CN112534083B - 绝缘被膜处理液、带有绝缘被膜的取向性电磁钢板及其制造方法 - Google Patents
绝缘被膜处理液、带有绝缘被膜的取向性电磁钢板及其制造方法 Download PDFInfo
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- CN112534083B CN112534083B CN201980050436.2A CN201980050436A CN112534083B CN 112534083 B CN112534083 B CN 112534083B CN 201980050436 A CN201980050436 A CN 201980050436A CN 112534083 B CN112534083 B CN 112534083B
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- insulating film
- steel sheet
- treatment liquid
- metal element
- oriented electrical
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- 239000007788 liquid Substances 0.000 title claims abstract description 101
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000576 coating method Methods 0.000 claims abstract description 109
- 239000011248 coating agent Substances 0.000 claims abstract description 106
- 239000002245 particle Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 30
- 235000021317 phosphate Nutrition 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008119 colloidal silica Substances 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002923 metal particle Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims description 21
- 239000003093 cationic surfactant Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 43
- 229910000831 Steel Inorganic materials 0.000 abstract description 35
- 239000010959 steel Substances 0.000 abstract description 35
- 230000007547 defect Effects 0.000 abstract description 32
- 238000010521 absorption reaction Methods 0.000 abstract description 22
- 229910052742 iron Inorganic materials 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 19
- 239000011572 manganese Substances 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 238000000137 annealing Methods 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000011669 selenium Substances 0.000 description 9
- 229910052711 selenium Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- -1 zirconium phosphate compound Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- AMTPYFGPPVFBBI-UHFFFAOYSA-N acedapsone Chemical compound C1=CC(NC(=O)C)=CC=C1S(=O)(=O)C1=CC=C(NC(C)=O)C=C1 AMTPYFGPPVFBBI-UHFFFAOYSA-N 0.000 description 1
