Preparation of rare earth permanent magnet

Abstract

A rare earth permanent magnet is prepared by immersing a portion of a sintered magnet body of R.sup.1—Fe—B composition (wherein R.sup.1 is a rare earth element) in an electrodepositing bath of a powder dispersed in a solvent, the powder comprising an oxide, fluoride, oxyfluoride, hydride or rare earth alloy of a rare earth element, effecting electrodeposition for letting the powder deposit on a region of the surface of the magnet body, and heat treating the magnet body with the powder deposited thereon at a temperature below the sintering temperature in vacuum or in an inert gas.

Claims

1. A method for preparing a rare earth permanent magnet, comprising the steps of: immersing a portion of a sintered magnet body in an electrodepositing bath of a powder dispersed in a solvent rather than immersing the magnet body entirely in the electrodepositing bath, said magnet body having a R.sup.1—Fe—B base composition wherein R is at least one element selected from rare earth elements inclusive of Y and Sc, said powder comprising at least one member selected from the group consisting of an oxide of R.sup.2, a fluoride of R.sup.3, an oxyfluoride of R.sup.4, a hydride of R.sup.5, and a rare earth alloy of R.sup.6 wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each are at least one element selected from rare earth elements inclusive of Y and Sc, electrodepositing the powder deposit on a region of the surface of the magnet body to form a coating consisting of particles of the powder, and heat treating the magnet body with the powder deposited on the region of its surface at a temperature equal to or less than a sintering temperature of the magnet body in vacuum or in an inert gas, wherein the step of electrodepositing is conducted plural times while the portion of the sintered magnet body to be immersed is changed each time, whereby the powder is electrodeposited on plural regions of the sintered magnet body.

2. The method of claim 1 wherein the electrodepositing bath contains a surfactant as a dispersant.

3. The method of claim 1 wherein the powder has an average particle size of up to 100 μm.

4. The method of claim 1 wherein the powder is deposited on the magnet body surface at an area density of at least 10 μg/mm.sup.2.

5. The method of claim 1 wherein at least one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 contains Dy and/or Tb in a total concentration of at least 10 atom %.

6. The method of claim 5 wherein the total concentration of Nd and Pr in R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is lower than the total concentration of Nd and Pr in R.sup.1.

7. The method of claim 1, further comprising aging treatment at a temperature lower than that of the heat treatment, the aging treatment being performed after the heat treatment.

8. The method of claim 1, further comprising cleaning the sintered magnet body with at least one of an alkali, acid and organic solvent, the cleaning being performed prior to the immersion step.

9. The method of claim 1, further comprising shot blasting the sintered magnet body to remove a surface layer thereof, the shot blasting being performed prior to the immersion step.

10. The method of claim 1, further comprising final treatment after the heat treatment, said final treatment being cleaning with at least one of an alkali, acid and organic solvent, grinding, plating or coating.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 schematically illustrates how particles are deposited during the electrodeposition step in the method of the invention.

(2) FIG. 2 schematically illustrates how particles are deposited during the electrodeposition step in Comparative Examples 1 and 2.

DESCRIPTION OF PREFERRED EMBODIMENTS

(3) Briefly stated, the method for preparing a rare earth permanent magnet according to the invention involves putting a particulate oxide, fluoride, oxyfluoride, hydride or alloy of rare earth element R.sup.2 to R.sup.6 onto the surface of a sintered magnet body having a R.sup.1—Fe—B base composition and heat treating the particle-coated magnet body.

(4) The R.sup.1—Fe—B base sintered magnet body may be obtained from a mother alloy by a standard procedure including coarse pulverization, fine pulverization, compacting, and sintering.

(5) As used herein, R, R.sup.1 and R.sup.2 to R.sup.6 each are selected from among rare earth elements inclusive of yttrium (Y) and scandium (Sc). R is mainly used for the magnet obtained while R.sup.1 and R.sup.2 to R.sup.6 are mainly used for the starting materials.

