METHOD FOR PRODUCING A RARE EARTH ALLOY AND RARE EARTH ALLOY

Abstract: A method for producing a rare earth alloy by reducing a mixture of corresponding rare earth oxides, Fe, and a boron containing material by Ca, contacting the reduced mass with water, and treating the resultant slurry with water whereby the resultant rare earth alloy for producing permanent magnet comprises 15-65 atomic % R₁, 35-83 atomic % Fe, and 0-15 atomic % B, where R₁ represents at least one of heavy rare earth elements Gd, Tb, Dy, Ho, Er, Tm and Yb. Using this alloy, Fe-B-R base magnets wherein R₁ is substituted for part of R (R representing lanthanide and/or Y) having a high performance are produced with modest costs.

Description: The present invention relates to a method for producing a rare earth alloy. Fe-B-R base magnets have attracted public attention as a novel permanent magnet with a high-performance using rare earth elements (R) represented by Nd, Pr etc. They have prominent advantages that they exhibit the characteristics comparable to those of a conventional high-performance magnet, e.g., the Sm-Co base magnet, do not require expensive and scarce Sm as R and do not necessarily use expensive Co which is difficult to be procured steadily, as disclosed in JP Patent Kokai No. 59-46008 or EP 0101552. Particularly, Nd has been hitherto regarded as having no utility value. Therefore, it is very valuable for industry that Nd can be used as a principal element. Recently, it has been attempted to provide high magnetic characteristics for the Fe-B-R base magnets and to produce them at lower costs. For example, the applicants' company developed a high-performance magnet using, as R, Nd and/or Pr mainly, and partly at least one of Gd, Tb, Dy, Ho, Er, Tm and Yb (hereinafter, these elements are referred to as R₁), and filed a patent application thereon (JP Appli­ cation No. 58-140590, now JP Patent Kokai No. 60-32306 or EP 0134305). In the JP Patent Kokai No. 60-32306, it was proposed that the superior R₁-R₂-Fe-B base rare earth magnets (wherein R₁ represents the same as hereinabove mentioned, and R₂ represents that the sum of Nd and/or Pr is at least 80 atomic % and the balance in R₂ is at least one of rare earth elements R other than R₁) are produced by substituting at least one of heavy rare earth elements R₁ for at most 5 atomic % of rare earth element such as Nd, Pr, etc. in the R-Fe-B base or P-Fe-Co-B Case rare earth magnets. These superior R₁-R₂-Fe-B base rare earth magnets enable to prominently raise the coercive force (iHc) to 796 k·A/m (10 kOe) or more and to be used at 100-150°C, i.e., temperatures higher than room temperature, while maintaining a high energy product of (BH) max of at least 159.2 k·TA/m (20 MGOe). As starting materials for the production of R₁-R₂-Fe-B base rare earth magnets, primarily there are used expensive bulk or lump metals having little impurities, such as electrolytic iron with a purity of at least 99.9%, and rare earth metals with a purity of at least 99.5% prepared by an electrolysis or a heat reduction. Therefore, any of these raw materials is the high quality material having little impurities previously refined from ores. Using these materials, the resultant magnets become considerably expensive in spite of the efforts for lowering the cost by using of Nd, Pr, etc. The content of the heavy rare earth metals R₁ such as Gd, Tb, Dy, Ho, Er, Tm, Yb, etc. which are effective for increasing the coercive force, is at most 7% in the ore, that is, less than the content of Nd which is 15%. Actually, such heavy rare earth metals are expensive, since their production requires high separating-refining , technics and their production efficiency is low. Consequently, R₁-R₂-Fe-B base permanent magnets having a high-performance and a high iHc are very valuable as the practical permanent magnet materials, but have a drawback in their high cost. It is a primary object of the present invention to provide a pro­ cess for inexpensive production of Fe-B-R alloys suitable for magnets showing higher magnetic characteristics. This object is solved by the process of claim 1. Further advantegeous features are evident from the subclaims. More specifically, the rare earth alloys prepared according to the method of the present invention have been developed for the purpose or producing high perfor­ mance permanent magnet