EP4027358A1 - Alliage magnétique doux et procédé de fabrication d'un alliage magnétique doux - Google Patents

Alliage magnétique doux et procédé de fabrication d'un alliage magnétique doux Download PDF

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EP4027358A1
EP4027358A1 EP21215751.5A EP21215751A EP4027358A1 EP 4027358 A1 EP4027358 A1 EP 4027358A1 EP 21215751 A EP21215751 A EP 21215751A EP 4027358 A1 EP4027358 A1 EP 4027358A1
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weight
gew
temperature
hydrogen
precursor
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EP4027358B1 (fr
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Niklas Volbers
Johannes Tenbrink
Jan Frederik Fohr
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Vacuumschmelze GmbH and Co KG
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Vacuumschmelze GmbH and Co KG
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    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/16—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 soft-magnetic materials metals or alloys in the form of sheets
    • H01F1/18—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 soft-magnetic materials metals or alloys in the form of sheets with insulating coating
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    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
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    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1233—Cold rolling
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1272—Final recrystallisation annealing
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
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    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • 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
    • C21D2201/05—Grain orientation
    • 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

Definitions

  • the invention relates to a soft magnetic alloy and a method for producing a soft magnetic alloy.
  • Soft-magnetic cobalt-iron alloys are used, among other things, in electrical machines due to their exceptionally high saturation induction.
  • Commercially available CoFe alloys typically have a composition of 49% Fe, 49% Co and 2% V by weight. With such a composition, a saturation induction of about 2.35 T is achieved with a simultaneously high electrical resistance of 0.4 ⁇ m. Due to the higher permeability, these alloys can be used in applications such as a rotor or a stator of an electric motor in order to reduce the size of the rotor or stator and thus the electric motor compared to an FeSi alloy and/or to increase the output. For example, with the same overall size and/or with the same weight, a higher torque can be generated, which would be advantageous when used in electrically or hybrid-powered motor vehicles.
  • the DE 10 2018 112 491 A1 discloses a high permeability soft magnetic FeCo alloy with 5 to 25 wt% Co that can have a maximum permeability in excess of 17,000 and lower hysteresis losses. Due to the lower Co content, the raw material costs of this alloy are reduced compared to an alloy based on 49% by weight Fe, 49% by weight Co, 2% V. At the same time, this alloy does not exhibit any significant order adjustment, so that, in contrast to alloys with more than 30% by weight of Co, it can be cold-rolled without an upstream quenching process, which simplifies large-scale production.
  • the object is therefore to provide a soft-magnetic CoFe alloy with a low Co content and good magnetic properties, which can also be produced more reliably using large-scale production processes.
  • the precursor has a phase transition from a BCC phase region in a BCC/FCC mixed region to an FCC phase region, with increasing temperature the phase transition between the BCC phase region and the BCC/FCC mixed region at a first transition temperature T ⁇ / ⁇ + ⁇ and with further increasing temperature the transition between the BCC/FCC mixed region and the FCC phase region takes place at a second transition temperature T ⁇ + ⁇ / ⁇ , where T ⁇ + ⁇ / ⁇ > T ⁇ / ⁇ + ⁇ .
  • the difference T ⁇ + ⁇ / ⁇ - T ⁇ / ⁇ + ⁇ is less than 45K, preferably less than 25K.
  • impurities are for example B, P, N, W, Hf, Y, Re, Sc, Be, other lanthanides except Ce.
  • This precursor is partially coated with a ceramic-forming layer, leaving 20% to 80% of the total surface of the precursor free of the ceramic-forming layer.
  • the partially coated precursor is then heat treated. This heat treatment is also described as final annealing, since the mechanical deformation steps, for example hot rolling and/or cold rolling, with which the preliminary product is produced, have been completed, so that the preliminary product is no longer mechanically deformed after the heat treatment.
  • the precursor is planar and has a first surface and a second opposing surface, wherein at least between 20% and 80%, preferably between 30% and 70%, more preferably between 50% and 70% of the first surface and between 20% and 80%, preferably between 30% to 70%, more preferably between 50% and 70% of the second surface remains free of the ceramic-forming layer.
  • the preliminary product can be a strip, a sheet or a sheet with its final contour.
  • the heat treating includes: Heating of the pre-product and after
  • Heat treating the precursor in a first stage with a total time t 1 wherein in the first stage the precursor is heat treated at a temperature in a temperature range between T ⁇ + ⁇ / ⁇ and T 1 , and then cooling the precursor to room temperature, where T 1 is above T ⁇ + ⁇ / ⁇ and t 1 is the total time at temperatures above T ⁇ + ⁇ / ⁇ .
  • the heat treatment is carried out at least temporarily in a hydrogen-containing atmosphere, during which time the exposed parts of the surface of the precursor are in direct contact with the hydrogen-containing atmosphere.
  • the temperature T 1 denotes a temperature at which the soft magnetic alloy is in the FCC phase region
  • T 2 denotes a temperature at which the soft magnetic alloy is in the BCC phase region.
  • the actual temperature of the oven can deviate from the value T 1 or T 2 , so that T 1 includes temperatures T 1 with a maximum deviation of +/-20°C that are above T ⁇ + ⁇ / ⁇ and T 2 temperatures T 2 with a maximum deviation of +/-20°C, which are below T ⁇ / ⁇ + ⁇ .
  • preliminary products are conventionally heat-treated at the same time.
  • These preliminary products are conventionally coated with a ceramic layer so that the preliminary products do not weld to one another during the heat treatment.
  • pre-products in the form of a strip or sheet are stacked on top of one another and thus heat-treated.
  • a ceramic layer is typically placed between the strips or sheets to prevent the strips or sheets from welding together.
  • the magnetic properties of these alloys depend on the proportion of the exposed surface of the pre-product during a heat treatment at temperatures above the transition temperature T ⁇ + ⁇ / ⁇ and thus in the FCC or ⁇ phase range. If a proportion of the preliminary product is in direct contact with the hydrogen-containing atmosphere at least temporarily during the heat treatment, the good magnetic properties can be achieved more reliably, even with larger batches. However, if the surface is completely covered with the ceramic layer, which is actually advantageous in order to avoid the risk of the preliminary products being welded together, it was found that the measured magnetic properties are not so good. It has been found that the good magnetic properties are related to the formation of texture in the soft magnetic alloy and that this formation of texture depends on the proportion of the exposed surface that is in direct contact with a hydrogen-containing atmosphere during the final anneal.
  • the preliminary product is only partially coated with the ceramic-forming layer, which is transformed into a ceramic layer during the subsequent heat treatment.
  • the applied coating can have, for example, a sol with ceramic nanoparticles distributed in an organic matrix, or metal ions from a metal oxide or metal hydroxide, so that a ceramic layer is not yet present in the applied form.
  • a ceramic layer is formed, which can also contain a metal oxide and/or a metal hydroxide and only partially covers the surface.
  • the pre-product has the form of a metal sheet with a first surface and a second opposite surface, with at least between 20% and 80%, preferably between 30% and 70%, particularly preferably between 50% and 70% of the first surface and between 20% and 80%, preferably between 30% and 70%, more preferably between 50% and 70% of the second surface is free of the ceramic-forming layer.
  • the remainder is iron, with Cr+Si+Al+Mn ⁇ 3.0% by weight and up to 0.2% by weight of other impurities caused by the smelting.
  • Other impurities are for example B, P, N, W, Hf, Y, Re, Sc, Be, other lanthanides except Ce.
  • the ceramic-forming layer is applied to the preliminary product in the form of a structure.
  • the structure can be formed by a pattern of stripes or dots or a mesh.
  • the ceramic-forming layer can be applied selectively to the surface of the precursor, for example by means of printing or profile printing or profile rolling.
  • a mask with openings can first be applied to the surfaces, the ceramic-forming layer applied over a large area, and the mask removed so that only the parts of the surface exposed in the openings in the mask are coated.
  • the maximum width of the coated areas is less than 2 mm, preferably less than 1.2 mm, particularly preferably less than 0.8 mm. It has been found that the magnetic properties can be achieved more reliably when the area of the coated parts is limited.
  • the preliminary product is in the form of a ribbon.
  • the structured coating can be applied to one side or both sides of the belt.
  • the ceramic layer formed has a metal oxyhydrate and/or metal oxide and/or metal hydroxide after the heat treatment.
  • the preliminary product is covered with a ceramic powder, a ceramic plate, or a metal plate during the heat treatment.
  • the ceramic powder can contain Al 2 O 3 or MgO or ZrO 2 or a mixture of ZrO 2 , SiO 2 and Al 2 O 3 .
  • the ceramic plate can have Al 2 O 3 or MgO or ZrO 2 or a mixture of ZrO 2 , SiO 2 and Al 2 O 3 .
  • a ceramic plate or a metal plate can be used to ensure the planarity of precursors in the form of sheet or strip or of stacks of strip or sheet.
