CN112639165A - 带有绝缘被膜的电磁钢板及其制造方法 - Google Patents
带有绝缘被膜的电磁钢板及其制造方法 Download PDFInfo
- Publication number
- CN112639165A CN112639165A CN201980057161.5A CN201980057161A CN112639165A CN 112639165 A CN112639165 A CN 112639165A CN 201980057161 A CN201980057161 A CN 201980057161A CN 112639165 A CN112639165 A CN 112639165A
- Authority
- CN
- China
- Prior art keywords
- steel sheet
- chromium
- treatment liquid
- insulating coating
- insulating film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 55
- 239000010959 steel Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 title claims description 61
- 239000011248 coating agent Substances 0.000 title claims description 58
- 239000011651 chromium Substances 0.000 claims abstract description 93
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 42
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 150000001845 chromium compounds Chemical class 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 5
- 238000010828 elution Methods 0.000 abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 13
- 230000006698 induction Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000009699 high-speed sintering Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- 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
-
- 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
-
- 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
-
- 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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- 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
- 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
- C23C22/24—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 hexavalent chromium compounds
-
- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
-
- 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
- B05D2301/00—Inorganic additives or organic salts thereof
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Abstract
本发明的目的在于提供在以有利于改善生产率的快速加热进行绝缘被膜的烧结的情况下耐铬溶出性也优异的带有绝缘被膜的电磁钢板及其制造方法。所述带有绝缘被膜的电磁钢板在电磁钢板表面的至少一面具备含有Fe、Cr、有机树脂、以及有机还原剂的绝缘被膜,所述绝缘被膜中的所述Fe的含量与所述Cr的含量之比(Fe/Cr)以摩尔比计为0.010~0.6。
Description
技术领域
本发明涉及带有绝缘被膜的电磁钢板及其制造方法。
背景技术
对于电动机、变压器等中使用的电磁钢板的绝缘被膜,不仅要求层间电阻还要求各种特性。例如,加工成型时的便利性、保管时的耐腐蚀性、外观稳定性、使用时的稳定的绝缘性(层间电阻)等。另外,由于电磁钢板被用于各种用途中,因此根据其用途正在开发各种绝缘被膜。大致分为(1)半有机系被膜、(2)无机系被膜、(3)有机系被膜这3种。
通常,在将电磁钢板冲裁后,进行层叠/固定而加工成电动机、变压器的铁芯。此时为了去除在电磁钢板上产生的加工应变来改善磁特性,大多数情况在700℃以上的温度下实施去应力退火。由于要求进行这样的去应力退火的用途的电磁钢板具有能耐受去应力退火时的热的程度的耐热性,因此使用了上述的(1)半有机系被膜、(2)无机系被膜。(1)和(2)的被膜的主要区别在于有无树脂,被膜特性的平衡因有无树脂而存在差异。因此,根据要重视的特性而分开使用(1)和(2)。
在形成(1)半有机系被膜、(2)无机系被膜时,使用了铬酸类、磷酸类、无机胶体类等各种主剂,其中,由于铬酸类的各种特性优异,因而被广泛使用。但是,在使用铬酸类的主剂的情况下,由于6价铬的有害性高,因此要求在形成被膜时还原为3价铬以使产品中不包含6价铬。因此,烧结条件和烧结温度成为制造时的重要管理项目。
因此,作为满足上述要求的方案,提出了在铬酸中含有铝化合物、并且将碱土金属抑制为一定量以下的带有绝缘被膜的电磁钢板(例如专利文献1、2)。对于这些带有绝缘被膜的电磁钢板,即使在使用了铬酸类的主剂的情况下,也能够实现烧结温度的低温化,也可以应对高速涂装,因此有效地有助于生产性的改善及节能。
现有技术文献
专利文献
专利文献1:日本特开平9-291368号公报
专利文献2:日本特开平11-92958号公报
发明内容
发明所要解决的课题
在带有绝缘被膜的电磁钢板的制造中,作为用于提高线速度来改善生产性的方法,如专利文献1和2的记载所述,低温烧结、高速涂装是有效的。作为除此以外的方法,使用快速加热来增大烧结时的升温速度的方法也是有效的。
然而,低温烧结、高速涂装原本并不是对改善耐铬溶出性有利的技术。另外,基于低温烧结、高速涂装所带来的生产率的改善效果也不充分,因此在为了进一步改善生产性而以快速加热进行绝缘被膜的烧结的情况下,从6价铬还原为3价铬的还原反应没有充分进行,有时在产品中残留有6价铬,在通过快速加热来制造时的耐铬溶出性方面存在课题。
本发明用于解决上述课题,其目的在于提供在以有利于改善生产性的快速加热进行绝缘被膜的烧结的情况下、耐铬溶出性也优异的带有绝缘被膜的电磁钢板及其制造方法。
用于解决课题的方法
发明人等为了实现上述目的,对基于快速加热的绝缘被膜的烧结进行了深入研究。其结果是新发现:如果绝缘被膜含有Fe、Cr、有机树脂、以及有机还原剂、且Fe的含量与Cr的含量之比(Fe/Cr)为给定的范围,则可以得到耐铬溶出性优异的带有绝缘被膜的电磁钢板。
另外,得到了如下见解:通过从被膜的下层、即钢板侧进行加热并烧结,而并非如以往常用的煤气炉、电炉那样从被膜表面侧进行烧结,从而使耐铬溶出性得到显著改善。
本发明是基于上述见解而完成的。即,本发明的主旨构成如下。
