CN104870665B - 方向性电磁钢板的制造方法和方向性电磁钢板制造用的一次再结晶钢板 - Google Patents
方向性电磁钢板的制造方法和方向性电磁钢板制造用的一次再结晶钢板 Download PDFInfo
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- CN104870665B CN104870665B CN201380068115.8A CN201380068115A CN104870665B CN 104870665 B CN104870665 B CN 104870665B CN 201380068115 A CN201380068115 A CN 201380068115A CN 104870665 B CN104870665 B CN 104870665B
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- 239000010959 steel Substances 0.000 title claims abstract description 79
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 78
- 238000001953 recrystallisation Methods 0.000 title claims abstract description 65
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 112
- 238000000137 annealing Methods 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 57
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 35
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 229910018509 Al—N Inorganic materials 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 238000005098 hot rolling Methods 0.000 claims description 7
- 238000003303 reheating Methods 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 description 27
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- 229910052782 aluminium Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 7
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- 239000002244 precipitate Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
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- 229910052742 iron Inorganic materials 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
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- 229910052839 forsterite Inorganic materials 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
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- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 238000010923 batch production Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000005204 segregation Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 use is with Si:3.2% Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
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- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
- C21D8/1222—Hot rolling
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C21D8/1244—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
- C21D8/1261—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 following hot rolling
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/48—Nitriding
- C23C8/50—Nitriding of ferrous surfaces
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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
- H01F1/16—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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Abstract
将以质量%或质量ppm计含有C:0.08%以下、Si:2.0~4.5%和Mn:0.5%以下,将S、Se和O抑制为分别小于50ppm,将sol.Al抑制为小于100ppm,将N控制为80ppm以下且满足sol.Al(ppm)-N(ppm)×(26.98/14.00)≤30ppm的范围,剩余部分由Fe和不可避免的杂质的组成构成的钢板坯作为原料制造方向性电磁钢板时,在一次再结晶退火前、退火中或退火后,实施氮增量(ΔN)以下式(1)或式(2)规定的氮化处理,使氮化硅(Si3N4)析出于晶界上,该氮化硅作为正常晶粒生长的抑制力发挥功能,从而,大幅度减少磁特性的偏差,在工业上稳定地制造具有良好的特性的方向性电磁钢板。sol.Al-N×(26.98/14.00)≤0时,50ppm≤ΔN≤1000ppm——(1);0<sol.Al-N×(26.98/14.00)≤30时,(N-sol.Al×14.00/26.98+100)≤ΔN≤(N-sol.Al×14.00/26.98+1000)——(2)。
Description
技术领域
本发明涉及可以廉价地得到具有优异的磁特性的方向性电磁钢板的、磁特性优异的方向性电磁钢板的制造方法以及适合于这样的方向性电磁钢板的制造的方向性电磁钢板用的一次再结晶钢板。
背景技术
方向性电磁钢板是作为变压器、发电机的铁芯材料使用的软磁性材料,作为铁的易磁化轴的<001>方位在钢板的轧制方向具有高度地整合的结晶组织。这种集合组织通过二次再结晶形成,该二次再结晶是在方向性电磁钢板的制造工序中在二次再结晶退火时使被称为所谓的高斯(Goss)取向的(110)〔001〕方位的晶粒优先地巨大生长。
以往,这种方向性电磁钢板可以通过以下方式制造:将含有4.5mass%以下左右的Si和MnS、MnSe、AlN等抑制剂成分的板坯加热至1300℃以上,使抑制剂成分临时固溶后,进行热轧,根据需要实施热延板退火,其后,通过1次或隔着中间退火的2次以上的冷轧制成最终板厚,接下来,在湿润氢气氛中实施一次再结晶退火,进行一次再结晶和脱碳,接下来,涂布以氧化镁(MgO)为主剂的退火分离剂后,为了提纯二次再结晶和抑制剂成分,以1200℃进行5h左右的最终退火(例如,专利文献1、专利文献2、专利文献3)。