  • covering with ceramic powder alone i.e. without a partial coating of the precursor, also allows the surface to be in direct contact with the hydrogen-containing atmosphere and thus texture and good magnetic properties can be achieved.
  • covering with ceramic powder alone is not as practical in large scale commercial manufacture.
  • the heat treatment takes place in an inert gas atmosphere with less than 5% by volume of hydrogen, preferably less than 1% by volume of hydrogen, and the cooling of T 1 at least in the temperature range from T ⁇ + ⁇ / ⁇ to T ⁇ / ⁇ + ⁇ in a hydrogen-containing atmosphere with more than 5% by volume of hydrogen.
  • This exemplary embodiment can also be used with a completely uncoated preliminary product.
  • the preliminary product after the preliminary product has been cooled to a temperature T 2 , where T 2 is below T ⁇ / ⁇ + ⁇ , the preliminary product is held at temperature T 2 for a period of time t 2 and only then further cooled.
  • the heat treatment of the preliminary product in the first stage is carried out for the total time t 1 in a protective gas atmosphere with less than 5% by volume of hydrogen, preferably less than 1% by volume of hydrogen.
  • the preliminary product is cooled from T 1 to T 2 in a hydrogen-containing atmosphere with more than 5% by volume of hydrogen.
  • the preliminary product is cooled from T 1 to room temperature in a hydrogen-containing atmosphere with more than 5% by volume of hydrogen.
  • Argon or nitrogen alone, or a mixture of argon or nitrogen with less than 5% by volume of hydrogen can be used as the protective gas.
  • the hydrogen-containing atmosphere with more than 5% by volume of hydrogen has an initial dew point of less than ⁇ 40° C.
  • the hydrogen-containing atmosphere with more than 5% by volume of hydrogen also has argon.
  • the following values apply: T ⁇ + ⁇ / ⁇ ⁇ T 1 ⁇ T ⁇ + ⁇ / ⁇ +50° C. and 15 minutes ⁇ t 1 ⁇ 10 hours, preferably 15 minutes ⁇ t 1 ⁇ 4 hours and 700°C ⁇ T 2 ⁇ 1050°C and 30 minutes ⁇ t 2 ⁇ 20 hours.
  • the heat treatment also includes a subsequent second final anneal in a hydrogen-containing inert gas atmosphere at a maximum temperature that is below the first transition temperature T ⁇ / ⁇ + ⁇ .
  • An ideal soft magnetic material has no preferred magnetic direction. As soon as a preferred direction exists, the magnetization processes are more difficult, since additional energy is required to generate the magnetic moments turn out of the preferred direction. In the case of crystalline, soft-magnetic materials, this direction-dependent energy is referred to as magnetocrystalline anisotropy energy. Due to the existing symmetry relationships, the magnetocrystalline anisotropy energy in a cubic crystal is expressed by a series expansion whose first-order coefficient is called the anisotropy constant K 1 .
  • FeCo alloys have a preferred magnetic direction that influences the magnetic properties.
  • the cube edges ⁇ 100> are the magnetically easy axes, while the space diagonals ⁇ 111> represent the magnetically hard axes.
  • the surface diagonals ⁇ 110> have average soft magnetic properties.
  • Soft magnetic materials in the form of thin sheets are used in transformers, stators and rotors to reduce the formation of eddy currents during magnetization reversal. For such applications, it is therefore advantageous if the magnetically favorable cube edges ⁇ 100> lie as far as possible in the sheet plane, while the magnetically unfavorable orientations ⁇ 111> lie as far as possible not in the sheet plane.
  • the cube-face texture the cube faces ⁇ 001 ⁇ also lie in the plane of the sheet, but the orientation of the cube edges is not fixed, but varies uniformly between the rolling direction and the direction transverse to the rolling direction.
  • the cube surface texture is thus described by ⁇ 100 ⁇ uvw>. This results in significantly more homogeneous magnetic properties.
  • this texture represents the best variant for use in stators or rotors, at least for the alloys considered here, in which K 1 is always significantly greater than zero.
  • the proportion of this texture should be reduced in order to reliably achieve good magnetic properties.
  • a high proportion of the ⁇ 100 ⁇ uvw> texture alone does not lead to the best magnetic properties if the proportion of the ⁇ 111 ⁇ uvw> texture is also too high.
  • the proportion of ⁇ 111 ⁇ uvw> texture is reduced by the method of the invention, ie using a final anneal performed temporarily in the FCC phase region, partially covering the surface and temporarily annealing under hydrogen leads to a suppression of the formation of the ⁇ 111 ⁇ uvw> texture.
  • the alloy after the heat treatment has an area proportion of a ⁇ 111 ⁇ uvw> texture which is at most 13%, preferably at most 6%, with grains having a tilt of up to +/-10° or even better up to +/- 15° from the nominal crystal orientation of the ⁇ 111 ⁇ planes.
  • the alloy after the heat treatment, has an area fraction of a ⁇ 100 ⁇ uvw> cube-face texture that is at least 30%, preferably at least 50%, with grains having a tilt of up to +/- 15° or better up to +/- 10° from the nominal crystal orientation of the ⁇ 100 ⁇ planes.
  • the heating rate over at least the temperature range from T ⁇ + ⁇ / ⁇ to T ⁇ / ⁇ + ⁇ , preferably 900° C. to T 1 is 10 K/h to 1000 K/h, preferably 20 K/h to 100 K /H.
  • the cooling rate over at least the temperature range from T ⁇ / ⁇ + ⁇ to T ⁇ + ⁇ / ⁇ , preferably T 1 to 900° C., is 10 K/h to 200 K/h and preferably 20 K/h to 100 K/h.
  • the pre-product is weighted down with an additional weight and the pre-product with the weight is subjected to the heat treatment.
  • the weight of the weight is at least 10%, preferably at least 30%, of the weight of the preliminary product.
  • the preliminary product for forming the electrically insulating layer is subjected to a further heat treatment in an atmosphere containing oxygen or water vapor.
  • the primary product has the shape of a plurality of stacked metal sheets, metal sheets in the final shape, or one or more stacks of metal sheets.
  • at least one laminated core is produced from the stacked metal sheets by eroding, laser cutting or water jet cutting after the heat treatment.
  • the sheets are glued together after the heat treatment using an insulating adhesive to form a laminated core, or oxidized on the surface to set an insulating layer and then glued to the laminated core or laser-welded or coated with an inorganic-organic hybrid coating and then to form a laminated core, for example by stacking and gluing or laser welding.
  • the soft-magnetic alloy after the heat treatment, has a maximum permeability ⁇ max ⁇ 6,000 and/or an electrical resistance p ⁇ 0.25 ⁇ m, hysteresis losses P Hys ⁇ 0.07 J/kg with an amplitude of 1.5 T and/or or a coercivity H c of ⁇ 0.8 A/cm and/or induction B 20 ⁇ 1.70 T at 20 A/cm.
  • the soft-magnetic alloy after the heat treatment, has a maximum permeability ⁇ max ⁇ 10,000 and/or an electrical Resistance p ⁇ 0.25 ⁇ m and/or hysteresis losses P Hys ⁇ 0.06 J/kg at an amplitude of 1.5 T and/or a coercivity H c of ⁇ 0.5 A/cm and induction B 20 ⁇ 1, 74 T at 20 A/cm.
  • the average grain size of the soft-magnetic alloy is at least 100 ⁇ m, preferably at least 200 ⁇ m, very particularly preferably at least 250 ⁇ m.
  • the mean grain size of the soft magnetic alloy is 1.0 to 2.0 times, preferably 1.0 to 1.5 times, the strip thickness.
  • the soft-magnetic alloy also has a surface proportion of a ⁇ 111 ⁇ uvw> texture that is at most 13%, preferably at most 6%, grains with a tilt of up to +/- 10° or preferably up to +/- - be included 15° to the nominal crystal orientation.
  • the soft magnetic alloy has an area fraction of a ⁇ 100 ⁇ uvw> cube-face texture that is at least 30%, preferably at least 50%, grains with a tilt of up to +/- 15° or preferably up to + /- 10° from the nominal crystal orientation.
  • the magnetic properties are obtained with the combination of an area percentage of a ⁇ 111 ⁇ uvw> texture of at most 13%, preferably at most 6% and an area percentage of a ⁇ 100 ⁇ uvw> cube-face texture of at least 30% at least 50% is further improved.
  • the mean grain size of the ⁇ 100 ⁇ uvw>-oriented grains is at least 1.5 times, preferably at least 2.0 times, the mean grain size of the ⁇ 111 ⁇ uvw>-oriented grains.
  • the area fraction of the ⁇ 100 ⁇ uvw>-oriented grains is at least 3 times, preferably at least 7 times, the area fraction of the ⁇ 111 ⁇ uvw>-oriented grains.
