R—Fe—B sintered magnet and making method

Abstract

The invention provides an RFeB sintered magnet consisting essentially of 12-17 at % of Nd, Pr and R, 0.1-3 at % of M.sub.1, 0.05-0.5 at % of M.sub.2, 4.8+2*m to 5.9+2*m at % of B, and the balance of Fe, containing R.sub.2(Fe,(Co)).sub.14B intermetallic compound as a main phase, and having a core/shell structure that the main phase is covered with grain boundary phases. The sintered magnet exhibits a coercivity of at least 10 kOe despite a low or nil content of Dy, Tb and Ho.

Claims

1. An RFeB base sintered magnet of a composition consisting essentially of: 12 to 17 at % of R which comprises at least Nd and Pr, and optionally one or more elements selected from a group consisting of yttrium and rare earth elements other than Nd and Pr, 0.1 to 3 at % of M.sub.1 which is at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi, 0.05 to 0.5 at % of M.sub.2 which is at least one element selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W, 4.8+2m to 5.9+2m at % of B wherein m stands for atomic concentration of M.sub.2, up to 10 at % of Co, up to 0.5 at % of carbon, up to 1.5 at % of oxygen, up to 0.5 at % of nitrogen, and the balance of Fe, the RFeB base sintered magnet containing R.sub.2(Fe,(Co)).sub.14B intermetallic compound as a main phase, and having a coercivity of at least 10 kOe at room temperature, wherein the magnet contains a M.sub.2 boride phases at grain boundary triple junctions, but not including R.sub.1.1Fe.sub.4B.sub.4 compound phase, has a core/shell structure that the main phase is covered with grain boundary phases comprising an amorphous and/or sub-10 nm nanocrystalline RFe(Co)-M.sub.1 phase consisting essentially of 25 to 35 at % of R, 2 to 8 at % of M.sub.1, up to 8 at % of Co, and the balance of Fe, or the RFe(Co)-M.sub.1 phase and a crystalline or a sub-10 nm nano-crystalline and amorphous R-M.sub.1 phase having at least 50 at % of R, wherein a surface area coverage of the RFe(Co)-M.sub.1 phase on the main phase is at least 50%, and the width of the intergranular grain boundary phase is at least 10 nm and at least 50 nm on the average.

2. The sintered magnet of claim 1 wherein in the RFe(Co)-M.sub.1 phase, M.sub.1 consists of 0.5 to 50 at % of Si and the balance of at least one element selected from the group consisting of Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi.

3. The sintered magnet of claim 1 wherein in the RFe(Co)-M.sub.1 phase, M.sub.1 consists of 1.0 to 80 at % of Ga and the balance of at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi.

4. The sintered magnet of claim 1 wherein in the RFe(Co)-M.sub.1 phase, M.sub.1 consists of 0.5 to 50 at % of Al and the balance of at least one element selected from the group consisting of Si, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi.

5. The sintered magnet of claim 1 wherein a total content of Dy, Tb and Ho is 0 to 5.0 at %.

6. A method for preparing the RFeB base sintered magnet of claim 1, comprising the steps of: shaping an alloy powder into a green compact, the alloy powder being obtained by finely pulverizing an alloy consisting essentially of 12 to 17 at % of R which comprises at least Nd and Pr, and optionally one or more elements selected from a group consisting of yttrium and rare earth elements other than Nd and Pr, 0.1 to 3 at % of M.sub.1 which is at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi, 0.05 to 0.5 at % of M.sub.2 which is at least one element selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W, 4.8+2m to 5.9+2m at % of B wherein m stands for atomic concentration of M.sub.2, up to 10 at % of Co, and the balance of Fe, sintering the green compact at a temperature of 1,000 to 1,150 C., cooling the sintered compact to a temperature of 400 C. or below, post-sintering heat treatment including heating the sintered compact at a temperature in the range of 700 to 1,100 C. which temperature is exceeding peritectic temperature of RFe(Co)-M.sub.1 phase, and cooling down to a temperature of 400 C. or below at a rate of 5 to 100 C./min, and aging treatment including exposing the sintered compact at a temperature in the range of 400 to 600 C. which temperature is lower than the peritectic temperature of RFe(Co)-M.sub.1 phase so as to form the RFe(Co)-M.sub.1 phase at a grain boundary, and cooling down to a temperature of 200 C. or below.

