Abstract:
Bulk hardened magnetic materials with compositions expressed by a general formula Sm u  Ce 1   -u  (Co 1   -x   -y  Fe x  Cu y ) z  are provided. Compositions in the limited range of 0.3≦u≦1.0, 0≦x≦0.1, 0.09≦y≦0.18, 6.0≦z≦7.5 lead to magnetic materials with unexpectedly large maximum energy product and with a newly found two phase structure. Magnetic materials with maximum energy product of over 13 MG.sup.. Oe (megagauss) oersted), residual induction over 7000 G and intrinsic coercive force over 3000 Oe are obtained by subjecting the compositions to a sintering process.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to a hard magnetic material, and more particularly to a rare earth cobalt magnet. 
     Some copper containing rare-earth cobalt materials are known to exhibit high coercive force independent of their grain size. This phenomenon is believed to originate from domain wall stabilization due to fine copper-rich nonmagnetic precipitates. The term &#34;bulk hardening&#34; will be used throughout the specification to denote such an effect. Thus &#34;bulk hardening&#34; means &#34;to invest rare earth cobalt alloys with high coercive force by adding copper&#34;. No additives other than copper have been found to cause the effect to the same extent as copper. 
     One of advantages of the bulk hardening method in producing rare earth cobalt magnets is that one need not pay any special attention to grain size control problem which is often essential in the other methods. Thus, bulk hardening affords easy production. 
     Shortcomings of the bulk hardening method include severe reduction of saturation induction, which is inevitably caused by a rather heavy incorporation of the nonmagnetic element. The fact that the degree of bulk hardening depends on the amount of copper has been noted for years. 
     However, the other factors influencing bulk hardening have been noted to a lesser degree. It is worth mentioning here that the degree of bulk hardening greatly depends on kind of rare-earth or rare-earth combinations employed and on rare-earth to cobalt (plus copper) ratio. 
     Cerium cobalt and samarium cobalt (iron may be added) with 1:5 stoichiometry are good examples in which the bulk hardening has been successfully employed to obtain excellent magnets with maximum energy product of 12 MG.Oe and residual induction of 7000 G. In contrast, PrCo 5  exhibits no significant bulk hardening. 
     U.S. Pat. No. 3,560,200 claims that bulk hardening effectively works in nonstoichiometric compositions in which rare-earth to cobalt (plus copper) ratio falls between 1:5 to 1:8.5 &#34;to a comparative degree&#34; with respect to the 1:5 stoichiometry cases. It is generally expected that increasing the relative amount of cobalt to rare earth increases intrinsic saturation induction, and thus improves maximum energy product. However, it has been generally believed that the increase in the relative amount of cobalt to rare earth weakens the bulk hardening effect, thus requiring more copper addition which in turn diminishes intrinsic saturation induction. Thus, the extension of the composition to the Co-rich side has been considered to bring a similar characteristics, at most to 1:5 stoichiometric cases. 
     Strnat, in a review article in IEEE Trans. on magnetics vol. MAG-8, No. 3, pp514 (1972), states that the attained maximum energy product of 12 MGOe (for 1:5 Ce-Co and Sm-Co cases) probably represents maximum obtainable with the bulk hardening method. However, since bulk hardening is greatly affected by the kind of rare earth employed, there is no reason to deny that special combinations of rare earth elements would possibly enhance bulk hardening even for the nonstoichiometric compositions. 
     An object of the present invention is to provide a novel and improved magnetic materials having high saturation induction, high coercive force and high maximum energy product. 
     Another object of the invention is to provide an improved magnetic materials having the CaCu 5  type hexagonal crystal structure and being characterized by the improved characteristics. 
     Further object of the invention is to provide a novel rare earth cobalt magnet made by sintering. 
     These objects are realized by providing the magnetic materials according to the invention having the compositions of Sm u  Ce 1   -u  (Co 1   -x   -y  Fe x  Cu y ) z  in which 0.3≦u≦1.0, 0≦x≦0.1, 0.09≦y≦0.18 and 6.0≦z≦7.5. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     These and objects and features and advantages of the present invention will be understood in consideration of the following detailed description, with reference to the attached drawings wherein: 
     FIG. 1 shows residual magnetic induction B r , intrinsic coercive force  I  H C  and maximum energy product (BH) max  for specimens having the compositions Sm  0 .3 Ce  0 .7 (Co 0 .86 Fe 0 .05 Cu 0 .09 ) z , as functions of Z. 
     FIG. 2 shows intrinsic coercive force  I  H C  for specimens having the compositions Sm 0 .8 Ce 0 .2 (Co 0 .79 Fe 0 .05 Cu 0 .16) z , as functions of z. 
     FIG. 3 shows the lattice parameters of Sm 0 .8 Ce 0 .2 (Co 0 .79 Fe 0 .05 Cu 0 .16) z . 
     FIG. 4 shows coervice force of various samples plotted against heating temperature. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The invention is most suitably described in terms of a general composition formula 
     
         Sm.sub.u Ce.sub.1.sub.-u (Co.sub.1.sub.-x.sub.-y Fe.sub.x Cu.sub.y).sub.z. 
    
     According to the invention, bulk hardening is unexpectedly marked when the parameters u,x,y,z are in a limited range of 0.3≦u≦1.0, 0≦x≦0.1, 0.09≦y≦0.18, and 6.0≦z≦7.5. Magnetic materials with maximum energy product of 13 to 20 MGOe can be obtained when suitable manufacturing methods are applied to a composition in the limited range. Such maximum energy product values are much higher than those previously attained with any other bulk hardened rare-earth cobalt magnets. 
     Although as cast bulk hardened materials exhibit substantial magnet properties, it is important to follow a sintering method in order to obtain a better alignment of the easy axis, and accordingly, higher residual induction and maximum energy product, and to obtain a product homogeneous both in metallurgical structures and magnetic properties. 
     According to the manufacturing method of the invention, mixed ingredient metals are melted in an inert atmosphere and cast into an iron mold. Ingots are crushed to a course grain and coarse grains are milled into fine grains. Powder thus obtained is pressed into a green tablet with or without an organic liquid under a magnetic field sufficient to cause the easy axis alignment. Green tablets are sometimes further compacted with an isostatic pressure. Green tablets are sintered in vacuum or an inert atmosphere to obtain a dense sintered body. Sintered bodies are furnace-cooled or rapidly cooled and heated at a lower temperature than the sintering temperature. If the heating temperature is proper, the rapidly cooled and heated specimens exhibit better magnetic characteristics than those of furnace-cooled specimens. 
     The most important features of the invention will be best understood by inspecting FIG. 1, FIG. 2 and FIG. 3. FIG. 1 shows the z-dependence of residual induction B r , intrinsic coercive force  I  H C , and maximum energy product (BH) max  in a special series of the compositions represented by Sm 0 .3 Ce 0 .7 (Co 0 .86 Fe 0 .05 Cu 0 .09) z . At the both ends of z, i.e.z=5 and z=8.5, intrinsic coercive force  I  H C  are not significantly large. It is consistent with the previous observations that significant bulk hardening does not occur for such a low y value as 0.09 in Ce(Co,Cu).sub. 5, Sm(Co,Cu) 5  and Sm(CO,Cu) 8 .5 ; However, for the z values between 6.0 and 7.5, intrinsic coercive force  I  H C  takes a significantly larger value than that for the other z values. Note that maximum energy product takes a maximum for a z value of about 6.5. For the extreme case of u= 0, no appreciable maximum occurs in  I  H C  vs. z curves. When 0.3≦u≦1.0 such a maximum in  I  H C  v.s. z curves as well as (BH) max  v.s.z curves occur at a z value between 6.0 and 7.5. 
     FIG. 2 shows the z dependence of intrinsic coercive force in Sm 0 .8 Ce 0 .2 (Co 0 .79 Fe 0 .05 Cu 0 .16) z . It is seen from this figure that coercive force is a maximum when 6≦z≦7.5. Table 1 summerizes the results of x-ray powder diffraction analysis of specimens with composition Sm 0 .8 Ce 0 .2 (Co 0 .79 Fe 0 .05 Cu 0 .16) z . It has been known that RCo 5  has the hexagonal CaCu 5  crystal structure and R 2  Co 17  has either hexagonal Th 2  Ni 17  or rhombohedral Th 2  Zn 17  structure. Therefore, one expects the present specimens to exist in either CaCu 5  type or 2-17 type (either Th 2  Ni 17  or Th 2  Zn 17 ) crystal structure or in two or more phases of these structures. 
     The alloys with z values of 5.0, 5.5 and 5.8 were identified as of CaCu 5  type. The alloys with z values of 6.2, 6.6, 6.8 and 7.2 were recognized as having as two phases both with CaCu 5  type structure with different lattice parameters. In these cases no superlattice lines of the Th 2  Ni 17  type structure were observed. The diffaction pattern of the alloys with z value of 7.6 and 8.5 were also conveniently indexed by assuming a CaCu 5  unit cell, although a few of very weak superlattice lines of the Th 2  Ni 17  type structure were also observed. 
