JPH03120376A - Magnesium oxide coating film for electric steel and method for coating - Google Patents
Magnesium oxide coating film for electric steel and method for coatingInfo
- Publication number
- JPH03120376A JPH03120376A JP2235992A JP23599290A JPH03120376A JP H03120376 A JPH03120376 A JP H03120376A JP 2235992 A JP2235992 A JP 2235992A JP 23599290 A JP23599290 A JP 23599290A JP H03120376 A JPH03120376 A JP H03120376A
- Authority
- JP
- Japan
- Prior art keywords
- magnesia
- chlorine
- silicon steel
- amount
- metal chloride
- 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.)
- Granted
Links
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 124
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 20
- 239000010959 steel Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 60
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 60
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910000976 Electrical steel Inorganic materials 0.000 claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000137 annealing Methods 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 45
- 239000000654 additive Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 14
- 230000035699 permeability Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 238000005261 decarburization Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 238000005097 cold rolling Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000005381 magnetic domain Effects 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 235000012245 magnesium oxide Nutrition 0.000 description 85
- 238000007792 addition Methods 0.000 description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 17
- 230000036571 hydration Effects 0.000 description 16
- 238000006703 hydration reaction Methods 0.000 description 16
- 239000013078 crystal Substances 0.000 description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910000379 antimony sulfate Inorganic materials 0.000 description 5
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 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 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000006557 surface reaction Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 150000001804 chlorine Chemical class 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003966 growth inhibitor Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- -1 hydroxyl ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000013532 laser treatment Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229940063921 nitrogen 75 % Drugs 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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
- C21D8/1277—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
- 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
- C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
-
- 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
- C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
- C21D3/02—Extraction of non-metals
- C21D3/04—Decarburising
Abstract
Description
【発明の詳細な説明】
発明の背景
本発明は良好な絶縁性を与え且つ仕上げ高温焼鈍中に方
向性電気鋼に焼鈍セパレーターとして作用する被覆組成
物に関する。マグネシアは冷間圧延後の電気鋼の高温焼
鈍用のセパレーターとして広く使用されている。被膜は
通常脱炭後に塗布され、仕上げ高温焼鈍中にガラス被膜
を形成する。DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION This invention relates to coating compositions that provide good insulation properties and act as annealing separators on grain-oriented electrical steels during finish high temperature annealing. Magnesia is widely used as a separator for high temperature annealing of electrical steel after cold rolling. The coating is usually applied after decarburization and forms a glass coating during the final high temperature annealing.
従来技術の記載
主として酸化マグネシウム及び水酸化マグネシラムより
なるマグネシア被膜がコイルラップの焼着を予防するた
めに高温焼鈍中電気鋼上にセパレーター被膜として広く
使用されている。ガラス被膜は鋼表面とマグネシアの間
の反応から形成される。マグネシア波膜は所定の物理的
特性を所持しなければならず、丈な、電気鋼の磁気特性
を全体的に向上しなければならない、これらの特性を全
て提供するために、従来から当業者は基本的なマグネシ
ア組成物の変成を広く行ってきた。Description of the Prior Art Magnesia coatings, consisting primarily of magnesium oxide and magnesium hydroxide, are widely used as separator coatings on electrical steel during high temperature annealing to prevent coil wrap burning. The glass coating is formed from the reaction between the steel surface and magnesia. The magnesia wave film must possess certain physical properties and must improve the overall magnetic properties of the electrical steel.In order to provide all these properties, those skilled in the art have traditionally The basic composition of magnesia has been extensively modified.
酸化マグネシウムは水が存在すると短期間に水酸化マグ
ネシウムへ水和できる。水和の程度はマグネシアスラリ
ーの粘度及び被膜を塗布するための操作の制御に大きく
影響する。被膜中の水の量はガラス被膜形成に悪影響を
及ぼす、水和を制御するために、従来から当業者はマグ
ネシア粒子の寸法と分布とを変化させてきた。マグネシ
ア粒子の寸法と分布の変化はマグネシア製造のための焼
成温度を調節することにより行ってきた。この研究は米
国特許下４，１６８，１８９号明細書［ハセルコーン（
ｌｌａｓｅｌｋｏｒｎ）］に記載されている。Magnesium oxide can be hydrated to magnesium hydroxide in a short period of time in the presence of water. The degree of hydration greatly affects the viscosity of the magnesia slurry and the control of the operation for applying the coating. The amount of water in the coating has a negative effect on glass coating formation, and in order to control hydration, those skilled in the art have traditionally varied the size and distribution of the magnesia particles. Changes in the size and distribution of magnesia particles have been achieved by adjusting the calcination temperature for magnesia production. This research was published in U.S. Pat. No. 4,168,189 [Hasselkorn
llaselkorn)].
ガラス被膜の形成を向上するために多くの研究がマグネ
シアの添加剤について行われてきた。薄い絶縁性ガラス
被膜は脱炭後の珪素鋼の表面上の酸化物被膜とマグネシ
アの間の昇温下での反応を必要とする。種々のシリカ及
びシリケート化合物を添加して前記反応を向上させてい
る。チタン、クロム及びマンガンの酸化物を添加して粘
着性及びガラス被膜を向上させている。燐酸塩添加剤は
被膜中で結合剤として作用し且つ吸湿性を向上すること
が教示されている０種々の被膜添加剤を使用して高温焼
鈍中に製造されるガラス被膜の外観、厚さ、耐酸化性及
び他の特性を改善されている。Much work has been done on magnesia additives to improve the formation of glass coatings. The thin insulating glass coating requires a reaction between the oxide coating on the surface of the silicon steel after decarburization and magnesia at elevated temperatures. Various silica and silicate compounds have been added to enhance the reaction. Oxides of titanium, chromium and manganese are added to improve adhesion and glass coating. Phosphate additives have been taught to act as binders in the coating and improve hygroscopic properties. Oxidation resistance and other properties have been improved.
また、マグネシアの組成を調節することにより珪素鋼の
磁気特性を向上させるための多くの研究が行われている
。マグネシアは大気相互作用及び結晶寸法制御に関する
表面反応に大きな影響を及ぼす、米国特許下３，６２７
，５９４号明細書では二酸化チタン及び酸化マンガンを
添加している。米国特許下３，６７６．２２７号明細書
ではマグネシアへ硼素化合物を添加している。Additionally, many studies have been conducted to improve the magnetic properties of silicon steel by adjusting the composition of magnesia. Magnesia has a significant impact on surface reactions related to atmospheric interactions and crystal size control, U.S. Patent No. 3,627
, 594, titanium dioxide and manganese oxide are added. No. 3,676,227, a boron compound is added to magnesia.
過去に、塩化物類が他の化合物と併用してマグネシアへ
添加されていた。米１１ｉ１特許第４，５４３，１３４
号明細害ではＳｂ、Ｓｒ、ＴｉまたはＺｒの塩化物をＳ
ｂ ２（Ｓ Ｏ４）３のようなアンチモン化合物と共
に添加して鋼帯表面をシールし且つ大気と母材金属との
反応を防止している。塩化物類を使用して鋼帯表面上に
形成されるシリカを増加し且つＦｅＯ含量を低減させる
。マグネシアのシール機能は抑制剤元素の除去及び吸着
を防止するアンチモン化合物によるものである。被膜中
の塩素レベルは０．００２５〜０．４％の範囲である。In the past, chlorides were added to magnesia in combination with other compounds. US 11i1 Patent No. 4,543,134
In the specification, Sb, Sr, Ti or Zr chloride is
It is added together with an antimony compound such as b2(S04)3 to seal the steel strip surface and prevent reaction between the atmosphere and the base metal. Chlorides are used to increase the silica formed on the steel strip surface and reduce the FeO content. The sealing function of magnesia is due to antimony compounds that prevent the removal and adsorption of inhibitory elements. The chlorine level in the coating ranges from 0.0025 to 0.4%.
