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EP4202068A1 - Procédé de production d'une bande électrique à grains orientés et bande électrique à grains orientés - Google Patents

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

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Publication number
EP4202068A1
EP4202068A1 EP22215198.7A EP22215198A EP4202068A1 EP 4202068 A1 EP4202068 A1 EP 4202068A1 EP 22215198 A EP22215198 A EP 22215198A EP 4202068 A1 EP4202068 A1 EP 4202068A1
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EP
European Patent Office
Prior art keywords
tio
ions
sub
bound
tof
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22215198.7A
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German (de)
English (en)
Inventor
Carsten Schepers
Dr. Christian Hecht
Alice Sandmann
Andreas Allwardt
Ludger Lahn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Electrical Steel GmbH
Original Assignee
ThyssenKrupp Electrical Steel GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ThyssenKrupp Electrical Steel GmbH filed Critical ThyssenKrupp Electrical Steel GmbH
Publication of EP4202068A1 publication Critical patent/EP4202068A1/fr
Pending legal-status Critical Current

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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
    • 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
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • C21D3/04—Decarburising
    • 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
    • C21D8/1277—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
    • 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
    • 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
    • C22C38/02—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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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 decarburization-annealed and primary recrystallized cold-rolled steel substrate of grain-oriented electrical strips of the type according to the invention typically consists of, in % by mass, 2.5 - 4.0% silicon (“Si”), ⁇ 0.20% 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
  • 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 then wound into a coil and coil annealed again to effect secondary recrystallization and subsequent purification of the steel of 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 predominantly consist of silicon oxide, and thus forms the desired layer of forsterite ("Mg2SiO4"), also known 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. With conventional production methods, it is only after this long annealing period that it can be determined whether the forsterite layer has formed properly or whether it is not sufficiently adhering to the steel substrate. Interventions in the production process to eliminate a faulty formation of the forsterite layer can therefore only be made with a considerable delay. Since production continues during this time, larger quantities may also be shipped defective electrical steels are produced until the cause of the error has been remedied.
  • the task was to develop a process that reliably enables the production of grain-oriented electrical steel with an optimally formed forsterite layer that adheres to the steel substrate of the respective electrical steel.
  • 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. It goes without saying that a person skilled in the art, when carrying out the method according to the invention and its variants and expansion options explained here, adds those work steps not explicitly mentioned here, which he knows from his practical experience that they are regularly used when carrying out such methods .
  • a grain-oriented electrical steel sheet which 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 2 .
  • the invention in the course of the production of grain-oriented electrical steel, it is possible to decide at a point in time based on fixed criteria whether an intermediate product obtained before high-temperature annealing is suitable for forming a forsterite layer that adheres optimally to the steel substrate of the electrical strip.
  • the invention makes it possible to measure the subsequent adhesive strength of the forsterite layer in the process and thus provides a safe range of process parameters, which leads to perfect adhesive strength of the forsterite layer after annealing.
  • the intermediate product provided in step a) of the method according to the invention as a cold-rolled and decarburization-annealed steel strip can be produced in accordance with the manner established in the prior art for the production of grain-oriented electrical steel sheets. It is crucial that the steel strip is produced with a composition that is typical for grain-oriented electrical steel sheets and that it is decarburized and primary recrystallized annealed. The alloy of the steel strip is also optimized to optimize the adhesion of the forsterite layer.
  • the invention provides, on the one hand, that in the standard base alloy of the steel strip, which is known per se, contents of 0.05-0.50% copper (“Cu”) or 0.005-0.2% tin ("Sn") are preferred grades of 0.05 - 0.50% copper (“Cu”) and 0.005 - 0.2% 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. In this context, it has proven to be advantageous if the composition of the steel strip contains a minimum content of 0.05% by weight of Cu.
  • the composition of the steel strip contains 0.05-0.3% Cu, particularly preferably 0.05-0.2% Cu.
  • the Cu content is 0.05-0.3% to at most 0.50% by mass, in particular at most 0.3% by mass, particularly preferably at most 0.2% by mass.
  • the addition of at least 0.005% Sn in particular has proven to be practical .
  • the composition of the steel strip contains 0.005 - 0.1% Sn, particularly preferably 0.005 - 0.08% Sn.
  • both Cu and Sn can be present in the composition of the steel strip in the aforementioned contents.
  • step b) of the method according to the invention it is then decided on the basis of the criteria specified according to the invention whether or not the steel strips provided have the potential for the formation of an optimally adhering forsterite layer. If the steel strip in question does not meet the requirements, it is no longer processed, but recycled as scrap and fed back into the steel strip production cycle for the manufacture of grain-oriented electrical steel strips. With the procedure according to the invention, only those cold-rolled steel strips reach the high-temperature annealing (step d)) in which it can be expected that the forsterite layer produced on them will meet the highest requirements with regard to their adhesion to the steel substrate of the electrical strip.
  • 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 with an acceleration voltage of 2keV and for analysis with Bi+ ions with an acceleration voltage of 25keV is bombarded, the adhesive strength of the forsterite layer produced in the following work steps can be predicted if at the same time a sludge is used to produce the anti-adhesive layer, the composition of which is determined by the invention specified requirements are met.
  • ToF-SIMS is an analytical method for the chemical characterization of surfaces. It is based on the time-resolved detection of secondary ions, which are generated from the examined surface by bombardment with high-energy primary ions (e.g. Bi). 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 "ToF-SIMS" characterization method according to the invention in the state after the decarburization annealing, i.e. before the high-temperature annealing (step e)), it can thus be reliably predicted if the result of the ToF-SIMS measurement satisfies condition 1 that the forsterite layer is optimally firm on the surface after step d)
  • the finished material obtained adheres if the sludge applied in step c) to produce the anti-adhesive layer is not only composed in accordance with requirement (i), but the forms in which the TiO 2 particles are contained in the sludge correspond to requirement (ii). .
  • Requirement (ii) is of particular importance because it takes into account the connection between the presence of TiO 2 in the anti-adhesive layer and the presence of N, which is unavoidable for production reasons. This prevents the formation of brittle TiN during the high-temperature anneal, which, if present in the forsterite layer after the high-temperature anneal, would significantly deteriorate the bond strength of the forsterite layer to the steel substrate of the resulting grain-oriented electrical steel.
  • the investigations carried out by the inventors indicate that the ToF-SIMS quotient "Al bound to Cs" / "Al not bound to Cs" of the steel strip provided in step a) is related to the release temperature of nitrogen from aluminum nitride. The nitrogen released by the aluminum nitrate contained in the steel substrate in the course of the high-temperature annealing should not be released at the same time as the TiO 2 is also decomposing, in order to also make TiN formation more difficult in this way.
  • the cold-rolled steel strip which forms the steel substrate of a grain-oriented electrical strip according to the invention and which is provided in step a), has an N content of at least 0.005% by mass.
  • Grain-oriented electrical steel according to the invention in which the forsterite film formed on its cold-rolled steel strip adheres excellently and which is obtained by the method according to the invention, is characterized in that in a ToF-SIMS examination by bombarding the forsterite layer with Cs ions with an acceleration voltage of 2keV as
  • Criteria A) and B) developed according to the invention as criteria for evaluating the adhesive strength of the forsterite layer on the steel substrate of a completely processed grain-oriented electrical strip according to the invention can be achieved by selecting the appropriate cold-rolled steel strip in accordance with the requirements of the invention (step b) of the method according to the invention). and an adjustment of the composition of the sludge which also corresponds to the specifications of the invention, from which the anti-adhesion layer is formed in step c) of the method according to the invention.
  • the TiO 2 content of the sludge is 2-10% by mass of the solids content, in particular 5-8% by mass.
  • Additives that can be added to the sludge include ammonium chloride or antimony chloride, which increase the density of the later forsterite layer and the gas exchange between Annealing atmosphere during high temperature annealing and metal is controlled.
  • the annealing of the steel strip, which is finally completed in step d), 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 grain-oriented electrical strips according to the invention produced by the method according to the invention, have a bending radius of less than 15 mm, in particular less than 12 mm, particularly preferably less than 10 mm.
  • the samples P1 - P7 separated from the cold strips produced in this way and made available for further processing are to be examined by ToF-SIMS, in which the surface of the respective steel strip is treated with Cs ions with a acceleration voltage of 2keV as sputtering material and Bi-ions with an acceleration voltage of 25keV as analysis ions, up to a depth of 10 ⁇ m measured from the surface of the respective sample, the curve of the from the signal "Al bound to Cs" and the signal "Al not bound to Cs" was determined and the resulting course of the quotient "Al bound to Cs"/"Al not bound to Cs" was determined.
  • the TiO 2 particles were present in the respective sludge as anatase and rutile structures with %TiO_anatase and %TiO-rutile contents.
  • the respective mixing ratio % TiO _anatase/% TiO rutile is listed in Table 4.
  • the N content is %N des cold-rolled steel strips of the respective sample as well as the AlCs/Al ToF-SIMS value of the quotient that was obtained in a ToF-SIMS investigation in which the surface of the respective steel strip was sputtered with Cs ions with an acceleration voltage of 2keV and Bi ions with an acceleration voltage of 25keV as analysis ions, signals "Al bonded to Cs" and "Al not bonded to Cs" have been determined at a sputtering depth of 3 ⁇ m measured from the surface of the steel strip.
  • 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 is shown determined by the initially provided cold rolled steel substrate.
  • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Soft Magnetic Materials (AREA)
EP22215198.7A 2021-12-21 2022-12-20 Procédé de production d'une bande électrique à grains orientés et bande électrique à grains orientés Pending EP4202068A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21216484 2021-12-21