of the R₁-R₂-Fe-B-Type (R₁ re­ presents at least one of rare earth elements including Gd, Tb, Dy, Ho, Er, Tm and Yb, and R₂ represents that the sum of Nd and/or Pr is at least 80 atomic % and the balance in R₂ is at least one of rare earth elements including Y other than R₁). Thus, the present invention provides a method for producing an R₁ base rare earth alloy with a reduced cost in an industrial scale. That is the present invention allow to eliminate the various drawbacks above-mentioned and to inexpensively provide a high-quality rare earth alloy containing the R₁-element in a mass-production scale and provides Fe-B-R base rare earth magnet materials having a high-performance, and particularly, a method for producing the same, where­ in R represents at least one of Nd, Pr, La, Ce, Tb, Dy, Ho, Er, Eu, Sm, Gd, Pm, Tm, yb, Lu, and Y. The present invention relates to a method for producing a rare earth alloy having said alloy composition with an oxygen content being at most 7000 ppm, and a carbon content being at most 1000 ppm, characterized in steps of: preparing a mixed raw material powder comprising at least one of the oxides of rare earth elements R₁, an iron powder and optionally a boron containing powder selected from the group consisting of boron, ferroboron, boron oxide, and alloys or mixed oxides of iron and boron in a manner such that the resultant alloy product consists essentially of: 15-65 atomic % R₁, 35-83 atomic % Fe, and 0-15 atomic % B, in which R₁ represents at least one of heavy rare earth elements selected from the group consisting of Gd, Tb, Dy, Ho, Er, Tm and Yb; said mixed raw material powder further comprising metallic Ca and/or Ca hydride in an amount of 1.2-3.5 times by weight of the amount stoichiometrically required for reducing oxygen in said raw material powder and at least one of the oxides of said rare earth elements R₁, and 1-15% by weight of calcium chloride based on the oxides of said rare earth elements R₁; subjecting the resultant mixture to reduction-diffusion treatment under a nonoxidizing atmosphere at a temperature of 950-1200°C; contacting the resultant reduced mass with water to form a slurry-like substance; and treating said slurry-like substance with water to recover the resultant alloy powder; whereby said alloy powder has an oxygen content of at most 7000 ppm, and a carbon content of at most 1000 ppm. Said R₁ is preferably 15-50 atomic %, and B is preferably 2-15 atomic %. In a further embodiment, said mixed raw material powder is prepared so that said alloy product consists essentially of: 25-40 atomic % R₁, 50-71 atomic % Fe, and 4-10 atomic % B. The reduction-diffusion treatment provides direct reduction of oxides in the starting materials. The reduced mass is preferably brought to a particle size from 2,38 mm (8 mesh) to 0.420 mm (35 mesh) prior to contacting with water. The contacting with water may be effected by bringing the reduced mass (or crushed or pulverized mass) in water. The reduction-diffusion treatment may be effected after compacting the resultant mixture, however, the compacting may be eliminated. As the heavy rare earth elements R₁ use of Ho, Tb and/or Dy is preferred, while most preferred is Dy. Tm and Yb might encounter some difficulty in procurement in a large amount and cost. Within this preferred range the alloy product may include R-Fe-B tetragonal crystal structure expressed by the formula R₂Fe₁₄B in an amount of, e.g., at least 50 vol %, more preferably at least 80 vol % of the entire alloy. In the following the preferred embodiments of the present invention will be described in detail. By using the R₁-Fe-B alloy powder obtained by the method of the present invention, it is possible to provide the inexpensive R₁-R₂-Fe-B base rare earth magnets which are used in a sufficiently stable state at temperatures higher than room temperature maintaining magnetic characteristics having a (BH) max of at least 159.2 k·TA/m (20 MGOe) and iHc of at least 796 k·A/m (10 kOe) The inexpensive heavy rare earth metal oxide as one of the starting materials used in the present invention includes Ho₂O₃, Tb₃O₄ and the like, which are present as the intermediates in the prestep for the preparation of rare earth metals. Since the rare earth alloy obtained by the process of the present invention is produced by using as starting materials such inexpensive