JP2020509216A - 方向性電磁鋼板用焼鈍分離剤組成物、方向性電磁鋼板および方向性電磁鋼板の製造方法 - Google Patents
方向性電磁鋼板用焼鈍分離剤組成物、方向性電磁鋼板および方向性電磁鋼板の製造方法 Download PDFInfo
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- JP2020509216A JP2020509216A JP2019534652A JP2019534652A JP2020509216A JP 2020509216 A JP2020509216 A JP 2020509216A JP 2019534652 A JP2019534652 A JP 2019534652A JP 2019534652 A JP2019534652 A JP 2019534652A JP 2020509216 A JP2020509216 A JP 2020509216A
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- steel sheet
- oriented electrical
- electrical steel
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- 238000000137 annealing Methods 0.000 title claims abstract description 103
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 37
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 22
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 22
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims description 74
- 239000011248 coating agent Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 54
- 239000010410 layer Substances 0.000 claims description 48
- 238000001953 recrystallisation Methods 0.000 claims description 40
- 229910000831 Steel Inorganic materials 0.000 claims description 38
- 239000010959 steel Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 30
- 229910052839 forsterite Inorganic materials 0.000 claims description 25
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 150000004692 metal hydroxides Chemical class 0.000 claims description 21
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000005121 nitriding Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005097 cold rolling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005098 hot rolling Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 4
- 239000011254 layer-forming composition Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000010586 diagram Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
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- 239000001257 hydrogen Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000003141 anti-fusion Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
