as a “base material” and is discriminated from an RFeB-based magnet after performing the grain boundary diffusion process. 
         [0007]    There are various methods of attaching the R H -containing powder to the base material. Patent Document 1 discloses that the base material is immersed in a turbid solution in which TbF 3  powder that is an R H -containing powder and ethanol are mixed, and then the base material is pulled up from the turbid solution and is dried, thereby attaching the R H -containing powder to the surface of the base material. However, in this method, it is difficult to control an amount of the R H -containing powder that is attached to the surface of the base material, and it is also difficult to uniformly attach the R H -containing powder to the surface of the base material in an arbitrary thickness. Therefore, the rare and expensive R H -containing powder is consumed more than necessary. 
         [0008]    On the other hand, Patent Document 2 discloses a method of applying (attaching) a mixture obtained by mixing the R H -containing powder and an organic solvent to the surface of the base material by using a screen printing method. Specifically, a plurality of flat plate-shaped base materials are arranged, and a screen in which a plurality of transmission portions capable of transmitting the mixture therethrough are provided in correspondence with the position of the base materials is extended on the surface of the base material. The mixture is supplied on the screen, and then a surface of the screen is scrubbed with a squeegee, thereby attaching the mixture to the surface of the base material through the screen at the transmission portions. Accordingly, it is possible to apply the mixture to the surface of the respective base materials in a uniform thickness, and thus the R H -containing powder is not consumed more than necessary. 
         [0009]    In addition, the RFeB-based magnet is largely classified into (i) a sintered magnet obtained by sintering a raw material alloy powder containing a main phase grain as a main component, (ii) a bonded magnet obtained by consolidating raw material alloy powders with a binding agent (binder composed of an organic material such as a polymer and an elastomer) and by molding the consolidated powders, and (iii) a hot-plastic worked magnet obtained by performing a hot press working and hot plastic working with respect to a raw material alloy powder (refer to Non-Patent Document 1). 
         [0010]    Among these magnets, the grain boundary diffusion process may be performed in (i) sintered magnet and (iii) hot-plastic worked magnet in which the binder of the organic material is not used and thus heating during the grain boundary diffusion process can be performed. 
         [0011]    [Patent Document 1] JP-A-2006-303433 
         [0012]    [Patent Document 2] WO2011/136223 
         [0013]    [Patent Document 3] JP-A-2006-019521 
         [0014]    [Non-Patent Document 1] “Development of Dy-omitted Nd—Fe—B-based hot worked magnet by using a rapidly quenched powder as a raw material” written by Hioki Keiko and Hattori Atsushi, Sokeizai, Vol. 52, No. 8, pages 19 to 24, General Incorporation Foundation Sokeizai Center, published on August, 2011. 
       SUMMARY OF THE INVENTION 
       [0015]    A target of Patent Document 2 is a flat plate-shaped base material, and thus a surface of the base material to which the mixture is applied is a planar surface. However, typically, a shape of the magnet is not limited to the flat plate shape. For example, in a rotor of a motor in which the RFeB-based magnet is frequently used, a plurality of the RFeB-based magnets are arranged in a rotational direction, and a magnet, in which a surface facing an inner surface of a stator is formed in a convex arc shape in correspondence with a shape of the inner surface of the stator, is used as the RFeB-based magnets. In the RFeB-based magnet for motors, to impart uniform magnetic properties, particularly, to the entirety of the arc-shaped surface that faces the stator, it is necessary for the mixture to be uniformly applied to the surface. However, in the screen printing method disclosed in Patent Document 2, the plurality of base materials are arranged, and then the screen printing is performed. Therefore, in a case where the surface of each of the base materials is a curved surface, it is difficult to apply the mixture to the surface of the base material in a uniform thickness. 
