WO2015115036A1 - クロムフリー張力被膜用処理液、クロムフリー張力被膜の形成方法、およびクロムフリー張力被膜付き方向性電磁鋼板 - Google Patents
クロムフリー張力被膜用処理液、クロムフリー張力被膜の形成方法、およびクロムフリー張力被膜付き方向性電磁鋼板 Download PDFInfo
- Publication number
- WO2015115036A1 WO2015115036A1 PCT/JP2015/000139 JP2015000139W WO2015115036A1 WO 2015115036 A1 WO2015115036 A1 WO 2015115036A1 JP 2015000139 W JP2015000139 W JP 2015000139W WO 2015115036 A1 WO2015115036 A1 WO 2015115036A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chromium
- coating film
- tensile stress
- free
- treatment liquid
- Prior art date
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 93
- 239000011248 coating agent Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims description 30
- 229910000831 Steel Inorganic materials 0.000 title description 13
- 239000010959 steel Substances 0.000 title description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000008119 colloidal silica Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 45
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 238000000137 annealing Methods 0.000 claims description 26
- 235000021317 phosphate Nutrition 0.000 claims description 26
- 239000010936 titanium Substances 0.000 claims description 25
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 9
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052742 iron Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 19
- 239000013522 chelant Substances 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 150000003016 phosphoric acids Chemical class 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 28
- 235000011007 phosphoric acid Nutrition 0.000 description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007922 dissolution test Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- -1 boric acid compound Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052726 zirconium 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
-
- 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
- C23C22/12—Orthophosphates containing zinc cations
-
- 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
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
- C21D8/1288—Application of a tension-inducing coating
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C22/182—Orthophosphates containing manganese cations containing also 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
- C23C22/188—Orthophosphates containing manganese cations containing also magnesium 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
- C23C22/20—Orthophosphates containing aluminium 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
- C23C22/22—Orthophosphates containing alkaline earth metal 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
- C23C22/73—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
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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
- C23C22/78—Pretreatment of the material to be coated
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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
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
Definitions
- the present invention relates to a treatment liquid for chromium-free tension coating.
- the present invention relates to a treatment liquid for a chromium-free tension coating capable of forming a tension coating having excellent moisture absorption resistance equivalent to a tension coating containing chromium.
- the present invention provides a method for forming a chromium-free tension coating using the above-described treatment liquid for chromium-free tension coating, and a chromium-free tension coating including a chromium-free tension coating formed using the treatment liquid for chromium-free tension coating.
- the present invention relates to a grain-oriented electrical steel sheet.
- a film is provided on the surface of a grain-oriented electrical steel sheet in order to provide insulation, workability, rust prevention, and the like.
- a film is composed of a base film mainly composed of forsterite formed at the time of final finish annealing and a phosphate-based topcoat film formed thereon. These coatings are formed at a high temperature and have a low coefficient of thermal expansion. Therefore, when the steel plate temperature is lowered to room temperature, tension resulting from the difference in thermal expansion coefficient between the steel plate and the coating is applied to the steel plate. Since this tension has the effect of reducing iron loss, it is desired to apply as high a tension as possible to the steel sheet.
- Patent Document 1 discloses a film mainly composed of magnesium phosphate, colloidal silica, and chromic anhydride.
- Patent Document 2 discloses a coating mainly composed of aluminum phosphate, colloidal silica, and chromic anhydride.
- Patent Document 3 and Patent Document 4 proposed a film forming method using a treatment liquid containing colloidal silica, aluminum phosphate, boric acid, and sulfate.
- the properties of the coating that is, the iron loss reduction effect due to moisture absorption resistance and tension can be improved to some extent, but the properties are sufficient compared to the conventional chromium-containing coating. I could not say.
- Patent Document 5 discloses a method of adding a boric acid compound instead of a chromium compound
- Patent Document 6 discloses a method of adding an oxide colloid
- No. 7 proposes a method of adding a metal organic acid salt.
- Patent Document 8 discloses a technique for containing a metal element such as Fe, Al, Ga, Ti, or Zr in a treatment liquid for forming a film in order to prevent moisture absorption.
