JP6863534B1 - 絶縁被膜付き電磁鋼板 - Google Patents
絶縁被膜付き電磁鋼板 Download PDFInfo
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- JP6863534B1 JP6863534B1 JP2020555935A JP2020555935A JP6863534B1 JP 6863534 B1 JP6863534 B1 JP 6863534B1 JP 2020555935 A JP2020555935 A JP 2020555935A JP 2020555935 A JP2020555935 A JP 2020555935A JP 6863534 B1 JP6863534 B1 JP 6863534B1
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- rolling
- insulating coating
- steel sheet
- rolling direction
- insulating film
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- 238000000576 coating method Methods 0.000 title claims abstract description 112
- 239000011248 coating agent Substances 0.000 title claims abstract description 109
- 229910000976 Electrical steel Inorganic materials 0.000 title description 4
- 238000005096 rolling process Methods 0.000 claims abstract description 122
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 85
- 239000010959 steel Substances 0.000 claims abstract description 85
- 239000000126 substance Substances 0.000 claims abstract description 41
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- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 238000000137 annealing Methods 0.000 description 23
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- 229910052878 cordierite Inorganic materials 0.000 description 10
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
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- 238000005452 bending Methods 0.000 description 9
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- 239000011651 chromium Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 241000282341 Mustela putorius furo Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 238000005261 decarburization Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
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- 230000005484 gravity Effects 0.000 description 3
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- 239000010410 layer Substances 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
- 239000011164 primary particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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Abstract
Description
[1]電磁鋼板の表面に結晶性の繊維状物質を含有する絶縁被膜を有し、前記絶縁被膜中での前記結晶性の繊維状物質の圧延方向断面における圧延方向長さ(LRD)と圧延直角方向断面における圧延直角方向長さ(LTD)の比(LRD/LTD)が1.5以上50.0以下である、絶縁被膜付き電磁鋼板。
[2]前記絶縁被膜中での前記結晶性の繊維状物質の圧延直角方向断面における板厚方向長さ(LND)と絶縁被膜の膜厚(d)の比(LND/d)が0.2以上2.0以下である、[1]に記載の絶縁被膜付き電磁鋼板。
[3]前記結晶性の繊維状物質の25℃から800℃の温度範囲における体積熱膨張率が30×10−6/K以下である、[1]または[2]に記載の絶縁被膜付き電磁鋼板。
[4]前記結晶性の繊維状物質の25℃から800℃の温度範囲における線熱膨張率が異方性を有する、[1]〜[3]のいずれかに記載の絶縁被膜付き電磁鋼板。
[5]前記絶縁被膜が、Mg、Al、Ca、Ba、Sr、Zn、Ti、Nd、Mo、Cr、B、Ta、Cu、Mnのうちから選ばれる金属元素を1種もしくは2種以上含むリン酸塩を含有する、[1]〜[4]のいずれかに記載の絶縁被膜付き電磁鋼板。
公知の方法で製造された板厚:0.20mmの仕上焼鈍済みの方向性電磁鋼板から、圧延方向300mm×圧延直角方向100mmの大きさの鋼板をせん断により切り出し、未反応の焼鈍分離剤を除去した後、歪取焼鈍(800℃、2時間、N2雰囲気)を施した。鋼板の表面にはフォルステライトを主体とする被膜が形成していた。次に、5質量%リン酸水溶液で軽酸洗した。その後、前記軽酸洗後の鋼板に対して、以下のようにして絶縁被膜を形成した。
