JP4380199B2 - Non-oriented electrical steel sheet and manufacturing method thereof - Google Patents
Non-oriented electrical steel sheet and manufacturing method thereof Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明は、無方向性電磁鋼板、特に高速回転モータのロータを典型例とする、大きな応力がかかる部品に用いて好適な、高強度でかつ低鉄損の特性を有する無方向性電磁鋼板およびその製造方法に関するものである。
【0002】
【従来技術】
近年、モータの駆動システムの発達により、駆動電源の周波数制御が可能となり、可変速運転や商用周波数以上で高速回転を行うモータが増加している。このような高速回転を行うモータでは、高速回転に耐え得るロータが必要になる。すなわち、回転体に作用する遠心力は回転半径に比例し、回転速度の2乗に比例して大きくなるため、中・大型の高速モータではロータに作用する応力が600MPaを超える場合もある。従って、こうした高速回転モータでは、ロータの強度が高いことが必要となる。
【0003】
また、近年のモータ効率向上の観点から増加した、ロータに永久磁石を埋め込んだ磁石埋設型DCインバータ制御モータでは、遠心力でロータから磁石が飛び出そうとするが、これを抑える際に、ロータに使用された電磁鋼板には大きな力が掛かる。このためにも、モータ、特にロータに使用される電磁鋼板には、高強度が必要とされている。
【0004】
モータ、発電機などの回転機器は、電磁気現象を利用するため、その素材には磁気特性、すなわち低鉄損、高磁束密度であることが望ましい。通常、ロータコアはプレス打ち抜きした無方向性電磁鋼板を積層して使用するが、高速回転モータにおいてロータ素材が上述の機械強度が満足できない場合は、より高強度の鋳鋼製ロー夕などを使用せざるを得ないのが現状である。しかしながら、鋳物製ロー夕は一体物であるため、ロータに作用するリップル損と呼ばれる高周波磁束による渦電流損が電磁鋼板を積層したロータより大きく、モータ効率が低下してしまう要因となっている。従って、磁気特性に優れ、かつ高強度の電磁鋼板がロータ用素材として要望されているのである。
【0005】
金属学的には、高強度化の手段として、固溶強化、析出強化および結晶粒微細化の3つの方法が知られており、電磁鋼板に適用した例も見られる。例えば、固溶強化を利用したものとしては、特許文献1には、Si含有量を3.5〜7.0%に高めたうえに固溶強化能の大きい元素を添加する方法が開示されている。また、特許文献2には、Si含有量を2.0〜3.5%とし、NiあるいはNiとMnの両方の含有量を高め、650〜850℃という低温焼鈍により製造することで再結晶粒径を制御する方法が開示されている。さらに、析出強化を利用する方法としては、特許文献3に、Si含有量を2.0〜4.0%とし、Nb,Zr,Ti,Vの微細な炭化物、窒化物を析出させる方法が開示されている。
【0006】
【特許文献1】
特開昭60−238421号公報
【特許文献2】
特開昭62−256917号公報
【特許文献3】
特開平6−330255号公報
【0007】
【発明が解決しようとする課題】
これらの方法により、ある程度の高強度を有する電磁鋼板が得られる。しかしながら、特許文献1に記載されるようなSi量が多い鋼では、冷間圧延性が著しく低下し、安定的な工業生産が困難となる不利がある。さらに、この技術により得られる鋼板は磁束密度B50が1.56〜1.60Tと大幅に低下してしまうという問題もあった。
【0008】
特許文献2における方法では、機械強度を高めるため低温焼鈍による再結晶粒成長の抑制が必要となるため、磁気特性、特に比較的周波数の低い商用周波数から数100Hzでの鉄損が低下するという問題があった。そのため、これらの周波数域での鉄損が重要となるステータ部材には使用することが出来ないため、モータ打ち抜き加工時の歩留まりが大幅な低下が余儀なくされていた。すなわち、ステータおよびロータを打抜く際、通常は同じ1枚の鋼板から、まず円環状のステータを打抜く一方で、その中空部からロータを打抜くことにより無駄を少なくしているが、特許文献2の方法では両者を別々の鋼板から打抜く必要があり、歩留まりが低下してしまうのである。
【0009】
一方、特許文献3に記載の方法では、炭、窒化物自体が磁壁移動の障壁となるため、また炭、窒化物が電磁鋼板の結晶粒成長を妨げるため、鉄損に劣るという問題がある。
【0010】
以上のように、従来の方法は、安定的に工業生産可能な電磁鋼板において、高強度と低鉄損とを両立するという観点からは、いずれも満足できるものでは無かった。
【0011】
本発明は、良好な磁気特性と高強度とを両立した無方向性電磁鋼板およびこの鋼板を工業的に安定して生産することを可能とする製造方法について提案することを目的とする。
【0012】
【課題を解決するための手段】
発明者らは、上記課題を解決するために、Cuを含んだ鋼の時効硬化現象に着目して種々の検討を行った結果、良好な鉄損と高強度とを両立するための手段を確立するに到った。すなわち、鋼中の析出物は高強度化に寄与すると同時に、磁壁移動を抑制して劣化させるという、従来の知見に反して、鋼中にCuを適量添加して時効処理を行うことにより、20nm以下の極微細にCuを析出させることが可能であること、そして、こうして得られた極微細析出物は、高強度化に非常に有効であるが、鉄損(履歴損)はほとんど劣化させないことを、新規に知見した。さらに、このCu析出に関し、CuとNiを複合添加すると、鋼板の製造工程における熱履歴により生じる析出が大幅に低減する結果、広範な焼鈍条件によっても安定的に高強度かつ低鉄損が得られることを新規に知見し、本発明を完成するに到った。
【0013】
本発明の要旨構成は、以下の通りである。
(1)質量%で、
C:0.02%以下、
Si:4.5%以下、
Mn:3.0%以下、
Al:3.0%以下、
P:0.50%以下、
Ni:0.5%以上5.0%以下および
Cu:0.2%以上4.0%以下
を含有し、残部Feおよび不可避的不純物の成分組成を有し、結晶粒の平均粒径が20〜89μmであり、引張強さが下記式で示されるCTS(MPa)以上であることを特徴とする無方向性電磁鋼板。
記
CTS=5600[%C]+87[%Si]+15[%Mn]+70[%Al]+430[%P]
+37[%Ni]+22d-1/2+230
ただし、d:結晶粒の平均粒径(mm)
【0014】
(2)上記(1)において、成分組成として、さらにZr、V、Sb、Sn、Ge、B、Ca、希土類元素およびCoから選んだ1種または2種以上を、
ZrおよびVについてはそれぞれ0.1〜3.0%、
Sb、SnおよびGeについてはそれぞれ0.002〜0.5%、
B,Caおよび希土類元素についてはそれぞれ0.001〜0.01%、そして
Coについては0.2〜5.0%
にて含有することを特徴とする無方向性電磁鋼板。
【0015】
(3)質量%で、
C:0.02%以下、
Si:4.5%以下、
Mn:3.0%以下、
Al:3.0%以下、
P:0.50%以下、
Ni:0.5%以上5.0%以下および
Cu:0.2%以上4.0%以下
