PERMANENT MAGNET AND PERMANENT MAGNETIC ALLOY

Abstract: A permanent magnet essentially consists of 10 to 40% by weight of R, 0.1 to 8% by weight of boron, 13% by weight or less of gallium and the balance of iron, where R is at least one component selected from the group consisting of yttrium and the rare-earth elements. The magnet having this composition has a high coercive force iHC and a high residual magnetic flux density and there­ fore has a high maximum energy product. A permanent magnetic alloy consisting essentially of 10 to 40% by weight of R, 0.1 to 8% by weight of boron, 0.2 to 13% by weight of cobalt and the balance of iron, the content of oxygen being 0.005 to 0.03% by weight and R being at least one component selected from the group of yttrium and rare­ earth elements is also disclosed.

Description: BACKGROUND OF THE INVENTION The present invention relates to a rare earth-iron-based permanent magnet which includes a rare earth element, boron, and iron as its principal constituents. In the past, a rare earth-Co-based magnet is known as a high performance magnet. Since, however, the maximum energy product (BH) max of the rare earth-Co-based magnet is not large enough, being about 30 MGOe at the most, the strong demand in recent years for more compactification and higher performance in electronic apparatus, makes it desirable to develop a permanent magnet with higher performance. In response to such a demand, development has been ongoing for a permanent magnet that has iron as its principal constituent (European Patent Application 101552, USP 4402770, USP 4533408, USP 4541877, and others). The iron-based permanent magnet includes a rare-earth element (R) such as Nd, and boron (B) with the balance occupied essentially by iron (Fe). It makes use of Fe which is less expensive than Co as the principal ingredient, and is capable of producing (BH) max that can exceed 30 MGOe. Therefore, it represents an extremely promising material that can provide a high performance magnet at low cost. The drawback of the iron-based permanent magnet is that the Curie temperature (Tc) is low compared with the permanent magnet of rare earth-Co-based permanent magnet, and has an inferior temperature characteristics of the magnetic characteristics. This will become a serious problem when it is to be used for a DC brushless motor or the like that is operated under conditions such as high temperature environment, and hence an improvement on this aspect has been desired. As such an improvement, there has been proposed a composition such as R-B-Co-Al-Fe (EP-A-106948). The present inventors have also filed applications, i.e. EP-A- 175 214, EP-A- 197 712. However, the addition of Co brings about a deterioration in the magnetic characteristics so that a demand is strong for improving the performance of the rare earth-Fe-based permanent magnet, with development efforts under way at various laboratories. SUMMARY OF THE INVENTION An object of the present invention is to provide a rare earth-Fe-based permanent magnet which has high (BH) max . Another object of the present invention is to provide a rare earth-Fe-based permanent magnet which has high coercive force (iHc). The invention is indicated in claim 1. More specifically, a permanent magnet of the present invention consists essentially of a magnetic alloy comprising 10 - 40% by weight of R which is at least one element of the group of yttrium and rare-earth elements, 0.1 - 8% by weight of boron, gallium in an amount of 13% by weight or less and the balance being iron. If necessary, Co may be added up to 30% by weight. This magnet may be produced by the sintering method, liquid quenching method, and the like. Further features of the invention are indicated in the dependent claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 and Fig. 2 are diagrams for showing the dependence of magnetic characteristics on the B content. Fig. 3 is a diagram for showing the dependence of magnetic characteristics on the 0 content. Fig. 4 is a diagram for showing the dependence of a magnetic characteristic on the aging temperature. Fig. 5 is a diagram for showing demagnetization curves. Fig. 6 and Fig. 7 are X-ray diffraction diagrams. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail. A permanent magnet according to the present invention contains 10 to 40% by weight of material R where R is at least one component selected from yttrium and rare-earth elements. In general, the coercive force iHc tends to to decrease at high temperatures. When the content of R is less than 10%, the coercive force iHc is low and satisfactory magnetic characteristics as a permanent magnet cannot be obtained. However, then the content of R exceeds 40%, the residual magnetic flux density Br decreases. The maximum energy product (BH) max is a value related to a product of the coercive force iHc and the residual magnetic flux density Br. Therefore, when either the coercive force iHc or residual magnetic flux density Br is low, the maximum energy product (BH) max is low. For these reasons, the content of R is selected to be 10 to 40% by weight. Among rare-earth elements, neodymium (Nd) and praseodymium (Pr) are particularly effective in increasing the maximum energy product (BH) max . In other words, Nd and Pr serve to improve both the residual magnetic flux density Br and the coercive force iHc. Therefore, selected R preferably include at least one of Nd and Pr. In this case, the content of Nd and/or Pr based on the total content of R is preferably 70% by weight or more. Boron (B) serves to increase the coercive force iHc. When the B content is less than 0.1% by weight, the coercive force iHc cannot be satisfactorily increased. However, when the B content exceeds 8% by weight, the residual magnetic flux density Br is decreased too much. For these reasons, the B content is set to fall within the range of 0.1 to 8% by weight. In obtaining permanent magnets of high coercive force type, it is preferable to have a B content of greater than 1.25% by weight. Further, although a part of B may be substituted by C, N, Si, P, Ge, and others to improve the sintering characteristics and the like, the substituted amount should be up to 80% by weight of the amount of B. Gallium (Ga) is an element which is effective for improving the magnetic characteristics such as iHC. Even an addition of a small amount of the element can prove to be effective (see Fig. 1 and Fig. 2). In practice, the content of Ga is 0.1% by weight or more, and preferably more than 0.2% by weight or more, is desired. Addition of an excessive amount of Ga leads to a conspicuous reduction in the value of Br so that the content should be restricted to less than 13% by weight. It should be mentioned that up to 90% by weight of Ga content may be replaced by Al. The remainder is substantially iron (Fe), but the presence of inevitable impurities such as oxygen (O) may be tolerated to the extent they do not affect the effects of the present invention. In addition, it is also effective to give an aging at a temperature in the range of 550 to 1,200 o C prior to the aging at a temperature in the range of 550 to 750 o C. Further, in performing such a two-stage aging, the aging of the second stage may be carried out at a temperature in the range of 500 to 750 o C. If the first stage aging processing is carried out at a temperature outside of the temperature range given above, the rectangular moldability is reduced, and if the second stage aging processing is carried out at a temperature outside of the above range of temperature, there occurs a reduction in coercive force. The magnet according to the present invention basically consists of R, Fe, B and Ga. However, the magnet of the present invention can additionally contain cobalt (Co), chromium (Cr), aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), vanadium (V), manganese (Mn), molybdenum (Mo), and tungsten (W) etc. These components are added in a total amount of 30% by weight or less. Co serves to increase the Curie temperature of the alloy and improve stability of magnetic characteristics against temperature change. The content of cobalt is preferably 30% by weight or less. In practice, the content of Co is 1% by weight or more. When the total amount of such components exceeds, the Fe content is decreased accordingly, and the residual magnetic flux density of the alloy is decreased. As a result, the maximum energy product (BH) max is decreased. the content of cobalt is more preferably 10 - 20% by weight. A permanent magnet in accordance with the present invention will be manufactured, for example, as follows. First, permanent magnetic alloy with prescribed composition is prepared and crushed by a crushing means such as a ball mill. In this case, in order to facilitate the formation and sintering in the subsequent processes and to provide the product with satisfactory magnetic characteristics, it is desirable to cruch it finely to powders with mean particle diameter of 2 to 10 µm. If the particle diameter is too large, it leads to a reduction in the coercive force. On the other hand, if it is too small, crushing becomes difficult and will result in a deterioration of magnetic characteristics such as Br. The powder obtained in this manner is compressed in a predetermined shape. In this process, as in a conventional process of manufacturing a normal sintered magnet, a magnetic field of about 15KOe is applied to obtain a predetermined magnetic orientation. The powder compact is sintered at 1,000 to 1,200 o C for 0.5 to 5 hours to obtain a sintered body. In the sintering