(従来例2)特開平9−78253号公報の実施例の絶縁被膜を前記文献に記載のとおり施した。なお、絶縁被膜の目付量は、鋼板両面合計の乾燥後目付量で9g/m2とした。
(発明例)第一リン酸マグネシウム水溶液を固形分換算で100質量部、コロイド状シリカをSiO2固形分換算で50質量部、コーディエライトを10質量部混合した水溶液を純水で希釈して比重1.20に調整した絶縁被膜形成用処理液(コート液)を作製した。前記コート液を、鋼板両面合計の乾燥後目付量で9g/m2となるようにロールコーターにて鋼板表面に塗布した。コーディエライトの一次粒子は六角柱状であり、a軸長さ0.8μm、c軸長さ4.5μmであった。また、前記コーディエライトの25℃から800℃までの温度範囲における線熱膨張率は、2.9×10−6/K(a軸方向)、−1.0×10−6/K(c軸方向)、25℃から800℃までの温度範囲における体積熱膨張率は4.8×10−6/Kであった。次に、乾燥炉に装入し、300℃で、1分間乾燥し、その後、850℃、30秒間、N2:100vol%雰囲気の条件で焼付を実施して鋼板表面に絶縁被膜を形成した。
Cは、ゴス方位結晶粒の発生に有用な成分であり、かかる作用を有効に発揮させるためには、Cを0.001%以上含有させることが好ましい。一方、C含有量が0.10%を超えると脱炭焼鈍によっても脱炭不良を起こす場合がある。したがって、C含有量は0.001〜0.10%の範囲が好ましい。
Siは、電気抵抗を高めて鉄損を低下させるとともに、鉄のBCC組織を安定化させて高温の熱処理を可能とするために必要な成分であり、Si含有量は1.0%以上とすることが好ましい。一方、Si含有量が5.0%を超えると通常の冷間圧延が困難となる場合がある。したがって、Si含有量は1.0〜5.0%の範囲が好ましい。Si含有量は2.0〜5.0%の範囲がより好ましい。
Mnは、鋼の熱間脆性の改善に有効に寄与するだけでなく、SやSeが混在している場合には、MnSやMnSe等の析出物を形成し結晶粒成長の抑制剤としての機能を発揮する。かかる機能を有効に発揮するためには、Mn含有量は0.01%以上とすることが好ましい。一方、Mn含有量が1.0%を超えるとMnSe等の析出物の粒径が粗大化してインヒビターとしての効果が失われる場合がある。したがって、Mn含有量は0.01〜1.0%の範囲が好ましい。
Alは、鋼中でAlNを形成して分散第二相としてインヒビターの作用をする有用成分であるので、sol.Alとして0.003%以上含有することが好ましい。一方、Al含有量がsol.Alとして0.050%を超えるとAlNが粗大に析出してインヒビターとしての作用が失われる場合がある。したがって、Al含有量はsol.Alとして0.003〜0.050%の範囲が好ましい。
NもAlと同様にAlNを形成するために必要な成分であるので、0.001%以上含有することが好ましい。一方、0.020%を超えてNを含有するとスラブ加熱時にふくれ等を生じる場合がある。したがって、N含有量は0.001〜0.020%の範囲が好ましい。
S、Seは、MnやCuと結合してMnSe、MnS、Cu2−xSe、Cu2−xSを形成し鋼中の分散第二相としてインヒビターの作用を発揮する有用成分である。有用な添加効果を得るためには、これらS、Seの合計の含有量を0.001%以上とすることが好ましい。一方、S、Seの合計の含有量が0.05%を超える場合はスラブ加熱時の固溶が不完全となるだけでなく、製品表面の欠陥の原因ともなる場合がある。したがって、S、Seの含有量は、SまたはSeの1種を含有する場合、SとSeの2種を含有する場合のいずれも合計で0.001〜0.05%の範囲が好ましい。
ここで鋼板ヤング率は、圧延方向の場合132GPa、圧延直角方向の場合220GPaとする。
質量%で、Si:3.25%、C:0.04%、Mn:0.08%、S:0.002%、sol.Al:0.015%、N:0.006%、Cu:0.05%、Sb:0.01%を含有する珪素鋼板スラブを1150℃、20分加熱後、熱間圧延して2.4mmの板厚の熱延板とした。前記熱延板に、1000℃、1分間の焼鈍を施した後、冷間圧延により0.27mmの最終板厚の冷延板とした。得られた冷延板から、圧延方向400mm×圧延直角方向100mmサイズの鋼板を採取し、ラボにて室温から820℃まで加熱速度80℃/sにて昇温し、湿潤雰囲気(50vol%H2,50vol%N2、露点60℃)下で、820℃、60秒の一次再結晶焼鈍をおこなった。引き続き100質量部のMgOに対して、TiO2を5質量部混合した焼鈍分離剤を水スラリ状にしてから塗布、乾燥した。この鋼板を300℃から800℃間を100時間かけて昇温させた後、1200℃まで50℃/hrで昇温させ、1200℃で5時間焼鈍する最終仕上げ焼鈍をおこないフォルステライトを主体とする下地被膜をもつ鋼板を準備した。
質量%で、Si:3.25%、C:0.04%、Mn:0.08%、S:0.002%、sol.Al:0.015%、N:0.006%、Cu:0.05%、Sb:0.01%を含有する珪素鋼板スラブを1150℃、20分加熱後、熱間圧延して2.2mmの板厚の熱延板とした。前記熱延板に、1000℃、1分間の焼鈍を施した後、冷間圧延により0.23mmの最終板厚の冷延板とした。引き続いて室温から820℃まで加熱速度50℃/sにて昇温し、湿潤雰囲気(50vol%H2,50vol%N2、露点60℃)下で820℃、60秒の一次再結晶焼鈍をおこなった。
Claims (5)
- 電磁鋼板の表面に結晶性の繊維状物質を含有する絶縁被膜を有し、前記絶縁被膜中での前記結晶性の繊維状物質の圧延方向断面における圧延方向長さ(LRD)と圧延直角方向断面における圧延直角方向長さ(LTD)の比(LRD/LTD)が1.5以上50.0以下である、絶縁被膜付き電磁鋼板。
- 前記絶縁被膜中での前記結晶性の繊維状物質の圧延直角方向断面における板厚方向長さ(LND)と絶縁被膜の膜厚(d)の比(LND/d)が0.2以上2.0以下である、請求項1に記載の絶縁被膜付き電磁鋼板。
- 前記結晶性の繊維状物質の25℃から800℃の温度範囲における体積熱膨張率が30×10−6/K以下である、請求項1または2に記載の絶縁被膜付き電磁鋼板。
- 前記結晶性の繊維状物質の25℃から800℃の温度範囲における線熱膨張率が異方性を有する、請求項1〜3のいずれかに記載の絶縁被膜付き電磁鋼板。
