Abstract:
A rare earth magnet of the invention has a composition represented by the compositional formula R a H b Fe c Co d B e M f , where:
       R is at least one rare earth element including Y;   H is at least one heavy rare earth element from among Dy and Tb;   M is at least one element from among Ga, Zn, Si, Al, Nb, Zr, Ni, Cu, Cr, Hf, Mo, P, C, Mg, and V;   13≦a≦20;   0≦b≦4;   c=100−a−b−d−e−f;   0≦d≦30;   4≦e≦20;   0≦f≦3, and has a structure constituted by a main phase: a (RH) 2 (FeCo) 14 B phase, and a grain boundary phase: a (RH)(FeCo) 4 B 4  phase and a RH phase, with a crystal grain size of the main phase of 10 nm to 200 nm.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The invention relates to a rare earth magnet constituted by a polycrystal having nanosize crystal grain size and to a manufacturing method therefor. 
     2. Description of the Related Art 
     Rare earth magnets such as a neodymium magnet (Nd 2 Fe 14 B) have been used for various applications as very powerful permanent magnets with a high magnetic flux density. A nanosize crystal grain size should be ensured to obtain even better magnetic properties. 
     A technique by which a melt of a magnet composition is rapidly cooled by a single roll method or a twin roll method to obtain a thin strip has been used to realize a nanosize crystal grain size. Where the cooling rate during rapid cooling is too high, an amorphous structure is obtained in the entire magnet or part thereof. The amorphous structure can be crystallized by appropriate annealing, but the grain size in this case becomes larger than that of the crystal structure directly formed by rapid cooling. 
     In sintered magnets using multi-domain Nd 2 Fe 14 B particles with a size of about several micron, a grain boundary phase should be present as a barrier preventing the movement or appearance of magnetic walls in order to realize a high coercive force. 
     For example, Japanese Patent Application Publication No. 2007-251037 (JP-A-2007-251037) and Japanese Patent Application Publication No. 2008-069444 (JP-A-2008-069444) disclose a method including the steps of feeding an alloy melt containing praseodymium (Pr), neodymium (Nd), iron (Fe), cobalt (Co), niobium (Nb), yttrium (Y), and boron (B) to a rotating cooling roll, rapidly cooling, obtaining a thin strip, and crystallizing the thin strip by heat treating at a temperature rise rate of 150 to 250° C./min. As a result, a thin alloy strip for a rare earth magnet constituted by a polycrystal and including the aforementioned constituent element can be obtained. 
     However, no consideration is given to a graph boundary phase and there is room for increasing a coercive force. 
     A coercive force of the aforementioned magnet at room temperature has been evaluated, but for a motor of a hybrid vehicle the evaluation should be conducted for a coercive force at a temperature close to 160° C. which is in the usage temperature range of the motor. 
     SUMMARY OF INVENTION 
     The invention provides a rare earth magnet in which the refinement of crystal grains to a nanometer size is enhanced and a coercive force is increased due to the presence of a grain boundary phase and also provides a method for manufacturing such a magnet. 
     The first aspect of the invention relates to a rare earth magnet having a composition represented by the compositional formula R a H b Fe c Co d B e M f , where:
         R is at least one rare earth element including Y;   H is at least one heavy rare earth element from among Dy and Tb;   M is at least one element from among Ga, Zn, Si, Al, Nb, Zr, Ni, Cu, Cr, Hf, Mo, P, C, Mg, and V;   13≦a≦20;   0≦b≦4;   c=100−a−b−d−e−f;   0≦d≦30;       

     4≦e≦20;
         0≦f≦3, and having a structure constituted by a main phase: a (RH) 2 (FeCo) 14 B phase, and a grain boundary phase: a (RH)(FeCo) 4 B 4  phase and a RH phase, with a crystal grain size of the main phase of 10 nm to 200 nm.       

     The second aspect of the invention relates to a method for manufacturing a rare earth magnet, including:
         rapidly cooling and solidifying an alloy melt having a composition represented by the compositional formula R a H b Fe c Co d B e M f , where:   R is at least one rare earth element including Y;   H is at least one heavy rare earth element from among Dy and Tb;   M is at least one element from among Ga, Zn, Si, Al, Nb, Zr, Ni, Cu, Cr, Hf, Mo, P, C, Mg, and V;   13≦a≦20;   0≦b≦4;   c=100−a−b−d−e−f;   0≦d≦30;   4≦e≦20;   0≦f≦3, thereby creating a structure constituted by a main phase: a (RH) 2 (FeCo) 14 B phase, and a grain boundary phase: a (RH)(FeCo) 4 B 4  phase and a RH phase, with a crystal grain size of the main phase of 10 nm to 200 nm.       

