EP0133758B1 - Iron-rare earth-boron permanent magnets by hot working - Google Patents

Iron-rare earth-boron permanent magnets by hot working Download PDF

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Publication number
EP0133758B1
EP0133758B1 EP84304731A EP84304731A EP0133758B1 EP 0133758 B1 EP0133758 B1 EP 0133758B1 EP 84304731 A EP84304731 A EP 84304731A EP 84304731 A EP84304731 A EP 84304731A EP 0133758 B1 EP0133758 B1 EP 0133758B1
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Prior art keywords
hot
permanent magnet
die
iron
making
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German (de)
English (en)
French (fr)
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EP0133758A2 (en
EP0133758A3 (en
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Robert Weir Lee
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Motors Liquidation Co
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Motors Liquidation Co
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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
    • H01F1/0576—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 pressed, e.g. hot working

Definitions

  • This invention relates to high temperature strain-anneal processing of extremely rapidly solidified compositions comprising iron, one or more rare earth metals and boron to produce useful permanent magnets. More particularly, this invention relates to the hot consolidation and hot working of overquenched compositions comprising iron, neodymium and/or praseodymium, and boron to form useful, magnetically-aligned permanent magnets.
  • High energy product, high coercivity permanent magnet compositions comprising, for example, iron, neodymium and/or praseodymium, and boron, and methods of making them are disclosed in European Patent Application 108 474 (General Motors Corporation).
  • An illustrative composition, expressed in atomic proportions, is It is substantially the composition of a specific stable intermetallic phase that possesses high coercivity when formed as fine crystallites about 20 to 400 nanometers in largest dimension.
  • melts of the above family of compositions can be very rapidly quenched, such as by melt-spinning, to produce a solid material, e.g., a thin ribbon.
  • rate of cooling has been controlled to produce a suitable fine crystalline microstructure (20 nm to 400 nm)
  • the material has excellent permanent magnet properties.
  • faster cooling overquenching
  • overquenched material can be annealed to form the suitable crystal size with the associated high coercivity and high energy product.
  • this neodymium-iron-boron composition (for example) is that it is magnetically isotropic.
  • a fine grain, melt spun ribbon can be broken up into flat particles. The particles can be pressed in a die at room temperature to form a unitary body of about 85% of the material's density. Bonding agents can be employed before or after the compaction.
  • the making of such bonded magnets is disclosed in European Patent Application 84301453.1 (General Motors Corporation), filed 6 March 1984. It was surprising to find that such bonded magnets displayed no preferred magnetic direction. Values of intrinsic coercivity or maximum energy product were not dependent upon the direction of the applied magnetic field. There was no advantage in grinding the ribbon to very fine particles and magnetically aligning the particles before compaction.
  • Such magnetically isotropic materials are very useful because they can be easily pressed (without magnetic alignment) into bonded shapes.
  • the shapes can be magnetized in the most convenient direction.
  • the iron-neodymium-boron type compositions might provide still higher energy products if at least a portion of the grains or crystallites in their microstructure could be physically aligned and if such alignment produced at least partial magnetic domain alignment.
  • the material would then have a preferred direction of magnetization.
  • the material would be magnetically anisotropic and would have higher residual magnetization and higher energy product in the preferred direction.
  • This has now been accomplished using overquenched melt-spun material by hot working the material to consolidate it to full density and to effect plastic flow that yields magnetic alignment.
  • the same improvement can be accomplished on finely crystalline, high coercivity material (e.g., H c ⁇ >1000 Oe) if the hot work is performed rapidly before excessive grain growth occurs and coercivity decreases.
  • EP-A-101 552 describes a sintered anisotropic permanent magnet of the Fe-B-R type.
  • This anisotropic magnet has higher residual magnetization and energy product than isotropic magnets of like composition.