7. The method of claim 6 wherein the alloy contains Dy, Tb and Ho in a total amount of 0 to 5.0 at %.

8. A method for preparing the RFeB base sintered magnet of claim 1, comprising the steps of: shaping an alloy powder into a green compact, the alloy powder being obtained by finely pulverizing an alloy consisting essentially of 12 to 17 at % of R which comprises at least Nd and Pr, and optionally one or more elements selected from a group consisting of yttrium and rare earth elements other than Nd and Pr, 0.1 to 3 at % of M.sub.1 which is at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi, 0.05 to 0.5 at % of M.sub.2 which is at least one element selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W, 4.8+2m to 5.9+2m at % of B wherein m stands for atomic concentration of M.sub.2, up to 10 at % of Co, and the balance of Fe, sintering the green compact at a temperature of 1,000 to 1,150 C., cooling the sintered compact to a temperature of 400 C. or below at a rate of 5 to 100 C./min, and aging treatment including exposing the sintered compact at a temperature in the range of 400 to 600 C. which temperature is lower than the peritectic temperature of RFe(Co)-M.sub.1 phase so as to form the RFe(Co)-M.sub.1 phase at a grain boundary, and cooling down to a temperature of 200 C. or below.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a Back scatter electron image (3000) in cross section of a sintered magnet in Example 1, observed under electron probe microanalyzer (EPMA).

(2) FIG. 2a is an electron image of grain boundary phase in the sintered magnet in Example 1, observed under TEM; FIG. 2b is an electron beam diffraction pattern at point a in FIG. 2a.

(3) FIG. 3 is a bright-field image of a sintered magnet in Example 11.

(4) FIG. 4 is a Back scatter electron image in cross section of a sintered magnet in Comparative Example 2, observed under EPMA.

DESCRIPTION OF PREFERRED EMBODIMENTS

(5) First, the composition of the RFeB sintered magnet is described. The magnet has a composition (expressed in atomic percent) consisting essentially of 12 to 17 at %, preferably 13 to 16 at % of R, 0.1 to 3 at %, preferably 0.5 to 2.5 at % of M.sub.1, 0.05 to 0.5 at % of M.sub.2, 4.8+2m to 5.9+2m at % of B wherein m stands for atomic concentration of M.sub.2, up to 10 at % of Co, up to 0.5 at % of carbon, up to 1.5 at % of oxygen, up to 0.5 at % of nitrogen, and the balance of Fe.

(6) Herein, R is at least two of yttrium and rare earth elements and essentially contains neodymium (Nd) and praseodymium (Pr). Preferably the total amount of Nd and Pr account for 80 to 100 at % of R. When the content of R in the sintered magnet is less than 12 at %, the coercivity of the magnet extremely decreases. When the content of R is more than 17 at %, the remanence (residual magnetic flux density, Br) of the magnet extremely decreases. Notably Dy, Tb and Ho may not be contained as R, and if any, the total amount of Dy, Tb and Ho is preferably up to 5.0 at % (i.e., 0 to 5.0 at %), more preferably up to 4.0 at % (i.e., 0 to 4.0 at %), even more preferably up to 2.0 at % (i.e., 0 to 2.0 at %), and especially up to 1.5 at % (i.e., 0 to 1.5 at %).

(7) M.sub.1 is at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi. When the content of M.sub.1 is less than 0.1 at %, the RFe(Co)-M.sub.1 grain boundary phase is present in an insufficient proportion to improve the coercivity. When the content of M.sub.1 is more than 3 at %, the squareness of the magnet get worse and the remanence of the magnet decreases significantly. The content of M.sub.1 is preferably 0.1 to 3 at %.

(8) An element M.sub.2 to form a stable boride is added for the purpose of inhibiting abnormal grain growth during sintering. M.sub.2 is at least one element selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W. M.sub.2 is desirably added in an amount of 0.05 to 0.5 at %, which enables sintering at a relatively high temperature, leading to improvements in squareness and magnetic properties.

(9) In particular, the upper limit of B is crucial. If the boron (B) content exceeds (5.9+2m) at % wherein m stands for atomic concentration of M.sub.2, the RFe(Co)-M.sub.1 phase is not formed in grain boundary, but an R.sub.1.1Fe.sub.4B.sub.4 compound phase, which is so-called B-rich phase, is formed. As long as the inventors' investigation is concerned, when the B-rich phase is present in the magnet, the coercivity of the magnet cannot be enhanced enough. If the B content is less than (4.8+2m) at %, the percent volume of the main phase is reduced so that magnetic properties of the magnet become worse. For this reason, the B content is better to be (4.8+2m) to (5.9+2m) at %, preferably (4.9+2m) to (5.7+2m) at %.

