JP7181441B1 - 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 - Google Patents
焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 Download PDFInfo
- Publication number
- JP7181441B1 JP7181441B1 JP2022542043A JP2022542043A JP7181441B1 JP 7181441 B1 JP7181441 B1 JP 7181441B1 JP 2022542043 A JP2022542043 A JP 2022542043A JP 2022542043 A JP2022542043 A JP 2022542043A JP 7181441 B1 JP7181441 B1 JP 7181441B1
- Authority
- JP
- Japan
- Prior art keywords
- magnesium oxide
- coating
- steel sheet
- less
- annealing separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 134
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000000137 annealing Methods 0.000 title claims abstract description 59
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 79
- 238000000576 coating method Methods 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052839 forsterite Inorganic materials 0.000 claims description 35
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 35
- 229910000831 Steel Inorganic materials 0.000 claims description 33
- 239000010959 steel Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 117
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 39
- 230000009257 reactivity Effects 0.000 description 22
- 239000000843 powder Substances 0.000 description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- 239000011701 zinc Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 13
- 239000000347 magnesium hydroxide Substances 0.000 description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000011592 zinc chloride Substances 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000011573 trace mineral Substances 0.000 description 5
- 235000013619 trace mineral Nutrition 0.000 description 5
- 229910000976 Electrical steel Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 241001131796 Botaurus stellaris Species 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- -1 seawater Chemical compound 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
- C21D1/72—Temporary coatings or embedding materials applied before or during heat treatment during chemical change of surfaces
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
- C21D8/1272—Final recrystallisation annealing
-
- 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
- C21D8/1283—Application of a separating or insulating 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
-
- 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
- H01F1/147—Alloys characterised by their composition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Power Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Abstract
Description
(1)金属元素の含有量の測定方法
測定試料を完全に酸溶解させた後、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、試料中の金属元素の含有量を測定した。
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。
比表面積測定装置(商品名:Macsorb、Mountech Co., Ltd.製)を使用して、ガス吸着法(BET法)によりBET比表面積を測定した。
測定試料をメタノールに分散し、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50%粒子径(D50)を測定した。その際、出力40Wの超音波で180秒間分散した。
0.4Nのクエン酸溶液100mLと、指示薬として適量(2mL)の1%フェノールフタレイン液とを、200mL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(2.0g)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。