     The rare earth magnet in accordance with the invention is constituted by a main phase: a (RH) 2 (FeCo) 14 B phase, and a grain boundary phase: a (RH)(FeCo) 4 B 4  phase and a RH phase, and has a crystal grain size of the main phase of 10 nm to 200 nm. As a result, a high coercive force can be obtained. 
     With the method for manufacturing a rare earth magnet in accordance with the invention, a rare earth magnet with a high coercive force can be manufactured by performing rapid cooling and solidification at a cooling rate at which the above-described crystal structure is generated. 
     When an amorphous phase is produced during rapid cooling and solidification, this phase can be crystallized by annealing. 
     When, b, d, and f are zero in the above-described rare earth magnet and manufacturing method therefor, it means that the respective elements are not contained in the compositional formula. For example, when b=d=f=0, the compositional formula is R a Fe c B e . 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
       The foregoing and further objects, features and advantages of the invention will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings, wherein like numerals are used to represent like elements and wherein: 
         FIG. 1  is a schematic diagram illustrating a single roll used in the fabrication of a rapidly cooled ribbon of a nano-polycrystalline rare earth magnet in accordance with the invention; 
         FIG. 2  is a graph illustrating results obtained in measuring magnetic properties of the rapidly cooled ribbon fabricated in Example 1; 
         FIG. 3  is a graph illustrating the relationship between a coercive force and a NdFe 4 B 4  phase ratio in the grain boundary phase of the rapidly cooled ribbon fabricated in Example 1; 
         FIG. 4  is a graph illustrating a X-Ray Diffraction (XRD) chart of the rapidly cooled ribbon fabricated in Example 1; 
         FIG. 5  is a graph illustrating the relationship between a coercive force and a NdFe 4 B 4  phase ratio in the grain boundary phase of the rapidly cooled ribbons with various volume ratio of grain boundary phase that were fabricated in Example 1; 
         FIG. 6  is a graph illustrating results obtained in measuring magnetic properties of the rapidly cooled ribbon fabricated in Example 2; 
         FIG. 7  is a graph illustrating the relationship between a coercive force and an amount of Ga added to the rapidly cooled ribbon fabricated in Example 2; 
         FIG. 8  is a graph illustrating the effect produced by addition of Dy on magnetic properties of the rapidly cooled ribbon fabricated in Example 2; 
         FIG. 9  is a graph illustrating results obtained in measuring magnetic properties of the rapidly cooled ribbon fabricated in Example 3; 
         FIGS. 10A to 10C  are photos illustrating Scanning Electron Microscope (SEM) images of fracture surfaces of the rapidly cooled ribbon fabricated in Example 3; 
         FIG. 11  is a graph illustrating the relationship between a crystal grain diameter and a coercive force of the rapidly cooled ribbon fabricated in Example 3; 
         FIG. 12  is a graph illustrating results obtained in measuring magnetic properties of the rapidly cooled ribbon fabricated in Example 4; 
         FIG. 13  is a graph illustrating results obtained in measuring magnetic properties of another rapidly cooled ribbon fabricated in Example 4; 
         FIG. 14  is a graph illustrating the relationship between a temperature rise rate of the rapidly cooled ribbon fabricated in Example 5 during annealing and a coercive force of the rapidly cooled ribbon fabricated in Example 5; 
         FIG. 15  is a schematic diagram illustrating structural changes during annealing in Example 5; 
         FIG. 16  is a graph illustrating the relationship between a coercive force of the rapidly cooled ribbon fabricated in Example 6 and a measurement temperature; 
         FIGS. 17A and 17B  are photos showing Transmission Electron Microscope (TEM) images of the rapidly cooled ribbon fabricated in Example 6; 
         FIG. 18  is a graph illustrating the relationship between a coercive force of another rapidly cooled ribbon fabricated in Example 6 and a measurement temperature; and 
         FIG. 19  is a schematic diagram illustrating the relationship between variations in a grain boundary phase of the rapidly cooled ribbon fabricated in Example 6 and a coercive force decrease rate with temperature. 
     