を含有し、残部Feおよび不可避的不純物の成分組成を有する鋼スラブに、熱間圧延を施した後、冷間圧延あるいは温間圧延を施して最終板厚とした後、最終到達温度が650〜1150℃かつ900℃〜400℃の温度域での冷却速度が1℃/s以上である、仕上げ焼鈍を施した後、400℃以上650℃以下の温度にて時効処理を施すことを特徴とする無方向性電磁鋼板の製造方法。
【0016】
(4)質量%で、
C:0.02%以下、
Si:4.5%以下、
Mn:3.0%以下、
Al:3.0%以下、
P:0.50%以下、
Ni:0.5%以上5.0%以下および
Cu:0.2%以上4.0%以下
を含み、さらにZr、V、Sb、Sn、Ge、B、Ca、希土類元素およびCoから選んだ1種または2種以上を、
ZrおよびVについてはそれぞれ0.1〜3.0%、
Sb、SnおよびGeについてはそれぞれ0.002〜0.5%、
B,Caおよび希土類元素についてはそれぞれ0.001〜0.01%、そして
Coについては0.2〜5.0%
にて含有し、残部Feおよび不可避的不純物の成分組成を有する鋼スラブに、熱間圧延を施した後、冷間圧延あるいは温間圧延を施して最終板厚とした後、最終到達温度が650〜1150℃かつ900℃〜400℃の温度域での冷却速度が1℃/s以上である、仕上げ焼鈍を施した後、400℃以上650℃以下の温度にて時効処理を施すことを特徴とする無方向性電磁鋼板の製造方法。
【0017】
【発明の実施の形態】
次に、本発明について、その構成要件毎に詳述する。
(鋼板の成分組成)
まず、成分組成範囲およびその限定理由を説明する。なお、本明細書において鋼組成を表す%は、特にことわらない限り質量%を意味するものである。
C:0.02%以下
C量が0.02%を超えると磁気時効により鉄損が著しく劣化するため、0.02%以下に制限する。
【0018】
Si:4.5%以下
Siは、脱酸剤として有用であることに加え、電気抵抗の増加により電磁鋼板の鉄損を低減する効果が大きい。さらに、固溶強化により強度向上に寄与する。脱酸剤としては、0.05%以上の含有で効果が顕著となる。また、鉄損低減および固溶強化のためには0.5%以上、さらに好適には1.2%以上で含有させる。しかし、4.5%を超えると、鋼板の圧延性の劣化が激しくなるため、その含有量は4.5%以下に制限する。
【0019】
Mn:3.0%以下
Mnは、固溶強化による強度向上に有効な元素であることに加え、熱間脆性の改善に有効な元素であり、好ましくは0.05%以上で含有させる。しかし、過剰な添加は鉄損の劣化をもたらすため、その含有量を3.0%以下に制限する。
【0020】
Al:3.0%以下
Alは、脱酸剤として有効であり、好ましくは0.5ppm以上含有させる。しかし、過剰な添加は圧延性の低下をもたらすので、その添加量を3.0%以下に制限する。
【0021】
P:0.50%以下
Pは、比較的少量の添加でも大幅な固溶強化能が得られるため高強度化に極めて有効であり、好ましくは0.01%以上で含有させる。一方、過剰な含有は偏析による脆化を引き起し、粒界割れや圧延性の低下をもたらすため、その含有量は0.50%以下に制限する。
【0022】
次に、CuおよびNiの添加は、本発明において最も重要な事項である。
Cu:0.2%以上4.0%以下
Cuは、時効処理によって微細な析出物を形成することにより、ほとんど鉄損(履歴損)の劣化を伴わずに、大幅な強度上昇をもたらす。その効果を得るには、後述するNiを含有する条件において0.2%以上が必要である。一方、4.0%を超えると粗大な析出物が形成されるため、鉄損の劣化が大きくなるとともに、強度上昇代も低下する。従って、Cuの含有量は0.2%以上4.0%以下、好適には0.3%以上2.0%以下の範囲とする。
【0023】
Ni:0.5%以上5.0%以下
Niは、それ自体が固溶強化による高強度化に有効な元素であるが、Cuとともに添加するとCuの固溶析出状態に影響し、時効により極めて微細なCu析出物を安定的に析出させる効果を有する。その結果、Cu時効析出による高強度化効果を大幅に高めることが可能となる。また、Niはへゲと呼ばれる熱延板表面欠陥を減少し鋼板歩留まりを改善する効果も有する。これらの効果を得るために、最低でも0.5%以上の添加が必要である。一方、5.0%を超えると、その効果は飽和しコスト高をまねくだけになるため、その上限を5.0%とする。より好適には、1.0%以上3.5%以下の範囲とする。
【0024】
上記元素の他は、Fe(鉄)および不可避的不純物である。不可避的不純物としてのSおよびNは、鉄損の観点からそれぞれ0.01%以下とすることが望ましい。
【0025】
本発明に係わる無方向性電磁鋼板の基本組成は以上の通りであるが、上記成分に加えて、磁気特性の改善元素として知られるZr,V,Sb,Sn,Ge,B,Ca,希土類元素およびCoを単独または複合で添加することが出来る。しかし、その添加量は本発明の目的を害さない程度にすべきである。具体的には、
Zr,Vについては0.1〜3.0%
Sb,Sn,Geについては0.002〜0.5%
B,Ca,および希土類元素については0.001〜0.01%
Coについては0.2〜5.0%
である。
【0026】
本発明では、上記の成分範囲ならびに後述の製造条件とすることにより、時効後のCu析出を適正化することができ、その結果、製品の引張強さTS(MPa)は、下記式で表されるCTS 以上となる。
記
CTS=5600[%C]+87[%Si]+15[%Mn]+70[%Al]+430[%P]
+37[%Ni]+22d-1/2+230
【0027】
ここで、各元素の係数は、各元素1%あたりの固溶あるいは析出強化量に相当する項、dは製品の平均結晶粒径(直径:mm)であり、ナイタール腐食液などでエッチングされた試料を光学顕微鏡により観察し、観察視野面積と視野内の結晶粒数より結晶粒の円相当径として求められるものである。平均結晶粒径dが小さいほど結晶粒微細化により高強度化されるが、鉄損が劣化する。そのため、求められる強度、鉄損特性に応じて結晶粒径dを調整する。
【0028】
(製造方法)
本発明に係わる鉄損に優れた高強度無方向性電磁鋼板を製造するためには、まず、転炉あるいは電気炉などにて、前記した所定成分に溶製された鋼を、連続鋳造あるいは造塊後の分塊圧延により鋼スラブとする。次いで、得られたスラブを熱間圧延し、必要に応じて熱延板焼鈍を施し、一回あるいは中間焼鈍を挟む二回以上の冷間圧延あるいは温間圧延を施して製品板厚とし、仕上げ焼鈍を施し、その後時効処理を施す。さらに、仕上げ焼鈍後のいずれかの段階において、必要に応じて絶縁被膜の塗布および焼き付け処理を行う。
【0029】
本発明では、素材のSi量を高めることなく後工程で高強度化するので、冷間圧延により製造することが可能である。なお、温間圧延には集合組織を改善し鉄損および磁束密度を向上させる効果を有するため、温間圧延を採用することもできる。
【0030】
上記の仕上げ焼鈍は、圧延による歪を除去するとともに、必要な鉄損特性を得るため再結晶により適切な結晶粒径を得ることを目的とする。適性な結晶粒径は求められる鉄損レベルにもよるが、20〜89μmであり、そのためには仕上げ焼鈍の最終到達温度は700℃以上が必要である。一方、1150℃を超える焼鈍を行うと粗大粒となり粒界割れを起こしやすくなるとともに、鋼板表面の酸化窒化に伴う鉄損劣化が大きくなるため、その上限は1150℃とする。
【0031】