  • the treatment is by a hot working process, such as hot pressing, hot die-upsetting, extrusion, forging, or rolling, to fully consolidate pieces of the material, to effect suitable grain growth and to produce a plastic flow therein that results in a body having magnetic anisotropy. It is found that the maximum magnetic properties in such a hot worked body are oriented parallel to the direction of pressing (perpendicular to the direction of flow). In the direction of preferred magnetic alignment, energy products are obtainable that are significantly greater than those in isotropic magnets of like composition.
  • a molten composition comprising iron, neodymium and/or praseodymium, and boron is prepared.
  • Other constituents may be present, as will be disclosed below.
  • An example of a preferred composition, expressed in terms of atomic proportions, is
  • the molten material is cooled extremely rapidly, as by melt spinning, to form a thin ribbon of solid material that does not have permanent magnet properties.
  • the material is amorphous in microstructure. It will not produce an x-ray pattern containing many discrete diffraction maxima like that obtained from diffraction in crystalline substances. When highly magnified, as in a scanning electron microscrope micrograph, no discrete grains (or crystallites) will be apparent.
  • the ribbon or other thin, solid form may be broken, if necessary, into particles of convenient size for an intended hot working operation.
  • the particles are heated under argon to a suitable elevated temperature, preferably 700°C or higher, and subjected to short term hot working under pressure, preferably at least 68,947.6 kPa (10,000 psi).
  • Such processing may be accomplished by any of a number of known hot working practices.
  • the material may be hot pressed in a die. It may be extruded, or rolled, or die-upset, or hammered, Whatever the particular form of hot working employed, the several individual particles are pressed and flowed together until the mass achieves full density for the composition. In addition, the hot mass is caused to undergo plastic flow.
  • the nonpermanent magnet microstructure is converted to a suitable fine grain crystalline material.
  • the flow of the hot, fine grain material produces a body, that upon cooling below its Curie temperature, has preferred direction of magnetization and provides excellent permanent magnet properties.
  • the high temperature working produces a finely crystalline or granular microstructure (for example, up to about 0.4 to 0.5 micrometers in greatest dimension). Care is taken to cool the material before excessive grain growth and loss of coercivity occurs.
  • the preferred direction of magnetization of the hot worked product is typically parallel to the direction of pressing and transverse to the direction of plastic flow. A significantly higher energy product is obtained when the body is magnetized transverse to the direction of plastic flow.
  • material of like composition and similar microstructure has been made without hot working. Such materials have been magnetically isotropic and had lower maximum energy product.
  • the starting material may be a high coercivity (>1000 Oe) isotropic material. Suitable hot working of the material will fully density it and effect plastic flow to orient the fine crystallites in a magnetically anisotropic structure. However the duration of the hot working must be short so that the crystallites do not grow so large that the desirable magnetic properties are lost.
  • the method of the present invention is applicable to compositions comprising a suitable transition metal component, a suitable rare earth component, and boron.
  • the transition metal component is iron or iron and (one or more of) cobalt, nickel, chromium or manganese. Cobalt is interchangeable with iron up to about 40 atomic percent. Chromium, manganese and nickel are interchangeable in lower amounts, preferably less than about 10 atomic percent. Zirconium and/or titanium in small amounts (up to about 2 atomic percent of the iron) can be substituted for iron. Very small amounts of carbon and silicon can be tolerated where low carbon steel is the source of iron for the composition.
  • the composition preferably comprises about 50 atomic percent to about 90 atomic percent transition metal component-largely iron.
  • the composition also comprises from about 10 atomic percent to about 50 atomic percent rate earth component.
  • Neodymium and/or praseodymium are the essential rare earth constituents. As indicated, they may be used interchangeably. Relatively small amounts of other rare earth elements, such as samarium, lanthanum, cerium, terbium and dysprosium, may be mixed with neodymium and praseodymium without substantial loss of the desirable magnetic properties. Preferably, they make up no more than about 40 atomic percent of the rare earth component. It is expected that there will be small amounts of impurity elements with the rare earth component.
  • the overquenched composition contains about 1 to 10 atomic percent boron.
