EP2735003A1 - Matériau magnétique et son procédé de production - Google Patents

Matériau magnétique et son procédé de production

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Publication number
EP2735003A1
EP2735003A1 EP12729553.3A EP12729553A EP2735003A1 EP 2735003 A1 EP2735003 A1 EP 2735003A1 EP 12729553 A EP12729553 A EP 12729553A EP 2735003 A1 EP2735003 A1 EP 2735003A1
Authority
EP
European Patent Office
Prior art keywords
kpa
during
recombination
desorption
magnetic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12729553.3A
Other languages
German (de)
English (en)
Inventor
Konrad Güth
Oliver Gutfleisch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Aichi Steel Corp
Original Assignee
Robert Bosch GmbH
Aichi Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH, Aichi Steel Corp filed Critical Robert Bosch GmbH
Publication of EP2735003A1 publication Critical patent/EP2735003A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • H01F1/0573—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 obtained by reduction or by hydrogen decrepitation or embrittlement
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/023—Hydrogen absorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • H01F1/0579—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B with exchange spin coupling between hard and soft nanophases, e.g. nanocomposite spring magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/03—Amorphous or microcrystalline structure
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • 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
    • H01F1/0553—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 obtained by reduction or by hydrogen decrepitation or embrittlement

Definitions

  • the invention relates to a magnetic material, and a method for its production.
  • Magnetic materials as well as methods for their preparation are known from the prior art.
  • finely crystalline, so-called nanocrystalline magnetic powders by ball milling or rapid solidification and subsequent hot-compacting or hot deformation or by "exchange coupling or Remanenzüberhöhung" obtained.
  • a disadvantage of this is the complex processing of the starting alloy, and the often low energy density and remanent magnetization of the resulting
  • DE 197 52 366 A1 describes a process for producing a hard magnetic samarium-cobalt base material by means of a H DDR process (hydrogenation - disproportionation - desorption - recombination), wherein the disproportionation at a hydrogen pressure of more than 0.5 MPa and a temperature from 500 ° C to 900 ° C is performed.
  • H DDR process hydrogenation - disproportionation - desorption - recombination
  • the inventive method with the features of claim 1 is characterized by a simplified feasibility. This is at least one soft magnetic phase having a sufficiently small crystallite size is uniformly and efficiently coupled to a hard magnetic phase, at the same time texturing the hard magnetic phase. Under texturing or texture formation is understood that a
  • hard magnetic phase is formed with a crystallographic preferred direction.
  • the formation of the magnetic material according to the invention takes place in a continuous process, wherein the desorption and recombination of the magnetic material take place either successively or in parallel.
  • the abbreviation "desorption / recombination” for both options mentioned above, namely for both a sequential drainage of desorption and recombination, as well as a parallel running of the
  • a magnetic material having a high remanent magnetization of preferably about 1.3 to 1.5 tesla is obtained.
  • the crystallites of the material according to the invention are characterized by a high degree of texturing, i. they have a crystallographic preferred direction. It has surprisingly been found that the nucleation, the crystal growth and in particular the texturing of the magnetic material can be positively influenced by the application of a magnetic field during at least one of the method steps. This increases the remanent magnetization of the material according to the invention. Furthermore, by appropriate choice of
  • the remanent magnetization can be set specifically.
  • the final crystallite size of the magnetic material according to the invention can be controlled by the method according to claim 1 so that it is smaller by at least one size unit than in conventional magnetic materials produced by the HDR method. Due to this very small crystallite size of preferably less than 300 nm, and more preferably less than 100 nm or even less than 50 nm, the
  • the magnetic field is applied during the desorption step and the recombination step.
  • the production of the magnetic material is preferably controlled so that between the disproportionation on the one hand and the desorption (for successive desorption and recombination) or the desorption and recombination (for parallel desorption and recombination) on the other side there is an equilibrium that can be shifted in one direction or another by targeted application of the magnetic field.
  • the crystallite size and especially the initiation or improvement of the texturing of the magnetic material are particularly strongly influenced by the magnetic field, so that it starts already during nucleation and during germ growth and thus the texturing of the magnetic material can be controlled specifically. This increases the remanent magnetization of the magnetic material.