発明者らは、Cuの微細析出を活用する場合、仕上げ焼鈍の冷却条件が重要であることを見出した。すなわち、仕上げ焼鈍の冷却過程において、Cuの固溶温度から600℃までの冷却速度が十分に速くないと、一部のCuが冷却中に粗大に析出するため、鉄損の劣化要因となり、またその後の時効焼鈍によっても粗大な析出物の量が増加し十分な強度が得られない場合があるのである。ここで、Cuのみ含有しNiを含有しない場合、その冷却速度は900℃〜400℃の温度域で10℃/s以上であることが必要であった。
【0032】
ところが、Cuとともに本発明範囲のNiを含有した場合、冷却速度は1℃/s以上であれば冷却中の粗大な析出が抑制出来、その後の時効処理によって鉄損の大幅な劣化を伴うことなく十分な強度上昇が得られる。つまり、CuとNiを複合添加して時効処理を行う場合には、Niを添加しない場合と比較して、より多様な仕上げ焼鈍条件で安定した特性を得ることができる。したがって、仕上げ焼鈍後の冷却の際、焼鈍における最高到達温度が900℃を超える場合には900℃から、焼鈍最高到達温度が900℃以下の場合には仕上げ焼鈍温度から、400℃までの温度域での冷却速度を1℃/s以上に制限する。
以上の条件を満足すれば、続く時効処理後の強度は、
CTS=5600[%C]+87[%Si]+15[%Mn]+70[%Al]+430[%P]
+37[%Ni]+22d-1/2+230
以上とすることができる。
【0033】
引き続く時効処理は、400℃以上650℃以下の温度で行う。すなわち、400℃未満の場合には、微細Cuの析出が不十分となり、高強度が得られない。一方、650℃を越えるとCu析出物が粗大化するため、鉄損が劣化し強度上昇量も減少するため、良好な強度−鉄損バランスを有する電磁鋼板が得られない。なお、適切な時効時間は処理温度にも依存するが、10min〜1000hが好適である。なお、この時効処理の実施時期は、絶縁被膜の塗布焼付け前、焼付け後、プレス打ち抜きなどの加工後、などのいずれのタイミングで実施してもよい。
【0034】
【実施例】
実施例1
表1に示す、Si:3%、Mn:0.2%およびAl:0.3%を基本成分として、CuおよびNi含有量を変化させた、残部が鉄および不可避不純物からなる鋼スラブを、熱間圧延により板厚2.0mmとし、ついで表2に示すように、無焼鈍または1000℃で300sの熱延板焼鈍を施した後、酸洗ならびに仕上げ板厚0.35mmの冷間圧延を行った。さらに、最高到達温度950℃で30s均熱保持の仕上げ焼鈍を施したのち、900℃〜400℃の温度域での冷却速度を6℃/sの条件で冷却した。その後、絶縁被膜を塗布焼付けしてから、時効のために550℃で5hの熱処理を施し製品板とした。
【0035】
かくして得られた製品板について、鉄損特性および機械特性を評価した。なお、製品板での成分組成は、スラブ段階とほぼ同様であった。鉄損は圧延方向と圧延直角方向の試料を等量用いて、エプスタイン法により評価した。機械的特性は、圧延方向と圧延直角方向とから切り出した試料の平均をもって評価した。その結果を、表1に示す。
【0036】
また、従来の、公知の固溶強化、結晶粒微細化強化、析出強化などによって高張力とした電磁鋼板として、以下に示すものも試作した。
すなわち、固溶強化を利用した例として、表2に示すように、C:0.002%、Si:4.5%、Mn:0.2%、P:0.01%、Al:0.6%、W:1.0%およびMo:1.0%を含み、残部が鉄および不可避不純物からなる鋼スラブを熱間圧延し、900℃で30sの熱延板焼鈍を行った後、400℃で温間圧延して0.35mm厚に仕上げ、950℃×30sの仕上げ焼鈍を行った。
固溶強化および結晶粒微細化を利用した例として、表2に示すように、C:0.005%、Si:3%、Mn:0.2%、P:0.05%およびNi:4.5%を含み、残部が鉄および不可避不純物からなる鋼を熱間圧延し、次いで冷間圧延して0.35mm厚としたのち、800℃で30sの仕上げ焼鈍を行った。
析出強化を利用した例として、表2に示すように、C:0.03%、Si:3.2%、Mn:0.2%、P:0.02%、Al:0.65%、N:0.003%、Nb:0.018%およびZr:0.022%を含み、残部が鉄および不可避不純物からなる鋼を、熱間圧延後0.35mm厚に冷間圧延し、750℃×30sの仕上げ焼鈍を施した。
なお、いずれの場合も、時効処理は行わなかった。
【0037】
【表1】
【0038】
【表2】
【0039】
本発明による鋼板No.7〜13は、ベース組成を有する比較例である鋼板No.1とほぼ同等の優れた磁気特性を有しつつ、大幅な高強度が得られている。さらに、従来の高強度電磁鋼板である鋼板No.14〜16と比較しても、大幅な低鉄損あるいは高磁束密度性を有し、強度−磁気特性バランスに優れている。
【0040】
実施例2
表1に示した比較鋼Cおよび発明鋼Jを、熱間圧延により板厚2.0mmとし、ついで1000℃で300sの熱延板焼鈍を施した後、酸洗並びに仕上げ板厚0.35mmの冷間圧延を行った。さらに、最高到達温度950℃にて30s均熱保持する仕上げ焼鈍を施し、900℃〜400℃の温度域での冷却速度を表3に示す種々の条件に変化させて冷却した。その後、絶縁被膜を塗布焼付けして焼鈍板とした。得られた焼鈍板に時効のため550℃で5hの熱処理を施して製品板とした。かくして得られた製品板について、鉄損特性および機械特性を評価した。なお、製品板での成分組成はスラブ段階とはぼ同様であった。その結果を表3、そして図1および2に示す。
【0041】
【表3】
【0042】
鋼Cは、鋼板No.18および19に示すように、10℃/s以上の比較的速い冷却速度の場合には優れた磁気特性と高強度を示すものの、10℃/s以下の条件では鉄損が劣化し、強度も低下する傾向にある。それに対して、Cuとともに適量のNiを添加した発明鋼Jは、鋼板No.22〜24に示すように、幅広い冷却速度条件で安定して優れた磁気特性と高強度を両立することが可能であった。
【0043】
実施例3
表4に示す組成を有する残部が鉄および不可避不純物からなる鋼を、熱間圧延により板厚2.0mmとし、ついで無焼鈍または表5に示す温度で300sの熱延板焼鈍を施した後、酸洗ならびに所定厚さまでの冷間圧延を行った。さらに、表5の温度で30s均熱保持の仕上げ焼鈍を施し、900℃〜400℃の温度域での冷却速度を6℃/sの条件で冷却した。その後、絶縁被膜を塗布焼付けして焼鈍板とした。得られた焼鈍板に時効のため表5に示す温度で10hの時効処理を施して製品板とした。かくして得られた製品板について、鉄損特性および機械特性を評価した。その結果を表5に併記する。なお、製品板での成分組成はスラブ段階とほぼ同様であった。表5から、いずれの試料もそれぞれの鋼板グレードにおいて、優れた磁気特性と非常に高い強度特性を有していることがわかる。
【0044】
【表4】
【0045】
【表5】
【0046】
【発明の効果】
以上のように本発明によれば、磁気特性に優れ、しかも高い強度を有する電磁鋼板を安定して提供することできる。
【図面の簡単な説明】
【図1】 時効処理後の鉄損に及ぼす仕上げ焼鈍冷却速度の影響を示す図である。
【図2】 時効処理後の引張強さに及ぼす仕上げ焼鈍冷却速度の影響を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-oriented electrical steel sheet, particularly a non-oriented electrical steel sheet having a characteristic of high strength and low iron loss, which is suitable for a part subjected to a large stress, such as a rotor of a high-speed rotary motor. It relates to the manufacturing method.