- 229950009438 acedapsone Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/20—Orthophosphates containing aluminium cations
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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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
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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
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
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- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
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Abstract
本发明提供一种绝缘被膜处理液,其能够形成耐吸湿性优异、可赋予高张力、铁损降低效果优异的无铬绝缘被膜,而且能够抑制因涂布于钢板时产生的涂布不均所导致的外观不良。所述绝缘被膜处理液用于在取向性电磁钢板的表面形成无铬绝缘被膜,所述绝缘被膜处理液含有:选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐;胶体状二氧化硅;以及包含金属元素的化合物的粒子,相对于所述磷酸盐100质量份,所述胶体状二氧化硅的含量以SiO2固体成分换算计为50~120质量份,且所述包含金属元素的化合物的粒子的含量以金属元素换算计为5~60质量份,所述绝缘被膜处理液的触变指数(TI)为1.00以上且10.00以下。
Description
技术领域
本发明涉及用于在取向性电磁钢板的表面形成无铬绝缘被膜的绝缘被膜处理液。另外,本发明涉及在表面具备将上述绝缘被膜处理液烧结而成的绝缘被膜的带有绝缘被膜的取向性电磁钢板及其制造方法。
背景技术
通常,对于取向性电磁钢板,为了赋予绝缘性、耐烧结性和防锈性等而在表面设置被膜。上述表面被膜包含在最终退火时形成的以镁橄榄石作为主体的基底被膜、以及在其上形成的磷酸盐系的表面涂被膜。
这些被膜在高温下形成,而且具有低热膨胀率。因此,这些被膜降低至室温时,由于钢板与被膜的热膨胀率的差异而对钢板赋予张力,具有降低铁损的效果。因此,对于上述被膜,期望对钢板赋予尽可能高的张力。
为了满足这样的要求,一直以来提出了各种被膜。例如,专利文献1中提出了以磷酸镁、胶体状二氧化硅及铬酸酐作为主体的被膜。另外,专利文献2中提出了以磷酸铝、胶体状二氧化硅及铬酸酐作为主体的被膜。
另一方面,由于近些年对保护环境的关注度的提高,对不含铬、铅等有害物质的产品的需求日益增高,对于取向性电磁钢板而言,也期望开发出无铬(不含铬的)被膜。然而,在无铬被膜的情况下,会发生显著的耐吸湿性降低、张力赋予不足的问题,因此难以实现无铬。
作为解决上述问题的方法,专利文献3中提出了含有磷酸二氢盐、胶体状二氧化硅及氧化物胶体的表面处理剂。专利文献4中提出了含有磷酸盐、胶体状二氧化硅及磷酸锆类化合物微粒的绝缘被膜处理液。专利文献5中提出了张力被膜中具有Ti、Zr、Hf的化合物的取向性电磁钢板。另外,专利文献6中提出了包含高杨氏模量的填充剂粒子的绝缘涂层。
根据这些提案可知,尽管耐吸湿性、赋予张力带来的铁损降低效果、耐烧结性等得到了改善,但特别是在提高钢板的输送速度并用辊涂机涂布绝缘被膜处理液的高速辊涂中,有时在涂布绝缘被膜处理液并进行烧结后显著发生出现外观不良的问题。
现有技术文献
专利文献
专利文献1:日本特开昭50-79442号公报
专利文献2:日本特开昭48-39338号公报
专利文献3:日本特开2000-169972号公报
专利文献4:日本特开2017-137540号公报
专利文献5:日本特开2008-266743号公报
专利文献6:日本特表2017-511840号公报
发明内容
发明所要解决的课题
