EP0106948A2 - Permanent magnetisierbare Legierungen, magnetische Materialien und Dauermagnete die FeBR oder (Fe,Co)BR (R=seltene Erden) enthalten - Google Patents

Permanent magnetisierbare Legierungen, magnetische Materialien und Dauermagnete die FeBR oder (Fe,Co)BR (R=seltene Erden) enthalten Download PDF

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Publication number
EP0106948A2
EP0106948A2 EP83107351A EP83107351A EP0106948A2 EP 0106948 A2 EP0106948 A2 EP 0106948A2 EP 83107351 A EP83107351 A EP 83107351A EP 83107351 A EP83107351 A EP 83107351A EP 0106948 A2 EP0106948 A2 EP 0106948A2
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Prior art keywords
permanent magnet
percent
less
rare earth
max
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EP83107351A
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French (fr)
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EP0106948A3 (en
EP0106948B1 (de
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Masato Sagawa
Setsuo Hanazonodanchi 14-106 Fujimura
Yutaka Matsuura
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Proterial Ltd
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Sumitomo Special Metals Co Ltd
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Priority claimed from JP57166663A external-priority patent/JPS5964733A/ja
Priority claimed from JP58005813A external-priority patent/JPS59132104A/ja
Priority claimed from JP58037897A external-priority patent/JPS59163803A/ja
Priority claimed from JP58037899A external-priority patent/JPS59163805A/ja
Priority claimed from JP58084858A external-priority patent/JPS59211551A/ja
Priority claimed from JP58084860A external-priority patent/JPS59211559A/ja
Priority claimed from JP58094876A external-priority patent/JPH0778269B2/ja
Application filed by Sumitomo Special Metals Co Ltd filed Critical Sumitomo Special Metals Co Ltd
Publication of EP0106948A2 publication Critical patent/EP0106948A2/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B

Definitions

  • the present invention relates to improvements in the temperature dependency of the magnetic properties of magnetic materials and permanent magnets based on Fe-B-R systems.
  • R denotes rare earth elements inclusive of yttrium.
  • Magnetic materials and permanent magnet materials are one of the important electric and electronic materials applied in an extensive range from various electrical appliances for domestic use to peripheral terminal devices of large-scaled computers. In view of recent needs for miniaturization and high efficiency of electric and electronic equipments, there has been an increasing demand for upgrading of permanent magnet materials and generally magnetic materials.
  • the permanent magnet materials developed yet include alnico, hard ferrite and samarium-cobalt (SmCo) base materials which are well-known and used in the art.
  • alnico has a high residual magnetic flux density (hereinafter referred to Br) but a low coercive force (hereinafter referred to Hc), whereas hard ferrite has high Hc but low Br.
  • the rare earth magnets could be used abundantly and with less expense in a wider range.
  • R-Fe 2 base compounds wherein R is at least one of rare earth metals, have been investigated.
  • melt-quenched ribbons or sputtered thin films are not any practical permanent magnets (bodies) that can be used as such. It would be practically impossible to obtain practical permanent magnets from these ribbons or thin films.
  • An essential object of the present invention is to provide novel magnetic materials and permanent magnets based on the fundamental composition of Fe-B-R having an improved temperature dependency of tha magnetic properties.
  • Another object of the present invention is to provide novel practical'permanent magnets and magnetic materials which do not share any disadvantages of the prior art magnetic materials hereinabove mentioned.
  • a further object of the present invention is to provide novel magnetic materials and permanent magnets having good temperature dependency and magnetic properties at room or elevated temperatures.
  • a still further object of the present invention is to provide novel magnetic materials and permanent magnets which can be formed into any desired shape and practical size.
  • a still further object of the present invention is to provide novel permanent magnets having magnetic anisotropy and excelling in both magnetic properties and mechanical strength.
  • a still further object of the present invention is to provide novel magnetic materials and permanent magnets in which as R use can effectively be made of rare earth element occurring abundantly in nature.
  • the magnetic materials and permanent magnets according to the present invention are essentially formed of alloys comprising novel intermetallic compounds, and are crystalline, said intermetallic compounds being characterized at least by new Curie points Tc.
  • percent or "%” denotes the atomic percent (abridged as “at %") if not otherwise specified.
  • a magnetic material comprising Fe, B, R (at least one of the rare earth elements including Y) and Co, and having its major phase formed of Fe-Co-B-R type compound that is of the substantially tetragonal system crystal structure.
  • a sintered magnetic material having its major phase formed of a compound consisting essentially of, in atomic ratio, 8 to 30 % of R (wherein R represents at least one of the rare earth elements including Y), 2 to 28 % of B, no more than 50 % of Co (except that the amount of Co is zero) and the balance being Fe and impurities.
  • a sintered magnetic material having a composition similar to that of the aforesaid sintered magnetic material, wherein the major phase is formed of an Fe-Co-B-R type compound that is of the substantially tetragonal system.