  • the overall composition may be expressed by the formula
  • the transition metal (TM) as used herein makes up about 50 to 90 atomic percent of the overall composition, with iron representing about 80 atomic percent of the transition metal content.
  • the other constituents such as cobalt, nickel, chromium or manganese, are called "transition metals" insofar as the above empirical formula is concerned.
  • compositions For convenience, the compositions have been expressed in terms of atomic proportions. Obviously these specifications can be readily converted to weight proportions for preparing the composition mixtures.
  • compositions of approximately the following atomic proportions For purposes of illustration, the invention will be described using compositions of approximately the following atomic proportions: However, it is to be understood that the method of the invention is applicable to a family of compositions as described above.
  • molten transition metal-rare earth-boron compositions can be solidified to have microstructures ranging from:
  • Fine grain microstructures where the grains have a maximum dimension of about 20 to 400 nanometers, have useful permanent magnet properties. Amorphous materials do not. However, some of the glassy microstructure materials can be annealed to convert them to fine grain permanent magnets having isotropic magnetic properties
  • the present invention is applicable to such overquenched, glassy materials. It is also applicable to "as-quenched" high coercivity, fine grain materials provided the materials are exposed only for short times, e.g., less than five minutes, at high temperatures, over 700°C, during the hot working.
  • Suitable overquenched compositions can be made by melt-spinning.
  • the material is contained in a suitable vessel, such as a quartz crucible.
  • the composition is melted by induction or resistance heating in the crucible under argon.
  • a small, circular ejection orifice about 500 microns in diameter. Provision is made to close the top of the crucible so that the argon can be pressurized to eject the melt from the vessel in a very fine stream.
  • the molten stream is directed onto a moving chill surface located about 6.35 mm (one-quarter inch) below the ejection orifice.
  • the chill surface is a 25 cm diameter, 1.3 cm thick copper wheel.
  • the circumferential surface is chrome plated.
  • the crucible and wheel are contained in a box that is evacuated of air and backfilled with argon. In the experiments the wheel is not cooled. Its mass is so much greater than the amount of melt impinging on it in any run that its temperature does not appreciably change. When the melt hits the turning wheel, it flattens, almost instantaneously solidifies and is thrown off as a ribbon.
  • the thickness of the ribbon and the rate of cooling are largely determined by the circumferential speed of the wheel. In this work, the speed can be varied to produce an amorphous ribbon, a fine grained ribbon or a large grained ribbon.
  • the cooling rate or speed of the chill wheel preferably is such that an amorphous or extremely fine crystal structure is produced.
  • Such a structure will be amorphous or will have finer crystals than that which produces a permanent magnet as is, for example, less than about 20 nanometers in largest dimension.
  • the distinction between an amorphous microstructure and such an extremely fine crystalline microstructure is probably not discernible.
  • an overquenched material that has less than optimum permanent magnetic properties but that can be annealed to produce improved permanent magnet properties.
  • the material is not separately annealed. It is, in effect, annealed while it is hot worked to produce a magnetic microstructure that has anisotropic magnetic properties.
  • An overquenched, melt spun ribbon was prepared.
  • a molten mixture was prepared in accordance with the following formula: About 40 grams of the mixture was melted in a quartz tube that was about 10 cm long and 2.54 cm in diameter. The quartz tube had an ejection orifice in the bottom, which was round and about 600 pm in diameter. The top of the tube was sealed and adapted to supply pressurized argon gas to the tube above the molten alloy. The alloy was actually melted in the tube using induction heating. When the melt was at 1400°C, an argon ejection pressure of about 20.68 kPa (3 psig) was applied.
  • a solidified melt spun ribbon came off the wheel. It was about 30 pm thick and about one mm wide.
  • This material was cooled too rapidly to have useful permanent magnet properties. In other words, it was overquenched. Had the wheel been rotated slightly slower, the ribbon could have been produced to have a microstructure affording useful hard magnetic properties.