(6) The mother alloy contains R.sup.1, iron (Fe), and boron (B). R.sup.1 represents one or more elements selected from among rare earth elements inclusive of Y and Sc, examples of which include Y, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu. Preferably R.sup.1 is mainly composed of Nd, Pr, and Dy. The rare earth elements inclusive of Y and Sc should preferably account for 10 to 15 atom %, especially 12 to 15 atom % of the entire alloy. More preferably, R.sup.1 should contain either one or both of Nd and Pr in an amount of at least 10 atom %, especially at least 50 atom %. Boron (B) should preferably account for 3 to 15 atom %, especially 4 to 8 atom % of the entire alloy. The alloy may further contain 0 to 11 atom %, especially 0.1 to 5 atom % of one or more elements selected from among Al, Cu, Zn, In, Si, P, S, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, and W. The balance consists of Fe and incidental impurities such as C, N and O. Iron (Fe) should preferably account for at least 50 atom %, especially at least 65 atom % of the entire alloy. It is acceptable that Co substitutes for part of Fe, for example, 0 to 40 atom %, especially 0 to 15 atom % of Fe.

(7) The mother alloy is obtained by melting the starting metals or alloys in vacuum or in an inert gas, preferably Ar atmosphere, and then pouring in a flat mold or book mold, or casting as by strip casting. An alternative method, called two-alloy method, is also applicable wherein an alloy whose composition is approximate to the R.sub.2Fe.sub.14B compound, the primary phase of the present alloy and an R-rich alloy serving as a liquid phase aid at the sintering temperature are separately prepared, crushed, weighed and admixed together. It is noted that since the alloy whose composition is approximate to the primary phase composition is likely to leave α-Fe phase depending on the cooling rate during the casting or the alloy composition, it is subjected to homogenizing treatment, if desired for the purpose of increasing the amount of R.sub.2Fe.sub.14B compound phase. The homogenization is achievable by heat treatment in vacuum or in an Ar atmosphere at 700 to 1,200° C. for at least 1 hour. The alloy approximate to the primary phase composition may be prepared by strip casting. For the R-rich alloy serving as a liquid phase aid, not only the casting technique described above, but also the so-called melt quenching and strip casting techniques are applicable.

(8) Furthermore, in the pulverizing step to be described below, at least one compound selected from a carbide, nitride, oxide and hydroxide of R.sup.1 or a mixture or composite thereof can be admixed with the alloy powder in an amount of 0.005 to 5% by weight.

(9) The alloy is generally coarsely pulverized to a size of 0.05 to 3 mm, especially 0.05 to 1.5 mm. For the coarse pulverizing step, a Brown mill or hydrogen decrepitation (HD) is used, with the HD being preferred for the alloy as strip cast. The coarse powder is then finely pulverized to a size of 0.2 to 30 μm, especially 0.5 to 20 μm, for example, on a jet mill using high pressure nitrogen. The fine powder is compacted in a magnetic field by a compression molding machine and introduced into a sintering furnace. The sintering is carried out in vacuum or an inert gas atmosphere, typically at 900 to 1,250° C., especially 1,000 to 1,100° C.

(10) The sintered magnet thus obtained contains 60 to 99% by volume, preferably 80 to 98% by volume of the tetragonal R.sub.2Fe.sub.14B compound as the primary phase, with the balance being 0.5 to 20% by volume of an R-rich phase, 0 to 10% by volume of a B-rich phase, and at least one of carbides, nitrides, oxides and hydroxides resulting from incidental impurities or additives or a mixture or composite thereof.

(11) The sintered block is then machined into a preselected shape. On the surface of a sintered magnet body as machined, a powder containing at least one member selected from among an oxide of R.sup.2, a fluoride of R.sup.3, an oxyfluoride of R.sup.4, a hydride of R.sup.5, and a rare earth alloy of R.sup.6 is attached by the electrodeposition technique. As defined above, each of R.sup.2 to R.sup.6 is at least one element selected from rare earth elements inclusive of Y and Sc, and at least one of R.sup.2 to R.sup.6 should preferably contain at least 10 atom %, more preferably at least 20 atom %, and even more preferably at least 40 atom % of Dy and/or Tb (in case two or more of R.sup.2 to R.sup.6 are used, they should preferably contain in total at least 10 atom % of Dy and/or Tb). In a preferred embodiment, R.sup.2 to R.sup.6 each contain at least 10 atom % of Dy and/or Tb, and the total concentration of Nd and Pr in R.sup.2 to R.sup.6 is lower than the total concentration of Nd and Pr in R.sup.1.