         [0016]    An object of the present invention is to provide a method for producing an RFeB-based magnet which is capable of attaching a mixture obtained by mixing an R H -containing powder and an organic solvent to a surface of a magnet base material in a grain boundary diffusion process even when the surface of the magnet base material is a nonplanar surface, and which is capable of uniformly attaching the mixture to the surface of the base material of the magnet in an arbitrary thickness regardless of a planar surface and a nonplanar surface. 
         [0017]    In order to solve the above-mentioned problems, the present invention provides a method for producing an RFeB-based magnet, the method including: disposing a nozzle so as to be opposed to an attachment surface of a base material that is a sintered magnet or hot-plastic worked magnet composed of an RFeB-based magnet containing a light rare earth element R L  that is at least one element selected from the group consisting of Nd and Pr, Fe, and B; ejecting a mixture, from the nozzle, obtained by mixing an organic solvent and an R H -containing powder containing a heavy rare earth element R H  that is at least one element selected from the group consisting of Dy, Tb and Ho so as to attach the mixture to the attachment surface; and heating the base material together with the mixture. 
         [0018]    In the present invention, the mixture is ejected from the nozzle, thereby attaching the mixture to the attachment surface. As a result, an operation may be performed in a non-contact manner with respect to the attachment surface of the base material, and thus there is no restriction in accordance with the shape of the attachment surface. Accordingly, it is also possible to uniformly attach the mixture in an arbitrary thickness to a nonplanar attachment surface such as an arc-shaped surface in an RFeB-based magnet that is used as rotor of a motor. 
         [0019]    On the other hand, different amounts of the mixture may be attached to the attachment surface based on each position on the attachment surface. 
         [0020]    The coercive force may locally decrease in the RFeB-based magnet in accordance with a shape of the attachment surface due to the following reason. In this case, it is preferable to attach a greater amount of the mixture to the attachment surface corresponding to the position at which the coercive force decreases. According to the method of the present invention, it is possible to easily adjust the attached amount of the mixture in accordance with the position on the attachment surface. As the reason of the local decrease in the coercive force, the following situations and the like may be exemplified. Firstly, a demagnetizing field due to magnetization, which is a cause of a decrease in the coercive force, becomes locally strong at a position at which a thickness in a magnetization direction is smaller than that of other positions. Secondly, temperature rising, which is a cause of the decrease in the coercive force, locally increases in accordance with the shape of the RFeB-based magnet due to an eddy current that is generated in the RFeB-based magnet along with a variation in an external magnetic field during use. 
         [0021]    In addition, a heating temperature may be substantially the same as a temperature in heating that is performed in a grain boundary diffusion process of the related art. Typically, the heating temperature is approximately 800° C. to 950° C., but may be in other temperature ranges as long as the grain boundary diffusion is realized. 
         [0022]    In the present invention, it is preferable that silicone grease is used as the organic solvent. Silicone is a polymer expressed by General Formula X 3 SiO—(X 2 SiO) n —SiX 3  (in which X represents organic groups, and it is not necessary for respective organic groups to be the same as each other), and has a main chain having a “siloxane bonds” in which a Si atom and an O atom are alternately coupled. When the silicone grease is used as the solvent in the mixture, adhesion of the mixture to the base material increases. Accordingly, when performing heating to diffuse the R H  to the grain boundary of the base material, it is possible to prevent the mixture from being peeled from the attachment surface. 