米国特許下３，８４１，９２５号明細書ではマグネシア
へ塩素寄与剤とメタ珪酸ナトリウムを添加して水和に対
する抵抗力を与え且つ無気孔絶縁性被膜を形成する。こ
れらの添加剤の臨界的なバランスは水和を遅延し且つ被
膜により長い滞留時間を提供する塩化ナトリウムと珪酸
マグネシウムをマグネシア中に生ずることになる。マグ
ネシアはマグネシアの重量を基準として通常的０，２２
〜３．４％の高レベルの塩素を含有する。In U.S. Pat. No. 3,841,925, a chlorine contributor and sodium metasilicate are added to magnesia to provide resistance to hydration and form a porous insulating coating. A critical balance of these additives results in sodium chloride and magnesium silicate in the magnesia which retards hydration and provides a longer residence time for the coating. Magnesia is usually 0.22 based on the weight of magnesia.
Contains high levels of chlorine, ~3.4%.
米国特許下４，２８７，００６号明細書の第１図には、
マグネシアの水和を制御するために１３００℃以上の焼
成温度を必要とすることにより塩素を除去する重要性を
明確に示すものである。米国特許下４．２８７，００６
号明細書の第７欄第２７行には塩化マグネシウムや硫酸
マグネシウムがガラス被膜の形成を阻害するために塩化
マグネシウムやｖｉ酸マグネシウムが焼鈍セパレーター
に含まれてはならないことが記載されている。FIG. 1 of U.S. Pat. No. 4,287,006 shows
This clearly demonstrates the importance of removing chlorine by requiring a firing temperature of 1300°C or higher to control the hydration of magnesia. U.S. Patent No. 4.287,006
Column 7, line 27 of the specification states that magnesium chloride and magnesium vicate should not be included in the annealing separator because magnesium chloride and magnesium sulfate inhibit the formation of a glass coating.
米国特許下３，９５６，０２９号明＃ｌＩ書には、塩素
が母材金属を侵食し且つ粗い表面を生ずる腐食性ガスを
形成するために、塩素はマグネシア被膜中に０．０４％
以下でなければならないことが記載されている。不規則
な被膜厚が生ずると、弱いガラス被膜を生ずることにな
り、結果としてピーリングの問題が生ずる。U.S. Pat.
It states that it must be as follows. Irregular coating thicknesses result in weak glass coatings, resulting in peeling problems.
米国特許下３，９４１，６２３号明Ｍ書は、仕上げ高温
焼鈍中に酸化マグネシウムを水和しないで残っで−いる
水分の制御方法を教示している。この特許は水分を消費
させ且つ露点を低下させるために焼鈍中に酸化物へ転化
される金属窒化物を使用するものである。これはｆＩ４
Ｉ４酸化物域少し、且つ改善されたガラス被膜と（１１
０）［００１］方向への結晶成長制御を提供する。U.S. Pat. No. 3,941,623 teaches a method for controlling the moisture that remains unhydrated in magnesium oxide during the final high temperature anneal. This patent uses metal nitrides that are converted to oxides during annealing to consume moisture and lower the dew point. This is fI4
I4 oxide area slightly and improved glass coating (11
0) Provides crystal growth control in the [001] direction.
１１００℃と１３００℃の間の温度での仕上げ焼鈍中に
電気謳を処理する際に焼鈍セパレーターとして使用され
る酸化マグネシウムは多くの方法により変成されている
。水和制御、ガラス被膜−金属表面反応、表面での不純
物除去及びガラス被膜と母材金属中の優れた磁気特性の
問題は部分的に改善されたのに過ぎない、また、過去に
おける、マグネシアへの添加は他の添加剤との相互作用
のために非常に複雑であった。Magnesium oxide, which is used as an annealing separator in processing electronics during final annealing at temperatures between 1100°C and 1300°C, has been modified by a number of methods. The problems of hydration control, glass coating-metal surface reactions, surface impurity removal, and excellent magnetic properties between glass coatings and base metals have only been partially improved; The addition of was very complicated due to interactions with other additives.
本発明は危険な作業環境を生ずることなく且つ安価に使
用できる焼鈍セパレーターに使用されるマグネシア添加
剤を提供することにある。マグネシア成分との相互作用
は余り複雑ではなく、高品質ガラス被膜及び磁気特性に
対する優れた改善の所望の利点を更に提供するものであ
る。添加剤を臨界的限度内で注意深く制御して所望の組
み合わせの特性を提供する。The object of the present invention is to provide a magnesia additive for use in annealing separators that does not create a dangerous working environment and can be used at low cost. The interaction with the magnesia component is less complex and further provides the desired benefits of high quality glass coatings and superior improvements to magnetic properties. Additives are carefully controlled within critical limits to provide the desired combination of properties.
発明の概要
本発明は金属塩化物（Ｍｇ、Ｎａ、Ｋ及びＣａから選択
された金属塩化物）をマグネシアへ添加すれば、メタ珪
酸ナトリウムまたは硫酸アンチモンを併用しなくても改
善された方向性及び磁気品質を提供できるとの知見に基
づくものである。前記塩化物添加から由来する０、０１
〜０．２％の範囲内の塩素レベルは先行技術マグネシア
に匹敵する優れたガラス被膜品質及び磁気特性向上をア
ンチモンの環境的問題なしに得られることを見出した。SUMMARY OF THE INVENTION The present invention provides that the addition of metal chlorides (metal chlorides selected from Mg, Na, K, and Ca) to magnesia provides improved directionality and properties without the need for concomitant use of sodium metasilicate or antimony sulfate. This is based on the knowledge that magnetic quality can be provided. 0,01 derived from said chloride addition
It has been found that chlorine levels in the range of .about.0.2% provide excellent glass coating quality and magnetic property enhancement comparable to prior art magnesia without the environmental concerns of antimony.
本発明の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。塩素と反応する他の添加剤を
必要とせずに塩化物を使用する被膜の気孔度の制御は塩
化物を用いる先行技術では予想できないものである。塩
化物の添加は拡散及び表面相互作用を制限することによ
り最終的な結晶の配向性及び結晶寸法の改善された制御
を提供する。また、塩素の供給源を提供するためのＭｇ
、Ｃａ、Ｎａ及び／またはＫの使用はガラス被膜の品質
及び電気鋼鋼帯の磁気特性に臨界的なものである。マグ
ネシア中の塩素の合計量は添加される金属塩化物の量を
最適化するように考慮しなければならないことに注意す
ることが重要である。マグネシア製品は元来若干量塩素
を含有することがありうるから、この塩素も金属塩化物
の添加と組み合わせて調節される。The addition of chloride in the present invention lowers the glass film formation temperature,
Seal the surface at low temperatures. The control of coating porosity using chloride without the need for other additives that react with chlorine is unexpected in the prior art using chloride. Addition of chloride provides improved control of final crystal orientation and crystal size by limiting diffusion and surface interactions. Also, Mg to provide a source of chlorine.
, Ca, Na and/or K are critical to the quality of the glass coating and the magnetic properties of the electrical steel strip. It is important to note that the total amount of chlorine in the magnesia must be considered to optimize the amount of metal chloride added. Since magnesia products may naturally contain some chlorine, this chlorine is also adjusted in combination with the addition of metal chlorides.
また、本発明のマグネシアは水性サスベンジョ４ンを安
定化し且つガラス被膜の品質及び電気鋼鋼帯の磁気特性
を改善するために二酸化チタンを添加してもよい。また
、硼素、クロム、シリカ及び燐酸カルシウム添加剤は本
発明の被膜組成物の任意成分である。また、本発明のマ
グネシアは普通の結晶配向または高透磁性結晶配向につ
いての利点を！＆辿化するために変成することができる
。The magnesia of the present invention may also be supplemented with titanium dioxide to stabilize the aqueous suspension and improve the quality of the glass coating and the magnetic properties of the electrical steel strip. Boron, chromium, silica and calcium phosphate additives are also optional components of the coating compositions of the present invention. In addition, the magnesia of the present invention has advantages regarding normal crystal orientation or high permeability crystal orientation! & Can be transmuted to trace.