  • the magnetic field strength of the applied magnetic field is more than 0 to about 100 Tesla, preferably more than 0 to 10 Tesla.
  • Field strength is sufficient to cause high texturing in the magnetic material and to promote a crystallite size of the desired size, and preferably of a few 100 nm or even less than 100 nm.
  • the magnetic field strength is not limited to the top. In the preferred range of up to 10 Tesla, the nucleation and growth rate of the crystallites and in particular the texturing of the material is optimally controllable with the lowest possible production costs. The optimum magnetic field strength can be easily found out by a person skilled in the art by simple comparative experiments. The state of equilibrium between disproportionation and
  • Desorption / recombination is preferably by lowering the
  • Desorption / recombination of the magnetic material is more easily targeted adjustable, which in turn is promoted the texturing of the magnetic material.
  • Hydrogenation step about 20 ° C to 350 ° C, preferably about 300 ° C and / or the temperature during the Disproportiontechnischs Colour.es 500 ° C to 1000 ° C, preferably 750 ° C to 850 ° C and / or the temperature during the
  • Temperature range between 750 ° C and 850 ° C in terms of speed and process costs promotes an optimal course of reaction.
  • the high temperature during desorption leads to an almost complete recombination to the final magnetic product.
  • the hydrogen partial pressure during the hydrogenation step is 20 kPa to 100 kPa and more, preferably 20 kPa to 40 kPa and especially 30 kPa and / or the hydrogen partial pressure during the disproportionation step 20 kPa to 40 kPa, preferably 30 kPa and / or the hydrogen partial pressure during the desorption step 0.5 kPa to 1, 5 kPa, preferably 1 kPa and / or the hydrogen partial pressure during the recombination step is 0 kPa to 1 kPa, preferably 0 kPa.
  • the high pressures of 100 kPa and more during the hydrogenation step are particularly advantageous for high alloyed starting materials, while for low alloyed starting materials pressures of 20 to about 40 kPa are sufficient.
  • the pressures during the disproportionation step and also during the recombination step may vary depending on the soft magnetic material used. That's how they are
  • Process management promotes the texturing of the magnetic material. Furthermore, it simplifies the reaction procedure and is therefore expedient. The optimum pressure for the respective magnetic material, the expert can easily find out by simple comparison experiments.
  • Hydrogen partial pressure is at low alloyed starting materials between 20 kPa and 40 kPa to a sufficient amount of hydrogen for the
  • Hydrogen partial pressure of 30 kPa is particularly preferred from a process engineering and economic point of view.
  • the hydrogen partial pressure during the desorption step is the hydrogen partial pressure of the desorption step
  • Disproportionation step in particular by ball milling, and in particular by reactive ball milling is reduced. If ball milling is already carried out in the hydrogenation step, this is preferably done by reactive ball milling.
  • the ball milling or reactive ball milling promotes the formation of the smallest possible crystallites, which has a positive effect on the crystallite size and the Texturing of the magnetic material according to the invention effects.
  • Another advantage of ball milling is that the particle size of the
  • Starting material can then be larger, since this is sufficiently crushed by the step of ball milling.
  • ball milling the crystallite size of the starting material and / or the during the
  • Hydrogenation step and / or the Disproportionierungs Coloures resulting material is preferably reduced to less than 50 nm and more preferably to 5 to 20 nm. If the ball milling is carried out before the hydrogenation step, this can also be done at a temperature of about 20 ° C, which significantly reduces the process costs.
  • the ball milling can also be carried out under a hydrogen atmosphere, resulting in a shortened grinding time and thus also reduced
  • the ball milling can be carried out by means of conventional devices.
  • the H 2 pressure applied for grinding is at least 0.1 MPa, preferably at least 1 MPa, more preferably at least 10
  • Hydrogenating step and / or disproportionation step resulting material has a crystallite size of less than 50 nm, and preferably from 5 to 20 nm.
  • the specified H 2 pressure ensures fast and sufficiently good, homogeneous grinding and thus disproportionation.
  • the Height of the applied H 2 pressure, the expert can easily find out by appropriate preliminary tests.
  • the time of addition of the soft magnetic material is after disproportionation. This means that said material can be added either directly after disproportionation or at a later stage of the process.