[0002]
[Prior art]
In recent years, with the development of motor drive systems, it is possible to control the frequency of the drive power supply, and the number of motors that perform variable speed operation and high-speed rotation above the commercial frequency is increasing. In such a motor that performs high-speed rotation, a rotor that can withstand high-speed rotation is required. That is, since the centrifugal force acting on the rotating body is proportional to the radius of rotation and increases in proportion to the square of the rotational speed, the stress acting on the rotor may exceed 600 MPa in medium and large high-speed motors. Therefore, in such a high-speed rotary motor, it is necessary that the strength of the rotor is high.
[0003]
In addition, the magnet-embedded DC inverter control motor with permanent magnets embedded in the rotor, which has increased from the viewpoint of improving motor efficiency in recent years, attempts to eject magnets from the rotor by centrifugal force. A large force is applied to the used electrical steel sheet. For this reason, high strength is required for electromagnetic steel sheets used in motors, particularly rotors.
[0004]
Since rotating devices such as motors and generators use electromagnetic phenomena, it is desirable that the material has magnetic properties, that is, low iron loss and high magnetic flux density. Normally, the rotor core is used by laminating non-oriented electrical steel sheets that have been stamped and punched. However, if the rotor material does not satisfy the above-mentioned mechanical strength in a high-speed rotary motor, it is necessary to use a higher strength cast steel material. It is the present condition that we do not get. However, since the casting made of cast iron is an integral object, the eddy current loss due to the high-frequency magnetic flux called ripple loss acting on the rotor is larger than that of the rotor laminated with the electromagnetic steel sheets, which causes a reduction in motor efficiency. Therefore, a magnetic steel sheet having excellent magnetic properties and high strength is demanded as a rotor material.
[0005]
In metallurgy, three methods of solid solution strengthening, precipitation strengthening, and crystal grain refinement are known as means for increasing strength, and examples applied to electrical steel sheets are also seen. For example, as a method utilizing solid solution strengthening, Patent Document 1 discloses a method of adding an element having a large solid solution strengthening capability while increasing the Si content to 3.5 to 7.0%. Further, in Patent Document 2, the recrystallized grain size is controlled by setting the Si content to 2.0 to 3.5%, increasing the content of Ni or both Ni and Mn, and manufacturing by low temperature annealing at 650 to 850 ° C. A method is disclosed. Furthermore, as a method of utilizing precipitation strengthening, Patent Document 3 discloses a method of precipitating fine carbides and nitrides of Nb, Zr, Ti, and V with a Si content of 2.0 to 4.0%. Has been.
