Abstract:
A permanent magnet consists of a rare earth element (RE) or a mixture thereof, cobalt, iron and a transition metal (TM) selected from the group consisting of chromium, manganese, titanium, tungsten, molybdenum, and mixtures thereof; wherein for each two moles of the rare earth elements there are 14-19 moles of all other elements.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a permanent magnet composed of at least one rare earth element and other elements, including cobalt, as well as a method of making it. 
     2. Description of the Prior Art 
     Permanent magnets of the above-mentioned type which are based on SmCo 5  and CeMMCo 5  are known. High coercive fields are attainable with these. However, their magnetic remanence is below 10KG in all cases. 
     For many uses, a lower coercive field and a higher magnetic remanence with, at the same time, an ideal demagnetization curve are required. Consequently, it is most desirable to improve rare earth-cobalt magnets so as to obtain, along with a high coercive field, a magnetic remanence of more than 9KG. 
     SUMMARY OF THE INVENTION 
     Accordingly, it is an object of this invention to provide a rare earth-cobalt magnet which simultaneously possesses high values of coercive field strength and remanence as well as an ideal demagnetization curve. 
     Briefly, this and other objects of this invention as will hereinafter become clear, have been attained by including along with at least one rare earth element and cobalt, the elements iron and at least one of the transition metals (TM) selected from the group consisting of chromium, manganese, titanium, tungsten and molybdenum wherein approximately 17 moles of all elements other than the rare earths are present for every 2 moles of the rare earths (RE). 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     A more complete appreciation of the invention and many of the attendant advantages thereof will be readily attained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein: 
     FIGS. 1 and 2 show the demagnetization curves of several alloys of this invention. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     To make the permanent magnets of this invention, a powder, with a mean grain size from 2.0 to 10μm, of a starting alloy of composition RE 2  (Co 1-x-y  Fe x  TM y ) 17+z  is mixed with from 8 to 14 wt.% of a samarium-rich sinter additive (composed, for example, of 50-60 wt.% of samarium and 40-50 wt.% of the alloy Co 1-x-y  Fe x  TM y ) wherein -2 ≦ z ≦ 1; 0.5 &lt; (1-x-y) &lt; 1; 0 &lt; x ≦ 0.4; 0 &lt; y &lt; 0.2. The mixture is magnetically aligned, compressed to a greenling and sintered to form a magnet. The magnet is subsequently subjected to a heat treatment above 400° C. 
     The permanent magnets of this invention, in contrast to known magnets, e.g. Alnico, exhibit a much higher coercive field and yet have a comparable remanence and an ideal demagnetization curve. 
     Preferred rare earths are (1) samarium and (2) a mixture of samarium and a light rare earth element from atomic elements 57-62, misch metal or mixtures thereof. 
     In the making of the permanent magnets of this invention, the following basic procedure is advantageous. A quantity of the desired RE 2  (Co 1-x-y  Fe x  TM y ) 17+z  starting alloy, i.e., from 92-86 wt.%, on the one hand, and from 8-14 wt.% of a samarium-rich sinter additive Sm/(Co,Fe,TM) on the other, are each melted together from their individual alloy components. The sinter additive should contain 50 to 60 wt.% of samarium. The proportion of Co:Fe:TM in the sinter additive is preferably the same as that of the starting alloy. The sinter additive creates, in a known way, particularly favorable sintering conditions. It does not figure quantitatively in the magnetic end-alloy, since, by appropriate selection, it only compensates the oxide losses occurring during the production process. 
     The fused starting alloy is subjected to a stabilizing annealing treatment at about 1150° C for about 6 hours, i.e., at a temperature below the liquidus temperature. The starting alloy, thus annealed, and the fused sinter additive are crushed to a grain size of ≦ 1mm. The crushed starting alloy is then mixed with 8 to 14 wt.% of the crushed sinter additive and the mixture reduced to a powder of average grain size from 2.0 to 10μm, desirably from 2.0-5.0μm, preferably less than 3μm, in a counter-jet mill. There can also be used, in place of the counter-jet mill, an attritor or a ball mill. The two alloys can also be ground separately and the powders subsequently mixed in the correct ratio. 