  • the time of addition can be, for example, in
  • the said soft magnetic material can also be added after recombination, provided that in this particular case the starting particle size of the magnetic material is less than 5 ⁇ m.
  • the soft magnetic material can be added by conventional methods such as physical blending or chemical addition, that is, for example, by vapor deposition or so-called co-milling in a low-intensity agitating mill.
  • the soft magnetic material is preferably mechanically mixed with the disproportionated material, thereby enabling effective exchange coupling. This promotes a homogeneous, nanoscale distribution of soft and hard magnetic phases and a small crystallite size of the magnetic material, which in turn the
  • the soft magnetic material is not limited in detail.
  • the soft magnetic material is formed of Fe and / or Co or of an alloy of these two elements.
  • the elements iron and cobalt, as well as their mixtures or alloys thereof promote the texturing of the magnetic material very well.
  • An alloy of the elements iron and cobalt, which is particularly suitable for the process according to the invention is Fe 65 Co 35 .
  • the amount of soft magnetic material is in a range of more than 0 to 50 wt .-%, preferably 10 to 30 wt .-%, more preferably about 20 wt .-%, each based on the starting material. In this range, the amount of soft magnetic material is sufficient to allow good exchange coupling associated with high overall magnetization of the magnetic material and thus to create a homogeneous high texture textured magnetic structure therein.
  • the magnetic material is hot-deformed during the desorption step and / or the recombination step and / or
  • the rare earth metal is selected from the group consisting of: Nd, Sm, La, Dy, Tb, Gd, more preferably: Nd, Sm, La.
  • These rare earth metals can be due to their physical and chemical properties particularly well with the invention
  • the transition metal is selected from the group consisting of Fe and Co. These two transition metals are readily available and relatively inexpensive and have very good magnetic properties. More preferably, the magnetic material, and preferably the starting material, contains at least one further element, in particular B and / or Ga and / or Nb and / or Si and / or Al. These elements can be the magnetic as well as physical and chemical properties of the material and its resistance, so its chemical or
  • Electrochemical resistance eg corrosion resistance
  • Boron is particularly preferred because it promotes the structure formation of the magnetic material, that is to say in particular the hard magnetic phase of the type Nd 2 Fei 4 B.
  • the process is carried out so that the intermediate product produced after the disproportionation step and / or after the grinding is a stoichiometric intermediate.
  • the intermediate is single phase, so none
  • the primary hydrogenated intermediate is thus SEH 2 , where SE is rare earth metal (s). This can be done by specific choice of the parameters temperature,
  • Nd 2 F 14 B is converted into the three disproportionated phases mentioned above, wherein NdH 2 + x is formed.
  • this powder is heated, for example at 650 ° C., this superstoichiometric phase changes to a stable NdH 2 phase at about 200-300 ° C. and hydrogen is released.
  • the process is carried out such that the intermediate product produced after the disproportionation step and / or after the grinding is a superstoichiometric Intermediate is.
  • SEH 2 there is also SEH 3 , which is also generally SEH 2 + x. This can be adjusted by specific selection of the parameters temperature, hydrogen partial pressure and reaction time.
  • a permanent magnet which comprises at least one rare earth metal and at least one transition metal and which has been prepared according to the method described above.
  • This permanent magnet is characterized by a particularly high
  • Preferred permanent magnet compositions are NdTM 12 and Sm 2 TM 17 where TM is transition metal. Especially preferred
  • Compositions are Sm 2 Fei 7 , SmCo 5 , and due to its
  • the permanent magnet of the invention has a remanent magnetization of 1, 3 to 1, 5 Tesla.
  • the invention relates to a method for producing a magnetic material from a starting material, wherein the
  • Starting material comprises at least one rare earth metal (SE) and at least one transition metal
  • SE rare earth metal
  • transition metal the method comprising the known from the conventional H DDR method steps: hydrogenation of the starting material, disproportionation of the starting material, desorption and recombination, wherein during at least one step, a magnetic field such is present that a textured magnetic material is obtained or the formation of a texture is promoted in the magnetic material.