- Patent Document 9 discloses a technique for improving the moisture absorption resistance of a coating by adding a Ti chelate to a treatment liquid for forming the coating.
- the film obtained by the method described in Patent Document 8 was inferior in long-term moisture absorption resistance. Further, the method described in Patent Document 9 has a problem that the cost is high because an expensive Ti chelate is used.
- the present invention was developed in view of the above circumstances, and without using an expensive Ti chelate, using an inexpensive Ti source, has excellent moisture absorption resistance and high iron loss reduction effect due to sufficient tension. It aims at providing the processing liquid for chromium free tension
- the present invention also provides a method for forming a chromium-free tension coating using the above-described treatment liquid for chromium-free tension coating, and a chromium-free tension coating having a chromium-free tension coating formed using the treatment liquid for chromium-free tension coating.
- An object is to provide a grain-oriented electrical steel sheet with a tension coating.
- the inventors have conducted intensive research and research in order to solve the above-described problems and obtain a desired moisture absorption resistance and an effect of reducing iron loss by applying tension with a chromium-free coating.
- the reason why the film obtained by the method described in Patent Document 8 is inferior in long-term moisture absorption is that the content of metal elements such as Fe, Al, Ga, Ti, Zr is not sufficient.
- the Ti content in the coating is the same, considering that Ti has the highest moisture absorption improvement effect next to Cr, in the technique disclosed in Patent Document 8, the Ti content should be further increased. Tried.
- the addition of a large amount of Ti causes crystallization of the film, resulting in a decrease in tension and clouding of the coating color.
- the inventors focused attention on Ti and repeated intensive studies on a method for further increasing the Ti content while avoiding crystallization.
- a treatment liquid containing metal phosphate and phosphoric acid is used, and the number of moles of metal in the metal phosphate is specified with respect to the number of moles of phosphorus (P) in the treatment liquid.
- P phosphorus
- the gist configuration of the present invention is as follows. 1.
- a treatment liquid for chromium-free tension coating One or more selected from among phosphates of Mg, Ca, Ba, Sr, Zn, Al, and Mn, Phosphate: 50 to 120 parts by mass of colloidal silica in terms of SiO 2 solid content with respect to 100 parts by mass, The phosphate: containing 30 to 50 parts by mass of Ti source in terms of TiO 2 with respect to 100 parts by mass, and H 3 PO 4 ,
- a treatment liquid for chromium-free tension coating wherein the number of moles of metal element in the phosphate and the number of moles of phosphorus in the treatment liquid for chromium-free tension coating satisfy the relationship of the following formula (1).
- a method for forming a chromium-free tension coating comprising the steps of:
- the treatment liquid described in any one of 1 to 3 above is applied to the surface of the grain-oriented electrical steel sheet after final finish annealing, and a baking treatment is performed at a temperature of 800 ° C. to 1000 ° C. for 10 seconds to 300 seconds.
- a grain-oriented electrical steel sheet with a chromium-free tension coating is applied to the surface of the grain-oriented electrical steel sheet after final finish annealing, and a baking treatment is performed at a temperature of 800 ° C. to 1000 ° C. for 10 seconds to 300 seconds.
- a chromium-free tension film having excellent moisture absorption resistance for a long period of time and having a sufficient tension imparting effect without using an expensive Ti chelate. Therefore, according to the present invention, a grain-oriented electrical steel sheet having both excellent moisture absorption resistance and low iron loss can be obtained at low cost.
- a sample was manufactured as follows. Thickness: 0.23 mm finished annealed grain-oriented electrical steel sheet produced by a known method was sheared to a size of 300 mm ⁇ 100 mm to obtain a sample piece. After removing the unreacted annealing separator remaining on the surface of the sample piece, strain annealing was performed at 800 ° C. for 2 hours. Next, the test piece was lightly pickled with 5% phosphoric acid, and then a tension coating solution was applied to the surface of the test piece. The tension coating solution was prepared by the following procedure.
- an aqueous solution of primary magnesium phosphate (Mg (H 2 PO 4 ) 2 ), colloidal silica, and TiO 2 sol were mixed to obtain a mixed solution.