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- C21D6/00—Heat treatment of ferrous alloys
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- C21D6/00—Heat treatment of ferrous alloys
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- 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
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- C21D8/1222—Hot rolling
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- 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
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- C22C—ALLOYS
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- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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Abstract
Description
従来の方向性電磁鋼板の製造工程において、フォルステライト被膜特性を改善するためにMgOを主成分とする融着防止剤を塗布する段階でMgOとTiO2粉末の表面特性を改善する方法が提案されている。
また、本発明において1ppmは0.0001%を意味する。
本発明の一実施例において追加成分をさらに含むことの意味は、追加成分の追加量分だけ残部に代替して含むことを意味する。
別に定義していないが、ここに使用される技術用語および科学用語を含む全ての用語は、本発明が属する技術分野における通常の知識を有する者が一般的に理解する意味と同一の意味を有する。普通使用される辞書に定義された用語は、関連技術文献と現在開示されている内容に合う意味を持つものと追加解釈され、定義されていない限り理想的や公式的過ぎる意味に解釈されない。
本発明の一実施例による方向性電磁鋼板用焼鈍分離剤組成物は、固形分を基準に、ムライト5〜70重量%、および残部を酸化マグネシウムまたは水酸化マグネシウムを含む。ここで固形分基準とは、溶媒などの成分を除いた固形分を100重量%に設定したことを意味する。
本発明の一実施例による焼鈍分離剤組成物は、方向性電磁鋼板基材10に塗布され、ムライトおよびフォルステライトを含む被膜20を形成する。ムライトは、シリカとアルミナとの間に安定して存在する唯一の化合物であり、3Al2O3・2SiO2の組成からなる。ムライトは、熱膨張率が小さいため(5×10−6/℃)被膜張力付与による鉄損改善が容易である。また、ムライトは、弾性率が比較的低いため、耐熱衝撃抵抗に優れる。
この時、水酸化金属は、前述した水酸化マグネシウムを除いた水酸化金属を意味する。具体的に水酸化金属は、Ni(OH)2、Co(OH)2、Cu(OH)2、Sr(OH)2、Ba(OH)2、Pd(OH)2、In(OH)3、Bi(OH)3およびSn(OH)2の中から選ばれる1種以上を含み得る。
セラミック粉末は、球状、板状、および針状を含む群より選ばれるいずれか一つ以上の形態であり得る。
シリコン(Si)は、鋼の比抵抗を増加させて鉄損を減少させる役割をするが、Siの含有量が過度に少ない場合には鋼の比抵抗が小さくなり、鉄損特性が損なわれ、高温焼鈍時の相変態区間が存在して2次再結晶が不安定になる問題が生じ得る。Siの含有量が過度に多い場合には脆性が大きくなり、冷間圧延が難しくなる問題が生じ得る。したがって、前述した範囲でSiの含有量を調整し得る。より具体的には、Siは3.0〜4.0重量%である。
アルミニウム(Al)は、最終的にAlN、(Al,Si)N、(Al,Si,Mn)N形態の窒化物になり抑制剤として作用する成分である。Alの含有量が過度に少ない場合には抑制剤として十分な効果を期待し難い。また、Alの含有量が過度に多い場合にはAl系の窒化物が過度に粗大に析出、成長するので、抑制剤としての効果が充分に発揮されない。したがって、前述した範囲でAlの含有量を調整する。