如上所述,在以往的方向性电磁钢板的制造时,可以采用以下工序:使板坯阶段含有MnS、MnSe、AlN等析出物(抑制剂成分),通过超过1300℃的高温的板坯加热,临时固溶这些抑制剂成分,在以下工序中使其微细析出,从而表达二次再结晶。如此,以往的方向性电磁钢板的制造工序中,需要超过1300℃的高温下的板坯加热,因此在其制造成本极其高、无法应对近年的制造成本减少的要求,在这方面存在问题。
为了解决上述问题,例如专利文献4中提出有含有0.010~0.060%的酸可溶性Al(sol.Al)且将板坯加热抑制在低温,脱碳退火工序中在适当的氮化气氛下进行氮化,从而在二次再结晶时使(Al、Si)N析出而用作抑制剂的方法。(Al、Si)N在钢中微细分散而作为有效的抑制剂发挥功能,但根据Al的含量决定抑制剂强度,因此有时在制钢中的Al量的精度不充分时,无法得到充分的晶粒生长抑制力。还提出有大量的这种在中途工序进行氮化处理,将(Al、Si)N或AlN作为抑制剂使用的方法,最近也公开有板坯加热温度超过1300℃的制造方法等。
另一方面,还研究有对板坯不含抑制剂成分而表达二次再结晶的技术,例如专利文献5中开发了不含抑制剂成分也可以二次再结晶的技术,所谓的无抑制剂法。该无抑制剂法是利用更高纯度化的钢,通过材质(集合组织的控制)表达二次再结晶的技术。
该无抑制剂法无需高温的板坯加热,可制造低成本的方向性电磁钢板,但由于不具有抑制剂,在制造时受到中途工序中的温度的偏差等影响,具有制品的磁特性也容易发生偏差的特征。另外,集合组织的控制是在该技术中重要的要素,提出有用于控制集合组织的温轧等大量的技术。但是,这样的集合组织控制无法充分地进行时,与使用抑制剂的技术相比,二次再结晶后的向高斯方位((110)〔001〕)的集合度较低,存在磁束密度也变低的趋势。
先行技术文献
专利文献
专利文献1:美国专利第1965559号公报
专利文献2:日本特公昭40-15644号公报
专利文献3:日本特公昭51-13469号公报
专利文献4:专利第2782086号公报
专利文献5:日本特开2000-129356号公报
发明内容
如上所述,使用到目前为止提出的无抑制剂法的方向性电磁钢板的制造方法中,稳定地实现良好的磁特性不一定容易。
本发明使用以将Al抑制为小于100ppm的无抑制剂成分为标准的成分,避免高温板坯加热,并且利用氮化,从而使得不是AlN而是氮化硅(Si3N4)析出,该氮化硅作为正常晶粒生长的抑制力发挥功能,从而大幅度减少磁特性的偏差,可以在工业上稳定地制造具有良好的磁特性的方向性电磁钢板。
本发明的发明人等进行了以下研究:为了抑制板坯加热温度且得到减少了磁特性的偏差的方向性电磁钢板,使用无抑制剂法进行一次再结晶集合组织的制作,其中通过在中途工序利用氮化使氮化硅析出,将其作为抑制剂使用。
即,本发明的发明人等认为如果可使方向性电磁钢板中一般含有数%左右的硅作为氮化硅析出,将其作为抑制剂使用,则是否能通过控制氮化处理时的氮化量,不论氮化物形成元素(Al、Ti、Cr、V等)的多少,可得到同等的晶粒生长抑制力。
另一方面,已知纯粹的氮化硅与AlN中固溶有Si的(Al、Si)N不同,与钢的晶格的整合性差,且具有共价结合性的复杂的晶体结构,因此使其在晶粒内微细地析出极其困难。因此,认为在如以往方法那样的氮化后,难以使其在晶粒内微细地析出。
然而,考虑如果将其反过来使用,则是否能够使氮化硅在晶界选择性地析出。进而,认为如果可使其在晶界选择性地析出,即使析出物变得粗大也可得到充分的抑制力。
因此,本发明的发明人等根据上述观点,从原料的成分组成开始,对氮化处理中的增量氮化量、用于使氮扩散至晶界而形成氮化硅的热处理条件等反复进行了深入研究。其结果发现了氮化硅的新的有用性,完成了本发明。
即,本发明的要旨构成如下所述。
1.一种方向性电磁钢板的制造方法,其中,将以质量%或质量ppm计含有C:0.08%以下、Si:2.0~4.5%和Mn:0.5%以下,并且将S、Se和O抑制为分别小于50ppm,将sol.Al抑制为小于100ppm,进一步将N控制为80ppm以下且满足sol.Al(ppm)-N(ppm)×(26.98/14.00)≤30ppm的范围,剩余部分由Fe和不可避免的杂质的组成构成的钢板坯,在不进行再加热或再加热后实施热轧而制成热延板后,通过退火和轧制制成最终板厚的冷轧板,接下来,在一次再结晶退火前或退火中或退火后,实施氮增量(ΔN)以下述式(1)或式(2)规定的氮化处理后,涂布退火分离剂,实施二次再结晶退火。