- the mass ratio of each component in the mixed solution was, in terms of solid content, primary magnesium phosphate: 30 g, colloidal silica: 20 g, and TiO 2 sol: 12 g.
- an aqueous solution (specific gravity 1.69) of orthophosphoric acid (H 3 PO 4 ) having a concentration of 85% was added to the mixed solution in the amount shown in Table 1 to obtain a treatment solution for tension coating.
- the ratio of the number of moles of Mg 2+ to the number of moles of phosphorus (total number of moles of phosphorus derived from both phosphate and phosphoric acid) (P) (Mg 2+ / P) was the value shown in Table 1.
- the tension coating treatment solution was applied to the surface of the test piece so that the basis weight after drying was 10 g / m 2 (both sides total).
- the test piece is placed in a drying furnace and dried (300 ° C., 1 minute), and then heat treatment (800 ° C., 2 minutes, N 2 : 100) that combines planarization annealing and tension film baking. %). Further, a second strain relief annealing (800 ° C., 2 hours) was then performed.
- the samples thus obtained were investigated for iron loss reduction effect and moisture absorption resistance by applying tension.
- the iron loss reduction effect was evaluated based on the magnetic characteristics measured with an SST (Single Seat Test) tester (single plate magnetic tester).
- the magnetic properties were measured for each sample immediately before application of the tension coating solution, after baking of the tension coating, and immediately after the second strain relief annealing.
- Hygroscopic resistance was evaluated by a phosphorus dissolution test.
- Three test pieces used in the dissolution test were prepared by cutting a steel plate immediately after baking of the tension coating and measuring 50 mm ⁇ 50 mm. This test piece for dissolution test was boiled in distilled water at 100 ° C. for 5 minutes, and the amount of phosphorus eluted at that time was measured. Based on the phosphorus elution amount, it is possible to determine the ease of dissolution of the tension coating in water.
- the steel plate used in the present invention is not particularly limited as long as it is a grain-oriented electrical steel plate.
- a grain-oriented electrical steel sheet is obtained by hot rolling a silicon-containing steel slab by a known method and finishing it to a final thickness by one or multiple cold rolling sandwiching intermediate annealing. It is manufactured by applying a crystal annealing, then applying an annealing separator and then performing a final finish annealing.
- phosphates of Mg, Ca, Ba, Sr, Zn, Al and Mn are used as phosphates.
- any one of the above-described phosphates is used, but the physical property value of the insulating coating (coating) can be precisely controlled by using a mixture of two or more.
- the phosphate primary phosphate (heavy phosphate) is preferable because it is easily available.
- phosphates of alkali metals Li, Na, etc.
- the colloidal silica is contained in the treatment liquid in an amount of 50 to 120 parts by mass in terms of SiO 2 solid content with respect to 100 parts by mass of the above-mentioned phosphate.
- Colloidal silica has the effect of reducing the thermal expansion coefficient of the coating.
- the colloidal silica content is less than 50 parts by mass, the effect of lowering the thermal expansion coefficient is small, and sufficient tension cannot be imparted to the steel sheet. And as a result, the iron loss improvement effect by tension
- the content is more than 120 parts by mass, not only the coating is easily crystallized during baking, but also the moisture absorption resistance of the film is lowered.
- the treatment liquid of the present invention contains 30 to 50 parts by mass of Ti source in terms of TiO 2 with respect to 100 parts by mass of phosphate.
- Ti source content is less than 30 parts by mass, the moisture absorption resistance of the coating deteriorates.
- content is more than 50 parts by mass, it becomes difficult to prevent crystallization even if phosphoric acid is added to control M / P.
- the treatment liquid of the present invention contains phosphoric acid (H 3 PO 4 ).
- [A] in the formula (1) represents the number of moles of component A contained in the chromium-free tension coating liquid. The number of moles of metal element not added to the treatment liquid as phosphate is considered to be zero.
- the coefficient 1.5 concerning [Al] is due to the fact that Al is trivalent while metal elements other than Al are divalent.
- the middle side in the above formula, that is, ([Mg] + [Ca] + [Ba] + [Sr] + [Zn] + [Mn] +1.5 [Al]) / [P] is referred to as “M / P”. . If this M / P is less than 0.20, P in the coating is excessive, so that the amount of phosphorus eluted from the coating increases and the moisture absorption resistance decreases. On the other hand, if M / P is larger than 0.45, the amount of Ti necessary for obtaining sufficient moisture absorption resistance cannot be contained in the coating without crystallization.
- the Ti source contained in the chromium-free tension coating solution of the present invention is preferably a TiO 2 sol from the standpoint of availability and cost.
- the TiO 2 sol may be acidic, neutral, or alkaline, but preferably has a pH of 5.5 to 12.5.
- the TiO 2 sol preferably contains titanium phosphate in a solid mass ratio of 0.1% to 50% with respect to TiO 2 .
- titanium phosphate By adding titanium phosphate, the dispersibility of the TiO 2 particles can be enhanced. Titanium phosphate has the effect of increasing the compatibility between TiO 2 and phosphate and increasing the stability of the coating solution. When the content of titanium phosphate is less than 0.1%, the effect of improving the compatibility is poor.
- the amount of phosphoric acid in the treatment liquid in Formula (1) is the total amount of phosphoric acid in the treatment liquid, and includes the amount of phosphoric acid added as titanium phosphate.
- fine powdery inorganic mineral particles such as silica and alumina can be added to the treatment liquid of the present invention.
- These inorganic mineral particles are effective in improving the sticking resistance of the coating.
- the content of the inorganic mineral particles is preferably 1 part by mass at most with respect to 20 parts by mass of colloidal silica so as not to lower the space factor.
- the above-mentioned treatment liquid is applied to the surface of the electrical steel sheet and baked to form a tension coating.
- the weight per unit area after drying of the coating is preferably 4 to 15 g / m 2 in total on both sides. This is because when the basis weight is less than 4 g / m 2 , the interlayer resistance decreases, and when the basis weight is more than 15 g / m 2 , the space factor decreases.
- the coating was formed so that the front and back surfaces had substantially the same weight per unit area. There is no need, and there may be a difference in the weight per unit area.
- Such a baking treatment of the tension coating may be performed also as flattening annealing.
- the baking treatment is performed under conditions of a temperature range of 800 to 1000 ° C. and a soaking time of 10 to 300 seconds. If the temperature is too low or the time is too short, the planarization is not sufficiently performed. As a result, a shape defect occurs and the yield decreases. On the other hand, if the temperature is too high, the effect of flattening annealing becomes excessively strong, so that the steel sheet creeps and the magnetic properties deteriorate.
- the magnetic flux density B 8 of a grain-oriented electromagnetic steel sheet at this time was 1.912T.
- the grain-oriented electrical steel sheet was washed with phosphoric acid, and then a chromium-free tension film was formed on the surface thereof.
- treatment solutions for chromium-free tension film having various compositions shown in Table 2 were used.
- the treatment liquid was applied to both sides of the grain-oriented electrical steel sheet such that the total weight per unit area after drying at 300 ° C. for 1 minute was 10 g / m 2 .
- baking was performed in an atmosphere of N 2 : 100% under the conditions of 850 ° C. and 30 seconds.
- strain relief annealing was performed at 800 ° C. for 2 hours in an atmosphere of N 2 : 100%.
- a primary phosphate aqueous solution was used.
- the amount of the phosphate converted to solid content is shown in Table 2.
- Ti source TiO 2 sol TKS-203 manufactured by Teika Co., Ltd. was used.
- phosphoric acid 85% phosphoric acid aqueous solution was used. Table 3 shows the results of investigations on the properties of the grain-oriented electrical steel sheet thus obtained.
- Example 2 Thickness: 0.23 mm finished annealed grain-oriented electrical steel sheet.
- the magnetic flux density B 8 of a grain-oriented electromagnetic steel sheet at this time was 1.912T.
- the grain-oriented electrical steel sheet was washed with phosphoric acid, and then a chromium-free tension film was formed on the surface thereof.
