Method of producing rare earth permanent magnet

Abstract

Disclosed is a method of producing a rare earth permanent magnet including preparing a NdFeB sintered magnet, coating a surface of the NdFeB sintered magnet with a grain boundary diffusion material including R hydrate or R fluoride, and R.sub.aM.sub.b or M, to form a grain boundary diffusion coating layer, and diffusing the grain boundary diffusion material into a grain boundary of the NdFeB sintered magnet by heat treatment, wherein M is a metal having a melting point higher than a heat treatment temperature during the diffusion, R is a rare earth element, and a and b each represent atomic percentages which satisfy the following Equations (1) and (2):
0.1<a<99.9(1)
a+b=100(2).

Claims

1. A method of producing a rare earth permanent magnet comprising: preparing a NdFeB sintered magnet; coating a surface of the NdFeB sintered magnet with a grain boundary diffusion material comprising R hydrate or R fluoride, and R.sub.aM.sub.b or M, wherein R is selected from dysprosium (Dy), terbium (Tb), neodymium (Nd), praseodymium (Pr), and holmium (Ho), and wherein M is cobalt (Co), to form a grain boundary diffusion coating layer; wherein the coating includes: melting R hydrate or R fluoride, and R.sub.aM.sub.b or M to prepare a cobalt molten alloy; cooling the cobalt molten alloy to prepare a cobalt alloy ingot; grinding the cobalt alloy ingot to prepare a powdery grain boundary diffusion material; and coating the surface of the NdFeB sintered magnet with the grain boundary diffusion material to form the grain boundary diffusion coating layer, and diffusing the grain boundary diffusion material into a grain boundary of the NdFeB sintered magnet by heat treatment, wherein M is a metal having a melting point higher than a heat treatment temperature during the diffusion, R is a rare earth element, and a and b each represent atomic percentages satisfying Equations (1) and (2):
0.1<a<99.9(1)
a+b=100(2).

2. The method according to claim 1, wherein M has a melting point of 1,000 C. or higher.

3. The method according to claim 2, wherein the diffusing is conducted by heating to a temperature of 700 to 1,000 C. under an inert atmosphere.

4. The method according to claim 1, wherein, in the preparing, the NdFeB sintered magnet includes 30 to 35 wt % of the total weight of rare earth elements including dysprosium (Dy), terbium (Tb), neodymium (Nd) and praseodymium (Pr), 0 to 10 wt % of the total weight of transition metals including cobalt (Co), aluminum (Al), copper (Cu), gallium (Ga), zirconium (Zr) and niobium (Nb), 1 wt % of boron (B) and the balance of iron (Fe).

5. The method according to claim 4, wherein the grain boundary diffusion material includes R in an amount that is greater than 30 wt % but equal to or less than 70 wt % and is higher than an amount of the rare earth element present in the NdFeB sintered magnet.

6. The method according to claim 1, wherein, in the coating, the grain boundary diffusion material includes 1 to 7 wt % of cobalt (Co).

7. The method according to claim 6, wherein, in the coating, R hydrate is any one of TbH.sub.2, TbH.sub.3, DyH.sub.2 and DyH.sub.3, and R fluoride is any one of TbF.sub.2, TbF.sub.3, DyF.sub.2, and DyF.sub.3.

8. The method according to claim 1, wherein, in the coating, the coating layer is formed by coating the surface of the NdFeB sintered magnet with the grain boundary diffusion material by spraying, suspension adhesion, or barrel painting.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flowchart illustrating a method of producing a rare earth permanent magnet according to an exemplary embodiment of the present invention;

(2) FIG. 2 is a schematic view illustrating a method of producing a rare earth permanent magnet according to an exemplary embodiment of the present invention;

(3) FIG. 3 is a table showing magnetic characteristics and thermal demagnetization rate before and after grain boundary diffusion with regard to rare earth permanent magnets provided using grain boundary diffusion materials according to various examples of the present invention;

(4) FIG. 4 is a table showing magnetic characteristics and thermal demagnetization rate before and after grain boundary diffusion with regard to rare earth permanent magnets including a low-melting point metal provided using various comparative examples; and

(5) FIG. 5 is an image showing diffusion into the grain boundary of the rare earth permanent magnet produced according to an exemplary embodiment of the present invention.

(6) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.

(7) In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.

DETAILED DESCRIPTION

(8) Reference will now be made in detail to various embodiments of the present invention(s), examples of which are illustrated in the accompanying drawings and described below. While the invention(s) will be described in conjunction with exemplary embodiments, it will be understood that the present description is not intended to limit the invention(s) to those exemplary embodiments. On the contrary, the invention(s) is/are intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.