  • a sintered permanent magnet (an Fe-Co-B-R base permanent magnet) consisting essentially of, in atomic ratio, 8 to 30 % of R (at least one of the rare earth elements including Y) , 2 to 28 % of B, no more than 50 % of Co (except that the amount of Co is zero) and the balance being Fe and impurities.
  • This magnet is anisotropic.
  • a sintered anisotropic permanent magnet having a composition similar to that of the fourth permanent magnet, wherein the major phase is formed by an Fe-Co-B-R type compound that is of the substantially tetragonal system crystal structure.
  • Fe-Co-B-R base magnetic materials according to the 6th to 8th aspects of the present invention are obtained by adding to the first - third magnetic materials the following additional elements M, provided, however, that the additional elements M shall individually be added in amounts less than the values as specified below, and that, when two or more elements M are added, the total amount thereof shall be less than the upper limit of the element that is the largest, among the elements actually added (For instance, Ti, V and Nb are added, the sum of these must be no more than 12.5 % in all.):
  • F-e-B-R-Co base permanent magnets according to the 9th to and 10th aspects of the present invention are obtained by adding respectively to the 4th and 5th permanent magnets the aforesaid additional elements M on the same condition.
  • the invented magnetic materials and permanent magnets have a Curie point higher than that of the Fe-B-R type system or the Fe-B-R-M type system.
  • the mean crystal grain size of the intermetallic compound is in a range of about 1 to about 100 ⁇ m for both the Fe-Co-B-R and Fe-Co-B-R-M systems.
  • inventive permanent magnets can exhibit good magnetic properties by containing 1 vol. % or higher of nonmagnetic intermetallic compound phases.
  • inventive magnetic materials are advantageous in that they can be obtained in the form of at least as-cast alloys, or powdery or granular alloys or sintered bodies in any desired shapes, and applied to magnetic recording media (such as magnetic recording tapes) as well as magnetic paints, magnetostrictive materials, thermosensitive materials and the like.
  • magnetic recording media such as magnetic recording tapes
  • magnetic paints such as magnetostrictive materials, thermosensitive materials and the like.
  • the magnetic materials are useful as the intermediaries for the production of permanent magnets.
  • the magnetic materials and permanent magnets according to the present invention are superior in. mechanical strength and machinability to the prior art alnico, R-Co type magnets, ferrite, etc., and has high resistance against chipping-off on machining.
  • the present inventors have found magnetic materials and permanent magnets of the Fe-B-R system the magnets comprised of magnetically anisotropic sintered bodies to be new high-performance permanent magnets without employing expensive Sm and Co, and disclosed them in a European patent application filed on July 5, 1983 No.83106573.5 based on a Japanese Patent Application No. 57-145072.
  • the Fe-B-R base permanent magnets contain Fe as the main component and light-rare earth elements as R,' primarily Nd and Pr, which occur abundantly in nature, and contain no Co. Nonetheless, they are excellent in that they can show an energy product reaching as high as 25 - 35 MGOe or higher.
  • the Fe-B-R base permanent magnets possess high characteristics at costs lower than required in the case with the conventional alnico and rare earth-cobalt alloys. That is to say, they offer higher cost-performance and, hence, greater advantages as they stand.
  • the Fe-B-R base permanent magnets have a Curie point of generally about 300°'C and at most 370°C.
  • the entire disclosure of said Application is herewith incorporated herein with reference thereto with respect to the Fe-B-R type magnets and magnetic materials.
  • Such a Curie point is considerably low, compared with the Curie points amounting to about 800°C of the prior art alnico or R-Co base permanent magnets.
  • the Fe-B-R base permanent magnets have their magnetic properties more dependent upon temperature, as compared with the alnico or R-Co base magnets, and are prone to deteriorate magnetically when used at elevated temperatures.
  • the present invention has for its principal object to improve the temperature dependency of the magnetic properties of the Fe-B-R base magnets and generally magnetic materials.
  • this object is achieved by substituting part of Fe, a main component of the Fe-B-R base magnets, with Co so as to increase the Curie point of the resulting alloy.
  • the results of researches have revealed that the Fe-B-R base .magnets are suitably used in a usual range of not higher than 70°C, since the magnetic properties deteriorate at temperature higher than about 100°C.
  • the substitution of Co for Fe is effective for improving the resistance to the temperature dependency of the Fe-B-R base permanent magnets and magnetic materials.
  • the present invention provides permanent magnets comprised of anisotropic sintered bodies consisting essentially of, in atomic percent, 8 to 30 % R (representing at least one of the :aare earth elements including yttrium), 2 to 28 % of B and the balance being Fe and inevitable impurities, in which part of Fe is substituted with Co to incorporate 50 at % or less of Co in the alloy compositions, whereby the temperature dependency of said permanent magnets are substantially increased to an extent comparable to those of the prior art alnico and R-Co base alloys.