(10) The addition of Cobalt (Co) to the magnet is optional. For the purpose of improving Curie temperature and corrosion resistance, Co may substitute for up to 10 at %, preferably up to 5 at % of Fe. Co substitution in excess of 10 at % is undesirable because of a substantial loss of the coercivity of the magnet.

(11) For the inventive magnet, the contents of oxygen, carbon and nitrogen are desirably as low as possible. In the production process of the magnet, contaminations of such elements cannot be avoided completely. An oxygen content of up to 1.5 at %, especially up to 1.2 at %, a carbon content of up to 0.5 at %, especially up to 0.4 at %, and a nitrogen content of up to 0.5 at %, especially up to 0.3 at % are permissible. The inclusion of up to 0.1 at % of other elements such as H, F, Mg, P, S, Cl and Ca as the impurity is permissible, and the content thereof is desirably as low as possible.

(12) The balance is iron (Fe). The Fe content is preferably 70 to 80 at %, more preferably 75 to 80 at %.

(13) An average grain size of the magnet is up to 6 m, preferably 1.5 to 5.5 m, and more preferably 2.0 to 5.0 m, and an orientation of the c-axis of R.sub.2Fe.sub.14B grains, which is an easy axis of magnetization, preferably is at least 98%. The average grain size is measured as follows. First, a cross-section of sintered magnet is polished, immersed into an etchant such as vilella solution (mixture of glycerol:nitric acid:hydrochloric acid=3:1:2) for selectively etching the grain boundary phase, and observed under a laser microscope. On analysis of the image, the cross-sectional area of individual grains is determined, from which the diameter of an equivalent circle is computed. Based on the data of area fraction of each grain size, the average grain size is determined. The average grain size is the average of about 2,000 grain sizes at the different 20 images. The average grain size of the sintered body is controlled by reducing the average particle size of the fine powder during pulverizing.

(14) The microstructure of the magnet contains R.sub.2(Fe,(Co)).sub.14B phase as a main phase, and RFe(Co)-M.sub.1 phase and R-M.sub.1 phase as a grain boundary phase. The RFe(Co)-M.sub.1 phase accounts for preferably at least 1% by volume. If the RFe(Co)-M.sub.1 grain boundary phase is less than 1 vol %, a enough high coercivity cannot be obtained. The RFe(Co)-M.sub.1 grain boundary phase is desirably present in a proportion of 1 to 20% by volume, more desirably 1 to 10% by volume. If the RFe(Co)-M.sub.1 grain boundary phase is more than 20 vol %, there may be accompanied a substantial loss of remanence. Herein, the main phase is preferably free of a solid solution of an element other than the above-identified elements. Also R-M.sub.1 phase may coexist. Notably precipitation of R.sub.2(Fe,(Co)).sub.17 phase is not confirmed. Also the magnet contains M.sub.2 boride phase at the grain boundary triple junction, but not R.sub.1.1Fe.sub.4B.sub.4 compound phase. R-rich phase, and phases formed from inevitable elements included in the production process of the magnet such as R oxide, R nitride, R halide and R acid halide may be contained.

(15) The RFe(Co)-M.sub.1 grain boundary phase is a compound containing Fe or Fe and Co, and considered as an intermetallic compound phase having a crystal structure of space group I4/mcm, for example, R.sub.6Fe.sub.13Ga.sub.1. On quantitative analysis by electron probe microanalyzer (EPMA), this phase consists of 25 to 35 at % of R, 2 to 8 at % of M.sub.1, 0 to 8 at % of Co, and the balance of Fe, the range being inclusive of measurement errors. A Co-free magnet composition may be contemplated, and in this case, as a matter of course, neither the main phase nor the RFe(Co)-M.sub.1 grain boundary phase contains Co. The RFe(Co)-M.sub.1 grain boundary phase is distributed around main phases such that neighboring main phases are magnetically divided, leading to an enhancement in the coercivity.