  • the soft-magnetic alloy has a maximum permeability ⁇ max ⁇ 6,000 and/or an electrical resistance p ⁇ 0.25 ⁇ m, hysteresis losses P Hys ⁇ 0.07 J/kg at an amplitude of 1.5 T and/or a coercive field strength H c of ⁇ 0.8 A/cm and/or induction B 20 ⁇ 1.70 T at 20 A/cm, or a maximum permeability ⁇ max ⁇ 10,000 and/or an electrical resistance p ⁇ 0.25 ⁇ m and/or hysteresis losses P Hys ⁇ 0.06 J/kg at an amplitude of 1.5 T and/or a coercivity H c of ⁇ 0.5 A/cm and induction B 20 ⁇ 1.74 T at 20 A/cm.
  • the remainder is iron, where Cr+Si+Al+Mn ⁇ 3.0% by weight and up to 0.2% by weight of other impurities caused by melting can be present.
  • Other impurities are for example B, P, N, W, Hf, Y, Re, Sc, Be, other lanthanides except Ce.
  • a laminated core of a plurality of stacked electrically insulated soft magnetic alloy laminations according to one of the preceding exemplary embodiments is also provided.
  • the laminated core has a fill factor F ⁇ 90%, preferably >94%, with a greater power density being able to be ensured.
  • the laminated core has at least two laminations, each of which has a thickness of 0.05 mm to 0.50 mm, and the electrical insulation layer, e.g. a ceramic layer or an oxide layer, between adjacent laminations has a thickness of ⁇ 0.1 ⁇ m to 5.0 ⁇ m, preferably 0.5 ⁇ m to 3.0 ⁇ m.
  • the electrical insulation layer e.g. a ceramic layer or an oxide layer
  • the invention also relates to the use of the laminated core according to one of the preceding exemplary embodiments in an electrical machine, for example as a stator tooth, stator segment, or in a stator and/or rotor of an electric motor and/or a generator, and/or in a transformer and/or in an electromagnetic actuator.
  • figure 1 shows a schematic representation of a phase diagram of an FeCo alloy with the composition of the precursor, in which the BCC phase region, also known as the ferritic ⁇ region, the BCC/FCC mixed region, also known as the two-phase ⁇ + ⁇ region , and the FCC phase region, which is also referred to as the austenitic ⁇ region, as well as the transition temperatures T ⁇ / ⁇ + ⁇ and T ⁇ + ⁇ / ⁇ are shown.
  • the transition temperatures T ⁇ / ⁇ + ⁇ and T ⁇ + ⁇ / ⁇ as well as the difference T ⁇ + ⁇ / ⁇ - T ⁇ / ⁇ + ⁇ depend on the composition of the alloy.
  • the alloy has a phase transition from a BCC phase region in a BCC/FCC mixed region to an FCC phase region, with increasing temperature the phase transition between the BCC phase region and the BCC/FCC mixed region at a first transition temperature T ⁇ / ⁇ + ⁇ and with further increasing temperature the transition between the BCC/FCC mixed region and the FCC phase region takes place at a second transition temperature T ⁇ + ⁇ / ⁇ , where T ⁇ + ⁇ / ⁇ > T ⁇ / ⁇ + ⁇ , as in figure 1 is shown.
  • the composition is chosen such that the difference T ⁇ + ⁇ / ⁇ - T ⁇ / ⁇ + ⁇ is less than 45K, preferably less than 25K.
  • this final anneal includes a heat treatment at a temperature at which the alloy is found in the FCC phase region.
  • figure 2 shows a schematic representation of a course of a heat treatment according to the invention according to an exemplary embodiment for an alloy with the above-mentioned composition.
  • the alloy can be heat treated in the form of a strip or sheet.
  • the sequence is divided into the three processes “heating” (E), "holding” (H) and “cooling” (A). Within these processes, a distinction is also made as to the crystallographic phase in which the precursor is located.
  • a denotes the ferritic region (BCC)
  • ⁇ denotes the austenitic region (FCC)
  • ⁇ + ⁇ denotes the two-phase (BCC/FCC) mixed region.
  • the material In the first heating phase E(a), the material is completely in the ferritic phase. After going through the phase transition T( ⁇ + ⁇ ), the material in phase E( ⁇ + ⁇ ) goes through the two-phase mixed region ⁇ + ⁇ . This relatively narrow area is limited at the top by the phase transition T( ⁇ + ⁇ ), so that the warming phase E( ⁇ ) is reached.
  • the holding phase H( ⁇ ) is completely in the austenitic ⁇ -region. After the cooling A( ⁇ ) from the first annealing stage in the austenitic ⁇ region and the phase transition T( ⁇ + ⁇ ) has been reached, the cooling A( ⁇ + ⁇ ) temporarily takes place in the two-phase region ⁇ + ⁇ , which descends through the phase transition T( ⁇ + ⁇ ) is limited. During the remaining cooling time A(a), the material is in the ferritic ⁇ -region. According to the invention, the maximum temperature of the heat treatment is in the FCC area.
  • the temperature ramps shown when heating or cooling serve to achieve a defined heating or cooling of the entire annealed material in a technical process.
  • the temperatures at which the phase transitions T( ⁇ + ⁇ ) and T( ⁇ + ⁇ ) take place during heating and the phase transitions T( ⁇ + ⁇ ) and T( ⁇ + ⁇ ) during cooling are basically identical. In practice, however, there can be shifts in the range of a few degrees Celsius due to finite heating and cooling rates, ie those during heating certain temperatures may be slightly higher than the temperatures determined during cooling.
  • stamped rings measuring 28.5 mm x 20.0 mm were made from 0.35 mm thick strip of the above alloy VACOFLUX X1 with a nominal composition: 16.8% Co, 2.3% V, no Si additive, remainder Fe manufactured.
  • the samples were annealed in a tube furnace under a dry hydrogen purge. Some samples (designated H) were suspended heat treated so that all surfaces are in contact with the hydrogen. Some samples (designated P) are covered with powder and thus heat treated.
  • the figure 3 shows the magnetic induction B20, where B20 denotes the induction at 20 A/cm, and figure 4 the coercivity Hc measured for these samples.
  • B20 denotes the induction at 20 A/cm
  • Hc coercivity
  • the rings of the P series which are annealed close together in the powder, show a completely different behavior.
  • the induction values B20 are significantly higher, which are more than 100 mT above the best value after annealing in the ⁇ -region.
  • the coercivity H c continues to decrease as the temperature increases.
  • the Hc value even falls below the best value obtained after annealing in the ⁇ -region.
  • the measurement of the magnetic properties included the new curve B(H) or ⁇ (H), the coercive field strength H c , and the remanence B r .
  • the area proportions A(001) and A(111) of the grains with (001) or (111) orientation were determined from the ESBD measurements with a maximum tilting of max. +/- 10°.
  • the area portion A'(001) was determined for samples B, C and D, in which the tilting was max. +/- 15°.
  • the average grain size GS was also determined from the EBSD measurements. Table 3 shows the magnetic characteristics, the area percentages of the texture and the mean grain size GS. In the case of sample A, no texture components were initially determined and only the parameter A'(001) was re-determined.
  • the unannealed sample A shows very low inductions and a very high H c > 1500 A/m, as is to be expected from a heavily cold-worked material.
  • Sample B annealed in the ⁇ -area, shows significantly improved properties, but with B(20 A/cm) of 1.682 T, it is still below the target value of at least 1.70 T. It can be assumed that there is little or no texture here , since the area fractions A(001) and A(111) of the grains with different orientations are of similar size.
  • Sample C powder annealed in the ⁇ -region shows the best magnetic properties.
  • the induction B(20 A/cm) is extremely high at 1.783 T.
  • the area portion A(001) is larger and the area portion A(111) is smaller.
  • the very low coercive field strength of 31 A/m and the high permeability also indicate large grain diameters.
  • sample D annealed in the ⁇ -area without powder, shows a significantly lower induction B(20 A/cm) ⁇ 1.65 T, similar to sample B.
  • the H c is lower and ⁇ max higher, which is probably due to the increased grain growth due to the higher annealing temperature and the associated higher diffusion rate in the ⁇ -region.
  • the area proportion A(001) is smaller and the area proportion A(111) larger than in sample C. It was thus found that the differences in the magnetic properties between the two test series can be attributed to the different annealing textures.
  • pole figures 001 are shown as an example, since they show the essential symmetries.
  • the other pole figures 110 and 111 can be found in the appendix.
  • A1 designates the rolling direction (RD, " rolling direction") and
  • A2 designates the transverse direction (TD, "transverse direction”). (axis A1
  • the rolling texture changes to an annealing texture containing both (001) components (intensities in the center and at the very edge) and (111) components ( intensities along half the diameter).
  • the pole figure looks completely different after an anneal in the ⁇ -region (sample C): This clearly corresponds to a cube surface texture (001).
  • annealing in the ⁇ -region without powder shows not only parts with (001) and (111) orientations, but also diffusely a large number of other orientations, which are in the range of the typical annealing and rolling textures of bcc materials .
  • Sample A (reference, as-rolled) has all the ⁇ -fiber components, i.e. from ⁇ 001 ⁇ 110> through ⁇ 112 ⁇ 110> to ⁇ 111 ⁇ 110>. This is typical of a cold rolled texture of bcc metals. In addition, parts of the ⁇ -fiber can be seen, i.e. ⁇ 111 ⁇ 121> and ⁇ 111 ⁇ 112>.
  • this ⁇ -fiber is shifted by 20° at the angle ⁇ 1, which corresponds to a rotation of the cube layer in the plane of the sheet.
  • the parts of the ⁇ -fiber that can be seen in the unannealed state are now intensified.
  • the magnetically hard axis, the space diagonal ⁇ 111> lies in the sheet plane.
  • Sample C according to the invention shows all portions of the ⁇ -fiber, ie from ⁇ 001 ⁇ 110> to ⁇ 001 ⁇ 010> to ⁇ 001 ⁇ 110>.
  • This corresponds to a magnetically favorable cube face texture in which the magnetically easy axis, the cube edge ⁇ 001> lies in the plane of the sheet and the orientation of these cube edges varies between the rolling direction and the direction transverse to the rolling direction.
  • magnetically unfavorable ⁇ -fiber there are hardly any shares of magnetically unfavorable ⁇ -fiber. These magnetically unfavorable parts could be significantly reduced by annealing.
  • the reference sample D which was also annealed in the ⁇ -region, but with a different annealing structure, also has cube layers. In contrast to sample C, however, these are much less pronounced and are also more strongly oriented. In addition, compared to sample C, there are significantly higher proportions of the magnetically unfavorable ⁇ -fiber, i.e. proportions of ⁇ 111 ⁇ 121> and ⁇ 111 ⁇ 112>.
  • the texture investigations show that the reason for the high induction values B20 of state C according to the invention lies on the one hand in the formation of a cube surface texture, i.e. the formation of orientations of the ⁇ -fibre, on the other hand in the avoidance of portions of the ⁇ -fibre.
  • Table 4 shows a list of the annealings carried out with general conditions and information on the sample. All samples were made from the same lot 74101563B, tape thickness 0.20 mm.
  • the assignment of the phase is based on the phase transitions ⁇ + ⁇ at 944°C and ⁇ + ⁇ at 965°C determined for this batch, which were determined from a DSC measurement based on the 1st onset during cooling or heating .
  • the annealing time ie the holding time t at the annealing temperature, was varied between 0.5 h and 20 h, with most annealing being carried out with a holding time of 4 h.
  • the atmosphere used was mainly dry hydrogen H 2 with an initial dew point of -40°C or lower.
  • annealing was carried out in vacuo under a pressure of 10 -1 mbar.
  • the annealing structure was also varied: the annealing "in the powder” took place in ceramic powder made of Al 2 O 3 .
  • the annealing samples were threaded onto a ceramic tube at a small distance from each other.
  • the samples (rings or sheets) were placed one on top of the other. This stack of metal sheets was placed on a base plate and weighed down with a top plate.
  • rings coated on both sides with HITCOAT were used as intermediate layers. Before the magnetic measurement, the intermediate layers, which only served as an annealing aid, were sorted out so that the magnetic values relate to the uncoated rings.
  • Sheets measuring 20 mm ⁇ 30 mm were annealed in the same way to determine the texture.
  • the panels were measured by EBSD after annealing as described above.
  • the parameters determined are the area proportions A(001) and A(111) of the orientations (001) and (111).
  • figure 9 shows the relationship between the magnetic induction B(20 A/cm) and the surface area A(001) of the magnetically advantageous (001) orientation.
  • the drawn line illustrates the course of series C according to the invention.
  • an area proportion of max. 27.9% forms.
  • area proportions A(001) of up to 65.6% are achieved.
  • the surface proportions were determined with a maximum tilt of +/- 10°. If a greater tilting of +/- 15° were tolerated, an area proportion A(001) of up to 82% would result.
  • figure 10 shows the relationship between the magnetic induction B(20 A/cm) and the surface area A(111) of the magnetically unfavorable (111) orientation.
  • the reference samples of series A and B show area proportions A(111) of at least 13%, which is accompanied by a low induction B20 of less than 1.70 T.
  • temper A1 which was annealed at a very low temperature of 750°C, shows an induction B20 of 1.715 T.
  • Hc very high coercivity
  • the C series states according to the invention consistently show inductions greater than 1.70 T.
  • the reason for this lies in the small proportion of the magnetically unfavorable (111) orientation.
  • the samples with the lowest area proportions A(111) show the highest induction values B20.
  • the drawn line illustrates the progression of series C according to the invention.
  • figure 11 shows the relationship between the magnetic induction B20 and the average grain size GS of all grains, regardless of their orientation.
  • the samples from series A which were annealed in the ferritic ⁇ -region, only achieve grain sizes of up to 200 ⁇ m.
  • the samples of series B annealed in the austenitic ⁇ -region already show significantly larger grains in the range of 400 to 500 ⁇ m. Nevertheless, the desired high induction B20 does not occur here. So the large grain itself is not the cause of the high B20 induction.
  • Sample C1 Only the samples of series C annealed under favorable conditions in the ⁇ -region show induction values B20 > 1.70 T.
  • Sample C1 has a grain size of 502 ⁇ m, i.e. about 0.5 mm, which is similar to the values of Row B lies, and in contrast to this shows a very high induction B20 of 1.794 T.
  • sample C8 has an average grain size of 2030 ⁇ m, ie about 2 mm.
  • the induction B20 is thus reduced to 1.711 T.
  • Sample C7 which was heat-treated only at 1000° C. but with an extended annealing time of 20 h, also has coarse grains with an average grain size of 1619 ⁇ m, ie about 1.6 mm, and shows only a low B20 induction of 1.71 T
  • the states C9 and C10 according to the invention are listed separately in the figures, since the changed annealing structure leads to a deviation here.
  • the samples were annealed "in the stack", i.e. the lamellas were placed on top of each other and weighed down with a cover plate.
  • the inductions B20 achieved are still very good, i.e. greater than 1.70 T.
  • the states C1 to C8 which were annealed in ceramic annealing powder, the inductions are lower with the same grain size. With such a structure, the annealing parameters have to be changed in order to achieve optimal conditions.
  • the results of the grain size can also be processed separately according to the orientation of the grains, cf. figure 12 for the magnetically advantageous (001) orientation or figure 13 for the magnetically unfavorable (111) orientation.
  • the interpretation is analogous to the interpretation of the total grain size.
  • the drawn line illustrates the course of the states C1 to C8 of the series according to the invention.
  • the line drawn illustrates the course of the states C1..C8 of the series C according to the invention.
  • annealing in order to set the highest possible induction, it is desirable to carry out annealing in the ⁇ -region while keeping the grain size to a minimum. Possibilities for this are, for example, lowering the annealing temperature as close as possible above the phase transition ⁇ + ⁇ or reducing the annealing time.
  • the annealing period it should be noted that the heating and cooling ramps have an indirect influence on the annealing period, i.e. a slow heating or cooling ramp also leads to a longer dwell time in the ⁇ -region.
  • the annealing structure also has a decisive influence.
  • Avoiding excessive grain growth is also useful in order to ensure the most uniform possible magnetization in all directions when a cube-face texture is present.
  • figure 14 shows the relationship between the area proportions A(001) and A(111 ).
  • the tempers C according to the invention which were annealed in the ⁇ -region under advantageous boundary conditions, show an area proportion (111) that is consistently below 13%.
  • the points marked with C* correspond to examples C7, C8 and C10. These are borderline in terms of the parameters, ie C7 was annealed with an extremely long holding time of 20 hours and C8 at a very high annealing temperature of 1100°C. In both cases, this results in strong growth of the unfavorable (111) orientation.
  • Sample C10 was provided with an annealing-resistant, continuous ceramic coating on one side, so that the advantageous (001) texture could only develop on the uncoated side during cooling and passing through the phase transition ⁇ + ⁇ . Accordingly, the (111) content in all three samples is still 9.6 to 12%. Furthermore, the (001) share is not yet pronounced and is relatively low at 10.0 to 25.2%. Examples C* show a B20 value between 1.70 T and 1.72 T, which is not optimal, but is still significantly better than states A and B, which are not according to the invention.
  • the points marked with C correspond to the remaining examples of group C. They are highly optimized with regard to the annealing, ie the annealing temperature was above the phase transition ⁇ + ⁇ , but not more than 100°C above this temperature, and the holding time was a maximum of 4 hours. Also was in In all examples, the surface did not have a continuous coating, so that the (001) texture was able to form on both sides when cooling and passing through the phase transition ⁇ + ⁇ . Accordingly, the samples C show the lowest surface proportions (111) of less than 6%. At the same time you can see a clear proportion of the dice layer (001), from at least 25% up to 66%. This favorable preferred orientation is also the reason that inductions B20 of over 1.72 T and up to 1.80 T were consistently achieved here.