  • the presence of Co does not only improve the temperature dependency of the Fe-B-R base permanent magnets, but also offer additional advantages. That is to say, it is possible to attain high magnetic properties through the use of light-rare. earth elements such as Nd and Pr which occur abundantly in nature.
  • the present Co-substituted Fe-B-R base magnets are superior to the existing R-Co base magnets from the standpoints of both natural resource and cost as well as magnetic properties.
  • the present invention makes it possible to ensure industrial production of high-performance sintered permanent magnets based on the Fe-Co-B-R system in a stable manner.
  • the Fe-Co-B-R base alloys have a high crystal magnetic anisotropy constant Ku and an anisotropic magnetic field Ha standing comparison with that of the existing Sm-Co base magnets.
  • magnetic substances having high anisotropy field H a potentially provide fine particle type magnets with high-performance as is the case with the hard ferrite or SmCo base magnets.
  • sintered, fine particle type magnets were prepared with wide ranges of composition and varied crystal grain size after sintering to determine the permanent magnet properties thereof.
  • the obtained magnet properties correlate closely with the mean crystal grain size after sintering.
  • the single magnetic domain, fine particle type magnets magnetic walls which are formed within each particles, if the particles are large. For this reason, inversion of magnetization easily takes place due to shifting of the magnetic walls, resulting in a low Hc.
  • the particles are reduced in size to below a certain value, no magnetic walls are formed within the particles. For this reason, the inversion of magnetization proceeds only by rotation, resulting in high Hc.
  • the critical size defining the single magnetic domain varies depending upon diverse materials, and has been thought to be about 0.01 um for iron, about 1 ⁇ m for hard ferrite, and about 4 ⁇ m for SmCo.
  • Hc of 1 kOe or higher is obtained when the mean crystal grain size ranges from 1 to 100 ⁇ m, while He of 4 kOe or higher is obtained in a range of 1.5 to 50 ⁇ m.
  • the permanent magnets according to the present invention are obtained as sintered bodies.
  • the crystal grain size of the sintered body after sintering is of the primary concern. It has experimentally been ascertained that, in order to allow the He of the sintered compact to exceed 1 kOe, the mean crystal grain size should be no less than about 1 ⁇ m after sintering. In order to obtain sintered bodies having a smaller crystal grain size than this, still finer powders should be prepared prior to sintering.
  • the He of the sintered bodies decrease considerably, since the fine powders of the Fe-Co-B-R alloys are susceptible to oxidation, the influence of distortion applied upon the fine particles increases, superparamagnetic substances rather than ferromagnetic substances are obtained when the grain size is excessively reduced, or the like.
  • the crystal grain size exceeds 100 pm, the obtained particles are not single magnetic domain particles, and include magnetic walls therein, so that the inversion of magnetization easily takes place, thus leading to a drop in Hc.
  • a grain size of no more than 100 ⁇ m is required to obtain Hc of no less than 1 kOe. Particular preference is given to a range of 1.5 to 50 ⁇ m, within which Hc of 4 kOe or higher is attained.
  • Fe-Co-B-R-M base alloys to be discussed later also exhibit the magnetic properties useful for permanent magnets, when the mean crystal grain size is between about 1 and about 100 ⁇ m, preferably 1.5 and 50 ⁇ m.
  • Tc increases with increases in the amount of Co, when Fe of the Fe-B-R system is substituted with Co.
  • Parallel tendencies have been observed in all the Fe-B-R type alloys regardless of the type of R.
  • Even a slight amount of Co is effective for the increase in Tc and, as will be seen from a (77-x)Fe-xCo-8B-15Nd alloy shown by way of example in Fig. 1, it is possible to obtain alloys having any desired Tc between about 310 and about 750°C by regulation of x.
  • the total composition of B, R and (Fe plus Co) is essentially identical with that of the Fe-B-R base alloys (without Co).
  • Boron (B) shall be used on the one hand in an amount no less than 2 % so as to meet a coercive force of 1 kOe or higher and, on the other hand, in an amount of not higher than 28 % so as to exceed the residual magnetic flux density Br of about 4 kG of hard ferrite.
  • R shall be used on the one hand in an amount no less than 8 % so as to obtain a coercive force of 1 kOe or higher and, on the other hand, in an amount of 30 % or less since it is easy to burn, incurs difficulties in handling and preparation, and is expensive.
  • the present invention offers an advantage in that less expensive light-rare earth element occurring abundantly in nature can be used as R since Sm is not necessarily requisite nor necessarily requisite as a main component.
  • the rare earth elements used in the magnetic materials and the permanent magnets according to the present invention include light- and heavy-rare earth elements inclusive of Y, and may be applied alone or in combination.
  • R includes Nd, Pr, La, Ce, Tb, Dy, Ho, Er, Eu, Sm, Gd, Pm, Tm, Yb, Lu and Y.