[1]一种带有绝缘被膜的电磁钢板,其在电磁钢板表面的至少一面具备含有Fe、Cr、有机树脂及有机还原剂的绝缘被膜,其中,
所述绝缘被膜中的所述Fe的含量与所述Cr的含量之比(Fe/Cr)以摩尔比计为0.010~0.6。
[2]根据[1]所述的带有绝缘被膜的电磁钢板,其中,所述有机树脂的粒径为30~1000nm。
[3]一种带有绝缘被膜的电磁钢板的制造方法,该方法包括:
在电磁钢板的至少一面涂布处理液,所述处理液含有3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、以及有机还原剂,然后,以100~350℃的温度范围的升温速度为20℃/秒以上的方式从钢板侧进行加热,对所述处理液进行烧结。
[4]一种带有绝缘被膜的电磁钢板的制造方法,该方法包括:
在电磁钢板的至少一面涂布处理液,所述处理液由3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、以及有机还原剂构成,然后,以100~350℃的温度范围的升温速度为20℃/秒以上的方式从钢板侧进行加热,对所述处理液进行烧结。
[5]根据[3]或[4]所述的带有绝缘被膜的电磁钢板的制造方法,其中,所述升温速度超过35℃/秒
发明效果
根据本发明,可以得到在通过有利于改善生产性的快速加热进行绝缘被膜的烧结的情况下耐铬溶出性也优异的带有绝缘被膜的电磁钢板。
具体实施方式
以下,对本发明具体地进行说明。
对于作为本发明的原材料的电磁钢板,没有特别限制,优选根据所需特性而适当进行成分调整。例如,由于使比电阻上升对于改善铁损是有效的,因此优选添加作为比电阻改善成分的Si、Al、Mn、Cr、P、Ni等。这些成分比率根据所需磁特性进行确定即可。
另外,其它微量成分和Sb、Sn等偏析元素等也没有限制,但C、S是对焊接性不利的元素,而且从磁特性的观点出发,也希望使其降低,因此,优选C为0.01质量%以下,S为0.01质量%以下。
另外,对于电磁钢板的制造方法也没有任何限制,可以使用现有公知的各种方法。另外,电磁钢板的表面粗糙度也没有特别限制,在重视占空因数时,优选将三维表面粗糙度SRa设为0.5μm以下。另外,对于电磁钢板的最终板厚没有特别限制,可以应用各种板厚的电磁钢板。需要说明的是,从磁特性的观点出发,电磁钢板的最终板厚优选设为0.8mm以下。
本发明的带有绝缘被膜的电磁钢板特征在于,在电磁钢板表面的至少一面具备含有Fe、Cr、有机树脂及有机还原剂的绝缘被膜,绝缘被膜中的Fe的含量与Cr的含量之比(Fe/Cr)以摩尔比计为0.010~0.6。以下,对本发明的绝缘被膜进行说明。
在本发明中,绝缘被膜含有Fe。含有Fe的绝缘被膜通过在形成绝缘被膜时使Fe从电磁钢板扩散至绝缘被膜中而形成。Fe的扩散量可以通过烧结时的升温速度而适当调整。特别是可以通过使用感应加热作为烧结时的方式,从而促进Fe的扩散。可以认为,通过利用感应加热从钢板侧对绝缘被膜(处理液)施加热,使扩散的Fe与铬发生反应,使6价铬有效地还原。
在本发明中,绝缘被膜含有Cr。含有Cr的绝缘被膜通过在形成绝缘被膜时对含有铬化合物的处理液进行烧结而形成。作为处理液中含有的铬化合物,如后所述是3价铬/全部铬的质量比为0.5以下的铬化合物。处理液中存在的6价铬通过在烧结时与有机还原剂的还原反应而被还原为3价铬,由此能够改善绝缘被膜的耐铬溶出性。
本发明的特征在于绝缘被膜中的Fe的含量与Cr的含量之比(Fe/Cr)以摩尔比计为0.010~0.6。在比值(Fe/Cr)以摩尔比计为0.010~0.6时,带有绝缘被膜的电磁钢板的被膜特性、特别是耐铬溶出性、耐腐蚀性得到改善。虽然其理由尚不清楚,但可以考虑是由于Cr和Fe通过O而键合,由此牢固地密合,抑制Cr的溶出,同时使绝缘被膜致密化。Fe/Cr比的优选范围为0.030~0.6。
需要说明的是,对于比值(Fe/Cr)而言,如下所述,可以通过在烧结处理液时以在给定的温度范围的升温速度成为给定范围的方式从钢板侧进行加热而对处理液进行烧结,从而进行控制,特别是通过使用感应加热,能够促进Fe的扩散。
