JP2019173172A - Magnesium oxide for annealing separation agent, and manufacturing method of directional electromagnetic steel sheet - Google Patents
Magnesium oxide for annealing separation agent, and manufacturing method of directional electromagnetic steel sheet Download PDFInfo
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- JP2019173172A JP2019173172A JP2019062376A JP2019062376A JP2019173172A JP 2019173172 A JP2019173172 A JP 2019173172A JP 2019062376 A JP2019062376 A JP 2019062376A JP 2019062376 A JP2019062376 A JP 2019062376A JP 2019173172 A JP2019173172 A JP 2019173172A
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- magnesium oxide
- steel sheet
- magnesium
- annealing
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 116
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000000137 annealing Methods 0.000 title claims abstract description 59
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 32
- 239000010959 steel Substances 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000926 separation method Methods 0.000 title abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 61
- 239000011734 sodium Substances 0.000 claims abstract description 38
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052796 boron Inorganic materials 0.000 claims abstract description 32
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 22
- 229910052839 forsterite Inorganic materials 0.000 claims description 29
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 29
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 235000012245 magnesium oxide Nutrition 0.000 description 97
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 48
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 35
- 239000000347 magnesium hydroxide Substances 0.000 description 35
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 229910052742 iron Inorganic materials 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000002002 slurry Substances 0.000 description 23
- 230000004907 flux Effects 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 230000036571 hydration Effects 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910000976 Electrical steel Inorganic materials 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 229960002337 magnesium chloride Drugs 0.000 description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011573 trace mineral Substances 0.000 description 5
- 235000013619 trace mineral Nutrition 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 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 3
- 239000004137 magnesium phosphate Substances 0.000 description 3
- 229960002261 magnesium phosphate Drugs 0.000 description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 3
- 235000010994 magnesium phosphates Nutrition 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- -1 sodium phosphate compound Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
本発明は、焼鈍分離剤用の酸化マグネシウム及びそれを用いる方向性電磁鋼板の製造方法に関する。 The present invention relates to magnesium oxide for an annealing separator and a method for producing a grain-oriented electrical steel sheet using the same.
変圧器や発電機に使用される方向性電磁鋼板は、一般に、ケイ素(Si)を約3%含有するケイ素鋼を熱間圧延し、次いで最終板厚に冷間圧延し、次いで脱炭焼鈍、仕上焼鈍して、製造される。脱炭焼鈍(一次再結晶焼鈍)では、鋼板表面に二酸化ケイ素被膜を形成し、その表面に焼鈍分離剤用酸化マグネシウムを含むスラリーを塗布して乾燥させ、コイル状に巻き取った後、仕上焼鈍することにより、以下の反応式に示すように、二酸化ケイ素(SiO2)と酸化マグネシウム(MgO)が反応してフォルステライト(Mg2SiO4)被膜が鋼板表面に形成されることになる。
2MgO+SiO2→Mg2SiO4 (I)
このフォルステライト被膜は、鋼板表面に張力を付与し、鉄損を低減して磁気特性を向上させ、また鋼板に絶縁性を付与する役割を果たすので重要である。
Oriented electrical steel sheets used for transformers and generators are generally hot-rolled silicon steel containing about 3% silicon (Si), then cold-rolled to the final thickness, and then decarburized and annealed. It is manufactured by finish annealing. In decarburization annealing (primary recrystallization annealing), a silicon dioxide film is formed on the surface of the steel sheet, a slurry containing magnesium oxide for annealing separator is applied to the surface, dried, wound into a coil, and then annealed to the finish. By doing so, as shown in the following reaction formula, silicon dioxide (SiO 2 ) and magnesium oxide (MgO) react to form a forsterite (Mg 2 SiO 4 ) coating on the steel sheet surface.
2MgO + SiO 2 → Mg 2 SiO 4 (I)
This forsterite film is important because it imparts tension to the surface of the steel sheet, reduces iron loss, improves magnetic properties, and provides insulation to the steel sheet.
他方、フォルステライト被膜下の地鉄部についてみると、塗布された焼鈍分離剤により析出物の生成・成長挙動や結晶粒の成長挙動が影響を及ぼされるため、このMgOの種々の特性により方向性電磁鋼板の製品特性は大きく変化する。例えば、MgOをスラリー化した際に持ち込まれる水分が多すぎると鋼板が酸化されて磁気特性が劣化したり被膜に点状欠陥が生成したりする。また、MgO中に含まれる不純物が焼鈍中に鋼中に侵入し、結晶粒成長抑制力が変化することを通じて二次再結晶挙動が変化すること等も知られており、方向性電磁鋼板の特性を向上するために、焼鈍分離剤用酸化マグネシウムに含有される微量成分について、以下に示す通り、種々の研究が行われている。焼鈍分離剤用酸化マグネシウム中の含有量の制御が検討されている微量成分として、酸化カルシウム(CaO)、ホウ素(B)、亜硫酸(SO3)、フッ素(F)、及び塩素(Cl)等が挙げられる。さらに、微量成分の含有量だけでなく、焼鈍分離剤用酸化マグネシウム中の、微量成分元素を含む化合物の構造を検討する試みが行われている。 On the other hand, when looking at the base metal part under the forsterite film, the applied annealing separator affects the formation and growth behavior of precipitates and the growth behavior of crystal grains. The product characteristics of electrical steel sheets vary greatly. For example, if too much moisture is brought into the slurry when MgO is slurried, the steel sheet is oxidized and the magnetic properties are deteriorated or point defects are generated in the coating. It is also known that impurities contained in MgO penetrate into steel during annealing, and the secondary recrystallization behavior changes through changes in the grain growth inhibition force. In order to improve the above, various studies have been conducted on trace components contained in magnesium oxide for annealing separators as described below. As trace components for which the control of the content in magnesium oxide for annealing separators is studied, calcium oxide (CaO), boron (B), sulfurous acid (SO 3 ), fluorine (F), chlorine (Cl), etc. Can be mentioned. Furthermore, not only the content of a trace component but also an attempt to examine the structure of a compound containing a trace component element in magnesium oxide for annealing separator.
そこで、まず、焼鈍分離剤用酸化マグネシウム中の含有量の制御が検討されている微量成分のうち、酸化マグネシウムを製造するに際し、不純物として残留するCaOに着目するものとして、CaOとB量との関係を特定値(〔CaO%〕×〔B%〕=0.025〜0.30)におき、CAA値(クエン酸活性度値)(60〜250秒)、粒度(10μm以下:60%以上)を満足するように調整することにより、低水和性でありながら、鋼板との付着性力が優れ、下地被膜との反応性に優れる焼鈍分離剤が提案され(特許文献1)、他方、MgCl2とCa(OH)2のスラリーからMg(OH)2を経由してMgOを得る工程を考慮して、不純物としてのCaOだけでなく、ハロゲン量を制限するものとして、CaOを0.35〜0.50wt%、SO3を0.3〜1.5wt%、ハロゲンを0.05wt%以下及びBを0.06〜0.10wt%含有する焼鈍分離剤が提案されている(特許文献2)。 Therefore, first, among the trace components for which the control of the content in the magnesium oxide for the annealing separator is being studied, when manufacturing magnesium oxide, attention is paid to CaO remaining as an impurity. The relationship is set to a specific value ([CaO%] × [B%] = 0.025 to 0.30), CAA value (citric acid activity value) (60 to 250 seconds), particle size (10 μm or less: 60% or more) ), An annealing separator having excellent adhesion to the steel sheet and excellent reactivity with the undercoat is proposed (Patent Document 1). Considering the process of obtaining MgO from the slurry of MgCl 2 and Ca (OH) 2 via Mg (OH) 2 , not only CaO as an impurity but also the amount of halogen is limited to 0.35. ~ 0.5 An annealing separator containing 0 wt%, SO 3 0.3 to 1.5 wt%, halogen 0.05 wt% or less and B 0.06 to 0.10 wt% has been proposed (Patent Document 2).