(12) The amount of R.sup.2 to R.sup.6 absorbed into the magnet body increases as the amount of the powder deposited in a space on the magnet body surface is larger. Preferably the amount of the powder deposited corresponds to an area density of at least 10 μg/mm.sup.2, more preferably at least 60 μg/mm.sup.2.

(13) The particle size of the powder affects the reactivity when the R.sup.2 to R.sup.6 in the powder is absorbed in the magnet body. Smaller particles offer a larger contact area available for the reaction. In order for the invention to attain its effects, the powder disposed on the magnet should desirably have an average particle size equal to or less than 100 μm, more desirably equal to or less than 10 μm. No particular lower limit is imposed on the particle size although a particle size of at least 1 nm is preferred. It is noted that the average particle size is determined as a weight average diameter D.sub.50 (particle diameter at 50% by weight cumulative, or median diameter) using, for example, a particle size distribution measuring instrument relying on laser diffractometry or the like.

(14) The oxide of R.sup.2, fluoride of R.sup.3, oxyfluoride of R.sup.4 and hydride of R.sup.5 used herein are preferably R.sup.2.sub.2O.sub.3, R.sup.3F.sub.3, R.sup.4OF and R.sup.5H.sub.3, respectively, although they generally refer to oxides containing R.sup.2 and oxygen, fluorides containing R.sup.3 and fluorine, oxyfluorides containing R.sup.4, oxygen and fluorine, and hydrides containing R.sup.5 and hydrogen, for example, R.sup.2O.sub.n, R.sup.3F.sub.n, R.sup.4O.sub.mF.sub.n and R.sup.5H.sub.n wherein m and n are arbitrary positive numbers, and modified forms in which part of R.sup.2, R.sup.3, R.sup.4 or R.sup.5 is substituted or stabilized with another metal element as long as they can achieve the benefits of the invention. The rare earth alloy of R.sup.6 typically has the formula: R.sup.6.sub.aT.sub.bM.sub.cA.sub.d wherein T is iron (Fe) and/or cobalt (Co); M is at least one element selected from among Al, Cu, Zn, In, Si, P, S, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, and W; A is boron (B) and/or carbon (C); a to d indicative of fractions (atom %) in the alloy are in the range: 15≦a≦80, 0≦c≦15, 0≦d≦30, and the balance of b.

(15) The powder disposed on the magnet body surface contains the oxide of R.sup.2, fluoride of R.sup.3, oxyfluoride of R.sup.4, hydride of R.sup.5, rare earth alloy of R.sup.6, or a mixture of two or more, and may additionally contain at least one compound selected from among carbides, nitrides, and hydroxides of R.sup.7, or a mixture or composite thereof wherein R.sup.7 is at least one element selected from rare earth elements inclusive of Y and Sc. Further, the powder may contain fines of boron, boron nitride, silicon, carbon or the like, or an organic compound such as stearic acid in order to promote the dispersion or chemical/physical adsorption of particles. In order for the invention to attain its effect efficiently, the powder should preferably contain at least 10% by weight, more preferably at least 20% by weight (based on the entire powder) of the oxide of R.sup.2, fluoride of R.sup.3, oxyfluoride of R.sup.4, hydride of R.sup.5, rare earth alloy of R.sup.6, or a mixture thereof. In particular, it is recommended that the powder contain at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 90% by weight of the oxide of R.sup.2, fluoride of R.sup.3, oxyfluoride of R.sup.4, hydride of R.sup.5, rare earth alloy of R.sup.6, or a mixture thereof as the main component.