heavy rare earth metal oxide, Fe-powder and at least one of pure boron powder, Fe-B powder and boron-containing powder (e.g., B₂O₃), by using as reducing material a metallic calcium powder and by using calcium chloride for easy collapse or disintegration of reduction-diffusion-reaction product, an inexpensive, improved alloy powder containing R₁ as the raw materials of R₁ for the R₁-R₂-Fe-B base magnets may be obtained easily in an industrial scale. Therefore, the method of the present invention is much superior in efficiency and economical effect, as compared with the conventional method using the produced R₁-rare earth metal of the bulk form. Hereupon, if the mixed powder of the R₁-rare earth metal oxide and metal powders such as Fe-powder, Fe-B powder, etc. as the starting materials is subjected to reduction-diffusion-reaction by metallic Ca, the rare earth metal in molten state at the reaction temperature in situ forms an alloy very easily and uniformly, together with Fe-powder or Fe-B powder. In this case, the R₁-rare earth alloy powder is recovered in a high yield from the R₁-rare earth metal oxide, and hence the R₁-rare earth metal oxide may be utilized effectively. The B (boron) content in the raw material powder serves to effectively drop the reaction temperature at the reduction-diffusion-reaction of the R₁-Fe-B alloy powder, and facilitates the reduction-diffusion-reaction of the alloy based on the present invention. Therefore, in order to produce R₁-heavy rare earth raw materials for the R₁-R₂-Fe-B base magnets in an industrial scale from the inexpensive heavy rare earth metal oxide, the inventors considered as most effective to produce the alloy powder from the heavy rare earth metal oxide, Fe which constitutes the main ingredient of the magnets and is produced inexpensively in a mass-production system, and B. From such points of view, the inventors have come to find a method for producing a R₁-Fe-B base alloy in a specific composition-range. Moreover, the method of the present invention has been developed for the purpose of producing the alloy for the above R₁-R₂-Fe-B base permanent magnet. However, the powder obtained by the method of the present invention is not limited to this purpose, and is applicable not only for the production of a wide range of Fe-B-R base magnets, but also for the production of various raw materials using Fe-B-R as a constituent ingredient. The method of the present invention may have the following steps, and the obtained alloy is usable to the alloys for the R₁-R₂-Fe-B base permanent magnets. The mixed raw material powder of at least one of various heavy rare earth metal oxides such as Ho oxide (Ho₂O₃), Tb oxide (Tb₄O₇), etc., and an iron powder, and at least one of pure boron powder, ferroboron (Fe-B) powder and boron trioxide (B₂O₃) powder is prepared in order to form the alloy product consisting essentially of: R₁ : 15-65 atomic %, Fe : 35-83 atomic %, and B : 0-15 atomic % in which R₁ represents one of heavy rare earth elements including Gd, Tb, Dy, Ho, Er, Tm and Yb. To the mixed raw material powder are added metallic calcium and/or calcium hydride as a reducing agent of the heavy rare earth metal oxide and CaCl₂-powder for promoting the collapse of the reaction product (briquette) after the reduction, consequently obtaining the incorporated materials. The amount of calcium (metallic or as hydride) required is 1.2-3.5 times (by weight) as much as the amount stoichiometrically required for the reduction of oxygen content of the mixed raw material powder. The amount of CaCl₂ is 1-15% by weight, based on the rare earth metal oxide raw materials. Mixing of all the materials may be done at once or sequentially. The above mixed materials including each raw material powder such as heavy rare earth metal oxide powder, Fe-powder, ferroboron powder, Ca as a reducing agent and the like, is (occasionally compacted and) subjected to reduction-diffusion treatment under the atmosphere of an inert gas (e.g., argon) for 1 to 5 hours preferably at a temperature ranging 950 to 1200°C, more preferably 950 to 1100°C, and then is cooled to room temperature to result in a reduction-reaction product. This reaction product is usually pulverized to a particle size of at most 8 mesh (at most 2.4 mm), and is brought into water, in which calcium oxide (CaO), CaO·2CaCl₂ and excess Ca in