     The lattice parameters are plotted against z in FIG. 3. Inspecting FIG. 3 together with FIG. 2, it is noted that coercive force is a maximum for the z values where the alloy exists in the two phases. It is also noted that the two phases recognized are both of CuCu 5  type and not a mixture of CuCu 5  and either Th 2  Ni 17  or Th 2  Zn 17  type. It is reasonable to consider that the said anomalous bulk hardening is correlated to this newly found two phase structure. 
     Following are the examples of the present invention. 
     Alloys of Sm 0 .8 Ce 0 .2 (Co 0 .79 Fe 0 .05 Cu 0 .16) 7 .2 were prepared by melting about 500 grams of ingredient mixed metals in an alumina crucible in argon by means of induction heating. The molten alloys were cast in an iron mold. The ingots thus obtained were crushed in an iron mortar into course grains and these were pulverized by nitrogen jet milling into fine powder of an average particle size of about 5μm. The powder was mixed with toluene and pressed into a green tablet under a magnetic field of about 15000 Oe perpendicular to the pressing direction. The green tablets were further compacted with a hydrostatic pressure of about 4 tons/cm 2  to a packing density of about 65 %. The tablets were then sintered in vacuum (10 -   4  to 10 -   5  Torr) in an electric furnace with a graphite heater at about 1080°C for 30 minutes. The sintered bodies were quenched on a cool iron plate in argon gas. The quenched samples were first heated at 460°C for 1 hour at approximately 5×10 -   5  Torr and then furnace-cooled to room temperature. The samples were heated repeatedly at successively higher temperatures and furnace-cooled. The coercive force of the samples was measured after each heat treatment. 
     The coercive force is shown as a function of the heating temperatures by curve (a) in FIG. 4. With increasing heating temperature, coercive force increases until a maximum value is reached and then decreases to a minimum value. Similar curves (b) and (c) taken on samples having z values of 5.8 and 5.0 are also plotted in the same figure for the purpose to make comparison with the present example. The optimum heating temperature at which the maximum coercive force occurs is higher when z is larger. 
     Table 2. lists magnetic properties of the samples with various compositions, prepared by the above stated method. It is seen from Table 2 that maximum energy product higher than 13 MGOe is obtained in the claimed range of u, x, y, z of the invention. 
     
                                           Table 1__________________________________________________________________________Compositional Parameter, Z (u=0.8, x=0.05, y=0.16)5.0            5.5      5.8      6.2      6.6h k 1 d(A) I   d(A) I   d(A) I   d(A) I   d(A) I__________________________________________________________________________1 0 0 4.308      w   4.287               vw  4.287                        vw0 0 1 3.987      m   4.017               wm  4.022                        wm  4.037                                 wm  4.055                                          vw1/3 1/3 11 0 1 2.930      vs  2.930               vs  2.937                        vs  2.943                                 vs  2.943                                          vs2/3 2/3 11 1 0 2.494      vs  2.476               s   2.475                        s   2.473                                 m   2.469                                          m                            2.440                                 wm  2.440                                          m2 0 0 2.160      vs  2.145               s   2.144                        s   2.140                                 ms  2.137                                          m                                     2.111                                          vs1 1 1 2.116      vs  2.111               vs  2.111                        vs  2.112                                 vs  2.096                                          vs                                     2.039                                          m0 0 2 2.000      s   2.011               ms  2.013                        s   2.021                                 m   2.028                                          m                                     1.890                                          w2 0 1 1.901      wm  1.894               wm  1.932                        wm  1.890                                 w   1.875                                          wm1 0 22/3 2/3 2--1 1 2 1.562      m   1.564               m   1.564                        m   1.564                                 wm  1.567                                          wm                                     1.500                                          vw2 1 1 1.513      m   1.507               wm  1.507                        wm  1.504                                 wm  