また、特に塩素に着目するものとして、製造工程における原料調整段階において、Mg,Ca,Ba,Cu,Fe,Zn,Mn,Zr,Co,Ni,Al,Sn,Vの中から選ばれる塩素化合物の1種又は2種以上を、Clとして0.005〜0.060%、およびBを〔Cl(%)〕×〔B(%)〕=0.001〜0.004となるように、それぞれ含有するよう調整され、且つ、測定温度30℃におけるCAA値50〜150秒で、粒子径10μm以下のものが70%以上であることを特徴とする、均一な高張力グラス被膜と優れた磁気特性を得るための方向性電磁鋼板用焼鈍分離剤が提案され(特許文献3)、同じく、仕上げ高温焼鈍前に冷間圧延方向性珪素鋼を被覆するための25℃以下に維持されたマグネシアスラリーであって、a)主要量のマグネシア粒子のクエン酸活性が200秒以下のマグネシア;b)Mg、Ca、Na及び/またはKからなる群から選択された金属塩化物からの少なくとも0.01重量%の塩素によるものであるマグネシアの重量を基準として0.01〜0.20重量%のマグネシア中の合計塩素レベル;c)15%までのTiO2;d)10%までのSiO2;e)15%までのCr;及びc)0.3%までの硼素より実質上なることを特徴とするマグネシアスラリーが提案され(特許文献4)、最終的にMgOを主成分とする焼鈍分離剤の水和水分を0.5〜2.0%とし、焼鈍分離剤へ塩素化合物の総塩素含有量が0.020%〜0.080%となるように添加し、かつ、焼鈍分離剤の水和水分とCl含有量の関係式が提案されている(特許文献5)。 In particular, as a focus on chlorine, a chlorine compound selected from Mg, Ca, Ba, Cu, Fe, Zn, Mn, Zr, Co, Ni, Al, Sn, and V in the raw material adjustment stage in the manufacturing process. 1 or 2 or more, and 0.005 to 0.060% as Cl, and B is [Cl (%)] × [B (%)] = 0.001 to 0.004, respectively. Uniform high-tensile glass coating and excellent magnetic properties, characterized by being contained and having a CAA value of 50 to 150 seconds at a measurement temperature of 30 ° C. and a particle size of 10 μm or less being 70% or more An annealing separator for grain-oriented electrical steel sheets is proposed (Patent Document 3), which is also a magnesia slurry maintained at 25 ° C. or lower for coating cold-rolled grain-oriented silicon steel before finish high temperature annealing. A A) magnesia with a major amount of magnesia particles having a citric acid activity of 200 seconds or less; b) with at least 0.01% by weight of chlorine from a metal chloride selected from the group consisting of Mg, Ca, Na and / or K Total chlorine level in magnesia from 0.01 to 0.20% by weight, based on the weight of magnesia, c) up to 15% TiO 2 ; d) up to 10% SiO 2 ; e) up to 15% Cr And c) a magnesia slurry characterized by being substantially composed of boron up to 0.3% (Patent Document 4), and finally the hydration moisture of the annealing separator mainly composed of MgO is set to 0. 5 to 2.0%, added to the annealing separator so that the total chlorine content of the chlorine compound is 0.020% to 0.080%, and the hydration moisture and Cl content of the annealing separator Relational expressions have been proposed ( Patent Document 5).
さらに、製造工程の塩素、CaOだけでなく、ホウ素(B)、亜硫酸(SO3)に着目し、CAA及び水和量を制御するものとして、前記焼鈍分離剤中のマグネシアとして、不純物のCl濃度が0.01〜0.04mass%、CaO濃度が0.25〜0.70mass%、B濃度が0.05〜0.15mass%、SO3濃度が0.05〜0.50mass%、CAA40%が50〜90秒を満足し、さらに20℃,30分の水和試験による水和量が1.5〜2.5mass%でかつ20℃,180分の水和試験による水和量が3.0〜5.0mass%である粉体を用いるもの(特許文献6)、マグネシアとして、BET比表面積が36〜50m2/g、不純物のCl濃度が0.02〜0.04%、CAA40%が35〜65秒、CAA80%が80〜160秒のものを、10mass%以上配合し、かつ、2種以上の混合物からなるマグネシアの平均特性が、BET比表面積:20〜35m2/g、不純物のCl濃度:0.01〜0.04%、CaO濃度:0.25〜0.70%、B濃度:0.05〜0.15%、SO3濃度:0.05〜0.50%、CAA40%:55〜85秒、CAA80%:100〜250秒および20℃,60分の水和試験による水和量:1.5〜3.5mass%を満足することを特徴とする焼鈍分離剤用のマグネシアが提案されている(特許文献7)。 Furthermore, focusing on not only chlorine and CaO but also boron (B) and sulfurous acid (SO 3 ) in the manufacturing process, and controlling CAA and the amount of hydration, as the magnesia in the annealing separator, the Cl concentration of impurities There 0.01~0.04mass%, CaO concentration 0.25~0.70mass%, B concentration 0.05~0.15mass%, SO 3 concentration 0.05~0.50mass%, is CAA40% 50 to 90 seconds were satisfied, and the hydration amount in a hydration test at 20 ° C. for 30 minutes was 1.5 to 2.5 mass%, and the hydration amount in a hydration test at 20 ° C. for 180 minutes was 3.0. Using powder having a mass of ˜5.0 mass% (Patent Document 6), as magnesia, the BET specific surface area is 36 to 50 m 2 / g, the Cl concentration of impurities is 0.02 to 0.04%, and the CAA 40% is 35 ~ 65 seconds, C What A80% is 80 to 160 seconds, blended least 10 mass%, and the average properties of magnesia consisting of a mixture of two or more kinds, BET specific surface area: 20-35 meters 2 / g, impurities Cl concentration: 0. from 01 to .04%, CaO concentration: 0.25 to 0.70%, B concentration: 0.05~0.15%, SO 3 concentration: 0.05~0.50%, CAA40%: 55~85 Second, CAA 80%: 100-250 seconds and 20 ° C., 60 minutes of hydration amount: 1.5-3.5 mass%, magnesia for annealing separator is proposed (Patent Document 7).
他方、酸化マグネシウムにリン酸ナトリウム化合物を少なくとも1種の添加剤として使用するもの(特許文献8)、酸化マグネシウムに窒化物系および/または硫化物系のインヒビターとして塩化アンモニウム(NH4ClまたはNH4Cl・nH2O)を用い、最終焼鈍のための昇温過程で早期劣化することを防止するもの(特許文献9)、マグネシアを主剤とする焼鈍分離剤に水溶性化合物を添加し、副インヒビターを含有する素材における問題点を解決するものも提案されている(特許文献10)。 On the other hand, a sodium phosphate compound is used as an additive for magnesium oxide (Patent Document 8), and ammonium chloride (NH 4 Cl or NH 4 ) is used as a nitride-based and / or sulfide-based inhibitor for magnesium oxide. Cl · nH 2 O), which prevents early deterioration in the temperature raising process for final annealing (Patent Document 9), a water-soluble compound is added to an annealing separator containing magnesia as a main component, and a secondary inhibitor The thing which solves the problem in the raw material which contains is proposed (patent document 10).
以上、方向性電磁鋼板の磁気特性の改善について、種々研究開発されているが、従来の焼鈍分離剤用酸化マグネシウムでは、方向性電磁鋼板の磁気特性を十分には向上できていない。すなわち十分な性能を有する焼鈍分離剤用酸化マグネシウムは未だ見出されていない。 As described above, various researches and developments have been made on improving the magnetic properties of grain-oriented electrical steel sheets. However, conventional magnesium oxide for annealing separators cannot sufficiently improve the magnetic properties of grain-oriented electrical steel sheets. That is, magnesium oxide for annealing separators having sufficient performance has not been found yet.
そこで本発明は、磁気特性に優れた方向性電磁鋼板を得るための焼鈍分離剤用酸化マグネシウムを提供することを目的とする。具体的には、優れたフォルステライト被膜を形成でき、鉄損及び磁束密度の特性に優れた方向性電磁鋼板を提供することができる焼鈍分離剤用酸化マグネシウム及びそれを用いた方向性電磁鋼板の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide magnesium oxide for an annealing separator for obtaining a grain-oriented electrical steel sheet having excellent magnetic properties. Specifically, magnesium oxide for an annealing separator capable of forming an excellent forsterite film and providing a grain-oriented electrical steel sheet having excellent iron loss and magnetic flux density characteristics, and a grain-oriented electrical steel sheet using the same. An object is to provide a manufacturing method.
本発明者らは上記従来技術を考慮して鋭意研究の結果、フォルステライト被膜の組成に関与するホウ素成分とナトリウム成分の総モル数を考慮し、フォルステライト被膜の形成速度に関与する塩素成分及び硫黄成分を制限しつつ、焼鈍分離剤中のホウ素とナトリウムの含有総モル数に対する塩素及び硫黄の含有総モル数を所定の比率に制限すると、優れたフォルステライト被膜を形成でき、方向性電磁鋼板の鉄損及び磁束密度の特性を向上することができることを見出した。 As a result of diligent research in consideration of the above-described prior art, the present inventors considered the total mole number of the boron component and sodium component involved in the composition of the forsterite film, the chlorine component involved in the formation rate of the forsterite film, and An excellent forsterite film can be formed by limiting the total number of moles of chlorine and sulfur with respect to the total number of moles of boron and sodium in the annealing separator while limiting the sulfur component, and a grain-oriented electrical steel sheet. It has been found that the iron loss and magnetic flux density characteristics can be improved.