(16) In the RFe(Co)-M.sub.1 phase, it is preferred that M.sub.1 consists of 0.5 to 50 at % (based on M.sub.1) of Si and the balance of at least one element selected from the group consisting of Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi; 1.0 to 80 at % (based on M.sub.1) of Ga and the balance of at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi; or 0.5 to 50 at % (based on M.sub.1) of Al and the balance of at least one element selected from the group consisting of Si, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi. These elements can form stable intermetallic compounds such as R.sub.6Fe.sub.13Ga.sub.1 and R.sub.6Fe.sub.13Si.sub.1 as mentioned above, and are capable of relative substitution at M.sub.1 site. Multiple additions of such elements at M.sub.1 site does not bring a significant difference in magnetic properties, but in practice, achieves stabilization of magnet quality by reducing the variation of magnetic properties and a cost reduction by reducing the amount of expensive elements.

(17) The width of the RFe(Co)-M.sub.1 phase in intergranular grain boundary is preferably at least 10 nm, more preferably 10 to 500 nm, even more preferably 20 to 300 nm. If the width of the RFe(Co)-M.sub.1 is less than 10 nm, a coercivity enhancement effect due to magnetic decoupling is not obtainable. Also preferably the width of the RFe(Co)-M.sub.1 grain boundary phase is at least 50 nm on an average, more preferably 50 to 300 nm, and even more preferably 50 to 200 nm.

(18) The RFe(Co)-M.sub.1 phase intervenes between neighboring R.sub.2Fe.sub.14B main phases as intergranular grain boundary phase, and is distributed around main phase so as to cover the main phase, that is, forms a core/shell structure with the main phase. A ratio of surface area coverage of the RFe(Co)-M.sub.1 phase relative to the main phase is at least 50%, preferably at least 60%, and more preferably at least 70%, and the RFe(Co)-M.sub.1 phase may even cover overall the main phase. The balance of the intergranular grain boundary phase around the main phase is R-M.sub.1 phase containing at least 50% of R.

(19) The crystal structure of the RFe(Co)-M.sub.1 phase is amorphous, nano-crystalline or nano-crystalline including amorphous while the crystal structure of the R-M.sub.1 phase is crystalline or nano-crystalline including amorphous. Preferably nano-crystalline grains have a size of up to 10 nm. As crystallization of the RFe(Co)-M.sub.1 phase proceeds, the RFe(Co)-M.sub.1 phase agglomerates at the grain boundary triple junction, and the width of the intergranular grain boundary phase becomes thinner and discontinuous, as a result the coercivity of the magnet decrease significantly. Also as crystallization of the RFe(Co)-M.sub.1 phase proceeds, R-rich phase may form at the interface between the main phase and the grain boundary phase as the by-product of peritectic reaction, but the formation of the R-rich phase itself does not contribute to a substantial improvement in the coercivity.

(20) Now the method for preparing an RFeB base sintered magnet having the above-defined structure is described. The method generally involves grinding and milling of a mother alloy, pulverizing a coarse powder, compaction into a green body applying an external magnetic field, and sintering.

(21) The mother alloy is prepared by melting raw metals or alloys in vacuum or an inert gas atmosphere, preferably argon atmosphere, and casting the melt into a flat mold or book mold or strip casting. If primary crystal of -Fe is left in the cast alloy, the alloy may be heat-treated at 700 to 1,200 C. for at least one hour in vacuum or in an Ar atmosphere to homogenize the microstructure and to erase -Fe phases.

(22) The cast alloy is crushed or coarsely grinded to a size of typically 0.05 to 3 mm, especially 0.05 to 1.5 mm. The crushing step generally uses a Brown mill or hydrogen decrepitation. For the alloy prepared by strip casting, hydrogen decrepitation is preferred. The coarse powder is then pulverized on a jet mill by a high-pressure nitrogen gas, for example, into a fine particle powder with a particle size of typically 0.2 to 30 m, especially 0.5 to 20 m on an average. If desired, a lubricant or other additives may be added in any of crushing, milling and pulverizing processes.

(23) Binary alloy method is also applicable to the preparation of the magnet alloy power. In this method, a mother alloy with a composition of approximate to the R.sub.2-T.sub.14-B.sub.1 and a sintering aid alloy with R-rich composition are prepared respectively. The alloy is milled into the coarse powder independently, and then mixture of alloy powder of mother alloy and sintering aid is pulverized as well as above mentioned. To prepare the sintering aid alloy, not only the casting technique mentioned above, but also the melt span technique may be applied.