マンガン(Mn)は、Siと同一に比抵抗を増加させて鉄損を減少させる効果があり、Siと共に窒化処理によって導入される窒素と反応して(Al,Si,Mn)Nの析出物を形成することで、1次再結晶粒の成長を抑制して2次再結晶を起こすのに重要な元素である。しかし、Mnの含有量が過度に多い場合、熱延途中にオーステナイト相変態を促すので、1次再結晶粒の大きさを減少させて2次再結晶を不安定にする。また、Mnの含有量が過度に少ない場合、オーステナイト形成元素として熱延再加熱時にオーステナイトの分率を高めて析出物の固溶量を多くして再析出時の析出物微細化とMnS形成による1次再結晶粒が粗大すぎないようにする効果が不充分である。したがって、前述した範囲でMnの含有量を調整し得る。
アンチモン(Sb)、錫(Sn)、ニッケル(Ni)は、結晶粒界偏析元素として結晶粒界の移動を妨害する元素であるため、結晶粒成長抑制剤として{110}<001>方位のゴス結晶粒の生成を促進して2次再結晶がよく発達するようにするので、結晶粒の大きさの制御に重要な元素である。仮に、Sb、SnまたはNiを単独または複合添加した含有量が過度に少ない場合、その効果が劣る問題が生じることがある。Sb、SnまたはNiを単独または複合添加した含有量が過度に多い場合、結晶粒界偏析が過度に起きて鋼板の脆性が大きくなり、圧延時の板破断が発生することがある。より具体的には、Sbを0.01〜0.05重量%、Snを0.01〜0.12重量%、Niを0.01〜0.06重量%含み得る。
Cは、本発明による実施例における方向性電磁鋼板の磁気的特性の向上に大きく役に立たない成分であるため、できるだけ除去することが好ましい。しかし、一定の水準以上含まれている場合、圧延過程では鋼のオーステナイト変態を促進して熱間圧延時の熱間圧延組織を微細化させて均一な微細組織の形成を助ける効果があるので、スラブでのC含有量は0.03重量%以上で含まれることが好ましい。しかし、C含有量が多すぎると粗大な炭化物が生成され、脱炭時の除去が困難になるので、0.08重量%以下であることが好ましい。方向性電磁鋼板の製造過程で脱炭焼鈍過程により炭素が脱炭され、最終的に製造される方向性電磁鋼板内にはCが0.01重量%以下で含まれることになる。
Nは、Alなどと反応して結晶粒を微細化させる元素である。これらの元素が適切に分布する場合には上述した通り、冷間圧延以後に組織を適切に微細にして適切な1次再結晶粒度の確保を助ける。しかし、その含有量が過度である場合、1次再結晶粒が過度に微細化し、その結果微細な結晶粒によって2次再結晶時に結晶粒成長を招く駆動力が大きくなり好ましくない方位の結晶粒まで成長し得る。また、N含有量が多すぎると最終焼鈍過程で除去にも多くの時間が必要とされるので好ましくない。したがって、スラブ内の前記窒素含有量の上限は0.005重量%とし、スラブ再加熱時に固溶される窒素の含有量が0.001重量%以上でならなければならないので、スラブ内の窒素含有量の下限は0.001重量%とすることが好ましい。方向性電磁鋼板の製造過程で浸窒焼鈍過程により窒素が一部浸透し、最終的に製造される方向性電磁鋼板内にはNが0.005〜0.05重量%で含まれることになる。
実施例1
シリコン(Si)を3.4重量%、アルミニウム(Al):0.03重量%、マンガン(Mn):0.05重量%アンチモン(Sb)を0.04重量%、錫(Sn)を0.09重量%、およびニッケル(Ni)を0.02重量%、炭素(C)を0.06重量%、窒素(N)を40重量ppm含み、残部はFeおよびその他不可避不純物からなるスラブを準備した。スラブを1150℃で220分間加熱した後2.3mmの厚さに熱間圧延して熱延板を製造した。
実施例1と同様に実施するが、焼鈍分離剤内のムライトおよび金属水酸化物の成分を下記表1のように交替して被膜を形成した。フォルステライト被膜の表面に下記表1に整理したセラミック粉末を適用した。
実施例1と同様に実施するが、セラミック層は形成しなかった
実施例1と同様に実施するが、マグネシウム酸化物90重量%、酸化チタン5重量%およびSb2(SO4)35重量%を含む焼鈍分離剤組成物を用いた。
実施例1と同様に実施するが、ムライト100重量%を含む焼鈍分離剤組成物を用いた。
実施例1と同様に実施するが、ムライト90重量%、酸化チタン5重量%およびSb2(SO4)35重量%を含む焼鈍分離剤組成物を用いた。
実施例10
シリコン(Si)を3.3重量%、アルミニウム(Al):0.03重量%、アンチモン(Sb)を0.03重量%、スズ(Sn)を0.05重量%、およびニッケル(Ni)を0.02重量%、炭素(C)を0.05重量%、窒素(N)を30重量ppm含み、残部はFeおよびその他不可避不純物からなるスラブを準備した。
実施例10と同様に実施するが、マグネシウム酸化物90重量%、酸化チタン5重量%およびSb2(SO4)35重量%を含む焼鈍分離剤組成物を用いた。
占積率は、JIS C2550国際規格に従い測定機を用いて測定した。電磁鋼板試験片を複数積層した後に表面に1MPaの均一な圧力を加えた後、試験片の4面の高さの精密測定により電磁鋼板積層による実際の重量比を理論重量で割って測定した。