(16) According to the invention, the means for disposing the powder on the magnet body surface (i.e., powder deposition means) is an electrodeposition technique involving immersing the sintered magnet body in an electrodepositing bath of the powder dispersed in a solvent, and effecting electrodeposition (or electrolytic deposition) for letting the powder (or particles) deposit on the magnet body surface. This powder deposition means is successful in depositing a large amount of the powder on the magnet body surface in a single step, as compared with the prior art immersion methods.

(17) According to the invention, only a necessary portion of the magnet body, which is dependent on the shape and the intended application of the magnet body, is partially immersed in the electrodepositing bath rather than immersing overall the magnet body. This is followed by electrodeposition, whereby the coating is locally formed on the necessary portion. The necessary portion refers to a part or the entirety of the area of a magnet body where a very high coercive force is required. When the magnet is used in a permanent magnet dynamoelectric machinery such as a motor or power generator, for example, the necessary portion refers to the area of the magnet which is directly exposed to the diamagnetic field. The necessary portion of the magnet body is selectively immersed in an electrodepositing bath whereupon the coating is formed on the necessary portion via electrodeposition. This leads to a substantial saving of the amount of the powder consumed and permits a coercivity-enhancing effect to exert in conformity with the intended application. Depending on the shape and intended application of the magnet body, the immersion and electrodeposition steps may be repeated plural times while changing the portion of the magnet body to be immersed, whereby the coating is formed on plural portions of the magnet body. Also if necessary, electrodeposition may be repeated plural times on the same portion, or electrodeposition may be effected on a plurality of portions which may partly overlap.

(18) The solvent in which the powder is dispersed may be either water or an organic solvent. Although the organic solvent is not particularly limited, suitable solvents include ethanol, acetone, methanol and isopropyl alcohol. Of these, ethanol is most preferred.

(19) The concentration of the powder in the electrodepositing bath is not particularly limited. A slurry containing the powder in a weight fraction of at least 1%, more preferably at least 10%, and even more preferably at least 20% is preferred for effective deposition. Since too high a concentration is inconvenient in that the resultant dispersion is no longer uniform, the slurry should preferably contain the powder in a weight fraction of up to 70%, more preferably up to 60%, and even more preferably up to 50%. A surfactant may be added to the electrodepositing bath as a dispersant to improve the dispersion of particles.

(20) The step of depositing the powder on the magnet body surface via electrodeposition may be performed by the standard technique. For example, as shown in FIG. 1, a tank is filled with an electrodepositing bath 1 having the powder dispersed therein. A portion of a sintered magnet body 2 is immersed in the bath 1. A counter electrode 3 is placed in the tank and opposed to the magnet body 2. A power source is connected to the magnet body 2 and the counter electrodes 3 to construct a DC electric circuit, with the magnet body 2 made a cathode or anode and the counter electrodes 3 made an anode or cathode. With this setup, electrodeposition takes place when a predetermined DC voltage is applied. Where it is desired to deposit the powder on opposite surfaces of the magnet body 2, first a selected portion of the magnet body 2 on one surface side is immersed in the bath 1, electrodeposition is effected as described herein, then the magnet body 2 is turned up-side-down, a selected portion of the magnet body 2 on opposite surface side is immersed in the bath 1, and electrodeposition is similarly effected again. It is noted that in FIG. 1, the magnet body 2 is made a cathode and the counter electrode 3 made an anode. Since the polarity of electrodepositing particles changes with a particular surfactant, the polarity of the magnet body 2 and the counter electrode 3 may be accordingly set.

(21) The material of which the counter electrode 3 is made may be selected from well-known materials. Typically a stainless steel plate is used. Also electric conduction conditions may be determined as appropriate. Typically, a voltage of 1 to 300 volts, especially 5 to 50 volts is applied between the magnet body 2 and the counter electrode 3 for 1 to 300 seconds, especially 5 to 60 seconds. Also the temperature of the electrodepositing bath is not particularly limited. Typically the bath is set at 10 to 40° C.