    
    
     DETAILED DESCRIPTION OF EMBODIMENTS 
     The nanosize crystal grain size in the embodiments of the invention is preferably equal to or less than a single domain particle diameter, that is 10 to 200 nm, more preferably 10 to 50 nm. 
     A representative rare earth magnet of an embodiment of the invention is represented by the compositional formula Nd a Fe c B e  with 13≦a≦20; 4≦c≦20; e=100−a−c, and has a structure constituted by a main phase: a Nd 2 Fe 14 B phase, and a grain boundary phase: a NdFe 4 B 4  phase and a Nd phase. 
     A phase ratio (volume ratio) of the NdFe 4 B 4  phase and the Nd phase constituting the graph boundary phase is preferably (NdFe 4 B 4  phase):(Nd phase)=20:80 to 80:20. 
     In the rare earth magnets of the embodiments of the invention, in the case of a pure three-component NdFeB system containing no additional element M, a coercive force at normal temperature in a state immediately after rapid cooling and solidification is equal to or higher than 15 kOe and in the case of a system including an additional element M, a coercive force of equal to or higher than 20 kOe can be obtained. 
     A reduction ratio of the coercive force with temperature in the rare earth magnets of the embodiments of the invention is equal to or less than 0.42%/° C., preferably equal to or less than 0.40%/° C. 
     A ratio (volume) of a crystalline phase in the structure is preferably equal to or higher than 95%. 
     In the method for manufacturing the rare earth magnet of the embodiment of the invention, the production of an amorphous structure is inhibited and a nanosize crystalline structure is readily produced by conducting rapid cooling at a cooling rate equal to or higher than 5×10 5  K/s, preferably equal to or lower than 2×10 6  K/s. When the cooling rate during rapid cooling is too high (for example, higher than 2×10 6  K/s), an amorphous phase is generated. A single roll method and a twin roll method can be used for rapid cooling, but these methods are not limiting. In the below-described Examples 1 to 4 and 6, rare earth magnet ribbons were manufactured by conducting rapid cooling and solidification at a cooling rate of 5×10 5  K/s to 2×10 6  K/s. 
     When an amorphous phase has appeared during rapid cooling and solidification, this phase may be crystallized by annealing. 
     In the manufacturing method in accordance with the invention, the process from a molten state of the alloy to completion of solidification is preferably performed in a nonoxidizing atmosphere. 
     EXAMPLE 1 
     Ingots of NdFeBGa alloys with compositions a to e shown in table 1 were produced by arc melting. The compositions a to e were selected on a NdFeB ternary equilibrium state diagram such as to obtain a volume fraction of a grain boundary phase (NdFe 4 B 4  phase+Nd phase) of 18% (constant). Table 1 also shows the NdFe 4 B 4  phase:Nd phase ratio in the grain boundary phase. This ratio was determined by calculations on the NdFeB ternary equilibrium state diagram. 
     
       
         
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 NdFe 4 B 4   
                 Nd 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 a. Nd 20 Fe 73.5 B 5.5 Ga 
                 15% 
                 85% 
               
               
                   
                 b. Nd 17.5 Fe 74 B 7.5 Ga 
                 39% 
                 61% 
               
               
                   
                 c. Nd 16 Fe 74 B 9 Ga 
                 56% 
                 44% 
               
               
                   
                 d. Nd 14 Fe 74.5 B 10.5 Ga 
                 76% 
                 24% 
               
               
                   
                 e. Nd 13 Fe 74.5 B 11.5 Ga 
                 87% 
                 13% 
               
               
                   
                   
               
             
          
         
       
     
     Ribbons were fabricated from the ingots by using the single roll furnace shown in  FIG. 1  and conducting rapid cooling and solidification under the conditions shown in Table 2. A ribbon  4  (referred to hereinbelow as “rapidly cooled ribbon”) is obtained by ejecting the alloy melt from a nozzle  3  on the outer peripheral surface of a single roll  2  rotating in the direction shown by arrow  1 , thereby causing rapid cooling and solidification. 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
             
             
               
                   
                 Nozzle diameter 
                 0.6 
                 mm 
               
               
                   
                 Clearance 
                 0.7 
                 mm 
               
               
                   
                 Ejection pressure 
                 0.4 
                 kg/cm 3   
               
               
                   
                 Roll speed 
                 2350 
                 rpm 
               
               
                   
                 Melting temperature 
                 1450° 
                 C. 
               