  • Table 6 shows the magnetic values B20, B100, ⁇ max , Hc and Br of the alloy according to the invention after a heat treatment in a tube furnace in ceramic annealing powder (examples R1, E1, E2, E3, E3, E4) and hanging (examples E5, E6, E7) shown.
  • the samples are threaded onto a ceramic or thin metal rod and are flushed very well from all sides.
  • the annealing atmosphere was varied in the individual phases, ie in addition to the dry hydrogen (H 2 ) with a dew point of ⁇ 40° C. or lower, argon (Ar) of quality 5.0 was sometimes used.
  • the same gas atmosphere was used within the individual stages, ie "E” designates the atmosphere in the heating phases E(a), E( ⁇ + ⁇ ) and E( ⁇ ), "H” the holding phase H( ⁇ ) and "A” the cooling phases A( ⁇ ), A( ⁇ + ⁇ ) and A(a).
  • Sample A1 corresponds to an annealing not according to the invention that took place only under argon.
  • Sample 1 has a very low inductance B20 of 1.672 T, a very low remanence Br of 1.28 T and a high coercivity Hc of 46.6 A/m.
  • sample A2 In the case of sample A2 according to the invention, the annealing was carried out entirely with a dry hydrogen purge.
  • the induction B20 of sample A2 is very high at 1.791 T, as is the remanence Br at 1.40 T.
  • the coercivity Hc is very low at just 31.8 A/m.
  • the inert gas argon was used in the heating phase and dry hydrogen was used for the holding and cooling phase.
  • the characteristic values B20, B100, ⁇ max and in particular Br are higher than the corresponding values for sample A2, which was only annealed under hydrogen.
  • An improvement in the squareness of the hysteresis loop could be achieved by using Ar alone in the heating phase. It is assumed that the phase transformations during heating, ie ⁇ + ⁇ , also depend on the surface energy and thus on the gas atmosphere. In contrast to cooling it seems though to be advantageous when heating that the surface area is not completely reduced.
  • Examples A3 and A4 show that the partial use of Ar results in a slight increase in coercivity compared to annealing under hydrogen only (Sample A2). This is presumably due to less pronounced grain growth. If lower coercive field strengths are required in the application, subsequent grain growth can be initiated by an additional holding stage during cooling in the a-region or a subsequent heat treatment in the ⁇ -region.
  • Sample A5 For the sample A5, the reduction of the surface area by H 2 was performed in the heating and holding stage. Cooling took place under argon. Sample A5 has an induction B20 of 1.74 T and a high remanence Br of 1.37 T.
  • the other exemplary embodiments A6 to A8 were subjected to overhead annealing.
  • the anneal was performed entirely under pure hydrogen. Due to the hanging structure, the sample was washed very well, which led to a strong reduction in contamination during the entire annealing period.
  • the induction B20 is low at 1.691 T.
  • the high remanence Br of 1.32 T and the high maximum permeability of 12,570 show that the magnetically unfavorable (111) orientation could be partially suppressed.
  • Sample A7 used the Ar shielding gas during the heating and dry hydrogen for the rest of the anneal, ie the soak and cool down.
  • the resulting magnetic values are even worse than those of sample E5 annealed purely under hydrogen.
  • the remanence Br and the maximum permeability ⁇ max are still slightly higher.
  • the exemplary embodiments show that the use of H 2 during cooling during annealing leads to the advantageous crystal orientations. H 2 should therefore preferably be available during the cooling phase.
  • an inert protective gas during the heating or holding phase can be advantageous in order to avoid the formation of an unfavorable intermediate structure. Structures with very good flushing require longer flushing with argon than structures in the powder or in the stack that are flushed less well.
  • the results can be transferred to mixed gases, ie instead of using pure argon, a mixture of argon and hydrogen can also be used.
  • a mixture of argon and hydrogen can also be used.
  • an H 2 /Ar gas mixture with 20% by volume argon and 80% by volume hydrogen or an Ar/H 2 gas mixture with 80% by volume hydrogen and 20% by volume argon can be used.
  • the exact mixing ratio can be adjusted depending on the annealing structure, annealing duration and rinsing conditions.
  • N 2 nitrogen
  • Ar inert and annealing under nitrogen can lead to the formation of vanadium nitrides due to the vanadium content of the claimed alloys.
  • Vanadium nitrides preferentially precipitate at grain boundaries and thereby prevent grain growth. Therefore, the formation of nitrides in soft magnetic alloys is undesirable in principle, since a fine-grain structure leads to a high coercive field strength Hc. In addition, the presence of precipitates generally leads to an increase in Hc, since the non-magnetic precipitates act as perturbations for domain wall motion.
  • the suppression of grain growth during the heating and holding phase is to be assessed as a positive effect, i.e. there is therefore the possibility that an intermediate structure that is advantageous for the further cooling process is formed.
  • a trade-off can be to limit the amount of precipitation, e.g. by limiting the time annealing under nitrogen, or by mixing nitrogen with hydrogen only in small amounts.
  • Sample B1 is a non-inventive anneal that took place continuously under N 2 purge.
  • the induction B20 is extremely low at 1.617 T, as is the maximum permeability ⁇ max at only 1.623.
  • the coercivity is very high at 274 A/m.
  • sample B2 according to the invention represents the reference annealing under pure hydrogen and corresponds to sample A2 from the examples with argon.
  • sample B3 nitrogen was used during the heating phase, but dry hydrogen was used for the remainder of the anneal.
  • the nitrogen has a positive effect on the magnetic parameters B20 and Br, which, at 1.808 T and 1.50 T respectively, are higher than in the pure hydrogen annealing of sample B2.
  • the short exposure time of the nitrogen minimized the negative effect on the coercivity Hc, i.e. the Hc at 44.1 A/m is still in an acceptable range for most applications.
  • both the heating phase and the holding phase were carried out under nitrogen.
  • the long exposure time to the nitrogen results in very poor magnetic characteristics, in particular a very low maximum permeability of 2427 and a very high coercivity Hc of 202 A/m.
  • sample B5 likewise not according to the invention, the surface area was first reduced by H 2 in the heating and holding stage, but the subsequent cooling took place under nitrogen.
  • the resulting magnetic values are just as bad as in state B4.
  • This exemplary embodiment shows that during the cooling process, the surface of the material must not only be free of oxides, but also of nitrides or other deposits.
  • the other exemplary embodiments B6 to B8 were subjected to hanging annealing.
  • Sample B6 was annealed hanging freely under pure hydrogen and corresponds to sample A6 from the exemplary embodiments with argon. Due to the good flushing, there is a low B20 induction of only 1.691 T despite the high maximum permeability.
  • sample B7 the sample was also subjected to a hanging anneal, but nitrogen was used during the heating phase. Surprisingly, there is a very significant increase in the B20 induction, which is at 1.818 T, and a very high Br remanence of 1.52 T. It is assumed that the nitrides formed in the heating phase inhibit grain growth, so that despite very good Flushing with hydrogen during the holding phase creates a favorable intermediate structure that allows the preferred formation of the (001) orientation or the suppression of the (111) orientation during the cooling phase.
  • Sample B8 was annealed analogously to sample B7, with not only the heating phase but also the holding phase being carried out under nitrogen. Similar to example B4, the negative influence of the nitrogen predominates and the desired magnetic properties can no longer be adjusted. In particular, the coercive field strength of 202 A/m is clearly too high.
  • the exemplary embodiments show that small amounts of nitrogen can be advantageous for increasing the induction B20 and the remanence Br. If nitrogen is provided in too large a quantity or for too long a period of time during the annealing, the deterioration in Hc is too great.
  • a holding stage can still take place in the ferritic ⁇ -region.
  • the purpose of this is to further promote grain growth, which leads to a further reduction in the coercive field strength Hc and a further increase in the maximum permeability.
  • this optional holding stage can also be carried out in a second heat treatment, which should, however, take place entirely in the ⁇ -region.
  • This subsequent heat treatment makes it possible to improve only part of the originally annealed material, e.g. the part that does not yet meet all magnetic requirements after the first annealing in the ⁇ -region.
  • Table 8 shows some examples that show the influence of a second heat treatment in the ⁇ -region.
  • the rows C1 to C5 each correspond to the states after the heat treatment in the ⁇ -region with a four-hour holding stage at 1000°C.
  • rows C1' to C5' the same samples were subjected to a second alpha-region heat treatment with a four-hour soak at 930°C.
  • Sample C1 corresponds to sample A6 already presented. Due to the hanging annealing under pure hydrogen, there is a high permeability ⁇ max and a low Hc, but the induction B20 is relatively low. Even post-annealing in the ⁇ -region, as in the case of sample C1', does not lead to any significant improvement in the B20.
  • Sample C2 corresponds to sample A3, already explained, annealed under Ar in the heating phase.
  • the partial use of Ar results in very good magnetic values.