the reaction product are converted into calcium hydroxide [Ca (OH)₂] etc. while the reaction product itself collapses to form a slurry mixed with water. From this slurry, the Ca contained is throughly removed with water, consequently obtaining a rare earth alloy powder having a particle size of 5 µm-1 mm according to the present invention. Considering the workability in a magnet production step and the magnetic characteristics, the particle size of the powder of the present invention is preferably 20 µm-1 mm, more preferably 20 µm- 500 µm. At a temperature below 950°C the reduction-diffution reaction becomes insufficient, while above 1200°C wear of furnace becomes serious. When the reduction-reaction product is brought into water without pulverization to a particle size of at most 2,38 mm (8 mesh), that is, as such or as a particle size of more than 2,38 mm (8 mesh), it might become occasionally unsuitable for the industrial production due to slow collapse and reaches a high temperature due to the accumulated destruction-reaction heat in its product if blocks are too large, so that the obtained rare earth alloy powder might have an oxygen content of more than 7000 ppm and hence become unsuitable for use in the subsequent magnet-production step. If the reduction-reaction product has a particle size of less than 0,420 mm (35 mesh), it starts to burn due to vigorous reaction. Preferably, water used in the present invention is ion-exchanged water or distilled water, considering the little oxygen content in the alloy powder, high yield in the magnet-producing step and good magnetic characteristics. Thus obtained alloy powder for the magnetic materials consists essentially of the following composition: R₁ : 15-65 atomic % (preferably 15-50 atomic %), Fe : 35-83 atomic %, and B : 0-15 atomic % (preferably 2-15 atomic %), in which R₁ represents at least one of heavy rare earth elements including Gd, Tb, Dy, Ho, Er, Tm and Yb, with an oxygen content being at most 7000 ppm, and a carbon content being at most 1000 ppm. Using this alloy powder, the R₁-R₂-Fe-B base permanent magnet may be produced, as described hereafter. More preferred composition range of the rare earth alloy powder obtained by the method of the present invention is as follows: R₁ : 25-40 atomic %, Fe : 50-71 atomic %, and B : 4-10 atomic %. In this composition, the oxygen content of the alloy powder comes to at most 4000 ppm, and the carbon content thereof comes to at most 600 ppm. This facilitates formation of the alloy, causes less generation of slag, increases yield of the alloy product and makes the effective use of the alloy powder possible, in the course of melt-alloying of the R₁-R₂-Fe-B magnetic alloy. If the alloy powder as such is used by being added in the pulverization step, the amounts of the oxides and the carbides are reduced in the permanent magnet, so that the R₁-R₂-Fe-B permanent magnet achieves a high coercive force and excellent magnetic characteristics. Further, the reducing temperature becomes 950-1100°C, which facilitates the production in an industrial scale. The rare earth alloy powder obtained by the method of the present invention can be used either by adding a required amount of the alloy powder obtained by the method of the present invention as a compact or sintered mass upon melt-alloying the R₁-R₂-Fe-B magnetic alloy, or by adding a required amount of the alloy powder obtained by the method of the present invention as such to a separately prepared R₂-Fe-B alloy powder in the pulverization-step to obtain the mixed R₁-R₂-Fe-B alloy powder. In any case, the method of the present invention has advantages that it shortens the process for the production of the magnets and lowers the costs of the produced magnet due to the use of inexpensive raw materials. Further, it has advantageous economical effects since it facilitates the mass-production of practical permanent magnets. The oxygen in the alloy powder obtained by the process of the present invention is combined with the rare earth element to be most easily oxidized to form rare earth metal oxide. Therefore, if the oxygen content is more than 7000 ppm, the melting of the alloy in the melting-step of the R₁-R₂-Fe-B magnetic alloy becomes difficult, which does not form an alloy, causes a considerable generation of slag, lowers the yield of the alloy product and hence prevents the effective use of the alloy powder obtained by the method the present invention. If the carbon content is more than 1000 ppm, carbides are left in the final permanent magnet product, which leads to an undesirable decrease of magnetic characteristics, particularly a decrease of the coercive force below 796 k·A/m (10 kOe) and deteriorates the loop squareness of the de­ magnetization curve of the magnet. If the oxygen content is more than 7000 ppm and the carbon content is more than 1000 ppm in the case where the alloy powder as such is used by adding in the pulverization-step, both ingredients are left as oxides and carbides (R₃C, R₂C₃, RC₂) in the resultant permanent magnet, which lowers the coercive force remarkably. If the Ca content as the reducing agent of the raw materials of the present invention exceeds 3.5 times as much as the amount required stoichiometrically, vigorous chemical reaction occurs in the reduction-diffusion-reaction, which causes prominent heat generation and brings about serious wear of a reaction vessel by the highly reductive Ca, and hence makes the steady mass-production impossible. Further, in this case, the residual Ca content in the alloy powder produced in the reduction-step becomes high, which wears out the furnace in the heat-treating-step of magnet production due to generation of much Ca vapor and deteriorates the magnetic characteristics due to the high Ca content in the magnet product. If the Ca content is less than 1.2 times as much as that required stoichiometrically, the reduction-diffusion-reaction is incomplete and non-reduced substances are left in a large amount, so that the alloy powder is not obtained. The amount of Ca is preferably 1.5-2.5 times, most preferably 1.6-2.0 times of the stoichiometric amount. If the amount of CaCl₂ exceeds 15% (by weight), the Cl⁻(Chlorine ion) in water increases remarkably in the treatment of the reduction-diffusion-reaction product with water, and reacts with the produced rare earth alloy powder, so that the oxygen content of the powder attains more than 7000 ppm, and the powder can not be utilized as raw materials for the R₁-R₂-Fe-B magnets. Besides, in case of less than 1 weight % of CaCl₂, the collapse does not occur even if the reduction-diffusion-reaction product is put into water, thus its treatment by water becomes impossible. The reasons for limiting the range of the composition of the rare earth alloy powder obtained by the method of the present invention are as follows. Where the R₁ element (at least one of Gd, Tb, Dy, Ho, Er, Tm and Yb), which is indispensable for improving the coercive force (iHc) of the R₁-R₂-Fe-B base rare earth magnets, is less than 15 atomic %, the residual Fe content increases and the oxygen content in the alloy powder attains more than 7000 ppm, the melting of the R₁-R₂-Fe-B base magnetic alloy in the melt production becomes difficult, which does not form the alloy, causes slag formation, ant lowers the yield of the melt-formed alloy. If the R₁ element is more than 65 atomic %, the amount of the rare metal oxide in the raw materials for the reduction is too large to be reduced sufficiently or to form the rare earth metal oxide adequately. In this case, the oxygen content of the alloy powder is more than 7000 ppm, which brings about, as is the case with the previous case, the difficult alloy formation and the drop in the alloy yield. Thus the R₁ element of no more than 50 atomic % is preferred. Fe is an indispensable element for directly obtaining the rare earth alloy, which is inexpensive and of good quality, by the process wherein the R₁ rare earth element obtained by the reduction of the heavy rare earth metal oxide with metallic calcium diffuses immediately. In the case of less than 35 atomic % or more than 83 atomic % of the Fe content, the oxygen content of the alloy powder becomes more than 7000 ppm, and the carbon content thereof becomes more than 1000 ppm, so that the production of a superior magnet from the alloy becomes difficult, the yield of the melt-produced alloy decreases and the alloy powder is unable to be used for the magnetic alloys. B (boron) is preferred element for lowering the reduction-diffusion temperature of the alloy. B is effective at 0.1 atomic % or more. In the case of less than 2 atomic % of B content, the reduction temperature of more than 1200°C is