EP4202066A1 - Procédé de production d'une bande électrique à grains orientés, bande laminée à froid et bande électrique à grains orientés - Google Patents

Procédé de production d'une bande électrique à grains orientés, bande laminée à froid et bande électrique à grains orientés Download PDF

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EP4202066A1
EP4202066A1 EP22215186.2A EP22215186A EP4202066A1 EP 4202066 A1 EP4202066 A1 EP 4202066A1 EP 22215186 A EP22215186 A EP 22215186A EP 4202066 A1 EP4202066 A1 EP 4202066A1
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Prior art keywords
steel strip
cold
mass
rolled steel
strip
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German (de)
English (en)
Inventor
Carsten Schepers
Dr. Christian Hecht
Alice Sandmann
Andreas Allwardt
Dr. Ludger Lahn
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ThyssenKrupp Electrical Steel GmbH
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ThyssenKrupp Electrical Steel GmbH
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    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D8/1216—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
    • 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
    • C21D8/1255—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 with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • 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
    • C21D8/1288—Application of a tension-inducing coating
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • 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
    • C22C38/06—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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • C22C38/18—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
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • 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

Definitions

  • the invention relates to a method for producing a grain-oriented electrical strip that is coated with a forsterite layer, and to a grain-oriented electrical strip with very good adhesion of a forsterite film formed on it.
  • Grain-oriented "electrical strip” is understood to mean steel strips produced by cold rolling, which are provided in a special way with a forsterite layer and optionally with at least one layer additionally applied to the forsterite layer.
  • the cold-rolled steel strip of a grain-oriented electrical strip is also referred to below as “steel substrate” or “steel material”.
  • grain-oriented electrical steels of the type in question are 0.10-0.35 mm thick.
  • the cold-rolled steel substrate of grain-oriented electrical steels of the type according to the invention typically consists of, in % by mass, 2.5-4.0% silicon (“Si”), ⁇ 0.30% manganese (“Mn”), ⁇ 0.50% Copper (“Cu”), ⁇ 0.065% aluminum (“Al”), ⁇ 0.1% nitrogen (“N”) and optionally one or more elements from the group “chromium (“Cr”), nickel (“Ni”), molybdenum (“Mo”), phosphorus (“P”), arsenic (“As”), sulfur (“S”), tin (“Sn”), selenium (“Se”), antimony (“Sb “), tellurium (“Te”), boron (“B”) or bismuth (“Bi”)” with the proviso that the contents of the elements of this group are ⁇ 0.2%, the remainder being iron and unavoidable impurities
  • Si silicon
  • Mn manganese
  • Cu Copper
  • Al aluminum
  • N ⁇ 0.1% nitrogen
  • N ⁇ 0.1% nitrogen
  • This steel contains (in mass %) 2.5 to less than 4.0% Si, 0.03 to less than 0.15% Mn, 0.03 to less than 0.5% Sn, 0.02 to less 0.3% Cu and the balance Fe and unavoidable impurities, the %Cu/%Sn ratio of the %Cu content of Cu to the %Sn content of Sn being in the range of 0.5 - 1.
  • a forsterite layer is built up on the respective electrical steel sheet in conventional production methods by subjecting a steel strip cold-rolled to its final thickness, which is composed within the framework of the general alloy specification given above, to a first annealing in order to bring about primary recrystallization and decarburization of the steel substrate and the Surface of the substrate to oxidize targeted.
  • the surface of the electrical strip treated in this way is then typically coated with a solution containing magnesium oxide (“MgO”) and suitable additives as a protection against adhesion. After the MgO coating has dried, the electrical steel is wound into a coil and annealed again in the coil to create a To bring about secondary recrystallization and subsequent cleaning of the steel from precipitate-forming elements.
  • MgO magnesium oxide
  • the anti-adhesive layer which consists essentially of MgO, reacts with the oxides present on the surface of the steel substrate, which mainly consist of silicon oxide, and thus forms the desired forsterite layer ("Mg2SiO4"), which also referred to as "glass film".
  • This layer of forsterite merges into the steel substrate with roots, which ensures its adhesion to the steel substrate.
  • the forsterite layer can in a further step, such as from the DE 22 47 269 C3 is known, a solution based on magnesium phosphate or aluminum phosphate or mixtures of both with various additives such as chromium compounds and Si oxide are applied and baked at temperatures above 350 °C.