- 100 g of primary magnesium phosphate as a phosphate was used in terms of solid content, and the other components used were treatment liquids having various compositions shown in Table 4. The treatment liquid was applied to the surface of the grain-oriented electrical steel sheet so that the total weight per unit area after drying at 300 ° C. for 1 minute was 15 g / m 2 .
- Example 5 shows the results of investigations on the properties of the grain-oriented electrical steel sheet thus obtained. Each characteristic was evaluated in the same manner as in Example 1.
- the present invention it is possible to prevent the crystallization of the coating when Ti is added to improve the moisture absorption resistance of the chromium-free tension coating. As a result, it is possible to avoid the adverse effect of lowering the tension applied to the steel sheet due to crystallization, and to add a sufficient amount of Ti. Therefore, by using the treatment liquid of the present invention, a chromium-free tension coating excellent in moisture absorption resistance and iron loss improvement effect can be obtained. Moreover, the grain-oriented electrical steel sheet having both excellent moisture absorption resistance and low iron loss can be obtained by coating the chromium-free tension coating.
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Abstract
Description
また、本発明は、上記のクロムフリー張力被膜用処理液を用いたクロムフリー張力被膜の形成方法および上記のクロムフリー張力被膜用処理液を用いて形成したクロムフリー張力被膜を備えるクロムフリー張力被膜付き方向性電磁鋼板に関するものである。
これらの被膜は高温で形成され、しかも低い熱膨張率を持つ。したがって、鋼板温度が室温まで低下したとき、鋼板と被膜との熱膨張率の差に起因する張力が鋼板に付与される。この張力は鉄損を低減させる効果を有しているため、できるだけ高い張力を鋼板に付与することが望まれている。
例えば、特許文献1には、リン酸マグネシウム、コロイド状シリカ、および無水クロム酸を主体とする被膜が開示されている。また、特許文献2には、リン酸アルミニウム、コロイド状シリカ、および無水クロム酸を主体とする被膜が開示されている。
また、硫酸塩の添加量を増す方法も試みられた。しかし、この方法においては、被膜の耐吸湿性は改善されるものの、張力付与性能が低下し、十分な鉄損低減効果を得ることができなかった。
このように、いずれの方法も、耐吸湿性と張力付与性能の両者を、必要とされる水準まで改善することはできなかった。
しかしながら、いずれの技術を用いても、耐吸湿性と張力付与による鉄損低減効果の両者を、従来のクロムを含有する被膜と同レベルまで到達させることはできず、完全な解決策とはなり得なかった。