[0006]
[Patent Document 1]
JP-A-60-238421 [Patent Document 2]
JP 62-256917 A [Patent Document 3]
JP-A-6-330255 [0007]
[Problems to be solved by the invention]
By these methods, an electrical steel sheet having a certain degree of strength can be obtained. However, the steel having a large amount of Si as described in Patent Document 1 has a disadvantage that the cold rolling property is remarkably lowered and stable industrial production becomes difficult. Furthermore, the steel plate obtained by this technique has a problem that the magnetic flux density B 50 is significantly reduced to 1.56 to 1.60 T.
[0008]
In the method in Patent Document 2, since it is necessary to suppress recrystallized grain growth by low-temperature annealing in order to increase mechanical strength, there is a problem that iron loss at several hundred Hz from a commercial frequency having a relatively low frequency is lowered. was there. For this reason, it cannot be used for a stator member in which iron loss in these frequency ranges is important, and the yield during motor punching has been significantly reduced. That is, when the stator and the rotor are punched, usually, the annular stator is first punched from the same sheet of steel, while the rotor is punched from the hollow portion to reduce waste. In the method 2, it is necessary to punch both from separate steel plates, and the yield decreases.
[0009]
On the other hand, the method described in Patent Document 3 has a problem that iron loss is inferior because charcoal and nitride itself serve as a barrier for domain wall movement and charcoal and nitride hinder crystal grain growth of the electromagnetic steel sheet.
[0010]
As described above, none of the conventional methods is satisfactory from the viewpoint of achieving both high strength and low iron loss in an electromagnetic steel sheet that can be stably industrially produced.
[0011]
An object of the present invention is to propose a non-oriented electrical steel sheet that achieves both good magnetic properties and high strength and a manufacturing method that enables industrially stable production of this steel sheet.
[0012]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the inventors have made various studies focusing on the age hardening phenomenon of Cu-containing steel, and as a result, established means for achieving both good iron loss and high strength. I arrived. That is, the precipitate in steel contributes to high strength, and at the same time, suppresses domain wall movement and deteriorates, contrary to the conventional knowledge, by adding an appropriate amount of Cu to the steel and performing an aging treatment, 20 nm It is possible to precipitate Cu in the following ultrafine, and the ultrafine precipitate obtained in this way is very effective for increasing the strength, but iron loss (historical loss) is hardly deteriorated. Was newly discovered. Furthermore, with regard to this Cu precipitation, when Cu and Ni are added in combination, the precipitation caused by the thermal history in the steel sheet manufacturing process is greatly reduced, resulting in stable high strength and low iron loss even under a wide range of annealing conditions. This has been newly discovered, and the present invention has been completed.
[0013]
The gist of the present invention is as follows.
(1) In mass%,
C: 0.02% or less,
Si: 4.5% or less,
Mn: 3.0% or less,
Al: 3.0% or less,
P: 0.50% or less,
Ni: 0.5% to 5.0% and
Cu: CTS (MPa containing 0.2% or more and 4.0% or less, having a component composition of the balance Fe and inevitable impurities, an average grain size of 20 to 89 μm, and a tensile strength represented by the following formula non-oriented electrical steel sheet you wherein a) or more.
Record
CTS = 5600 [% C] +87 [% Si] +15 [% Mn] +70 [% Al] +430 [% P]
+37 [% Ni] + 22d -1/2 +230
Where d: average grain size (mm) of crystal grains
[0014]
(2) In the above (1), as the component composition, one or more selected from Zr, V, Sb, Sn, Ge, B, Ca, rare earth elements and Co,
For Zr and V, 0.1 to 3.0%,
0.002 to 0.5% for Sb, Sn and Ge,
0.001 to 0.01% for B, Ca and rare earth elements, respectively
0.2 to 5.0% for Co
Non-oriented electrical steel sheet you characterized by containing at.
[0015]
(3) In mass%,
C: 0.02% or less,
Si: 4.5% or less,
Mn: 3.0% or less,
Al: 3.0% or less,
P: 0.50% or less,
Ni: 0.5% to 5.0% and
Cu: contains 0.2% or more and 4.0% or less, the steel slab to have a component composition of the balance Fe and inevitable impurities, was subjected to hot rolling, final thickness Metropolitan subjected to cold rolling or warm rolling After the final annealing, the final achieved temperature is 650-1150 ° C and the cooling rate in the temperature range of 900 ° C-400 ° C is 1 ° C / s or higher. method for producing a non-oriented electrical steel sheet you characterized by applying aging treatment.
[0016]
(4) In mass%,
C: 0.02% or less,
Si: 4.5% or less,
Mn: 3.0% or less,
Al: 3.0% or less,
P: 0.50% or less,
Ni: 0.5% to 5.0% and
Cu: 0.2% to 4.0%, and one or more selected from Zr, V, Sb, Sn, Ge, B, Ca, rare earth elements and Co,
For Zr and V, 0.1 to 3.0%,
0.002 to 0.5% for Sb, Sn and Ge,
0.001 to 0.01% for B, Ca and rare earth elements, respectively
0.2 to 5.0% for Co
Contained in, the steel slab to have a component composition of the balance Fe and inevitable impurities, was subjected to hot rolling, after the final thickness is subjected to cold rolling or warm rolling, the final temperature reached The cooling rate in the temperature range of 650-1150 ° C and 900 ° C-400 ° C is 1 ° C / s or higher, and after the finish annealing, the aging treatment is performed at a temperature of 400 ° C-650 ° C. method for producing a non-oriented electrical steel sheet shall be the.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail for each constituent requirement.
(Component composition of steel sheet)
First, the component composition range and the reason for limitation will be described. In the present specification, “%” representing a steel composition means “% by mass” unless otherwise specified.
C: 0.02% or less Since the iron loss significantly deteriorates due to magnetic aging when the C content exceeds 0.02%, it is limited to 0.02% or less.
[0018]
Si: 4.5% or less
In addition to being useful as a deoxidizer, Si has a great effect of reducing the iron loss of the electrical steel sheet by increasing the electrical resistance. Furthermore, it contributes to strength improvement by solid solution strengthening. As a deoxidizer, the effect becomes remarkable when the content is 0.05% or more. Further, for reducing iron loss and strengthening solid solution, it is contained at 0.5% or more, more preferably 1.2% or more. However, if it exceeds 4.5%, the rollability of the steel sheet deteriorates severely, so its content is limited to 4.5% or less.
[0019]
Mn: 3.0% or less
Mn is an element effective for improving hot brittleness in addition to being an element effective for improving strength by solid solution strengthening, and is preferably contained at 0.05% or more. However, excessive addition causes deterioration of iron loss, so its content is limited to 3.0% or less.