即ち、本発明は、ホウ素を400〜1500質量ppm、ナトリウムを1〜650質量ppm、塩素を500質量ppm以下、硫黄をSO3換算で0.10〜0.70質量%含有し、かつホウ素及びナトリウムの合計含有モルに対する塩素及び硫黄の合計含有モル比(Cl+S)/(B+Na)が0.50〜0.80である焼鈍分離剤用酸化マグネシウムを提供するものである。 That is, the present invention contains 400 to 1500 ppm by mass of boron, 1 to 650 ppm by mass of sodium, 500 ppm by mass or less of chlorine, 0.10 to 0.70% by mass of sulfur in terms of SO 3 , and boron and Provided is a magnesium oxide for an annealing separator having a total content molar ratio of chlorine and sulfur (Cl + S) / (B + Na) of 0.50 to 0.80 with respect to the total content of sodium.
本発明によれば、酸化マグネシウムを主剤とする焼鈍分離剤において、ホウ素成分とナトリウム成分の総モル数を考慮し、塩素成分及び硫黄成分を制限しつつ、焼鈍分離剤中のホウ素とナトリウムの含有総モル数に対する塩素及び硫黄の含有総モル数を所定の比率に制限すると、磁気特性に優れた方向性電磁鋼板を得ることができる。具体的には、本発明に係る焼鈍分離剤用酸化マグネシウムを用い、鋼板表面に二酸化ケイ素被膜を形成した後、二酸化ケイ素被膜の表面に上記焼鈍分離剤を塗布し、焼鈍することにより、鋼板の表面に、優れたフォルステライト被膜を形成することができ、方向性電磁鋼板の鉄損及び磁束密度の特性を向上することができる。 According to the present invention, in the annealing separator having magnesium oxide as the main component, considering the total number of moles of the boron component and the sodium component, while limiting the chlorine component and the sulfur component, the inclusion of boron and sodium in the annealing separator When the total number of moles of chlorine and sulfur relative to the total number of moles is limited to a predetermined ratio, a grain-oriented electrical steel sheet having excellent magnetic properties can be obtained. Specifically, by using the magnesium oxide for annealing separator according to the present invention, after forming a silicon dioxide film on the surface of the steel sheet, by applying the annealing separator on the surface of the silicon dioxide film and annealing, An excellent forsterite film can be formed on the surface, and the iron loss and magnetic flux density characteristics of the grain-oriented electrical steel sheet can be improved.
リンを100〜1000質量ppm含有することにより、更に優れたフォルステライト被膜を形成することができ、更に方向性電磁鋼板の鉄損及び磁束密度の特性を向上することができる。 By containing 100 to 1000 ppm by mass of phosphorus, a further excellent forsterite film can be formed, and the iron loss and magnetic flux density characteristics of the grain-oriented electrical steel sheet can be further improved.
本発明の酸化マグネシウムは、酸化マグネシウムを主体とし、ホウ素を400〜1500質量ppm、ナトリウムを1〜650質量ppm、塩素を500質量ppm以下、硫黄をSO3換算で0.10〜0.70質量%含有し、かつホウ素及びナトリウム合計含有モルに対する塩素及び硫黄の合計含有モル比(Cl+S)/(B+Na)が0.50〜0.80であって、リンを100〜1000質量ppm含有し、方向性電磁鋼板の焼鈍分離剤として使用される。その物性は、例えば、体積基準の累積10%粒子径(D10)が3μm以下であり、例えば、CAA40%が50〜200秒である。なお、本明細書中、特に断りのない限り、ppmは質量ppmを意味し、%は質量%を意味する。 The magnesium oxide of the present invention is mainly composed of magnesium oxide, boron is 400 to 1500 mass ppm, sodium is 1 to 650 mass ppm, chlorine is 500 mass ppm or less, and sulfur is 0.10 to 0.70 mass in terms of SO 3. %, And the total molar ratio of chlorine and sulfur to the total moles of boron and sodium (Cl + S) / (B + Na) is 0.50 to 0.80, containing 100 to 1000 ppm by mass of phosphorus, direction Used as an annealing separator for heat-resistant electrical steel sheets. As for the physical properties, for example, the volume-based cumulative 10% particle diameter (D 10 ) is 3 μm or less, and for example, CAA 40% is 50 to 200 seconds. In the present specification, unless otherwise specified, ppm means mass ppm, and% means mass%.
まず、本発明の酸化マグネシウムに添加成分として含有される各成分の含有率から順に説明する。 First, the content of each component contained in the magnesium oxide of the present invention as an additive component will be described in order.
ホウ素(B)は、焼鈍分離剤MgOと電磁鋼板の表面SiO2との反応で形成されるフォルステライトMg2SiO4の被膜形成を促進する元素であり、通常、焼鈍分離剤MgOの製造工程で所定量を添加すればよく、例えばホウ酸、ホウ酸マグネシウム、ホウ酸カルシウム、ホウ酸ナトリウム、及び酸化ホウ素から選択できる少なくとも1種類以上を反応前の水酸化マグネシウムの原料である塩化マグネシウム溶液又は水酸化カルシウムスラリー中に添加することができ、また、反応後の水酸化マグネシウムスラリー中に添加することができる。さらに、ろ過、水洗、乾燥後の水酸化マグネシウム粉体に混合添加することもできる。その後水酸化マグネシウムを焼成して酸化マグネシウムの粉末を得るが、酸化マグネシウム中のホウ素は400〜1500ppmとなるように調整される。酸化マグネシウム中のホウ素量はさらに、同様の製造方法によって得られたホウ素含有量が違う酸化マグネシウムを混合することで調整することもできる。ここで、400ppm未満ではフォルステライトの十分な被膜が形成されず、一方1500ppmより多いと過剰に厚い被膜が形成されて点状欠陥の原因となり、いずれも良好な被膜特性が得られない。したがって、400〜1500ppm、好ましくは550〜1400ppmの範囲、より好ましくは700〜1300ppmの範囲とする。 Boron (B) is an element that promotes film formation of forsterite Mg 2 SiO 4 formed by the reaction between the annealing separator MgO and the surface SiO 2 of the electrical steel sheet. Usually, in the manufacturing process of the annealing separator MgO A predetermined amount may be added, for example, at least one selected from boric acid, magnesium borate, calcium borate, sodium borate, and boron oxide, magnesium chloride solution or water that is a raw material of magnesium hydroxide before the reaction It can be added to the calcium oxide slurry, and can be added to the magnesium hydroxide slurry after the reaction. Further, it can be mixed and added to the magnesium hydroxide powder after filtration, washing and drying. Thereafter, magnesium hydroxide is baked to obtain a magnesium oxide powder, and boron in the magnesium oxide is adjusted to 400 to 1500 ppm. The amount of boron in magnesium oxide can be further adjusted by mixing magnesium oxides having different boron contents obtained by the same production method. Here, if it is less than 400 ppm, a sufficient film of forsterite cannot be formed. On the other hand, if it exceeds 1500 ppm, an excessively thick film is formed, causing point-like defects, and none of the good film characteristics can be obtained. Therefore, the range is 400-1500 ppm, preferably 550-1400 ppm, more preferably 700-1300 ppm.
ナトリウム(Na)は、フォルステライト被膜形成速度を調整する元素であり、通常、焼鈍分離剤MgOの製造工程で所定量を添加すればよく、例えば塩化ナトリウム、硝酸ナトリウム、リン酸ナトリウム、硫酸ナトリウム、及びホウ酸ナトリウムから選択できる少なくとも1種類以上を反応前の水酸化マグネシウムの原料である塩化マグネシウム溶液又は水酸化カルシウムスラリー中に添加することができ、また、反応後の水酸化マグネシウムスラリー中に添加することができる。さらに、ろ過、水洗、乾燥後の水酸化マグネシウム粉体に混合添加することもできる。その後水酸化マグネシウムを焼成して酸化マグネシウムの粉末を得るが、酸化マグネシウム中のナトリウムは1〜650ppmとなるように調整される。酸化マグネシウム中のナトリウムはさらに、同様の製造方法によって得られたナトリウム含有量が違う酸化マグネシウムを混合することで調整することもできる。ここで、1ppm未満ではフォルステライト被膜形成速度が遅く、十分な被膜が形成されず、一方650ppmより多いと被膜形成速度が速くなりすぎ、過剰に厚い被膜が形成されて点状欠陥の原因となり、いずれも良好な被膜特性が得られない。したがって、1〜650ppm、好ましくは5〜640ppm、より好ましくは10〜630ppm、特に好ましくは10〜620ppmの範囲とする。 Sodium (Na) is an element that adjusts the forsterite film formation rate, and usually a predetermined amount may be added in the manufacturing process of the annealing separator MgO. For example, sodium chloride, sodium nitrate, sodium phosphate, sodium sulfate, And at least one selected from sodium borate can be added to the magnesium hydroxide solution or calcium hydroxide slurry, which is the raw material of magnesium hydroxide before the reaction, and added to the magnesium hydroxide slurry after the reaction. can do. Further, it can be mixed and added to the magnesium hydroxide powder after filtration, washing and drying. Thereafter, magnesium hydroxide is calcined to obtain a magnesium oxide powder, and sodium in the magnesium oxide is adjusted to 1 to 650 ppm. Sodium in magnesium oxide can be further adjusted by mixing magnesium oxides having different sodium contents obtained by the same production method. Here, if it is less than 1 ppm, the forsterite film formation rate is slow and a sufficient film is not formed, while if it exceeds 650 ppm, the film formation rate is too high, and an excessively thick film is formed, causing point defects. In either case, good film properties cannot be obtained. Therefore, the range is 1 to 650 ppm, preferably 5 to 640 ppm, more preferably 10 to 630 ppm, and particularly preferably 10 to 620 ppm.