occasionally required, and the utilization of the equipment of an industrial scale becomes difficult since the extremely high reductive Ca is used. Further, in the case of more than 15 atomic % of the B content, the oxygen content of the rare earth alloy powder obtained reaches more than 7000 ppm since boron is subjected to oxidation easily, so that, as the previous case, the magnet production from the alloy becomes difficult, the yield of the melt-formed alloy decreases and the alloy powder is not effective as the alloy powder for magnetic materials. As mentioned previously, the alloy produced in accordance with the present invention includes one having an Fe-B-R tetragonal crystal structure within the preferred alloy composition, while the presence of such crystal structure is not essential for the entire compositional scope of the present invention. However, even the alloy product having no FeBR tetragonal crystal structure may be utilized to prepare the FeBR₁R₂ alloy having the said crystal structure. Generally the directly reduced alloy product is of the crystalline nature (e.g., crystal grain size of 20-120 µm). In order to produce a FeBR₁R₂ sintered magnet a mixture (or preferably an alloy thereof) of said alloy product and appropriate FeBR₂ (e.g., FeBNd) is prepared and pulverized to preferably 1-20 µm in size, then compacted and sintered, usually followed by aging. For preparing the FeBR₁R₂ alloy, said FeBR₁ alloy product is preferably consolidated by compacting, melting and/or sintering, or hot pressing or the like manner, then melted together with the FeBR₂ alloy. This consolidation provides easy alloying by high frequency melting. The resultant permanent magnet is generally of the FeBR tetragonal crystal structure (i.e., at least 80 vol % of the entire magnet), the crystal grain being preferably 1-40 µm (most preferably 3-20 µm) for excellent permanent magnet properties. The detailed disclosure about the FeBR tetragonal crystal structure is disclosed in EP 0101552 and herewith referred to. It should be noted that the alloy produced in accordance with the method of the invention may be utilized in producing FeCoBR₁R₂ type permanent magnet (refer to EP 0134304) wherein Co is present to be substituted for a part of Fe in the FeBR₁R₂ type magnet. Furthermore, the alloy powder obtained by the method of the present invention may contain at most 2 % by weight of impurities inevitable in the technically available raw materials or in the manufacturing steps, for examples, Al, Si, P, Ca, Mg, Cu, S, Nb, Ni, Ta, V, Mo, Mn, W, Cr, Hf, Ti, Co etc., however the impurities should be as less as possible, e.g., at most 1 % by weight, or even at most 0.5 % by weight. Cu, S and P are particularly not preferred. When the calcium content exceeds 2000 ppm, a large amount of strongly reducing Ca vapor is generated in the intermediate sintering step of the subsequent steps for making magnets from the alloy powders obtained by the method of the present invention. The Ca vapor contaminates the heat-treatment furnace used to a considerable extent and, in some cases, give rise to serious damage to the wall thereof, such that it becomes impossible to effect the industrially stable production of magnets. In addition, if the amount of Ca contained in the alloy powders formed by reduction is so large that a large amount of Ca vapor is generated at the time of heat treatment involved in the subsequent steps for making magnets to give damage to the heat treatment furnace used. This also leads to a large amount of Ca remaining in the resulting magnets, entailing deteriorations in the magnet properties thereof as a result. Thus a calcium content of 2000 ppm or less is preferred, most preferred is 1000 ppm or less. Usually, the amount of rare earth elements in the rare earth metal oxides as the starting materials is calculated in considering the yield, and may be, e.g., 1.1 times of the amount in the alloy product. Examples Various rare earth alloy powders will now be described in detail with reference to the following examples. Example 1. Tb₄O₇ powder : 75.2 g Fe powder : 35.1 g Ferroboron powder (19.5 wt% B-Fe alloy powder) : 2.2 g Metallic Ca : 72.4 g (2.5 times as much as the amount required stoichiometrically) CaCl₂ : 3.8 g (5.1 wt% based on the rare earth metal oxide materials) 188.7 g of all the raw materials above-described