[0020]
Al: 3.0% or less
Al is effective as a deoxidizer and is preferably contained at 0.5 ppm or more. However, excessive addition causes a decrease in rollability, so the addition amount is limited to 3.0% or less.
[0021]
P: 0.50% or less P is extremely effective for increasing the strength because a large solid solution strengthening ability can be obtained even when added in a relatively small amount, and is preferably contained at 0.01% or more. On the other hand, an excessive content causes embrittlement due to segregation and causes intergranular cracking and a decrease in rollability, so the content is limited to 0.50% or less.
[0022]
Next, addition of Cu and Ni is the most important matter in the present invention.
Cu: 0.2% to 4.0%
By forming fine precipitates by aging treatment, Cu brings about a significant increase in strength with almost no deterioration of iron loss (history loss). In order to obtain the effect, 0.2% or more is necessary under the condition of containing Ni described later. On the other hand, if it exceeds 4.0%, coarse precipitates are formed, so that the deterioration of the iron loss increases and the strength increase margin also decreases. Therefore, the Cu content is in the range of 0.2% to 4.0%, preferably 0.3% to 2.0%.
[0023]
Ni: 0.5% to 5.0%
Ni itself is an element effective for increasing the strength by solid solution strengthening, but when added with Cu, it affects the solid solution precipitation state of Cu, and the effect of stably depositing extremely fine Cu precipitates by aging Have As a result, it is possible to greatly enhance the effect of increasing the strength due to Cu aging precipitation. Ni also has the effect of reducing hot-rolled sheet surface defects called heges and improving steel sheet yield. In order to obtain these effects, the addition of at least 0.5% is necessary. On the other hand, if it exceeds 5.0%, the effect will be saturated and only increase the cost, so the upper limit is set to 5.0%. More preferably, the range is 1.0% or more and 3.5% or less.
[0024]
In addition to the above elements, they are Fe (iron) and inevitable impurities. S and N as inevitable impurities are each preferably 0.01% or less from the viewpoint of iron loss.
[0025]
The basic composition of the non-oriented electrical steel sheet according to the present invention is as described above. In addition to the above components, Zr, V, Sb, Sn, Ge, B, Ca, rare earth elements known as elements for improving magnetic properties are known. And Co can be added alone or in combination. However, the amount added should be such that the object of the present invention is not impaired. In particular,
For Zr and V, 0.1 to 3.0%
0.002 to 0.5% for Sb, Sn, and Ge
0.001 to 0.01% for B, Ca, and rare earth elements
0.2 to 5.0% for Co
It is.
[0026]
In the present invention, Cu precipitation after aging can be optimized by using the above-mentioned component ranges and the production conditions described later. As a result, the tensile strength TS (MPa) of the product is expressed by the following formula. Over CTS.
Record
CTS = 5600 [% C] +87 [% Si] +15 [% Mn] +70 [% Al] +430 [% P]
+37 [% Ni] + 22d -1/2 +230
[0027]
Here, the coefficient of each element is a term corresponding to the amount of solid solution or precipitation strengthening per 1% of each element, d is the average crystal grain size (diameter: mm) of the product, and was etched with a nital etchant or the like The sample is observed with an optical microscope, and is obtained as the equivalent circle diameter of the crystal grain from the observation visual field area and the number of crystal grains in the visual field. The smaller the average crystal grain size d, the higher the strength due to the refinement of crystal grains, but the iron loss deteriorates. Therefore, the crystal grain size d is adjusted according to the required strength and iron loss characteristics.
[0028]
(Production method)
In order to produce a high-strength non-oriented electrical steel sheet having excellent iron loss according to the present invention, first, a steel melted in the above-mentioned predetermined components is continuously cast or manufactured in a converter or an electric furnace. A steel slab is formed by rolling after ingot. Next, the obtained slab is hot-rolled, subjected to hot-rolled sheet annealing as necessary, and subjected to cold rolling or warm rolling at least twice with one or intermediate annealing in between to obtain a product thickness. Annealing and then aging treatment. Furthermore, at any stage after finish annealing, an insulating coating is applied and baked as necessary.
[0029]
In the present invention, the strength is increased in a subsequent process without increasing the amount of Si in the material, and therefore it can be manufactured by cold rolling. In addition, since warm rolling has the effect of improving the texture and improving iron loss and magnetic flux density, warm rolling can also be employed.
[0030]
The above-mentioned finish annealing is intended to remove distortion caused by rolling and to obtain an appropriate crystal grain size by recrystallization in order to obtain necessary iron loss characteristics. The appropriate crystal grain size is 20 to 89 μm, although it depends on the required iron loss level. For this purpose, the final ultimate temperature of finish annealing needs to be 700 ° C. or higher. On the other hand, if annealing exceeding 1150 ° C. is performed, the grains become coarse and easily cause intergranular cracking, and the iron loss deterioration accompanying oxynitriding on the steel sheet surface increases, so the upper limit is made 1150 ° C.
[0031]
The inventors have found that the cooling conditions for finish annealing are important when utilizing the fine precipitation of Cu. That is, in the cooling process of finish annealing, if the cooling rate from the solid solution temperature of Cu to 600 ° C is not fast enough, some Cu precipitates coarsely during cooling, which causes deterioration of iron loss. Subsequent aging annealing may increase the amount of coarse precipitates and may not provide sufficient strength. Here, when only Cu was contained and Ni was not contained, the cooling rate was required to be 10 ° C./s or more in the temperature range of 900 ° C. to 400 ° C.
[0032]
However, when Ni within the scope of the present invention is contained together with Cu, if the cooling rate is 1 ° C./s or more, coarse precipitation during cooling can be suppressed, and the subsequent aging treatment does not cause significant deterioration of iron loss. A sufficient strength increase can be obtained. That is, when performing an aging treatment by adding Cu and Ni in combination, stable characteristics can be obtained under more various finish annealing conditions than when Ni is not added. Therefore, when cooling after finish annealing, the temperature range from 900 ° C if the maximum temperature reached in annealing exceeds 900 ° C, and from the finish annealing temperature to 400 ° C if the maximum temperature reached in annealing is 900 ° C or less. The cooling rate is limited to 1 ° C / s or more.
If the above conditions are satisfied, the strength after the subsequent aging treatment is
CTS = 5600 [% C] +87 [% Si] +15 [% Mn] +70 [% Al] +430 [% P]
+37 [% Ni] + 22d -1/2 +230
This can be done.