また、本発明は、上記のクロムフリー張力被膜用処理液を用いたクロムフリー張力被膜の形成方法、さらには上記のクロムフリー張力被膜用処理液を用いて形成したクロムフリー張力被膜をそなえるクロムフリー張力被膜付き方向性電磁鋼板を提供することを目的とする。
その結果、特許文献8に記載された方法で得られる被膜が長期の耐吸湿性に劣る原因が、Fe,Al,Ga,Ti,Zrなどの金属元素の含有量が十分ではないところにあることが判明した。また、コーティング中の含有量が同じであれば、TiがCrに次いで高い耐吸湿性改善効果を有することを考慮して、特許文献8に開示の技術において、さらにTiの含有量を増加させることを試みた。その結果、多量のTiの添加が、被膜の結晶化と、それに起因する張力の低下およびコーティング色調の白濁化を引き起こすことが判明した。
その結果、金属リン酸塩とリン酸とを含有する処理液を使用し、かつ、前記処理液中のリンのモル数(P)に対する、前記金属リン酸塩中の金属のモル数を特定の式に応じて合計した値(M)の比(M/P)を制御することによって、上記のような弊害なしにTi含有量を無理なく増加できることを新たに見出し、本発明を完成させるに到った。
1.クロムフリー張力被膜用処理液であって、
Mg、Ca、Ba、Sr、Zn、Al、およびMnのリン酸塩のうちから選ばれる1種または2種以上、
前記リン酸塩:100質量部に対しSiO2固形分換算で50~120質量部のコロイド状シリカ、
前記リン酸塩:100質量部に対しTiO2換算で30~50質量部のTi源、ならびに
H3PO4を含有し、
前記リン酸塩中の金属元素のモル数と、前記クロムフリー張力被膜用処理液中のリンのモル数とが、下記(1)式の関係を満たすクロムフリー張力被膜用処理液。
記
0.20≦([Mg]+[Ca]+[Ba]+[Sr]+[Zn]+[Mn]+1.5[Al]) / [P]≦0.45 ……(1)
(ここで、[A]は前記クロムフリー張力被膜用処理液に含まれるAのモル数を表す)
800℃以上1000℃以下の温度で10秒から300秒の焼付け処理を行う工程を備えるクロムフリー張力被膜の形成方法。
従って、本発明によれば、優れた耐吸湿性と低鉄損とを兼ね備える方向性電磁鋼板を安価に得ることができる。
まず、試料を次のようにして製作した。
公知の方法で製造された板厚:0.23mmの仕上げ焼鈍済みの方向性電磁鋼板を300mm×100mmの大きさにせん断し、試料片を得た。前記試料片表面に残存している未反応の焼鈍分離剤を除去したのち、800℃、2時間の歪取焼鈍を施した。
ついで、前記試験片を5%リン酸で軽酸洗したのち、張力被膜用処理液を前記試験片の表面に塗布した。前記張力被膜用処理液は、次の手順で調製した。まず、第一リン酸マグネシウム(Mg(H2PO4)2)の水溶液、コロイド状シリカ、およびTiO2ゾルを混合し、混合液を得た。前記混合液中における各成分の質量比は、固形分換算で、第一リン酸マグネシウム:30g、コロイド状シリカ:20g、およびTiO2ゾル:12gとした。次に、前記混合液に、濃度85%のオルトリン酸(H3PO4)の水溶液(比重1.69)を表1に示す量加え、張力被膜用処理液を得た。得られた張力被膜用処理液中におけるリンのモル数(リン酸塩とリン酸の両者に由来するリンの合計のモル数)(P)に対するMg2+のモル数の比(Mg2+/P)は、表1に示す値とした。
前記張力被膜用処理液を、乾燥後目付量で10g/m2(両面合計)となるように前記試験片の表面に塗布した。次に、前記試験片を乾燥炉に装入して乾燥(300℃、1分間)を行い、その後、平坦化焼鈍と張力被膜の焼付けを兼ねた熱処理(800℃、2分間、N2:100%)を施した。さらにその後、2回目の歪取焼鈍(800℃、2時間)を行った。
鉄損低減効果は、SST(Single Seat Test)試験機(単板磁気試験機)で測定した磁気特性に基づいて評価した。磁気特性の測定は、各試料について張力被膜用処理液の塗布直前、張力被膜の焼付け後、および2回目の歪取焼鈍直後に、それぞれ行った。
耐吸湿性は、リンの溶出試験により評価した。前記溶出試験に用いる試験片は、張力被膜の焼付け直後の鋼板を切断して、50mm×50mmの寸法で、3枚作製した。この溶出試験用試験片を、100℃の蒸留水中で5分間煮沸し、その際に溶出したリンの量を測定した。前記リンの溶出量に基づいて、張力被膜の水に対する溶解しやすさを判断することができる。