  • the ribbon was broken into short pieces and they were placed into a cylindrical cavity 12 of a round die 10 like that depicted in Figure 1.
  • the cavity was 9.525 mm (3/8 inch) in diameter and the material was contained by upper and lower punches 14.
  • the die was made of a high temperature nickel alloy with a tool steel liner, and the punches were tungsten carbide.
  • the die and the contents were rapidly heated under argon with an induction coil 16 to a maximum temperature of 750°C.
  • the temperature was measured using a thermocouple (not shown) in the die adjacent the cavity.
  • the upper punch was then actuated to exert a maximum pressure of 220632.32 kPa (32,000 psi) on the broken-up ribbon particles. Heating and pressure were stopped.
  • the workpiece was cooled to room temperature on the die. However, the total time that the workpiece was at a temperature above 700°C was only about five minutes.
  • the consolidated workpiece was removed from the die.
  • the resulting cylinder was hard and strong. It had a density of about 7.5 grams per cubic centimeter, which is susbtantially its full density.
  • the magnetic properties of the material were determined by cutting a piece from the cylinder and grinding a small sphere, about 2 mm in diameter, from the cut off piece.
  • the sphere was then placed in a vibrating sample magnetometer with the positive magnetic pole of the sphere aligned with the positive pole of the magnetometer.
  • the second quadrant demagnetization plot (4nM versus H) was obtained for the particular direction of magnetization.
  • the sample was removed from the magnetometer and magnetized in a pulsed field as before in a different direction. It was returned to the magnetometer and a new demagnetization curve determined. This process was again repeated and the respective curves compared. The sample displayed magnetic anisotropy.
  • Figure 2 contains four different second quadrant plots of 4nM versus H.
  • the second quadrant portion of a hysteresis loop provides useful information regarding permanent magnet properties.
  • Three of these plots in Figure 2 represent good properties.
  • the upper curve 18 represents a favorable direction of magnetization obtained in the spherical sample.
  • the lowest curve 20 represents the data obtained from a direction relatively far removed from the aligned direction of the hot pressed compact.
  • the middle line 22 is the demagnetization plot also generated in the vibrating sample magnetometer of an isotropic array of the same ribbon from which its hot compact was made.
  • plot 22 is of an isotropic magnet of the same composition as the anisotropic magnet produced in this example.
  • a hysteresis curve was also prepared from a sample of the original overquenched ribbon.
  • the second quadrant portion is produced as curve 24 in Figure 2. It has relatively low intrinsic coercivity and residual magnetization.
  • the hot pressing operation produced a fully densified body and also produced flow in the material that oriented the microstructure so that it became magnetically anisotropic.
  • the residual magnetization and energy product are greater than in the isotropic material.
  • hot pressed body In addition to having excellent permanent properties at room temperature the hot pressed body retains its properties during exposure at high temperatures in air.
  • a hot pressed body of this example was exposed at 160°C in air to a reverse field of 4 kOe for 1507 hours. It suffered only minimal loss in permanent magnet properties.
  • Figure 3a is a photomicrograph of a cross-section of a bonded magnet that was compacted at room temperature to 85% of full density. The plate-like sections of the original ribbon are seen to line up and be preserved in the bonded magnet.
  • Figure 3b is a photomicrograph at the same magnification of a hot pressed specimen fully densified in accordance with the invention. The flat ribbon fragments are still perceptible at about the same size as in the bonded magnet, but there are no voids in this fully densified specimen.
  • Example 2 Another overquenched, melt spun ribbon was prepared by the method described in Example 1.
  • the nominal composition of the ribbon was in accordance with the empirical formula
  • the ribbons were produced by quenching the melt on a chill wheel rotating at a velocity of 32 m/ s.
  • the thickness of the ribbon was approximately 30 um and the width approximately one millimeter. This cooling rate produced a microstructure that could not be magnetized to form a magnet having useful permanent magnet properties.
  • Ribbon pieces were compacted at room temperature in a die to form a precompacted body of about 85% full density.