process, in order not to increase the oxygen concentration in the alloy, the compact is heated in an inert gas atmosphere such as Ar gas or in a vacuum (not more than 10⁻³ Torr). The resultant sintered body is heated at 550 to 750 o C for 1 to 10 hours to perform aging, thereby improving the magnetic characteristics such as iHc and rectangular moldability of the magnet. In addition, it is also effective to give an aging at a temperature in the range of 550 to 1,200 o C prior to the aging at a temperature in the range of 550 to 750 o C. Further, in performing such a two-stage aging, the aging of the second stage may be carried out at a temperature in the range of 500 to 750 o C. If the first stage aging processing is carried out at a temperature outside of the temperature range given above, the rectangular moldability is reduced, and if the second stage aging processing is carried out at a temperature outside of the above range of temperature, there occurs a reduction in coercive force. A permanent magnet prepared in this manner has a high coercive force iHc and residual magnetic flux density Br and therefore has a high maximum energy product (BH) max . Thus, the permanent magnet of the present invention has excellent magnetic characteristics. In employing such a sintering method, the content of oxygen in the permanent magnet alloy has an important significance. Since large amount of oxygen leads to a decrease in the coercive force, it becomes impossible to obtain a large value of (BH) max . Therefore, it is preferred to include less than 0.03% by weight. Moreover, if the content is too small, pulverization which is required to be done to a fine particle size of about 2 to 10 m, becomes difficult to be accomplished, and moreover, there will arise a nonuniformity in the particle diameter. Accordingly, it leads to a decrease in the value of Br that accompanies a reduction in the orientability during the formation in a magnetic field, which eventually leads also to a lowering in the value of (BH) max . For these reasons, it is desirable to choose the content of oxygen in the range of 0.005 to 0.03% by weight. Although the role of oxygen in the alloy is not elucidated yet, it may be considered that a high performance permanent magnet is obtained for the reasons described below. Namely, a part of oxygen in molten alloy is combined with R and Fe atoms that represent the major constituents, to form oxides. These oxides are considered segregated and exist in the grain boundaries and are absorbed especially by the R-rich phase to hamper the magnetic characteristics. Taking into consideration that the rare earth-Fe-based permanent magnet consists of corpuscular magnets and its coercive force is determined by the magnetic field that generates reversed magnetic domains, it is considered, when there exist many defects such as oxides and segregations, that the coercive force will be decreased by the action of these defects as the generating sources of the reversed magnetic domains. On the other hand, when there are too few defectes, boundary breakdown or the like are not easy to take place and it is considered that the pulverization characteristics will be deteriorated. The oxygen content in the alloy for permanent magnet can be controlled by the use of highly pure raw materials and by a strict control of the oxygen content in the molten raw material alloy in the furnance. The sintered permanent magnet of R-B-Fe system has a ferromagnetic Fe-rich phase of a tetragonal system of Nd₂Fe₁₄B type as the principal phase. Besides it may include a nonmagnetic R-rich phase of a cubic system such as Nd₉₇Fe or Nd₉₅Fe₅ that has more than 90% by weight of the R component, a nonmagnetic B-rich phase of a cubic system such as Nd 1+ε Fe₄B₄ (where is appropriately 0.1), and others as the constituent phases, in addition to including some oxides. The composition is similar when an R component other than Nd is used. Incidentally, although the state in which gallium exists in the magnet is not known in detail, it is principally concentrated in the R-rich phase. Now, a magnet of the present invention can be manufactured by methods other than the sintering method. Namely, one of such methods includes a first process of obtaining thin ribbons or powder consisting of a permanent magnetic alloy by the liquid quenching method, a process of uniting these thin ribbons or powder obtained from the first process into a desired shape by heating, or a process of uniting these thin ribbons or powder obtained from the first process by crushing them to a size of about 10 to 100 µm, mixing and tempering with a binder such as resin, and molding and solidifying in a magnetic field or in a space with no magnetic field. The permanent magnetic alloy contains as the principal constituents