[0033]
The subsequent aging treatment is performed at a temperature of 400 ° C. or higher and 650 ° C. or lower. That is, when the temperature is lower than 400 ° C., the precipitation of fine Cu becomes insufficient and high strength cannot be obtained. On the other hand, when the temperature exceeds 650 ° C., the Cu precipitates become coarse, so that the iron loss is deteriorated and the increase in strength is also reduced, so that an electrical steel sheet having a good strength-iron loss balance cannot be obtained. An appropriate aging time depends on the processing temperature, but is preferably 10 min to 1000 h. The aging treatment may be performed at any timing before or after the insulating film is applied and baked, after baking, or after processing such as press punching.
[0034]
【Example】
Example 1
The steel slab shown in Table 1, with Si: 3%, Mn: 0.2%, and Al: 0.3% as the basic components, with the Cu and Ni contents varied, and the balance consisting of iron and inevitable impurities is obtained by hot rolling. The plate thickness was 2.0 mm, and then, as shown in Table 2, after annealing or hot-rolled plate annealing at 1000 ° C. for 300 s, pickling and cold rolling with a finished plate thickness of 0.35 mm were performed. Further, after finishing annealing at a maximum attained temperature of 950 ° C. for 30 s soaking, the cooling rate in the temperature range of 900 ° C. to 400 ° C. was cooled at 6 ° C./s. Thereafter, an insulating film was applied and baked, and then heat treated at 550 ° C. for 5 hours for aging to obtain a product plate.
[0035]
The product board thus obtained was evaluated for iron loss characteristics and mechanical characteristics. In addition, the component composition in the product plate was almost the same as that in the slab stage. The iron loss was evaluated by the Epstein method using equal amounts of samples in the rolling direction and the direction perpendicular to the rolling direction. The mechanical properties were evaluated based on the average of samples cut from the rolling direction and the direction perpendicular to the rolling direction. The results are shown in Table 1.
[0036]
In addition, the following electrical steel sheets having high tension by conventional solid solution strengthening, crystal grain refinement strengthening, precipitation strengthening, etc., were also made as trial products.
That is, as an example using solid solution strengthening, as shown in Table 2, C: 0.002%, Si: 4.5%, Mn: 0.2%, P: 0.01%, Al: 0.6%, W: 1.0% and Mo: A steel slab containing 1.0% and the balance consisting of iron and inevitable impurities is hot-rolled, hot-rolled sheet annealed at 900 ° C for 30 s, then hot-rolled at 400 ° C to finish 0.35 mm thick, 950 Finish annealing was performed at a temperature of 30 ° C. for 30 seconds.
As an example using solid solution strengthening and grain refinement, as shown in Table 2, C: 0.005%, Si: 3%, Mn: 0.2%, P: 0.05% and Ni: 4.5%, the balance being Steel made of iron and inevitable impurities was hot-rolled, then cold-rolled to a thickness of 0.35 mm, and then subjected to a final annealing at 800 ° C. for 30 s.
As an example using precipitation strengthening, as shown in Table 2, C: 0.03%, Si: 3.2%, Mn: 0.2%, P: 0.02%, Al: 0.65%, N: 0.003%, Nb: 0.018% and A steel containing Zr: 0.022%, the balance being iron and inevitable impurities, was hot-rolled and then cold-rolled to a thickness of 0.35 mm and subjected to finish annealing at 750 ° C. × 30 s.
In either case, no aging treatment was performed.
[0037]
[Table 1]
[0038]
[Table 2]
[0039]
Steel plates No. 7 to 13 according to the present invention have excellent magnetic properties substantially equivalent to those of steel plate No. 1 which is a comparative example having a base composition, and a significantly high strength is obtained. Furthermore, even when compared with steel plates No. 14 to 16, which are conventional high-strength electromagnetic steel plates, it has a significant low iron loss or high magnetic flux density and is excellent in strength-magnetic property balance.
[0040]
Example 2
The comparative steel C and invention steel J shown in Table 1 were hot rolled to a sheet thickness of 2.0 mm, then subjected to hot-rolled sheet annealing at 1000 ° C. for 300 s, followed by pickling and cold finishing with a thickness of 0.35 mm. Rolled. Furthermore, the finish annealing which hold | maintains soaking | uniform-heating for 30 s at the highest achieved temperature of 950 degreeC was performed, and it cooled by changing the cooling rate in the temperature range of 900 to 400 degreeC into the various conditions shown in Table 3. Thereafter, an insulating coating was applied and baked to obtain an annealed plate. The obtained annealed plate was heat treated at 550 ° C. for 5 hours for aging to obtain a product plate. The product board thus obtained was evaluated for iron loss characteristics and mechanical characteristics. The component composition in the product plate was almost the same as that in the slab stage. The results are shown in Table 3 and FIGS.
[0041]
[Table 3]
[0042]
Steel C is steel plate no. As shown in 18 and 19, excellent magnetic properties and high strength are exhibited at relatively fast cooling rates of 10 ° C / s or higher, but iron loss deteriorates and strength is reduced at 10 ° C / s or lower. It tends to decrease. On the other hand, Invention Steel J, to which an appropriate amount of Ni is added together with Cu, is Steel No. As shown in 22 to 24, it was possible to achieve both excellent magnetic properties and high strength stably under a wide range of cooling rate conditions.
[0043]
Example 3
Steel with the balance shown in Table 4 consisting of iron and unavoidable impurities is hot rolled to a thickness of 2.0 mm, and then subjected to non-annealing or hot-rolled sheet annealing at a temperature shown in Table 5 for 300 s, Washing and cold rolling to a predetermined thickness were performed. Further, finish annealing was performed for 30 s soaking at the temperatures shown in Table 5, and the cooling rate in the temperature range of 900 ° C. to 400 ° C. was cooled at 6 ° C./s. Thereafter, an insulating coating was applied and baked to obtain an annealed plate. The obtained annealed plate was subjected to an aging treatment at a temperature shown in Table 5 for 10 hours for aging to obtain a product plate. The product board thus obtained was evaluated for iron loss characteristics and mechanical characteristics. The results are also shown in Table 5. The component composition on the product plate was almost the same as in the slab stage. From Table 5, it can be seen that each sample has excellent magnetic properties and very high strength properties in each steel plate grade.
[0044]
[Table 4]
[0045]
[Table 5]
[0046]
【The invention's effect】
As described above, according to the present invention, an electrical steel sheet having excellent magnetic properties and high strength can be stably provided.