另外,比值(Fe/Cr)的计算方法可以通过基于热碱的被膜溶解来测定。在基于热碱的被膜溶解的情况下,例如,通过将带有被膜的钢板在加热的20质量%NaOH水溶液中使被膜溶解,并对溶解液中的Fe和Cr进行ICP分析,从而能够测定。
在本发明中,绝缘被膜含有有机树脂。有机树脂的种类没有特别限制,可以应用丙烯酸类树脂、环氧树脂、氨基甲酸酯树脂、酚醛树脂、苯乙烯树脂、酰胺树脂、酰亚胺树脂、脲树脂、乙酸乙烯酯树脂、醇酸树脂、聚烯烃树脂及聚酯树脂等各种树脂,另外,它们可以使用单体或以共聚物、混合物的形式使用。此外,在水性树脂的情况下,形态可以是任意的,可以考虑乳液树脂、分散树脂、悬浮树脂及粉末树脂等各种形态。由于能够抑制烧结后的被膜裂纹,因此还可以组合使用不具有粒径的水溶性树脂。
有机树脂优选相对于全部铬以质量比计添加0.05~0.4。有机树脂的量低于0.05时,无法获得足够的冲裁性。另一方面,超过0.4时,耐热性变差。
需要说明的是,有机树脂的固体成分的粒径优选为30nm以上。粒径小时比表面积增大,因此妨害绝缘被膜形成所使用的处理液的稳定性。上限没有特别限制,在重视提高作为最终产品的电动机、变压器中的电磁钢板的占空因数的情况下,优选为1μm(1000nm)以下。
在本发明中,为了促进铬的还原反应,使绝缘被膜含有有机还原剂。有机还原剂的种类没有特别限制,优选使用选自二醇类中的一种和/或选自糖类中的至少1种。特别是在二醇中,更希望使用乙二醇、丙二醇、三亚甲基二醇、以及1,4-丁二醇;在糖类中,更希望使用甘油、聚乙二醇、蔗糖、乳糖、蔗糖、葡萄糖及果糖。
有机还原剂量优选相对于全部铬以质量比计添加0.1~2。这是由于,还原剂的量低于0.1时,铬酸/还原剂反应无法充分进行,另一方面,超过2时,反应达到饱和,还原剂残留于被膜中而导致焊接性变差。
为了进一步提高被膜的性能、均匀性,本发明的绝缘被膜优选根据需要含有添加剂。作为添加剂,可以使用目前已知的适用于铬酸类的绝缘被膜的公知的添加剂,例如可列举出表面活性剂(非离子型、阳离子型、阴离子型表面活性剂、有机硅类表面活性剂、乙炔二醇等)、防锈剂(胺类、非胺类防锈剂等)、硼酸、硅烷偶联剂(氨基硅烷、环氧硅烷等)、润滑剂(蜡等)、氧化铝溶胶、二氧化硅溶胶、铁溶胶、二氧化钛溶胶、锡溶胶、铈溶胶、锑溶胶、钨溶胶、钼溶胶等的氧化物溶胶这样的有机和无机添加剂。
在使用这些添加剂的情况下,为了保持充分的被膜特性,优选相对于本发明的绝缘被膜的全部固体成分质量为10质量%以下。
接下来,对本发明的带有绝缘被膜的电磁钢板的制造方法进行说明。
在本发明中,在电磁钢板的至少一面涂布处理液,所述处理液含有3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、以及有机还原剂,然后,以100~350℃的温度范围的升温速度为20℃/秒以上的方式从钢板侧进行加热,对处理液进行烧结。
绝缘被膜用的处理液包含3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、有机还原剂。在本发明中,3价铬/全部铬的质量比需要为0.5以下。组合物中存在的6价铬通过烧结时与还原剂的还原反应而被还原为3价铬,并吸附于钢板。处理液中的3价铬/全部铬的质量比超过0.5时,由于在处理液中发生聚合的3价铬的电影响、空间影响,6价铬在烧结时的反应性受损,结果是作为被膜的耐Cr溶出性差。另外,这是由于,处理液中的3价铬/全部铬的质量比超过0.5时,由于在处理液中发生聚合的3价铬形成凝胶状的沉淀物而难以保持作为处理液的性状。
需要说明的是,本发明的处理液是主剂中使用了铬酸酐、铬酸盐、重铬酸盐中的至少1种作为铬化合物的水溶液。作为铬酸盐或重铬酸盐,可示例出包含选自Ca、Mg、Zn、K、Na、Al等金属中至少1种的铬酸盐或重铬酸盐。
另外,本发明的处理液是包含3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、有机还原剂的处理液,不包含Fe(Fe离子、Fe化合物等)。在处理液与钢板接触时,钢板表面溶解而生成Fe离子。在烧结工序中将作为处理液的溶剂的水干燥而成为被膜时,优选以与处理液混合的形式引入Fe。在本发明中,将Fe的供给源限定于从钢板表面溶出的原因在于,对于因溶解而生成的新生成面而言,在烧结过程中,在处理液中发生了聚合的3价铬的极性基团(Cr-O-、Cr-OH-)与Fe牢固地密合,由此具有提高耐腐蚀性、密合性的效果。