               
                   
                   
               
             
          
         
       
     
     Magnetic properties of the obtained rapidly cooled ribbon were measured with a Vibrating Sample Magnetometer (VSM) (manufactured by Lake Shore Co., model 7410). A crystal structure of the ribbon was analyzed with a XRD (manufactured by Rigaku Co., RINT-2000). 
       FIG. 2  shows the results obtained in measuring magnetic properties. A coercive force increased with the increase in the NdFe 4 B 4  phase ratio in the grain boundary phase in the order of a→c, assumed a maximum value in the c composition of Nd 16 Fe 74 B 9 Ga 1  and then decreased in the order of c→e with the increase in the NdFe 4 B 4  phase ratio. Since the Mr/Mr at27kOe  value is constant, there is no difference in exchange coupling ability between the crystal grains, and the difference in grain size of the main phase Nd 2 Fe 14 B apparently became the difference in coercive force. In  FIG. 3 , a coercive force is plotted against a NdFe 4 B 4  phase ratio in the grain boundary phase. 
     It is considered that the main phase grain size varied depending on the phase ratio in the grain boundary phase apparently because the main phase coarsening was inhibited as the ratio (volume ratio) of the NdFe 4 B 4  phase that was in a peritectic relationship with the main phase increased from that of the composition a to that of the composition c and the coercive force increased due to crystal grain refinement. However, where the ratio (volume ratio) of the NdFe 4 B 4  phase increased in excess of that of the composition c, the nucleation frequency of the main phase decreased, crystal grains of the main phase were coarsened, and the coercive force decreased. 
       FIG. 4  is diffraction chart of XRD. In the composition a, the diffraction intensity of NdGa is high and a clear peak is observed. Therefore, it is obvious that Ga used as the additional element M formed a compound with Nd contained in the grain boundary phase. 
     In the composition b and compositions with a lower content ratio of neodymium, a NdGa peak was eliminated and a peak intensity of the NdFe 4 B 4  phase increased. In the composition b and compositions with a lower content ratio of neodymium, the NdFe 4 B 4  phase contained in the grain boundary phase was a crystalline phase, but the Nd phase (NdGa phase) apparently became amorphous. In the composition a, a volume fraction of the Nd phase in the finally solidified portion was high, the Nd phase that has locally aggregated was slowly cooled and crystallized, whereas in the composition b and compositions with a lower content ratio of neodymium, the volume fraction of the Nd phase was low and the uniformly dispersed Nd phase was rapidly cooled and amorphousized. 
     In the composition e, the peak intensity of the NdFe 4 B 4  phase increased abruptly. Therefore, the reaction path was different from that of the compositions a to d and it is possible than the initial crystals were not of the Nd 2 Fe 14 B phase. This is apparently why the coarsening of the Nd 2 Fe 14 B phase could not be prevented by the peritectic reaction of the NdFe 4 B 4  phase and the coercive force decreased. 
     As a result, the highest coercive force was obtained in the composition c in which the Nd phase was uniformly dispersed and the peritectic reaction of the NdFe 4 B 4  phase could be used. 
     &lt;Effect of Volume Fraction of Grain Boundary Phase&gt; 
     The above-described results were obtained in the case in which the volume fraction of grain boundary phase was 18% (constant). Rapidly cooled ribbons were also fabricated in the same manner as described above and magnetic properties thereof were measured with the VSM in the cases in which the volume fraction of grain boundary phase was 28% (constant) and 12% (constant). 
     In  FIG. 5 , a coercive force is plotted against the NdFe 4 B 4  phase ratio in the grain boundary phase for volume fractions of 12%, 18%, and 28%. 
     As shown in  FIG. 5 , the maximum value of coercive force and the phase ratio of the NdFe 4 B 4  phase at which the coercive force becomes maximum increase with the increase in the volume fraction of the grain boundary phase. Thus, a peak position of a curve representing a coercive force with respect to a phase ratio of the NdFe 4 B 4  phase shifts up and to the right as shown by a broken line in the figure. From this standpoint, the preferred phase ratios of the NdFe 4 B 4  phase can be generally classified in the following manner. 
     When the volume fraction of the grain boundary phase is &lt;15%, the phase ratio of the NdFe 4 B 4  phase is &lt;50%. 
     When the volume fraction of the grain boundary phase is 15% to 23%, the phase ratio of the NdFe 4 B 4  phase is 15 to 80%. 
     When the volume fraction of the grain boundary phase is &gt;23%, the phase ratio of the NdFe 4 B 4  phase is 30 to 80%. 
     EXAMPLE 2 
     Effect of Additional Element 
     Arc ingots were prepared of compositions obtained by adding 2 at. % of Ga, Cr, Si, V, or Ni as an element other than a heavy rare earth element, to Nf 16 Fe 47 B 10  according to the example 2 of the invention. A rapidly cooled ribbon was fabricated from each ingot under the conditions shown in Table 3 by using a single roll furnace shown in  FIG. 1 . 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
               
                   
                   
               
             
             
               
                   
                 Nozzle diameter 
                 0.6 
                 mm 
               
               
                   
                 Clearance 
                 0.7 
                 mm 
               
               
                   
                 Ejection pressure 
                 0.4 
                 kg/cm 3   
               
               
                   
                 Roll speed 
                 2350 
                 rpm 
               
               
                   
                 Melting temperature 
                 1450° 
                 C. 
               
               
                   
                   
               
             
          
         
       
     
     Magnetic properties of the obtained rapidly cooled ribbon were measured with the VSM. 
       FIG. 6  shows the results obtained in measuring magnetic properties. The addition of the elements increased the coercive force by comparison with that of the composition Nd 16 Fe 47 B 10  containing no additional elements. This is apparently because the additional elements produce a compound or a solid solution with the grain boundary phase, thereby inhibiting the growth of crystal grains of the main phase. 
     &lt;Effect of the Amount Added&gt; 
       FIG. 7  shows a coercive force obtained when Ga was added within a range of up to 2 at. % to Nd 16 Fe 47 B 10 . The coercive force increased with the increase in the amount of Ga added. However, no significant changes in the coercive force were observed after the amount added was higher than 1 at. %. Since magnetization decreases with the increase in the amount added, the amount of 2-3 at. % can be considered as an upper limit. 
     &lt;Effect of Addition of Heavy Rare Earth Element&gt; 
       FIG. 8  shows magnetization curves obtained when Dy was added at a ratio of 0.5 at. % to Nd 16 Fe 47 B 10  and when no addition was made. The coercive force could be increased without decreasing the magnetization with respect to the composition Nd 16 Fe 47 B 10  by adding merely 0.5 at. % of Dy. When Dy was added at 2 at. %, the coercive force exceeded 30 kOe and thus exceeded the measurement limit of the VSM. As a result, the measurements could not be conducted. 
     EXAMPLE 3 
     Effect of Crystal Grain Size 
     Rapidly cooled ribbons of compositions (1) to (5) shown in Table S were fabricated in the same manner as in Example 1 under the conditions shown in Table 4 by using a single roll. 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
               
                   
                   
               
             
             
               
                   
                 Nozzle diameter 
                 0.6 
                 mm 
               
               
                   
                 Clearance 
                 0.7 
                 mm 
               
               
                   
                 Ejection pressure 
                 0.4 
                 kg/cm 3   
               
               
                   
                 Roll speed 
                 2350 
                 rpm 
               
               
                   
                 Melting temperature 
                 1450° 
                 C. 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 5 
               
               
                   
                   
               
               
                   
                   
                   
                 Grain size 
                 Grain size 
               
               
                   
                   
                 Coercive 
                 (nm)/number 
                 (nm)/volume 
               
               
                   
                 Composition 
                 force (kOe) 
                 calculation 
                 calculation 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 (1) 
                 Nd 14 Fe 76 B 8 GaCu 
                 20.5 
                 65 
                 93 
               
               
                 (2) 
                 Nd 14 Fe 75 B 10 Ga 
                 22.8 
                 60.5 
                 87 
               
               
                 (3) 
                 Nd 15 Fe 70 B 14 Ga 
                 23.9 
                 51 
                 64.5 
               
               
                 (4) 
                 Nd 15 Fe 65 B 19 Ga 
                 26.7 
                 32 
                 44 
               
               
                 (5) 
                 Nd 15 Fe 65 B 19 Ga 
                 28.1 
                 24.5 
                 40 
               
               
                   
               
             
          
         
       
     