at least one kind selected from yttrium and rare-earth metals such as Ce, Pr, Nd, (it may be a mischmetal (M.M.) which contains more than one kind of rare-earth elements), and iron. In addition, it contains B for stabilization. The method of manufacture of the alloy is similar to the case of manufacture by sintering. However, in the case of liquid quenching method the ranges of composition become wider than in the case of sintering. For example, it is as shown below. R 1-α-β-γ-δ B α Fe β Co γ Ga δ 0.001 ≦ α ≦ 0.5 0.5 < β ≦ 0.95 0 ≦ γ ≦ 0.3 0 < δ ≦ 0.1 α + β + γ + δ < 1.0 (α,β,γ,δ; atomic ratio) If α < 0.001, β > 0.95, and γ > 0.3, the product is inadequate as a permanent magnetic alloy due to insufficient improvement in the coercive force. On the other hand, if α > 0.5 and β < 0.5, the product is again inadequate as a permanent magnetic alloy due to a reduction of the magnetic flux density. It may be noted that a part of Ga may be replaced by Al and Ti. When such a permanent magnetic alloy is made into a thin ribbon by the liquid quenching method, C axis is oriented under certain cooling conditions in the direction perpendicular to the thin ribbon. This is a phenomenon which can not be observed in the Sm - Co system. In manufacturing such an alloy, a method similar to the manufacture of amorphous alloys is employed. Namely, a thin ribbon is formed by ejecting liquid of an alloy onto a rotating roll which is being kept cool. In that case, if the speed of rotation of the roll cooler is too large, the thin ribbon becomes noncrystalline without orientation so that it will not work as a permanent magnet. On the other hand, if the speed of rotation is too slow, the product will be crystalline. However, the crystal grains have an inferior orientability so that the resulting magnetic characteristics are unsatisfactory. In view of these circumstances, the surface speed of the roll is desirable to be within the range of 3 to 20 m/sec. A magnet may be made from the crystalline thin ribbons obtained in the above manner according to the following methods. A first method is to laminate crystalline thin ribbons so as to form a desired shape, and unite them by heating. Although the temperature of heating differs depending upon the composition, a temperature above 600 o C is required for bringing them into a united body, and a temperature below 1,100 o C is preferred for preventing crystallization from liquid phase. The duration for processing is 0.1 to 5 hours. In addition, it is preferable to apply a pressure in the range of 0.1 to 2 ton/cm², during unification by heating, in order to obtain a large energy product. The second method is as follows. The alloy is coarsely cruched by a jaw crusher, and further is made into powders of magnet with average particle diameter of 5 to 30 µm by means of a jet mill or the like. A surface treatment is given to the magnetic powders by the use of silane-based coupling agent or the like in order to prevent oxidation of the magnetic powders as well as to improve the coupling with a thermally plastic resin. Following the above treatment, the magnetic powder which went through the surface treatment and the thermally plastic resin are brought together, and are mixed thoroughly in a mortor or in an tempering machine of stirring type. The mixing ratio in this case of the resin to the magnetic powder is 3 to 10% by weight, and preferably 6 to 10% by weight. this is because the deterioration in the mechanical properties of the magnetic powder is conspicuous if the ratio is less than 3% by weight, whereas if the ratio exceeds 10% by weight there begins to appear deterioration of magnetic properties. Here, as a thermally plastic resin various kinds of resins may be applicable such as those of polyamide series like nylon 6 and nylon 66, those of polyolefine series like ethylene, polypropylene, vinyl chloride, and polyester. Then, a permanent magnet is manufactured by molding the above mixture of powders with heating and applying magnetic field by the projection molding method. In this process, the heating temperature is in the range of 230 to 300 o C, the applied pressure is in the range of 0.3 to 2 ton/cm², and the applied magnetic field is greater than 15 kOe. If the heating temperature is below 230 o C, the fluidity of the mixed powders is unsatisfactory and the mixing of the magnetic powders and the resin is insufficient, resulting in an increased nonuniformity of the molded body as well as a deterioration in the magnetic characteristics. On the other hand, if the heating temperature exceeds 300 o C, gases are generated by the decomposition of the resin which obstructs the obtaining of satisfactory characteristics of magnet, due to the interposition of buffles and the like. Example 1 A mixture of elements in the