(22) After the powder comprising the oxide of R.sup.2, fluoride of R.sup.3, oxyfluoride of R.sup.4, hydride of R.sup.5, rare earth alloy of R.sup.6 or a mixture thereof is disposed on the magnet body surface via electrodeposition as described above, the magnet body and the powder are heat treated in vacuum or in an atmosphere of an inert gas such as argon (Ar) or helium (He). This heat treatment is referred to as “absorption treatment.” The absorption treatment temperature is equal to or below the sintering temperature (designated Ts in ° C.) of the sintered magnet body.

(23) If heat treatment is effected above the sintering temperature Ts, there arise problems that (1) the structure of the sintered magnet can be altered to degrade magnetic properties, (2) the machined dimensions cannot be maintained due to thermal deformation, and (3) R can diffuse not only at grain boundaries, but also into the interior of the magnet body, detracting from remanence. For this reason, the temperature of heat treatment is equal to or below Ts° C. of the sintered magnet body, and preferably equal to or below (Ts-10)° C. The lower limit of temperature may be selected as appropriate though it is typically at least 350° C. The time of absorption treatment is typically from 1 minute to 100 hours. Within less than 1 minute, the absorption treatment may not be complete. If the time exceeds 100 hours, the structure of the sintered magnet can be altered and oxidation or evaporation of components inevitably occurs to degrade magnetic properties. The preferred time of absorption treatment is from 5 minutes to 8 hours, and more preferably from 10 minutes to 6 hours.

(24) Through the absorption treatment, R.sup.2 to R.sup.6 in the powder deposited on the magnet surface is concentrated in the rare earth-rich grain boundary component within the magnet so that R.sup.2 to R.sup.6 are incorporated in a substituted manner near a surface layer of R.sub.2Fe.sub.14B primary phase grains.

(25) The rare earth element contained in the oxide of R.sup.2, fluoride of R.sup.3, oxyfluoride of R.sup.4, hydride of R.sup.5, or rare earth alloy of R.sup.6 is one or more elements selected from rare earth elements inclusive of Y and Sc. Since the elements which are particularly effective for enhancing magnetocrystalline anisotropy when concentrated in a surface layer are Dy and Tb, it is preferred that a total of Dy and Tb account for at least 10 atom % and more preferably at least 20 atom % of the rare earth elements in the powder. Also preferably, the total concentration of Nd and Pr in R.sup.2 to R.sup.6 is lower than the total concentration of Nd and Pr in R.sup.1.

(26) The absorption treatment effectively increases the coercive force of the R—Fe—B sintered magnet without substantial sacrifice of remanence. Since the absorption treatment can be locally assigned to the preselected area of the magnet where coercive force is required, the amount of expensive powder used is effectively saved and yet satisfactory performance is obtainable.

(27) According to the invention, the absorption treatment may be carried out by effecting electrodeposition for letting the powder containing at least one of R.sup.2 to R.sup.6 deposit on the magnet body surface, and heat treating the magnet body having the powder deposited on its surface. When a plurality of magnet bodies each locally coated with the powder are simultaneously subjected to absorption treatment, it is avoided that the magnet bodies are fused together after the absorption treatment which is a heat treatment at a high temperature, because the magnet bodies are spaced apart from each other by the powder coating during the absorption treatment. In addition, the powder is not fused to the magnet bodies after the absorption treatment. It is then possible to place a multiplicity of magnet bodies in a heat treating container where they are simultaneously treated. Thus the inventive method is highly productive.

(28) Since the powder is deposited on the magnet body surface via electrodeposition according to the invention, the coating weight of the powder on the surface can be readily controlled by adjusting the applied voltage and time. This ensures that a necessary amount of the powder is fed to the magnet body surface without waste. Since the powder is locally deposited on the necessary portion of the magnet body depending on the shape and intended application thereof, but not on the magnet body overall, the amount of powder consumed may be effectively saved without detracting from the coercivity-enhancing effect. It is also ensured that a powder coating having a minimal variation of thickness, increased density, and mitigated deposition unevenness forms on the magnet body surface. Thus absorption treatment can be carried out with a minimum necessary amount of the powder until the increase of coercive force reaches saturation. In addition to the advantages of efficiency and economy, the electrodeposition step is successful in forming a powder coating of quality on the necessary portion of the magnet body in a short time. Further, the powder coating formed by electrodeposition is more tightly bonded to the magnet body than those powder coatings formed by immersion and spray coating, ensuring to carry out ensuing absorption treatment in an effective manner. The overall process is thus highly efficient.