- 前記絶縁被膜が、Mg、Al、Ca、Ba、Sr、Zn、Ti、Nd、Mo、Cr、B、Ta、Cu、Mnのうちから選ばれる金属元素を1種もしくは2種以上含むリン酸塩を含有する、請求項1〜4のいずれかに記載の絶縁被膜付き電磁鋼板。
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Citations (8)
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JPH08239771A (ja) * | 1995-03-02 | 1996-09-17 | Nippon Steel Corp | 高張力絶縁被膜を有する方向性電磁鋼板とその絶縁被膜形成方法 |
JPH09235679A (ja) * | 1996-02-29 | 1997-09-09 | Nippon Steel Corp | 低鉄損一方向性珪素鋼板の製造方法 |
WO2007136115A1 (ja) * | 2006-05-19 | 2007-11-29 | Nippon Steel Corporation | 高張力絶縁被膜を有する方向性電磁鋼板及びその絶縁被膜処理方法 |
WO2010146821A1 (ja) * | 2009-06-17 | 2010-12-23 | 新日本製鐵株式会社 | 絶縁被膜を有する電磁鋼板及びその製造方法 |
JP2012031498A (ja) * | 2010-06-29 | 2012-02-16 | Jfe Steel Corp | 方向性電磁鋼板およびその製造方法 |
WO2018079845A1 (ja) * | 2016-10-31 | 2018-05-03 | 新日鐵住金株式会社 | 方向性電磁鋼板 |
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JP2019021920A (ja) * | 2017-07-18 | 2019-02-07 | Jfeスチール株式会社 | 方向性電磁鋼板およびその製造方法 |
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JPH064507B2 (ja) * | 1988-10-21 | 1994-01-19 | 三井造船株式会社 | 低熱膨張コージェライトの製造方法 |
JP3475258B2 (ja) * | 1994-05-23 | 2003-12-08 | 株式会社海水化学研究所 | セラミック被膜形成剤およびその製造方法 |
JP3473494B2 (ja) * | 1999-05-12 | 2003-12-02 | Jfeスチール株式会社 | 鉄損値の低い方向性珪素鋼板 |
JP3882103B2 (ja) * | 2000-04-25 | 2007-02-14 | Jfeスチール株式会社 | 張力付与異方性被膜を有する低鉄損一方向性電磁鋼板 |
JP2005133149A (ja) * | 2003-10-30 | 2005-05-26 | Nippon Steel Corp | 電気伝導性に優れた表面処理金属材料 |
JP4700691B2 (ja) * | 2005-07-14 | 2011-06-15 | 新日本製鐵株式会社 | クロムを含まない絶縁皮膜を有する方向性電磁鋼板及びその絶縁皮膜剤 |
KR101318527B1 (ko) * | 2010-03-17 | 2013-10-16 | 신닛테츠스미킨 카부시키카이샤 | 방향성 전자기 강판의 제조 방법 |
WO2020196657A1 (ja) * | 2019-03-25 | 2020-10-01 | 日本製鉄株式会社 | 方向性電磁鋼板被膜形成用塗布剤および方向性電磁鋼板の製造方法 |
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JPH08239771A (ja) * | 1995-03-02 | 1996-09-17 | Nippon Steel Corp | 高張力絶縁被膜を有する方向性電磁鋼板とその絶縁被膜形成方法 |
JPH09235679A (ja) * | 1996-02-29 | 1997-09-09 | Nippon Steel Corp | 低鉄損一方向性珪素鋼板の製造方法 |
WO2007136115A1 (ja) * | 2006-05-19 | 2007-11-29 | Nippon Steel Corporation | 高張力絶縁被膜を有する方向性電磁鋼板及びその絶縁被膜処理方法 |
WO2010146821A1 (ja) * | 2009-06-17 | 2010-12-23 | 新日本製鐵株式会社 | 絶縁被膜を有する電磁鋼板及びその製造方法 |
JP2012031498A (ja) * | 2010-06-29 | 2012-02-16 | Jfe Steel Corp | 方向性電磁鋼板およびその製造方法 |
WO2018079845A1 (ja) * | 2016-10-31 | 2018-05-03 | 新日鐵住金株式会社 | 方向性電磁鋼板 |
WO2018174275A1 (ja) * | 2017-03-23 | 2018-09-27 | 新日鐵住金株式会社 | 電磁鋼板 |
JP2019021920A (ja) * | 2017-07-18 | 2019-02-07 | Jfeスチール株式会社 | 方向性電磁鋼板およびその製造方法 |
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US20240102172A1 (en) | 2024-03-28 |
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CA3151419C (en) | 2024-01-09 |
EP4026930A4 (en) | 2022-10-26 |
CN114555860B (zh) | 2024-06-18 |
KR20220065863A (ko) | 2022-05-20 |
CN114555860A (zh) | 2022-05-27 |
EP4026930A1 (en) | 2022-07-13 |
MX2022004763A (es) | 2022-05-16 |
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