また、本発明は仕上げ高温焼鈍前に粘着性絶縁性被膜で
珪素含有電気鋼帯鋼を被膜する方法を提供することにあ
る。マグネシアの水性スラリーを脱炭済鋼帯へ従来通り
塗布し、加熱して水を除去し、被膜を乾燥し、約１００
０℃以上で焼鈍してガラス被膜を形成し且つ所望の磁気
特性を発現させる。Another object of the present invention is to provide a method of coating a silicon-containing electrical steel strip with an adhesive insulating coating before finishing high temperature annealing. An aqueous slurry of magnesia is conventionally applied to a decarburized steel strip, heated to remove water, and the coating is dried to a
It is annealed at 0° C. or higher to form a glass coating and develop desired magnetic properties.
発明の詳細な記載
本発明の焼鈍用セパレーターは水性スラリーの慣用の処
理により塗布することができるように制御されたレベル
の水和状心にあるマグネシアである。マグネシアスラリ
ー中のマグネシアはある程度の水和水をもつから、この
ことは高温焼鈍中に水和水を除去することが必要となる
。乾燥後に水が残存すると最終ガラス被膜に気孔を生ず
る。制御された水和状態を有するマグネシアスラリーを
提供するために、主要量の粒子は２００以下、好ましく
は１００以下のクエン酸活性（ＣＡＡ）をもつものでな
ければならない。ＣＡＡは所定量のヒドロキシルイオン
が所定重量のクエン酸を中和するために必要とする時間
により決定されるマグネシアの活性の尺度である。試験
方法は米国特許筒３．８４１，９２５号明細書の第４欄
第２２〜４６行に詳細に記載されている。また、本発明
のマグネシアは２００より上、通常的５００〜５０００
のＣＡＡをもつ不活性マグネシアを約４５％まで含んで
いてもよい。不活性マグネシアは比較的ゆっくり水和す
るために水和を制御する傾向にあり、また、安価である
。有効に使用することができる不活性マグネシアの量は
ガラス被膜の品質及び被膜の気孔度の制御に関（系する
。DETAILED DESCRIPTION OF THE INVENTION The annealing separator of the present invention is magnesia in a hydrated core at controlled levels so that it can be applied by conventional processing of an aqueous slurry. Since the magnesia in the magnesia slurry has some water of hydration, this requires removal of the water of hydration during high temperature annealing. Any remaining water after drying will cause porosity in the final glass coating. In order to provide a magnesia slurry with a controlled state of hydration, the major amount of particles should have a citric acid activity (CAA) of less than 200, preferably less than 100. CAA is a measure of magnesia activity determined by the time required for a given amount of hydroxyl ions to neutralize a given weight of citric acid. The test method is described in detail in U.S. Pat. No. 3,841,925, column 4, lines 22-46. In addition, the magnesia of the present invention is higher than 200, and the normal magnesia is 500 to 5000.
It may contain up to about 45% inert magnesia with a CAA of . Inert magnesia tends to control hydration because it hydrates relatively slowly, and is also inexpensive. The amount of inert magnesia that can be effectively used is related to the quality of the glass coating and the control of the porosity of the coating.
本発明のマグネシアは方向性電気鋼における良好なガラ
ス被膜形成性及び改善された磁気特性を提供するために
０．０１〜０．２０重量％の臨界範囲内の塩素添加を必
要とする。必要とする塩素レベルはマグネシア製品によ
り部分的に提供でき、少なくとも０．０１％の金属塩化
物と併用される。The magnesia of the present invention requires chlorine addition within the critical range of 0.01-0.20% by weight to provide good glass coating and improved magnetic properties in grain-oriented electrical steels. The required chlorine levels can be provided in part by magnesia products, combined with at least 0.01% metal chloride.
存在する塩素の合計量は０．０１〜０．２０％の範囲内
に制御しなければならない。The total amount of chlorine present must be controlled within the range of 0.01-0.20%.
Ｍ８、Ｎａ、Ｋ及びＣａよりなる群から選択された金ぶ
化合物中の塩素はマグネシアに最初に存在する塩素のレ
ベルに依存してＭｇＯの重量を基準として０．０１〜０
．２ＣＩＪ！％の量でマグネシアへ添加される。塩化物
として使用される金属顕は安全面、コスト及びガラス被
膜にいかなる悪影響を及ぼすことなしに改善された磁気
特性を提供するように選択され、単独で使用しても、２
種以上を併用してもよい０本発明のマグネシアは主要量
の粒子が２００以下のクエン酸活性をもつ、また、マグ
ネシアは２００以上、通常５００〜５０００のクエン酸
活性をもつ不活性マグネシア粒子を約４５％まで含有し
ていてもよい。The chlorine in the metal compound selected from the group consisting of M8, Na, K and Ca may range from 0.01 to 0 based on the weight of MgO, depending on the level of chlorine initially present in the magnesia.
．． 2CIJ! % to magnesia. The metal microscope used as chloride was selected to provide improved magnetic properties without any adverse effects on safety, cost and glass coating, and when used alone,
In the magnesia of the present invention, the main amount of particles have a citric acid activity of 200 or less, and inert magnesia particles have a citric acid activity of 200 or more, usually 500 to 5000. It may contain up to about 45%.
本発明のマグネシア被膜は仕上げ高温焼鈍前に電気鋼の
冷間圧延済鋼帯へ塗布される。電気鋼鋼帯は通常４％ま
での珪素、０．０８％までの炭素及びＡｌＮ、ＭｎＳ、
ＭｎＳｅ、ＢＮ他のような既知の結晶成長抑制剤を含有
する方向性珪素鋼である。The magnesia coating of the present invention is applied to cold rolled electrical steel strip prior to final high temperature annealing. Electrical steel strip usually contains up to 4% silicon, up to 0.08% carbon and AlN, MnS,
It is a grain-oriented silicon steel containing known crystal growth inhibitors such as MnSe, BN, etc.
高透磁性珪素鋼は通常７９６ Ａ ／ ｍで約１８８０
以上の透磁率を所持するものとみなされ、約０．０１〜
０．０６５％のアルミニウムを添加する結果として窒化
アルミニウム抑制剤系を含有する。High permeability silicon steel is typically around 1880 at 796 A/m
It is considered to have a magnetic permeability of about 0.01~
Contains an aluminum nitride inhibitor system as a result of adding 0.065% aluminum.
米国特許筒３，６７６．２２７号明細書はこの技術の代
表的なものである。鋼帯の脱炭処理は約０．００３％以
下の炭素レベル及び仕上げ高温焼鈍中にマグネシアと反
応してフォルステライトのガラス被膜を形成する表面酸
化物を生ずる。脱炭処理中に形成される酸化物被膜は基
本的には鉄カンラン石及びＳ ｉ Ｏ２であり、若干の
酸１ヒ鉄が存在する。U.S. Pat. No. 3,676,227 is representative of this technology. Decarburization of the steel strip results in carbon levels below about 0.003% and surface oxides that react with magnesia during the final high temperature annealing to form a glass coating of forsterite. The oxide film formed during the decarburization process is essentially ferruginous olivine and S i O2, with some arsenic oxide present.
本発明の塩化物添加は表面反応を変成し、従って塩化物
の添加レベルは注意深く制御しなければならない、０．
２０％より多い合計塩素レベルは許容できる品質では高
過ぎるレベルの鉄を含むガラス被膜を形成する。過剰レ
ベルの塩素は表面の鉄＆−１により貧弱な耐酸化性及び
表面抵抗率を生ずる。また、ガラス被膜とけ材金戊の間
の界面は高レベルの塩素のために粗くなりすぎる。塩素
は約０，１５％以下のレベル、より好ましくは約０．１
２％以下のレベルで添加することが好ましい、電気鋼に
磁気特性の向上を付与するために、０．０１％の最低レ
ベルの塩素が存在しなければならない０本発明において
、金属塩化物として添加される好Ｎ最最小量塩素は約０
．０１５％（より好ましくは０．０２％）であり、ガラ
ス被膜の改善及び母材金属の磁気特性の間の最適なバラ
ンスを提供する。The chloride addition of the present invention alters the surface reaction and therefore the chloride addition level must be carefully controlled, 0.