     Magnetic properties of the obtained rapidly cooled ribbon were measured with the VSM. 
     Fracture surfaces of the rapidly cooled ribbons were observed with a SEM and a crystal grain size was calculated. 
       FIG. 9  shows magnetic properties, and  FIGS. 10A to 10C  show SEM images. 
     The coercive force obtained increased with the decrease in the crystal grain diameter. Since the ribbon used had compositions obtained by adding Ga or GaCu to the NdFeB base composition, crystal period anisotropy of the main phase Nd 2 Fe 14 B did not vary among the ribbons. Therefore, the increase in the coercive force can be attributed to crystal grain refinement of the main phase. 
     In a region of a single domain (SD) crystal grain size, the volume-recalculated grain size was found to lay on a line with a constant inclination. In a rapidly cooled ribbon of composition (1) that had a coercive force of 20.5 kOe, because the grain size distribution was large ( FIG. 10A ), the effect of coarse crystal grains with a small coercive force increased and the calculated coercive force could be below the coercive force predicted on the basis of the average grain size. Experimental results suggest that when an anisotropic magnetic field of Nd 2 Fe 14 B is 67 kOe, a crystal grain size of about 10 nm is necessary to realize 33.5 kOe (67 kOe×½), which is a theoretical value for an isotropic system. 
       FIG. 11  shows a relationship between a crystal grain size and a coercive force for compositions (1) to (5). In this case, a black rhombic mark shows a grain size and coercive force after the rapidly cooled ribbon of composition (3) has been annealed (575° C.×1 min). The coercive force decreased as the crystal grains coarsened and the result laid almost on the extension of a line connecting points of five other plots. It is clear that within this range of composition variations, there is a strong correlation between the coercive force and the crystal grain size. 
     EXAMPLE 4 
     Fabrication of Rapidly Cooled Ribbon of Pure Ternary NdFeB 
     Rapidly cooled ribbons a to d of pure ternary NdFeB obtained by changing x in a succession of 11.8, 14, 15, and 17 (at. %) in Nd x Fe 100-3x/2 B x/2  were fabricated under the conditions shown in Table 6 by using a single roll, and magnetic properties were measured by using the VSM. The phase ratio Nd:NdFe 4 B 4  of the grain boundary phase was fixed at 59:41. 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 6 
               
               
                   
                   
               
             
             
               
                   
                 Nozzle diameter 
                 0.6 
                 mm 
               
               
                   
                 Clearance 
                 0.7 
                 mm 
               
               
                   
                 Ejection pressure 
                 0.4 
                 kg/cm 3   
               
               
                   
                 Roll speed 
                 2350 
                 rpm 
               
               
                   
                 Melting temperature 
                 1450° 
                 C. 
               
               
                   
                   
               
             
          
         
       
     
     Rapidly cooled ribbons were also fabricated by using a Nd-rich composition e (Nd 15 Fe 70 B 15 , phase ratio Nd:NdFe 4 B 4  of the grain boundary phase was 22:78) and a B-rich composition f (Nd 20 Fe 65 B 15 , phase ratio Nd:NdFe 4 B 4  of the grain boundary phase was 41:59), and magnetic properties of the ribbons were measured. 
       FIGS. 12 and 13  show the results obtained in measuring magnetic properties. 
     As shown in  FIG. 12 , when the Nd amount was increased in compositions a to d, the coercive force reached saturation at 22 kOe. This is apparently because even when the Nd amount was increased, crystal grains of the Nd 2 Fe 14 B phase of the main phase could not be refined when the amount of neodymium was equal to or higher than a predetermined value. 
     As shown in  FIG. 13 , in the Nd-rich and B-rich compositions e and f, the volume fraction of the grain boundary phase NdFe 4 B 4  increased and magnetization decreased, but the coercive force increased and a coercive force with a maximum of 24.5 kOe was realized in the Nd 20 Fe 65 B 15  composition. Therefore, it was shown that by optimizing the composition, it was possible to refine crystal grains and fabricate rapidly cooled ribbons with high magnetization and high coercive force that are nano-polycrystalline magnets. 
     EXAMPLE 5 
     A rapidly cooled ribbon of a Nd 20 Fe 65 B 15  composition was fabricated by using a single roll under the conditions shown in Table 7. When the cooling rate during rapid cooling and solidification was equal to or higher than 2×10 6  K/s, a rapidly cooled ribbon that was mostly amorphous was fabricated. The obtained amorphous phase was crystallized by annealing, thereby making it possible to obtain a coercive force close to that of the rapidly solidified ribbon produced at a cooling rate of 5×10 5  K/s to 2×10 6  K/s. 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 7 
               
               
                   
                   
               
             
             
               
                   
                 Nozzle diameter 
                 0.6 
                 mm 
               
               
                   
                 Clearance 
                 0.7 
                 mm 
               
               
                   
                 Ejection pressure 
                 0.4 
                 kg/cm 3   
               
               
                   
                 Roll speed 
                 3500 
                 rpm 
               
               
                   
                 Melting temperature 
                 1450° 
                 C. 
               