  • the light rare earth elements amount to no less than 50 at % of the overall rare earth elements R, and particular preference is given to Nd and Pr. More preferably Nd plus Pr amounts to no less than 50 at % of the overall R.
  • the use of one rare earth element will suffice, but, practically, mixtures of two or more rare earth elements such as mischmetal, didymium, etc.
  • rare earth elements R are not always pure rare earth elements and, hence, may contain impurities which are inevitably entrained in the production process, as long as they are technically available.
  • Boron represented by B may be pure boron or ferroboron, and those containing as impurities Al, Si, C etc. may be used.
  • the permanent magnets according to the present invention have magnetic properties such as coercive force He of Z 1 kOe, and residual magnetic flux density Br of > 4 kG, and provide a maximum energy product (BH)max value which is at least equivalent or superior to the hard ferrite (on the order of up to 4 MGOe). Due to the presence of Co in an amount of 5 % or more the thermal coefficient of Br is about 0.1 %/°C or less. If R ranges from 12 to 24 %, and B from 3 to 27 %, (BH) max ⁇ about 7 MGOe is obtainable so far as R and B concern.
  • BH maximum energy product
  • the light rare earth elements are mainly used as R (i.e., those elements amount to 50 at % or higher of the overall R) and a composition is applied of 12 - 24 at % R, 4 - 24 at % B, 5 - 45 at % Co, with the balance being Fe, maximum energy product (BH)max of ⁇ 10 M G Oe and said thermal coefficient of Br as above are attained. These ranges are more preferable, and (BH)max reaches 33 MGOe or higher.
  • the ranges surrounded with contour lines of (BH)max 10, 20, 30 and 33 MGOe in Fig. 12 define the respective energy products.
  • the Fe-20Co-B-R system can provide substantially the same results.
  • the Co-containing Fe-B-R base magnets of the present invention have better resistance against the temperature dependency, substantially equivalent Br, equivalent or slightly less iHc, and equivalent or higher (BH)max since the loop squareness or rectangularity is improved due to the presence of Co.
  • Co has a corrosion resistance higher than Fe, it is possible to afford corrosion resistance to the Fe-B-R base magnets by incorporation of Co. Particularly Oxidation resistance will simplify the handling the powdery materials and for the final powdery products.
  • the present invention provides embodiments of magnetic materials and permanent magnets which comprise 8 to 30 at % R (R representing at least one of rare earth element including yttrium), 2 to 28 at % B, 50 at % or less Co (except that the amount of Co is zero), and the balance being Fe and impurities which are inevitably entrained in the process of production (referred to "Fe-Co-B-R type".
  • the present invention provides further embodiments which contain one or more additional elements M selected from the group given below in the amounts of no more than the values specified below wherein when two or more elements of M are contained, the sum of M is no more than the maximum value among the values specified below of said elements M actually added and the amount of M is more than zero:
  • the allowable limits of typical impurities contained in the final or finished products of magnetic materials or magnets are up to 3.5, preferably 2.3, at % for Cu; up to 2.5, preferably 1.5, at % for S; up to 4.0, preferably 3.0, at % for C; up to 3.5, preferably 2.0, at % for P; and at most 1 at % for O (oxygen), with the proviso that the total amount thereof is up to 4.0, preferably 3.0, at %. Above the upper limits, no energy product of 4 MGOe is obtained, so that such magnets as contemplated in the present invention are not obtained (see Fig. 11).
  • Mg and Si are allowed to exist each in an amount up to about 8 at %, preferably with the proviso that their total amount shall not exceed about 8 at %. It is noted that, although Si has effect" upon increases in Curie point, its amount is preferably about 8 at % or less, since iHc decreases sharply in an amount exceeding 5 at %. In some cases, Ca and Mg may abundantly be contained in R raw materials such as commercially available Neodymium or the like.
  • Iron as a starting material includes following impurities (by wt %) not exceeding the values below: 0.03 C, 0.6 Si, 0.6 Mn, 0.5 P, 0.02 S, 0.07 Cr, 0.05 Ni, 0.06 Cu, 0.05 Al, 0.05 0 2 and 0.003 N 2 .
  • Electrolytic iron generally with impurities as above mentioned of 0.005 wt % or less is available.
  • Starting neodymium material includes impurities, e.g., other rare earth element such as La, Ce, Pr and Sm; Ca, Mg, Ti, Al, 0, C or the like; and further Fe, Cl, F or Mn depending upon the refining process.
  • impurities e.g., other rare earth element such as La, Ce, Pr and Sm
  • Ca, Mg, Ti, Al, 0, C or the like and further Fe, Cl, F or Mn depending upon the refining process.
  • the permanent magnets according to the present invention are prepared by a so-called powder metallurgical process, i.e., sintering, and can be formed into any desired shape and size, as already mentioned.
  • desired practical permanent magnets were not obtained by such a melt-quenching process as applied in the preparation of amorphous thin film alloys, resulting in no practical coercive force at all.
