JP7507157B2 - 方向性電磁鋼板およびその製造方法 - Google Patents
方向性電磁鋼板およびその製造方法 Download PDFInfo
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- JP7507157B2 JP7507157B2 JP2021536312A JP2021536312A JP7507157B2 JP 7507157 B2 JP7507157 B2 JP 7507157B2 JP 2021536312 A JP2021536312 A JP 2021536312A JP 2021536312 A JP2021536312 A JP 2021536312A JP 7507157 B2 JP7507157 B2 JP 7507157B2
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- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 238000005096 rolling process Methods 0.000 claims description 87
- 238000001953 recrystallisation Methods 0.000 claims description 70
- 238000000137 annealing Methods 0.000 claims description 62
- 230000004907 flux Effects 0.000 claims description 58
- 229910000831 Steel Inorganic materials 0.000 claims description 57
- 239000010959 steel Substances 0.000 claims description 57
- 238000005098 hot rolling Methods 0.000 claims description 40
- 230000009467 reduction Effects 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000005097 cold rolling Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000005261 decarburization Methods 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229910052711 selenium Inorganic materials 0.000 claims description 19
- 238000005121 nitriding Methods 0.000 claims description 16
- 230000001186 cumulative effect Effects 0.000 claims description 13
- 229910052785 arsenic Inorganic materials 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 55
- 239000002244 precipitate Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 34
- 230000000694 effects Effects 0.000 description 34
- 230000008569 process Effects 0.000 description 24
- 238000005204 segregation Methods 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 239000011162 core material Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 229910052787 antimony Inorganic materials 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000003966 growth inhibitor Substances 0.000 description 8
- 239000010960 cold rolled steel Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910000976 Electrical steel Inorganic materials 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000009628 steelmaking Methods 0.000 description 6
- 206010053759 Growth retardation Diseases 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000009036 growth inhibition Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003887 surface segregation Methods 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 238000005162 X-ray Laue diffraction Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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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
- C21D8/1205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular fabrication or treatment of ingot or slab
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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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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/1255—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 with diffusion of elements, e.g. decarburising, nitriding
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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
- 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
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
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Description
本発明によれば、最終二次再結晶後に二次再結晶粒の方位が正確な(exact){110}<001>方位との方位差(deviation angle、°)(α2+β2)1/2が4°以下にゴス方位集積度が高い方向性電磁鋼板を得ることができる。
本発明によれば、磁束密度が高くて磁気的特性に優れた方向性電磁鋼板を製造することができ、このような方向性電磁鋼板を利用して鉄心材料として利用した電子機器は磁気的特性に優れている。