1.485                                          w                            1.489                                 w2 0 2 1.470      m   1.470               ms  1.470                        m   1.472                                 m   1.470                                          wm3 0 0 1.443      w   1.434               vvw 1.434                        vvw 1.430                                 vvw--                                     1.344                                          vw301,003 1.357      m   1.350               wm  1.350                        m   1.348                                 w   1.332                                          vw1 0 3 1.276      vvw 1.280               vvw 1.283                        vvw          1.292                                          vvw2 2 0 1.248      wm  1.243               wm  1.240                        wm  1.237                                 vw  1.219                                          vvw221,113 1.178      wm  1.181               wm  1.181                        wm  1.184                                 w   1.186                                          w3 0 2 1.171      w   1.168               vvw 1.167                        vw3 1 1 1.150      vw  1.143               vvw 1.142                        vvw4 0 0 1.033      vvw 1.074               vvw                   1.056                                          vw2 2 2 1.060      wm  1.057               w   1.057                        wm  1.057                                 vw2 1 3 1.035      vvw 1.036               vvw__________________________________________________________________________   6.8        7.2        7.6        8.5h k 1   d(A)  I    d(A)  I    d(A)  I    d(A)  I__________________________________________________________________________1 0 0                                    4.207 vw0 0 1   4.053 vw   4.070 vw   4.092 vvw  4.075 vvw1/3 1/3 1                                3.497 vvw1 0 1   2.939 vs   2.938 s    2.938 s    2.932 s2/3 2/3 1                     2.704 vvw  2.696 vvw   2.466 m    2.471 m1 1 0   2.437 ms   2.440 ms   2.439 s    2.435 s   2.135 s    2.139 m2 0 0   2.111 vs   2.111 vs   2.110 vs   2.110 vs1 1 1   2.097 vs   2.097 vs   2.092 vs   2.093 vs   2.043 m0 0 2   2.026 m    2.043 m    2.043 m    2.042 s   1.889 wm2 0 1   1.875 wm   1.876 m    1.943 vvw  1.874 m1 0 2                         1.874 m    1.838 vvw2/3 2/3 2                                1.779 vvw--                                       1.657 vvw1 1 2   1.566 wm   1.567 wm   1.567 vw   1.565 w   1.502 w2 1 1   1.487 wm   1.487 wm   1.487 wm   1.485 m2 0 2   1.467 m    1.468 m    1.468 wm   1.467 wm3 0 0                         1.407 vvw  1.407 vvw--                            1.363 vvw   1.346 vw301,003 1.330 w    1.331 wm   1.330 w    1.330 wm1 0 3                         1.295 vvw  1.296 vvw2 2 0   1.219 w    1.219 w    1.218 wm   1.218 m221,113 1.186 wm   1.188 wm   1.189 wm   1.189 wm3 0 23 1 1                         1.125 vvw  1.124 vvw4 0 0   1.055 w    1.056 w    1.055 w    1.055 wm2 2 2              1.046 w    1.046 w    1.046 w2 1 3__________________________________________________________________________ 
    
     
                       Table 2______________________________________Composition  Sint.   Heat.   Magnetic Properties______________________________________u    x      y      z   Temp. Temp. Br   Hc   (BH) max______________________________________0.80 0.05   0.16   5.0 1150  400   8000 1950  9.10.80 0.05   0.16   5.5 1160  540   8250 2850 13.80.70 0.05   0.16   5.8 1150  540   8050 6400 15.10.80 0.05   0.16   5.8 1200  540   8000 5150 15.60.80 0.05   0.16   6.2 1180  540   8100 6850 16.00.80 0.05   0.16   6.6 1180  540   8950 7200 17.40.70 0.05   0.15   6.8 1160  790   7650 6100 13.10.65 0.05   0.15   7.0 1160  790   8500 6050 16.50.70 0.05   0.13   7.0 1180  790   9050 3050 17.00.70 0.05   0.15   7.0 1170  790   8850 6400 18.20.70 0.10   0.18   7.0 1150  790   9000 5500 15.80.80 0.05   0.15   7.0 1170  790   9050 6800 19.70.80 0.10   0.15   7.0 1160  790   9900 5000 16.70.65 0.05   0.16   7.2 1160  790   8400 6000 16.00.70 0.05   0.14   7.2 1170  790   9050 6900 18.60.70 0.05   0.16   7.2 1160  790   9150 6450 18.30.70 0.06   0.15   7.2 1170  790   9350 5000 18.30.75 0.03   0.15   7.2 1170  790   8950 5000 17.90.75 0.04   0.15   7.2 1170  790   9200 5200 20.20.75 0.05   0.16   7.2 1170  790   9250 6500 18.70.80 0.05   0.13   7.2 1180  790   8900 3000 13.80.80 0.05   0.14   7.2 1180  790   9700 4850 20.00.80 0.05   0.15   7.2 1170  790   9350 4150 18.70.80 0.05   0.16   7.2 1180  790   9150 6750 19.70.90 0.05   0.16   7.2 1180  790   8350 6500 16.60.90 0.05   0.17   7.2 1180  790   8050 6300 15.10.90 0.05   0.18   7.2 1180  790   7650 6100 13.30.70 0.05   0.15   7.3 1170  790   9100 5950 18.60.70 0.05   0.15   7.6 1170  810   9450 4000 17.00.80 0.05   0.16   8.5 1180  810   8950 2550  9.7______________________________________