Total chlorine levels greater than 20% form glass coatings containing iron at levels too high for acceptable quality. Excessive levels of chlorine result in poor oxidation resistance and surface resistivity due to surface iron &-1. Also, the interface between the glass coating and the metal coating becomes too rough due to the high levels of chlorine. Chlorine is at a level below about 0.15%, more preferably about 0.1
A minimum level of 0.01% chlorine must be present to impart improved magnetic properties to the electrical steel, preferably added at a level below 2%. In the present invention, added as a metal chloride. The minimum amount of chlorine that can be used is approximately 0.
．． 0.015% (more preferably 0.02%), providing the optimum balance between glass coating improvement and base metal magnetic properties.
本発明において、塩化物は焼鈍中に表面をシールする作
用をして結晶成長抑制剤を制御する。これは２次結晶成
長の安定性に主要な役割を演する。In the present invention, chloride acts to seal the surface during annealing to control crystal growth inhibitors. This plays a major role in the stability of secondary crystal growth.
米国特許筒３，８４１，９２５号明細書のようなマグネ
シアへの従来の塩化物の添加においては、無気孔被膜の
形成は塩化物と化学量論的に釣り合ったメタ珪酸ナトリ
ウムのような化合物との反応によって提供されていた。In conventional chloride additions to magnesia, such as in U.S. Pat. provided by the reaction.
該反応は気孔のない被膜を形成し且つ水和を制御する珪
酸マグネシウムと塩化ナトリウムを生じた。本発明の範
囲内の塩化マグネシウムを用いた例は被膜には不適当で
あることが示されていた（粘度が低く、スラリーが薄過
ぎ、過度の気孔が生ずる）、この特許において行われた
研究は塩化マグネシウムと反応する化学量論量より少な
い量の珪酸ナトリウムが絶縁特性が不足し且つ多孔質で
ある被膜を生ずることを明確に示すものである０本発明
は臨界的な低レベルの塩素は珪酸ナトリウムの添加を必
要としないことを見出した。The reaction produced magnesium silicate and sodium chloride which formed a pore-free film and controlled hydration. Examples using magnesium chloride within the scope of the present invention were shown to be unsuitable for coatings (low viscosity, too thin slurry, excessive porosity), research conducted in this patent. clearly shows that less than stoichiometric amounts of sodium silicate reacting with magnesium chloride results in a film that lacks insulating properties and is porous. It has been found that the addition of sodium silicate is not necessary.
興味ある他の従来の研究は米国特許第
４．５４３，１３４号明ａｔ書におけるＳｂ、Ｓ（Ｔｉ
またはＺ「の塩化物と硫酸アンチモンの添加であった。Other previous works of interest are Sb, S(Ti) in U.S. Pat. No. 4,543,134
Or it was the addition of Z' chloride and antimony sulfate.
塩素は０．００２５〜０．４％の量で選択された。Chlorine was selected in an amount of 0.0025-0.4%.
０．０５％以下の硫酸アンチモンを用いる場合には、こ
の特許では磁気特性が向上しない旨教示されている０本
発明は、この特許に教示された硫酸アンチモンを必要と
せずに同様の改善を提供することにある。また、本発明
は塩素の添加するために前記特許の塩化物とは異なる金
属を使用するものである。This patent teaches that magnetic properties do not improve if less than 0.05% antimony sulfate is used. The present invention provides similar improvements without the need for the antimony sulfate taught in this patent. It's about doing. Further, the present invention uses a different metal than the chloride of the above-mentioned patent to add chlorine.
慣用の手段により本発明のマグネシアを塗布するために
、マグネシアの水和を制御して作業可能な範囲で且つ手
頃な範囲の操作を提供するに十分安定な範囲の粘度をも
つスラリーを提供しなければならない、これはマグネシ
アスラリーの温度、マグネシアの粒子寸法及び種々の添
加剤の使用を制御することにより得られる。In order to apply the magnesia of the present invention by conventional means, the hydration of the magnesia must be controlled to provide a slurry with a range of viscosities stable enough to provide a workable and affordable range of operation. This can be achieved by controlling the temperature of the magnesia slurry, the particle size of the magnesia and the use of various additives.
マグネシアの温度は凍結する温度以上で約２５℃（７５
°Ｆ）以下、好適には約０〜７℃（３２〜４５°Ｆ）に
制御される。これはガラス被膜の品質や珪素鋼の磁気特
性に悪影響を及ぼす水相制御のための付加的な添加剤の
必要性を削除する。スラリーの温度範囲を維持するため
に、マグネシアは冷却用コイルを備える断熱性容器中に
保持される。The temperature of magnesia is about 25℃ (75℃) above the freezing temperature.
°F), preferably about 0-7 °C (32-45 °F). This eliminates the need for additional additives for water phase control that adversely affect the quality of the glass coating and the magnetic properties of the silicon steel. To maintain the temperature range of the slurry, the magnesia is kept in an insulated container with cooling coils.
マグネシアは冷水と混合されるが、長期間にわたり貯蔵
してはならない。マグネシアのこの冷却状態での保持に
より、スラリーは被膜の厚さまたはガラス被膜の均一性
に影響を及ぼすほど顕著に水和することはない、マグネ
シアの温度と、水和が被膜の塗布に悪影響を及ぼすよう
になるまでのスラリーの貯蔵寿命との関係は普通の関係
である。Magnesia may be mixed with cold water, but should not be stored for long periods of time. By keeping the magnesia in this cooled state, the slurry does not hydrate significantly enough to affect coating thickness or glass coating uniformity; the temperature of the magnesia and hydration do not adversely affect coating application. The relationship between the shelf life of the slurry and the time it takes to develop is a normal relationship.
温度か高ければ、より素早くスラリーを使用しなければ
ならない。The higher the temperature, the faster the slurry must be used.
高透磁性珪素鋼用のマグネシアの粒子寸法及びクエン酸
はガラス被膜の品質に重要な役割を演する０粒子の主要
量は２００以下、好ましくは１００以下のＣＡＡをもつ
、マグネシアは２００より上、通常５００〜５０００の
ＣＡＡをもつ不活性マグネシアを約４５％まで含むこと
ができる。The particle size of magnesia and citric acid for high magnetic permeability silicon steel play an important role in the quality of the glass coating. It can contain up to about 45% inert magnesia, typically with a CAA of 500-5000.
普通の方向性珪素鋼にはより大きな粒子寸法のマグネシ
アを使用することができ、より不活性なマグネシアを含
有することができる。大気との相互反応及び鋼上での表
面反応を調節する乾燥したマグネシア被膜の嵩密度すな
わち充填係数は粒子寸法分布及びＣＡＡに依存する。ま
た、水和の程度は乾燥中にマグネシア粒子に影響を及ぼ
す、水和水の量は粒子が大きくなる程減少する０粒子が
粗過ぎると、スラリーが沈降する傾向にあり、仕上げ焼
鈍中にシリカとの反応を受けなくなる。過度の水和のな
めに被膜が多孔質になるのを回避し且つ浸漬、吹付また
は計量ロールにより水性スラリーとして塗布することが
できるマグネシアであるためには、上記の変数を全て制
御しなければならない０本発明のマグネシア被膜は上述
の条件下で良好なガラス被膜を生じ、且つ従来の被膜に
必要な硫酸塩及び珪酸塩添加の必要性を削除することが
できる。Ordinary grain-oriented silicon steels can use magnesia with larger particle sizes and can contain more inert magnesia. The bulk density or packing factor of the dried magnesia coating, which controls interaction with the atmosphere and surface reaction on the steel, depends on the particle size distribution and CAA. Also, the degree of hydration affects magnesia particles during drying, the amount of hydration water decreases as the particles get larger. If the particles are too coarse, the slurry tends to settle, and silica particles during final annealing will not receive any reaction. All of the above variables must be controlled in order for the magnesia to avoid porous coatings due to excessive hydration and to be able to be applied as an aqueous slurry by dipping, spraying or metering rolls. The magnesia coatings of the present invention produce good glass coatings under the conditions described above and can eliminate the need for sulfate and silicate additions required in conventional coatings.