         [0023]    The smaller the maximum particle size of the R H -containing powder is and the lower a viscosity of the mixture is, the easier the mixture passes through the nozzle. Accordingly, it is preferable that a ratio of the maximum particle size of the R H -containing powder to a diameter of the nozzle is 0.15 or less, and more preferably 0.10 or less. In addition, with regard to the maximum particle size, a different value is obtained in accordance with a measurement method. However, in the present specification, a value that is measured by a laser diffraction type particle size distribution measuring method is used. In addition, it is preferable that the viscosity of the mixture is 30 Pa˜s or less, more preferably 10 Pa·s or less, and still more preferably 5 Pa˜s or less. 
         [0024]    According to the present invention, in a grain boundary diffusion process, it is possible to uniformly attach a mixture obtained by mixing an R H -containing powder and an organic solvent to a nonplanar attachment surface of a base material in an arbitrary thickness in a non-contact manner. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0025]      FIG. 1  is a schematic configuration view illustrating a mixture supply apparatus that is used in a method for producing an RFeB-based magnet according to Examples. 
           [0026]      FIG. 2  is a perspective view illustrating a shape of a base material of the RFeB-based magnet that is manufactured in Examples. 
           [0027]      FIGS. 3A and 3B  are views illustrating an example of a mixture attaching position in the base material of the RFeB-based magnet that is manufactured in Examples. 
           [0028]      FIG. 4  is a perspective view illustrating another example of the shape of the base material. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0029]    Examples of a method for producing an RFeB-based magnet according to the present invention will be described with reference to  FIGS. 1 to 4 . 
       EXAMPLES 
       [0030]      FIG. 1  illustrates a schematic configuration of a mixture supply apparatus  10  that is used to attach a mixture of the R H -containing powder and an organic solvent to a nonplanar attachment surface  21  of a base material  20  of an RFeB-based magnet in a method for producing the RFeB-based magnet according to Examples. The mixture supply apparatus  10  includes a base material holding unit  11 , a nozzle head  12 , a base material transporting unit  13 , and a mixture supply unit  14 . 
         [0031]    The base material holding unit  11  holds the base material  20  in a state in which the attachment surface  21  faces an upper side. In Examples, as the base material holding unit  11 , a plate-shaped member, in which a concave portion having a planar shape that is slightly larger than a lower surface  22  of the base material  20  is provided on an upper surface, is used. One piece of the base material  20  is shown in  FIG. 1 , but a plurality of the base materials  20  may be held by one base material holding unit  11 . In this case, the plurality of base materials  20  may be arranged in a depth direction or in a right and left direction of  FIG. 1 . In addition, the plurality of base materials  20  may be two-dimensionally arranged in both of the depth directions and the right and left directions. 
         [0032]    The nozzle head  12  includes a plurality of nozzles  121 , an ejection device (not shown) that is attached to each of the nozzles  121 , and a controller (not shown) that controls the ejection device. The nozzle head  12  is disposed so as to be opposed to the attachment surface  21  of the base material  20  that is held by the base material holding unit  11 . A plurality of nozzles  121  are disposed to the nozzle head  12  to cover the entirety of the attachment surface  21 . In  FIG. 1 , the plurality of nozzles  121  are shown to be arranged only in a transverse direction, but actually, the plurality of nozzles  121  are also arranged in the depth direction of the drawing in the same way. In addition, the number of the nozzle heads  12  is appropriately changed in accordance with the number of the base materials  20 . For example, in a case where the plurality of base materials  20  are held by one base material holding unit  11 , the nozzle head  12  may also be provided in the same number as that of the base materials  20  so as to be opposed to the attachment surface  21  of each of the base materials  20 . The ejection device is provided with a pneumatic or electromagnetic solenoid type actuator. In the ejection device, when a signal is transmitted to the actuator from the controller, a valve element or a piston moves, thereby extruding a mixture  30  from each of the nozzles  121 . In addition, as the actuator, a piezo element (piezoelectric element) may be used. In addition, the number of the nozzles  121  that are used in one nozzle head  12  is appropriately changed in accordance with the size of each of the base materials  20  and an application area. For example, the nozzle head  12  may be set as a single nozzle having only one nozzle  121  instead of a multi-nozzle having a plurality of nozzles  121  as shown in  FIG. 1 . 