本发明是鉴于上述实际情况而完成的,其目的在于提供一种绝缘被膜处理液,所述绝缘被膜处理液能够形成耐吸湿性优异,可赋予高张力、铁损降低效果优异的无铬绝缘被膜,而且能够抑制涂布于钢板并进行烧结后的外观不良。另外,本发明的目的在于提供在表面具备将上述绝缘被膜处理液烧结而成的绝缘被膜的带有绝缘被膜的取向性电磁钢板及其制造方法。
用于解决课题的方法
为了解决上述课题,本发明人等对涂布、烧结后产生外观不良的原因进行了深入研究。
如本发明这样含有粒子的液体(分散液)的剪切速度依赖于粘度,是所谓的非牛顿流体。即,在低剪切速度范围内粘度高,在高剪切速度范围内粘度低。
带有绝缘被膜的取向性电磁钢板通常使用辊涂机将绝缘被膜处理液涂布于钢板表面后进行烧结而制造。此时,在将绝缘被膜处理液涂布于钢板表面时,该绝缘被膜处理液在高剪切速度下的粘度变得重要,在涂布后至烧结的期间的流平时,该绝缘被膜处理液在低剪切速度下的粘度变得重要。
在高剪切速度下的绝缘被膜处理液的粘度高时,钢板与辊之间的液面变得不稳定而容易产生被称为棱纹缺陷(ribbing defect)的条纹状的缺陷。
另一方面,由涂布产生的棱纹缺陷等涂布不均只要能够通过直至烧结为止的期间的流平而实现均匀化即可,可以避免烧结后出现外观不良,因此,为了促进流平,重要的是绝缘被膜处理液的粘度低。由此,为了使涂布、烧结后的外观变得良好,除了改善涂布不均以外,改善流平也是有效的。
众所周知,在任意情况下,绝缘被膜处理液的粘度在高剪切速度下当然需要低,而且在低剪切速度下也需要足够低。
然而,在绝缘被膜处理液的粘度的剪切速度依赖性大的情况下,在由于绝缘被膜生产线的速度变动而导致偏离适合涂布条件时,有时在涂布绝缘被膜处理液后发生涂布不均,在流平不充分的状况下被烧结,导致外观变得不良。为了防止该情况,已知重要的是将绝缘被膜处理液的粘度的剪切速度依赖性保持为一定水平以下。
即,本发明的主旨构成如下。
[1]一种绝缘被膜处理液,其用于在取向性电磁钢板的表面形成无铬绝缘被膜,
所述绝缘被膜处理液含有:
选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐;
胶体状二氧化硅;以及
包含金属元素的化合物的粒子,
相对于所述磷酸盐100质量份,所述胶体状二氧化硅的含量以SiO2固体成分换算计为50~120质量份,且所述包含金属元素的化合物的粒子的含量以金属元素换算计为5~60质量份,
所述绝缘被膜处理液的触变指数(TI)为1.00以上且10.00以下。
[2]根据[1]所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子为选自Ti、Zr、Hf、V、Mg、Zn、Nb的氧化物的粒子、Ti、Zr、Hf、V、Mg、Zn、Nb的氮化物的粒子中的一种或两种以上。
[3]根据[1]或[2]所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子为选自TiO2、ZrO2、HfO2、MgO、ZnO、Nb2O5、V2O5、TiN、ZrN的粒子中的一种或两种以上。
[4]根据[1]~[3]中任一项所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子的粒径为0.05μm以上且1.0μm以下。
[5]根据[1]~[4]中任一项所述的绝缘被膜处理液,其还含有阳离子型表面活性剂。
[6]根据[5]所述的绝缘被膜处理液,其中,阳离子型表面活性剂为季铵盐型阳离子型表面活性剂。
[7]根据[5]或[6]所述的绝缘被膜处理液,其中,相对于选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐100质量份,阳离子型表面活性剂的含量为0.20~2.0质量份。
[8]一种带有绝缘被膜的取向性电磁钢板,其在表面具备绝缘被膜,所述绝缘被膜是将[1]~[7]中任一项所述的绝缘被膜处理液烧结而成的。
[9]一种带有绝缘被膜的取向性电磁钢板的制造方法,该方法包括:在取向性电磁钢板的表面涂布[1]~[7]中任一项所述的绝缘被膜处理液后,进行烧结。
[10]根据[9]所述的带有绝缘被膜的取向性电磁钢板的制造方法,其中,在将绝缘被膜处理液涂布于取向性电磁钢板的表面时,一边输送所述取向性电磁钢板,一边使用辊涂机将所述绝缘被膜处理液涂布于所述取向性电磁钢板的表面。
发明效果
根据本发明,可以提供一种绝缘被膜处理液,其能够形成耐吸湿性优异,可赋予高张力、铁损降低效果优异的无铬绝缘被膜,而且能够抑制涂布于钢板进行烧结后的外观不良。
根据本发明的绝缘被膜处理液,即使在实施高速辊涂的情况下、在绝缘被膜的生产线中发生速度变动的情况下,也能够抑制涂布绝缘被膜处理液并进行烧结后的外观不良。
另外,涂布上述绝缘被膜处理液并进行烧结而成的带有绝缘被膜的取向性电磁钢板的耐吸湿性、铁损降低效果优异,而且具备绝缘被膜处理液的涂布不均痕迹受到了抑制的均匀且美观的表面外观。