塩素(Cl)は、フォルステライト被膜形成を促進する元素であり、塩化物の添加はガラス被膜形成温度を低下し、低温で表面をシールする。通常、MgCl2とCa(OH)2のスラリーからMg(OH)2を製造する工程で反応条件(反応温度、反応時間、反応率)により塩素量を制御することができるが、塩素量が不足する場合は、さらに金属塩化物を、反応前の水酸化マグネシウムの原料である塩化マグネシウム溶液又は水酸化カルシウムスラリー中に添加することができ、また、反応後の水酸化マグネシウムスラリー中に添加することができる。さらに、ろ過、水洗、乾燥後の水酸化マグネシウム粉体に混合添加することもできる。前記金属塩化物としては塩素を含む組成物であれば特に限定されないが、例えば塩化ナトリウム、塩化マグネシウム、塩化カルシウムから選択できる少なくとも1種類以上を添加することで制御できる。また、反応条件により水酸化マグネシウムの粒子形状、粒子径、凝集状態を制御し、さらに洗浄条件(時間、水洗時の水量等)により塩素量を制御できる。酸化マグネシウム中の塩素はさらに、同様の製造方法によって得られた塩素含有量が違う酸化マグネシウムを混合することで調整することもできる。ここで、500ppmより多いと過剰に被膜形成が促進され、過剰に厚い被膜が形成されて点状欠陥の原因となり、良好な被膜特性が得られない。最終的に焼成されて得られる酸化マグネシウム中の塩素量は500ppm以下、好ましくは50〜450ppmの範囲、より好ましくは150〜400ppmの範囲とする。 Chlorine (Cl) is an element that promotes forsterite film formation, and the addition of chloride lowers the glass film formation temperature and seals the surface at a low temperature. Usually, the amount of chlorine can be controlled by the reaction conditions (reaction temperature, reaction time, reaction rate) in the process of producing Mg (OH) 2 from a slurry of MgCl 2 and Ca (OH) 2 , but the amount of chlorine is insufficient In this case, the metal chloride can be added to the magnesium chloride solution or calcium hydroxide slurry, which is the raw material of the magnesium hydroxide before the reaction, and added to the magnesium hydroxide slurry after the reaction. Can do. Further, it can be mixed and added to the magnesium hydroxide powder after filtration, washing and drying. Although it will not specifically limit if it is a composition containing chlorine as said metal chloride, For example, it can control by adding at least 1 or more types selected from sodium chloride, magnesium chloride, and calcium chloride. Moreover, the particle shape, particle diameter, and aggregation state of magnesium hydroxide can be controlled by reaction conditions, and the chlorine amount can be controlled by washing conditions (time, amount of water at the time of washing, etc.). Chlorine in magnesium oxide can be further adjusted by mixing magnesium oxides having different chlorine contents obtained by the same production method. Here, if it exceeds 500 ppm, film formation is excessively promoted, an excessively thick film is formed, causing point defects, and good film characteristics cannot be obtained. The chlorine content in the magnesium oxide finally obtained by firing is 500 ppm or less, preferably in the range of 50 to 450 ppm, more preferably in the range of 150 to 400 ppm.
硫黄(S)は、フォルステライト被膜形成を促進し、被膜の形態に影響を与える元素である。通常、焼鈍分離剤MgOの製造工程で所定量を添加すればよく、例えば硫酸マグネシウム、硫酸カルシウム、及び硫酸ナトリウムから選択できる少なくとも1種類以上を反応前の水酸化マグネシウムの原料である塩化マグネシウム溶液又は水酸化カルシウムスラリー中に添加することができ、また、反応後の水酸化マグネシウムスラリー中に添加することができる。さらに、ろ過、水洗、乾燥後の水酸化マグネシウム粉体に混合添加することもできる。その後水酸化マグネシウムを焼成して酸化マグネシウムの粉末を得るが、酸化マグネシウム中の硫黄はSO3換算で0.10から0.70質量%となるように調整される。酸化マグネシウム中の硫黄はさらに、同様の製造方法によって得られた硫黄含有量が違う酸化マグネシウムを混合することで調整することもできる。ここで、0.10質量%未満では地鉄と被膜の界面の凹凸がなくなって被膜が剥離しやすくなり、一方0.70質量%より多いと十分な被膜が形成されず、いずれも良好な被膜特性が得られない。従って、0.10〜0.70質量%、好ましくは0.20〜0.60質量%の範囲、より好ましくは0.30〜0.50質量%の範囲とする。 Sulfur (S) is an element that promotes forsterite film formation and affects the form of the film. Usually, a predetermined amount may be added in the manufacturing process of the annealing separator MgO. For example, at least one selected from magnesium sulfate, calcium sulfate, and sodium sulfate may be a magnesium chloride solution that is a raw material of magnesium hydroxide before the reaction or It can be added to the calcium hydroxide slurry and can be added to the magnesium hydroxide slurry after the reaction. Further, it can be mixed and added to the magnesium hydroxide powder after filtration, washing and drying. Thereafter, magnesium hydroxide is fired to obtain a magnesium oxide powder, and the sulfur in the magnesium oxide is adjusted to be 0.10 to 0.70% by mass in terms of SO 3 . The sulfur in the magnesium oxide can be further adjusted by mixing magnesium oxides having different sulfur contents obtained by the same production method. Here, if the amount is less than 0.10% by mass, the unevenness at the interface between the base iron and the film is lost, and the film is easily peeled off. Characteristics are not obtained. Accordingly, the range is 0.10 to 0.70 mass%, preferably 0.20 to 0.60 mass%, more preferably 0.30 to 0.50 mass%.
塩素及び硫黄は被膜形成を促進する元素である一方、ホウ素も被膜形成を促進する元素である。しかしながら塩素及び硫黄は、MgOの表面水和層の反応性に寄与する結果、被膜促進するものであるのに対し、ホウ素はガラス状になったホウ素化合物がMgO粒子の表面に存在することで焼結を促進するもので、被膜形成への関与因子として塩素及び硫黄の過剰は被膜の過酸化による不良に直接影響するが、ホウ素の過剰はそれほどでもない。そこで、まず、被膜促進元素のバランスを、塩素及び硫黄合計含有モルに対するホウ素モルの比率(Cl+S)/Bで考慮するのが肝要である。一方、ナトリウムは被膜抑制元素であるが、他の金属イオンと容易に結合して、低融点化合物を形成し、被膜促進元素が過多となると、深さ方向へのアンカーとなる被膜が過剰に形成され、磁束密度に悪影響を与える。したがって、ナトリウムはガラス状になったホウ素化合物をMgO粒子の表面に存在させるホウ素との関係で塩素及び硫黄合計含有モルに対するバランスをとることにより、密着性と高磁束密度のバランスをとることが肝要である。よって、ホウ素及びナトリウム含有モルに対する塩素及び硫黄合計含有モル比(Cl+S)/(B+Na)は0.50〜0.80範囲に調整され、フォルステライト被膜の形成を良好に保持するのが好ましい。 Chlorine and sulfur are elements that promote film formation, while boron is also an element that promotes film formation. However, while chlorine and sulfur contribute to the reactivity of the surface hydration layer of MgO and promote coating, boron is baked due to the presence of glassy boron compounds on the surface of MgO particles. As a factor that contributes to film formation, excess of chlorine and sulfur directly affects defects due to overoxidation of the film, but excess of boron is not so much. Therefore, it is important to first consider the balance of the film-promoting elements by the ratio of the mole of boron to the total moles of chlorine and sulfur (Cl + S) / B. On the other hand, although sodium is a film-inhibiting element, it easily binds to other metal ions to form a low-melting compound, and when the film-promoting element is excessive, an excessive film that becomes an anchor in the depth direction is formed. Adversely affects the magnetic flux density. Therefore, it is important for sodium to balance adhesion and high magnetic flux density by balancing the total content of chlorine and sulfur with respect to the boron containing glassy boron compound on the surface of MgO particles. It is. Therefore, it is preferable that the total molar content ratio of chlorine and sulfur (Cl + S) / (B + Na) with respect to the boron and sodium-containing mole is adjusted in the range of 0.50 to 0.80 and the formation of the forsterite film is favorably maintained.