正確な{110}<001>結晶方位に対する方位差:(α2+β2)1/2
つまり、二次再結晶されたGoss結晶粒の方位が正確な{110}<001>結晶方位に対する(α2+β2)1/2値が小さければ小さいほど磁束密度が高い。本発明の一実施形態による方向性電磁鋼板が1.92テスラ(Tesla)以上の高磁束密度特性を確保するために製造された方向性電磁鋼板の二次再結晶粒方位を測定した結果、正確な{110}<001>結晶方位に対する方位差は約4°以下に確認された。以下、前述した本発明の一実施形態による方向性電磁鋼板の成分(本発明で成分元素の%は、他の説明がない限り、全て重量%を意味する)の限定理由について詳しく説明する。
Mnは、Siと同様に比抵抗を増加させて鉄損を減少させる効果があり、SおよびSeと反応してMn[S、Se]析出物を形成することによって一次再結晶粒の成長を抑制する抑制剤として使用する。本発明には0.200%以上添加するとMn[S、Se]析出物が粗大になって抑制力が低下し、また、Mn[S、Se]析出物を溶体化させるためにスラブを高温で加熱しなければならない問題が発生する。反対に、0.01%以下に制御するためには製鋼で精練の負担が大きくなり、Mn[S、Se]析出が少なく形成されて抑制剤としての効果が低下するため、Mnの含有量は0.01~0.20%に限定する。具体的に、Mnの含有量は0.05~0.15%含まれる。
Snは、本発明の重要な偏析元素のうちの一つとして、結晶粒界に偏析して粒界の移動を妨害する効果に優れた補助的結晶粒成長抑制剤として作用する。また高温でも安定的に結晶粒系に存在し、脱炭および表面酸化層形成に大きい影響を与えない。また、熱間圧延時にゴス方位の結晶粒生成を促進して優れた磁性の二次再結晶が良好に発達するように助ける。本発明でSnが0.005%より小さいと添加効果が微々であり、反対に0.200%以上添加されると粒界および表面偏析が激しく起こるようになって脱炭工程の負荷が順次に増加し、冷間圧延時に板破断の可能性が高まる。したがって、Sn含有量は0.005~0.20%に限定する。具体的にSnの含有量は、0.005~0.08%含まれ得る。より具体的にSnは0.005~0.04%含まれる。
以上のような組成を有するスラブを加熱炉に装入した後、1,280℃以下で加熱する。具体的に、スラブを1100~1280℃で加熱する。加熱されたスラブを利用して熱間圧延を施すようになる。熱間圧延工程は、加熱されたスラブを900℃以上の高温で粗圧延と仕上げ圧延をして冷間圧延するのに適正な厚さである1.0~3.5mmの厚さに圧延する。熱間圧延過程においてスラブ厚さと圧延ロール直径による構造的剪断変形が発生し、それによって剪断変形組織内にゴス方位結晶粒が形成される。このような熱延過程の根本的な剪断変形機構に加えて前述した固溶強化元素と粒界偏析元素の添加によりゴス方位の結晶粒形成がより促進されるようになる。また、粗圧延および熱間圧延時に圧延率によっても変形量が大きく変わり、ゴス方位結晶粒形成に大きい影響を与えるようになる。なお、粗圧延のように初期圧延厚さが厚い素材の変形時に剪断変形が大きくなるように粗圧延条件を制御すれば(つまり、圧延率を大きく付与する場合)ゴス方位結晶粒形成を大きく促進するようになる。
反対に、0.05%以上に総窒素含有量が増加することは、過剰のAlN形成で結晶成長が過度に増加する二次再結晶がよく形成されなくなる。また、過剰の窒素が1100℃以上の高温領域で、鋼板で分解されて出る時、鋼板表面に窒素放出口のような表面欠陥を誘発するようになる。したがって、総窒素含有量は0.01~0.05%範囲に限定して窒化処理することが好ましい。
また、スラブ加熱後粗圧延過程で1回圧延率が20%以上である粗圧延を少なくとも1回以上施して累積圧下率全体が60%以上になるように粗圧延を施すことによって、剪断変形量増加によるゴス方位結晶粒形成を促進してバー(Bar)を製造し、これを熱間圧延し、最終製品厚さに冷間圧延した後、600℃以上の温度領域で20℃/sec以上の昇温率で加熱して脱炭および一次再結晶させ、同時に窒化処理を施して鋼板内に総窒素含有量を0.01~0.05%範囲に調整した結果、最終高温焼鈍後に二次再結晶されたゴス方位結晶粒の結晶方位を測定した結果、正確な{110}<001>結晶方位に対する方位差は約4°以下であった。
冷間圧延時に圧延温度を50~350℃まで変更して最終製品厚さまで圧延を施した後、冷延鋼板を70℃/secの昇温速度で855℃まで加熱し、湿った水素と窒素およびアンモニアの混合ガス雰囲気中で180秒間維持することによって一次再結晶を形成しながら鋼板の総窒素含有量が220ppmになるように窒化処理を同時に施した。次いで、鋼板にMgOを主成分とする焼鈍分離剤を塗布してコイル状で二次再結晶高温焼鈍を施した。
実施例3で評価された発明材2(表1の発明材8の組成)の冷延板を利用して脱炭および一次再結晶焼鈍を施すに当たり、表4に示す条件で昇温速度を変化させて昇温し、次いで、追加的に昇温して850℃領域で脱炭および窒化処理を施した。窒化処理は、脱炭焼鈍中にアンモニアガスを使用して総窒素含有量を200ppmになるように窒化処理した。次いで、窒化処理された鋼板は、MgOを主成分とする焼鈍分離剤を塗布してコイル状で二次再結晶高温焼鈍を施した。高温焼鈍は、1200℃までは75% N2+25% H2の混合ガス雰囲気とし、1200℃到達後には100% H2ガス雰囲気で20時間維持後に徐冷した。表4は、脱炭および一次再結晶時に昇温速度による最終高温焼鈍後に二次再結晶粒に対するexact{110}<001>方位との方位差(deviation angle、°)(α2+β2)1/2、そして磁束密度および鉄損の変化を示したものである。
Claims (5)
- 重量%で、C:0.01%~0.1%、Si:2.0%~4.0%、Mn:0.01%~0.20%、酸可溶性Al:0.010%~0.040%、N:0.001%~0.008%、S:0.004%~0.008%、Se:0.0001~0.008%、Cu:0.002~0.1%、Ni:0.005~0.1%、Cr:0.005~0.1%、P:0.005%~0.1%、Mo:0.001~0.1%およびSn:0.005%~0.20%を含有し、Sb:0.0005%~0.10%、Ge:0.0005%~0.10%、As:0.0005%~0.10%、Pb:0.0001%~0.10%およびBi:0.0001%~0.10%のうちの1種以上を含有し、残部Feおよびその他不可避な不純物からなるスラブを準備する段階と、
前記スラブを1280℃以下で加熱する段階と、
前記加熱されたスラブを熱間圧延および熱延板焼鈍して熱延板を製造する段階と、
前記熱延板を冷間圧延および中間焼鈍して冷延板を製造する段階と、
前記冷延板を600℃以上の温度で20℃/sec以上の昇温率で加熱して脱炭焼鈍と窒化処理をして一次再結晶させる段階と、
前記一次再結晶された鋼板をMgOを主成分とする焼鈍分離剤を塗布して最終焼鈍して二次再結晶させる段階とを含み、
前記熱間圧延する前のスラブ粗圧延段階において累積圧下率60%以上で粗圧延を施し、1回の圧下率が20%以上である粗圧延を1回以上施した後に熱間圧延を施し、
最終焼鈍後の磁束密度(B8)が1.92テスラ以上であることを特徴とする方向性電磁鋼板の製造方法。 - 前記一次再結晶させる段階において脱炭焼鈍と窒化処理を施して鋼板の総窒素含有量が0.01~0.05%であることを特徴とする請求項1に記載の方向性電磁鋼板の製造方法。
- 前記スラブ粗圧延段階において累積圧下率が70%以上で粗圧延を施すことを特徴とする請求項2に記載の方向性電磁鋼板の製造方法。
- 前記冷間圧延時に圧延温度を150~300℃の温度範囲で冷間圧延することを特徴とする請求項3に記載の方向性電磁鋼板の製造方法。
- 前記一次再結晶させる段階において、前記冷延板を600℃以上の温度で50℃/sec以上の昇温率で加熱して焼鈍することを特徴とする請求項4に記載の方向性電磁鋼板の製造方法。
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