塩化物の添加は従来技術では扱われなかった他の重要な
ｒｆｉＭをもつ、磁区ｍ細化のためにレーザーけがき処
理が高透磁性方向性珪素鋼について必要となってきたこ
とである０表面被膜の性質はガラス被膜を通過するレー
ザーからのエネルギーのＩ及び磁区微細化中にガラス被
膜に生ずる損傷量に顕著な影響を及ぼす９本発明の塩化
物添加により開発された本発明のガラス被膜を制御して
表面損傷なしにレーザー処理できるガラス被膜を提供す
る。米国特許筒４，４５６，８１２号明細書に教示され
ているようなレーザー処理はガラス被膜へ損傷なしに磁
区微細化するために極めて有益であることが見出された
。The addition of chloride has another important rfiM not addressed by the prior art, which is that laser scribing has become necessary for high permeability grain-oriented silicon steels due to domain refinement. The properties of the coating have a significant effect on the energy I from the laser passing through the glass coating and the amount of damage caused to the glass coating during domain refinement. To provide a glass coating that can be laser processed in a controlled manner without surface damage. Laser treatment, as taught in U.S. Pat. No. 4,456,812, has been found to be extremely useful for domain refinement without damage to the glass coating.
本発明の化合物を使用する塩素添加を行ったマグネシア
から製造されたガラス被膜の特性を評価するために、一
連の実験を行った。ＡｌＮ抑制剤系を含有する高透磁性
珪素鋼の冷間圧延鋼帯に種々の量のＭｇＣｌ２を含有す
るマグネシアを被覆した。結果を米国特許筒４，５４３
，１３４号明４Ｉｓに記載するような硫酸アンチモンを
添加したマグネシアと比較し、第１表に示す、該鋼帯は
厚さ０．２３＋１転幅７６ｍａ＋及び長さ３０５ＩＩ１
１であった。結果は５％のＴ ｉ Ｏ２を含むタテホ（
Ｔａｔｅｈｏ）＾１１２０マグネシアで被覆した１０個
のサンプルの平均である。A series of experiments were conducted to evaluate the properties of glass coatings made from chlorinated magnesia using the compounds of the present invention. Cold rolled strips of high permeability silicon steel containing an AlN inhibitor system were coated with magnesia containing various amounts of MgCl2. The result is US patent cylinder 4,543
, No. 134 Mei 4Is, the steel strip has a thickness of 0.23 + 1 width of 76 ma + and a length of 305 II 1 as shown in Table 1.
It was 1. The results show that Tateho containing 5% T i O2 (
Tateho)^1120 is the average of 10 samples coated with magnesia.
サンプルは４℃露点をもつ２５％窒素−７５％水素雰囲
気中１２００℃まで加熱した。サンプルを１００％Ｈ、
中で１５時間にわたり１２００℃で均熱処理し、仕上げ
焼鈍が完了した後、サンプルをけがき処理し、応力除去
焼鈍を行った。使用するマグネシアは０．０２重量％の
塩素レベルのも策−よ−嚢
なし ０．０２ ０．３９７
０．５８６ １９２５Ｓｂ２（ＳＱ、）、＋ＳｂＣム
０．０３５ ０．３９２ ０．５４９ １
９３８Ｓｂｚ（ＳＯＪｚ÷５ｂＣ１，０，０６５０，３
８９０，５３１１９３９Ｓｂｚ（ＳＯ＜）ｚ＋５ｂｃ１
＊ ０．０９５ ０゜３９６ ０．５６１
１９３１なし ０．０２ ０．３
９７ ０．５６６ １９２５ＨｇＣＴｏ
Ｏ，０３５０，３９２０，５４８１９２７ＨｇＣ
Ｔｏ Ｏ，０６５０，３９８０，５４７１
９４０ＨｇＣ１ｘ Ｏ，０９５０，３９
３０，５３３１９４１マグネシアへの２種の添加剤の間
の磁気特性の比較は約０．０１５〜０．０７５％の塩素
を添加した塩化マグネシウムの添加が約０．０３〜０．
１０％の合計塩素範囲内で同様量の塩化物添加と共に硫
酸アンチモンを添加したものと同様かまたはより良好な
磁気特性を生ずることを示す、０．２０％までの塩素レ
ベルは０．１０％レベルまでの傾向に基づいて本発明の
塩化マグネシウム添加によるより良好な磁気特性を生ず
ることを明確に示唆するものである。塩素レベルが高い
ほど、塩化アンチモン添加剤より塩化マグネシウムが好
適である。The samples were heated to 1200°C in a 25% nitrogen-75% hydrogen atmosphere with a 4°C dew point. sample to 100% H,
After soaking at 1200° C. for 15 hours and finishing annealing, the sample was scribed and subjected to stress relief annealing. The magnesia used has a chlorine level of 0.02% by weight (no bag) 0.02 0.397
0.586 1925Sb2(SQ, ), +SbCmu 0.035 0.392 0.549 1
938Sbz(SOJz÷5bC1,0,0650,3
890,5311939Sbz(SO<)z+5bc1
* 0.095 0°396 0.561
1931 None 0.02 0.3
97 0.566 1925HgCTo
O,0350,3920,5481927HgC
To O, 0650, 3980, 5471
940HgC1x O,0950,39
30,5331941 A comparison of the magnetic properties between the two additives to magnesia shows that the addition of magnesium chloride with about 0.015-0.075% chlorine is about 0.03-0.
Chlorine levels up to 0.20% have been shown to produce magnetic properties similar to or better than the addition of antimony sulfate with similar amounts of chloride additions within the 10% total chlorine range to the 0.10% level. Based on the above trends, this clearly suggests that the addition of magnesium chloride according to the present invention produces better magnetic properties. At higher chlorine levels, magnesium chloride is preferred over antimony chloride additives.
また、実験の一部として、他のサンプルで、ガラス被膜
の二次被膜密着性、耐酸化性及びフランクリン抵抗の測
定における比較評価を使用してガラス被膜品質を評価し
た。Additionally, as part of the experiment, glass coating quality was evaluated on other samples using comparative evaluations of secondary coating adhesion, oxidation resistance, and Franklin resistance measurements of the glass coating.
北じしＬ
ガラス被膜の物理的性質
０．０１１ 良好 普通
０．５０６０．０３１ 非常に良好 非常に良好
０．５８７０．０６１ 普通
非常に良好 ０．６６５０．１１１ 悪
い 良好 ０．７５５塩化物
添加剤は全てＭ ｇ Ｃ１２であり、ＭｇＯは０．０１
１％の０１を含有する。Kitajishi L Physical properties of glass coating 0.011 Good Fair
0.5060.031 Very good Very good 0.5870.061 Fair
Very Good 0.6650.111 Poor Good 0.755 All chloride additives are M g C12 and MgO is 0.01
Contains 1% 01.
被膜の重量は全て０．２３ＬＬ１ｍの高透磁性珪素鋼側
回当たり約６．４ｇ／論２である。The weight of all coatings is approximately 6.4 g/2 x 0.23 mm high permeability silicon steel.
合計塩素の好適レベルは約０．０１５〜０．１５％であ
ることが測定された。塩素のより好適なレベルは磁気特
性の向上と良好な物理特性をもつガラス被膜の良好なバ
ランスを提供する約０．０１５〜０．１２％である。Ｒ
適合計塩素レベルは０．０２〜０．１０％であることが
明らかである。A suitable level of total chlorine has been determined to be about 0.015-0.15%. A more preferred level of chlorine is about 0.015-0.12%, which provides a good balance of improved magnetic properties and a glass coating with good physical properties. R
It appears that a suitable total chlorine level is between 0.02 and 0.10%.