(9) The present invention can facilitate diffusion of rare earth elements through the diffusion of the rare earth elements together with a metal having a melting point of 1,000 C. or higher in the production of a rare earth permanent magnet, wherein the magnetic characteristics including coercive force of the produced rare earth permanent magnet can be improved, thermal demagnetization rate can be reduced, and the overall process can be simplified through omission of an additional process of removing an oxide film.

(10) FIG. 1 is a flowchart illustrating a method of producing a rare earth permanent magnet according to an exemplary embodiment of the present invention, and FIG. 2 is a schematic view illustrating a method of producing a rare earth permanent magnet according to an exemplary embodiment of the present invention.

(11) As shown in FIG. 1 and FIG. 2, the method of producing a rare earth permanent magnet according to an exemplary embodiment of the present invention includes preparing a NdFeB sintered magnet 10, coating to form a grain boundary diffusion coating layer on the surface of the NdFeB sintered magnet 10, and diffusing a grain boundary diffusion material 200.

(12) In the preparation step, for the prepared NdFeB sintered magnet 10 to include about 30 wt % to about 35 wt % (e.g., about 30 wt %, about 31 wt %, about 32 wt %,) about 33 wt %, about 34 wt %, or about 35 wt %) of the total weight of rare earth elements including dysprosium (Dy), terbium (Tb), neodymium (Nd), and praseodymium (Pr), 0 wt % to about 10 wt % (e.g., about 0 wt %, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, or 10 wt %) of the total weight of transition metals including cobalt (Co), aluminum (Al), copper (Cu), gallium (Ga), zirconium (Zr), and niobium (Nb), 10 wt % of boron (B) and the balance of iron (Fe), these elements are mixed in a predetermined weight ratio, are melted by heating the material to a temperature of about 1,300 C. to about 1,550 C. (e.g., about 1,300 C., about 1,350 C., about 1,400 C., about 1,450 C., or about 1,550 C.) using a high frequency furnace, and are then produced into a NdFeB alloy by strip casting.

(13) The prepared NdFeB alloy is coarsely crushed by hydrogenation and dehydrogenation and finely ground using a jet-mill to prepare a NdFeB powder. In the present case, the NdFeB powder preferably has a diameter of about 3 m to 5 m (e.g., about 3 m, about 4 m, or about 5 m).

(14) After the NdFeB powder is provided as such, the NdFeB powder is sintered and heat-treated using a magnetic field forming machine having a magnetic field direction and a forming direction vertical to each other to produce a NdFeB sintered magnet 10.

(15) The preparation according to an exemplary embodiment of the present invention is preferably conducted under an inert atmosphere charged with nitrogen (N) or argon (Ar) gas. The reason for the present conditions is that deterioration in magnetic characteristics of the NdFeB sintered magnet 10 can be minimized by minimizing impurities including carbon (C) or oxygen (O).

(16) After completion of the NdFeB sintered magnet 10 as such, in the coating step, the surface of the NdFeB sintered magnet 10 is coated with a grain boundary diffusion material 200 to form a grain boundary diffusion coating layer.

(17) The grain boundary diffusion material 200 according to an exemplary embodiment of the present invention includes a rare earth element represented by R hydrate or R fluoride, and cobalt (Co) or a cobalt alloy represented by M or R.sub.aM.sub.b.

(18) In the present case, R is a rare earth element which is any one selected from dysprosium (Dy), terbium (Tb), neodymium (Nd), praseodymium (Pr), and holmium (Ho), M is a metal with a melting point of about 1,000 C. or higher, and a and b each represent atomic percentages which satisfy the following Equations (1) and (2):
0.1<a<99.9(1)
a+b=100(2)

(19) More specifically, in an exemplary embodiment of the present invention, R hydrate is any one selected from TbH.sub.2, TbH.sub.3, DyH.sub.2, and DyH.sub.3, R fluoride is any one selected from TbF.sub.2, TbH.sub.3, DyF.sub.2, and DyF.sub.3, and M is cobalt (Co).

(20) The cobalt (Co) used in an exemplary embodiment of the present invention is one of high-melting point metals, which has a relatively high melting point of 1,498 C. In the subsequent diffusion step, as heating is conducted for grain boundary diffusion of the rare earth element, cobalt (Co) is melted together with R hydrate or R fluoride to form a molten cobalt compound, that is, a liquid grain boundary diffusion material with a lowered melting point.

(21) Accordingly, facilitation of diffusion through improvement in dispersibility and elevation of the grain boundary diffusion rate of the grain boundary diffusion material 200 including a rare earth element can advantageously bring about improvements in the magnetic characteristics of the produced rare earth permanent magnet, not to mention the uniform quality of the rare earth permanent magnet.