were mixed in a V-type mixer, aiming at an alloy composed of 35% Tb -61% Fe-4% B (atomic %) (61.72 wt% Tb-37.80 wt% Fe-0.48 wt% B). Then, compacts of the mixed raw materials were charged in a stainless steel vessel, then placed in a muffle furnace, and heated in argon gas flow. After having been held constant at 1075°C for 3 hours, the furnace was cooled to room temperature. The resultant reductive reaction product was pulverized to a particle size of 2,38 mm-through (8 mesh-through), then was introduced into an ion-exchanged water, in which calcium oxide (CaO), CaO·2CaCl₂ and unreacted residual calcium were converted into calcium hydroxide allowing the reaction products to collapse to form a slurry-like product. After stirring for 1 hour, the product was allowed to stand for 30 minutes, and then the suspension of calcium hydroxide was removed. The product was again diluted with water. The Steps of stirring, standing and suspension-removing were repeated many times. Thus separated and withdrawn Tb-Fe-B base alloy powder was dried under vacuum. In this manner, there were obtained 76 g of the heavy rare earth alloy powder for the magnet raw materials of a 20-300 µm particle size. The elementary analysis values of this powder were as follows: Tb : 60.11 wt% Fe : 39.45 wt% B : 0.37 wt% Ca : 0.08 wt% O₂ : 1900 ppm C : 250 ppm As a result, the desired alloy powder was obtained. A sintered body was prepared by treating the above alloy powder at 1150°C for 2 hours in order to prepare a magnetic alloy composed of 14 Nd-1.5 Tb-77.5 Fe-7 B (atomic %). This sintered body as the raw material of Tb was melted with the beforehand prepared metallic Nd, ferroboron alloy and Fe material. The resultant melt-formed alloy piece was pulverized to a powder having an average particle size of 2.70 µm, then was compacted in a magnetic field of 796 k·A/m (10 kOe) under a pressure of 1471 bar (1.5t/cm²), thereafter was sintered at 1120°C for 2 hours, and was aged at 600°C for 1 hour to pro­ duce a permanent magnet specimen. The obtained magnet specimen exhibited excellent magnetic characteristics as follows: Br = 1.15 T (11.5 kG) iHc = 1512.4 k·A/m (19 kOe) (BH)max = 249.1 k·TA/m (31.3 MGOe) Example 2 Tb ₄ O₇ : 22.9 g Dy ₂ O₃ : 5. 9 g Ho₂O₃ : 16.3 g Fe powder : 42.6 g Ferroboron powder (20.4 wt% B-Fe alloy powder) : 8.0 g Metallic Ca : 26.6 g (1.5 times as much as the amount required stoichiometrically) CaCl₂ : 2.7 g (5.9 wt% base on the rare earth metal oxide materials) 122.3 g of all the raw materials above-described were treated in the same manner as in Example 1 except that this example aimed at obtaining an alloy composition of 8% Tb-5% Ho-2% Dy-73% Fe-12% B (atomic %) (19.18% Tb-12.44% Ho ­ 4.90% Dy-61.51% Fe-1.96% B, by weight %). There was obtained 86g of an alloy powder having a 50-500 µm particle size. The elementary analysis values of this powder were as follows: Tb : 19.74 wt% Dy : 4.23 wt% Fe : 60.73 wt% Ho : 13.28 wt% B : 1.86 wt% Ca : 0.16 wt % O₂ : 5500 ppm C : 750 ppm As a result, the required alloy powder was obtained. A compact was prepared by compacting the above alloy powder under a pressure of 1961 bar (2 t/cm²) for preparing a magnetic alloy composed of 14 Nd-0.2 Tb-0.15 Ho-0.05 Dy-78.6 Fe -7 B (atomic %). The compact as the raw material of Tb-Ho-Dy was melted with metallic Nd, ferroboron alloy and Fe material. The resultant melt-produced alloy piece was pulverized to a powder having an average particle size of 2.67 µm, then was compacted in a magnetic field of 796 k·A/m (10 kOe) under a pressure of 1471 bar (1.5 t/cm²), thereafter was sintered at 1120°C for 2 hours and was aged at 600°C for 1 hour to produce a permanent magnet. The obtained magnet exhibited excellent magnetic characteristics as follows: Br = 1.24 T (12.4 kG) iHc = 915.4 k·A/m (11.5 kOe) (BH)max. = 285.0 k·TA/m (358 MGOe) Example 3 Mixed heavy rare earth metal oxides ; 91.4 g The composition of the mixed heavy rare earth metal oxides is as follows: Dy₂O₃ : 80 wt% Tb₄O₇ : 10 wt% Ho₂O₃ : 3 wt% Er₂O₃ : < 0.5 wt% Tm₂O₃ : < 0.5 wt% Gd₂O₃ : 6 wt% Yb₂O₃ : < 0.5 wt% Fe powder : 22.1 g Ferroboron powder (20.0 wt% B-Fe alloy powder) : 1.8 g Metallic Ca : 97.3 g (3.3 times as much as the amount required stoichiometrically) CaCl₂ : 11.0 g (12.0 wt% based on the rare earth metal oxide materials) 223.6 g of all the raw materials above-described were treated