また、得られたガラス被膜は被膜損傷なしにレーザーけ
がき処理が可能でなければならない、米国特許筒４，４
５６，８１２号明Ｋ１書記載のレーザーけがき処理は本
発明のガラス被膜により改善された磁区微細化を行い且
つ被膜損傷を回避する１本発明のマグネシア組成物はレ
ーザー処理に対して改善された光学特性を提供する。Ｍ
ｇ、Ｃａ、ＫまたはＮａの群から選択される金属を単独
で、または併用することができるが、Ｍ、またはＮａの
使用が好適である。ＴｉＯ２を添加する場合には、マグ
ネシアは１５重量％まで、好適には約５〜１０重量％の
Ｔ ｉ Ｏｔを含有することができる。また、１０ｆｆ
ｉ量％までの量でコロイドシリカを添加することができ
る。高透磁性方向性珪素鋼について、シリカのレベルは
約３〜７％が好適であり、硼素は約０．０５〜０．１５
％が好適である。また、クロムを適宜１５重量％まで添
加することができる。クロムを添加する場合には、好適
なレベルは約２．５〜５％に制限される。Additionally, the resulting glass coating must be capable of laser scribing without damaging the coating, US Pat.
The laser scribing treatment described in No. 56,812 Mei K1 provides improved domain refinement and avoids coating damage by the glass coating of the present invention.1 The magnesia composition of the present invention is improved with respect to laser treatment. Provides optical properties. M
Metals selected from the group G, Ca, K or Na can be used alone or in combination, but the use of M or Na is preferred. If TiO2 is added, the magnesia may contain up to 15% by weight of TiOt, preferably about 5-10% by weight. Also, 10ff
Colloidal silica can be added in amounts up to i% by weight. For high permeability grain-oriented silicon steels, silica levels of about 3-7% are preferred and boron levels of about 0.05-0.15%.
% is preferred. Further, chromium can be added as appropriate up to 15% by weight. When adding chromium, preferred levels are limited to about 2.5-5%.
また、本発明のマグネシアは普通の方向性電気鋼用の絶
縁性被膜として使用することもできる。The magnesia of the present invention can also be used as an insulating coating for ordinary grain-oriented electrical steel.
これらのマグネシアはわずかに変化させることができ、
約２０％までの燐酸塩添加剤好ましくは４〜１５％の範
囲内のｆｌＪ酸カルシウム添加剤、１５％まで、好まし
くは２〜１０％のクロム添加剤、１０％まで、好ましく
は約３〜７％のシリカ及び０．１５％まで、好ましくは
最高０．１０％の硼素を含有することができる。These magnesias can be slightly varied,
up to about 20% phosphate additive, preferably in the range 4-15% flJ calcium additive, up to 15%, preferably 2-10% chromium additive, up to 10%, preferably about 3-7 % silica and up to 0.15%, preferably up to 0.10% boron.
マグネシアから形成されるガラス被膜は被膜表面上に塗
布される絶縁性被膜をもつことができ、二次被膜は良好
な密着性を有する。Glass coatings formed from magnesia can have an insulating coating applied over the coating surface, and the secondary coating has good adhesion.
本発明の金属塩化物の添加は米国特許箱３．９４１，６
２２号明細書に特許請求されるような珪酸塩溶液との沈
澱反応を必要としない、マグネシア−シリカ錯化合物は
本発明においては塗布されない、以下の第３表はマグネ
シウム、カルシウム及びナトリウムについての本発明の
範囲内の金属塩化物添加の影響を示すものである。透磁
性及び鉄損は第３表に記載のレベルの塩化物の添加によ
りよ著に改善される。また、マグネシウムやナトリウム
についてのより好適なレベルへカルシウムを増加しても
、付加的な利点は何ら提供されず、事実、特性の僅かな
劣化が生ずることもある。カリウムについてのデータは
記載しなかったが、カリウムはナトリウムと同様な利点
を得るために必要なレベルでナトリウムと同様に挙動す
るものと思われる。ナトリウムとカリウムは金属界面を
平滑にする傾向にある。マグネシウムはこの点に関して
より中立的な傾向にある。カルシウムはガラス被膜の密
着性を改善することは明らかである。本発明の金属塩化
物添加剤は全て鋼帯表面を粗くする塩素レベルを提供す
る。上述のように、塩素はガラス被膜形成温度を低下す
る。マグネシアは第３表の第１行目の例に記載のように
もともと０．０１１％のような固有レベルの塩素をもつ
ことに留意することが重要である。この塩素レベルは系
において反応する塩素の合計レベルに寄与するものとし
て考慮しなければならない、ｏ、ｏｉ％の塩素を提供す
る最低金属塩化物の添加はマグネシアの塩素含量に拘わ
らず堅持しなければならない、好適なより高い塩素含量
の一部はマグネシアからの塩素を包含し、金属塩化物を
併用する。The addition of metal chlorides of the present invention is disclosed in U.S. Patent Box 3.941,6.
Magnesia-silica complexes, which do not require precipitation reactions with silicate solutions as claimed in No. 22, are not applied in the present invention; Table 3 below shows the results for magnesium, calcium and sodium. Figure 2 shows the effect of metal chloride addition within the scope of the invention. Magnetic permeability and core loss are significantly improved by addition of chloride at the levels listed in Table 3. Also, increasing calcium to more favorable levels with respect to magnesium and sodium does not provide any additional benefit and may in fact result in a slight deterioration of properties. Although no data were provided for potassium, it appears that potassium behaves similarly to sodium at the levels necessary to obtain similar benefits. Sodium and potassium tend to smooth metal interfaces. Magnesium tends to be more neutral in this regard. It is clear that calcium improves the adhesion of glass coatings. All metal chloride additives of this invention provide chlorine levels that roughen the steel strip surface. As mentioned above, chlorine lowers the glass coating formation temperature. It is important to note that magnesia originally has an inherent level of chlorine, such as 0.011%, as shown in the example in the first row of Table 3. This chlorine level must be considered as a contribution to the total level of chlorine reacting in the system; the minimum metal chloride addition that provides o.i.% chlorine must be maintained regardless of the chlorine content of the magnesia. Some of the preferred higher chlorine contents include chlorine from magnesia, in combination with metal chlorides.
なし ０．０１１ ０．９０１ １．２５８ １．
９１４ ０．８３５ＭｇＣ１ｚ Ｏ，０４１０，８８
１１，２３１１，９２５０，８０２ＭｇＣ１ｚ Ｏ，
０７１０，８７２１，２１８１，９２７０，７９３Ｎａ
Ｃ１Ｏ，０４１０，８７４１，２２５１，９２３０，８
０ＯＮａＣ１Ｏ，０７１０，８７４１，２０３１，９３
２０，７８６ＣａＣ１’ｚ Ｏ，０４１０，８８１１
，２３１１，９２３０，８０２Ｃａ（Ｊ、 ０．０７
１ ０．８９４ １．２４２ １．９２７ ０．８０
４応力除去焼鈍は８２９℃（１５２５°Ｆ）で、９５％
Ｎ２−５％Ｈ２中で行った。None 0.011 0.901 1.258 1.
914 0.835MgC1z O,0410,88
11,2311,9250,802MgC1zO,
0710,8721,2181,9270,793Na
C1O,0410,8741,2251,9230,8
0ONaC1O, 0710, 8741, 2031, 93
20,786CaC1'z O,0410,8811
,2311,9230,802Ca(J, 0.07
1 0.894 1.242 1.927 0.80
4 stress relief annealing at 829°C (1525°F), 95%
Performed in N2-5% H2.
１．１４１
ｉ、ｏｓｔ
１．０フ０
１．０８４
１．０４８
１．０８４
１．０７９
２時間
ガラス被膜及び磁気特性を改善するために必要な金属塩
化物のレベルは選択する金属に依存して僅かに変化する
ことが判る。塩化カルシウムによる塩素の好適な最高レ
ベルは塩化マグネシウム、塩化ナトリウムまたは塩化カ
リウム添加剤による塩素レベルよりも低いことが判る。1.141 i, ost 1.0f0 1.084 1.048 1.084 1.079 2 hours The level of metal chloride needed to improve the glass coating and magnetic properties depends on the metal selected. It can be seen that there is a slight change. It is found that the preferred maximum level of chlorine with calcium chloride is lower than the chlorine level with magnesium chloride, sodium chloride or potassium chloride additives.