(24) The composition of the alloy is essentially 12 to 17 at % of R which is at least two of yttrium and rare earth elements and essentially contains Nd and Pr, 0.1 to 3 at % of M.sub.1 which is at least one element selected from the group consisting of Si, Al, Mn, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pt, Au, Hg, Pb, and Bi, 0.05 to 0.5 at % of M.sub.2 which is at least one element selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W, 4.8+2m to 5.9+2m at % of B wherein m stands for atomic concentration of M.sub.2, up to 10 at % of Co, and the balance of Fe.

(25) The fine powder above obtained is compacted under an external magnetic field by a compression molding machine. The green compact is then sintered in a furnace in vacuum or in an inert gas atmosphere typically at a temperature of 900 to 1,250 C., preferably 1,000 to 1,150 C. for 0.5 to 5 hours.

(26) In a first embodiment of the method for preparing a sintered magnet having the above-defined structure, the compact as sintered above is cooled to a temperature of 400 C. or below, especially 300 C. or below, typically room temperature. The cooling rate is preferably 5 to 100 C./min, more preferably 5 to 50 C./min, though not limited thereto. After sintering, the sintered compact is heated at a temperature in the range of 700 to 1,100 C. which temperature is exceeding peritectic temperature of RFe(Co)-M.sub.1 phase. (It is called post-sintering heat treatment.) The heating rate is preferably 1 to 20 C./min, more preferably 2 to 10 C./min, though not limited thereto. The peritectic temperature depends on the additive elements of M.sub.1. For example, the peritectic temperature is 640 C. at M.sub.1=Cu, 750 to 820 C. at M.sub.1=Al, 850 C. at M.sub.1=Ga, 890 C. at M.sub.1=Si, and 1,080 C. at M.sub.1=Sn. The holding time at the temperature is preferably at least 1 hour, more preferably 1 to 10 hours, and even more preferably 1 to 5 hours. The heat treatment atmosphere is preferably vacuum or an inert gas atmosphere such as Ar gas.

(27) After the post-sintering heat treatment, the sintered compact is cooled down to a temperature of 400 C. or below, preferably 300 C. or below. The cooling rate down to 400 C. or below is 5 to 100 C./min, preferably 5 to 80 C./min, and more preferably 5 to 50 C./min. If the cooling rate is less than 5 C./min, then RFe(Co)-M.sub.1 phase segregates at the grain boundary triple junction, and magnetic properties are degraded substantially. A cooling rate of more than 100 C./min is effective for inhibiting precipitation of RFe(Co)-M.sub.1 phase during the cooling, but the dispersion of R-M.sub.1 phase in the microstructure is insufficient. As a result, squareness of the sintered magnet becomes worse.

(28) The aging treatment is performed after post-sintering heat treatment. The aging treatment is desirably carried out at a temperature of 400 to 600 C., more preferably 400 to 550 C., and even more preferably 450 to 550 C., for 0.5 to 50 hours, more preferably 0.5 to 20 hours, and even more preferably 1 to 20 hours, in vacuum or an inert gas atmosphere such as Ar gas. The temperature is lower than the peritectic temperature of RFe(Co)-M.sub.1 phase so as to form the RFe(Co)-M.sub.1 phase at a grain boundary. If the aging temperature is blow 400 C., a reaction rate of forming RFe(Co)-M.sub.1 phase is too slow. If the aging temperature is above 600 C., the reaction rate to form RFe(Co)-M.sub.1 phase increases significantly so that the RFe(Co)-M.sub.1 grain boundary phase segregates at the grain boundary triple junction, and magnetic properties are degraded substantially. The heating rate to a temperature in the range of 400 to 600 C. is preferably 1 to 20 C./min, more preferably 2 to 10 C./min, though not limited thereto.

(29) In a second embodiment of the method for preparing a sintered magnet having the above-defined structure, the compact as sintered above is cooled to a temperature of 400 C. or below, especially 300 C. or below. The cooling rate is critical. The sintered compact is cooled down to a temperature of 400 C. or below at a cooling rate of 5 to 100 C./min, preferably 5 to 50 C./min.

(30) If the cooling rate is less than 5 C./min, then RFe(Co)-M.sub.1 phase segregates at the grain boundary triple junction, and magnetic properties are substantially degraded. A cooling rate of more than 100 C./min is effective for inhibiting precipitation of RFe(Co)-M.sub.1 phase during the cooling, but the dispersion of R-M.sub.1 phase in the microstructure is insufficient. As a result, squareness of the sintered magnet becomes worse.