·sol.Al-N×(26.98/14.00)≤0时
50ppm≤ΔN≤1000ppm---(1)
·0<sol.Al-N×(26.98/14.00)≤30时
(N-sol.Al×14.00/26.98+100)≤ΔN≤
(N-sol.Al×14.00/26.98+1000)---(2)
2.一种方向性电磁钢板的制造方法,其中,将以质量%或质量ppm计含有C:0.08%以下、Si:2.0~4.5%和Mn:0.5%以下,并且将S、Se和O抑制为分别小于50ppm,将sol.Al抑制为小于100ppm,进一步将N控制为80ppm以下且满足sol.Al(ppm)-N(ppm)×(26.98/14.00)≤30ppm的范围,剩余部分由Fe和不可避免的杂质的组成构成的钢板坯,在不进行再加热或再加热后实施热轧而制成热延板后,通过退火和轧制制成最终板厚的冷轧板,接下来,在一次再结晶退火前或退火中或退火后,实施氮增量(ΔN)以下述式(1)或式(2)规定的氮化处理后,涂布退火分离剂,进而,从一次再结晶退火到二次再结晶开始之间,使N扩散于钢板基体中,使不含粒径为100nm以上的Al的氮化硅析出,从而作为正常晶粒生长抑制力使用。
·sol.Al-N×(26.98/14.00)≤0时
50ppm≤ΔN≤1000ppm---(1)
·0<sol.Al-N×(26.98/14.00)≤30时
(N-sol.Al×14.00/26.98+100)≤ΔN≤
(N-sol.Al×14.00/26.98+1000)---(2)
3.如上述1或2所述的方向性电磁钢板的制造方法,其中,上述钢板坯以质量%计进一步含有选自
Ni:0.005~1.50%、Sn:0.01~0.50%、
Sb:0.005~0.50%、Cu:0.01~0.50%、
Cr:0.01~1.50%、P:0.0050~0.50%、
Mo:0.01~0.50%和Nb:0.0005~0.0100%
中的1种或2种以上。
4.一种方向性电磁钢板制造用的一次再结晶钢板,其组成以质量%或质量ppm计含有C:0.08%以下、Si:2.0~4.5%和Mn:0.5%以下,S、Se和O分别小于50ppm,sol.Al小于100ppm,N为50ppm~1080ppm,剩余部分满足Fe和不可避免的杂质的组成范围。
5.如上述4所述的方向性电磁钢板制造用的一次再结晶钢板,其中,上述一次再结晶钢板以质量%计进一步含有选自
Ni:0.005~1.50%、Sn:0.01~0.50%、
Sb:0.005~0.50%、Cu:0.01~0.50%、
Cr:0.01~1.50%、P:0.0050~0.50%、
Mo:0.01~0.50%和Nb:0.0005~0.0100%
中的1种或2种以上。
根据本发明,可以在无需高温板坯加热的情况下,大幅度减少磁特性的偏差,在工业上稳定地制造具有良好的磁特性的方向性电磁钢板。
此外,本发明利用不是与Al的复合析出的纯粹的氮化硅,因此在提纯时,仅通过提纯扩散相对较早的氮就可以达成钢的提纯。
进而,利用如以往的Al、Ti作为析出物时,从最终的提纯和可靠的抑制剂效果的观点出发,需要ppm等级的控制,但如本发明这样利用Si作为析出物时,在制钢时完全不需要这种控制。
附图说明
图1是表示脱碳退火后,进行氮增量成为100ppm(同图a)、500ppm(同图b)的氮化处理,以规定的升温速度升温至800℃后,立即进行水冷的组织的电子显微镜照片,以及利用上述组织中的析出物的EDX(能量分散型X射线分光法)的鉴定结果的图(同图c)。
图2是钢块A、B的氮化处理后的电子显微镜照片(A-1、B-1)和升温后的电子显微镜照片(A-2、B-2)。
具体实施方式
以下,具体地说明本发明。
首先,对本发明中将钢板坯的成分组成限定于上述范围的理由进行说明。应予说明,成分所涉及的“%”和“ppm”表述只要无特别说明,则意味着“质量%”和“质量ppm”。
C:0.08%以下
C是在改善一次再结晶集合组织方面有用的元素,但若含量超过0.08%则反而导致一次再结晶集合组织的劣化,因此C量限定于0.08%以下。从磁特性的观点出发,优选含量为0.01~0.06%的范围。另外,所需的磁特性的水平并不那么高的情况下,为了省略或简化一次再结晶退火中的脱碳,也可以将C量设为0.01%以下。
Si:2.0~4.5%