  • the precompact was then placed in the cavity of a high temperature alloy die similar to that described in Example 1. However, the die had a graphite liner. Carbide punches confined the precompact in the die cavity.
  • the die and its contents were quickly heated under argon to 740°C and a ram pressure of 68,947.6 kPa (10 kpsi) was applied in an attempt to extrude the preform.
  • An unexpected form of backward extrusion was obtained as the precompacted material flowed out from between the punches and displaced graphite die liner to form a cup-like piece. After cooling to room temperature this piece was removed from the die and it was found that the extruded portion of the sample was of sufficient dimensions to allow density measurement as well as magnetic measurement. The extruded portion was fully densified.
  • a 2 mm cube was ground from a portion of the extruded metal and it was tested in a vibrating sample magnetometer. By magnetizing and demagnetizing the sample transverse to the cube faces it was observed that the specimen displayed magnetic anisotropy. Three orthogonal directions are displayed in Figure 4 by curves 26, 28 and 30. The separations of these second quadrant plots from different directions of magnetization results from physical alignment of magnetic domains within the sample. The greater the separation of the plots, the greater the degree of magnetic alignment. It is seen that the alignment for the extruded sample was even more pronounced than for the sample of Figure 1.
  • the demagnetization curves for the annealed ribbon 22 and the overquenched ribbon 24 are also included in this figure as in Figure 2.
  • Figure 3c is a photomicrograph at 600x magnification of a cross-section of the extruded sample. It is seen that greater plastic flow occurred in the extruded sample as evidenced by the reduction in thickness of the original ribbon particles. It is believed that this plastic flow is essential to alignment of the magnetic moments within the material and that this alignment is generally transverse to the plastic flow. In other words, with respect to this sample, the magnetic alignment is transverse to the long dimension of the extruded ribbons (i.e., up and down in Figure 3c).
  • Figure 5 is a scanning electron microscope micrograph at nearly 44,000x magnification of a fracture surface of the extruded sample. It shows the fine grain texture.
  • Example 1 Additional hot press tests, like Example 1, and modified extrusion tests, like Example 2, were carried out at various die temperatures in the range of 700 to 770°C and pressures in the range of 68,947.6 to 206,842.8 kPa (10,000 to 30,000 psi). These tests showed thaf full densification could be realized even at the lower pressures and temperatures. However, the samples prepared at the lower temperatures and pressures appeared to be more brittle. Optical micrographs revealed the ribbon pieces to have cracks similar to those present in Figure 3a. Evidently, higher pressure is required at temperatures of 750°C and lower before such cracks disappear as in Figure 3b.
  • the preferred magnetization direction for the hot pressed samples is parallel to the press direction and perpendicular to the direction of plastic flow. Greater directional anisotropy develops when more plastic flow is allowed, as in the extrusion tests.
  • This example illustrates a die upsetting practice.
  • Overquenched ribbon fragments of Example 2 were hot pressed under argon in a heated die, like that in Figure 1, at a maximum die temperature of 770°C and pressure of 103,421.4 kPa (15 kpsi).
  • This hot pressed cylinder was sanded to a smaller cylinder (diameter less than 1 cm) with its cylindrical axis transverse to the axis of the original cylinder.
  • This cylinder was re-hot pressed in the original diameter cavity along its axis (perpendicular to the original press direction) so that it was free to deform to a shorter cylinder of 9.525 mm (3/8") diameter (i.e., die upsetting).
  • the die upsetting operation was conducted at a maximum temperature of 770°C and a pressure of 110,316.16 kPa (16 kpsi). As in previous examples the part was cooled in the die. A cubic specimen was machined from the die upset body and its magnetic properties measured parallel and transverse to the press direction in a vibrating sample magnetometer, as in the above Examples 1 and 2. Second quadrant, room temperature 4nM versus H plots for these two directions are depicted in Figure 6. Curve 32 was obtained in the direction parallel to the die upset press direction and curve 34 in the direction transverse thereto and thus parallel to the direction of material flow. It is seen that this die upset practice produced greater anisotropy than the single hot pressing operation or the extrusion test.