この差異の理由は完全には理解できないが、改善された
特性は約０．０１５〜０．０７％の好適なカルシウム添
加により生ずる１本発明の他の金属塩化物添加による好
適なレベルは約０．０１５〜０．１０％である。Although the reason for this difference is not completely understood, improved properties result from the preferred calcium addition of about 0.015-0.07%. Preferred levels for other metal chloride additions of the present invention are about 0.015-0.07%. It is .015 to 0.10%.
これらの添加レベルを調節してマグネシア中に存在する
塩素レベルを補うことができる。These addition levels can be adjusted to compensate for the chlorine levels present in the magnesia.
本発明を特定の実施態様を参照することにより説明した
が、本発明の範囲を逸脱せずに多くの改変を行うことが
できる。従属する特許請求の範囲の記載は本発明の精神
及び範囲内にあるような同等の改変を全て網羅すること
を意図するものである。Although the invention has been described with reference to particular embodiments, many modifications can be made without departing from the scope of the invention. The dependent claims are intended to cover all equivalent modifications that fall within the spirit and scope of the invention.
Claims (26)
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ＴｉＯ＿２； ｄ）１０％までのＳｉＯ＿２； 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。1. A magnesia slurry maintained at 25° C. or lower for coating cold rolled grain-oriented silicon steel before finishing high temperature annealing, comprising: a) magnesia in which the major amount of magnesia particles has a citric acid activity of 200 or less; b) Mg 0, based on the weight of magnesia, by at least 0.01% by weight of chlorine from a metal chloride selected from the group consisting of , Ca, Na and/or K.
．． Total chlorine level in magnesia from 01 to 0.20% by weight; c) TiO_2 up to 15%; d) SiO_2 up to 10%; e) Cr up to 15%; and c) from boron up to 0.3%. A magnesia slurry characterized by substantially
１記載のマグネシアスラリー。2. The magnesia slurry according to claim 1, wherein the amount of TiO_2 added is 5 to 10% by weight.
請求項１記載のマグネシアスラリー。3. The magnesia slurry according to claim 1, wherein the magnesia slurry is maintained at a temperature of 0 to 15°C.
項１記載のマグネシアスラリー。4. The magnesia slurry according to claim 1, wherein the total amount of chlorine is 0.01 to 0.15% by weight.
素レベルを生ずる量である請求項１記載のマグネシアス
ラリー。5. 2. The magnesia slurry of claim 1, wherein the amount of metal chloride added is to produce a chlorine level of 0.015 to 0.12%.
レベルを生ずる量である請求項１記載のマグネシアスラ
リー。6. A magnesia slurry according to claim 1, wherein the amount of metal chloride added is in an amount to produce a chlorine level of 0.02 to 0.10%.
択され、０．０１５〜０．１０％の合計塩素レベルを生
ずる量で添加されてなる請求項１記載のマグネシアスラ
リー。7. A magnesia slurry according to claim 1, wherein the metal chloride is selected from the group of Mg, Na and/or K and is added in an amount to produce a total chlorine level of 0.015-0.10%.
の合計塩素レベルを生ずる量で添加されてなる請求項１
記載のマグネシアスラリー。8. Metal chloride is Ca, 0.015-0.07%
Claim 1 added in an amount to produce a total chlorine level of
Magnesia slurry as described.
磁性珪素鋼であり、且つ３〜７％のＳｉＯ＿２及び０．
０５〜０．１５％の硼素がマグネシアへ添加されている
請求項１記載のマグネシアスラリー。9. The cold-rolled grain-oriented silicon steel is a high permeability silicon steel containing an AlN inhibitor system and contains 3-7% SiO_2 and 0.
2. The magnesia slurry according to claim 1, wherein 0.05 to 0.15% of boron is added to the magnesia.
のマグネシアスラリー。10. The magnesia slurry according to claim 1, wherein the amount of Cr added is 2.5 to 5%.
り、マグネシアが２０％までの燐酸塩添加剤と０．１５
％までの硼素を含む請求項１記載のマグネシアスラリー
。11. Cold rolled grain oriented silicon steel is ordinary grain oriented silicon steel with magnesia up to 20% phosphate additive and 0.15%
The magnesia slurry of claim 1 containing up to % boron.
であり、ＳｉＯ＿２が３〜７％であり、Ｃｒが２〜１０
％であり、硼素が０．１０％までである請求項１１記載
のマグネシアスラリー。12. The phosphate additive is calcium phosphate in an amount of 4-15%, SiO_2 is 3-7% and Cr is 2-10%.
% and boron is up to 0.10%.
いて、 ａ）前記珪素鋼を鋼帯へ冷間圧延し； ｂ）脱炭焼鈍を施して前記鋼帯中の炭素レベルを０．０
０３％以下に低減し； ｃ）凝固点以上２５℃までの温度にマグネシア浴を維持
し； ｄ）少なくとも０．０１％がＭｇ、Ｃａ、Ｎａ及び／ま
たはＫの群から選択された金属塩化物添加剤によるもの
である０．０１〜０．２０重量％の合計塩素を含み且つ
主要量のマグネシア粒子のクエン酸活性が２００以下の
マグネシア被膜を塗布し；ｅ）マグネシアを乾燥して過
剰の水を除去し；且つｆ）仕上げ高温焼鈍を施してガラ
ス被膜を形成し且つ改善された磁気特性を発現させるこ
とを特徴とする方向性珪素鋼上へ絶縁性被膜を製造する
方法。13. A method for producing an insulating coating on grain-oriented silicon steel, comprising: a) cold rolling said silicon steel into a steel strip; b) subjecting said steel strip to a decarburization annealing to reduce the carbon level in said steel strip to 0.0.
c) maintaining the magnesia bath at a temperature above the freezing point and up to 25°C; d) addition of a metal chloride of at least 0.01% selected from the group Mg, Ca, Na and/or K; applying a magnesia coating containing 0.01 to 0.20% by weight of total chlorine and having a citric acid activity of the major amount of magnesia particles of 200 or less; e) drying the magnesia to remove excess water; and f) a final high temperature annealing to form a glass coating and to develop improved magnetic properties.
１３記載の方法。14. 14. The method according to claim 13, wherein a magnetic domain refinement step is performed after the final high-temperature annealing.
れる金属塩化物として０．０１５〜０．１５％の塩素を
添加する請求項１３記載の方法。15. 14. Process according to claim 13, characterized in that 0.015-0.15% of chlorine is added as a metal chloride selected from the group Mg, Na, Ca and/or K.
維持する請求項１３記載の方法。16. 14. The method of claim 13, wherein the magnesia is maintained at a temperature of 0 DEG to 15 DEG C. before coating onto the steel strip.
マグネシア粒子を４５％まで含有する請求項１３記載の
方法。17. 14. The method of claim 13, wherein the magnesia contains up to 45% inert magnesia particles with a citric acid activity above 200.
載の方法。18. 14. The method of claim 13, wherein the magnesia contains up to 45% particles with a citric acid activity of 500 to 5000.
とを合わせて０．０１５〜０．１２％の合計塩素レベル
を提供する請求項１３記載の方法。19. 14. The method of claim 13, wherein the metal chloride and the chlorine level present in the magnesia are combined to provide a total chlorine level of 0.015 to 0.12%.
とを合わせて０．０２〜０．１０％の合計塩素レベルを
提供する請求項１３記載の方法。20. 14. The method of claim 13, wherein the metal chloride and the chlorine level present in the magnesia are combined to provide a total chlorine level of 0.02 to 0.10%.
塩化物がＭｇ、Ｎａ及び／またはＫの群から選択される
請求項１３記載の方法。21. 14. Process according to claim 13, wherein the total chlorine is 0.015-0.10% and the metal chloride is selected from the group Mg, Na and/or K.