(22) In the present case, when a low-melting point metal including zinc (Zn) or aluminum (Al) having a relatively low melting point lower than 700 C. is used as M, there is an advantage that dysprosium (Dy) and terbium (Tb) can be rapidly diffused into the grain boundary of the sintered magnet due to the lowered melting point of dysprosium (Dy) and terbium (Tb), but there is no effect on the Curie temperature of the produced magnet and the thermal demagnetization characteristics thus cannot be improved.

(23) On the other hand, cobalt (Co), a metal with a high melting point that is used in an exemplary embodiment of the present invention, can improve the magnetic characteristics at high temperatures owing to weaker oxidizing power and a higher Curie temperature than neodymium (Nd). Cobalt (Co) is substituted by neodymium (Nd) present in the grain boundary of the NdFeB sintered magnet 10 and grains adjacent thereto, advantageously reducing thermal demagnetization rate of the produced magnet and improving corrosion resistance.

(24) The The grain boundary diffusion material 200 according to an exemplary embodiment of the present invention includes the rare earth element represented by R in an amount that is within the range from about 10 wt % to about 70 wt % (e.g., about 10 wt %, about 20 wt %, about 30 wt %, about 40 wt %, about 50 wt %, about 60 wt %, or about 70 wt %) and is higher than an amount of the rare earth element present in the NdFeB sintered magnet 10.

(25) The reason for limiting the content of the rare earth element within the above range is that, when the amount of the rare earth element in the grain boundary diffusion material 200 is less than 10 wt %, magnetic characteristics cannot be satisfactorily improved due to the small amount of the rare earth element diffused into the grain boundary 100, and when the amount exceeds 70 wt %, the price of the produced rare earth permanent magnet increases due to the waste of expensive rare earth elements and thus increased production costs.

(26) In addition, when the amount of the rare earth element present in the grain boundary diffusion material 200 is lower than the amount of the rare earth element present in the NdFeB sintered magnet, the magnetic characteristics cannot be satisfactorily improved due to the lowered diffusion effect into the grain boundary of the NdFeB sintered magnet. Accordingly, the diffusion efficiency is preferably improved by incorporating the rare earth element in the grain boundary diffusion material in a predetermined amount higher than an amount of the rare earth element in the NdFeB sintered magnet.

(27) Meanwhile, cobalt (Co) is preferably present in an amount of about 1 wt % to about 7 wt % (e.g., about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, or about 7 wt %). The reason for the present amounts is that, when the content of the cobalt (Co) is less than 1 wt %, the effect of cobalt (Co) on improving the coercive force can be barely obtained and the desired heat resistance of the magnet cannot be acquired. When the cobalt (Co) content exceeds 7 wt %, the magnetic characteristics including the coercive force of the rare earth permanent magnet are somewhat deteriorated due to the low proportion of cobalt (Co) melted with R hydrate or R fluoride to form the molten cobalt compound.

(28) The coating step according to an exemplary embodiment of the present invention includes melting R hydrate or R fluoride with R.sub.aM.sub.b or M to prepare a molten cobalt alloy, charging the molten cobalt alloy in a mold and allowing the alloy to cool to prepare a cobalt alloy ingot, grinding the prepared cobalt alloy ingot using a ball-mill to prepare a powdery grain boundary diffusion material 200, and coating the surface of the NdFeB sintered magnet 10 with the powdery grain boundary diffusion material 200 to form a grain boundary diffusion coating layer.

(29) At the present time, the grain boundary diffusion coating layer can be formed by any method of spraying, suspension adhesion, and barrel painting.

(30) Spraying is a method of spraying the powdery grain boundary diffusion material 200 together with a solvent onto the surface of the NdFeB sintered magnet 10 using a spray. Suspension adhesion is a method including suspending the powdery grain boundary diffusion material 200 in a solvent including alcohol, immersing the NdFeB sintered magnet 10 in the suspension and drying the suspension adhered to the surface of the NdFeB sintered magnet 10 while raising the magnet.

(31) In addition, barrel painting is a method of coating the surface of the NdFeB sintered magnet 10 with the grain boundary diffusion material 200 including applying an adhesive material including liquid paraffin to the surface of the NdFeB sintered magnet 10 to form an adhesive layer, mixing the powdery grain boundary diffusion material 200 with a metallic or ceramic impact media having a diameter of approximately 1 mm, incorporating the NdFeB sintered magnet 10 in the mixture and stirring under vibration to attach the grain boundary diffusion material 200 to the adhesive layer by the impact media.