in the same manner as in Example 1 except that this example aimed at obtaining an alloy composition of 50% R₁ -46% Fe-4% B (atomic %) (75.7 wt% R₁-23.9 wt% Fe-0.4 wt% B). There was obtained 73 g alloy powder having a 10-650 µm particle size. The elementary analysis values of this powder were as follows: As a result, the required alloy powder was obtained. This alloy powder having a particle size of at most 500 µm (_35 mesh) and the Nd-Fe-B alloy powder beforehand prepared to a particle size of at most-0,420 mm (35 mesh) after ist melting were mixed, aimed at the production of an alloy composed of 14 Nd-1.5 R₁-77.5 Fe-7 B (atomic %). The mixed powder was pulverized by means of a ball mill for 3.5 hours to produce a fine powder having an average particle size of 2.7 µm. A permanent magnet specimen was produced from this fine powder in the manner as in Example 1. The obtained magnet speciment exhibited excellent magnetic characteristics as follows : Br = 1,14 T (11.4 kG) iHc = 1393.0 k·A/m (17.50 kOe) (BH)max = 246.0 k·TA/m (30.9 MGOe)

Claims: 1. A method for producing a rare earth alloy which comprises: preparing a mixed raw material powder comprising at least one of the oxides of rare earth elements R₁, an iron powder and optionally a boron containing powder selected from the group consisting of boron, ferroboron, boron oxide, and alloys or mixed oxides of iron and boron in a manner such that the resultant alloy product consists essentially of: 15-65 atomic % R₁, 35-83 atomic % Fe, and 0-15 atomic % B, in which R₁ represents at least one of heavy rare earth elements selected from the group consisting of Gd, Tb, Dy, Ho, Er, Tm and Yb; said mixed raw material powder further comprising metallic Ca and/or Ca hydride in an amount of 1.2-3.5 times by weight of the amount stoichiometrically required for reducing oxygen in said raw material powder and at least one of the oxides of said rare earth elements R₁, and 1-15% by weight of calcium chloride based on the oxides of said rare earth elements R₁; subjecting the resultant mixture to reduction-diffusion treatment under a nonoxidizing atmosphere at a temperature of 950-1200°C. contacting the resultant reduced mass with water to form a slurry-like substance; and treating said slurry-like substance with water to recover the resultant alloy powder; whereby said alloy powder has an oxygen content of at most 7000 ppm, and a carbon content of at most 1000 ppm. 2. The method according to claim 1, in which said mixed raw materiel powder is prepared so that said alloy product consists essentially of : 25-40 atomic % R₁, 50-71 atomic % Fe, and 4-10 atomic % B. 3. The method according to claim 1, in which said mixed raw material powder is prepared so that it comprises at least 35 atomic % R₁. 4. The method according to claim 1 or 3, in which said mixed raw material powder is prepared so that said alloy product consists essentially of : 35 atomic % R₁ 61 atomic % Fe, and 4 atomic % B. 5. The method according to claim 1 or 3, in which said mixed raw material powder is prepared so that said alloy product consist essentially of : 50 atomic % R₁, 46 atomic % Fe, and 4 atomic % B. 6. The method according to one of the preceding claims in which said reduced mass is brought to a particle size from 2,38 mm (8 mesh) to 0,420 mm (35 mesh) prior to contacting with water. 7. The method according to one of the preceding claims, in which said reduced mass is brought to a particle size from 20 µm to 1 mm after contacting it with water. 8. The method according to one of the preceding claims, which further comprises a step of compacting said resultant mixture prior to the reduction-diffusion treatment. 9. The method according to one of the preceding claims, wherein the treating with water is effected until the amount of Ca becomes no more than 2000 ppm in the resultant alloy powder. 10. The method according to one of the preceding claims, wherein the reduction-diffusion treatment is effected at a temperature from 950 to 1100°C. 11. The method according to one of the preceding claims, wherein the method further comprises consolidation of the resultant alloy powder.

Inventors: FUJIMURA, SETSUO 473-2-205 MORINOKI-CHO, HAMADA, TAKAKI, ISHIGAKI, NAOYUKI
Applicants: SUMITOMO SPECIAL METALS CO., LTD.
Application year: 1986
Main classification: C22B5
IPC codes: C22C1, C22B5, C22B59, B22F9, H01F1