         [0033]    The base material transporting unit  13  sequentially transports the base material holding unit  11  that holds the base material  20  to a position immediately below the nozzle head  12 , and transports the base material holding unit  11  after the mixture is applied to the attachment surface  21  to another position from the position immediately below the nozzle head  12 . In Examples, a belt conveyor is used as the base material transporting unit  13 , but an XY stage, a robot arm, and the like may be used. 
         [0034]    The mixture supply unit  14  includes a mixture tank  141  that stores the mixture  30  of the R H -containing powder and the organic solvent, and a supply tube  142  that supplies the mixture  30  from the mixture tank  141  to each of the nozzles  121 . 
         [0035]    Operation of the mixture supply apparatus  10  will now be described. The base material holding unit  11  in which the base material  20  is held in a state in which the attachment surface  21  faces an upper side is moved by the base material transporting unit  13  in such a manner that the attachment surface  21  is disposed immediately below the nozzle head  12 . Next, when receiving an electrical signal from a driver, the ejection device ejects the mixture  30  from the nozzle  121  toward the attachment surface  21 , whereby the mixture  30  is attached to the attachment surface  21 . Then, the base material transporting unit  13  moves the base material holding unit  11 , which is positioned immediately below the nozzle head  12 , from the position, and moves the subsequent base material holding unit  11  to the position. A process of sequentially attaching the mixture  30  to the attachment surface  21  of the plurality of base materials  20  is performed by repeating the above-described operation. 
         [0036]    In addition, the mixture supply apparatus  10  uses the nozzle head  12  in which the plurality of nozzles  121  are disposed to cover the entirety of the attachment surface  21 , but the nozzle head  12  is appropriate for mass production of the RFeB-based magnet by using the base materials  20  which have the attachment surface  21  of the same shape. On the other hand, in a case of handling a plurality of kinds of base materials  20 , in which the shape of the attachment surface  21  is different in each case, with one mixture supply apparatus, or in a case of partially attaching the mixture  30 , a nozzle head which is movable in the right and left directions and/or the depth direction in  FIG. 1 , and in which the number of the nozzles  121  is reduced in comparison to that shown in the same drawing may be used as the nozzle head  12 . That is, it is possible to uniformly supply the mixture  30  even to the attachment surface  21  having a different shape by supplying the mixture  30  to the attachment surface  21  while moving the nozzle head  12  in accordance with the shape of the attachment surface  21 . 
         [0037]    Next, the shape of the base material  20  of the RFeB-based magnet which is used in Examples is shown in  FIG. 2 . The base material  20  that is used in Examples has a rectangular lower surface  22  in which the length of a long side  201  is 16 mm and the length of a short side  202  is 14 mm, first and second side surfaces  231  and  232  which erect from two long sides  201  and are opposite to each other, third and fourth side surfaces  233  and  234  which erect from two short sides  202  and are opposite to each other, and an upper surface  21  that is opposite to the lower surface  22 . The upper surface  21  has an upwardly convex arc shape in a cross-section that is parallel with the short side  202  of the lower surface  22 , and the cross-sectional shape is the same regardless of a position in a direction parallel with the long side  201  of the lower surface  22 . A radius of curvature of the arc in the cross-section is R32 mm, and a height (a distance between the upper surface  21  and the lower surface  22 ) is 4.7 mm at opposite ends of the cross-section and 5.7 mm at the central portion thereof. In correspondence with the shape of the upper surface  21 , the first and second side surfaces  231  and  232  have a rectangular shape, and the third and fourth side surfaces  233  and  234  have an upwardly convex shape. 