               
                   
                   
               
             
          
         
       
     
     In the present example, the rapidly solidified ribbon was crystallized by annealing with am infrared lamp (575° C.×1 min). Magnetic properties were then measured with the VSM. 
       FIG. 14  shows the relationship between a temperature rise rate during annealing and a coercive force. The higher was the temperature rise rate, the higher was the coercive force. This is apparently because the final crystal grain size and coercive force are determined by the nucleation frequency and grain growth of the main phase, as shown by a schematic diagram in  FIG. 15 . 
     The general annealing conditions for crystallization were as follows: inactive atmosphere, temperature of 550 to 650° C., holding time 0.1 to 10 min, temperature rise rate equal to or higher than 20° C./min, preferably equal to or higher than 120° C./min. 
     EXAMPLE 6 
     Dependence of Coercive Force on Temperature 
     Rapidly cooled ribbons of compositions (1) Nd 15 Fe 70 B 15  and (2) Nd 15 Fe 77 B 8  in accordance with the example 6 of the invention were fabricated by using a single roll under the conditions shown in Table 8. Magnetic properties were measured at various temperature with the VSM. 
     
       
         
               
               
               
               
             
           
               
                   
                 TABLE 8 
               
               
                   
                   
               
             
             
               
                   
                 Nozzle diameter 
                 0.6 
                 mm 
               
               
                   
                 Clearance 
                 0.7 
                 mm 
               
               
                   
                 Ejection pressure 
                 0.4 
                 kg/cm 3   
               
               
                   
                 Roll speed 
                 2350 
                 rpm 
               
               
                   
                 Melting temperature 
                 1450° 
                 C. 
               
               
                   
                   
               
             
          
         
       
     
       FIG. 16  shows the relationship between a coercive force and a measurement temperature for various samples. For comparison, the figure also shows properties of (3) Dy-added sintered magnet Nd 11.5 Dy 2 Fe 80 B 6.5  and (4) Dy-free sintered magnet Nd 13.5 Fe 80 B 6.5 . 
     The coercive force at room temperature of the Dy-added sintered magnet (3) is higher than that of the nano-polycrystalline magnets (1) and (2) of the examples, but at a high temperature of 160° C., the relationship is inverted, and the nano-polycrystalline magnets (1) and (2) show a higher coercive force. This is because the reduction ratio of coercive force with respect to temperature of the nano-polycrystalline magnets (1) and (2) is 0.35%/° C. and 0.39%/° C. respectively, and lower than that of Comparative Example (3) (0.48%/° C.). 
     Further, where the nano-polycrystalline magnets (1) and (2) are compared to each other, the coercive force of the nano-polycrystalline magnet (1) is higher and the reduction ratio of the coercive force is lower than those of the nano-polycrystalline magnet (2). This is apparently because the volume fraction of the grain boundary phase of the nano-polycrystalline magnet (1) increased over than of the nano-polycrystalline magnet (2) and, therefore, isolation between Nd 2 Fe 14 B phases of the main phase increased. 
     A grain boundary phase can be observed with a TEM, typically as shown in  FIGS. 17A and 17B . 
     &lt;When Additional Elements are Present&gt; 
       FIGS. 18 and 19  show variations in the coercive force caused by a volume fraction of the grain boundary phase and increase in a B content in the case in which Ga was added. 
     As the volume fraction of the grain boundary phase increased and the ratio of the NdFe 4 B 4  phase in the grain boundary phase also increased, grain refinement of the main phase and isolation between the main phases increased, the coercive force increased, and the reduction ratio of coercive force caused by temperature simultaneously decreased. 
     The invention provides a rare earth magnet in which formation of nanosize crystal grains is enhanced and a coercive force is increased due to the presence of a grain boundary phase and also a manufacturing method for such a magnet.