  • FIG. 1 shows a schematic overview of the conventional H DDR method
  • FIG. 2 is a schematic overview of the first invention
  • FIG. 3 is a schematic overview of a second invention
  • FIG. 4 is a schematic overview of a third invention
  • FIG. 5 is a schematic overview of a fourth invention
  • Figure 6 is a schematic overview of a fifth invention
  • FIG. 7 is a schematic overview of a sixth invention
  • Figure 8a is a graph showing the dependence of the crystallite size
  • Coercive field strength ( ⁇ 0 ) of a superstoichiometric ball milled magnetic material from the temperature during the recombination step is Coercive field strength ( ⁇ 0 ) of a superstoichiometric ball milled magnetic material from the temperature during the recombination step.
  • Figure 8b is a graph showing the dependence of the crystallite size
  • Coercive field strength ( ⁇ 0 ) of a stoichiometric ball milled magnetic material from the temperature during the recombination step is Coercive field strength ( ⁇ 0 ) of a stoichiometric ball milled magnetic material from the temperature during the recombination step.
  • 9a shows a high resolution SEM (LEO Gemini 1530 FEG) of a Nd28,78Fe ba iB 1, 1 Gao, 35Nbo, 26 material, which means
  • FIG. 9b shows a high-resolution SEM image (LEO FEG 1530 Gemini) of a Nd28.78Fe ba 1 , 1 Gao, 35Nbo, 26 material, which was produced by means of HDDR process and additional ball milling.
  • the H DDR method 10 comprises the
  • an Nd 2 Fe-i 4 B block piece having an initial particle size of, for example, about 50 to 100 ⁇ is fed at 840 ° C increasing temperature hydrogen.
  • Hydrogen partial pressure is thereby raised in the system to 30 kPa, which leads to a disproportionation of the starting material under
  • NdH 2 , Fe and Fe 2 B Hydrogen absorption and thus the formation of NdH 2 , Fe and Fe 2 B comes.
  • the hydrogen partial pressure is maintained until an equilibrium has been established in which several phases, ie NdH 2 and NdH 2 + x in addition to NdH 3 , are present (superstoichiometric intermediate).
  • Composition of the reaction mixture is determined by conventional methods (eg X-ray diffractometry). In the subsequent desorption or recombination steps 3 and 4, the temperature is still maintained at 840 ° C, the hydrogen partial pressure but lowered to 1 kPa to finally 0.1 kPa. In this case, a recombination of the individual phases to Nd 2 Fe-i 4 B takes place with liberation of hydrogen.
  • the crystallite size of the resulting magnetic material is typically 200-400 nm
  • Magnetization of typically about 0.8 Tesla is achieved.
  • FIG. 2 shows a first exemplary embodiment.
  • a Nd 2 Fei 4 B block piece with a starting particle size of 50 to 300 ⁇ is hydrogenated and
  • the starting alloy material is stoichiometric. There are no intergranular rare earth metal-rich phases.
  • Composition of the reaction mixture is determined by conventional methods (e.g., X-ray diffractometry).
  • the temperature of the system during the hydrogenation step is 1 200 ° C, during the
  • Disproportionation step 2 and the desorption step 3 800 ° C wherein the hydrogen partial pressure is maintained until the desorption step 3 to 30 kPa and during the desorption step 3 is lowered to 1 kPa and then further to 0 kPa.
  • Recombination step 4 and alternatively in the equilibrium state between disproportionation 2 and desorption 3 / recombination 4, is also due to a magnetic field 5 of 8 Tesla on the system.
  • the final magnetic final product is typically about 50 nm.
  • the crystals are characterized by X-ray diffractometry.
  • the texturing of the obtained magnetic material is high.
  • the remanent magnetization of the magnetic material thus obtained is typically about 1.4 Tesla.
  • FIG. 3 shows a second exemplary embodiment.
  • an Nd 2 Fei 4 B block piece with a starting particle size of 100 to 150 ⁇ is hydrogenated and
  • the starting alloy material is stoichiometric. There are no intergranular rare earth metal-rich phases.
  • Composition of the reaction mixture is determined by conventional methods (eg: X-ray diffractometry).
  • the starting compound is ground by means of ball milling 6, so that the resulting particle size is 2 to 10 ⁇ m.
  • Ball milling is carried out during the hydrogenation and disproportionation steps with an H 2 pressure of at least 0.1 MPa.