  • the layer system formed in this way on the electrical strip forms an insulating layer which transfers tensile stresses to the steel material, which have a favorable effect on the electromagnetic properties of the electrical strip or sheet.
  • the high-temperature annealing step that forms the forsterite layer typically takes 6-7 days and requires significant energy input.
  • the task was to develop a process that reliably enables the production of grain-oriented electrical steel strips with an optimally developed forsterite layer that adheres to the steel substrate of the respective electrical steel strip.
  • a cold-rolled steel strip should be mentioned that is suitable for the production of a grain-oriented electrical steel sheet in which the forsterite layer adheres particularly well to the steel substrate.
  • a grain-oriented electrical strip should be specified in which the forsterite layer adheres optimally firmly to the steel substrate of the electrical strip.
  • the invention has achieved this object in that at least the work steps specified in claim 1 are completed in the production of grain-oriented electrical strips with an optimally adhering forsterite layer.
  • a grain-oriented electrical steel sheet that achieves the above-specified object according to the invention and is produced by the method according to the invention has at least the features specified in claim 3 .
  • the invention is based on the finding that the formation of an optimally adhering Forster film on the steel substrate of a grain-oriented electrical strip according to the invention can be ensured beyond the procedure known from the prior art by three measures that are already required during the production of the cold-rolled steel strip , which forms the steel substrate of the electrical strip according to the invention and is then covered with the forsterite layer.
  • the invention makes use of the fact that there is an accumulation of Si in the outer surface layers that adjoin the surfaces of a cold-rolled steel strip processed according to the invention, since the steel strip and the preliminary products from which it was produced not only hot-rolled but also annealed. This is accompanied by oxidation, in particular of the edge region of the steel strip close to the surface, with Si already oxidizing at temperatures which are lower than the temperatures at which oxidation of iron (“Fe”) occurs. These Si enrichments contribute to the formation of the forsterite layer and its connection to the steel substrate.
  • the invention provides that during the decarburizing annealing, which is carried out in the usual way, in which the cold-rolled steel strip is heated in an annealing atmosphere consisting of (in vol. %) 40-90% H 2, , remainder N 2 in particular 50-80% H 2 , remainder N 2 , is heated at an annealing temperature of 900-1200 K, in particular 1100-1200 K, the cold-rolled steel strip being heated to the annealing temperature in the temperature range of 300-1000 K with a Heating rate dR is heated, which is more than 40 Kls in particular more than 50 K / s.
  • the maximum set heating rates are up to 1000 K/s.
  • the decarburizing annealing can be combined with a recrystallizing annealing in a manner known per se, it being possible for the decarburizing and the recrystallizing annealing to be carried out in one go.
  • the decarburizing annealing and the recrystallizing annealing optionally carried out in combination therewith, optionally simultaneously taking place, are carried out continuously through a continuous furnace.
  • the heating of the material during cold rolling results in a near-surface enrichment of Si.
  • the goal of rapid heating during decarburization annealing is then not to change or destroy this layer containing the Si enrichments.
  • the alloy of the steel strip which forms the basis of a grain-oriented electrical strip according to the invention, is additionally optimized.
  • the invention provides, on the one hand, that in the standard base alloy of the steel strip, which is known per se, contents of 0.01-0.50% copper ("Cu") or 0.003-0.1% tin ("Sn") are preferred Concentrations of 0.01 - 0.50% copper (“Cu”) and 0.003 - 0.1% tin ("Sn”) are present.
  • the presence of copper and/or tin not only refines the secondary recrystallization grains, but also promotes the formation of the forsterite layer.
  • the presence of both Cu and Sn in the specified contents is particularly favorable for an optimized connection of the forsterite layer to the steel substrate, with the steel substrate requiring a Cu content that is significantly higher than the content of Sn in the steel substrate.
  • the invention stipulates that the %Cu content of Cu must be more than three times greater than the tin content, with particularly good effects being achieved by the presence of Cu and Sn if the mass ratio %Cu/%Sn of the %Cu content of Cu and the %Sn content of Sn of the steel strip applies: %Cu/%Sn > 4.