(29) The absorption treatment is preferably followed by aging treatment although the aging treatment is not essential. The aging treatment is desirably at a temperature which is below the absorption treatment temperature, preferably from 200° C. to a temperature lower than the absorption treatment temperature by 10° C., more preferably from 350° C. to a temperature lower than the absorption treatment temperature by 10° C. The atmosphere is preferably vacuum or an inert gas such as Ar or He. The time of aging treatment is preferably from 1 minute to 10 hours, more preferably from 10 minutes to 5 hours, and even more preferably from 30 minutes to 2 hours.

(30) Notably, when a sintered magnet block is machined prior to the coverage thereof with the powder by electrodeposition, the machining tool may use an aqueous cooling fluid or the machined surface may be exposed to a high temperature. If so, there is a likelihood that the machined surface is oxidized to form an oxide layer thereon. This oxide layer sometimes inhibits the absorption reaction of R.sup.2 or the like from the powder into the magnet body. In such a case, the magnet body as machined is cleaned with at least one agent selected from alkalis, acids and organic solvents or shot blasted for removing the oxide layer. Then the magnet body is ready for absorption treatment.

(31) Suitable alkalis which can be used herein include potassium hydroxide, sodium hydroxide, potassium silicate, sodium silicate, potassium pyrophosphate, sodium pyrophosphate, potassium citrate, sodium citrate, potassium acetate, sodium acetate, potassium oxalate, sodium oxalate, etc. Suitable acids include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, tartaric acid, etc. Suitable organic solvents include acetone, methanol, ethanol, isopropyl alcohol, etc. In the cleaning step, the alkali or acid may be used as an aqueous solution with a suitable concentration not attacking the magnet body. Alternatively, the oxide surface layer may be removed from the sintered magnet body by shot blasting before the powder is deposited thereon.

(32) Also, after the absorption treatment or after the subsequent aging treatment, the magnet body may be cleaned with at least one agent selected from alkalis, acids and organic solvents, or machined again into a practical shape. Alternatively, plating or paint coating may be carried out after the absorption treatment, after the aging treatment, after the cleaning step, or after the last machining step.

EXAMPLE

(33) Examples are given below for further illustrating the invention although the invention is not limited thereto. In Examples, the area density of terbium oxide deposited on the magnet body surface is computed from a weight gain of the magnet body after powder deposition and the coated surface area.

Example 1

(34) An alloy in thin plate form was prepared by a strip casting technique, specifically by weighing Nd, Al, Fe and Cu metals having a purity of at least 99% by weight, Si having a purity of 99.99% by weight, and ferroboron, radio-frequency heating in an argon atmosphere for melting, and casting the alloy melt on a copper single roll. The alloy consisted of 14.5 atom % of Nd, 0.2 atom % of Cu, 6.2 atom % of B, 1.0 atom % of Al, 1.0 atom % of Si, and the balance of Fe. Hydrogen decrepitation was carried out by exposing the alloy to 0.11 MPa of hydrogen at room temperature to occlude hydrogen and then heating at 500° C. for partial dehydriding while evacuating to vacuum. The decrepitated alloy was cooled and sieved, yielding a coarse powder under 50 mesh.

(35) Subsequently, the coarse powder was finely pulverized on a jet mill using high-pressure nitrogen gas into a fine powder having a mass median particle diameter of 5 μm. The fine powder was compacted in a nitrogen atmosphere under a pressure of about 1 ton/cm.sup.2 while being oriented in a magnetic field of 15 kOe. The green compact was then placed in a sintering furnace with an argon atmosphere where it was sintered at 1,060° C. for 2 hours, obtaining a sintered magnet block. The magnet block was machined on all the surfaces into a block magnet body having dimensions of 50 mm×80 mm×20 mm (magnetic anisotropy direction). It was cleaned in sequence with alkaline solution, deionized water, nitric acid and deionized water, and dried.