なお、表中の各項目は、次のとおりである。
・塗布前B8(R):張力被膜用処理液塗布直前の磁束密度
・塗布後ΔB=B8(C)-B8(R) 但し、B8(C):張力被膜の焼付け直後の磁束密度
・歪取焼鈍後ΔB=B8(A)-B8(R) 但し、B8(A):2回目の歪取焼鈍直後の磁束密度
・塗布前W17/50(R):張力被膜用処理液塗布直前の鉄損
・塗布後ΔW=W17/50(C)-W17/50(R) 但し、W17/50(C):張力被膜の焼付け直後の鉄損
・歪取焼鈍後ΔW=W17/50(A)-W17/50(R) 但し、W17/50(A):2回目の歪取焼鈍直後の鉄損
・リンの溶出量:張力被膜の焼付け直後に測定
・被膜外観:目視にて歪取り焼鈍後のコーティングの透明度を判定
本発明で対象とする鋼板は、方向性電磁鋼板であれば特に鋼種を問わない。通常、かような方向性電磁鋼板は、含珪素鋼スラブを、公知の方法で熱間圧延し、1回または中間焼鈍を挟む複数回の冷間圧延により最終板厚に仕上げたのち、一次再結晶焼鈍を施し、ついで焼鈍分離剤を塗布してから、最終仕上げ焼鈍を行うことによって製造される。
0.20≦([Mg]+[Ca]+[Ba]+[Sr]+[Zn]+[Mn]+1.5[Al]) / [P]≦0.45 ……(1)
ここで、(1)式における[A]は、クロムフリー張力被膜用処理液に含まれる成分Aのモル数を表す。リン酸塩として処理液に添加されていない金属元素のモル数はゼロとみなされる。また、[Al]にかかる係数1.5は、Al以外の金属元素が2価であるのに対して、Alが3価であることによるものである。以下、前記式における中辺、すなわち([Mg]+[Ca]+[Ba]+[Sr]+[Zn]+[Mn]+1.5[Al]) / [P]を、「M/P」と記す。
このM/Pが0.20未満であると、コーティング中のPが過剰であるため、被膜からのリンの溶出量が多くなり、耐吸湿性が低下する。一方、M/Pが0.45よりも大きいと、十分な耐吸湿性を得るために必要な量のTiを被膜中に結晶化させずに含有させることができない。
また、前記TiO2ゾルには、リン酸チタンを、TiO2に対して固形質量比率で0.1%から50%含有させることが好ましい。リン酸チタンを添加することによって、TiO2粒子の分散性を高めることができる。また、リン酸チタンは、TiO2とリン酸塩との相溶性を高め、コーティング液安定性を高める作用を有している。リン酸チタンの含有量が0.1%未満では相溶性を高める効果に乏しい。一方、リン酸チタンの含有量が50%よりも多くなると、コストが高くなってしまう。なお、式(1)での処理液中のリン酸量は、処理液中の全リン酸量であり、リン酸チタンとして添加したリン酸量も含む。
かかる張力被膜の焼付け処理は、平坦化焼鈍を兼ねて行ってもよい。前記焼付け処理は、800~1000℃の温度範囲、10~300秒の均熱時間の条件で実施する。温度が低すぎたり、時間が短すぎたりすると、平坦化が十分に行われない。その結果、形状不良が発生して、歩留りが低下する。一方、温度が高すぎると、平坦化焼鈍の効果が過剰に強くなるため、鋼板がクリープ変形して磁気特性が劣化する。
板厚:0.23mmの仕上げ焼鈍済みの方向性電磁鋼板を準備した。このときの方向性電磁鋼板の磁束密度B8は1.912Tであった。この方向性電磁鋼板を、リン酸酸洗した後、その表面にクロムフリー張力被膜を形成した。前記張力被膜の形成には、表2に示す種々の組成のクロムフリー張力被膜用処理液を使用した。前記処理液は、前記方向性電磁鋼板の両面に、300℃で1分乾燥後の両面合計の目付量が10g/m2となるように塗布された。次いで、N2:100%の雰囲気中にて、850℃、30秒の条件で焼付け処理を行った。その後、N2:100%の雰囲気中で800℃、2時間の歪取焼鈍を実施した。
リン酸塩としては、各々第一リン酸塩水溶液を使用した。前記リン酸塩の、固形分換算した量を表2に示した。Ti源としては、テイカ(株)製TiO2ゾルTKS-203を使用した。リン酸としては、85%リン酸水溶液を使用した。
このようにして得られた方向性電磁鋼板の諸特性について調査した結果を表3に示す。
・塗布前W17/50(R):張力被膜用処理液塗布直前の鉄損
・塗布後ΔW=W17/50(C)-W17/50(R) 但し、W17/50(C):張力被膜の焼付け直後の鉄損
・歪取焼鈍後ΔW=W17/50(A)-W17/50(R) 但し、W17/50(A):歪取焼鈍直後の鉄損