Si是通过提高电阻而改善铁损的有用元素,但若含量超过4.5%则冷轧性显著劣化,因此Si量限定于4.5%以下。另一方面,Si需要作为氮化物形成元素发挥功能,因此需要含有2.0%以上。此外,从铁损的观点出发优选的含量也为2.0~4.5%的范围。
Mn:0.5%以下
Mn具有使制造时的热加工性提高的效果,因此优选含有0.01%以上,但是含量超过0.5%时,一次再结晶集合组织变差而导致磁特性的劣化,因此Mn量限定于0.5%以下。
S、Se和O:分别小于50ppm
S、Se和O量分别为50ppm以上,则二次再结晶变得困难。其理由是因为粗大的氧化物、通过板坯加热而粗大化的MnS、MnSe使得一次再结晶组织不均匀。因此,S、Se和O均抑制为小于50ppm。它们的含量也可以为0ppm。
sol.Al:小于100ppm
Al在表面形成致密的氧化膜,使得在氮化时难以控制其氮化量,或有时也阻碍脱碳,因此将Al抑制为以sol.Al量计小于100ppm。但是,氧亲和力高的Al通过在制钢工序中微量添加可减少钢中的溶解氧量,有望可减少导致特性劣化的氧化物系夹杂物等,因此在抑制磁性劣化方面,添加10ppm以上是有利的。也可以为0ppm。
N:80ppm以下且sol.Al(ppm)-N(ppm)×(26.98/14.00)≤30ppm
本发明是应用无抑制剂的制造方法进行至集合组织的制作,因此N需要抑制为80ppm以下。若N超过80ppm,则由于晶界偏析的影响、微量氮化物的形成,产生集合组织劣化这样的弊病。此外,有时也成为板坯加热时气泡等缺陷的原因,因此N量需要抑制为80ppm以下。优选为60ppm以下。
本发明中,仅将N量抑制为80ppm以下是不充分的,需要以与sol.Al量的关系,控制在sol.Al(ppm)-N(ppm)×(26.98/14.00)≤30ppm的范围。
本发明中具有通过氮化处理而使氮化硅析出的特征,残留了过量的Al时,大多在氮化处理后以(Al、Si)N的形式析出,无法析出纯粹的氮化硅。
然而,将N量控制为与sol.Al量的关系为sol.Al-N×(26.98/14.00)≤0的范围,换言之,若含有相对于所含的Al量作为AlN析出的量以上N,则可能在氮化处理以前将Al作为AlN析出固定,通过氮化处理在钢中追加的N(ΔN)仅用于氮化硅的形成。这里,ΔN是指通过氮化处理在钢中增量的氮。
另一方面,sol.Al-N×(26.98/14.00)的值大于0且为30以下的范围时,为了氮化处理后形成纯粹的氮化硅,需要更过量的氮(ΔN)。
进而,sol.Al-N×(26.98/14.00)的值超过30时,氮化处理时追加的N引起的微细析出的AlN或(Al、Si)N的影响变大,二次再结晶温度变得过高而产生二次再结晶不良,因此sol.Al-N×(26.98/14.00)的值需要抑制为30ppm以下。
以上,对基本成分进行了说明,本发明中,作为工业上稳定地改善磁特性的成分,可以适当含有以下元素。
Ni:0.005~1.50%
Ni具有通过提高热延板组织的均匀性而改善磁特性的作用,因此优选含有0.005%以上,另一方面,若含量超过1.50%则二次再结晶变得困难,磁特性劣化,因此优选在0.005~1.50%的范围含有Ni。
Sn:0.01~0.50%
Sn是抑制二次再结晶退火中的钢板的氮化、氧化,促进具有良好的结晶取向的晶粒的二次再结晶而使磁特性提高的有用元素,因此优选含有0.01%以上,另一方面,若含有超过0.50%则冷轧性劣化,因此优选在0.01~0.50%的范围含有Sn。
Sb:0.005~0.50%
Sb是抑制二次再结晶退火中的钢板的氮化、氧化,促进具有良好的结晶方位的晶粒的二次再结晶而有效地提高磁特性的有用元素,为了该目的,优选含有0.005%以上,另一方面,若含有超过0.5%则冷轧性劣化,因此,优选在0.005~0.50%的范围含有Sb。
Cu:0.01~0.50%
Cu具有抑制二次再结晶退火中的钢板的氧化,促进具有良好的结晶取向的晶粒的二次再结晶而有效地提高磁特性的作用,因此优选含有0.01%以上,另一方面,若含有超过0.50%则导致热轧性的劣化,因此优选在0.01~0.50%的范围含有Cu。
Cr:0.01~1.50%
Cr具有使镁橄榄石被膜的形成稳定化的作用,因此优选含有0.01%以上,另一方面,若含量超过1.50%则二次再结晶变得困难,磁特性劣化,因此,优选在0.01~1.50%的范围含有Cr。
P:0.0050~0.50%
P具有使镁橄榄石被膜的形成稳定化的作用,因此优选含有0.0050%以上,另一方面,若含量超过0.50%则冷轧性劣化,因此,优选在0.0050~0.50%的范围含有P。
Mo:0.01~0.50%、Nb:0.0005~0.0100%
Mo和Nb均具有介由抑制由板坯加热时的温度变化所致的裂纹等而抑制热延后的疤痕的效果。如果它们没有分别含有0.01%以上的Mo、0.0005%以上的Nb,则疤痕抑制的效果较小,另一方面,若Mo超过0.50%、Nb超过0.0100%,则形成碳化物、氮化物等而残留到最终制品中时,引起铁损的劣化,因此优选分别设为上述范围。
接着,对本发明的制造方法进行说明。
将调整至上述优选成分组成范围的钢板坯在不进行再加热或再加热后供给于热轧。应予说明,将板坯再加热时,再加热温度优选设为1000℃~1300℃左右。这是因为超过1300℃的板坯加热在板坯阶段的钢中几乎不含抑制剂的本发明中基本无意义,仅增加了成本,另一方面,小于1000℃时,轧制负荷变高,轧制变得困难。
接下来,根据需要对热延板实施热延板退火后,实施1次冷轧或隔着2次以上中间退火的冷轧,制成最终冷延板。该冷轧可以在常温下进行,也可以设为将钢板温度提升至高于常温的温度例如250℃左右而进行轧制的温轧。
接下来,对最终冷轧板实施一次再结晶退火。
该一次再结晶退火的目的是使具有轧制组织的冷轧板一次再结晶,调整成最适合二次再结晶的一次再晶粒径。因此,一次再结晶退火的退火温度优选设为800℃以上且小于950℃左右。此外,通过将此时的退火气氛设为湿氢氮或湿氢氩气氛,还可以兼作脱碳退火。
进而,在上述的一次再结晶退火前、或退火的中途或退火后实施氮化处理。对于氮化的方法,只要可以控制氮化量即可,没有特别的限定。例如,可以是以往实施的钢圈形态原样下的使用NH3气氛气体进行气体氮化,也可以相对于移动的带钢连续地进行气体氮化。此外,也能够利用与气体氮化相比氮化能力高的盐浴氮化。这里,作为利用盐浴氮化时的盐浴,优选为以氰酸盐为主成分的盐浴。
上述的氮化处理中重要的方面是在表层形成氮化物层。为了抑制扩散至钢中,优选以800℃以下的温度进行氮化处理,通过将时间设为短时间(例如30秒左右),即使更高的温度也可以使氮化物层仅形成于表面。
本发明中,通过上述氮化处理在钢中增量的氮量(ΔN:也称为氮增量)由于与处理前的N量和sol.Al量的关系而不同。
即,N量与sol.Al量满足sol.Al-N×(26.98/14.00)≤0的关系时,可以在事前将钢中N作为AlN析出,因此通过氮化处理增加的氮仅用于不含Al的氮化硅的形成。在这种情况下,利用氮化处理的氮增量(ΔN)设为下式(1)的范围。
50ppm≤ΔN≤1000ppm---(1)
另一方面,N量与sol.Al量满足0<sol.Al-N×(26.98/14.00)≤30的关系时,通过氮化处理增加的N作为与氮化硅相比在热力学上稳定的AlN或固溶有Si的(Al、Si)N析出,因此为了析出适量的氮化硅,需要更过量的氮。具体而言,需要设为满足下式(2)的范围。
(N-sol.Al×14.00/26.98+100)≤ΔN≤
(N-sol.Al×14.00/26.98+1000)---(2)
氮增量(ΔN)小于(1)、(2)式的下限值时,无法充分得到其效果,另一方面,若超过上限值,则氮化硅的析出量变得过多,难以产生二次再结晶。
另外,氮化处理在一次再结晶退火前、退火中、退火后均可应用,有时以最终冷轧前的退火将一部分AlN固溶,在存在sol.Al的状态下冷却,因此若在一次再结晶退火前应用,则有时由于残留的sol.Al的影响析出状态成为与理想状态不同的状况。因此,优选的是再次将固溶Al作为AlN析出的一次再结晶退火升热后的时机,即,在一次再结晶退火中或退火后进行氮化处理可以控制稳定的析出。
实施上述一次再结晶退火和氮化处理后,在钢板表面涂布退火分离剂。为了在二次再结晶退火后的钢板表面形成镁橄榄石被膜,需要将退火分离剂的主剂设为氧化镁(MgO),无需镁橄榄石被膜的形成时,作为退火分离剂主剂,可以使用氧化铝(Al2O3)、氧化钙(CaO)等具有高于二次再结晶退火温度的熔点的适当的氧化物。
随后进行二次再结晶退火。该二次再结晶退火中,需要将升温过程的300~800℃的温度区域中的滞留时间设为5小时~150小时。在此期间表层的氮化物层分解,N扩散至钢中。本发明的成分***中未残留可形成AlN的Al,因此作为晶界偏析元素的N以晶界为扩散路径,扩散至钢中。
氮化硅与钢的晶格的整合性差(misfit率较大),因此析出速度极慢。然而,氮化硅的析出是以抑制正常晶粒生长为目的,因此在进行正常晶粒生长的800℃的阶段需要使足够的量选择性地析出于晶界上。对于该方面,通过将300~800℃的温度区域中的滞留时间设为5小时以上,虽然无法使氮化硅在晶粒内析出,但可以与从晶界扩散而来的N结合,选择性地析出于晶界上。对滞留时间的上限不必一定设置,但即使进行超过150小时的退火效果也不会提高,因此,本发明中将150小时设为上限值。应予说明,退火气氛适合N2,Ar,H2或它们的混合气体中的任一者。
如上所述,抑制钢中的Al量且抑制利用氮化处理的AlN或(Al、Si)N的析出,此外,相对于几乎不含以MnS、MnSe等为代表的抑制剂成分的板坯,经过上述工序制造的方向性电磁钢板在二次再结晶退火的升温过程中、直至二次再结晶开始的阶段中,可以使与以往抑制剂相比粗大的尺寸(100nm以上)的氮化硅在晶界上选择性地析出。另外,对氮化硅的粒径的上限值没有特别的限制,优选设为5μm以下。
图1(a)、(b)是将在脱碳退火后分别进行成为100ppm、500ppm的氮增量的氮化处理,以300~800℃的温度区域中的滞留时间为8小时的升温速度升温至800℃后,立即进行水冷的组织利用电子显微镜观察、鉴定而成的图。此外,图1(c)是表示利用上述组织中的析出物的EDX(能量分散型X射线分光法)的鉴定结果的图。
由图1可明确,与以往使用的微细析出物(<100nm)不同,最小也超过100nm的粗大的氮化硅被确认在晶界上析出。
此外,作为钢成分,使用以Si:3.2%、sol.Al<5ppm、N:10ppm熔炼的钢块A以及以Si:3.2%、sol.Al:150ppm、N:10ppm熔炼的钢块B,在实验室对实施至兼作脱碳的一次再结晶退火的试样利用NH3-N2混合气体,进行氮增量成为200ppm的气体氮化处理。对于如此得到的氮化处理后的试样,使用电子显微镜观察其组织。其后,通过与二次再结晶退火同样的加热模式将氮化处理后的试样升温至800℃后,对于水冷而得到的试样,使用电子显微镜观察其组织。
将观察结果示于图2。图2中,A-1、B-1为钢块A、B的氮化处理后的电子显微镜照片,A-2、B-2为钢块A、B的升温后的电子显微镜照片。
可知不含Al的钢块A在氮化处理后(A-1)几乎没有析出物,在升温·水冷后(A-2),在晶界Si3N4以100nm以上的粒径析出。另一方面,含有Al的钢块B在氮化处理后(B-1)与钢块A同样,几乎没有确认到析出物,但升温后(B-2)在晶粒内观察到以往型的(Al、Si)N析出的样子。
在作为本发明的特征的利用不是与Al的复合析出的纯粹的氮化硅的方面,在钢中以数%的等级存在且有效地活用对铁损改善具有效果的Si的方面具有极高的稳定性。即,目前为止的技术中使用的Al、Ti这样的成分是与氮的亲和力较高、在高温下也稳定的析出物,因此有可能最终容易残留于钢中,且由于残留而成为使磁特性劣化的主要原因。
然而,利用氮化硅时,仅通过提纯扩散相对较早的氮就可达成对磁特性有害的析出物的提纯。此外,对于Al、Ti,从最终必须提纯的观点以及必须可靠地得到抑制剂效果的观点出发,需要ppm等级的控制,但利用Si时,在制钢时无需这样的控制也是本发明的重要特征。
另外,毫无疑问在制造上在氮化硅的析出中利用二次再结晶升温过程是在能量效率上最有效的,但若利用同样的热循环则有可能氮化硅的晶界选择析出,因此在长时间的二次再结晶退火之前,也可以通过氮化硅分散退火的方式实施而制造。
上述二次再结晶退火后,也可以在钢板表面进一步涂布、烧结绝缘被膜。对于该绝缘被膜的种类,没有特别的限定,以往公知的所有绝缘被膜是适合的。例如,优选将日本特开昭50-79442号公报、日本特开昭48-39338号公报中记载的含有磷酸盐-铬酸盐-胶体二氧化硅的涂布液涂布于钢板,在800℃左右烧结的方法。
此外,也能够通过平坦化退火调整钢板的形状,进而也可以将该平坦化退火兼作绝缘被膜的烧结处理。
实施例
(实施例1)