desired composition was melted by arc in a watercooled copper boat in an Ar atmosphere. the magnet alloy obtained (oxygen concentration of 0.02 wt%) was coarsely crushed in an Ar atmosphere, and was pulverized further to the grain size of about 3 µm in a jet mill. The pulverized powder was filled into a predetermined mold, and was formed under a pressure of 2 ton/cm² while applying a magnetic field of 20 kOe . After sintering the formed body in Ar atmosphere for one hour at 1020 to 1120 o C and rapidly cooling to the room temperature, an aging treatment was given for 3 - 10 hours at 550 - 750 o C, and is then cooled rapidly to the room temperature. The characteristics for the magnets with various compositions manufactured in a similar manner and presented in the following Table 1. In set Table 1, permanent magnets obtained by the present invention show excellent characteristics. Example 2 Each elements were blended so as to have a composition of 30.8% by weight of neodymium, 0.86% of weight of boron, 1.0% by weight of gallium, and the balance iron. Two kilograms of the mixture was melted by arc in a water-cooled copper boat under an argon atmosphere. In the process, by strictly controlling the amount of oxygen in the furnace, the oxygen content in the prepared alloy was adjusted. Then finely pulverized by a stainless steel ball mill to an average particle size of 3 to 5 µm. the resultant fine powder was packed in a predetermined press mold and compressed at a pressure of 2 ton/cm² while applying a magnetic field of 20,000 Oe . The obtained compact was sintered in an Ar gas atmosphere at 1,080 o C for 1 hour. Then, the sintered body was cooled to room temperature and was aged in a vacuum at 600 o C for 5 hour. The sintered body was then rapidly cooled to room temperature. Fig. 3 shows the residual magnetic flux density Br, the coercive force iHc, and the maximum energy product (BH) max as a function of oxygen concentration in the permanent magnetic alloys. As can be seen from Fig. 3, the magnetic characteristics of the permanent magnet largely depend on the oxygen concentration in the alloy. Thus, when the oxygen concentration is less than 0.005% by weight, orientation performance in a magnetic field is impaired. Thus, the residual magnetic flux density Br is also decreased. However, when the oxygen concentration exceeds 0.003% by weight, the coercive force is significantly decreased. Therefore, in a composition wherein the oxygen concentration is less than 0.005% by weight or more than 0.03% by weight, a high maximum energy product (BH) max cannot be obtained. Example 3 By a method analogons to that of Example 2, there was obtained a permanent magnetic alloy which has a composition of 31.0% by weight of neodymium, 0.84% by weight of boron, 14.6% by weight of cobalt, 1.1% by weight of gallium, 0.03% by weight of oxygen, and the balance iron. Using the permanent magnetic alloy obtained, a permanent magnet was manufactured by pulverizing, molding under compression, and sintering in a manner analogous to Example 1. After sintered specimens were aged for 1 hour at various temperatures in the range or 300 to 900 o C and were quenched, their coercive force was examined. The results are shown in Fig. 4. As may be clear from Fig. 4, the aging temperature affects the coercive force sharply, and an optimum characteristic was obtained for the temperature range of 550 to 750 o C. Example 4-1 A permanent magnet alloy consisting of 31.3% by weight of neodymium, 0.9% by weight of boron, 14.1% by weight of cobalt, 1.0% by weight of gallium, 0.02% by weight of oxygen, and the balance iron, was prepared by arc fusion in an argon atmosphere. The permanent magnet alloy obtained was coarsely crushed in an argon atmosphere, and then was finely pulverized in a jet mill under a nitrogen atmosphere to an average particle diameter of 3 µm. The fine powder was filled in a predetermined mold, and a molded body was obtained by compressing the powder with a pressure of 2 ton/cm², while applying a magnetic field of 20,000 Oe . The obtained molded was sintered in vacuum for 1 hour at the temperature of 1,080 o C, and was then quenched to the room temperature. Following that, a processing for a first stage aging was applied in vacuum for 1 hour at 900 o C, and then was quenched to the room temperature. In addition, the molded body was heated again in vacuum to 600 o C to give a second stage aging for 3 hours, and then was quenched to the room temperature. This specimen was designated as sample 1. Another magnet was manufactured by a method analogons to that of sample 1, except for giving an aging treatment which consists only of heating at 900 o C for 1 hour. This specimen was designated as sample 2. Still another magnet was prepared by a method which is analogons to that of sample 1, except for the adoption as the method of aging treatment of the first stage aging in which after holding the magnet at 600 o C for 3 hours it was quenched to the room temperature. This specimen was designated as sample 3. For each of these samples, magnetization curve was measured. The form of the demagnetization curve is shown in Fig. 5, and the values for the magnetic flux density, the coercive force, and the maximum energy product are shown in Table 2. Sample No. Magnetic Flux Density (KG) Coercive Force (KOe) Energy Product (MGOe) 4 - 1 13.2 12.4 42.0 4 - 2 13.2 6.6 39.5 4 - 3 13.2 10.5 40.4 1kG = 10⁻¹T, 1kOe = 79,6·10³ A/m, 1MGOe = 7,96 KJ/m³ Example 4-2 A magnet with a composition as shown in Table 3 was obtained by a method analogous to that of Example 4-1. Sintering for the magnet was carried out in argon atmosphere at a temperature in the range of 1,020 to 1,120 o C for 1 hour. After sintering and quenching to the room temperature, an aging treatment was given in vacuum at 900 o C for 1 hour. Following that, another aging treating was given at 600 o C for 3 to 10 hours, and then was quenched to the room temperature. The characteristics of the permanent magnet obtained are shown in Table 3. Composition (wt %) Br (kG) iHc (kOe) (BH) max (MGOe) 30.8Nd - 14.5Co -1.6B - 1.1Ga - Fe bal 12.2 15.8 34.6 31.3Nd - 14.1Co - 0.8B - 1.0Ga - 0.4Al - Fe bal 12.8 12.3 38.6 30.9Nd - 14.5Co - 1.4B - 1.1Ga - 0.6Al - Fe bal 12.4 14.2 35.5 30.8Nd - 0.86B - 1.0Ga - Fe bal 13.1 12.6 40.8 32.3Nd - 1.2B - 0.5Ga - 0.3Al - Fe bal 12.6 13.3 37.7 1kG = 10⁻¹T, 1kOe = 79,6·10³ A/m, 1MGOe = 7,96 kJ/m³ Example 4-3 Magnet with a compositions as shown in Table 4 were obtained by a method analogous to that of Example 4-1. The sintering for the magnet was carried out in vacuum at a temperature in the range of 1,020 to 1,120 o C for 1 hour. The specimens I, II, and III in Table 3 were obtained in the following manner. I After sintering magnet was quenched to the room temperature. II After sintering and quenching to the room temperature, an aging treatment of 600 o C for 3 to 10 hours was given. III After sintering and quenching to the room temperature, an aging treatment of 900 o C for 1 hour was given, followed by a second stage aging treatment of 600 o C for 3 to 7 hours. Results of measurements on magnetic characteristics are shown in Table 4. As may be clear from Table 4, the coercive force and the maximum energy product are improved sharply by a single stage aging treatment or a two-stage aging treatment. Example 5-1 Using the liquid quenching method, a ribbon was obtained from an alloy that has a composition of Nd 0.17, B 0.06, Fe 0.59, Co 0.16, and Ga 0.02 (in atm % for each). Namely, a crystalline thin ribbon of 10 mm width and 100 µm thickness was obtained by ejecting and cooling liquid alloy via a quartz nozzle by means of the pressure of argon gas, on the surface of a roll which is rotated at a speed of about 10 m/sec. The result of measurements on the thin ribbon obtained, by means of an X-ray diffraction apparatus, is shown in Fig. 6. In addition, the result of an X-ray diffraction measurement on an alloy powder material is shown in Fig. 7 for comparison. From the above results, it will be seen that a C-axis is oriented in the direction perpendicular to the ribbon surface, in the case of the thin ribbon obtained by liquid quenching method compared with the alloy powder material. A thin ribbon obtained by the liquid quenching method was cut in strips with length of 10 mm. One hundred pieces of the strip were laminated, and a heat treatment at 700 o C for 10 minutes was given while a pressurized molding with a pressure of 2 ton/cm² was proceeding. The magnetic characteristics of the magnet obtained are shown in Table 5. Example 5-2 A thin ribbon of magnet alloy with a composition of Nd 0.10, Pr 0.08, B 0.10, Fe 0.56, Co 0.14, Ga 0.01, and Al 0.01 (atm % for each) was prepared. After lamination of the thin ribbon in the form of flakes as they are, a heat treatment at 680 o C for 10 minutes was given while a pressurized molding with a pressure of 2 ton/cm² was proceeding. The magnetic characteristics of the magnet obtained are shown in Table 5. Example 5-3 A thin ribbon of magnet alloy with a composition of Nd 0.15, B 0.06, Fe 0.61, Co 0.16, and Ga 0.02 (atm ratio for each) was prepared. Strips of the thin ribbon were laminated analogously to Example 5-1 and a heat treatment at 710 o C for 20 minutes was given while a pressurized molding under a pressure of 2 ton/cm² was proceeding. The magnetic characteristics of the magnet obtained are shown in Table 5. Example 5-4 A thin ribbon of magnetic alloy with a composition of Nd 0.15, B 0.08, Fe 0.59, Co 0.16, Ga 0.01, and Ti 0.01 (atm ratio for each) was prepared. Strips of the thin ribbon