具体实施方式
以下,对本发明的各构成条件的限定理由进行说明。
本发明中成为对象的钢板只要是取向性电磁钢板即可,可以是任何的钢种类。作为一个例子,取向性电磁钢板优选利用例如以下所示的方法来制造。
首先,对优选的钢的成分组成进行说明。以下,只要没有特别声明,则表示各元素的含量的%是指质量%。
C:0.001~0.10%
C(碳)是对产生高斯(Goss)位向晶粒有用的成分,为了有效地发挥上述作用,C含量优选为0.001%以上。另一方面,C含量超过0.10%时,有时通过脱碳退火而发生脱碳不良。因此,C含量优选为0.001~0.10%的范围。
Si:1.0~5.0%
Si(硅)是为了提高电阻而使铁损降低、且使铁的BCC组织稳定而可进行高温的热处理所需要的成分,Si含量优选为1.0%以上。另一方面,Si含量超过5.0%时,难以进行冷轧。因此,Si含量优选为1.0~5.0%的范围。Si含量更优选为2.0~5.0%的范围。
Mn:0.01~1.0%
Mn(锰)不仅有效地有助于改善钢的热脆性,在混合存在S、Se的情况下,形成MnS、MnSe等析出物而发挥作为晶粒生长的抑制剂的功能,因此Mn含量优选为0.01%以上。另一方面,Mn含量超过1.0%时,MnSe等析出物的粒径粗大化,有时会失去作为抑制剂的效果。因此,Mn含量优选为0.01~1.0%的范围。
sol.Al:0.003~0.050%
Al(铝)是在钢中形成AlN、并作为分散第二相而发挥抑制剂的作用的有用成分,因此,以sol.Al计优选含有0.003%以上。另一方面,Al含量以sol.Al计含有超过0.050%时,粗大地析出AlN,有时失去作为抑制剂的作用。因此,Al含量以sol.Al计优选为0.003~0.050%的范围。
N:0.001~0.020%
N(氮)也与Al同样地是形成AlN所需要的成分,因此N含量优选为0.001%以上。另一方面,N含量超过0.020%时,在板坯加热时有时发生起泡等。因此,N含量优选0.001~0.020%的范围。
选自S及Se中的一种或两种的总计:0.001~0.05%
S(硫)、Se(硒)是与Mn、Cu结合而形成MnSe、MnS、Cu2-xSe、Cu2-xS、并作为钢中的分散第二相而发挥抑制剂的作用的有用成分,因此S、Se中的一种或两种的总含量优选为0.001%以上。另一方面,S、Se中的一种或两种的总含量超过0.05%时,不仅板坯加热时的固溶变得不完全,而且有时也成为产品表面缺陷的原因。因此,对于S、Se的含量而言,在含有S或Se中的1种的情况、含有S和Se这两种的情况下,总计均优选为0.001~0.05%的范围。
优选将以上成分作为钢的基本成分。另外,除上述以外的余量可以设为Fe及不可避免的杂质的成分组成。
另外,上述成分组成中可以进一步添加选自Cu:0.01~0.2%、Ni:0.01~0.5%、Cr:0.01~0.5%、Sb:0.01~0.1%、Sn:0.01~0.5%、Mo:0.01~0.5%、Bi:0.001~0.1%中的一种或两种以上。通过添加具有作为辅助性抑制剂的作用的元素,能够进一步改善磁性。作为这样的元素,可列举出易于在晶体粒径、表面发生偏析的上述元素。通过将上述任意元素设为上述含量的下限以上,可以获得有用的效果。另外,在超过上述含量的上限时,变得容易发生二次再结晶不良,因此优选为上述范围。
此外,除了上述成分以外,还可以含有选自B:0.001~0.01%、Ge:0.001~0.1%、As:0.005~0.1%、P:0.005~0.1%、Te:0.005~0.1%、Nb:0.005~0.1%、Ti:0.005~0.1%、V:0.005~0.1%中的一种或两种以上。通过含有这些成分中的一种或两种以上,晶粒生长的抑制力进一步增强,能够稳定地获得更高的磁通密度。
接着,对带有绝缘被膜的取向性电磁钢板的制造方法进行说明。
利用现有公知的精炼工艺对具有上述说明的成分组成的钢进行熔炼,使用连续铸造法或铸锭-开坯轧制法制成钢原材料(钢板坯),然后,将上述钢板坯热轧而制成热轧板,根据需要实施了热轧板退火后,实施一次或其间夹有中间退火的2次以上的冷轧而制成最终板厚的冷轧板。然后,在实施了一次再结晶退火和脱碳退火后,涂布以MgO作为主成分的退火分离剂并实施最终退火,形成了以镁橄榄石作为主体的被膜层,然后,为了形成玻璃质的绝缘被膜,涂布绝缘被膜处理液,并根据需要实施了干燥处理后,经过兼具烧结的平坦化退火,通过包含上述一系列工序的制造方法,可以制造带有绝缘被膜的取向性电磁钢板。
本发明的绝缘被膜处理液含有:选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐;胶体状二氧化硅;以及包含金属元素的化合物的粒子。作为上述处理液的溶剂,优选为水。
对于绝缘被膜处理液,首先,作为磷酸盐,使用选自Mg、Ca、Ba、Sr、Zn、Al及Mn的磷酸盐中一种或两种以上。碱金属(Li、Na等)的磷酸盐的耐吸湿性非常差,因此是不适合的。通常使用上述磷酸盐中的任意1种,还可以混合两种以上来使用。通过将上述磷酸盐混合两种以上来使用,能够精确地控制绝缘被膜(涂覆)的物性值。作为磷酸盐的种类,磷酸二氢盐(dihydrogen phosphate salt)获得容易,因此是适合的。
相对于选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐100质量份,胶体状二氧化硅以SiO2固体成分换算计含有50~120质量份。相对于上述磷酸盐100质量份,胶体状二氧化硅的含量以SiO2固体成分换算计低于50质量份时,涂覆的热膨胀系数降低效果减小,对钢板赋予的张力降低,因此无法获得由形成绝缘被膜(张力被膜)所带来的铁损改善效果。另外,相对于上述磷酸盐100质量份,胶体状二氧化硅的含量以SiO2固体成分换算计多于120质量份时,涂覆的耐吸湿性变差。相对于上述磷酸盐100质量份,胶体状二氧化硅的含量以SiO2固体成分换算计优选为60质量份以上。另外,相对于上述磷酸盐100质量份,胶体状二氧化硅的含量以SiO2固体成分换算计优选为100质量份以下。
为了改善因不含铬而变差的耐吸湿性、被膜张力、耐腐蚀性等,含有包含金属元素的化合物的粒子。相对于选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐100质量份,包含金属元素的化合物的粒子以金属元素换算计含有5质量份~60质量份。相对上述磷酸盐100质量份,包含金属元素的化合物的粒子的含量以金属元素换算计少于5质量份时,耐吸湿性、被膜张力、耐腐蚀性不足。另一方面,相对于上述磷酸盐100质量份,包含金属元素的化合物的粒子的含量以金属元素换算计多于60质量份时,绝缘被膜处理液的粘度增高而难以形成没有因涂布不均所导致的外观不良的均匀的被膜。相对于上述磷酸盐100质量份,包含金属元素的化合物的粒子的含量以金属元素换算计优选为10质量份以上。另外,相对上述磷酸盐100质量份,包含金属元素的化合物的粒子的含量以金属元素换算计优选为40质量份以下。
作为包含金属元素的化合物的金属元素,从改善耐吸湿性的方面考虑,优选为Ti、Zr、Hf、V、Mg、Zn及Nb,作为化合物的形态,优选为氧化物、氮化物。
作为包含金属元素的化合物的粒子,优选为选自TiO2、ZrO2、HfO2、MgO、ZnO、Nb2O5、V2O5、TiN、ZrN的粒子中的一种或两种以上。
通过使用这些粒子,易于进一步提高被膜张力、耐腐蚀性。
本发明的绝缘被膜处理液以粒子(微粒)的形态含有上述包含金属元素的化合物。从改善被膜张力的方面考虑,包含金属元素的化合物的粒子的粒径优选为0.05μm以上且1.0μm以下。包含金属元素的化合物的粒子的粒径更优选为0.10μm以上。另外,包含金属元素的化合物的粒子的粒径更优选为0.80μm以下。这里,粒径是绝缘被膜处理液中的粒子(在粒子凝聚的情况下为次级粒子(凝聚粒子))的平均粒径,是利用激光衍射法测得的值。平均粒径是以体积基准计50%粒径,即中值粒径(d50)。
本发明的绝缘被膜处理液的触变指数(TI)为1.00以上且10.00以下。
上述触变指数(TI)是使用JIS Z 8803的单圆筒型旋转粘度计、所谓的B型粘度计进行测定,并根据液体温度20℃、转速6rpm时的粘度η(L)[mPa·s]和转速60rpm时的粘度η(H)[mPa·s],通过下述式(1)计算出的值。优选此时使用的转子(spindle)在6rpm的测定和60rpm的测定中不改变。
TI=η(L)/η(H)···(1)
TI值为1.00表示绝缘被膜处理液为牛顿流体,且表示不具有粘度的剪切速度依赖性。如果TI低于1.00,则提高剪切速度时粘度增加,非常容易出现棱纹缺陷,因此是不适合的。另一方面,如果TI大于10.00,则剪切速度降低时的粘度上升率变得过大,因此流平变得不充分,涂布、烧结后无法得到均匀的表面。在实施高速辊涂的情况下、在绝缘被膜的生产线中发生速度变动的情况下,该倾向变得显著。TI优选为1.00以上且8.00以下。Ti更优选为1.20以上。另外,Ti更优选为6.00以下。
需要说明的是,上述η(L)没有特别限定,优选为2.0~60.0mPa·s。另外,上述η(H)没有特别限定,优选为2.0~30.0mPa·s。
作为将触变指数(TI)控制在适合的范围的方法,可列举出如下方法:改变绝缘被膜处理液的pH的方法、通过表面处理来控制胶体状二氧化硅的表面电荷的方法等各种方法。作为改变绝缘被膜处理液的pH的方法,例如可列举出在绝缘被膜处理液中添加无机酸等的方法。其中,作为对绝缘被膜的特性产生的影响最小的方法,优选为在绝缘被膜处理液中添加少量的分散剂来控制TI的方法。