初期反応性は市販のpHスタット装置(東亜ディーケーケー株式会社製自動滴定装置:AUT-701)を用いて、pHスタット法で評価した。具体的には、まず、200mLビーカーに100mLの脱イオン水を入れ、恒温槽にセットし、285Kに保持した。pH電極をセットし、マグネチックスターラーを用いて800rpmで攪拌しながら、秤量した試料粉末400mgを投入し、すぐに0.4N・クエン酸水溶液の滴下を開始した。滴下開始後、pHを10に維持しつつ、反応率が10mol%及び20mol%となる量のクエン酸水溶液が消費されるのに要した時間(秒)を測定した。本測定条件の場合、試料粉末400mg(約0.1mol)に対して、反応率10mol%となる0.4N・クエン酸水溶液の量は5mL、反応率20mol%となる0.4N・クエン酸水溶液の量は10mLである。
試験試料供試鋼として、方向性電磁鋼板用の珪素鋼スラブを、公知の方法で熱間圧延、冷間圧延を行って、最終板厚0.28mm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である。この鋼板上に酸化マグネシウムを塗布して、フォルステライト被膜の被膜特性を調査した。
フォルステライト被膜の外観は、洗浄後の被膜の外観から判断した。すなわち、灰色のフォルステライト被膜が、均一に厚く形成されている場合を◎、被膜が均一であるがやや薄く形成されている場合を○、被膜が不均一で薄いが、下地の鋼板が露出している部分がない場合、もしくは被膜が不均一で非常に薄く、下地の鋼板が明らかに露出した部分がある場合を×とした。
フォルステライト被膜の密着性は、被膜状態から判断した。すなわち、被膜が均一に形成され、剥離部位が存在しない場合、もしくは被膜が僅かに不均一であるが、剥離部分が存在しない場合を○、被膜が不均一で、ピンホール状の剥離部位が存在する場合、もしくは被膜が不均一で、明確な剥離部位が存在する場合を×とした。
濃度2.0mol/L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1.2mol/Lになるように添加し、混合液を得た。混合液を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、塩化亜鉛(関東化学製、試薬特級)を焼成後の酸化マグネシウム中のZnが720ppmとなるように混合した後、ロータリーキルンにより1173Kで0.5時間焼成したのち粉砕し、実施例1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70~90秒の範囲となる条件で行った。
塩化亜鉛(特級)を焼成後の酸化マグネシウム中のZnが2250ppmとなるように混合した以外は、実施例1と同様にして、酸化マグネシウム粉末を得た。
塩化亜鉛(特級)を焼成後の酸化マグネシウム中のZnが4300ppmとなるように混合した以外は、実施例1と同様にして、酸化マグネシウム粉末を得た。
塩化亜鉛(特級)を混合しなかった以外は、実施例1と同様にして、酸化マグネシウム粉末を得た。
濃度2.0mol/L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1.2mol/Lになるように添加し、混合液を得た。この混合液に塩化亜鉛(関東化学製、試薬特級)を焼成後の酸化マグネシウム中のZnが8800ppmとなるように混合した後、混合液を600rpmで攪拌しながら323Kにて7.0時間反応させ、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をロータリーキルンにより1173Kで0.5時間焼成したのち粉砕し、実施例4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70~95秒の範囲となる条件で行った。
塩化亜鉛に代えて、酸化亜鉛(和光純薬製、試薬特級)を、焼成後の酸化マグネシウム中のZnが5250ppmとなるように混合した以外は、実施例4と同様にして、酸化マグネシウム粉末を得た。
塩化亜鉛を混合しなかった以外は、実施例4と同様にして、酸化マグネシウム粉末を得て、これにZnが5150ppmとなるように酸化亜鉛(和光純薬製、試薬特級)を混合することで、目的の酸化マグネシウム粉末を得た。
塩化亜鉛(特級)を焼成後の酸化マグネシウム中のZnが10300ppmとなるように混合した以外は、実施例4と同様にして、酸化マグネシウム粉末を得た。
Claims (6)
- CAA40%が50秒以上170秒以下であり、pHスタット法において反応率20mol%に到達するまでの時間(T2)と反応率10mol%に到達するまでの時間(T1)の比(T2/T1)が3.0以上11.0未満である、焼鈍分離剤用酸化マグネシウム。
- BET比表面積が12.0m2/g以上30.0m2/g以下、Clの含有量が500ppm以下、体積基準の累積50%粒子径(D50)が0.5μm以上7.0μm以下である、請求項1記載の焼鈍分離剤用酸化マグネシウム。
- Zn、Zr、Ni、Co、及びMnの合計含有量が200ppm以上10000ppm以下である、請求項1または2記載の焼鈍分離剤用酸化マグネシウム。
- Znの含有量が200ppm以上10000ppm以下である、請求項1または2記載の焼鈍分離剤用酸化マグネシウム。
- 請求項1~4のいずれか一項に記載の焼鈍分離剤用酸化マグネシウムを含む焼鈍分離剤。
- 鋼板表面にSiO2被膜を形成する工程と、
請求項5に記載の焼鈍分離剤をSiO2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。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021060801 | 2021-03-31 | ||
JP2021060801 | 2021-03-31 | ||
PCT/JP2022/016406 WO2022211001A1 (ja) | 2021-03-31 | 2022-03-31 | 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2022211001A1 JPWO2022211001A1 (ja) | 2022-10-06 |
JP7181441B1 true JP7181441B1 (ja) | 2022-11-30 |
Family
ID=83456538
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2022542043A Active JP7181441B1 (ja) | 2021-03-31 | 2022-03-31 | 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP7181441B1 (ja) |
KR (1) | KR20230163429A (ja) |
CN (1) | CN117083396A (ja) |
WO (1) | WO2022211001A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5315205A (en) * | 1976-07-29 | 1978-02-10 | Nippon Steel Corp | Annealing separating agent and iron loss improving method in unidirectional silicon steel sheet |
JPH06101059A (ja) * | 1992-09-18 | 1994-04-12 | Nippon Steel Corp | 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 |