作为上述的处理液的涂布方法,只要能将处理液涂布在钢板上即可,可以是任意的方法,可以使用辊涂法、棒涂法、气刀涂布法及喷涂法等各种方法。
涂布处理液后,用于形成绝缘被膜的烧结以100~350℃的温度范围的升温速度为20℃/秒以上的方式从钢板侧加热而进行。将上述温度范围的升温速度设为20℃/秒以上的快速加热的理由在于,促进Fe从钢板的溶出,使绝缘被膜中的Fe量与Cr量之比(Fe/Cr)处于给定范围。在低于100℃的温度范围进行快速加热时,作为处理液的溶剂的水发生局部的暴沸等,有时使被膜变得不均匀。
需要说明的是,烧结处理液时的最高到达板温设为通过涂敷的成膜所需的温度即可,由于使用含有有机树脂的水溶液作为处理液,因此设为100~350℃。低于100℃时,作为溶剂的水容易残留,另一方面,超过350℃时,存在有机树脂开始发生热分解的隐患。特别优选为150~350℃的范围。
因此,在本发明中,将100~350℃的温度范围的升温速度设为20℃/秒以上。升温速度优选超过35℃/秒。需要说明的是,升温速度的上限没有特别限定,升温速度过大时,导致加热装置的大型化和设备成本的增加,因此升温速度优选为200℃/秒以下,更优选为150℃/秒以下。
对于用于形成绝缘被膜的处理液的烧结方法,重要的是从钢板侧进行加热。对于煤气炉、电炉等一直以来常用的从涂敷表面进行加热的方式而言,升温速度过快时,最表层首先干燥,内部残留低沸点物质(溶剂、反应产物)而膨胀等成为外观不良的原因。另外,有机还原剂未充分地反应,在溶出试验时溶出至试验液中,使相同溶出的6价铬还原,存在无法准确评价耐铬溶出性的隐患。从钢板侧进行加热时,从涂敷下层进行烧结,因此,可使6价铬被有效地还原,而且即使是升温速度为150℃/秒左右的超高速烧结也完全不会发生外观不良。
从钢板侧进行加热的方式无需在整个烧结工序中进行,可以是在部分工序中进行。在部分采取从钢板侧进行加热的方式的情况下,优选在烧结工序中为0.5秒钟以上。
需要说明的是,本发明中的“从钢板侧进行加热”是指,通过使钢板本身发热而非从外部对钢板进行加热,从而从内部对钢板进行加热。例如,可示例出:通过磁力线的作用而使涡电流通过钢板、并利用由此产生的焦耳热使钢板本身发热的感应加热;或者使电流直接通过钢板本身、并利用由此产生的焦耳热使钢板本身发热的直接通电加热等。然而,在实际的生产线上,难以实施使电流直接通过行进的钢板的直接通电加热,因此,通过由外部电流产生的磁力线使行进的钢板产生涡电流的感应加热是适合的。
如上所述,作为用于从钢板侧进行加热的加热方式,特别优选利用由外部电流产生的磁力线在钢板中产生的涡电流来进行加热的感应加热方式。此时,感应加热的频率、升温速度等没有特别限制,可以根据受设备方面制约的加热时间、效率、电磁钢板的性质(板厚、导磁率等)等而适当确定。
根据以上说明,通过从钢板侧进行加热,与从涂敷表面进行加热的情况相比,耐铬溶出性得到改善。
需要说明的是,绝缘被膜的单位面积重量优选为0.05~7.0g/m2。绝缘被膜的单位面积重量低于0.05g/m2时,由于难以均匀涂布而使被膜性能变得不稳定。另一方面,绝缘被膜的单位面积重量超过7.0g/m2时,被膜密合性降低。
实施例
以下,为了进一步理解本发明而使用实施例进行说明。需要说明的是,本发明并不受这些实施例的限定。
使用板厚0.5mm的电磁钢板,利用辊涂来涂布表1所示的作为水溶液的处理液,所述电磁钢板的成分组成含有C:0.003质量%、S:0.003质量%、Si:0.25质量%、Al:0.25质量%及Mn:0.25质量%,余量由Fe及不可避免的杂质构成。需要说明的是,任意的处理液均是包含铬化合物、有机树脂、有机还原剂的处理液,且不包含Fe(Fe离子、Fe化合物等)。接着,以表1所示的升温速度及最高到达板温实施了烧结处理。