         [0038]    The base material  20  was prepared by the following sintering method. First, flake-shaped alloy pieces having a thickness of approximately 0.3 mm were prepared from an alloy having a composition of Nd: 25.8, Pr: 4.7, Dy: 0.3, B: 0.99, Co: 0.9, Cu: 0.1, Al: 0.2, and Fe: the remainder in terms of a weight percentage by a strip cast method. Next, the flake-shaped alloy pieces were crushed by a known hydrogen crushing method, thereby preparing an irregular powder of the alloy which has a size of approximately 0.1 mm to 1 mm. Continuously, the irregular powder was pulverized by a jet mill apparatus, thereby preparing an alloy fine powder having a particle size of approximately 3 μm. The obtained alloy fine powder was filled in a mold having a cavity corresponding to the shape of the base material  20 . Next, the alloy fine powder inside the mold was oriented in a magnetic field as is without compression molding. In addition, in a state in which the alloy fine powder after the orientation was filled in the mold, heating was performed in vacuo until the temperature reached 1000° C. without performing the compression molding, and the alloy fine powder was retained at the temperature for 4 hours, thereby sintering the alloy fine powder. According to this, the base material  20  was obtained. In addition, the method of preparing the RFeB-based sintered magnet in this manner without performing the compression molding is called a PLP (Press-less Process) method, and is known as a method which is capable of increasing the coercive force while suppressing a decrease in the residual magnetic flux density and which is capable of obtaining a sintered body having a shape corresponding to the shape of the cavity of the mold. Details of the PLP method are described in Patent Document 3. 
         [0039]    Next, the mixture  30  of the R H -containing powder and the organic solvent will now be described. The mixture  30 , which is used in Examples, contains Tb as the R H  and also contains silicone grease as the organic solvent. The mixture  30  was prepared as follows. First, a TbNiAl alloy containing Tb, Ni, and Al in a weight ratio of 92:4.3:3.7 was pulverized, thereby preparing a Tb-containing powder (R H -containing powder). Next, the obtained Tb-containing powder, the silicone grease, a silicone fluid, and methyl laurate as a dispersing agent were mixed in the following mixing ratio, thereby obtaining the mixture  30 . As the mixture  30 , a plurality of kinds of mixtures, in which the maximum particle size of the Tb-containing powder and the mixing ratio were different in each case, were prepared. In addition, in Example 1 to be described later, the silicone fluid was not used. In addition, the silicone fluid was added to adjust a viscosity of the mixture  30 , and the dispersing agent was added to increase dispersibility of the Tb-containing powder in the mixture  30 . The silicone fluid and the dispersing agents are not requisite in the present invention. 
         [0040]    The mixture  30  was ejected from the nozzle  121  in a state in which the upper surface  21  of the base material  20  obtained as described was set as the attachment surface, thereby attaching the mixture  30  to the attachment surface. Similarly, the mixture  30  was also attached to the lower surface  22  of the base material  20 . Here, an experiment was performed using four examples (Examples 1 to 4) in which the mixing ratio in the mixture  30 , the maximum particle size of the Tb-containing powder, the viscosity of the mixture  30 , and the diameter of the nozzles were different in each case. 
         [0041]    Experiment conditions and results are shown in Table 1. In addition, in Table 1, with regard to the mixing ratio, the total content rate of the Tb-containing powder, the silicone grease, and the silicone fluid was set to 100% by weight for convenience, and a content rate of the dispersing agent having a content rate lower than that of these three kinds was expressed as a ratio with respect to the total weight of these three kinds. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Mixtures that were prepared, and results of an experiment of attaching 
               
               
                 the mixtures to the attachment surface of the base material 
               
             
          
           
               
                   
                 Mixing ratio 
                 Maximum particle size of 
                 Viscosity (room 
                   
                   
                   
                   
               
               
                   
                 (weight ratio) 
                 Tb-containing powder 
                 temperature) 
                 Diameter φ of 
                   
                 Clogging 
                 Film thickness 
               
               
                   
                 (TB:G:O:L) 
                 R max  [μm] 
                 [Pa · s] 
                 nozzle [μm] 
                 R max /φ 
                 of nozzle 
                 of mixture [μm] 
               
               
                   
                   
               
             
          
           
               
                 Example 1 
                 80:20:0:0.2  
                 30 
                 25 
                 200 
                 0.15 
                 None 
                 516 
               
               
                 Example 2 
                 80:10:10:0.2 
                 20 
                 2 
                 200 
                 0.10 
                 None 
                 103 
               
               
                 Example 3 
                 80:10:10:0.2 
                 10 
                 10 
                 150 
                 0.067 
                 None 
                 48 
               
               
                 Example 4 
                 75:10:15:0.2 
                 10 
                 1 
                 100 
                 0.10 
                 None 
                 28 
               
               
                   
               
               
                 TB: Tb-containing powder, 
               
               
                 G: Silicone grease, 
               
               
                 O: Silicone fluid, 
               
               
                 L: Dispersing agent 
               
             
          
         
       
     
         [0042]    As a result of the experiment, in all Examples, the mixture  30  could be attached to not only the flat lower surface  22  but also the nonplanar upper surface  21  in an approximately uniform thickness. In addition, a film thickness of the mixture  30  that was attached to the attachment surface could be adjusted in a broad range of 28 μm to 516 μm. Here, the smaller the diameter of the nozzle was and the lower the viscosity of the mixture  30  was, the less an ejected amount of the mixture  30  was, and thus it was possible to make the film thickness small. As the amount of the Tb-containing powder is small, as the amount of the silicone grease having a high viscosity is small, or as the amount of silicone fluid having a low viscosity is large, the viscosity of the mixture  30  can be made to be lower. In addition, in all Examples, clogging of the nozzle (clogging due to the mixture  30 ) did not occur. However, in a case where the clogging of the nozzle occurs, adjustment may be performed in such a manner that the viscosity of the mixture  30  decreases, or the diameter of the nozzle increases. 
         [0043]    With regard to Examples 1 to 4, the base material  20  in which the mixture  30  was attached to the upper surface (attachment surface)  21  was heated in vacuo at 900° C. for 10 hours in order for the mixture  30  to be supplied to the vicinity of the surface of crystal grains through a grain boundary thereof Then, the base material  20  was subject to an aging process of performing heating at a temperature of 500° C. for 3 hours, and a magnetizing process of applying a magnetic field of 4.5 T in a thickness direction of the base material  20 , thereby obtaining an RFeB-based magnet that is a final product. 
         [0044]    Next, magnetic properties of the RFeB-based magnet that was obtained in Examples 1 to 4, and an RFeB-based magnet that was obtained in Reference Example to be described below were measured. In Reference Example, the mixture was applied in a thickness of 32 μm to an upper surface and a lower surface of a rectangular parallelepiped, which has a thickness of 6 mm and in which the upper surface and the lower surface have a rectangular shape having long sides of 16 mm and short sides of 14 mm, by using a screen printing method. A mixture, in which the mixing ratio of the Tb-containing powder, the silicone grease, the silicone fluid, and the dispersing agent was 80:10:10:0.2 (weight ratio), and the maximum value of the particle size of the Tb-containing powder was 30 μm, was used as the mixture in Reference Example. With regard to measurement of the magnetic properties, test specimens of 7 mm×7 mm×4 mm were cut from the RFeB-based magnets which were obtained in Examples 1 to 4 and Reference Example, and measurement on a residual magnetic flux density and a coercive force at room temperature was performed with respect to the test specimens by using a BH tracer. Measurement results of the magnetic properties are shown in Table 2. 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Magnetic properties of specimens that were prepared 
               
             
          
           
               
                   
                 Residual magnetic flux 
                 Coercive force 
               
               
                   
                 density B r [kG] 
                 H cj  [kOe] 
               
               
                   
                   
               
             
          
           
               
                   
                 Example 1 
                 14.1 
                 24.7 
               
               
                   
                 Example 2 
                 14.2 
                 24.6 
               
               
                   
                 Example 3 
                 14.3 
                 24.3 
               
               
                   
                 Example 4 
                 14.3 
                 24.0 
               
               
                   
                 Reference 
                 13.9 
                 23.9 
               
               
                   
                 Example 
               
               
                   
                   
               
             
          
         
       
     
         [0045]    From the experiment results, it was confirmed that all of the RFeB-based magnets that were obtained in Examples 1 to 4 have substantially the same residual magnetic flux density and coercive force as Reference Example. That is, according to Examples, through the grain boundary diffusion process in which the nonplanar surface of the base material having the nonplanar surface is set as the attachment surface of the mixture, it is possible to obtain substantially the same magnetic properties as that obtained in the grain boundary diffusion process that has been performed with respect to a rectangular parallelepiped base material of the related art. 
         [0046]    The present invention is not limited to Examples. 
         [0047]    For example, in Examples, the Tb-containing powder obtained by making the TbNiAl alloy into a powder was used as the R H -containing powder, but a Dy-containing powder or a Ho-containing powder may be used, and an elementary substance or a compound (a fluoride and the like) of the R H  may be used in addition to the alloy. In addition, as the organic solvent, in addition to the silicone grease or the silicone fluid which are used in Examples, liquid hydrocarbon such as flowable paraffin, hexane, and cyclohexane may be used. 
         [0048]    In addition, in Examples, the mixture  30  is uniformly attached to the entirety of the upper surface  21  ( FIG. 3A ), but the mixture  30  may be attached to both ends of the upper surface  21  in a direction of the short side  202  along a direction of the long side  201  in a thickness larger than that of other positions of the upper surface  21  to provide a thick attached-material region  31  ( FIG. 3B ). According to this, it is possible to provide a large amount of R H  to the both ends  25  of the base material  20  in the direction of the short side  202 . The both ends  25  have the smallest thickness in the base material  20 , and magnetization faces a thickness direction. Therefore, a demagnetizing field that is generated due to the magnetization is the largest in the base material  20 , and thus a decrease in the coercive force tends to occur. In addition, when being mounted to a motor and the like, heat generation due to the demagnetizing field is large in the both ends  25 , and thus a decrease in the coercive force tends to occur. In Examples, a large amount of R H  is supplied to the both ends  25 , and thus a decrease in the coercive force along with the heat generation may be prevented by local improvement of the coercive force at the both ends  25 . In addition,  FIG. 3B  illustrates a configuration in which the mixture  30  is not attached to the lower surface  22 , but the mixture  30  may also be attached to the lower surface  22 . 
         [0049]    In Examples, the base material  20 , in which only one surface (upper surface  21 ) is set as a nonplanar surface, and the nonplanar surface has a convex shape, was used. However, the shape of the base material is not limited thereto. For example, as shown in  FIG. 4 , a base material  20 A, in which an upper surface  21 A has an upwardly convex arc shape and a lower surface  22 A also has an upwardly convex arc shape in the same manner as the upper surface  21 A, may be used. In the base material  20 A, when the lower surface  22 A is set as the attachment surface of the mixture  30  in combination with the upper surface  21 A, the mixture  30  is attached to a concave surface, but according to Examples, it is possible to uniformly attach the mixture  30  to the concave surface in an arbitrary thickness similar to the convex surface. 
         [0050]    While the mode for carrying out the present invention has been described in detail above, the present invention is not limited to these embodiments, and various changes and modifications can be made therein without departing from the purport of the present invention. 
         [0051]    This application is based on Japanese patent application No. 2013-196922 filed Sep. 24, 2013, the entire contents thereof being hereby incorporated by reference. 
       DESCRIPTION OF REFERENCE NUMERALS AND SIGNS 
       [0000]    
       
           10 : Mixture supply apparatus 
           11 : Base material holding unit 
           12 : Nozzle head 
           121 : Nozzle 
           13 : Base material transporting unit 
           14 : Mixture supply unit 
           141 : Mixture tank 
           142 : Supply tube 
           20 ,  20 A: Base material 
           201 : Long side of lower surface  22   
           202 : Short side of lower surface  22   
           21 ,  21 A: Upper surface (attachment surface) 
           22 : Lower surface 
           22 A: Lower surface (attachment surface) 
           231 : First side surface 
           232 : Second side surface 
           233 : Third side surface 
           234 : Fourth side surface 
           30 : Mixture