リン(P)は、被膜形成を促進する元素である。通常、焼鈍分離剤MgOの製造工程で所定量を添加すればよく、例えばリン酸、リン酸マグネシウム、及びリン酸カルシウムから選択できる少なくとも1種類以上を反応前の水酸化マグネシウムの原料である塩化マグネシウム溶液又は水酸化カルシウムスラリー中に添加することができ、反応後の水酸化マグネシウムスラリー中に添加することができ、ろ過、水洗、乾燥後の水酸化マグネシウム粉体に混合添加することもできる。その後水酸化マグネシウムを焼成して酸化マグネシウムの粉末を得るが、酸化マグネシウム中のリンは100〜1000ppmとなるように調整される。酸化マグネシウム中のリンはさらに、同様の製造方法によって得られたリン含有量が違う酸化マグネシウムを混合することで調整することもできる。すなわち、100ppm未満では十分な被膜が形成されず、一方1000ppmより多いと過剰に厚い被膜が形成されて点状欠陥の原因となり、いずれも良好な被膜特性が得られない。従って、100〜1000ppm、好ましくは120〜900ppmの範囲、より好ましくは150〜600ppmの範囲とする。 Phosphorus (P) is an element that promotes film formation. Usually, a predetermined amount may be added in the manufacturing process of the annealing separator MgO, for example, a magnesium chloride solution that is a raw material of magnesium hydroxide before reaction with at least one kind selected from phosphoric acid, magnesium phosphate, and calcium phosphate or It can be added to the calcium hydroxide slurry, can be added to the magnesium hydroxide slurry after the reaction, and can be mixed and added to the magnesium hydroxide powder after filtration, washing with water and drying. Thereafter, magnesium hydroxide is fired to obtain a magnesium oxide powder, and the phosphorus in the magnesium oxide is adjusted to 100 to 1000 ppm. The phosphorus in the magnesium oxide can be further adjusted by mixing magnesium oxides having different phosphorus contents obtained by the same production method. That is, if it is less than 100 ppm, a sufficient film is not formed. On the other hand, if it exceeds 1000 ppm, an excessively thick film is formed, causing point defects, and none of the film characteristics are good. Therefore, the range is 100 to 1000 ppm, preferably 120 to 900 ppm, more preferably 150 to 600 ppm.
なお、リンも、硫黄及び塩素と同様、MgOの表面水和層の反応性に寄与する結果、被膜促進するものである。酸化マグネシウム中のリンは100〜1000ppmとなるように調整されるが、ホウ素及びナトリウム含有モルに対する塩素及び硫黄合計含有モル比(S+Cl)/(B+Na)はリン含有モル数を含め、(S+Cl+P)/(B+Na)は好ましくは、0.55〜0.85の範囲、より好ましくは0.60〜0.80の範囲とする。 Phosphorus, like sulfur and chlorine, contributes to the reactivity of the MgO surface hydrated layer, and as a result, promotes coating. The phosphorus in the magnesium oxide is adjusted to 100 to 1000 ppm, but the total molar ratio of chlorine and sulfur to the boron and sodium-containing moles (S + Cl) / (B + Na) includes the number of moles containing phosphorus, (S + Cl + P) / (B + Na) is preferably in the range of 0.55 to 0.85, more preferably in the range of 0.60 to 0.80.
体積基準の累積10%粒子径(D10)は3μm以下が好ましく、クエン酸活性度(CAA40%)は50〜200秒が好ましい。体積基準の累積10%粒子径(D10)が3μmを超えると、酸化マグネシウムの一次粒子径が粗大になり、酸化マグネシウム粒子の反応性が悪くなるため、フォルステライト被膜形成速度が遅くなり、十分な被膜が形成されず、方向性電磁鋼板の鉄損及び磁束密度の特性が悪くなる。よって、好ましくは3μm以下、より好ましくは2.9μm以下の範囲とする。 The volume-based cumulative 10% particle diameter (D 10 ) is preferably 3 μm or less, and the citric acid activity (CAA 40%) is preferably 50 to 200 seconds. When the volume-based cumulative 10% particle diameter (D 10 ) exceeds 3 μm, the primary particle diameter of magnesium oxide becomes coarse, and the reactivity of the magnesium oxide particles becomes poor. The film is not formed, and the iron loss and magnetic flux density characteristics of the grain-oriented electrical steel sheet are deteriorated. Therefore, the range is preferably 3 μm or less, more preferably 2.9 μm or less.
他方、CAAは固相−液相反応により、実際の電磁鋼板の表面で起こる二酸化ケイ素と酸化マグネシウムとの固相−固相反応の反応性を、経験的にシミュレートしており、一次粒子を含む酸化マグネシウム粒子の反応性を測定するものである。酸化マグネシウムのCAA40%が200秒より大きければ、酸化マグネシウム粒子の反応性が悪く、フォルステライト被膜形成速度が遅くなることから、十分な被膜が形成されず、方向性電磁鋼板の鉄損及び磁束密度の特性が悪くなる。他方、酸化マグネシウムのCAA40%が50秒未満であれば、酸化マグネシウム粒子の反応性が速くなりすぎ、均一なフォルステライト被膜ができなくなり、方向性電磁鋼板の鉄損及び磁束密度の特性が悪くなる。すなわち、上述したクエン酸活性度は50秒未満では水和量が大きくなりすぎ、一方200秒を超えると反応性が低すぎて、いずれの場合も良好な被膜特性が得られない。よって、好ましくは50〜200秒の範囲、より好ましくは60〜150秒の範囲とする。なお、ここでクエン酸活性度(CAA40%)とは、温度:303K、0.4Nのクエン酸水溶液中に40%の最終反応当量の酸化マグネシウムを投与して攪拌したときの、最終反応までの時間、つまりクエン酸が消費され溶液が中性となるまでの時間を意味する。 On the other hand, CAA empirically simulates the reactivity of solid phase-solid phase reaction between silicon dioxide and magnesium oxide that occurs on the surface of an actual electrical steel sheet by solid phase-liquid phase reaction. The reactivity of the magnesium oxide particle contained is measured. If CAA 40% of magnesium oxide is greater than 200 seconds, the reactivity of magnesium oxide particles is poor and the forsterite film formation rate is slow, so that a sufficient film is not formed, and the iron loss and magnetic flux density of the grain-oriented electrical steel sheet The characteristics of become worse. On the other hand, if the CAA 40% of magnesium oxide is less than 50 seconds, the reactivity of the magnesium oxide particles becomes too fast, a uniform forsterite film cannot be formed, and the iron loss and magnetic flux density characteristics of the grain-oriented electrical steel sheet deteriorate. . That is, when the above-mentioned citric acid activity is less than 50 seconds, the amount of hydration becomes too large, while when it exceeds 200 seconds, the reactivity is too low, and in any case, good film properties cannot be obtained. Accordingly, the range is preferably 50 to 200 seconds, more preferably 60 to 150 seconds. Here, citric acid activity (CAA 40%) is the temperature up to the final reaction when 40% of the final reaction equivalent of magnesium oxide is administered and stirred in a 0.4N citric acid aqueous solution at a temperature of 303K. It means time, that is, the time until citric acid is consumed and the solution becomes neutral.
本発明において、酸化マグネシウムの製造方法は公知の方法を用いることができる。例えば、原料として塩化マグネシウムを用い、この水溶液に水酸化カルシウムをスラリーの状態で添加し反応させ、水酸化マグネシウムを形成する。次いで、この水酸化マグネシウムを、ろ過、水洗、乾燥させた後、加熱炉で焼成し、酸化マグネシウムを形成し、これを所望の粒径まで粉砕して、製造することができる。 In the present invention, a known method can be used as a method for producing magnesium oxide. For example, magnesium chloride is used as a raw material, and calcium hydroxide is added to this aqueous solution in a slurry state and reacted to form magnesium hydroxide. Next, this magnesium hydroxide can be filtered, washed with water, dried and then fired in a heating furnace to form magnesium oxide, which can be pulverized to a desired particle size.
また、水酸化カルシウムの代わりに、水酸化ナトリウム、水酸化カリウム等の水酸基を有するアルカリ性化合物を用いることもできる。また、海水、潅水、苦汁等のような塩化マグネシウム含有水溶液を反応器に導入し、1773〜2273Kで直接酸化マグネシウムと塩酸を生成させるアマン法(Aman process)により酸化マグネシウムを生成させ、これを所望の粒径まで粉砕して、酸化マグネシウムを製造することができる。 Further, instead of calcium hydroxide, an alkaline compound having a hydroxyl group such as sodium hydroxide or potassium hydroxide can be used. Also, magnesium oxide containing aqueous solution such as seawater, irrigation, bitter juice, etc. is introduced into the reactor, and magnesium oxide is generated by the Aman process in which magnesium oxide and hydrochloric acid are directly generated at 1773 to 2273K. It can grind | pulverize to the particle size of this, and can manufacture a magnesium oxide.