  • the Cu content is limited to a maximum of 0.5% by mass, in particular at most 0.3% by mass, in order to avoid negative effects on the magnetic properties of a grain-oriented electrical strip according to the invention. It has proven to be particularly practical if the base alloy of the steel strip contains at least 0.05% by weight Cu. Likewise, at least 0.003% by mass, in particular at least 0.005% by mass, of Sn is required in order to achieve the effects used according to the invention. At the same time, the content of Sn is limited to at most 0.1% by mass, in particular at most 0.08% by mass, in order to ensure good workability of the steel strip when it is produced.
  • the setting of the contents of Cu and Sn which is set in relation to a preferred embodiment, also serves to To protect the Si-enriched layer formed by cold rolling from being altered. If the Cu content is lower in relation to the Sn content, there would be a risk that Sn would displace Si as a surface-sensitive element, so that only limited amounts of Si would be available on the surface of the steel strip for the formation and bonding of the forsterite layer.
  • step e the combination of measures according to the invention in the production of the cold-rolled steel strip, on which the MgO layer is then applied and the forsterite layer is formed in the subsequent high-temperature annealing (step e) of the method according to the invention), enables an optimized adhesive strength of the forsterite layer to be reliably achieved .
  • the powder applied to the cold-rolled steel strip to produce the forsterite layer consists of at least 90% by mass of MgO and can contain up to 10% by mass of additives in a manner known per se.
  • additives can be, for example, titanium oxide, ammonium chloride or antimony chloride, the addition of which controls the density of the subsequent forsterite layer and the gas exchange between the annealing atmosphere during high-temperature annealing and the metal.
  • the annealing of the steel strip, which is finally completed in step e), during which the forsterite layer (Mg2SiO4) forms, can also be carried out in a manner known per se.
  • the cold-rolled steel strip obtained after step d) and coated with the anti-tack layer formed from the MgO powder can be wound into a coil and kept in a hood furnace for 10-200 hours at a temperature of 1000-1600 K under an atmosphere that consists of at least 50% H 2 consists.
  • the invention also proposes a criterion that enables a precise assessment of the suitability of a 0.10-0.35 mm thick cold-rolled steel strip, provided in the decarburized annealed state, for the production of a grain-oriented electrical strip that has a forsterite layer that adheres optimally to the cold-rolled steel strip .
  • Such a cold-rolled steel strip which is suitable according to the invention for use in the production of grain-oriented electrical strip consists in a conventional manner of, in % by mass, 2.5-4.0% Si, ⁇ 0.30% Mn, ⁇ 0.50% Cu , ⁇ 0.1% Sn, ⁇ 0.065% Al, ⁇ 0.1% N and optionally one or more elements from the group "Cr, Ni, Mo, P, As, S, Sb, Se, Te, B or Bi" with the proviso that the contents of the elements of this group are ⁇ 0.2%, the remainder being iron and unavoidable impurities, the steel strip containing at least 0.01% by mass Cu or at least 0.003% by mass Sn.
  • the cold-rolled steel strip intended for use according to the invention for the production of a grain-oriented electrical strip has an Sn content of at least 0.003% by mass or a Cu content of at least 0.01% by mass, preferably a Sn -Content of at least 0.003% by mass and a Cu content of at least 0.01% by mass, provided here also preferred for the mass ratio %Cu/% formed from the %Cu content of Cu and the %Sn content of Sn Sn is %Cu/%Sn>3.
  • the configurations of the Cu and Sn contents which have already been explained above in connection with the method according to the invention have proven to be particularly practical.
  • a steel strip obtained as an intermediate product in the production of a grain-oriented electrical strip after decarburizing annealing is suitable for the reliable production of a grain-oriented electrical strip in which particularly good adhesion of the forsterite layer formed on it is guaranteed if it is in a ToF -SIMS examination, in which the surface of the respective steel strip is bombarded with Cs ions with an acceleration voltage of 2keV as sputtering material and Bi ions with an acceleration voltage of 25keV as analysis ions, the following condition 1 is met: Condition 1: The curve of the quotient "Si on” formed from the signal "Si bound to Cs" and the signal "Si not bound to Cs". Cs bound” / "Si not bound to Cs" shows exactly a local maximum in the depth profile of 0.5 - 3.0 ⁇ m.
  • condition 1 defined by the invention also opens up the possibility of using a measurement to precisely predict whether a steel strip produced in any other way, which has a composition typical of grain-oriented electrical strips and is intended for coating with the MgO layer, the potential for the development of an optimally adhering forsterite layer.