％の塩素レベルを生ずる量で添加される請求項１３記載
の方法。22. The metal chloride is Ca, 0.015 to 0.07
14. The method of claim 13, wherein the chlorine is added in an amount to produce a chlorine level of %.
ネシアが２０％までの燐酸塩及び０．１５％までのＢを
含有する請求項２３記載の方法。24. 24. The method of claim 23, wherein the grain-oriented silicon steel is a regular grain-oriented silicon steel and the magnesia contains up to 20% phosphate and up to 0.15% B.
１０％のＣｒ、０．１０％までのＢ及び３〜７％のＳｉ
Ｏ＿２を含有する請求項２４記載の方法。25. Calcium phosphate with 4-15% magnesia, 2-
10% Cr, up to 0.10% B and 3-7% Si
25. The method according to claim 24, comprising O_2.
グネシアが５〜１０％のＴｉＯ＿２、３〜７％のＳｉＯ
＿２、２．５〜５％のＣｒ及び０．０５〜０．１５％の
Ｂを含有する請求項２３記載の方法。26. The grain-oriented silicon steel is a high magnetic permeability grain-oriented silicon steel, and the magnesia is 5-10% TiO_2, 3-7% SiO
24. The method of claim 23, containing _2, 2.5-5% Cr and 0.05-0.15% B.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40471489A | 1989-09-08 | 1989-09-08 | |
| US404,714 | 1989-09-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03120376A true JPH03120376A (en) | 1991-05-22 |
| JP2686455B2 JP2686455B2 (en) | 1997-12-08 |
Family
ID=23600734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2235992A Expired - Lifetime JP2686455B2 (en) | 1989-09-08 | 1990-09-07 | Magnesium oxide coating for electric steel and coating method |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0416420B1 (en) |
| JP (1) | JP2686455B2 (en) |
| KR (1) | KR0173781B1 (en) |
| BR (1) | BR9004444A (en) |
| CA (1) | CA2024226C (en) |
| DE (1) | DE69015060T2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06101059A (en) * | 1992-09-18 | 1994-04-12 | Nippon Steel Corp | Separation agent for annealing for grain-oriented silicon steel sheet for obtaining uniform high tensile strength glass film and excellent magnetic property |
| JPH07316831A (en) * | 1994-05-23 | 1995-12-05 | Kaisui Kagaku Kenkyusho:Kk | Ceramic coating film forming agent and its production |
| WO1996015291A1 (en) * | 1994-11-16 | 1996-05-23 | Nippon Steel Corporation | Process for producing directional electrical sheet excellent in glass coating and magnetic properties |
| KR100245032B1 (en) * | 1994-11-16 | 2000-03-02 | 아사무라 타카싯 | Process for producing directional sheet excellent in glass coating and magnetic properties |
| KR100435477B1 (en) * | 1999-12-27 | 2004-06-10 | 주식회사 포스코 | A method for manufacturing grain-oriented electrical steel sheet having no surface defects and superior punching property |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4409691A1 (en) * | 1994-03-22 | 1995-09-28 | Ebg Elektromagnet Werkstoffe | Process for the production of electrical sheets with a glass coating |
| DE19750066C1 (en) * | 1997-11-12 | 1999-08-05 | Ebg Elektromagnet Werkstoffe | Process for coating electrical steel strips with an annealing separator |
| KR19990042456A (en) * | 1997-11-26 | 1999-06-15 | 성재갑 | Aerosol composition of hair treatment lotion and valve for injecting same |
| DE102008039326A1 (en) | 2008-08-22 | 2010-02-25 | IWT Stiftung Institut für Werkstofftechnik | Preparing electrically insulated electric sheet, to prepare laminated magnetic core, comprises coating one side of sheet using liquid mixture comprising hydrolyzed and condensed metal organic monomer, and heat treating coated sheet |
| CN102453793B (en) * | 2010-10-25 | 2013-09-25 | 宝山钢铁股份有限公司 | Annealing isolation agent used for preparing mirror surface-oriented silicon steel with excellent magnetic property |
| CN104066857B (en) | 2012-02-13 | 2016-06-01 | 索拉劳尼克斯股份有限公司 | The cooling of cated sheet metal band |
| WO2021085421A1 (en) * | 2019-10-31 | 2021-05-06 | Ｊｆｅスチール株式会社 | Grain-oriented electromagnetic steel sheet and method for manufacturing same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231296B2 (en) * | 1973-06-07 | 1977-08-13 | ||
| US3841925A (en) * | 1973-09-12 | 1974-10-15 | Morton Norwich Products Inc | Magnesium oxide steel coating composition and process |
| US4032366A (en) * | 1975-05-23 | 1977-06-28 | Allegheny Ludlum Industries, Inc. | Grain-oriented silicon steel and processing therefor |
| BR7804962A (en) * | 1977-08-04 | 1979-05-08 | Armco Inc | PROCESS TO STABILIZE VISCOSITY AND INCREASE THE CONCENTRATION OF Aqueous MAGNESIA PASTE |
| JPS5441220A (en) * | 1977-09-09 | 1979-04-02 | Nippon Steel Corp | Manufacture of oriented electrical steel sheet with superior magnetic characteristics |
| JPS5466935A (en) * | 1977-11-09 | 1979-05-29 | Kawasaki Steel Co | Method of forming forsterite insulating layer in directive silicon steel plate |
| JPS54128928A (en) * | 1978-03-31 | 1979-10-05 | Nippon Steel Corp | Protective coating material for annealing of anisotropic silicon steel plate |
| JPS6096770A (en) * | 1983-10-28 | 1985-05-30 | Nippon Steel Corp | Preparation of oriented electromagnetic steel plate excellent in iron loss |
| DE3875676T2 (en) * | 1987-08-31 | 1993-03-18 | Nippon Steel Corp | METHOD FOR PRODUCING CORNORIENTED STEEL SHEETS WITH METAL GLOSS AND EXCELLENT PUNCHABILITY. |
-
1990
- 1990-08-27 EP EP90116384A patent/EP0416420B1/en not_active Expired - Lifetime
- 1990-08-27 DE DE69015060T patent/DE69015060T2/en not_active Expired - Lifetime
- 1990-08-29 CA CA002024226A patent/CA2024226C/en not_active Expired - Fee Related
- 1990-09-06 BR BR909004444A patent/BR9004444A/en not_active IP Right Cessation
- 1990-09-07 JP JP2235992A patent/JP2686455B2/en not_active Expired - Lifetime
- 1990-09-08 KR KR1019900014201A patent/KR0173781B1/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06101059A (en) * | 1992-09-18 | 1994-04-12 | Nippon Steel Corp | Separation agent for annealing for grain-oriented silicon steel sheet for obtaining uniform high tensile strength glass film and excellent magnetic property |
| JPH07316831A (en) * | 1994-05-23 | 1995-12-05 | Kaisui Kagaku Kenkyusho:Kk | Ceramic coating film forming agent and its production |
| WO1996015291A1 (en) * | 1994-11-16 | 1996-05-23 | Nippon Steel Corporation | Process for producing directional electrical sheet excellent in glass coating and magnetic properties |
| US5840131A (en) * | 1994-11-16 | 1998-11-24 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel sheet having excellent glass film and magnetic properties |
| KR100245032B1 (en) * | 1994-11-16 | 2000-03-02 | 아사무라 타카싯 | Process for producing directional sheet excellent in glass coating and magnetic properties |
| KR100435477B1 (en) * | 1999-12-27 | 2004-06-10 | 주식회사 포스코 | A method for manufacturing grain-oriented electrical steel sheet having no surface defects and superior punching property |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0416420A3 (en) | 1992-11-19 |
| BR9004444A (en) | 1991-09-10 |
| KR910006518A (en) | 1991-04-29 |
| CA2024226C (en) | 2000-02-15 |
| DE69015060T2 (en) | 1995-04-27 |
| EP0416420A2 (en) | 1991-03-13 |
| DE69015060D1 (en) | 1995-01-26 |
| KR0173781B1 (en) | 1999-02-18 |
| CA2024226A1 (en) | 1991-03-09 |
| JP2686455B2 (en) | 1997-12-08 |
| EP0416420B1 (en) | 1994-12-14 |
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