  • the sintered bodies can be used in the as-sintered state as useful permanent magnets, and may of course be subjected to aging as is the case in the conventional magnets.
  • the magnetic materials of the present invention may be prepared by the process forming the previous stage of the overall process for the preparation of the permanent magnets of the present invention. For example, various elemental metals are melted and cast into alloys having a tetragonal system crystal structure, which are then finely ground into fine powders.
  • the magnetic material use may be made of the powdery rare earth oxide R 2 0 3 (a raw material for R). This may be heated with powdery Fe, powdery Co, powdery FeB and a reducing agent (Ca, etc) for direct reduction.
  • the resultant powder alloys show a tetragonal system as well.
  • the powder alloys can further be sintered into magnetic materials. This is true for both the Fe-Co-B-R base'and the Fe-Co-B-R-M base magnetic materials.
  • F ig. 1 typically illustrates changes in Curie point Tc of 77Fe-8B-15Nd wherein part of Fe is substituted with Co(x), and (77-x)Fe-xCo-8B-15Nd wherein x varies from 0 to 77.
  • the samples were prepared in the following steps.
  • Alloys were melted by high-frequency melting and cast in a water-cooled copper mold.
  • Co electrolytic Co having a purity of 99.9 % was used.
  • Blocks weighing about 0.1 g were obtained from the sintered bodies by cutting, and measured on their Curie points using a vibrating sample magnetometer in the following manner. A magnetic field of 10 kOe was applied to the samples, and changes in 4 ⁇ I depending upon temperature were determined in a temperature range of from 250°C to 800°C. A temperature at which 4 ⁇ I reduced virtually to zero was taken as Curie point Tc.
  • Tc increased rapidly with the increase in the amount of C o replaced for Fe, and exceeded 600°C in Co amounts of no less than 30 %.
  • Table 1 also shows the magnetic properties of the respective samples at room temperature.
  • iHc In most of the compositions, iHc generally decreases due to the Co substitution, but (BH)max increases due to the improved loop rectangularity of the magnetization curves. However, iHc decreases if the amount of Co increases from 25 to 50 7% finally reaching about the order of 1.5 kOe. Therefore the amount of Co shall be no higher than 50 % so as to obtain iHc Z 1 kOe suitable for permanent magnets.
  • Fig. 2 shows an initial magnetization curve 1 for 57Fe-20Co-8B-15Nd at room temperature.
  • the initial magnetizaton curve 1 rises steeply in a low magnetic field, and reaches saturation.
  • the demagnetization curve 2 shows very high loop rectangularity, which indicates that the magnet is a typical high-performance anisotropic magnet. From the form of the initial magnetization curve 1, it is thought that this magnet is a so-called nucleation type permanent magnet since the SmCo type magnets of the nucleation type shows an analogous curve, wherein the coercive force of which is determined by nucleation occurring in the inverted magnetic domain.
  • the high loop rectangularity of the demagnetization curve 2 indicates that this mgnet is a typical high-performance anisotropic magnet.
  • Other samples according to the present invention set forth in Table 1 all showed magnetization curves similar to that of Fig. 4.
  • Permanent magnet samples of Fe-Co-B-R-M alloys containing as M one or two additional elements were prepared in a manner similar to that applied for the preparation of the Fe-Co-B-R base magnets.
  • the additional elements M used were Ti, Mo, Bi, Mn, Sb, Ni, Sn, Ge and Ta each having a purity of 99 %, by weight so far as the purity concerns as hereinbelow, W having a purity of 98 %, Al having a purity of 99.9 %, and Hf having a purity of 95 %.
  • V ferrovanadium containing 81.2 % of V; as Nb ferroniobium containing 67.6 % of Nb; as Cr ferrochromium - containing 61.9 % of Cr; and as Zr ferrozirconium containing 75.5 % of Zr were used, respectively.
  • Table 2 shows the maximum energy product (BH)max, which is the most important factor of the permanent magnet properties, of typical samples.
  • Fe is the balance.
  • the Fe-Co-B-R-M base magnets have high energy product of 10 MGOe or greater over a wide compositional range.
  • This table mainly enumerates the examples of alloys containing Nd and Pr, but any of 15 rare earth element (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) give rise. to increase in (BH)max.
  • the alloys containing Nd and Pr according to the present invention are more favorable than those containing as the main materials other rarer rare earth element (Sm, Y and heavy-rare element), partly because Nd and Pr occur relatively abundantly in rare earth ores, and especially because no applications of Nd in larger amounts have been found.
  • the Fe-Co-B-R-M magnets according to the present invention have Curie points higher than the Fe-B-R-M magnets without Co.
  • FIG. 6 shows the demagnetization curves of the typical examples of the Fe-Co-B-R-M magnets and M-free Fe-Co-B-R magnets given for the purpose of comparison.
  • reference numerals 1 to 3 denote the demagnetization curves of a M-free magnet, a Nb-containing magnet (Table 1 No.3) and a W-containing magnet (Table 1 No. 83), respectively.