Publications (1)

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EP4202068A1 true EP4202068A1 (fr) 2023-06-28

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000951A1 (fr) 2001-06-22 2003-01-03 Thyssenkrupp Electrical Steel Ebg Gmbh Tole electrique a cristaux orientes dotee d'un revetement electriquement isolant
EP1411139A1 (fr) * 2001-07-16 2004-04-21 Nippon Steel Corporation Tole magnetique unidirectionnelle a densite de flux magnetique tres elevee, a caracteristiques de pertes dans le fer et de revetement dans un champ magnetique puissant excellentes, et procede de production associe
EP3904543A1 (fr) * 2018-12-27 2021-11-03 JFE Steel Corporation Séparateur de recuit pour tôle d'acier électrique à grains orientés et procédé de fabrication de tôle d'acier électrique à grains orientés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000951A1 (fr) 2001-06-22 2003-01-03 Thyssenkrupp Electrical Steel Ebg Gmbh Tole electrique a cristaux orientes dotee d'un revetement electriquement isolant
EP1411139A1 (fr) * 2001-07-16 2004-04-21 Nippon Steel Corporation Tole magnetique unidirectionnelle a densite de flux magnetique tres elevee, a caracteristiques de pertes dans le fer et de revetement dans un champ magnetique puissant excellentes, et procede de production associe
EP3904543A1 (fr) * 2018-12-27 2021-11-03 JFE Steel Corporation Séparateur de recuit pour tôle d'acier électrique à grains orientés et procédé de fabrication de tôle d'acier électrique à grains orientés

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