(31) After the sintered compact is cooled as above described, aging treatment is carried out as well as the first embodiment of the method. That is, the aging treatment is by holding the sintered compact at a temperature in the range of 400 to 600 C. and not higher than the peritectic temperature of RFe(Co)-M.sub.1 phase so as to form the RFe(Co)-M.sub.1 phase at a grain boundary. If the aging temperature is blow 400 C., a reaction rate to form RFe(Co)-M.sub.1 phase is too slow. If the aging temperature is above 600 C., the reaction rate to form RFe(Co)-M.sub.1 phase increases significantly so that the RFe(Co)-M.sub.1 grain boundary phase segregates at the grain boundary triple junction, and magnetic properties are substantially degraded. The aging time is preferably 0.5 to 50 hours, more preferably 0.5 to 20 hours, and even more preferably 1 to 20 hours in vacuum or an inert gas atmosphere such as Ar gas. The heating rate to a temperature in the range of 400 to 600 C. is preferably 1 to 20 C./min, more preferably 2 to 10 C./min, though not limited thereto.

EXAMPLE

(32) Examples are given below for further illustrating the invention although the invention is not limited thereto.

Examples 1 to 12 & Comparative Examples 1 to 7

(33) The alloy was prepared specifically by using rare earth metals (Neodymium or Didymium), electrolytic iron, Co, ferro-boron and other metals and alloys, weighing them with a designated composition, melting at high-frequency induction furnace in an Ar atmosphere, and casting the molten alloy on the water-cooling copper roll. The thickness of the obtained alloy was about 0.2 to 0.3 mm. The alloy was powdered by the hydrogen decrepitation process, that is, hydrogen absorption at normal temperature and subsequent heating at 600 C. in vacuum for hydrogen desorption. A stearic acid as lubricant with the amount of 0.07 wt % was added and mixed to the coarse alloy powder. The coarse powder was pulverized into a fine powder with a particle size of about 3 m on an average by using a jet milling machine with a nitrogen jet stream. Fine powder was molded while applying a magnetic field of 15 kOe for orientation. The green compact was sintered in vacuum at 1,050 to 1,100 C. for 3 hours, and cooled below 200 C. The sintered body was post-sintered at 900 C. for 1 hour, cooled to 200 C., and heat-treated for aging for 2 hours. Table 1 tabulates the composition of a magnet, although oxygen, nitrogen and carbon concentrations are shown in Table 2. The condition of the heat treatment such as a cooling rate from 900 C. to 200 C., aging treatment temperature, and magnetic properties are shown in Table 2. The composition of RFe(Co)-M.sub.1 phase is shown in Table 3.

(34) TABLE-US-00001 TABLE 1 Nd Pr Fe Co B Al Cu Zr Si Ga Ag (at %) (at %) (at %) (at %) (at %) (at %) (at %) (at %) (at %) (at %) (at %) Example 1 11.6 3.4 bal. 0.5 5.4 0.2 0.2 0.07 0.05 0.80 2 11.6 3.4 bal. 0.5 5.4 0.5 0.2 0.07 0.05 0.50 3 11.6 3.4 bal. 1.0 5.2 0.5 0.2 0.07 0.50 0.50 4 11.6 3.4 bal. 1.0 5.2 0.5 0.7 0.07 0.25 0.25 5 11.6 3.4 bal. 0.5 5.4 0.2 0.2 0.07 0.05 0.80 6 11.6 3.4 bal. 0.5 5.1 0.2 0.2 0.07 0.05 0.80 7 11.6 3.4 bal. 0.5 5.4 0.5 0.5 0.07 0.05 0.50 8 11.6 3.4 bal. 0.5 5.4 0.5 0.5 0.07 0.05 0.50 9 11.6 3.4 bal. 0.5 5.3 0.2 0.2 0.07 0.05 0.30 0.20 10 11.6 3.4 bal. 0.5 5.3 0.2 0.2 0.07 0.20 0.30 0.20 11 11.8 3.5 bal. 0.5 5.4 0.2 0.2 0.15 0.20 0.50 12 11.8 3.5 bal. 0.5 5.5 0.2 0.2 0.30 0.20 0.50 Comparative 1 12.0 3.8 bal. 1.0 5.3 Example 2 11.6 3.4 bal. 0.5 5.4 0.5 0.2 0.07 0.05 0.50 3 11.6 3.4 bal. 1.0 5.2 0.5 0.7 0.07 0.25 0.25 4 11.6 3.4 bal. 0.5 6.2 0.2 0.2 0.07 0.80 5 11.6 3.4 bal. 0.5 5.4 0.5 0.2 0.07 0.05 0.50 6 11.6 3.4 bal. 0.5 5.4 0.5 0.2 0.07 0.05 0.50 7 11.6 3.4 bal. 1.0 5.2 0.5 5.0 0.00 0.00 0.20