  • the invention is based on the knowledge that by time-of-flight secondary ion mass spectroscopy (English “Time of Flight Secondary Ion Mass Spectrometry", short “ToF-SIMS"), in which the surface to be examined of the intermediate product present after the decarburizing annealing with Cs Ions are bombarded with an acceleration voltage of 2keV and for analysis with Bi+ ions with an acceleration voltage of 25keV, the adhesive strength of the forsterite layer produced in further work steps on the steel strip provided in each case can be predicted.
  • This prediction is based on an evaluation of the proportion of the element Si on the examined surface of the steel substrate which is bound with the element Cs in relation to the proportion of the element Si which is not bound with Cs.
  • the "proportion of the element Si which is not bonded to Cs" is understood to mean only atomic Si, ie Si which is not bonded to other atoms such as Cs, O etc., but is completely unbound.
  • ToF-SIMS is an analytical method for the chemical characterization of surfaces. It is based on the time-resolved detection of secondary ions, which escape from the surface under investigation by bombardment with high-energy primary ions (e.g. Bi) are generated. These primary ions, directed at the surface to be examined in a short ion pulse, penetrate the upper atomic layers of the surface and release so-called "secondary ions" from it. The kinetic energy of the primary ions is transferred to the released secondary ions, so that the secondary ions are accelerated and run through a drift path until they hit a detector system that records the intensity of the secondary ions as a function of the flight time with high time resolution.
  • primary ions e.g. Bi
  • the material to be examined is bombarded with sputter ions (e.g. Cs) in addition to the primary ions, so that material is continuously removed.
  • sputter ions e.g. Cs
  • the depth-resolved degree of affinity for this binding is the basis of the invention.
  • the steel substrate of a grain-oriented electrical strip according to the invention that is produced in this way typically consists of a steel produced above in connection with the step a) of the method according to the invention.
  • the use of the method according to the invention reliably results in electrical steel strips whose forsterite film satisfies requirements A and B in an examination carried out in the manner indicated above.
  • samples P1 - P6 were divided from seven cold-rolled steel strips originating from the normal manufacturing process.
  • the production of the cold-rolled steel strips, from which the samples P1 - P6 originated, was carried out in a conventional manner in that seven steels, the composition of which is given in Table 1, were melted and cast and rolled to form hot strips.
  • the components of the alloy of the steels of the samples P1 - P6 not specified in Table 1 are to be assigned to the unavoidable impurities, the individual contents and total content of which are so severely limited according to the standard that they have no influence on the properties of the grain-oriented electrical steel sheets produced from the samples P1 - P6 have.
  • the hot strips were cold-rolled in 5 cold-rolling passes to form cold-rolled steel strip.
  • the respective last stage of cold rolling was carried out in such a way that the cold-rolled strips were heated to a temperature T aging by the forming work carried out in the course of this forming stage.
  • the associated degree of deformation ⁇ U and the temperature T aging are given in Table 2 for samples P1-P6.
  • the cold-rolled steel strips thus obtained then passed through an annealing furnace in which they were heated under an annealing atmosphere consisting of 60% by volume H2 and 40% by volume N2 at a heating rate dR to an annealing temperature TG, at which they annealing time tG have been held in order to anneal them recrystallizing and decarburizing.
  • the heating rate dR, the annealing temperature TG and the annealing time tG are also given in Table 2 for the samples P1 - P6.
  • samples P1 - P6 examined in this way were then coated with an aqueous MgO suspension, the thickness of which was adjusted by means of squeezing rollers.
  • the MgO powder used consisted of 94% by mass MgO and 6% by mass TiO 2 .
  • the samples coated in this way were subjected to high-temperature annealing, during which they were kept in a top hat furnace for a period of 24 h at a temperature of 1450 K under a dry atmosphere of pure hydrogen.
  • the strength of the adhesion of the forsterite layer on the initially provided, cold-rolled steel substrate was determined on the samples P1 - P6 produced and tested in the manner explained above.
  • a sample was clamped in a cone mandrel bending device. The sample was bent 180° around a cone mandrel ranging continuously from a bending radius of 5 mm (cone apex) to 30 mm (cone base). After removal, the bending radius from which the coating flaked off was checked. The smaller this bending radius, the better the adhesion.