  • the temperature of the system is during the
  • Hydrogenation step 1 250 ° C, during the disproportionation step 2 and the desorption step 3 800 ° C, wherein the hydrogen partial pressure is maintained until the desorption step 3 to 30 kPa and during the
  • Desorption step 3 to 1 kPa and then further lowered to 0 kPa.
  • desorption step 3 and recombination step 4 and alternatively in the equilibrium state between disproportionation 2 and
  • Desorption 3 / recombination 4 a magnetic field 5 of 8.5 Tesla is also applied to the system.
  • the crystal size of the final magnetic product is typically about 30 nm.
  • the crystals are characterized by X-ray diffractometry. The texturing of the obtained magnetic material is high.
  • the remanent magnetization is typically about 1.4 Tesla.
  • FIG. 4 shows a third exemplary embodiment.
  • a Nd 2 Fei 4 B block piece with a starting particle size of 50 to 150 ⁇ is hydrogenated and
  • the starting alloy material is superstoichiometric. So there are more rare earth metal-rich phases.
  • the composition of the reaction mixture is determined by conventional methods (e.g.
  • the starting compound is ground in step 1 and 2 by means of ball milling 6, so that the resulting crystallite size is 2 to 4 ⁇ .
  • the temperature of the system is during the
  • Desorption step 3 to 1 kPa and then further lowered to 0 kPa.
  • desorption step 3 and the recombination step 4 and alternatively in the equilibrium state between disproportionation 2 and
  • Desorption 3 / recombination 4 a magnetic field 5 of 8.5 Tesla is also applied to the system.
  • the crystallite size of the final magnetic product is typically about 40 nm.
  • the crystals are characterized by X-ray diffractometry. The texturing of the obtained magnetic material is high.
  • the remanent magnetization is typically about 1.4 Tesla.
  • FIG. 5 shows a fourth exemplary embodiment.
  • an Nd 2 Fei 4 B block piece with a starting particle size of 30 to 100 ⁇ m ⁇ is hydrogenated and
  • the starting alloy material is stoichiometric. There are no intergranular rare earth metal-rich phases.
  • Composition of the reaction mixture is determined by conventional methods (e.g., X-ray diffractometry).
  • the temperature of the system during the hydrogenation step is 1 300 ° C, during the
  • Disproportionation step 2 and the desorption step 3 800 ° C wherein the Hydrogen partial pressure is maintained until the desorption step 3 to 30 kPa and during the desorption step 3 is lowered to 1 kPa and then further to 0 kPa.
  • Recombination step 4 and alternatively in the equilibrium state between disproportionation 2 and desorption 3 / recombination 4, is also present
  • Disproportionation step 2 are additionally more than 0 wt .-% to 50 wt .-%, preferably 25 wt .-% nanoparticulate iron 7 based on the
  • the particle size of the iron is typically 5 to 50 nm.
  • the crystallite size of the final magnetic product is typically less than 30 nm
  • the texturing of the obtained magnetic material is high.
  • the remanent magnetization is typically about 1.4 Tesla.
  • FIG. 6 shows a fifth exemplary embodiment.
  • a Nd 2 Fei 4 B block piece with a starting particle size of 50 to 150 ⁇ is hydrogenated and
  • the starting alloy material is stoichiometric. There are no intergranular rare earth metal-rich phases.
  • Composition of the reaction mixture is determined by conventional methods (e.g., X-ray diffractometry).
  • the starting compound is ground in step 1 and 2 by means of ball milling 6, so that the resulting primary crystallite size is 2 to 5 ⁇ .
  • the temperature of the system during the hydrogenation step is 1 300 ° C, during the
  • Hydrogen partial pressure is maintained until the desorption step 3 to 30 kPa and during the desorption step 3 is lowered to 1 kPa and then further to 0 kPa. During the desorption step 3 and the
  • Recombination step 4 and alternatively in the equilibrium state between disproportionation 2 and desorption 3 / recombination 4, is also present
  • Disproportionation step 2 are additionally more than 0 wt .-% to 50 wt .-%, preferably 30 wt .-% nanoparticulate iron 7 based on the
  • the particle size of the iron is typically 5 to 50 nm.