  • each amount of the individual elements M are within each aforesaid range, and the total amount thereof is no more than the maximum values among the values specified for the individual elements which are actually added and present in a system. For instance, if Ti, V and Nb are added the total amount of these must be mo more than 12.5% in all.
  • a more preferable range for the amount of M is determined from a range of (BH)max within which it exceeds 10 MGOe of the highest grade alnico. In order that (BH)max is no less than 10 MGOe, Br of 6.5 kG or higher is required.
  • the upper limits of the amounts of M are preferably defined at the following values: wherein two or more additional elements M are used, the preferable ranges for M are obtained when the individual elements are no higher than the aforesaid upper limits, and the total amount thereof is,no higher than the maximum values among the values allowed for the individual pertinent elements which are actually added and present.
  • the Fe-Co-B-R base system preferably comprises 4 to 24 % of B, 11 to 24 % of R (light-rare earth elements, primarily Nd and Pr), and the balance being the given amounts of" Fe and Co
  • (BH)max of 10 MGOe or higher is obtained within the preferable ranges of the additional elements M, and reaches or exceeds the (BH)max level of hard ferrite within the upper limit of M.
  • the permanent magnets have (BH)max of 15, 20, 25, 30 and even 33 MGOe or higher.
  • (BH)max assumes a value practically similar to that obtained with the case where no M is applied, through the addition of an appropriate amount of M, and may reach at most 33 MGOe or higher.
  • the increase in coercive force serves to stabilize the magnetic properties, so that permanent magnets are obtained which are practically very stable and have a high energy product.
  • Ni is a ferromagnetic element (see Fig. 8). Therefore, the upper limit of Ni is 8 %, preferably 6.5 %, in view of Hc.
  • Mn upon decrease in Br is not strong but larger than is the case with Ni.
  • the upper limit of Mn is 8 %, preferably 6 %, in view of iHc.
  • the pulverization procedure as previously mentioned was carried out for varied periods of time selected in such a manner that the measured mean particle sizes of the powder ranged from 0.5 to 100 ⁇ m. In this manner, various samples having the compositions as specified in Table 3 were obtained.
  • Comparative Examples To obtain a crystal grain size of 100 ⁇ m or greater, the sintered bodies were maintained for prolonged time in an argon atmosphere at a temperature lower than the sintered temperature by 5 - 20°C.
  • the samples were polished and corroded on their surfaces, and photographed through an optical microscope at a magnification ranging from x100 to x1000. Circles having known areas were drawn on the photographs, and divided by lines into eight equal sections. The number of grains present on the diameters were counted and averaged. However, grains on the borders (circumferences) were counted as half grains (this method is known as Heyn's method). Pores were omitted from calculation.
  • the composition comes within the range as defined in the present invention and the mean crystal grain size D is 1 - 100 ⁇ m, and that, in order to obtain Hc of no less than 4 kOe, the mean crystal grain size should be in a range of 1.5 - 50 ⁇ m.
  • Control of the crystal grain size of the sintered compact can be carried out by controlling process conditions such as pulverization, sintering, post heat treatment, etc.
  • Fe-Co-B-R-M magnets Fe-Co-B-R-M magnets
  • Tables 4 - 1 to 4 - 3 show properties of the permanent magnets comprising a variety of Fe-Co-B-R-M compounds, which were prepared by melting and pulverization of alloys, followed by forming of the resulting powders in a magnetic field then sintering. Permanent magnets departing from the scope of the present invention are also shown with mark * . It is noted that the preparation of samples were substantially identical with that of the Fe-Co-B-R base magnets.
  • Fig. 11 shows the demagnetization curves of the typical examples of the invented Fe-Co-B-R-M base magnets and the M-free Fe-Co-B-R base magnets.
  • reference numerals 1 - 3 denote the demagnetization curves of a M-free magnet, a Mo-containing magnet (Table 4 - 1 No. 20) and a Nb-containing magnet (Table 4 - 1 No. 16), all of which show the loop squareness useful for permanent magnet materials.
  • the curve 4 represents ones with a mean crystal grain size D of 52 ⁇ m for the same composition as 3.
  • the composition comes within the range as defined in the present invention and the mean crystal grain size is about 1 - about 100 ⁇ m, and that, in order to obtain Hc of no less than 4 kOe, the mean crystal grain size should be in a range of about 1.5 - about 50 ⁇ m.
  • Control of the crystal grain size of the sintered compact can be controlled as is the case of the Fe-Co-B-R system.
  • the invented permanent magnets of the Fe-Co-B-R-M base magnetically anisotropic sintered bodies may contain, in addition to Fe, Co, B, R and M,_ impurities which are entrained therein in the process of production as is the case for the Fe-Co-B-R system.