(36) Subsequently, terbium oxide having an average particle size of 0.2 μm was thoroughly mixed with deionized water at a weight fraction of 40% to form a slurry having terbium oxide particles dispersed therein. The slurry served as an electrodepositing bath.

(37) With the setup shown in FIG. 1, the magnet body 2 was immersed in the slurry 1 to a depth of 1 mm in the thickness direction (i.e., magnetic anisotropic direction). A stainless steel plate (SUS304) was immersed as a counter electrode 3 while it was opposed to and spaced 20 mm apart from the magnet body 2. A power supply was connected to construct an electric circuit, with the magnet body 2 made a cathode and the counter electrode 3 made an anode. A DC voltage of 10 volts was applied for 10 seconds to effect electrodeposition. The magnet body was pulled out of the slurry and immediately dried in hot air. The magnet body 2 was turned up-side-down. As above, it was immersed in the slurry 1 to a depth of 1 mm, and similarly treated. The same operations were repeated, forming a thin coating of terbium oxide on the front and back surfaces and some of the four side surfaces of the magnet body 2. The particle-coated portions summed to about 62% of the surface area of the magnet body 2. The area density of terbium oxide deposited was 100 μg/mm.sup.2 on both the front and back surfaces of the magnet body.

(38) The magnet body having a thin coating of terbium oxide particles locally deposited thereon was subjected to absorption treatment in an argon atmosphere at 900° C. for 5 hours. It was then subjected to aging treatment at 500° C. for one hour, and quenched, obtaining a magnet body. From a central area on the front surface of the magnet body, a piece of 17 mm×17 mm×2 mm (magnetic anisotropic direction) was cut out and measured for magnetic properties. An increase of coercive force to 720 kA/m due to the absorption treatment was confirmed.

Example 2

(39) The procedure of Example 1 was repeated except that the magnet body 2 was immersed in the slurry 1 to a depth of 3 mm, forming a thin coating of terbium oxide on the front and back surfaces and some of the four side surfaces of the magnet body 2. The particle-coated portions summed to about 64% of the surface area of the magnet body 2. The area density of terbium oxide deposited was 100 μg/mm.sup.2 on both the front and back surfaces of the magnet body.

(40) The magnet body having a thin coating of terbium oxide particles locally deposited thereon was subjected to absorption treatment and aging treatment as in Example 1. A piece of 17 mm×17 mm×2 mm (magnetic anisotropic direction) was cut out of the magnet body and measured for magnetic properties. An increase of coercive force to 720 kA/m due to the absorption treatment was confirmed.

Example 3

(41) The procedure of Example 1 was repeated except that the magnet body 2 was immersed in the slurry 1 to a depth of 5 mm, forming a thin coating of terbium oxide on the front and back surfaces and some of the four side surfaces of the magnet body 2. The particle-coated portions summed to about 66% of the surface area of the magnet body 2. The area density of terbium oxide deposited was 100 μg/mm.sup.2 on both the front and back surfaces of the magnet body.

(42) The magnet body having a thin coating of terbium oxide particles locally deposited thereon was subjected to absorption treatment and aging treatment as in Example 1. A piece of 17 mm×17 mm×2 mm (magnetic anisotropic direction) was cut out of the magnet body and measured for magnetic properties. An increase of coercive force to 720 kA/m due to the absorption treatment was confirmed.

Comparative Example 1

(43) Electrodeposition was carried out as in Example 1 except that as shown in FIG. 2, a magnet body 2 was longitudinally and entirely immersed in the electrodepositing bath or slurry 1 and interposed between a pair of counter electrodes 3 at a spacing of 20 mm. A thin coating of terbium oxide deposited on the entire magnet body surfaces. The area density of terbium oxide deposited was 100 μg/mm.sup.2.

(44) The magnet body having a thin coating of terbium oxide particles deposited on the entire surfaces was subjected to absorption treatment and aging treatment as in Example 1. A piece of 17 mm×17 mm×2 mm (magnetic anisotropic direction) was cut out of the magnet body and measured for magnetic properties. An increase of coercive force to 720 kA/m due to the absorption treatment was confirmed.