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EP22215186.2A 2021-12-21 2022-12-20 Procédé de production d'une bande électrique à grains orientés, bande laminée à froid et bande électrique à grains orientés Pending EP4202066A1 (fr)

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Citations (10)

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Publication number Priority date Publication date Assignee Title
DE3229295C2 (de) 1981-08-05 1986-09-18 Nippon Steel Corp., Tokio/Tokyo Kornorientiertes Elektrostahlblech und Verfahren zu seiner Herstellung
JPH11152518A (ja) * 1997-09-09 1999-06-08 Kawasaki Steel Corp 磁気特性及び被膜特性に優れる方向性けい素鋼板の製造方法
WO2003000951A1 (fr) 2001-06-22 2003-01-03 Thyssenkrupp Electrical Steel Ebg Gmbh Tole electrique a cristaux orientes dotee d'un revetement electriquement isolant
JP2009235568A (ja) * 2008-03-03 2009-10-15 Nippon Steel Corp 方向性電磁鋼板及びその製造方法
JP2009256713A (ja) * 2008-04-15 2009-11-05 Nippon Steel Corp 方向性電磁鋼板の製造方法
WO2016059099A1 (fr) * 2014-10-15 2016-04-21 Sms Group Gmbh Procédé de production de bande d'acier électrique à grains orientés et bande d'acier électrique à grains orientés obtenue selon ce procédé
EP3225704A1 (fr) * 2014-11-27 2017-10-04 JFE Steel Corporation Procédé permettant de fabriquer une tôle d'acier électromagnétique orientée
WO2021054371A1 (fr) * 2019-09-19 2021-03-25 日本製鉄株式会社 Tôle d'acier électromagnétique orientée
EP3822385A1 (fr) * 2018-07-13 2021-05-19 Nippon Steel Corporation Tôle d'acier électromagnétique à grains orientés et procédé de fabrication de celle-ci
EP3913089A1 (fr) * 2019-01-16 2021-11-24 Nippon Steel Corporation Tôle d'acier électromagnétique à grains orientés et son procédé de fabrication

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3229295C2 (de) 1981-08-05 1986-09-18 Nippon Steel Corp., Tokio/Tokyo Kornorientiertes Elektrostahlblech und Verfahren zu seiner Herstellung
JPH11152518A (ja) * 1997-09-09 1999-06-08 Kawasaki Steel Corp 磁気特性及び被膜特性に優れる方向性けい素鋼板の製造方法
WO2003000951A1 (fr) 2001-06-22 2003-01-03 Thyssenkrupp Electrical Steel Ebg Gmbh Tole electrique a cristaux orientes dotee d'un revetement electriquement isolant
JP2009235568A (ja) * 2008-03-03 2009-10-15 Nippon Steel Corp 方向性電磁鋼板及びその製造方法
JP2009256713A (ja) * 2008-04-15 2009-11-05 Nippon Steel Corp 方向性電磁鋼板の製造方法
WO2016059099A1 (fr) * 2014-10-15 2016-04-21 Sms Group Gmbh Procédé de production de bande d'acier électrique à grains orientés et bande d'acier électrique à grains orientés obtenue selon ce procédé
EP3225704A1 (fr) * 2014-11-27 2017-10-04 JFE Steel Corporation Procédé permettant de fabriquer une tôle d'acier électromagnétique orientée
EP3822385A1 (fr) * 2018-07-13 2021-05-19 Nippon Steel Corporation Tôle d'acier électromagnétique à grains orientés et procédé de fabrication de celle-ci
EP3913089A1 (fr) * 2019-01-16 2021-11-24 Nippon Steel Corporation Tôle d'acier électromagnétique à grains orientés et son procédé de fabrication
WO2021054371A1 (fr) * 2019-09-19 2021-03-25 日本製鉄株式会社 Tôle d'acier électromagnétique orientée

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AUTORENKOLLEKTIV: "Spurenelemente im Stahl - Moeglichkeiten zur Beeinflussung im Smelzbetrieb", SPURENELEMENTE IN STAEHLEN, VERLAG STAHLEISEN, DUESSELDORF, DE, 1 January 1985 (1985-01-01), pages 19 - 22, XP002433212 *
CESAR MARIA DAS G M M ET AL: "Effect of Sn on the oxide subscale structure formed on a 3% Si steel", AIP ADVANCES, AMERICAN INSTITUTE OF PHYSICS, 2 HUNTINGTON QUADRANGLE, MELVILLE, NY 11747, vol. 8, no. 4, 20 October 2017 (2017-10-20), XP012223014, DOI: 10.1063/1.4994051 *
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