更に、鉱物マグネサイトを焼成して得た酸化マグネシウムを、水和させ、得られた水酸化マグネシウムを焼成し、これを所望の粒径まで粉砕して、酸化マグネシウムを製造することもできる。 Furthermore, magnesium oxide obtained by firing mineral magnesite can be hydrated, and the resulting magnesium hydroxide can be fired and pulverized to a desired particle size to produce magnesium oxide.
MgO中の微量含有物の量は、公知の方法により制御できる。MgO中の微量含有物の量を制御する方法としては、例えば、MgO中の微量含有物の量が所定の範囲となるように、粗生成物の製造工程中に、又は得られた粗生成物の微量含有物量を最終焼成前に制御することにより行うことができる。粗生成物の製造工程中での制御は、例えば、原料に含まれる微量含有物の量を分析し、その結果を踏まえ、制御する対象の微量含有物が所定量となるように、湿式又は乾式で添加するか、湿式で除去することにより制御することができる。微量含有物の添加は、例えば、添加する元素を混合し、乾燥させることにより行うことができる。また、微量含有物の除去は、例えば、湿式で過剰な含有物を物理的に洗浄するか、化学的に分離することにより行うことができる。化学的な分離は、例えば、可溶性の水和物を形成させて、溶解させ、ろ過し、洗浄して分離するか、又は不溶性の化合物を形成させて、析出させ、析出物を吸着して分離することにより行うことができる。最終焼成前での粗生成物の微量含有物量の制御は、例えば、異なる組成を有する粗生成物を組み合わせて混合することで、微量含有物が所定の範囲となるように微量元素の量の過不足を調整し、これを最終焼成することにより制御できる。更に、微量含有元素の量を制御するため、いずれの場合も、粗生成物MgOを製造し、得られたMgOを分析した後、微量含有元素の量に関する個々の結果に応じて、上記の手順を繰り返し・組み合わせることができる。 The amount of the trace content in MgO can be controlled by a known method. As a method for controlling the amount of the trace content in MgO, for example, during the manufacturing process of the crude product, or the obtained crude product so that the amount of the trace content in MgO falls within a predetermined range. Can be carried out by controlling the amount of the trace amount before the final firing. The control during the production process of the crude product is, for example, analyzed by analyzing the amount of the trace amount contained in the raw material, and based on the result, wet or dry so that the amount of the trace amount to be controlled becomes a predetermined amount. It can be controlled by adding in or removing by wet. The addition of the trace amount can be performed, for example, by mixing the elements to be added and drying. Moreover, the removal of the trace content can be performed by, for example, physically washing excess chemical content or chemically separating it. Chemical separation can be achieved by, for example, forming a soluble hydrate, dissolving, filtering, washing and separating, or forming an insoluble compound, precipitating, adsorbing and separating the precipitate. This can be done. Control of the amount of trace elements contained in the crude product before the final firing can be achieved, for example, by mixing and mixing crude products having different compositions so that the amount of trace elements can be controlled so that the amount of trace elements falls within a predetermined range. It can be controlled by adjusting the shortage and final firing. Furthermore, in order to control the amount of trace elements, in each case, after producing the crude product MgO and analyzing the resulting MgO, the above procedure is followed according to the individual results regarding the amount of trace elements Can be repeated and combined.
酸化マグネシウムのD10及びCAAは、公知の方法により調整でき、例えば、次のような方法により行うことができる。すなわち、水酸化マグネシウムの製造工程中の反応温度及びアルカリ源の濃度を調整することにより、水酸化マグネシウムの一次粒子径及び二次粒子径を制御し、酸化マグネシウムのD10及びCAAを調整することができる。また、粒子径を制御した水酸化マグネシウムの焼成温度及び時間を制御することによっても、酸化マグネシウムのD10及びCAAを調整することができる。また、D10及びCAAの調整方法として、粉砕後のD10及びCAAを測定し、複数回焼成を行うことでも調整することができる。更に、焼成した酸化マグネシウムを、ジョークラッシャー、ジャイレトリークラッシャー、コーンクラッシャー、インパクトクラッシャー、ロールクラッシャー、カッターミル、スタンプミル、リングミル、ローラーミル、ジェットミル、ハンマーミル、ピンミル、回転ミル、振動ミル、遊星ミル、ボールミル等の粉砕機を使用して粉砕することによっても、酸化マグネシウムのCAAを調整することができる。また、D10及びCAAの調整方法として、粉砕後のD10及びCAAを測定し、複数回粉砕を行うことでも調整することができる。 Magnesium oxide D 10 and CAA can be adjusted by a known method, for example, by the following method. That is, by adjusting the concentration of the reaction temperature and the alkali source in the manufacturing process of the magnesium hydroxide to control the primary particle diameter and secondary particle diameter of magnesium hydroxide, adjusting the D 10 and the CAA of magnesium oxide Can do. Also, by controlling the sintering temperature and time of magnesium hydroxide having a controlled particle diameter, it is possible to adjust the D 10 and the CAA of magnesium oxide. Further, as a method for adjusting the D 10 and CAA, measured D 10 and CAA after grinding, it can also be adjusted by performing a plurality of times firing. In addition, calcined magnesium oxide, jaw crusher, gyratory crusher, cone crusher, impact crusher, roll crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, hammer mill, pin mill, rotary mill, vibration mill, The CAA of magnesium oxide can also be adjusted by pulverization using a pulverizer such as a planetary mill or a ball mill. Further, as a method for adjusting the D 10 and CAA, D were measured 10 and CAA after grinding, can also be adjusted by performing a plurality of times grinding.
本発明の方向性電磁鋼板は、例えば、下記のような方法で製造することができる。方向性電磁鋼板はSi 2.5〜4.5%を含有するケイ素鋼スラブを熱間圧延し、酸洗後、冷間圧延を行うか、中間焼鈍をはさむ2回冷間圧延を行って、所定の板厚に調整する。次に、冷間圧延したコイルを923〜1173Kの湿潤水素雰囲気中で、脱炭を兼ねた再結晶焼鈍を行い、このとき鋼板表面にシリカ(SiO2)を主成分とする酸化被膜を形成させる。本発明の焼鈍分離剤用MgOを水に均一に分散させ、水スラリーを得て、この鋼板上に、水スラリーを、ロールコーティング又はスプレーを用いて連続的に塗布し、約573Kで乾燥させる。こうして処理された鋼板コイルを、例えば、1473Kで20時間の最終仕上げ焼鈍を行って、鋼板表面にフォルステライト被膜(Mg2SiO4)を形成する。フォルステライト被膜は、絶縁被膜であるとともに、鋼板表面に張力を付与して、方向性電磁鋼板の鉄損値を向上させることができる。 The grain-oriented electrical steel sheet of the present invention can be manufactured, for example, by the following method. The grain-oriented electrical steel sheet hot-rolls a silicon steel slab containing Si 2.5 to 4.5%, and after pickling, performs cold rolling or performs cold rolling twice with intermediate annealing, Adjust to a predetermined plate thickness. Next, the cold-rolled coil is subjected to recrystallization annealing also serving as decarburization in a wet hydrogen atmosphere of 923 to 1173K, and at this time, an oxide film mainly composed of silica (SiO 2 ) is formed on the steel plate surface. . The MgO for annealing separator of the present invention is uniformly dispersed in water to obtain a water slurry, and the water slurry is continuously applied onto the steel plate by roll coating or spraying and dried at about 573K. The steel plate coil thus treated is subjected to, for example, final finishing annealing at 1473K for 20 hours to form a forsterite film (Mg 2 SiO 4 ) on the steel plate surface. The forsterite film is an insulating film, and can impart tension to the steel sheet surface to improve the iron loss value of the grain-oriented electrical steel sheet.
下記の実施例により本発明を詳細に説明するが、これらの実施例は本発明をいかなる意味においても制限するものではない。 The following examples illustrate the invention in detail but are not intended to limit the invention in any way.
<測定方法・試験方法>
(1)ホウ素(B)の含有量の測定方法
測定試料を塩酸に完全に溶解させた後、超純水で希釈し、ICP発光分光分析装置(PS3520 VDD 株式会社日立ハイテクサイエンス製)を用いて、試料中のホウ素(B)の含有量を測定した。
<Measurement method / Test method>
(1) Method for Measuring Content of Boron (B) After completely dissolving the measurement sample in hydrochloric acid, it is diluted with ultrapure water and using an ICP emission spectrometer (PS3520 VDD, manufactured by Hitachi High-Tech Science Co., Ltd.). The content of boron (B) in the sample was measured.