作为分散剂的种类,有离子型表面活性剂、非离子型表面活性剂等各个种类,在本发明中,优选添加阳离子型表面活性剂。作为其理由,可以认为是是由于在绝缘被膜处理液中,包含金属元素的化合物的粒子的表面带有负电,阳离子型的表面活性剂容易吸附于该表面。在阳离子型表面活性剂中,季铵盐型的表面活性剂的发泡性低,最优选用作本发明的绝缘被膜处理液用途。分散剂的含量根据各成分的混合比率而不同,相对于选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐100质量份,优选为0.20质量份以上且2.0质量份以下。相对于上述磷酸盐100质量份,分散剂的含量更优选为0.25质量份以上。另外,相对于上述磷酸盐100质量份,分散剂的含量更优选为1.5质量份以下。需要说明的是,在用溶剂稀释了分散剂的情况下,上述分散剂的质量份是指不包含溶剂的量。
作为本发明的带有绝缘被膜的取向性电磁钢板的制造方法,可列举出:将上述绝缘被膜处理液涂布于取向性电磁钢板的表面,根据需要在干燥后进行烧结的制造方法。在将上述绝缘被膜处理液涂布于取向性电磁钢板的表面时,优选一边输送上述取向性电磁钢板,一边使用辊涂机将上述绝缘被膜处理液涂布于上述取向性电磁钢板的表面。根据本发明,在实施高速辊涂的情况下、在绝缘被膜的生产线中发生速度变动的情况下,也能够抑制涂布绝缘被膜处理液并进行烧结后的外观不良。作为上述高速辊涂,例如可列举出:将绝缘被膜处理液涂布于取向性电磁钢板的表面时的上述钢板的输送速度为180mpm(米/分)以上的制造条件。
另外,作为上述速度变动,例如可列举出:在将绝缘被膜处理液涂布于取向性电磁钢板的表面的生产线中上述钢板的输送速度的最高速度与最低速度之差为50mpm以上的制造条件。
本发明的带有绝缘被膜的取向性电磁钢板在两面具备绝缘被膜,所述绝缘被膜是将上述绝缘被膜处理液涂布于钢板的表面、并在根据需要干燥后进行烧结而形成的。通过使本发明的带有绝缘被膜的取向性电磁钢板具备上述绝缘被膜,耐吸湿性、铁损降低效果优异,并且具有因绝缘被膜处理液的涂布不均而导致的凹凸受到抑制的均匀且美观的表面外观。
本发明的带有绝缘被膜的取向性电磁钢板的铁损优选为0.88W/kg以下。另外,在本发明的带有绝缘被膜的取向性电磁钢板中,通过绝缘被膜赋予至取向性电磁钢板的张力(被膜张力)优选为10.0MPa以上。另外,本发明的带有绝缘被膜的取向性电磁钢板优选具有磷溶出量为100[μg/150cm2]以下的耐吸湿性。需要说明的是,上述铁损、赋予张力、耐吸湿性的测定方法如以下的实施例中的记载所述。
实施例
(实施例1)
准备了板厚0.20mm的经最终退火的取向性电磁钢板。该取向性电磁钢板的磁通密度B8为1.920T。对该取向性电磁钢板进行磷酸酸洗后,以烧结后的两面总计为8.0g/m2的方式涂布了表1中记载的各种无铬绝缘被膜处理液。此时,使用辊涂机以120mpm和240mpm这两个水平的输送速度输送取向性电磁钢板并涂布上述绝缘被膜处理液。然后,在820℃、30秒、N2:100vol%气体氛围的条件下进行烧结处理,制造了带有绝缘被膜的取向性电磁钢板。
表1中,作为磷酸盐,使用了各自的磷酸二氢盐水溶液,作为胶体状二氧化硅,使用了日产化学株式会社制造的SNOWTEX C。其含量均表示固体成分换算后的值。
作为包含金属元素的化合物的粒子,使用了TiO2、ZrO2、HfO2、Nb2O5、V2O5、MgO、ZnO。粒径均为0.1~0.8μm的范围。绝缘被膜处理液中的包含金属元素的化合物的粒径通过株式会社岛津制作所制造的激光衍射式粒度分布测定装置SALD-3100进行测定。粒径表示平均粒径,表示以体积基准计50%粒径、即中值粒径。另外,包含金属元素的化合物的粒子的含量表示以金属元素计进行了固体成分换算后的值。
作为用作分散剂的表面活性剂,使用了花王株式会社制造的QUARTAMIN 24P(季铵盐型阳离子型表面活性剂),以不含溶剂的量表示其含量。
绝缘被膜处理液的比重使用纯水调整为1.180。
利用以下的方法进行了绝缘被膜处理液的粘度测定、绝缘被膜处理液涂布、烧结后的表面的外观的评价、带有绝缘被膜的取向性电磁钢板的铁损、赋予张力及耐吸湿性的评价。将结果示于表1。
(绝缘被膜处理液的粘度)
对于被膜处理液的粘度,通过东机产业株式会社制造的B型粘度计并使用No.1转子测定了液体温度20℃、转速6rpm时的粘度η(L)及转速60rpm时的粘度η(H)。然后,根据下述式(1)计算出触变指数(TI)。
TI=η(L)/η(H)···(1)
(绝缘被膜处理液涂布、烧结后的表面外观)
使用辊涂机以120mpm和240mpm这两个水平的输送速度输送取向性电磁钢板并涂布绝缘被膜处理液、进行烧结,然后,通过肉眼观察表面的状态,如下所述进行了评价。以下的评价中将○作为合格。
两个条件(120mpm、240mpm)下无棱纹缺陷:○