  • the magnetic materials and permanent magnets based on the Fe-Co-B-R base alloys according to the present invention can satisfactorily exhibit their own magnetic properties due to the fact that the major phase is formed by the substantially tetragonal crystals of the Fe-B-R type.
  • the Fe-Co-B-R type alloy is a novel alloy in view of its Curie point.
  • it has further been experimentally ascertained that the presence of the substantially tetragonal crystals of the Fe-Co-B-R type contributes to the exhibition of magnetic properties.
  • the Fe-Co-B-R type tetragonal system alloy is unknown in the art, and serves to provide a vital guiding principle for the production of magnetic materials and permanent magnets having high magnetic properties as aimed at in the present invention.
  • the desired magnetic properties can be obtained, if the Fe-Co-B-R crystals are of the substantially tetragonal system.
  • ao bo co.
  • the term "substantially tetragonal" encompasses ones that have a slightly deflected angle between a, b and c axes, e.g., within about 1°, or ones that have O o slightly different from l o , e.g., within about 1 %.
  • the magnetic materials and permanent magnets of the present invention are required to contain as the major phase an intermetallic compound of the substantially tetragonal system crystal structure.
  • major phase it is intended to indicate a phase amounting to 50 vol % or more of the crystal structure, among phases constituting the crystal structure.
  • Fe-Co-B-R base permanent magnets having various compositions and prepared by the manner as hereinbelow set forth as well as other various manners were examined with an X-ray diffractometer, X-ray microanalyser (XMA) and optical microscopy.
  • indices are given at the respective X-ray peaks.
  • the major phase simultaneously containing Fe, Co, B and R, as confirmed in the XMA measurement, has turned out to exhibit such a structure.
  • This structure is characterized by its extremely large lattice constants. No tetragonal system compounds having such large lattice constants are found in any one of the binary system compounds such as R-Fe, Fe-B and B-R.
  • Fe-Co-B-R base permanent magnets having various compositions and prepared by the aforesaid manner as well as other various manners were examined with an X-ray diffractometer, XMA and optical microscopy. As a result, the following matters have turned out:
  • the fine particles having a high anisotropy constant are ideally separated individually from one another by nonmagnetic phases, since a high Hc is then obtained.
  • the presence of 1 vol % or higher of nonmagnetic phases contributes to the high Hc.
  • the nonmagnetic phases should be present in a volume ratio between 1 and 45 vol %, preferably between 2 and 10 vol %. The presence of 45 % or higher of the nonmagnetic phases is unpreferable.
  • the nonmagnetic phases are mainly comprised of intermetallic compound phases containing much of R, while oxide phases serve partly effectively.
  • Alloys containing, in addition to the Fe-Co-B-R base components, one or more additional elements M and/or impurities entrained in the process of production can also exhibit good permanent magnet properties, as long as the major phases are comprised of tetragonal system compounds.
  • the aforesaid fundamental tetragonal system compounds are stable and provide good permanent magnets, even when they contain up to 1 % of H, Li, Na, K, Be, Sr, Ba, Ag, Zn, N, F, Se, Te, Pb, or the like.
  • the Fe-Co-B-R type tetragonal system compounds are new ones which have been entirely unknown in the art. It is thus new fact that high properties suitable for permanent magnets are obtained by forming the major phases with these new compounds.
  • the invented magnets are different from the ribbon magnets in the following several points. That is to say, the ribbon magnets can exhibit permanent magnet properties in a transition stage from the amorphous or metastable crystal phase to the stable crystal state. Reportedly, the ribbon magnets can exhibit high coercive force only if the amorphous state still remains, or otherwise metastable Fe 3 B and R 6 Fe 23 are present as the major phases.
  • the invented magnets have no sign of any alloy phase remaining in the amorphous state, and the major phases thereof are not Fe 3 B and R 6 Fe 23 .
  • An alloy of 10 at % Co, 8 at % B, 15 at % Nd and the balance Fe was pulverized to prepare powders having an average particle size of 1.1 ⁇ m.
  • the powders were compacted under a pressure of 2 t/cm 2 and in a magnetic field of 12 kOe, and the resultant compact was sintered at 1080°C for 1 hour in argon of 1.5 Torr.
  • the major phase contains simultaneously Fe, Co, B and Pr, which amount to 90 volume % thereof.
  • Nonmagnetic compound phases having a R content of no less than 80 % assumed 4.5 % in the overall with the remainder being substantially oxides and pores.
  • the mean crystal grain size was 3.1 ⁇ m.
  • the typical sample of the present invention has also been found to have high mechanical strengths such as bending strength of 25 kg/mm 2 , compression strength of 75 kg/mm 2 and tensile strength of 8 kg/mm 2 .
  • This sample could effectively be machined, since chipping hardly took place in machining testing.
  • the present invention makes it possible to prepare magnetic materials and sintered anisotropic permanent magnets having high remanence, high coercive force and high energy product with the use of less expensive alloys containing light-rare earth elements, a relatively small amount of Co and based on Fe, and thus present a technical breakthrough.