(2)ナトリウム(Na)の含有量の測定方法
測定試料を硝酸に完全に溶解させた後、超純水で希釈し、日立偏光ゼーマン原子吸光光度計(Z−2300 株式会社日立ハイテクノロジーズ製)を用いて、試料中のナトリウム(Na)の含有量を測定した。
(2) Method for measuring content of sodium (Na) After completely dissolving the measurement sample in nitric acid, the sample was diluted with ultrapure water, and Hitachi Polarized Zeeman atomic absorption photometer (Z-2300, manufactured by Hitachi High-Technologies Corporation). Was used to measure the content of sodium (Na) in the sample.
(3)塩素(Cl)の含有量の測定方法
測定試料を硝酸に溶解した後、超純水で希釈し、分光光度計(UV−2550 島津製作所製)を用いて質量を測定することで、試料中の塩素(Cl)濃度を算出した。
(3) Measurement method of chlorine (Cl) content After dissolving a measurement sample in nitric acid, it is diluted with ultrapure water, and the mass is measured using a spectrophotometer (manufactured by Shimadzu UV-2550). The chlorine (Cl) concentration in the sample was calculated.
(4)リン(P)の含有量の測定方法
測定試料を塩酸と硫酸の混酸に溶解させた後、超純水で希釈し、ICP発光分光分析装置(PS3520 VDD 株式会社日立ハイテクサイエンス製)を用いて、試料中のリン(P)の含有量を測定した。
(4) Method for measuring phosphorus (P) content After dissolving the measurement sample in a mixed acid of hydrochloric acid and sulfuric acid, dilute with ultrapure water, and use an ICP emission spectroscopic analyzer (PS3520 VDD, manufactured by Hitachi High-Tech Science Corporation). Used to measure the phosphorus (P) content in the sample.
(5)硫黄の酸化物(SO3)の含有量の測定方法
測定試料をアルミリング35mmφを使用し全圧30MPaにて加圧成形し、ケイ光X線分析装置(Simultix12型 株式会社リガク製)を用いて、試料中の硫黄の酸化物(SO3)の含有量を測定した。本測定結果から、硫黄(S)のモル数を算出した。
(5) Method for measuring the content of sulfur oxide (SO 3 ) A measurement sample was molded under pressure using an aluminum ring 35 mmφ at a total pressure of 30 MPa, and a fluorescent X-ray analyzer (simultix12 type, manufactured by Rigaku Corporation) Was used to measure the content of sulfur oxide (SO 3 ) in the sample. From this measurement result, the number of moles of sulfur (S) was calculated.
(6)CAA40%の測定方法
0.4Nのクエン酸溶液1×10−4m3と、指示薬として適量(2×10−6m3)の1%フェノールフタレイン液とを、2×10−4m3ビーカーに入れ、液温を303Kに調整し、マグネチックスターラーを使用して700rpmで攪拌しながら、クエン酸溶液中に40%の最終反応当量の酸化マグネシウムを投入して、最終反応までの時間、つまりクエン酸が消費され溶液が中性となるまでの時間を測定した。
(6) and CAA40% measurement methods citric acid solution 1 × 10 -4 m 3 of 0.4 N, and a 1% phenolphthalein solution in an appropriate amount as an indicator (2 × 10 -6 m 3) , 2 × 10 - Put in a 4 m 3 beaker, adjust the liquid temperature to 303 K, and stir at 700 rpm using a magnetic stirrer, and add 40% of the final reaction equivalent of magnesium oxide into the citric acid solution until the final reaction. , That is, the time until citric acid is consumed and the solution becomes neutral.
(7)体積基準の累積10%粒子径(D10)
測定試料をメタノールで溶解し、レーザー回折散乱式粒子径分布測定装置(MT3300EX−II LEEDS & NORTHRUP製)を用いて、試料の体積基準の累積10%粒子径(D10)を測定した。その際、出力40Wの超音波で180秒間分散した。
(7) Volume-based cumulative 10% particle size (D 10 )
The measurement sample was dissolved in methanol, and the volume-based cumulative 10% particle size (D 10 ) of the sample was measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by MT3300EX-II LEEDS & NORTHUP). At that time, dispersion was performed for 180 seconds with ultrasonic waves of 40 W output.
(8)鉄損値及び磁束密度の測定方法
試験試料供試鋼として、方向性電磁鋼板用のケイ素鋼スラブを、公知の方法で熱間圧延、冷間圧延を行って、最終板厚0.28×10−3mとし、更に、窒素25%+水素75%の湿潤雰囲気中で脱炭焼鈍した鋼板を用いた。脱炭焼鈍前の鋼板の組成は、質量%で、C:0.01%、Si:3.29%、Mn:0.09%、Al:0.03%、S:0.07%、N:0.0053%、残部は不可避的な不純物とFeであった。試験対象の酸化マグネシウムをスラリー状にして、乾燥後の質量で14×10−3kg・m−2になるように鋼板に塗布し、乾燥後、1473Kで20.0時間の最終仕上焼鈍を行った。最終仕上焼鈍が終了したのち冷却し、鋼板を水洗し、塩酸水溶液で酸洗浄した後、再度水洗して、乾燥させ、鋼板上にフォルステライト被膜を形成させた。この鋼板を20mm×80mmのサイズに加工し、磁気特性評価装置(交流磁化特性試験装置SK−200 メトロン技研株式会社製)を用いて、鋼板の鉄損及び磁束密度を測定した。ここで、鉄損は、磁束密度1.7T、周波数50Hzにおける鉄損であり、磁束密度は、800A/mの磁場における磁束密度である。
(8) Measuring method of iron loss value and magnetic flux density As a test sample test steel, a silicon steel slab for a grain-oriented electrical steel sheet is hot-rolled and cold-rolled by a known method to obtain a final thickness of 0. The steel plate was 28 × 10 −3 m, and further decarburized and annealed in a humid atmosphere of 25% nitrogen + 75% hydrogen. The composition of the steel sheet before decarburization annealing is mass%, C: 0.01%, Si: 3.29%, Mn: 0.09%, Al: 0.03%, S: 0.07%, N : 0.0053%, the balance being inevitable impurities and Fe. The test target magnesium oxide is made into a slurry and applied to a steel plate so that the mass after drying is 14 × 10 −3 kg · m −2. After drying, final finishing annealing is performed at 1473 K for 20.0 hours. It was. After the final finish annealing was completed, the steel sheet was cooled, washed with water, acid washed with an aqueous hydrochloric acid solution, washed again with water and dried to form a forsterite film on the steel sheet. This steel plate was processed into a size of 20 mm × 80 mm, and the iron loss and magnetic flux density of the steel plate were measured using a magnetic property evaluation device (AC magnetization property test device SK-200, manufactured by Metron Giken Co., Ltd.). Here, the iron loss is an iron loss at a magnetic flux density of 1.7 T and a frequency of 50 Hz, and the magnetic flux density is a magnetic flux density in a magnetic field of 800 A / m.
<実施例1〜2及び比較例1〜2>
試薬を用いて、実施例1〜2及び比較例1〜2の酸化マグネシウムを得た。具体的には、まず、塩化マグネシウム(試薬特級)を純水に溶解させ0.5×103mol・m−3の塩化マグネシウム水溶液を作製した。次に水酸化カルシウム(試薬特級)を純水に入れ、0.5×103mol・m−3の水酸化カルシウム分散液を作製した。これらの塩化マグネシウム水溶液及び水酸化カルシウム分散液をMgCl2/Ca(OH)2=1.1のモル比で1.0×10−3m3になるように混合し、混合液を得た。その後、ホウ酸(特級)、硫酸マグネシウム(特級)、塩化ナトリウム(特級)、リン酸マグネシウム(一級)を適量混合液に投入し、4枚ばねの攪拌羽を使用して、600rpmで攪拌しながら313Kにて5.5時間反応させ、水酸化マグネシウムスラリーを得た。その後、水酸化マグネシウムスラリーを濾過し、得られた水酸化マグネシウムをその質量の100倍の質量の純水で洗浄し、378Kで12.0時間乾燥して、水酸化マグネシウム粉末を得た。得られた水酸化マグネシウム粉末に、塩化マグネシウム六水和物(特級)を適量混合した後、電気炉で焼成し、表1に示す成分を含有する実施例1〜2及び比較例1〜2の酸化マグネシウム粉末を得た。なお、焼成は、酸化マグネシウムのCAA40%が80〜100秒の範囲となる条件で行った。
<Examples 1-2 and Comparative Examples 1-2>
The magnesium oxide of Examples 1-2 and Comparative Examples 1-2 was obtained using the reagent. Specifically, first, magnesium chloride (reagent special grade) was dissolved in pure water to prepare a 0.5 × 10 3 mol · m −3 magnesium chloride aqueous solution. Next, calcium hydroxide (special reagent grade) was put in pure water to prepare a 0.5 × 10 3 mol · m −3 calcium hydroxide dispersion. These magnesium chloride aqueous solution and calcium hydroxide dispersion were mixed so that the molar ratio of MgCl 2 / Ca (OH) 2 = 1.1 was 1.0 × 10 −3 m 3 to obtain a mixed solution. Thereafter, boric acid (special grade), magnesium sulfate (special grade), sodium chloride (special grade), and magnesium phosphate (primary grade) are put in an appropriate amount, and the mixture is stirred at 600 rpm using a four-blade stirring blade. The mixture was reacted at 313K for 5.5 hours to obtain a magnesium hydroxide slurry. Thereafter, the magnesium hydroxide slurry was filtered, and the obtained magnesium hydroxide was washed with 100 times the mass of pure water and dried at 378 K for 12.0 hours to obtain a magnesium hydroxide powder. After mixing an appropriate amount of magnesium chloride hexahydrate (special grade) to the obtained magnesium hydroxide powder, it was baked in an electric furnace and contains the components shown in Table 1 and Examples 1-2 and Comparative Examples 1-2. Magnesium oxide powder was obtained. The firing was performed under the condition that the CAA 40% of magnesium oxide was in the range of 80 to 100 seconds.