任意一个条件下有棱纹缺陷:△120或△240(△120是指在120mpm的条件下产生了棱纹缺陷,△240是指在240mpm的条件下产生了棱纹缺陷)
在两个条件下有棱纹缺陷:×
(铁损)
对于铁损(W17/50),利用JIS C 2550中规定的方法,使用由带有绝缘被膜的取向性电磁钢板制作的宽度30mm×长度280mm的试验片进行了测定。将铁损(W17/50)为0.88W/kg以下作为合格。
(赋予张力)
对于对钢板赋予的张力(被膜张力),设为轧制方向的张力,用粘合胶带遮蔽由带有绝缘被膜的取向性电磁钢板制作的与轧制成直角方向的长度30mm×轧制方向长度280mm的试验片的一面,然后,使用碱、酸等去除另一面的绝缘被膜,接着,固定上述试验片的一端30mm,以试验片250mm的部分作为测定长度,测定翘曲量,根据下式求出。需要说明的是,钢板杨氏模量为132GPa。将赋予张力为10.0MPa以上作为合格。
对钢板赋予的张力(MPa)=钢板杨氏模量(GPa)×板厚(mm)×翘曲量(mm)÷(翘曲测定长度(mm))2×103
(耐吸湿性)
对于耐吸湿性,将3张由带有绝缘被膜的取向性电磁钢板制作的50mm×50mm的试验片在100℃的蒸馏水中浸渍煮沸5分钟,由此使磷从绝缘被膜表面溶出,通过ICP发射光谱分析对其溶出量[μg/150cm2]进行定量分析,进行了测定、评价。将磷溶出量为100[μg/150cm2]以下作为合格。
如表1所示,通过使用本发明的绝缘被膜处理液,能够形成耐吸湿性优异,可赋予高张力、铁损降低效果优异的无铬绝缘被膜,而且能够抑制因涂布于钢板时产生的涂布不均所导致的外观不良。
(实施例2)
准备了板厚0.27mm的经最终退火的取向性电磁钢板。该取向性电磁钢板的磁通密度B8为1.928T。对该取向性电磁钢板进行磷酸酸洗后,以烧结后的两面总计为12.0g/m2的方式涂布了表2中记载的各种无铬绝缘被膜处理液。此时,使用辊涂机以100mpm和300mpm这两个水平的输送速度输送取向性电磁钢板并涂布上述绝缘被膜处理液。然后,在900℃、30秒、N2:90vol%-H2:10vol%气体氛围的条件下进行烧结处理,制造了带有绝缘被膜的取向性电磁钢板。
在表2中,作为磷酸盐,使用了各自的磷酸二氢盐水溶液,作为胶体状二氧化硅,使用了ADEKA公司制造的AT-30。其含量均表示固体成分换算后的值。
作为包含金属元素的化合物的粒子,使用了日产化学株式会社制造的ZrO2SolNanoUse ZR30AH,其添加量相对于磷酸盐100质量份以金属元素(Zr)计进行固体成分换算为20质量份。粒径为0.1μm(与实施例1同样地测定)。
作为用作分散剂的表面活性剂,使用了SAN NOPCO公司制造的SN-DISPERSANT4215(季铵盐型阳离子型表面活性剂)、花王株式会社制造的ACETAMIN 24(烷胺型阳离子型表面活性剂),以不含溶剂的量表示各自的添加量。
绝缘被膜处理液的比重使用纯水调整为1.250。
与实施例1同样地进行了绝缘被膜处理液的粘度测定、带有绝缘被膜的取向性电磁钢板的铁损、赋予张力及耐吸湿性的评价。另外,利用以下的方法进行了绝缘被膜处理液涂布、烧结后的表面的外观的评价。将结果示于表2。
(绝缘被膜处理液涂布、烧结后的表面外观)
使用辊涂机以100mpm和300mpm这两个水平的输送速度输送取向性电磁钢板并涂布绝缘被膜处理液、进行烧结,然后,通过肉眼观察表面的状态,如下所述进行了评价。以下的评价中将○作为合格。
两个条件(100mpm、300mpm)下无棱纹缺陷:○
任意一个条件下有棱纹缺陷:△100或△300(△100是指在100mpm的条件下产生了棱纹缺陷,△300是指在300mpm的条件下产生了棱纹缺陷)
在两个条件下有棱纹缺陷:×
如表2所示,通过使用本发明的绝缘被膜处理液,能够形成耐吸湿性优异,可赋予高张力、铁损降低效果优异的无铬绝缘被膜,而且能够抑制因涂布于钢板时产生的涂布不均所导致的外观不良。
(实施例3)
准备了板厚0.23mm的经最终退火的取向性电磁钢板。该取向性电磁钢板的磁通密度B8为1.923T。对该取向性电磁钢板进行磷酸酸洗后,以烧结后的两面总计为10.0g/m2的方式涂布了表3中记载的各种无铬绝缘被膜处理液。此时,使用辊涂机以150mpm和380mpm这两个水平的输送速度输送取向性电磁钢板并涂布上述绝缘被膜处理液。然后,在950℃、10秒、N2:85vol%-H2:15vol%气体氛围的条件下进行烧结处理,制造了带有绝缘被膜的取向性电磁钢板。
表3中,作为磷酸盐,使用了磷酸二氢铝水溶液,作为胶体状二氧化硅,使用了ADEKA公司制造的AT-30。其含量均表示固体成分换算后的值。
作为包含金属元素的化合物的粒子,使用了TiO2、ZrN、HfO2、MgO。添加量表示金属元素的固体成分换算后的值。这些绝缘被膜处理液中的粒径与实施例1同样地进行了测定。