(32) According to an exemplary embodiment of the present invention, the thickness of the grain boundary diffusion coating layer coated onto the surface of the NdFeB sintered magnet 10 is preferably about 5 m to about 150 m (e.g., about 5 m, about 10 m, about 15 m, about 20 m, about 25 m, about 30 m, about 40 m, about 50 m, about 60 m, about 70 m, about 80 m, about 90 m, about 100 m, about 110 m, about 120 m, about 130 m, about 140 m, or about 150 m). The reason for the present dimensions is that, when the thickness of the grain boundary diffusion coating layer exceeds 150 m, grain boundary diffusion of the grain boundary diffusion material 200 including expensive rare earth elements is difficult and, when the thickness is less than 5 m, the effect of the grain boundary diffusion regarding improvement in coercive force is not sufficient.

(33) After formation of the grain boundary diffusion coating layer is completed as described above, the liquid grain boundary diffusion material 200 melted by heating to a temperature of 700 to 1,000 C. in the diffusion step diffuses into the grain boundary 100 of the NdFeB sintered magnet 10 to form a grain boundary 300 where the grain boundary diffusion material diffuses, producing a rare earth permanent magnet.

(34) Hereinafter, an exemplary embodiment of the present invention will be described in detail with reference to the annexed drawings.

(35) TABLE-US-00001 TABLE 1 Items Nd Pr Dy Tb Co B Al Cu C O Fe wt % 27 1 1 1 2 1 0.5 0.25 0.01 0.12 Bal.

(36) Table 1 shows a composition of the NdFeB sintered magnet produced according to an exemplary embodiment of the present invention.

(37) The surface of the NdFeB sintered magnet 10 having the composition of Table 1 was coated with a grain boundary diffusion material 200 having a variety of compositions and heat-treated at 800 C. for 4 hours to induce grain boundary diffusion. Magnetic characteristics and thermal demagnetization rates were determined, and are shown in FIG. 3 and FIG. 4.

(38) As seen from Table 1, FIG. 3, and FIG. 4, when a grain boundary diffusion material including a low-melting point metal including zinc or aluminum is used, the coercive force, magnetic flux density and the like are improved, but the thermal characteristics of the rare earth permanent magnet with a similar thermal demagnetization rate cannot be improved.

(39) On the other hand, when the composition of the grain boundary diffusion material 200 satisfies the conditions defined in an exemplary embodiment of the present invention, magnetic characteristics including coercive force are excellent and thermal characteristics of the produced rare earth permanent magnet are improved due to a deteriorated thermal demagnetization rate.

(40) In the present case, The The grain boundary diffusion material 200 according to an exemplary embodiment of the present invention has a cobalt content of about 1 wt % to about 7 wt % (e.g., about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, or about 7 wt %). The present case is because, when the cobalt content is less than 1 wt %, the improvement in thermal characteristics and coercive force is insufficient, but when the cobalt content exceeds 7 wt %, thermal characteristics and coercive force are deteriorated. FIG. 5 is an image showing diffusion into the grain boundary of the rare earth permanent magnet produced according to an exemplary embodiment of the present invention.

(41) As seen from FIG. 5, according to an exemplary embodiment of the present invention, the grain boundary diffusion material 200 homogeneously diffuses along the grain boundary of the NdFeB sintered magnet 10, thereby advantageously imparting uniform quality to the produced rare earth permanent magnet.

(42) According to the exemplary embodiment of the present invention, by diffusing rare earth elements together with cobalt (Co) with an excellent corrosion resistance and a high melting point, advantageously, the thermal demagnetization rate of the produced rare earth permanent magnet is reduced wherein the thermal characteristics can be improved and diffusion efficiency of the rare earth elements is reduced so that the coercive force of the rare earth permanent magnet can be improved.

(43) In addition, advantageously, an additional process of removing an oxide film after the grain boundary diffusion of the produced rare earth permanent magnet can be omitted so that production efficiency can be improved and production costs can be reduced.

(44) In addition, by offering uniform grain boundary diffusion of rare earth elements in the sintered magnet, the qualities of the produced rare earth permanent magnet can be advantageously uniform.

(45) For convenience in explanation and accurate definition in the appended claims, the terms upper, lower, up, down, upwards, downwards, inner, outer, inside, outside, inwardly, outwardly, interior, exterior, front, rear, back, forwards, and backwards are used to describe features of the exemplary embodiments with reference to the positions of such features as displayed in the figures.

(46) The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to thereby enable others skilled in the art to make and utilize various exemplary embodiments of the present invention, as well as various alternatives and modifications thereof. It is intended that the scope of the invention be defined by the Claims appended hereto and their equivalents.