     The powder is next magnetically aligned in a pressing die and compressed isostatically or uniaxially to a greenling with pressures up to 8000 atm. The greenling is then sintered at temperatures between 1110° and 1180° C in a protective gas atmosphere. After the sintering, its density should be at least 92% of the theoretical density. 
     Next the magnet is advantageously subjected to homogenization annealing at temperatures between 900° and 1100° C, preferably 1000°-1100° C, and cooled to room temperature. After cooling, it is tempered at 400° to 600° C and finally magnetized. The tempering is particularly important. The heating and cooling rates used during tempering are relatively irrelevant to the magnetic properties of this type of alloy unless exaggerated values lead to mechanical destruction of the magnet by thermal stresses. Regarding the heating time, values of 1 hour up to a maximum of 300 hours are suitable, the range of 80 to 100 hours being preferred. The resultant products typically have a predominantly single-phase structure. 
     Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are included for purposes of illustration only and are not intended to be limiting unless otherwise specified. 
     The demagnetization curves of the finished permanent magnets of the Examples were obtained in the field of a superconducting solenoid at a maximum field strength of 50 KOe. 
     EXAMPLES FOR A VARIABLE Z 
     Example 1 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .125 Mn 0 .05 Cr 0 .025) 16 .5 
     Sinter additive: 10g of (Sm 60 wt.%, Co 32 wt.%, Fe 6 wt.%, Mn 2 wt.%) 
     Grain size: 2.7μm 
     Sinter temperature: 1140° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/30 hours 
     Result: 
     remanence Br = 10.3KG 
     coercive field strength  I  H C  = 10.6KOe 
     Example 2 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .125 Mn 0 .05 Cr 0 .025) 17 .0 
     Sinter additive: 10g of (Sm 60 wt.%, Co 32 wt.%, Fe 6 wt.%, Mn 2 wt.%) 
     Grain size: 2.6μm 
     Sinter temperature: 1145° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/80 hours 
     Result: 
     remanence Br = 10.2KG 
     coercive field strength  I  H C  = 6KOe 
     Example 3 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .125 Mn 0 .05 Cr 0 .025) 17 .5 
     Sinter additive: 10g of (Sm 60 wt.%, Co 32 wt.%, Fe 6 wt.%, Mn 2 wt.%) 
     Grain size: 2.8μm 
     Sinter temperature: 1145° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/70 hours 
     Result: 
     remanence Br = 9.3KG 
     coercive field strength  I  H C  = 2KOe 
     Example 4 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .125 Mn 0 .05 Cr 0 .025) 16 .0 
     Sinter additive: 10 g of (Sm 60 wt.%, Co 32 wt.%, Fe 6 wt.%, Mn 2 wt.%) 
     Grain size: 2.6μm 
     Sinter temperature: 1135° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/60 hours 
     Result: 
     remanence Br = 9.5KG 
     coercive field strength  I  H C  = 3KOe 
     EXAMPLES FOR A VARIABLE MANGANESE, CHROMIUM AND COBALT CONTENT 
     Example 5 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .1 Mn 0 .1) 17   
     Sinter additive: 10g of (Sm 60 wt.%, Co 32 wt.%, Mn 4 wt.%, Fe 4 wt.%) 
     Grain size: 2.5μm 
     Sinter temperature: 1135° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/77 hours 
     Result: 
     remanence Br = 11KG 
     coercive field strength  I  H C  = 1.8KOe 
     Example 6 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .15 Cr 0 .05) 17   
     Sinter additive: 12g of (Sm 60 wt.%, Co 32 wt.%, Fe 6 wt.%, Cr 2 wt.%) 
     Grain size: 2.7μm 
     Sinter temperature: 1130° C 
     Homogenization temperature/time: 1100° C/1 hour 
     Tempering temperature/time: 500° C/21 hours, 60 hours, 139 hours 
     Result: FIG. 1, demagnetization curves 
     The dashed curve is for material that was only sintered. The other curves show the important influence of the tempering treatment. 