为了控制绝缘被膜处理液的粘度特性,添加了表3中记载的量的该表所述的无机酸。添加量以不含除无机酸以外的溶剂等的量表示。
绝缘被膜处理液的比重使用纯水调整为1.100。
与实施例1同样地进行了绝缘被膜处理液的粘度测定、带有绝缘被膜的取向性电磁钢板的铁损、赋予张力及耐吸湿性的评价。另外,利用以下的方法进行了绝缘被膜处理液涂布、烧结后的表面的外观的评价。将结果示于表3。
(绝缘被膜处理液涂布、烧结后的表面外观)
使用辊涂机以150mpm和380mpm这两个水平的输送速度输送取向性电磁钢板并涂布绝缘被膜处理液、进行烧结,然后,通过肉眼观察表面的状态,如下所述进行了评价。以下的评价中将○作为合格。
两个条件(150mpm、380mpm)下无棱纹缺陷:○
任意一个条件下有棱纹缺陷:△150或△380(△150是指在150mpm的条件下产生了棱纹缺陷,△380是指在380mpm的条件下产生了棱纹缺陷)
在两个条件下有棱纹缺陷:×
如表3所示,通过使用本发明的绝缘被膜处理液,能够形成耐吸湿性优异,可赋予高张力、铁损降低效果优异的无铬绝缘被膜,而且能够抑制因涂布于钢板时产生的涂布不均所导致的外观不良。
Claims (15)
1.一种绝缘被膜处理液,其用于在取向性电磁钢板的表面形成无铬绝缘被膜,
所述绝缘被膜处理液含有:
选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐;
胶体状二氧化硅;以及
包含金属元素的化合物的粒子,
相对于所述磷酸盐100质量份,所述胶体状二氧化硅的含量以SiO2固体成分换算计为50~120质量份,且所述包含金属元素的化合物的粒子的含量以金属元素换算计为5~60质量份,
所述绝缘被膜处理液的触变指数(TI)为1.20以上且10.00以下。
2.根据权利要求1所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子为选自Ti、Zr、Hf、V、Mg、Zn、Nb的氧化物的粒子、Ti、Zr、Hf、V、Mg、Zn、Nb的氮化物的粒子中的一种或两种以上。
3.根据权利要求1所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子为选自TiO2、ZrO2、HfO2、MgO、ZnO、Nb2O5、V2O5、TiN、ZrN的粒子中的一种或两种以上。
4.根据权利要求2所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子为选自TiO2、ZrO2、HfO2、MgO、ZnO、Nb2O5、V2O5、TiN、ZrN的粒子中的一种或两种以上。
5.根据权利要求1所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子的粒径为0.05μm以上且1.0μm以下。
6.根据权利要求2所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子的粒径为0.05μm以上且1.0μm以下。
7.根据权利要求3所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子的粒径为0.05μm以上且1.0μm以下。
8.根据权利要求4所述的绝缘被膜处理液,其中,包含金属元素的化合物的粒子的粒径为0.05μm以上且1.0μm以下。
9.根据权利要求1~8中任一项所述的绝缘被膜处理液,其还含有阳离子型表面活性剂。
10.根据权利要求9所述的绝缘被膜处理液,其中,阳离子型表面活性剂为季铵盐型阳离子型表面活性剂。
11.根据权利要求9所述的绝缘被膜处理液,其中,相对于选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐100质量份,阳离子型表面活性剂的含量为0.20~2.0质量份。
12.根据权利要求10所述的绝缘被膜处理液,其中,相对于选自Mg、Ca、Ba、Sr、Zn、Al、Mn的磷酸盐中一种或两种以上的磷酸盐100质量份,阳离子型表面活性剂的含量为0.20~2.0质量份。
13.一种带有绝缘被膜的取向性电磁钢板,其在表面具备绝缘被膜,所述绝缘被膜是将权利要求1~12中任一项所述的绝缘被膜处理液烧结而成的。
14.一种带有绝缘被膜的取向性电磁钢板的制造方法,该方法包括:在取向性电磁钢板的表面涂布权利要求1~12中任一项所述的绝缘被膜处理液后,进行烧结。
15.根据权利要求14所述的带有绝缘被膜的取向性电磁钢板的制造方法,其中,在将绝缘被膜处理液涂布于取向性电磁钢板的表面时,一边输送所述取向性电磁钢板,一边使用辊涂机将所述绝缘被膜处理液涂布于所述取向性电磁钢板的表面。
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