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EP83107351A 1982-09-27 1983-07-26 Permanent magnetisierbare Legierungen, magnetische Materialien und Dauermagnete die FeBR oder (Fe,Co)BR (R=seltene Erden) enthalten Expired EP0106948B1 (de)

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
JP57166663A JPS5964733A (ja) 1982-09-27 1982-09-27 永久磁石
JP166663/82 1982-09-27
JP5813/83 1983-01-19
JP58005813A JPS59132104A (ja) 1983-01-19 1983-01-19 永久磁石
JP58037899A JPS59163805A (ja) 1983-03-08 1983-03-08 永久磁石用合金
JP58037897A JPS59163803A (ja) 1983-03-08 1983-03-08 永久磁石用合金
JP37897/83 1983-03-08
JP37899/83 1983-03-08
JP58084858A JPS59211551A (ja) 1983-05-14 1983-05-14 永久磁石材料
JP84860/83 1983-05-14
JP84858/83 1983-05-14
JP58084860A JPS59211559A (ja) 1983-05-14 1983-05-14 永久磁石材料
JP94876/83 1983-05-31
JP58094876A JPH0778269B2 (ja) 1983-05-31 1983-05-31 永久磁石用希土類・鉄・ボロン系正方晶化合物

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EP0106948A2 true EP0106948A2 (de) 1984-05-02
EP0106948A3 EP0106948A3 (en) 1985-03-13
EP0106948B1 EP0106948B1 (de) 1989-01-25

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EP0196123A1 (de) * 1985-02-26 1986-10-01 Koninklijke Philips Electronics N.V. Permanent Magneten aus einer intermetallischen Verbindung von seltenen Erden und übergangsmetallen und Bor
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US4767474A (en) * 1983-05-06 1988-08-30 Sumitomo Special Metals Co., Ltd. Isotropic magnets and process for producing same
US4773950A (en) * 1983-08-02 1988-09-27 Sumitomo Special Metals Co., Ltd. Permanent magnet
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US5110377A (en) * 1984-02-28 1992-05-05 Sumitomo Special Metals Co., Ltd. Process for producing permanent magnets and products thereof
US4826546A (en) * 1984-02-28 1989-05-02 Sumitomo Special Metal Co., Ltd. Process for producing permanent magnets and products thereof
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US4588439A (en) * 1985-05-20 1986-05-13 Crucible Materials Corporation Oxygen containing permanent magnet alloy
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US4933009A (en) * 1985-06-14 1990-06-12 Union Oil Company Of California Composition for preparing rare earth-iron-boron-permanent magnets
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US5560784A (en) * 1985-08-13 1996-10-01 Seiko Epson Corporation Rare earth cast alloy permanent magnets and methods of preparation
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US4859254A (en) * 1985-09-10 1989-08-22 Kabushiki Kaisha Toshiba Permanent magnet
US5041172A (en) * 1986-01-16 1991-08-20 Hitachi Metals, Ltd. Permanent magnet having good thermal stability and method for manufacturing same
US4814139A (en) * 1986-01-16 1989-03-21 Hitachi Metals, Ltd. Permanent magnet having good thermal stability and method for manufacturing same
EP0237416A1 (de) * 1986-03-06 1987-09-16 Shin-Etsu Chemical Co., Ltd. Permanentmagnet auf Basis seltener Erden
US4769063A (en) * 1986-03-06 1988-09-06 Sumitomo Special Metals Co., Ltd. Method for producing rare earth alloy
US5085715A (en) * 1986-03-20 1992-02-04 Hitachi Metals, Ltd. Magnetically anisotropic bond magnet, magnetic powder for the magnet and manufacturing method of the powder
US4952239A (en) * 1986-03-20 1990-08-28 Hitachi Metals, Ltd. Magnetically anisotropic bond magnet, magnetic powder for the magnet and manufacturing method of the powder
US4921553A (en) * 1986-03-20 1990-05-01 Hitachi Metals, Ltd. Magnetically anisotropic bond magnet, magnetic powder for the magnet and manufacturing method of the powder
EP0239031A1 (de) * 1986-03-20 1987-09-30 Hitachi Metals, Ltd. Verfahren zur herstellung von magnetpulver fuer einen megnetisch anisotropen gebundenen magneten
US4954186A (en) * 1986-05-30 1990-09-04 Union Oil Company Of California Rear earth-iron-boron permanent magnets containing aluminum
US4878958A (en) * 1986-05-30 1989-11-07 Union Oil Company Of California Method for preparing rare earth-iron-boron permanent magnets
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Also Published As

Publication number Publication date
DE3379084D1 (en) 1989-03-02
SG48390G (en) 1991-02-14
EP0106948A3 (en) 1985-03-13
HK68490A (en) 1990-09-07
EP0106948B1 (de) 1989-01-25
CA1315571C (en) 1993-04-06

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