騒音評価方法は、国際規程IEC61672−1と同様に評価するが、音圧の代わりに電磁鋼板の震え(振動)データを得て騒音換算値[dBA]で評価する。電磁鋼板の震えは周波数60Hzの磁場を1.7Teslaまで交流で磁化させたとき、レーザドップラー方式を用いて非接触式で時間に応じて振動パターンを測定する。
10:方向性電磁鋼板基材
20:被膜
30:セラミック層
Claims (21)
- 全体固形分100重量%を基準に、ムライト5〜70重量%、および残部を酸化マグネシウムまたは水酸化マグネシウムを含むことを特徴とする方向性電磁鋼板用焼鈍分離剤組成物。
- 水酸化金属を0.1〜20重量%さらに含むことを特徴とする請求項1に記載の方向性電磁鋼板用焼鈍分離剤組成物。
- 前記水酸化金属は、Ni(OH)2、Co(OH)2、Cu(OH)2、Sr(OH)2、Ba(OH)2、Pd(OH)2、In(OH)3、Bi(OH)3およびSn(OH)2の中から選ばれる1種以上を含むことを特徴とする請求項2に記載の方向性電磁鋼板用焼鈍分離剤組成物。
- セラミック粉末を0.5〜10重量%さらに含むことを特徴とする請求項1に記載の方向性電磁鋼板用焼鈍分離剤組成物。
- 前記セラミック粉末は、MnO、Al2O3、SiO2、TiO2およびZrO2の中から選ばれる1種以上を含むことを特徴とする請求項4に記載の方向性電磁鋼板用焼鈍分離剤組成物。
- Sb2(SO4)3、SrSO4、BaSO4またはこれらの組み合わせを1〜10重量%さらに含むことを特徴とする請求項1に記載の方向性電磁鋼板用焼鈍分離剤組成物。
- 方向性電磁鋼板基材の一面または両面にムライトおよびフォルステライトを含む被膜が形成されていることを特徴とする方向性電磁鋼板。
- 前記被膜は、Alを0.5〜50重量%含むことを特徴とする請求項7に記載の方向性電磁鋼板。
- 前記被膜は、Mgを3〜80重量%、Siを3〜80重量%、Oを3〜80重量%およびFeを残部としてさらに含むことを特徴とする請求項7に記載の方向性電磁鋼板。
- 前記被膜は、厚さが0.1〜10μmであることを特徴とする請求項7に記載の方向性電磁鋼板。
- 前記被膜上に形成されたセラミック層をさらに含むことを特徴とする請求項7に記載の方向性電磁鋼板。
- 前記セラミック層は、セラミック粉末を含むことを特徴とする請求項11に記載の方向性電磁鋼板。
- 前記セラミック粉末は、Al2O3、SiO2、TiO2、ZrO2、Al2O3・TiO2、Y2O3、9Al2O3・2B2O3、BN、CrN、BaTiO3、SiCおよびTiCの中から選ばれる1種以上を含むことを特徴とする請求項12に記載の方向性電磁鋼板。
- 前記セラミック層は、金属リン酸塩をさらに含むことを特徴とする請求項12に記載の方向性電磁鋼板。
- 前記金属リン酸塩は、Mg、Ca、Ba、Sr、ZN、AlおよびMnの中から選ばれる1種以上を含むことを特徴とする請求項14に記載の方向性電磁鋼板。
- 前記方向性電磁鋼板基材は、シリコン(Si):2.8〜4.5重量%、アルミニウム(Al):0.020〜0.040重量%、マンガン(Mn):0.01〜0.20重量%およびアンチモン(Sb)、スズ(Sn)、ニッケル(Ni)またはこれらの組み合わせを0.01〜0.15重量%含み、残部はFeおよびその他不可避不純物からなることを特徴とする請求項7に記載の方向性電磁鋼板。
- 鋼スラブを準備する段階;
前記鋼スラブを加熱する段階;
前記加熱した鋼スラブを熱間圧延して熱延板を製造する段階;
前記熱延板を冷間圧延して冷延板を製造する段階;
前記冷延板を1次再結晶焼鈍する段階;
前記1次再結晶焼鈍した鋼板の表面上に焼鈍分離剤を塗布する段階;および
前記焼鈍分離剤が塗布された鋼板を2次再結晶焼鈍する段階を含み、
前記焼鈍分離剤は、全体固形分100重量%を基準に、ムライト5〜70重量%、および残部を酸化マグネシウムまたは水酸化マグネシウムを含むことを特徴とする方向性電磁鋼板の製造方法。 - 前記2次再結晶焼鈍する段階以後に、ムライトおよびフォルステライトを含む被膜上にセラミック層を形成する段階をさらに含むことを特徴とする請求項17に記載の方向性電磁鋼板の製造方法。
- 前記セラミック層を形成する段階は、
前記被膜上にセラミック粉末を噴射してセラミック層を形成する段階であることを特徴とする請求項18に記載の方向性電磁鋼板の製造方法。 - 前記セラミック層を形成する段階は、
前記被膜上にセラミック粉末および金属リン酸塩を含むセラミック層形成組成物を塗布してセラミック層を形成する段階であることを特徴とする請求項18に記載の方向性電磁鋼板の製造方法。 - 前記冷延板を1次再結晶焼鈍する段階は、
前記冷延板を同時に脱炭焼鈍および窒化焼鈍する段階を含むか、脱炭焼鈍以後に窒化焼鈍する段階を含むことを特徴とする請求項17に記載の方向性電磁鋼板の製造方法。
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