  • Example 3 illustrates a die upsetting practice similar to Example 3, except a fully dense, hot pressed sample was die-upset with pressure applied in the same direction as the original hot press pressure.
  • Overquenched ribbon fragments of Example 2 were hot pressed under argon in a heated die, like that depicted in Figure 1, at a maximum temperature of 760°C and pressure of 103,421.4 kPa (15 kpsi).
  • This hot pressed piece was sanded to a smaller diameter (less than about 1 cm) and die upset in the same diameter cavity in a direction parallel to the first press direction.
  • the die upset operation was conducted at a maximum temperature of 750°C and a pressure of 82,737.1 kPa (12 kpsi). The sample was cooled in the die.
  • This practice of high temperature consolidation and plastic flow can be viewed as a strain anneal process.
  • This process produces magnetic alignment of the grains of the workpiece and grain growth.
  • the grain growth is excessive, coercivity is decreased. Therefore consideration (and probably trial and error testing) must be given to the grain size of the starting material in conjunction with the time that the material is at a temperature at which grain growth can occur. If, as is preferred, the starting material is overquenched, the workpiece can be held at a relatively high temperature for a longer time because some grain growth is desired. If one starts with near optimal grain size material, the hot working must be rapid and subsequent cooling prompt to retard excessive grain growth.
  • Hot pressure eperiments were also conducted on annealed ingot that had a homogenized, large grain microstructure. When magnetized, such ingots contained very low coercivity, less than 500 oersted.
  • the present hot pressing strain-anneal practice produced a significant directional dependence of B r in the ingot samples, but no coercivity increase. It had been hoped that the strain-anneal practice would induce recrystallization in the ingot which would allow for development of the optimal grain size. The failure to obtain a coercivity increase in these experiments indicates that the strain-anneal practice is not beneficially applicable to large grained materials.
  • this high temperature-high pressure consolidation and hot working of suitable, transition metal, rare earth metal, boron compositions yields magnetically anisotropic product of excellent permanent magnet properties.
  • the practice of the present invention has been described, using specific composition of neodymium, iron and boron.
  • other materials may be substituted or present in suitably small amounts.
  • Praseodymium may be substituted for neodymium or used in combination with it.
  • Other rare earth metals may be used with neodymium and/or praseodymium.
  • other metals, such as cobalt, nickel, manganese and chromium, in suitably small amounts may be used in combination with iron.
  • the preferred compositional ranges are described above.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
EP84304731A 1983-08-04 1984-07-11 Iron-rare earth-boron permanent magnets by hot working Expired - Lifetime EP0133758B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52017083A 1983-08-04 1983-08-04
US520170 1983-08-04

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EP0133758A2 EP0133758A2 (en) 1985-03-06
EP0133758A3 EP0133758A3 (en) 1987-05-20
EP0133758B1 true EP0133758B1 (en) 1990-09-19

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JP (1) JPS60100402A (es)
AU (1) AU574697B2 (es)
BR (1) BR8403875A (es)
CA (1) CA1236381A (es)
DE (1) DE3483226D1 (es)
ES (1) ES534879A0 (es)
MX (1) MX167658B (es)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN108428541A (zh) * 2017-02-14 2018-08-21 中国科学院宁波材料技术与工程研究所 一种超细晶高性能各向异性钕铁硼永磁体的制备方法

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AU574697B2 (en) 1988-07-14
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JPS60100402A (ja) 1985-06-04
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DE3483226D1 (de) 1990-10-25
JPH0420242B2 (es) 1992-04-02
CA1236381A (en) 1988-05-10
EP0133758A2 (en) 1985-03-06
EP0133758A3 (en) 1987-05-20
AU3096284A (en) 1985-02-07
BR8403875A (pt) 1985-07-09

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