     Example 7 
     Starting alloy: 100g of Sm 2  (Co 0 .85 Fe 0 .125 Cr 0 .025) 17   
     Sinter additive: 11g of (Sm 60 wt.%, Co 34 wt.%, Fe 5 wt.%, Cr 1 wt.%) 
     Grain size: 2.8μm 
     Sinter temperature: 1140° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/130 hours 
     Result: 
     remanence Br = 9.8KG 
     coercive field strength  I  H C  = 3.7KOe 
     Example 8 
     Starting alloy: 100g of Sm 2  (Co 0 .75 Fe 0 .225 Cr 0 .025) 17   
     Sinter additive: 12g of (Sm 60 wt.%, Co 30 wt.%, Fe 9 wt.%, Cr 1 wt.%) 
     Grain size: 2.6μm 
     Sinter temperature: 1150° C 
     Homogenization temperature/time: 1060° C/4 hours 
     Tempering temperature/time: 500° C/60 hours 
     Result: 
     remanence Br = 9.8KG 
     coercive field strength  I  H C  = 4.2KOe 
     EXAMPLES FOR VARIABLE HOMOGENIZATION TEMPERATURES 
     Example 9 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .15 Cr 0 .05) 17   
     Sinter additive: 10g of (Sm 60 wt.%, Co 32 wt.%, Fe 4 wt.%, Cr 4 wt.%) 
     Grain size: 2.5μm 
     Sinter temperature: 1140° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/200 hours 
     Result: 
     remanence Br = 9.4KG 
     coercive field strength  I  H C  = 8.2KOe 
     Example 10 
     Same as Example 9 
     Homogenization temperature/time: 980° C/1 hour 
     Tempering temperature/time: 500° C/200 hours 
     Result: 
     remanence Br = 9.3KG 
     coercive field strength  I  H C  = 7KOe 
     Example 11 
     Same as Examples 9 and 10 
     Homogenization temperature/time: 1060° C/1 hour 
     Tempering temperature/time: 500° C/200 hours 
     Result: 
     remanence Br = 9.4KG 
     coercive field strength  I  H C  = 8.8KOe 
     As can be seen from Examples 9-11, homogenization annealing after sintering does not have as strong an influence as does tempering. However, positive results are obtained when the homogenization annealing is carried out at temperatures above 980° C and below the sintering temperature. 
     EXAMPLES FOR VARIABLE TEMPERING TEMPERATURES 
     Example 12 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .15 Cr 0 .05) 17   
     Sinter additive: 10g of (Sm 60 wt.%, Co 32 wt.%, Fe 4 wt.%, Cr 4 wt.%) 
     Grain size: 2.7μm 
     Sinter temperature: 1130° C 
     No homogenization annealing 
     Tempering temperature/time: none 
     Result: 
     remanence Br = 9KG 
     coercive field strength  I  H C  = 1.5KOe 
     Example 13 
     Same as Example 12 
     Tempering temperature/time: 500° C/200 hours 
     Result: 
     remanence Br = 9KG 
     coercive field strength  I  H C  = 5KOe 
     Example 14 
     Same as Example 12 
     Tempering temperature/time: 500° C/200 hours 
     Result: 
     remanence Br = 9KG 
     coercive field strength  I  H C  = 5.8KOe 
     Example 15 
     Same as Example 12 
     Tempering temperature/time: 600° C/200 hours 
     Result: 
     remanence Br = 9KG 
     coercive field strength  I  H C  = 1KOe 
     Example 16 
     Starting alloy: 100g of Sm 2  (Co 0 .8 Fe 0 .1 Mn 0 .1) 17   
     Sinter additive: 11g of (Sm 50 wt.%, Co 40 wt.%, Fe 5 wt.%, Mn 5 wt.%) 
     Grain size: 2.75μm 
     Sinter temperature: 1155° C 
     No homogenization annealing 
     Tempering temperature/time: 500° C/6 hours 
     Result: 
     remanence Br = 11.2KG 
     coercive field strength  I  H C  = 4KOe 
     FIG. 2 shows the demagnetization curve of this alloy. 
     Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.