Examples 4 to 6

(45) As in Example 1, a block magnet body having dimensions of 50 mm×80 mm×35 mm (magnetic anisotropy direction) was prepared. The procedure of Example 1 was repeated, forming a thin coating of terbium oxide on the front and back surfaces and some of the four side surfaces of the magnet body. Notably, the magnet body was immersed in the slurry to a depth of 1 mm in Example 4, 3 mm in Example 5, or 5 mm in Example 6. The particle-coated portions summed to about 48% in Example 4, about 49% in Example 5, or about 51% in Example 6 of the surface area of the magnet body. The area density of terbium oxide deposited was 100 μg/mm.sup.2 on the coated surface.

(46) The magnet body having a thin coating of terbium oxide particles locally deposited thereon was subjected to absorption treatment and aging treatment as in Example 1. A piece of 17 mm×17 mm×2 mm (magnetic anisotropic direction) was cut out of the magnet body and measured for magnetic properties. An increase of coercive force to 720 kA/m due to the absorption treatment was confirmed.

Comparative Example 2

(47) Electrodeposition was carried out as in Examples 4 to 6 except that as shown in FIG. 2, a magnet body 2 was longitudinally and entirely immersed in the electrodepositing bath or slurry 1 and interposed between a pair of counter electrodes 3 at a spacing of 20 mm. A thin coating of terbium oxide deposited on the entire magnet body surfaces. The area density of terbium oxide deposited was 100 μg/mm.sup.2.

(48) The magnet body having a thin coating of terbium oxide particles deposited on the entire surfaces was subjected to absorption treatment and aging treatment as in Example 1. A piece of 17 mm×17 mm×2 mm (magnetic anisotropic direction) was cut out of the magnet body and measured for magnetic properties. An increase of coercive force to 720 kA/m due to the absorption treatment was confirmed.

(49) The conditions and results of Examples 1 to 6 and Comparative Examples 1 and 2 are tabulated in Tables 1 and 2. The powder consumption, which is an amount of powder deposited, is computed from a weight gain of a magnet body before and after electrodeposition.

(50) TABLE-US-00001 TABLE 1 Magnet body of dimensions: 50 mm wide × 80 mm long × 20 mm thick Coercive Area Powder Relative force Immersion density consumption powder increase depth (μg/mm.sup.2) (g/body) consumption* (kA/m) Comparative entirety 100 1.320 100 720 Example 1 (electrodeposition on all surfaces) Example 1 1 mm 100 0.852 64.5 720 Example 2 3 mm 100 0.956 72.4 720 Example 3 5 mm 100 1.060 80.3 720 *Relative powder consumption is a powder consumption in Example relative to the powder consumption in Comparative Example 1 which is 100.

(51) TABLE-US-00002 TABLE 2 Magnet body of dimensions: 50 mm wide × 80 mm long × 35 mm thick Coercive Area Powder Relative force Immersion density consumption powder increase depth (μg/mm.sup.2) (g/body) consumption* (kA/m) Comparative entirety 100 1.710 100 720 Example 2 (electrodeposition on all surfaces) Example 4 1 mm 100 0.852 49.82 720 Example 5 3 mm 100 0.956 55.91 720 Example 6 5 mm 100 1.060 61.99 720 *Relative powder consumption is a powder consumption in Example relative to the powder consumption in Comparative Example 2 which is 100.

(52) As is evident from Tables 1 and 2, Examples wherein a portion of a magnet body is immersed in an electrodepositing bath to a depth of 1 to 5 mm, and terbium oxide particles are locally electrodeposited on the magnet body achieve a significant saving of the amount of terbium oxide particles consumed, as compared with Comparative Examples wherein the magnet body is immersed overall and particles are deposited on the entire surfaces. A greater saving of powder consumption is available as a magnet block becomes thicker.

(53) Japanese Patent Application No. 2014-029667 is incorporated herein by reference.

(54) Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.