JP2002309378A (ja) * | 2001-04-11 | 2002-10-23 | Nippon Steel Corp | 焼鈍分離剤、及び、グラス被膜の優れる方向性電磁鋼板の製造方法 |
JP2005171387A (ja) * | 2004-12-22 | 2005-06-30 | Jfe Steel Kk | 焼鈍分離剤用のMgOの製造方法 |
WO2008047999A1 (en) * | 2006-10-18 | 2008-04-24 | Posco | Annealing separating agent for grain oriented electrical steel sheet having uniform glass film and excellent magnetic properties and method of manufacturig the same |
JP2008260668A (ja) * | 2007-04-13 | 2008-10-30 | Jfe Steel Kk | 焼鈍分離剤用のマグネシアおよび方向性電磁鋼板の製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2650817B2 (ja) | 1992-07-20 | 1997-09-10 | 川崎製鉄株式会社 | 被膜特性及び磁気特性に優れた一方向性けい素鋼板の製造方法 |
JP4192282B2 (ja) | 1997-12-01 | 2008-12-10 | Jfeスチール株式会社 | 焼鈍分離剤用MgOの製造方法 |
JP3650525B2 (ja) | 1998-03-25 | 2005-05-18 | 新日本製鐵株式会社 | 方向性電磁鋼板の焼鈍分離剤およびグラス被膜と磁気特性の優れた方向性電磁鋼板の製造方法 |
-
2022
- 2022-03-31 KR KR1020237034051A patent/KR20230163429A/ko unknown
- 2022-03-31 CN CN202280025229.3A patent/CN117083396A/zh active Pending
- 2022-03-31 JP JP2022542043A patent/JP7181441B1/ja active Active
- 2022-03-31 WO PCT/JP2022/016406 patent/WO2022211001A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5315205A (en) * | 1976-07-29 | 1978-02-10 | Nippon Steel Corp | Annealing separating agent and iron loss improving method in unidirectional silicon steel sheet |
JPH06101059A (ja) * | 1992-09-18 | 1994-04-12 | Nippon Steel Corp | 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 |
JP2002309378A (ja) * | 2001-04-11 | 2002-10-23 | Nippon Steel Corp | 焼鈍分離剤、及び、グラス被膜の優れる方向性電磁鋼板の製造方法 |
JP2005171387A (ja) * | 2004-12-22 | 2005-06-30 | Jfe Steel Kk | 焼鈍分離剤用のMgOの製造方法 |
WO2008047999A1 (en) * | 2006-10-18 | 2008-04-24 | Posco | Annealing separating agent for grain oriented electrical steel sheet having uniform glass film and excellent magnetic properties and method of manufacturig the same |
JP2008260668A (ja) * | 2007-04-13 | 2008-10-30 | Jfe Steel Kk | 焼鈍分離剤用のマグネシアおよび方向性電磁鋼板の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2022211001A1 (ja) | 2022-10-06 |
WO2022211001A1 (ja) | 2022-10-06 |
CN117083396A (zh) | 2023-11-17 |
KR20230163429A (ko) | 2023-11-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7454334B2 (ja) | 焼鈍分離剤用の酸化マグネシウム及び方向性電磁鋼板の製造方法 | |
US11591232B2 (en) | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet | |
JP6472767B2 (ja) | 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 | |
US11097955B2 (en) | Magnesium oxide for annealing separator, and grain-oriented electromagnetic steel sheet | |
JP2004238668A (ja) | 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 | |
JP7181441B1 (ja) | 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 | |
JP7454335B2 (ja) | 焼鈍分離剤用の酸化マグネシウム及び方向性電磁鋼板の製造方法 | |
JP7328777B2 (ja) | チタン酸マグネシウムを含有する焼鈍分離剤用酸化マグネシウム、その製造方法、焼鈍分離剤及び方向性電磁鋼板 | |
US11001907B2 (en) | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet | |
JP7360572B1 (ja) | 焼鈍分離剤用酸化マグネシウム及び方向性電磁鋼板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220707 |
|
A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20220707 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220927 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220929 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20221108 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221117 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7181441 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |