EP4202067A1 - Procédé de fabrication d'une bande électrique à grains orientés et bande électrique à grains orientés - Google Patents
Procédé de fabrication d'une bande électrique à grains orientés et bande électrique à grains orientés Download PDFInfo
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- EP4202067A1 EP4202067A1 EP21216455.2A EP21216455A EP4202067A1 EP 4202067 A1 EP4202067 A1 EP 4202067A1 EP 21216455 A EP21216455 A EP 21216455A EP 4202067 A1 EP4202067 A1 EP 4202067A1
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- Prior art keywords
- bound
- ions
- steel
- layer
- mgo
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- 238000000034 method Methods 0.000 title claims description 20
- 239000010410 layer Substances 0.000 claims abstract description 66
- 229910052839 forsterite Inorganic materials 0.000 claims abstract description 64
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 58
- 239000010959 steel Substances 0.000 claims abstract description 58
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 26
- 230000001133 acceleration Effects 0.000 claims abstract description 18
- 238000004544 sputter deposition Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 10
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 8
- 229910001417 caesium ion Inorganic materials 0.000 claims abstract description 8
- 238000005261 decarburization Methods 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 239000012790 adhesive layer Substances 0.000 claims abstract description 4
- 230000000181 anti-adherent effect Effects 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 238000000137 annealing Methods 0.000 claims description 27
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 8
- 235000010234 sodium benzoate Nutrition 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 238000011835 investigation Methods 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 description 38
- 239000000395 magnesium oxide Substances 0.000 description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 32
- 229910000976 Electrical steel Inorganic materials 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C22C38/008—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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—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
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based 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, decarburization-annealed and primary recrystallized 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”), ⁇ 0.30% 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% in each case, the remainder being iron and unavoidable impurities.
- Si silicon
- Mn manganese
- Cu copper
- 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.
- MgO magnesium oxide
- the electrical steel strip is wound into a coil and annealed again in the coil in order to effect secondary recrystallization and subsequent purification of the steel from precipitate-forming elements.
- the anti-adhesive layer which essentially consists of MgO, reacts with the surface of the steel substrate existing oxides, consisting mainly of silicon oxide, and thus forms the desired forsterite layer ("Mg2SiO4"), which is also referred to as a "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. Because during this period the production continues to run, larger quantities of defective electrical steel may be produced until the cause of the defect has been rectified.
- 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 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 that achieves the above-specified object according to the invention has at least the features specified in claim 5 .
- the invention during the production of grain-oriented electrical steel, it is possible to use fixed criteria to decide at one point in time whether an intermediate product obtained before high-temperature annealing is suitable for forming a forsterite layer that optimally adheres to the steel substrate of the electrical steel.
- 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 invention is based on the knowledge that by time-of-flight secondary ion mass spectroscopy (English “Time of Flight Secondary Ions 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 the following work steps 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 larger this relation is for the examined surface before the annealing step, the better the adhesion of the forsterite layer after the annealing step (step e)).
- 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 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 and decarburized with a composition that is typical for grain-oriented electrical steel sheets.
- 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 e)) 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 steel substrate of a grain-oriented electrical steel sheet according to the invention consists of a steel which has the alloy specified above for step a) of the method according to the invention.
- This MgO powder consists of at least 90% by mass of MgO, it being possible for the optionally remaining remainder of the powder to be filled with at least one additive. The sum of the contents of the additives is at most 10% by mass.
- Additives that can be added to the MgO powder include, for example, titanium oxide, ammonium chloride or antimony chloride, the addition of which controls the density of the later forsterite layer and the gas exchange between the annealing atmosphere during high-temperature annealing and the metal.
- Each of the measures i) - iii) can, seen alone, contribute to a grain-oriented electrical sheet according to the invention with optimal adhesion To generate forsterite layer, this succeeds particularly safely if all three measures i) - iii) are carried out.
- the particle size distribution of the MgO powder can be determined in measure i) using methods known per se. For example, there are measuring instruments available on the market, such as the Mastersizer 2000 (see https://www.malvernpanalytical.com/de/support/productsupport/mastersizer-range/mastersizer-2000, accessed on December 7, 2019). Disposal.
- the pH value can be recorded with any pH measuring device available on the market for this purpose, which enables a continuously updated measurement over a period beginning with the addition of the MgO powder to the citric acid solution.
- 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.
- samples P1 - P7 were divided from eight cold-rolled steel strips originating from the normal production process, the respective composition of which is given in Table 1.
- samples P1 - P8 examined in this way were then coated with an aqueous MgO suspension, the mass 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 .
- Table 3 shows an example of the result of the investigation of the citric acid activity CAA for samples 1, 2 and 7, with the MgO powder used in samples 1 and 2 complying with requirement iii) of the invention, whereas this is the case with the MgO powder used in sample 7 has been used is not the case.
- 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 - P8 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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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21216455.2A EP4202067A1 (fr) | 2021-12-21 | 2021-12-21 | Procédé de fabrication d'une bande électrique à grains orientés et bande électrique à grains orientés |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21216455.2A EP4202067A1 (fr) | 2021-12-21 | 2021-12-21 | Procédé de fabrication d'une bande électrique à grains orientés et bande électrique à grains orientés |
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| Publication Number | Publication Date |
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| EP4202067A1 true EP4202067A1 (fr) | 2023-06-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21216455.2A Withdrawn EP4202067A1 (fr) | 2021-12-21 | 2021-12-21 | Procédé de fabrication d'une bande électrique à grains orientés et bande électrique à grains orientés |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2247269C3 (de) | 1971-09-27 | 1981-05-14 | Nippon Steel Corp., Tokyo | Verfahren zur Herstellung einer isolierenden sowie die Magnetostriktions-Charakteristika und den Eisenverlust verbessernden Schicht auf einem Silicimstahlblech |
| EP0239688A1 (fr) * | 1986-04-03 | 1987-10-07 | Nippon Steel Corporation | Séparateur pour le recuit final d'une tôle en acier électrique à grain orienté |
| 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 |
| JP2007138199A (ja) * | 2005-11-15 | 2007-06-07 | Jfe Steel Kk | 一方向性電磁鋼板の製造方法 |
| DE102015114358A1 (de) * | 2015-08-28 | 2017-03-02 | Thyssenkrupp Electrical Steel Gmbh | Verfahren zum Herstellen eines kornorientierten Elektrobands und kornorientiertes Elektroband |
-
2021
- 2021-12-21 EP EP21216455.2A patent/EP4202067A1/fr not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2247269C3 (de) | 1971-09-27 | 1981-05-14 | Nippon Steel Corp., Tokyo | Verfahren zur Herstellung einer isolierenden sowie die Magnetostriktions-Charakteristika und den Eisenverlust verbessernden Schicht auf einem Silicimstahlblech |
| EP0239688A1 (fr) * | 1986-04-03 | 1987-10-07 | Nippon Steel Corporation | Séparateur pour le recuit final d'une tôle en acier électrique à grain orienté |
| 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 |
| JP2007138199A (ja) * | 2005-11-15 | 2007-06-07 | Jfe Steel Kk | 一方向性電磁鋼板の製造方法 |
| DE102015114358A1 (de) * | 2015-08-28 | 2017-03-02 | Thyssenkrupp Electrical Steel Gmbh | Verfahren zum Herstellen eines kornorientierten Elektrobands und kornorientiertes Elektroband |
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