(35) TABLE-US-00002 TABLE 2 Oxygen Nitrogen Carbon Cooling Temperature concentration concentration concentration Particle rate of aging (at %) (at %) (at %) size (m) ( C./min) treatment ( C.) Br (kG) Example 1 1.04 0.06 0.33 2.9 25 450 13.2 2 0.95 0.06 0.33 2.9 25 470 13.3 3 0.95 0.06 0.33 3.8 25 450 12.9 4 1.04 0.06 0.33 2.8 25 500 13.2 5 0.87 0.06 0.33 2.8 25 500 13.2 6 1.04 0.06 0.33 2.8 25 500 13.0 7 0.95 0.06 0.33 2.9 10 450 13.2 8 1.04 0.06 0.33 2.9 5 450 13.2 9 0.95 0.06 0.33 2.8 5 450 13.2 10 0.95 0.06 0.33 2.7 5 450 13.2 11 0.95 0.06 0.33 2.9 25 450 13.1 12 0.95 0.06 0.33 2.9 25 450 13.0 Comparative 1 1.65 0.06 0.38 4.5 25 500 13.6 Example 2 1.04 0.06 0.36 2.9 2 500 13.2 3 0.95 0.06 0.33 2.8 2 650 12.9 4 0.91 0.06 0.33 2.8 25 490 13.5 5 1.04 0.06 0.36 2.9 25 700 13.0 6 1.04 0.06 0.33 2.9 25 850 13.6 7 0.87 0.06 0.33 3 25 500 12.6 Average thickness Surface Average of intergranular area RFe(Co)M.sub.1 RM.sub.1 R.sub.1.1Fe.sub.4B.sub.4 grain HcJ (kOe) grain boundary (nm) coverage (%) phase phase phase size (m) Example 1 20.0 250 95 A + NC NC nil 3.8 2 19.5 250 95 A + NC NC nil 3.8 3 18.5 250 95 A + NC NC nil 4.9 4 17.0 200 90 A + NC NC nil 3.6 5 20.0 270 90 A + NC NC nil 3.6 6 21.5 300 95 A + NC NC nil 3.6 7 19.5 280 95 A + NC NC nil 3.8 8 19.0 220 95 A + NC NC nil 3.8 9 20.5 180 95 A + NC NC nil 3.6 10 19.5 170 90 A + NC NC nil 3.5 11 20.0 150 90 A + NC NC nil 3.8 12 21.5 180 95 A + NC NC nil 3.8 Comparative 1 9.5 <5 <5 nil NC nil 5.9 Example 2 12.5 300 30 A + NC NC nil 3.8 3 12. 280 30 A + NC NC nil 3.6 4 16.0 <5 <5 nil NC found 3.6 5 17.0 300 35 A + NC NC nil 3.8 6 12.0 <5 <5 nil NC nil 3.8 7 12 <5 <5 nil NC nil 3.9 A: amorphous NC: nanocrystalline (up to 10 nm)

(36) TABLE-US-00003 TABLE 3 RFe(Co)M.sub.1 phase (at %) Nd Pr Fe Co Cu Al Ga Si Ag Example 1 21.9 7.1 61.4 1.3 0.6 1.0 4.3 0.1 2 21.5 6.9 62.3 1.4 0.8 0.9 5.1 0.1 3 22.3 7.6 59.8 1.8 0.7 1.0 2.9 2.5 4 22.8 7.2 59.7 1.6 0.9 0.8 3.2 2.1 5 22.2 7.1 61.7 1.2 0.8 0.9 5.0 0.1 6 21.7 7.0 62.4 1.1 0.8 0.8 4.8 0.1 7 22.5 7.1 61.3 1.1 0.9 1.0 5.2 0.1 8 22.3 7.0 61.1 1.2 0.8 1.0 5.1 0.1 9 22.8 7.5 59.8 1.1 0.7 0.7 4.2 0.1 2.1 10 21.5 6.9 61.0 1.1 0.7 0.7 3.5 1.1 1.9 11 21.9 7.0 61.5 1.0 0.7 1.0 4.2 1.9 12 22.1 6.8 61.2 1.1 0.6 0.8 3.8 2.1

(37) In those examples with Cu and Ag added, although the cooling rate after post-sintering heat treatment was slower than other examples, values of the coercivity after aging heat treatment keep same level such as more than 19 kOe because the peritectic temperatures of RFe(Co)-M.sub.1 phase were decreased due to addition of Cu and Ag.