  • Examples C3 and C3' show the effect of a second heat treatment on a sample annealed in the first heat treatment in the heating phase under nitrogen. All of the specified magnetic characteristics improve slightly, although even after this heat treatment, the maximum permeability is still relatively low at 7747 and the coercivity is still relatively high at 77.1 A/m.
  • the non-inventive reference example C4 was only annealed under nitrogen in the first heat treatment. By not using hydrogen, the magnetic characteristics could not be achieved, and the long presence of nitrogen during the annealing results in a very high Hc of 274 A/m. This is probably due to the formation of nitrides on the surface and in the material. These can no longer be dissolved by the second heat treatment at 930° C. carried out in example C4', so that the magnetic values can no longer be improved.
  • the reference example C5 corresponds to the example A1, ie an annealing not according to the invention only under Ar.
  • the afterglow also does not result in any significant improvement in the magnetics in example C5'.
  • the examples illustrate that the second heat treatment is particularly effective for the samples where the first heat treatment in the ⁇ region was partially under Ar.
  • the pre-products are conventionally coated with a ceramic layer so that the pre-products do not stick to one another and there is electrical insulation between the layers to minimize eddy current losses.
  • the preliminary products are stacked so that a ceramic layer is arranged between the strips or sheets.
  • the magnetic properties depend on the proportion of the exposed surface of the precursor. However, if a portion of the precursor is in direct contact with the hydrogen-containing atmosphere at least temporarily during the heat treatment, the good magnetic properties can be achieved more reliably. It was found that these good magnetic properties are related to the formation of a texture in the soft magnetic alloy.
  • the preliminary product is only partially coated with the ceramic-forming layer, which is transformed into a ceramic layer during the subsequent heat treatment.
  • the ceramic-forming layer which is transformed into a ceramic layer during the subsequent heat treatment.
  • one or both of the opposing major surfaces is only partially coated, so that portions of one or both opposing major surfaces are free of the coating during heat treatment.
  • the precursor is partially coated with a ceramic-forming layer, leaving 20% to 80% of the total surface of the precursor free of the ceramic-forming layer.
  • the partially coated precursor is then heat treated.
  • the applied coating can, for example, have a sol with metal ions, so that a ceramic in the applied form does not yet exist. It is also possible for the applied layer to have ceramic nanoparticles in the form of a sol.
  • the preliminary product has the form of a metal sheet with a first surface and a second opposite surface, with at least between 20 and 80%, preferably between 30% and 70%, particularly preferably between 50% and 70% of the first surface and between 20% and 80%, preferably between 30% to 70%, particularly preferably between 50% to 70% of the second surface is free of the ceramic layer containing metal oxide or metal hydroxide.
  • Ceramic coil coatings are used for coils made of Fe-Co to prevent metal surfaces that come into contact with each other during the necessary magnetic final annealing of sheets or sheet metal sections.
  • Examples include the DL1 coating based on Mg methoxide, which converts to magnesium oxide on annealing, and the HITCOAT coating, based on Zr propylate, which converts to zirconium oxide on annealing. After annealing, both coatings are present as a two-sided, thin film with a thickness of typically 0.5 ⁇ m or thinner on each side. Since the coatings are applied in a thin liquid with a solvent, they spread evenly over the belt surface and form a continuous coating.
  • Table 9 shows the magnetic properties after a final anneal for 4 hours at 1000°C as a function of the coating.
  • the table shows the magnetic characteristics ⁇ max , B3, B20, B100, Hc and Br for different coating variants. All tests were carried out on batch 7410163B with a strip thickness of 0.20 mm, which has already been described in several places. Rings measuring 28.5 mm ⁇ 20.0 mm were punched out of the strips and annealed in a chamber furnace at 1000° C. and a holding time of 4 h while flushing with dry hydrogen.
  • Example E represents the uncoated reference sample. After annealing, there are very good soft magnetic characteristics. In particular, the very high B20 induction of 1.77 T is an indicator of a very high proportion of cube-face texture (001)[uvw], which was successfully formed by annealing in the ⁇ -region. Due to the advantageous orientation, there is also a very high maximum permeability of almost 13,000 and a low coercivity Hc of only 37.3 A/m.
  • the strip was provided with a zirconium propylate coating on both sides before punching. During the annealing, this is transformed into planar zirconium oxide. This dense coverage suppressed the formation of the cube face texture. As a result, the induction B20 is only 1.687 T. Also at 46.4 A/m, the coercivity Hc is significantly higher than the value of reference sample E.
  • one of the coatings mentioned above can still be used, as long as they are sufficiently thin or as long as the coating is only on one side of the strip .
  • the strip was first coated regularly, i.e. on both sides, and then the coating was chemically removed on one side using a solvent.
  • the free side was then post-coated with a highly diluted coating solution, so that one side of the tape was regularly coated with a coating thickness between 100 nm and 500 nm, while the second side only had a very thin coating, which is in the range below 100 nm.
  • the soft magnetic properties of this sample are better than with the regular, thicker coating in example B.
  • the induction B(20) at 1.719 T is still well below the reference value of the uncoated sample.
  • the very thin coating leads to initial adhesions as a result of the annealing, i.e. the main function of the coating, the layer separation, is severely impaired.
  • a strip was first coated in a regular manner and the coating was chemically removed on one side using a solvent. After annealing, magnetic properties emerge that indicate that a significant portion of cube-face texture could be formed here. In addition to a high induction B20 of 1.737 T, maximum permeability of almost 12,500 is also achieved, which almost corresponds to reference state A.
  • Coating on one side thus enables sheet metal to be annealed in a stack.
  • the prerequisite for this is that the sheets are placed in the correct position, ie the coated side of the sheet always faces upwards, so that there is no contact between the uncoated and coated sides of the sheet.
  • Other methods can also be used to adjust a one-sided strip coating: In one example, when applying the coating by means of rollers, the coating is squeezed off on one side by a surface-ground roller under pressure. This process can be used on a system that is also used for coating on both sides.
  • the strip is regularly coated, i.e. the coating is even on both sides.
  • the coating is then removed on one side by mechanical brushing.
  • a coating with good adhesion was therefore developed, which consists of plastic-bonded, very fine particles and in which the particles only transform into a thermally stable ceramic oxide during the final annealing.
  • particles of aluminum hydroxide with a size of 10 to 300 nm, preferably 20 to 150 nm, are used in a binder based on aqueous acrylate dispersions, which also contains wetting agents and ammonia as additional components to adjust and control the pH and dispersed by filling with deionized water.
  • aqueous acrylate dispersions which also contains wetting agents and ammonia as additional components to adjust and control the pH and dispersed by filling with deionized water.
  • the resulting dispersion is applied to both sides of a VACOFLUX X1 tape with a thickness of 0.20 mm using profiled rollers in a continuous process.
  • a striped structure is initially created in the roll gap.
  • the viscosity of the coating dispersion is adjusted by the ceramic content and optionally by an additional rheologically active additive in such a way that these stripes do not run or run only very slightly when they exit the roll gap.
  • the coated strip is dried with warm air (280°C) so that the binder forms a film.
  • the tape then has a well-adhering coating with a striped structure.
  • FIG 15 exemplary illustrations for surface patterns are shown, with examples a, b representing the reference states and the other examples being surfaces according to the invention.
  • Example a shows a sheet without a coating. While the formation of a cube surface texture is possible here, uncoated sheets cannot be annealed without further ado, since they weld together at the high temperatures of typically over 900°C, and increased eddy current losses result from layer welding during the annealing of laminated cores from such sheets.
  • Example b shows a flat coating without interruptions. This corresponds to coatings such as HITCOAT or DL1. While a very good layer separation is also achieved with such a coating in the final annealing in the ⁇ -region, it is not possible to form a significant proportion of cube-face texture.
  • Example c shows a striped structure.
  • the dark stripes correspond to areas with a very dense coverage of Al-containing particles.
  • the light areas between the stripes contain no or only very few particles, so these layers typically appear transparent.
  • Example d also shows a striped structure.
  • the dark stripes enriched with Al particles are narrower than in example c. This allows a special formation of the cube surface structure, but increases the risk of sheet metal adhesions due to the annealing
  • Example e shows a lattice structure in which the lines run diagonally to the strip direction.
  • Example f shows a coating in which local accumulations of particles have formed, which are surrounded by free areas. The particles are bonded prior to annealing so that the coating adheres.
  • Example g shows schematically the appearance of an actually applied coating.
  • the dispersion used has a lower viscosity than in examples c and d, so that the coating had a longer opportunity to run laterally after application. The result is a streaky course with ramifications.
  • This representation also shows that the free areas, which appear completely white in the idealized representations, always contain a proportion of fine Al particles in practice. However, the concentration in these areas is very low compared to the thick strips.