得られた実施例1〜2及び比較例1〜2の酸化マグネシウム粉末について、上記のとおり、含有成分の測定を行い、これら酸化マグネシウム粉末を用いて得た方向性電磁鋼板の鉄損及び磁束密度を測定した。結果を表1に示す。 About the obtained magnesium oxide powder of Examples 1-2 and Comparative Examples 1-2, as above-mentioned, a content component is measured and the iron loss and magnetic flux density of the grain-oriented electrical steel sheet obtained using these magnesium oxide powders Was measured. The results are shown in Table 1.
表1から明らかなように、(Cl+S)/(B+Na)が0.50〜0.80の範囲にあり、かつそれぞれの成分含有量が所定の範囲にある実施例1〜2の酸化マグネシウムは、この酸化マグネシウムを使用してフォルステライト被膜を形成した鋼板の鉄損が1.10W/kg以下、磁束密度が1.90T以上であり優れていた。一方、(Cl+S)/(B+Na)が0.50〜0.80の範囲にない比較例1の酸化マグネシウムについては、この酸化マグネシウムを使用してフォルステライト被膜を形成した鋼板の鉄損は大きく、磁束密度は低かった。また、(Cl+S)/(B+Na)が0.50〜0.80の範囲にあっても、ホウ素及び硫黄の含有量が少ない比較例2の酸化マグネシウムについても、この酸化マグネシウムを使用してフォルステライト被膜を形成した鋼板の鉄損は大きく、磁束密度は低かった。 As apparent from Table 1, the magnesium oxides of Examples 1 and 2 in which (Cl + S) / (B + Na) is in the range of 0.50 to 0.80 and the respective component contents are in the predetermined range are as follows. The steel sheet on which the forsterite film was formed using this magnesium oxide had excellent iron loss of 1.10 W / kg or less and magnetic flux density of 1.90 T or more. On the other hand, for the magnesium oxide of Comparative Example 1 in which (Cl + S) / (B + Na) is not in the range of 0.50 to 0.80, the iron loss of the steel sheet in which the forsterite film is formed using this magnesium oxide is large, The magnetic flux density was low. Further, even when (Cl + S) / (B + Na) is in the range of 0.50 to 0.80, the forsterite is also used for the magnesium oxide of Comparative Example 2 having a low boron and sulfur content. The iron loss of the steel sheet on which the film was formed was large, and the magnetic flux density was low.
<実施例3〜7及び比較例3〜5>
苦汁を用いて、実施例3〜7及び比較例3〜5の酸化マグネシウムを得た。具体的には、まず、濃度2.0×103mol・m−3のマグネシウムイオンを含む苦汁に、水酸化カルシウムスラリーを、反応後の水酸化マグネシウム濃度が2.0×103mol・m−3になるように添加し、混合液を得た。その後、ホウ酸(特級)、硫酸マグネシウム(特級)、塩化ナトリウム(特級)、リン酸マグネシウム(一級)を適量混合液に投入し、600rpmで攪拌しながら323Kにて7.0時間反応させた。その後、フィルタープレスで濾過し、水洗し、乾燥して水酸化マグネシウムを得た。この水酸化マグネシウムに、塩化マグネシウム六水和物(特級)を適量混合した後、ロータリーキルンで焼成したのち粉砕し、実施例3〜7及び比較例3〜5の酸化マグネシウム粉末を得た。なお、焼成は、酸化マグネシウムのCAA40%が80〜100秒の範囲となる条件で行った。
<Examples 3-7 and Comparative Examples 3-5>
Using bitter juice, magnesium oxides of Examples 3 to 7 and Comparative Examples 3 to 5 were obtained. Specifically, first, calcium hydroxide slurry is added to bitter juice containing magnesium ions at a concentration of 2.0 × 10 3 mol · m −3 , and the magnesium hydroxide concentration after reaction is 2.0 × 10 3 mol · m. -3 was added to obtain a mixed solution. Thereafter, boric acid (special grade), magnesium sulfate (special grade), sodium chloride (special grade), and magnesium phosphate (primary grade) were added in appropriate amounts and reacted at 323 K for 7.0 hours while stirring at 600 rpm. Then, it filtered with the filter press, washed with water, and dried and obtained magnesium hydroxide. An appropriate amount of magnesium chloride hexahydrate (special grade) was mixed with this magnesium hydroxide, followed by firing in a rotary kiln and pulverization to obtain magnesium oxide powders of Examples 3 to 7 and Comparative Examples 3 to 5. The firing was performed under the condition that the CAA 40% of magnesium oxide was in the range of 80 to 100 seconds.
得られた実施例3〜7及び比較例3〜5の酸化マグネシウム粉末について、上記のとおり、含有成分の測定を行い、これら酸化マグネシウム粉末を用いて得た方向性電磁鋼板の鉄損及び磁束密度を測定した。結果を表2に示す。 About the obtained magnesium oxide powder of Examples 3-7 and Comparative Examples 3-5, a content component is measured as mentioned above, and the iron loss and magnetic flux density of the grain-oriented electrical steel sheet obtained using these magnesium oxide powders Was measured. The results are shown in Table 2.
表2から明らかなように、(Cl+S)/(B+Na)が0.50〜0.80の範囲にあり、かつそれぞれの成分含有量が所定の範囲にある実施例3〜7の酸化マグネシウムは、この酸化マグネシウムを使用してフォルステライト被膜を形成した鋼板の鉄損が1.10W/kg以下、磁束密度が1.90T以上であり優れていた。一方、(Cl+S)/(B+Na)が0.50〜0.80の範囲にない比較例3〜5の酸化マグネシウムについては、比較例3の酸化マグネシウムを使用してフォルステライト被膜を形成した鋼板の鉄損は大きく、かつ磁束密度は低く、比較例4及び5の酸化マグネシウムを使用してフォルステライト被膜を形成した鋼板の鉄損は大きかった。 As is apparent from Table 2, the magnesium oxides of Examples 3 to 7 in which (Cl + S) / (B + Na) is in the range of 0.50 to 0.80 and each component content is in the predetermined range are The steel sheet on which the forsterite film was formed using this magnesium oxide had excellent iron loss of 1.10 W / kg or less and magnetic flux density of 1.90 T or more. On the other hand, for the magnesium oxide of Comparative Examples 3 to 5 where (Cl + S) / (B + Na) is not in the range of 0.50 to 0.80, the steel plate in which the forsterite film was formed using the magnesium oxide of Comparative Example 3 was used. The iron loss was large and the magnetic flux density was low, and the iron loss of the steel sheet in which the forsterite film was formed using the magnesium oxides of Comparative Examples 4 and 5 was large.
以上より、本発明の焼鈍分離剤用酸化マグネシウムを用いることにより、磁気特性に優れた方向性電磁鋼板を製造することができることが明らかとなった。 From the above, it became clear that the grain-oriented electrical steel sheet having excellent magnetic properties can be produced by using the magnesium oxide for annealing separator of the present invention.
本発明によれば、優れたフォルステライト被膜を形成でき、鉄損及び磁束密度の特性に優れた方向性電磁鋼板を提供することができる焼鈍分離剤用酸化マグネシウムを提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the magnesium oxide for annealing separation agents which can form the outstanding forsterite film and can provide the grain-oriented electrical steel sheet excellent in the characteristic of an iron loss and magnetic flux density can be provided.
Claims (6)
請求項5に記載の焼鈍分離剤を二酸化ケイ素被膜の表面に塗布し、焼鈍することにより、鋼板表面にフォルステライト被膜を形成する工程
とを含む、方向性電磁鋼板の製造方法。 Forming a silicon dioxide film on the steel sheet surface;
A method for producing a grain-oriented electrical steel sheet, comprising: applying a annealing separator according to claim 5 to a surface of a silicon dioxide film and forming a forsterite film on the surface of the steel sheet by annealing.
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