(38) In those examples with various amounts of Zr addition, ZrB.sub.2 phase formed preferentially during sintering and precipitated at the grain boundary triple junction. This inhibits abnormal grain growth during sintering and enables sintering at a higher temperature, for thereby improving squareness of sintered magnets.

(39) The content of R in R-M.sub.1 phase was 50 to 92 at %.

(40) A cross section of the sintered magnet obtained in Example 1 was observed under an electron probe microanalyzer (EPMA). As shown in FIG. 1, a grain boundary phase (RFe(CO)-M.sub.1 phase, R-M.sub.1 phase) covering a main phase (R.sub.2(Fe,Co).sub.14B) was observed. Further, the grain boundary phase covering the main phase was observed under a transmission electron microscope (TEM). As shown in FIG. 2a, the grain boundary phase had a thickness (or phase width) of about 200 nm. The EDX and the diffraction image of FIG. 2b at point a in FIG. 2a demonstrate the presence of R.sub.3(CoGa).sub.1 phase and RFe(Co)-M.sub.1 phase which are amorphous or nanocrystalline.

(41) FIG. 3 is a bright-field image of intergranular grain boundary phase in the magnet prepared in Example 11. It is seen that an interface extends obliquely from the upper side to the lower side of the figure. On the right of the interface, the presence of R.sub.2(Fe,(Co)).sub.14B phase with a crystalline could be observed, and on the other side of the interface, nanocrystalline RFe(Co)-M.sub.1 phase with a size of about 5 nm in grain boundary could be observed.

(42) FIG. 4 is an image of a cross section of the sintered magnet in Comparative Example 2 as observed under EPMA. Since the cooling rate of the post-sintering heat treatment was too slow, the RFe(Co)-M.sub.1 phase was discontinuous at the intergranular grain boundary and segregates corpulently at the grain boundary triple junction. It was confirmed that a size of the RFe(Co)-M.sub.1 phase segregated at the grain boundary triple junction were more than 10 nm by the observation under TEM.

Example 13

(43) The alloy was prepared specifically by using rare earth metals (Neodymium or Didymium), electrolytic iron, Co, ferro-boron and other metals and alloys, weighing them with the same composition as in Example 1, melting at high-frequency induction furnace in an Ar atmosphere, and casting the molten alloy on the water-cooling copper roll. The thickness of the obtained alloy was about 0.2 to 0.3 mm. The alloy was powdered by the hydrogen decrepitation process, that is, hydrogen absorption at normal temperature and subsequent heating at 600 C. in vacuum for hydrogen desorption. A stearic acid as lubricant with the amount of 0.07 wt % was added and mixed to the coarse alloy powder. The coarse powder was pulverized into a fine powder with a particle size of about 3 m on an average by using a jet milling machine with a nitrogen jet stream. Fine powder was molded while applying a magnetic field of 15 kOe for orientation. The green compact was sintered in vacuum at 1,080 C. for 3 hours, and cooled below 200 C. at a cooling rate of 25 C./min. Then, the sintered body was heat-treated for aging at 450 C. for 2 hours. The aging treatment temperature, and magnetic properties are shown in Table 4. The composition of RFe(Co)-M.sub.1 phase was substantially the same as in Example 1.

(44) TABLE-US-00004 TABLE 4 Temperature Oxygen Nitrogen Carbon Particle Cooling of aging concentration concentration concentration size rate treatment (at %) (at %) (at %) (m) ( C./min) ( C.) Br (kG) HcJ (kOe) Example 1.04 0.06 0.33 2.9 25 450 13.2 19.5 13 Average thickness Surface Average of intergranular area RFe(Co)M.sub.1 RM.sub.1 R.sub.1.1Fe.sub.4B.sub.4 grain grain boundary (nm) coverage (%) phase phase phase size (m) Example 230 95 A + NC NC nil 3.8 13 A: amorphous NC: nanocrystalline (up to 10 nm)

(45) Japanese Patent Application Nos. 2015-072228 and 2016-025511 are incorporated herein by reference.

(46) 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.