将含有C:0.06%、Si:3.3%、Mn:0.08%、S:0.001%、Se:5ppm以下、O:11ppm、Cu:0.05%和Sb:0.01%,且以表1所示的比例含有Al和N,剩余部分由Fe和不可避免的杂质构成的钢板坯,以1100℃加热30分钟后,通过热轧制成2.2mm厚的热延板,实施1000℃、1分钟的退火后,通过冷轧制成0.23mm的最终板厚,接下来,从所得的冷轧钢圈的中央部提取100mm×400mm尺寸的试样,在实验室进行兼作一次再结晶和脱碳的退火。对于一部分试样,进行兼作一次再结晶退火、脱碳和氮化(连续氮化处理:利用NH3和N2、H2的混合气体的氮化处理)的退火。其后,对不实施氮化的试样,在表1所示的条件下进行氮化处理(间歇处理:利用使用以氰酸盐为主成分的盐的盐浴的氮化处理、以及利用NH3和N2的混合气体的氮化处理),使钢中氮量增加。氮量是对以总厚为对象的试样,以及用砂纸削掉表层(两面)各3μm,以除去了表层的试样作为对象的试样分别通过化学分析进行定量。
对于相同条件的钢板,每一个条件各制作21张,将以MgO为主成分且含有5%的TiO2的退火分离剂制成水浆状后进行涂布干燥,烧结于钢板上。对其中20张进行最终退火,接下来,涂布烧结磷酸盐系的绝缘张力涂层而制成制品。
对于所得的制品,评价磁化力:800A/m下的磁束密度B8(T)。磁特性以各条件20张的平均值进行评价。此外,对于剩余的1张,在最终退火和以相同加热模式升温至800℃后,取出试样,对于直接水淬的试样,通过电子显微镜观察组织中的氮化硅,测定50个氮化硅的平均粒径。
如表1所示,明确了发明例与通过无抑制剂的制造工序制造的例子相比改善了磁特性。
(实施例2)
将含有表2所示的成分的钢板坯(其中,S、Se、O含量均小于50ppm)以1200℃加热20分钟后,通过热轧制成2.0mm厚的热延板,在1000℃、1分钟退火后,通过冷轧进行直至板厚:1.5mm为止的冷轧后,在1100℃、进行2分钟的中间退火后,通过以下所示的冷轧制成0.27mm的最终板厚后,进行在P(H2O)/P(H2)=0.3的气氛下在退火温度:820℃的条件下保持2分钟的脱碳退火。其后,使对一部分钢圈以间歇处理进行氮化处理(NH3气氛下)的钢中N量增量70ppm或550ppm后,涂布将以MgO为主成分且添加了10%的TiO2的退火分离剂与水混合而制成糊状的糊状物后,缠绕于钢圈,以300~800℃间的滞留时间为30小时的升温速度进行最终退火,接下来,以磷酸盐系的绝缘张力涂层的涂布烧结和钢带的平坦化为目的实施平坦化退火而制成制品。
从如此得到的制品钢圈提取Epstein试验片,测定磁束密度B8,将其结果示于表2。
由表2可明确地知道按照本发明而得到的发明例均可得到高磁束密度。
Claims (2)
1.一种方向性电磁钢板的制造方法,其中,将以质量%或质量ppm计含有C:0.08%以下、Si:2.0~4.5%和Mn:0.5%以下,并且将S、Se和O抑制为分别小于50ppm,将sol.Al抑制为小于100ppm,进一步将N控制为60ppm以下且满足sol.Al(ppm)-N(ppm)×(26.98/14.00)≤30ppm的范围,剩余部分由Fe和不可避免的杂质的组成构成的钢板坯,在不进行再加热或再加热后,实施热轧而制成热延板后,通过退火和轧制,制成最终板厚的冷轧板,接下来,在一次再结晶退火前或退火中或退火后,实施氮增量ΔN以下述式(1)或式(2)规定的氮化处理而在所述冷轧板的表层形成氮化物层,涂布含有MgO的退火分离剂,进而实施升温过程的300~800℃的温度区域中的滞留时间为5小时~150小时的二次再结晶退火,将所述氮化物层分解,以晶界为扩散路径使N扩散于钢板基体中,使粒径为100nm以上的不含Al的氮化硅在晶界上析出,从而作为正常晶粒生长抑制力使用,
·sol.Al-N×(26.98/14.00)≤0时,
50ppm≤ΔN≤1000ppm---(1),
·0<sol.Al-N×(26.98/14.00)≤30时,
(N-sol.Al×14.00/26.98+100)≤ΔN≤
(N-sol.Al×14.00/26.98+1000)---(2)。
2.如权利要求1所述的方向性电磁钢板的制造方法,其中,所述钢板坯以质量%计进一步含有选自
Ni:0.005~1.50%、Sn:0.01~0.50%、
Sb:0.005~0.50%、Cu:0.01~0.50%、
Cr:0.01~1.50%、P:0.0050~0.50%、
Mo:0.01~0.50%和Nb:0.0005~0.0100%
中的1种或2种以上。
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