另外,用于进行烧结处理的加热方式为感应加热方式(A)或热风炉加热方式(C)、或组合使用两者的方式(B)。需要说明的是,在感应加热方式中,通过设为30kHz的频率、改变涌入电流,从而对升温速度进行了各种改变。通过进行这样的加热,如表1所示,对在100~350℃的温度范围的升温速度进行了各种改变。
对于得到的带有绝缘被膜的电磁钢板,进行了以下的评价。
<耐铬溶出性>
根据EPA3060A进行了耐铬溶出性的评价。将氢氧化钠20g、碳酸钠30g(和光纯药工业株式会社制特级试剂)溶解于纯水中,并定容至1升,制成溶出液。将该溶出液50ml加入烧杯中,在液温达到90~95℃后,添加带有绝缘被膜的电磁钢板的样品、MgCl2(无水)0.4g及缓冲液(将87g的K2HPO4和68g的KH2PO4溶解于1升的纯水中制作)0.5ml,搅拌5分钟后,在90~95℃下溶出60分钟。然后,将溶出液过滤,向得到的滤液中加入5摩尔/升的HNO3,调节至pH=7.5±0.5并定容至250ml。分取其中的95ml,用10%的H2SO4溶液调节至pH=2.0±0.5,添加0.5%的二苯碳酰二肼溶液2ml后,定容至100ml。将该溶液静置5~10分钟后测定Cr6+,换算成6价铬的溶出量。按照以下的基准进行判定,将△或×作为不合格。
◎:低于0.2mg/m2
○:0.2mg/m2以上且低于0.5mg/m2
△:0.5mg/m2以上且低于1.0mg/m2
×:1.0mg/m2以上
<沸腾水蒸气暴露试验>
评价暴露于沸腾水蒸气中30分钟后的外观,将△或×作为不合格。
◎:无变化
○:基本上无变化
△:稍有变化(变白、生锈等)
×:变化大(变白、生锈等)
<耐腐蚀性>
通过依据JIS-Z2371的盐水喷雾试验进行了评价。条件为5%NaCl、温度35℃。对锈的产生情况进行肉眼观察判定,以5%锈产生时间进行判定。将△或×作为不合格。
◎:24小时以上
○:12小时以上且低于24小时
△:7小时以上且低于12小时
×:低于7小时
<基于SEM的外观评价>
使用SEM(扫描电子显微镜)以1000倍对绝缘被膜的表面的任意10个视场进行观察,观察绝缘被膜中的裂纹。按照以下的基准进行判定,将△或×作为不合格。
◎:根据10个视野总计,裂纹的观察个数为0个
○:根据10个视野总计,裂纹的观察个数为1个以上且低于10个
△:根据10个视野总计,裂纹的观察个数为10个以上且低于30个
×:根据10个视野总计,裂纹的观察个数为30个以上
<占空因数>
依据JIS C 2550测定了占空因数。按照以下的基准进行判定,将×作为不合格。
◎:99%以上
○:98%以上且低于99%
△:97%以上且低于98%
×:低于97%
将结果示于表1。
根据表1的结果,本发明例的被膜性能均优异,特别是耐铬溶出性优异。
Claims (5)
1.一种带有绝缘被膜的电磁钢板,其在电磁钢板表面的至少一面具备含有Fe、Cr、有机树脂及有机还原剂的绝缘被膜,其中,
所述绝缘被膜中的所述Fe的含量与所述Cr的含量之比(Fe/Cr)以摩尔比计为0.010~0.6。
2.根据权利要求1所述的带有绝缘被膜的电磁钢板,其中,所述有机树脂的粒径为30~1000nm。
3.一种带有绝缘被膜的电磁钢板的制造方法,该方法包括:
在电磁钢板的至少一面涂布处理液,所述处理液含有3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、以及有机还原剂,然后,以100~350℃的温度范围的升温速度为20℃/秒以上的方式从钢板侧进行加热,对所述处理液进行烧结。
4.一种带有绝缘被膜的电磁钢板的制造方法,该方法包括:
在电磁钢板的至少一面涂布处理液,所述处理液由3价铬/全部铬的质量比为0.5以下的铬化合物、有机树脂、以及有机还原剂构成,然后,以100~350℃的温度范围的升温速度为20℃/秒以上的方式从钢板侧进行加热,对所述处理液进行烧结。
5.根据权利要求3或4所述的带有绝缘被膜的电磁钢板的制造方法,其中,所述升温速度超过35℃/秒。
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