  • Table 10 # picture Tmax in °C identifier B3 in T B20 in T B100 in T ⁇ max Hc to A/m Br in T 1 a 1000 1901543 1,537 1,770 2,020 12,814 37.3 1.43 2 b 1000 2001969 1,437 1,687 1,963 10,240 46.4 1.36 3 b 1000 2000230 1.406 1,663 1,940 11,417 48.1 1.38 4 b 1000 2000231 1,437 1,696 1,956 12.148 46.7 1.38 5 f 1000 2000200 1,507 1,734 1,998 14,523 39.9 1.42 6 G 1000 2000252 1,502 1,732 1,995 12,959 42.2 1.41 7 i.e 1000 2001968 1,493 1,727 1,995 12,694 40.8 1.40 8th i.e 1100 2002008 1,537 1,755 2.016 14046.6 35.8 1.39
  • VACOFLUX X1 batch 7610163B, strip thickness 0.20 mm was used as the starting material. Punched rings measuring 28.5 mm ⁇ 20.0 mm were produced for each coating state.
  • the measurement of the magnetic induction B3 B(3 A/cm), B20, B100, the maximum permeability ⁇ max , the coercivity Hc and the remanence Br was carried out in accordance with the measurement standard IEC 60404-4.
  • Sample #1 represents the uncoated reference sample. Due to the completely free surface, similar to figure a, the highest proportion of cube-face texture (001)[uvw] can form here as a result of the annealing.
  • the induction B20 is 1.770 T. However, due to the lack of coating, it is not possible to anneal these sheets in contact with one another.
  • Sample #2 represents the reference sample with an areal, continuous coating, i.e. as in figure b.
  • the strip was previously coated on both sides with HITCOAT, a coating based on zirconium propylate, which is present as ceramic zirconium oxide after the final annealing. Since the entire surface is covered here, there is no preferred formation of a cube surface texture, which is reflected in a very low induction B20 of 1.687 T.
  • Sample #3 and sample #4 were coated with the new coating TX1, but are not according to the invention due to the dense surface.
  • the formulation used in Sample #3 had a relatively high ceramic content of 11%.
  • the coating was applied in a laboratory test by manually pressing on a profiled roller. This composition and method of application resulted in thick stripes, similar to surface image c, but the high concentration combined with the low contact pressure led to a dense base coating between the stripes, so that this state overall corresponds to surface image b.
  • the extensive, continuous coating results in a very low induction, which is at a B20 of 1.663 T, as in sample #2 after the final annealing.
  • Samples #5, #6, #7 and #8 represent states according to the invention. In all of these states, the sheets could be separated after annealing without damage.
  • Sample #5 was coated with the same formulation as Sample #3, i.e., 11% ceramic. However, the strip ran through two profiled rollers with a contact pressure of 2 bar. This resulted in the striped surface image d. Due to the partially exposed surface, a significant proportion of cube surface texture was able to form during the final annealing, the induction B20 was 1.734 T.
  • Sample #6 similar to sample #4, was chosen to have a lower ceramic content of 7%. In order to still obtain a non-surface coating despite the lower ceramic content, an additional additive was added to the coating, which increases the basic viscosity. This change made it possible to set a non-surface coating as shown in figure g. Here, too, there was a high B20 induction of 1.732 T.
  • sample #7 the ceramic content was further reduced, i.e., to 4%, and an additive was added as in sample #6.
  • the surface image was image d, i.e. fine, well-separated lines.
  • the induction B20 of 1.727 T is due to the formation of the cube surface texture.
  • sample #8 illustrates that the very good layer insulation of the coating also makes it possible to further increase the annealing temperature.
  • Increasing the annealing temperature can be advantageous for stack annealing.
  • a strip with the same coating as sample #7 (4% ceramic content + additive) was annealed at an elevated holding temperature of 1100° C. in the ⁇ range, with the same holding time of 4 hours. The result is an increased induction B20 of 1.755 T compared to the other examples according to the invention.
  • the exemplary embodiments illustrate that the chemistry of the coating is not decisive for the formation of the cube surface texture, but rather that this is an aid in order to set the correct surface covering. It is therefore essential that after the annealing the coating is present as a non-continuous layer with free surface areas in between.
  • figure 16 shows an example of a streaky surface after coating with TX1, 11% ceramic content (inventive sample #5).
  • the analysis of the coating strips reveals proportions of the ceramic (AI and O) and the binder (C).
  • the EDX analysis also shows a coating-free surface between the strips, ie only elements of the base material VACOFLUX X1.
  • FIG 17 shows a photograph of a coating strip of TX1 (11% ceramic content) after the final anneal (Sample #5 according to the invention).
  • the coated regions are narrower than the resulting grains, leaving sufficient free surface area within each grain to allow the cube-face texture to develop.

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Publication number Priority date Publication date Assignee Title
DE102019110872A1 (de) * 2019-04-26 2020-11-12 Vacuumschmelze Gmbh & Co. Kg Blechpaket und Verfahren zum Herstellen einer hochpermeablen weichmagnetischen Legierung
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008039326A1 (de) * 2008-08-22 2010-02-25 IWT Stiftung Institut für Werkstofftechnik Verfahren zum elektrischen Isolieren von Elektroblech, elektrisch isoliertes Elektroblech, lamellierter magnetischer Kern mit dem Elektroblech und Verfahren zum Herstellen eines lamellierten magnetischen Kerns
WO2014194881A2 (fr) * 2013-06-07 2014-12-11 VDM Metals GmbH Procédé de production d'une feuille de métal
WO2019081672A1 (fr) * 2017-10-27 2019-05-02 Vacuumschmelze Gmbh & Co Kg Alliage magnétique doux à perméabilité élevée et procédé pour produire l'alliage magnétique doux à perméabilité élevée
EP3730286A1 (fr) * 2019-04-26 2020-10-28 Vacuumschmelze GmbH & Co. KG Paquet de tôles et procédé de fabrication d'un alliage magnétique souple à haute perméabilité
US20210225571A1 (en) * 2020-01-16 2021-07-22 Toyota Jidosha Kabushiki Kaisha Laminated core

Family Cites Families (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1862559A (en) 1931-08-14 1932-06-14 Bell Telephone Labor Inc Workable magnetic compositions containing principally iron and cobalt
US2717223A (en) 1952-02-13 1955-09-06 Westinghouse Electric Corp Process for producing ductile magnetic cobalt-iron alloy members
US2992952A (en) 1955-12-01 1961-07-18 Vacuumschmelze Ag Method of manufacturing magnetic sheets
DE1101471B (de) 1955-12-01 1961-03-09 Vacuumschmelze Ag Verfahren zur Erzeugung von Wuerfeltextur bei der Herstellung von Gegenstaenden aus Eisen-Silizium-Legierungen
DE1115279C2 (de) 1955-12-01 1974-02-07 Vacuumschmelze Ag Verfahren zur Erzeugung von Wuerfeltextur bei der Herstellung von Gegenstaenden aus Eisen-Silizium-Legierungen
DE1049409B (de) 1955-12-01 1959-01-29 Vacuumschmelze Aktiengesellschaft, Hanau/M Verfahren zur Erzeugung von Wuerfeltextur bei der Herstellung von Gegenstaenden aus Eisen-Silizium-Legierungen
DE1029845B (de) 1955-12-01 1958-05-14 Vacuumschmelze Ag Verfahren zur Erzeugung von Wuerfeltextur bei der Herstellung von Gegenstaenden aus Eisen-Silizium-Legierungen
DE1106354C2 (de) 1955-12-01 1973-01-04 Vacuumschmelze Ag Verfahren zur Erzeugung von Wuerfeltextur bei der Herstellung von Gegenstaenden aus Eisen-Silizium-Legierungen
DE1109197C2 (de) 1958-08-30 1973-05-03 Vacuumschmelze Ag Verfahren zur Erzeugung von Wuerfeltextur bei der Herstellung von Gegenstaenden aus Eisen-Silizium-Legierungen