  • the crystallite size of the final magnetic product is typically less than 30 nm. The crystals are formed by means of
  • the texturing of the obtained magnetic material is high.
  • the remanent magnetization is typically about 1.4 Tesla.
  • FIG. 7 shows a sixth exemplary embodiment.
  • a Nd 2 Fe-i 4 B block piece having a starting particle size of 120 to 200 ⁇ m is hydrogenated and disproportionated.
  • the starting alloy material is stoichiometric. There are no intergranular rare earth metal-rich phases.
  • Composition of the reaction mixture is determined by conventional methods (e.g., X-ray diffractometry).
  • the starting compound is ground in step 1 and 2 by means of ball milling 6, so that the resulting crystallite size is 2 to 5 ⁇ .
  • the temperature of the system during the hydrogenation step 1 is 250 ° C, during the disproportionation step 2 and the desorption step 3 800 ° C, the hydrogen partial pressure is maintained until the desorption step 3 to 30 kPa and during the
  • Desorption step 3 to 1 kPa and then further lowered to 0 kPa.
  • disproportionation step 2 in addition more than 0 wt .-% to 50 wt .-%, preferably 25 wt .-% nanoparticulate iron 7 based on the starting compound, add.
  • the particle size of the iron is typically 5 to 50 nm.
  • a magnetic field 5 of 8.0 Tesla on the system and Reaction mixture is hot-deformed in step 3 and 4 by a hot deformation 8 at a temperature of 850 ° C and a pressure of 150 MPa by means of a press.
  • the crystallite size of the final magnetic product is typically less than 30 nm.
  • the crystals are characterized by X-ray diffractometry. The texturing of the obtained magnetic material is high.
  • the remanent magnetization is typically 1.4 Tesla.
  • Nd28.78Fe ba 1 1 Gao, 35Nbo, 26 (more than stoichiometric, rich in Nd)
  • Nd27, o7FebaiB 1 oGa 0 , 32Nbo, 28 (near-stoichiometric, negligible Nd excess).
  • the starting materials were homogenized for about 40 hours in an oven at a temperature of 1140 ° C under argon atmosphere, i. through the
  • the Nd 2 Fei 4 B phase was set in the material. Then, the obtained material was coarsely ground and sieved to obtain a particle size of about 250 ⁇ m. The coarse powders were then ground mechanically by ball milling in a grinding jar for five hours under 5-10 MPa hydrogen partial pressure. Das_Material hydrogenated and disproportioniert here. The desorption and recombination step was then carried out in a temperature range of 600 ° C to 840 ° C within about 15 minutes, during the desorption step 3 and the
  • Recombination step 4 and alternatively in the equilibrium state between disproportionation 2 and desorption 3 / recombination 4, a magnetic field 5 of about 8 Tesla was.
  • each phase of the magnetic material was determined by X-ray diffraction (Rietveld refinement as described in JI Langford, Proc. Int Conf: Accuracy in Powder Diffraction II, Washington, DC: NIST Special Publication No. 846 US Government Printing Office, 10 (1992) ") .
  • the morphology of the obtained magnetic powder material was determined by means of high-resolution SEM (LEO FEG 1530 Gemini)
  • VSM vibrating sample magnetometer
  • FIG. 8a shows the dependence of the crystallite size
  • FIG. 8a shows the temperature range in which the
  • FIG. 8a thus illustrates that the
  • Recombination at temperatures of less than 650 ° C is incomplete, while recombination at temperatures of 840 ° C or above leads to a significantly larger crystallite size of the Nd2Fe-14B product of about 15 nm, presumably due to melting of the Nd-rich phase at temperatures above 670 ° C is due. This leads to an increased diffusion and thus increased crystallite growth.
  • An increase in the temperature during the recombination step above 700 ° C in this case leads to no appreciable increase in the crystallite size of the ⁇ -Fe.
  • the crystallite size of the a-Fe was largely around 30 nm.
  • the stoichiometric product was also composed of ⁇ -Fe and NdH 2 (Fe 2 B was not detected for the same reasons as mentioned above). After recombination too
  • FIG. 8b shows the dependence of the crystallite size of the magnetic material on the temperature and the coercive force H c ( ⁇ 0 ⁇ ⁇ ) during the recombination step of the stoichiometric material mentioned above under b),
  • the shaded area in Figure 8b again shows the temperature range in which the recombination is incomplete.