were laminated analogously to Example 5-1 and a heat treatment at 700 o C for 10 minutes was given while a pressurized molding under a pressure of 2 ton/cm² was proceeding. The magnetic characteristics of the magnet obtained are shown in Table 5. As may be clear from Table 5, it was possible to obtain magnets with satisfactory values of the coercive force (;Hc) and the energy product ((BH) max ) by the use of the liquid quenching method. This is considered to be the results of the absence of the possibilities of impurity mixing due to the lack of the process of crushing, and the effect of the laminated heating treatment. Moreover, manufacture of magnets can be simplified due to omission of such processes as pulverization and pressing in magnetic field that are required in the existing method of powder sintering. Example 5-5 The thin ribbons obtained in Examples 5-1 to 5-4 by the liquid quenching method were pulverized in a ball mill to the average particle diameter of 30 m. After coating the powder of each magnet with a silane-based coupling agent, 6% by weight of nylon was added. Then, using each of these mixtures a permanent magnet was manufactured by ejection molding under the conditions of a heating temperature of 280 o C, a molding pressure of 2 ton/cm², and an applied magnetic field of 15 kOe. The results of measurements of the magnetic characteristics of these permanent magnets are summarized in Table 6. Composition Characteristics of Magnet Br(G) iHc(Oe) (BH)max(MGOe) Same as Example 5-1 8300 12400 16.3 Same as Example 5-2 7100 13100 12.6 Same as Example 5-3 7700 13800 14.5 Same as Example 5-4 7200 11900 12.6 1G = 10⁻⁴T, 1Oe = 79,6 A/m, 1MGOe = 7,96 kJ/m³ As may be clear from Table 6, it was possible to manufacture easily ejection molded magnets which possess a characteristic that exceeds 10 MGOe by the use of the liquid quenching method.

Claims: A permanent magnet consisting essentially of a magnetic alloy comprising 10 - 40% by weight of R which is at least one element of the group of yttrium and rare-earth elements, 0.1 - 8% by weight of boron, gallium in an amount of 13% by weight or less and the balance being iron. A permanent magnet according to claim 1, further including 30% by weight or less of cobalt. A permanent magnet according to claim 1, wherein the content of boron is more than 1.25% by weight. A permanent magnet according to claim 1, wherein the content of gallium is 0.1 - 13% by weight. A permanent magnet according to claim 1, wherein up to 90% by weight of gallium is replaced by aluminium. A permanent magnet according to claim 1, wherein the content of neodymium and praseodymium is 70% by weight or more of the material R. A permanent magnet according to claim 2, wherein the content of cobalt is 1 - 30% by weight. A permanent magnet according to claim 1, obtainable by sintering method. A permanent magnet according to claim 8, wherein the magnetic alloy is a permanent magnetic alloy. A permanent magnet according to claim 9, wherein the permanent magnetic alloy further includes 30% by weight or less of cobalt. A permanent magnet according to claim 10, wherein the content of oxygen in the permanent magnetic alloy is 50 - 300 ppm by weight. A permanent magnet according to claim 8, aged at a temperature of 550 - 750° C after sintering. A permanent magnet according to claim 12, aged at a temperature of 550 - 1200° C before aging at a temperature of 550 - 750° C. A permanent magnet according to claim 8, aged at a temperature of 550 - 1200° C and further aged at a temperature of 550 - 750° C, after sintering. A permanent magnet according to claim 14, wherein the permanent magnetic alloy consists essentially of 10 - 40% by weight of R consisting of at least one element from the group of yttrium and rare-earth elements, 0.1 - 8% by weight of boron, 0.2 - 13% by weight of gallium, 5 - 20% by weight of cobalt and the balance of iron, and the content of oxygen in the permanent alloy is 0.005 - 0.03% by weight. A permanent magnet according to claim 1, wherein the magnetic material is obtainable by using the liquid quenching method. A permanent magnet according to claim 16, obtainable by compressing the powder produced by liquid quenching method and heating. A permanent magnet according to claim 16, obtainable by mixing the powder produced by liquid quenching method and a binder, and compressing the mixture. A permanent magnet according to claim 1, wherein the content of neodymium is 80% by weight or more of the material R. A permanent magnet according to claim 1, wherein the content of neodymium is 90% by weight or more of the material R.

Inventors: INOMATA, KOICHIRO, MIZOGUCHI, TETSUHIKO, SAKAI, ISAO, TSUTAI, AKIHIKO
Applicants: KABUSHIKI KAISHA TOSHIBA
Application year: 1987
Main classification: H01F1
IPC codes: H01F1