US3065118A (en) 1959-01-16 1962-11-20 Gen Electric Treatment of iron-cobalt alloys
US3148092A (en) 1960-11-17 1964-09-08 Westinghouse Electric Corp Process for producing sheets of magnetic materials
US3078198A (en) 1961-06-07 1963-02-19 Westinghouse Electric Corp Process for producing oriented silicon steel
US3166408A (en) 1961-11-16 1965-01-19 Westinghouse Electric Corp Magnetic alloys
DE1180954B (de) 1961-12-09 1964-11-05 Vacuumschmelze Ag Verfahren zur Verbesserung der magnetischen Eigenschaften von Eisen-Kobalt-Legierungen
US3282747A (en) 1964-04-13 1966-11-01 Westinghouse Electric Corp Annealing cube texture iron-silicon sheets
US3240638A (en) 1964-10-21 1966-03-15 Westinghouse Electric Corp Use of silicon steel alloy having a critical sulfur range to insure cube-onface orientation
US3597286A (en) 1968-02-23 1971-08-03 Westinghouse Electric Corp Method of treating a high strength high ductility iron-cobalt alloy
US3634072A (en) 1970-05-21 1972-01-11 Carpenter Technology Corp Magnetic alloy
US3695944A (en) 1970-06-17 1972-10-03 Allegheny Ludlum Ind Inc Iron cobalt vanadium alloy
BE789262A (fr) 1971-09-27 1973-01-15 Nippon Steel Corp Procede de formation d'un film isolant sur un feuillard d'acierau silicium oriente
US3868278A (en) 1972-02-22 1975-02-25 Westinghouse Electric Corp Doubly oriented cobalt iron alloys
US3977919A (en) 1973-09-28 1976-08-31 Westinghouse Electric Corporation Method of producing doubly oriented cobalt iron alloys
US4367100A (en) 1979-10-15 1983-01-04 Allegheny Ludlum Steel Corporation Silicon steel and processing therefore
JPS6014105B2 (ja) 1982-10-07 1985-04-11 新日本製鐵株式会社 方向性電磁鋼板の焼鈍分離剤塗布方法
JPS6240344A (ja) 1985-08-13 1987-02-21 Hitachi Metals Ltd Ｆｅ−Ｃｏ系高透磁率合金
GB8715726D0 (en) 1987-07-03 1987-08-12 Telcon Metals Ltd Soft magnetic alloys
CN1039915C (zh) * 1989-07-05 1998-09-23 新日本制铁株式会社 方向性电磁钢板上的绝缘皮膜成型方法
US5394721A (en) 1990-03-10 1995-03-07 Nippon Steel Corporation Method of producing permalloy cores
US5507883A (en) 1992-06-26 1996-04-16 Nippon Steel Corporation Grain oriented electrical steel sheet having high magnetic flux density and ultra low iron loss and process for production the same
US5685920A (en) 1994-05-13 1997-11-11 Nippon Steel Corporation Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same
JPH0845723A (ja) 1994-08-01 1996-02-16 Hitachi Metals Ltd 絶縁性に優れたナノ結晶合金薄帯およびナノ結晶合金磁心ならびにナノ結晶合金薄帯の絶縁皮膜形成方法
US5501747A (en) 1995-05-12 1996-03-26 Crs Holdings, Inc. High strength iron-cobalt-vanadium alloy article
DE19750066C1 (de) 1997-11-12 1999-08-05 Ebg Elektromagnet Werkstoffe Verfahren zum Beschichten von Elektrostahlbändern mit einem Glühseparator
DE19754996C2 (de) 1997-12-11 2000-07-06 Krupp Vdm Gmbh Verfahren zur Beschichtung magnetischer Bänder oder Bleche
IL128067A (en) 1998-02-05 2001-10-31 Imphy Ugine Precision Iron-cobalt alloy
GB2339798B (en) 1998-07-24 2002-12-11 Telcon Ltd High Strength soft magnetic alloys
DE19928764B4 (de) * 1999-06-23 2005-03-17 Vacuumschmelze Gmbh Eisen-Kobalt-Legierung mit geringer Koerzitivfeldstärke und Verfahren zur Herstellung von Halbzeug aus einer Eisen-Kobalt-Legierung
US6685882B2 (en) 2001-01-11 2004-02-03 Chrysalis Technologies Incorporated Iron-cobalt-vanadium alloy
US20040126483A1 (en) 2002-09-23 2004-07-01 Heimann Robert L. Coating compositions for electronic components and other metal surfaces, and methods for making and using the compositions
DE10320350B3 (de) 2003-05-07 2004-09-30 Vacuumschmelze Gmbh & Co. Kg Hochfeste weichmagnetische Eisen-Kobalt-Vanadium-Legierung
DE10324910B4 (de) 2003-05-30 2005-05-25 Vacuumschmelze Gmbh & Co. Kg Metallisches Halbzeug mit elektrisch isolierender Beschichtung sowie Verfahren zur Herstellung einer elektrisch isolierenden Beschichtung
US7905965B2 (en) 2006-11-28 2011-03-15 General Electric Company Method for making soft magnetic material having fine grain structure
DE112009004598B4 (de) 2009-03-26 2023-02-23 Vacuumschmelze Gmbh & Co. Kg Verfahren zum stoffschlüssigen fügen von paketlamellen zu einem weichmagnetischen blechpaket
DE102009038730B4 (de) 2009-08-27 2014-03-13 Vacuumschmelze Gmbh & Co. Kg Blechpaket aus weichmagnetischen Einzelblechen, elektromagnetischer Aktor und Verfahren zu deren Herstellung sowie Verwendung eines weichmagnetischen Blechpakets
GB2495465B (en) 2011-07-01 2014-07-09 Vacuumschmelze Gmbh & Co Kg Soft magnetic alloy and method for producing a soft magnetic alloy
GB2492406B (en) 2011-07-01 2013-12-18 Vacuumschmelze Gmbh & Co Kg Soft magnetic alloy and method for producing a soft magnetic alloy
US20140283953A1 (en) 2011-12-16 2014-09-25 Aperam Method for producing a soft magnetic alloy strip and resultant strip
KR101376507B1 (ko) 2012-02-22 2014-03-21 포항공과대학교 산학협력단 Ｆｅ-Ｃｏ계 합금 판재의 집합조직 형성 방법 및 이를 이용하여 제조된 연자성 강판
DE102013208618A1 (de) 2013-05-10 2014-11-13 Henkel Ag & Co. Kgaa Chromfreie Beschichtung zur elektrischen Isolierung von kornorientiertem Elektroband
KR101811249B1 (ko) 2013-11-28 2017-12-21 제이에프이 스틸 가부시키가이샤 절연 피막 부착 전자 강판
WO2017016604A1 (fr) 2015-07-29 2017-02-02 Aperam Tôle ou bande en alliage feco ou fesi ou en fe et son procédé de fabrication, noyau magnétique de transformateur réalisé à partir d'elle et transformateur le comportant
KR101762339B1 (ko) 2015-12-22 2017-07-27 주식회사 포스코 방향성 전기강판 및 방향성 전기강판의 제조방법
KR101796234B1 (ko) 2015-12-22 2017-11-09 주식회사 포스코 방향성 전기강판용 절연피막 조성물, 이를 이용한 방향성 전기강판의 절연피막 형성방법, 및 방향성 전기강판
GB2550593A (en) 2016-05-24 2017-11-29 Vacuumschmelze Gmbh & Co Kg Soft magnetic laminated core, method of producing a laminated core for a stator and/or rotor of an electric machine
DE102016222805A1 (de) 2016-11-18 2018-05-24 Vacuumschmelze Gmbh & Co. Kg Halbzeug und Verfahren zum Herstellen einer CoFe-Legierung
DE102016222750A1 (de) 2016-11-18 2018-05-24 Contitech Antriebssysteme Gmbh Verfahren und Vorrichtung zur Herstellung eines selbstführenden geschlossenen Endloszahnriemens
KR102179215B1 (ko) 2018-12-19 2020-11-16 주식회사 포스코 방향성 전기강판용 소둔 분리제 조성물, 방향성 전기강판 및 방향성 전기강판의 제조방법
DE102019107422A1 (de) 2019-03-22 2020-09-24 Vacuumschmelze Gmbh & Co. Kg Band aus einer Kobalt-Eisen-Legierung, Blechpaket und Verfahren zum Herstellen eines Bands aus einer Kobalt-Eisen-Legierung
DE102020134300A1 (de) * 2020-12-18 2022-06-23 Vacuumschmelze Gmbh & Co. Kg Wasserbasierte alkalische Zusammensetzung zum Bilden einer Isolationsschicht eines Glühseparators, beschichtete weichmagnetische Legierung und Verfahren zum Herstellen eines beschichteten weichmagnetischen Bandes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008039326A1 (de) * 2008-08-22 2010-02-25 IWT Stiftung Institut für Werkstofftechnik Verfahren zum elektrischen Isolieren von Elektroblech, elektrisch isoliertes Elektroblech, lamellierter magnetischer Kern mit dem Elektroblech und Verfahren zum Herstellen eines lamellierten magnetischen Kerns
WO2014194881A2 (fr) * 2013-06-07 2014-12-11 VDM Metals GmbH Procédé de production d'une feuille de métal
WO2019081672A1 (fr) * 2017-10-27 2019-05-02 Vacuumschmelze Gmbh & Co Kg Alliage magnétique doux à perméabilité élevée et procédé pour produire l'alliage magnétique doux à perméabilité élevée
DE102018112491A1 (de) 2017-10-27 2019-05-02 Vacuumschmelze Gmbh & Co. Kg Hochpermeable weichmagnetische Legierung und Verfahren zum Herstellen einer hochpermeablen weichmagnetischen Legierung
EP3730286A1 (fr) * 2019-04-26 2020-10-28 Vacuumschmelze GmbH & Co. KG Paquet de tôles et procédé de fabrication d'un alliage magnétique souple à haute perméabilité
US20210225571A1 (en) * 2020-01-16 2021-07-22 Toyota Jidosha Kabushiki Kaisha Laminated core

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EP4027358B1 (fr) 2023-09-27

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