  • the crystallite size at temperatures up to about 700 ° C was almost identical to that obtained for the superstoichiometric product in the same temperature range. However, an increase in the temperature during the recombination step to over 700 ° C led here to a
  • Magnetization was 0.85 Tesla, regardless of the temperature during the recombination step and can be increased if necessary by adding iron.
  • the recombined material from the stoichiometric starting alloy showed a coercive field strength of 1.05 Tesla.
  • composition of the materials as follows: 70 wt .-% a-Fe, 25.4 wt .-% NdH 2 and 4.6 wt .-% Fe 2 B.
  • the crystallite size of the individual phases was 30 nm, 15 nm and 20 nm and was thus significantly larger than that obtained in the above method by additional ball milling.
  • the micro-deformation of ⁇ -Fe was 0.20%, that of NdH 2 0.77% and that of Fe 2 B 0.08%, and was thus significantly lower than in the above-mentioned method.
  • FIGS. 9a and 9b show high-resolution SEM images (LEO FEG 1530
  • a textured magnetic material having a very high remanent magnetization of preferably 1.3 to 1.5 tesla can be obtained by the methods according to the invention. Accordingly, improved permanent magnets can be produced from this magnetic material.
  • the magnetic material according to the invention can be produced in a particularly cost-effective manner.
  • Magnetic field also only during a step, in particular the step 3 or 4, may be applied.
  • the magnetic field in all described embodiments may also be applied during step 1 and / or 2.

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Abstract

L'invention concerne un procédé de production d'un matériau magnétique, le matériau magnétique étant constitué d'un matériau de départ comprenant un métal des terres rares (SE) et au moins un métal de transition, et le procédé comprenant les étapes suivantes : Hydratation du matériau départ, dismutation du matériau de départ, désorption et recombinaison. Un champ magnétique est appliqué au cours d'au moins une étape de manière à permettre l'obtention d'un matériau magnétique texturé et à activer la création d'une texture dans le matériau magnétique.
EP12729553.3A 2011-07-20 2012-06-20 Matériau magnétique et son procédé de production Withdrawn EP2735003A1 (fr)

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PCT/EP2012/061774 WO2013010741A1 (fr) 2011-07-20 2012-06-20 Matériau magnétique et son procédé de production

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DE102015218560A1 (de) * 2015-09-28 2017-03-30 Robert Bosch Gmbh Hartmagnetphase, Verfahren zu ihrer Herstellung und magnetisches Material
CN108766701B (zh) * 2018-04-26 2020-08-21 安徽省瀚海新材料股份有限公司 一种钕铁硼甩带片的粉碎工艺

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JPH07312307A (ja) * 1994-05-18 1995-11-28 Tokin Corp 高分子複合型希土類磁石用粉末
DE19751367C2 (de) * 1997-11-20 2002-06-27 Dresden Ev Inst Festkoerper Verfahren zur Herstellung eines hartmagnetischen, aus einer Samarium-Kobalt-Basis-Legierung bestehenden Pulvers
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US6444052B1 (en) * 1999-10-13 2002-09-03 Aichi Steel Corporation Production method of anisotropic rare earth magnet powder
JP3452254B2 (ja) * 2000-09-20 2003-09-29 愛知製鋼株式会社 異方性磁石粉末の製造方法、異方性磁石粉末の原料粉末およびボンド磁石
EP1457998A4 (fr) * 2001-12-19 2009-06-17 Hitachi Metals Ltd Alliage d'elements de terres rares-fer-bore, poudre d'aimant permanent anisotrope magnetiquement et son procede de production
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CN100483570C (zh) * 2007-04-29 2009-04-29 哈尔滨工业大学 一种制备纳米晶NdFeB各向异性磁粉的方法
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KR20140053108A (ko) 2014-05-07
JP2014523142A (ja) 2014-09-08
US20140346388A1 (en) 2014-11-27
WO2013010741A1 (fr) 2013-01-24
TW201310481A (zh) 2013-03-01
DE102011108173A1 (de) 2013-01-24

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