・リンの溶出量:50mm×50mmの試験片3枚(皮膜表面積150cm2)を100℃の蒸留水中で5分間煮沸した後、分析
・被膜外観:目視にて歪取り焼鈍後のコーティングの透明度を判定
板厚:0.23mmの仕上げ焼鈍済みの方向性電磁鋼板を準備した。このときの方向性電磁鋼板の磁束密度B8は1.912Tであった。この方向性電磁鋼板を、リン酸酸洗した後、その表面にクロムフリー張力被膜を形成した。前記張力被膜の形成には、リン酸塩として第一リン酸マグネシウムを固形分換算で100g用い、その他の成分は表4に示す種々の組成の処理液を使用した。前記処理液は、前記方向性電磁鋼板の表面に、300℃で1分乾燥後の両面合計の目付量が15g/m2となるように塗布された。次いで、N2:100%の雰囲気中にて950℃、10秒の条件で焼付け処理を行った。その後、N2:100%の雰囲気中で800℃、2時間の歪取焼鈍を実施した。
かくして得られた方向性電磁鋼板の諸特性について調査した結果を表5に示す。
なお、各特性の評価は実施例1と同様の方法で行った。
また、上記のクロムフリー張力被膜を被覆することにより、優れた耐吸湿性と低鉄損とを兼ね備える方向性電磁鋼板を得ることができる。
Claims (5)
- クロムフリー張力被膜用処理液であって、
Mg、Ca、Ba、Sr、Zn、Al、およびMnのリン酸塩のうちから選ばれる1種または2種以上、
前記リン酸塩:100質量部に対しSiO2固形分換算で50~120質量部のコロイド状シリカ、
前記リン酸塩:100質量部に対しTiO2換算で30~50質量部のTi源、ならびに
H3PO4を含有し、
前記リン酸塩中の金属元素のモル数と、前記クロムフリー張力被膜用処理液中のリンのモル数とが、下記(1)式の関係を満たすクロムフリー張力被膜用処理液。
記
0.20≦([Mg]+[Ca]+[Ba]+[Sr]+[Zn]+[Mn]+1.5[Al]) / [P]≦0.45 ……(1)
(ここで、[A]は前記クロムフリー張力被膜用処理液に含まれるAのモル数を表す) - 前記チタン源が、TiO2ゾルを含有する請求項1に記載のクロムフリー張力被膜用処理液。
- 前記チタン源が、前記TiO2ゾル中のTiO2に対して固形質量比率で0.1~50%のリン酸チタンをさらに含有する請求項2に記載のクロムフリー張力被膜用処理液。
- 最終仕上げ焼鈍後の方向性電磁鋼板の表面に、請求項1~3のいずれか一項に記載の処理液を塗布する工程および
800℃以上1000℃以下の温度で10秒から300秒の焼付け処理を行う工程を備えるクロムフリー張力被膜の形成方法。 - 最終仕上げ焼鈍後の方向性電磁鋼板の表面に、請求項1~3のいずれか一項に記載の処理液を塗布し、800℃以上1000℃以下の温度で10秒から300秒の焼付け処理を行って得たクロムフリー張力被膜付き方向性電磁鋼板。
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US20180371621A1 (en) | 2018-12-27 |
EP3101157A1 (en) | 2016-12-07 |
US10087529B2 (en) | 2018-10-02 |
RU2016135201A (ru) | 2018-03-05 |
US10458021B2 (en) | 2019-10-29 |
KR101774187B1 (ko) | 2017-09-01 |
US10435791B2 (en) | 2019-10-08 |
WO2015115036A8 (ja) | 2016-06-02 |
US20160305026A1 (en) | 2016-10-20 |
RU2649608C2 (ru) | 2018-04-04 |
US20180371620A1 (en) | 2018-12-27 |
CN106414802A (zh) | 2017-02-15 |
KR20160098313A (ko) | 2016-08-18 |
EP3101157A4 (en) | 2017-01-18 |
RU2016135201A3 (ja) | 2018-03-05 |
EP3101157B1 (en) | 2017-11-08 |
JPWO2015115036A1 (ja) | 2017-03-23 |
JP5900705B2 (ja) | 2016-04-06 |
CN106414802B (zh) | 2018-11-06 |
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