[Brief description of the drawings]
FIG. 1 is a graph showing the influence of a finish annealing cooling rate on iron loss after aging treatment.
FIG. 2 is a diagram showing the influence of the finish annealing cooling rate on the tensile strength after aging treatment.
Claims (4)
C:0.02%以下、
Si:4.5%以下、
Mn:3.0%以下、
Al:3.0%以下、
P:0.50%以下、
Ni:0.5%以上5.0%以下および
Cu:0.2%以上4.0%以下
を含有し、残部Feおよび不可避的不純物の成分組成を有し、結晶粒の平均粒径が20〜89μmであり、引張強さが下記式で示されるCTS(MPa)以上であることを特徴とする無方向性電磁鋼板。
記
CTS=5600[%C]+87[%Si]+15[%Mn]+70[%Al]+430[%P]
+37[%Ni]+22d-1/2+230
ただし、d:結晶粒の平均粒径(mm)% By mass
C: 0.02% or less,
Si: 4.5% or less,
Mn: 3.0% or less,
Al: 3.0% or less,
P: 0.50% or less,
Ni: 0.5% to 5.0% and
Cu: CTS (MPa containing 0.2% or more and 4.0% or less, having a component composition of the balance Fe and inevitable impurities, an average grain size of 20 to 89 μm, and a tensile strength represented by the following formula non-oriented electrical steel sheet you wherein a) or more.
Record
CTS = 5600 [% C] +87 [% Si] +15 [% Mn] +70 [% Al] +430 [% P]
+37 [% Ni] + 22d -1/2 +230
Where d: average grain size (mm) of crystal grains
ZrおよびVについてはそれぞれ0.1〜3.0%、
Sb、SnおよびGeについてはそれぞれ0.002〜0.5%、
B,Caおよび希土類元素についてはそれぞれ0.001〜0.01%、そして
Coについては0.2〜5.0%
にて含有することを特徴とする無方向性電磁鋼板。In Claim 1, as a component composition, 1 type (s) or 2 or more types further selected from Zr, V, Sb, Sn, Ge, B, Ca, rare earth elements, and Co,
For Zr and V, 0.1 to 3.0%,
0.002 to 0.5% for Sb, Sn and Ge,
0.001 to 0.01% for B, Ca and rare earth elements, respectively
0.2 to 5.0% for Co
Non-oriented electrical steel sheet you characterized by containing at.
C:0.02%以下、
Si:4.5%以下、
Mn:3.0%以下、
Al:3.0%以下、
P:0.50%以下、
Ni:0.5%以上5.0%以下および
Cu:0.2%以上4.0%以下
を含有し、残部Feおよび不可避的不純物の成分組成を有する鋼スラブに、熱間圧延を施した後、冷間圧延あるいは温間圧延を施して最終板厚とした後、最終到達温度が650〜1150℃かつ900℃〜400℃の温度域での冷却速度が1℃/s以上である、仕上げ焼鈍を施した後、400℃以上650℃以下の温度にて時効処理を施すことを特徴とする無方向性電磁鋼板の製造方法。% By mass
C: 0.02% or less,
Si: 4.5% or less,
Mn: 3.0% or less,
Al: 3.0% or less,
P: 0.50% or less,
Ni: 0.5% to 5.0% and
Cu: contains 0.2% or more and 4.0% or less, the steel slab to have a component composition of the balance Fe and inevitable impurities, was subjected to hot rolling, final thickness Metropolitan subjected to cold rolling or warm rolling After the final annealing, the final achieved temperature is 650-1150 ° C and the cooling rate in the temperature range of 900 ° C-400 ° C is 1 ° C / s or higher. method for producing a non-oriented electrical steel sheet you characterized by applying aging treatment.
C:0.02%以下、
Si:4.5%以下、
Mn:3.0%以下、
Al:3.0%以下、
P:0.50%以下、
Ni:0.5%以上5.0%以下および
Cu:0.2%以上4.0%以下
を含み、さらにZr、V、Sb、Sn、Ge、B、Ca、希土類元素およびCoから選んだ1種または2種以上を、
ZrおよびVについてはそれぞれ0.1〜3.0%、
Sb、SnおよびGeについてはそれぞれ0.002〜0.5%、
B,Caおよび希土類元素についてはそれぞれ0.001〜0.01%、そして
Coについては0.2〜5.0%
にて含有し、残部Feおよび不可避的不純物の成分組成を有する鋼スラブに、熱間圧延を施した後、冷間圧延あるいは温間圧延を施して最終板厚とした後、最終到達温度が650〜1150℃かつ900℃〜400℃の温度域での冷却速度が1℃/s以上である、仕上げ焼鈍を施した後、400℃以上650℃以下の温度にて時効処理を施すことを特徴とする無方向性電磁鋼板の製造方法。% By mass
C: 0.02% or less,
Si: 4.5% or less,
Mn: 3.0% or less,
Al: 3.0% or less,
P: 0.50% or less,
Ni: 0.5% to 5.0% and
Cu: 0.2% to 4.0%, and one or more selected from Zr, V, Sb, Sn, Ge, B, Ca, rare earth elements and Co,
For Zr and V, 0.1 to 3.0%,
0.002 to 0.5% for Sb, Sn and Ge,
0.001 to 0.01% for B, Ca and rare earth elements, respectively
0.2 to 5.0% for Co
Contained in, the steel slab to have a component composition of the balance Fe and inevitable impurities, was subjected to hot rolling, after the final thickness is subjected to cold rolling or warm rolling, the final temperature reached The cooling rate in the temperature range of 650-1150 ° C and 900 ° C-400 ° C is 1 ° C / s or higher, and after the finish annealing, aging treatment is performed at a temperature of 400 ° C-650 ° C. method for producing a non-oriented electrical steel sheet shall be the.
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| PCT/JP2003/015462 WO2004050934A1 (en) | 2002-12-05 | 2003-12-03 | Non-oriented magnetic steel sheet and method for production thereof |
| EP03777194.6A EP1580289B1 (en) | 2002-12-05 | 2003-12-03 | Non-oriented magnetic steel sheet and method for production thereof |
| EP12002344.5A EP2489753B1 (en) | 2002-12-05 | 2003-12-03 | Non-oriented magnetic steel sheet and method for production thereof |
| KR1020057010094A KR100709056B1 (en) | 2002-12-05 | 2003-12-03 | Non-oriented magnetic steel sheet and method for production thereof |
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