Rare earth permanent magnets and their preparation

Abstract

A sintered magnet body (R a T 1 b M c B d ) coated with a powder mixture of an intermetallic compound R 1 i M 1 j , R 1 x T 2 y M 1 z , R 1 i M 1 j H k ), alloy (M 1 d M 2 e )or metal (M 1 ) powder and a rare earth (R 2 ) oxide is diffusion treated. The R 2 oxide is partially reduced during the diffusion treatment, so a significant amount of R 2 can be introduced near interfaces of primary phase grains within the magnet through the passages in the form of grain boundaries. The coercive force is increased while minimizing a decline of remanence.

1 . A method for preparing a rare earth permanent magnet, comprising the steps of:
 disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R 1   i M 1   j  wherein R 1  is at least one element selected from rare earth elements inclusive of Y and Sc, M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, “i” and “j” indicative of atomic percent are in the range: 15<j≦99, the balance of i, and i+j=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and   heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R 1 , R 2  and M 1  in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.   
     
     
         2 . A method for preparing a rare earth permanent magnet, comprising the steps of:
 disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “2c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R 1   i M 1   j H k wherein R 1  is at least one element selected from rare earth elements inclusive of Y and Sc, M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, H is hydrogen, “i,” “j” and “k” indicative of atomic percent are in the range: 15<j≦99, 0<k (i×2.5), the balance of i, and i+j+k=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and   heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R 1 , R 2 , and M 1  in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.   
     
     
         3 . The method of  claim 1  wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts-10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body. 
     
     
         4 . The method of  claim 1  wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture. 
     
     
         5 . A method for preparing a rare earth permanent magnet, comprising the steps of:
 disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R 1   x T 2   y M 1   z  wherein R 1  is at least one element selected from rare earth elements inclusive of Y and Sc, T 2  is one or both of Fe and Co, M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, x, y and z indicative of atomic percent are in the range: 5≦x≦85, 15<z≦95, x+z<100, the balance of y, y>0, and x+y+z=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and   heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R 1 , R 2 , M 1  and T 2  in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.   
     
     
         6 . The method of  claim 5  wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts-10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body. 
     
     
         7 . The method of  claim 5  wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture. 
     
     
         8 . The method of  claim 1  wherein the sintered magnet body has a shape including a minimum portion with a dimension equal to or less than 20 mm. 
     
     
         9 . A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R 1   i M 1   j  wherein R 1  is at least one element selected from rare earth elements inclusive of Y and Sc, M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, “i” and “j” indicative of atomic percent are in the range: 15<j≦99, the balance of i, and i+j=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein
 the elements R 1 , R 2  and M 1  in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body. 
 
     
     
         10 . A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition wherein R 1  is at least one element selected from rare earth elements inclusive of Y and Sc, M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, H is hydrogen, “i,” “j” and “k” indicative of atomic percent are in the range: 15<j≦99, 0<k≦(i×2.5), the balance of i, and i+j+k=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein the elements R 1 , R 2  and M 1  in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body. 
     
     
         11 . A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition R 1   x T 2   y M 1   z  wherein R 1  is at least one element selected from rare earth elements inclusive of Y and Sc, T 2  is one or both of Fe and Co, M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, x, y and z indicative of atomic percent are in the range: 5≦x≦85, 15<z≦95, x+z<100, the balance of y, y>0, and x+y+z=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein
 the elements R 1 , R 2 , M 1  and T 2  in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body. 
 
     
     
         12 . A method for preparing a rare earth permanent magnet, comprising the steps of:
 disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition M 1   d M 2   e  wherein M 1  and M 2  each are at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, M 1  and M 2  are different, “d” and “e” indicative of atomic percent are in the range: 0.1≦e≦99.9, the balance of d, and d+e=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and   heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R 2 , M 2  and M 2  in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.   
     
     
         13 . A method for preparing a rare earth permanent magnet, comprising the steps of:
 disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an M 1  powder wherein M 1  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and   heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, for causing the elements R 2  and M 1  in the powder mixture to diffuse to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains.   
     
     
         14 . The method of  claim 12  wherein the heat treating step includes heat treatment at a temperature from 200° C. to (Ts-10)° C. for 1 minute to 30 hours wherein Ts represents the sintering temperature of the sintered magnet body. 
     
     
         15 . The method of  claim 12  wherein the disposing step includes dispersing the powder mixture in an organic solvent or water, immersing the sintered magnet body in the resulting slurry, taking up the sintered magnet body, and drying for thereby covering the surface of the sintered magnet body with the powder mixture. 
     
     
         16 . The method of  claim 12  wherein the sintered magnet body has a shape including a minimum portion with a dimension equal to or less than 20 mm. 
     
     
         17 . A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 1  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an alloy powder having the composition M 1   d M 2   e  wherein M 1  and M 2  each are at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, M 2  and M 2  are different, “d” and “e” indicative of atomic percent are in the range: 0.1≦e≦99.9, the balance of d, and d+e=100, containing at least 70% by volume of an intermetallic compound phase, and having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein
 the elements R 2 , M 1  and M 2  in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body. 
 
     
     
         18 . A rare earth permanent magnet, which is prepared by disposing a powder mixture on a surface of a sintered magnet body having the composition R a T 1   b M c B d  wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, T 2  is one or both of Fe and Co, M is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, B is boron, “a,” “b,” “c” and “d” indicative of atomic percent are in the range: 12≦a≦20, 0≦c≦10, 4.0≦d≦7.0, the balance of b, and a+b+c+d=100, the powder mixture comprising an M 2  powder wherein M 2  is at least one element selected from the group consisting of Al, Si, C, P, Ti, V, Cr, Mn, Ni, Fe, Co, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ag, In, Sn, Sb, Hf, Ta, W, Pb, and Bi, having an average particle size of up to 500 μm, and at least 10% by weight of an R 2  oxide wherein R 2  is at least one element selected from rare earth elements inclusive of Y and Sc, having an average particle size of up to 100 μm, and heat treating the sintered magnet body having the powder mixture disposed on its surface at a temperature lower than or equal to the sintering temperature of the sintered magnet body in vacuum or in an inert gas, wherein
 the elements R 2  and M 1  in the powder mixture are diffused to grain boundaries in the interior of the sintered magnet body and/or near grain boundaries within the sintered magnet body primary phase grains so that the coercive force of the rare earth permanent magnet is increased over the original sintered magnet body.