JP6504372B2 - Method of manufacturing directional magnetic steel sheet excellent in magnetic properties - Google Patents
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- 229910000831 Steel Inorganic materials 0.000 title claims description 55
- 239000010959 steel Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000000137 annealing Methods 0.000 claims description 115
- 238000001953 recrystallisation Methods 0.000 claims description 48
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005097 cold rolling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000004763 sulfides Chemical class 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 14
- 238000005261 decarburization Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000005381 magnetic domain Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000001631 hypertensive effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Soft Magnetic Materials (AREA)
Description
本発明は、磁気特性に優れる方向性電磁鋼板を、安定的かつ安価に製造する方向性電磁鋼板の製造方法に関するものである。 The present invention relates to a method for producing a grain-oriented electrical steel sheet for stably and inexpensively producing a grain-oriented electrical steel sheet excellent in magnetic properties.
電磁鋼板は、変圧器やモーターの鉄心材料等として広く用いられている軟磁性材料であり、中でも方向性電磁鋼板は、結晶方位がＧｏｓｓ方位と呼ばれる｛１１０｝＜００１＞方位に高度に集積していることで、優れた磁気特性を示すため、主として大型変圧器の鉄心材料等として使用されている。上記Ｇｏｓｓ方位への集積度を高める方法としては、二次再結晶現象を利用するのが一般的である。したがって、磁気特性に優れる方向性電磁鋼板を安定的に製造するためには、上記二次再結晶を制御することが重要となる。 The electromagnetic steel sheet is a soft magnetic material widely used as a core material for transformers and motors, etc. Among them, the grain-oriented electrical steel sheet is highly integrated in the {110} <001> orientation whose crystal orientation is called Goss orientation. In order to exhibit excellent magnetic properties, it is mainly used as a core material for large transformers. As a method of increasing the degree of integration in the Goss orientation, it is general to use a secondary recrystallization phenomenon. Therefore, it is important to control the secondary recrystallization in order to stably manufacture the grain-oriented electrical steel sheet excellent in magnetic properties.
ところで、方向性電磁鋼板を安定かつ安価に製造する技術の一つとして、特許文献１には、鋼素材（スラブ）中にインヒビタ形成成分を含有させずに、脱炭焼鈍後、二次再結晶完了前に、地鉄中のＳ量を増加することによって、二次再結晶を発現させる技術（「増硫法」）が提案されている。この増硫法では、地鉄中のＳ量を増加することによって、粒界に偏析するＳ量が増加し、Ｇｏｓｓ方位以外の方位を囲む粒界の移動が大きく抑制されるため、二次再結晶が安定的に発現し、磁気特性が向上するとされている。 By the way, as one of the techniques for stably and inexpensively producing a grain-oriented electrical steel sheet, Patent Document 1 discloses secondary recrystallization after decarburization annealing without containing an inhibitor forming component in a steel material (slab). Prior to completion, techniques have been proposed to develop secondary recrystallization by increasing the amount of S in the base iron ("the method of vulcanization"). In this method, the amount of sulfur segregated in grain boundaries is increased by increasing the amount of sulfur in the base iron, and the movement of grain boundaries surrounding orientations other than the Goss orientation is greatly suppressed. It is said that crystals appear stably and magnetic properties are improved.
しかし、上記特許文献１に開示の技術は、仕上焼鈍後のコイル内における磁気特性の偏差（バラツキ）が大きいという問題がある。そこで、この問題を改善する技術として、特許文献２には、焼鈍分離剤中に、硫化物および／または硫酸塩を含有させることにより、仕上焼鈍工程の昇温過程において鋼板に対して増硫処理を施し、その際、コイル最内巻部からコイル径がコイル外径の９０％となる位置に塗布される焼鈍分離剤中の硫化物および／または硫酸塩の濃度を、コイル径がコイル外径の９０％を超えたところから最外巻部までの位置に塗布される焼鈍分離剤中の硫化物および／または硫酸塩の濃度の５０％以上４００％以下の範囲で増加させ、昇温過程の８００℃でのコイル内における増硫量の最大値と最小値の差を３０ｐｐｍ以下に抑制することによって、鋼板内における磁気特性の偏差を低減する技術が提案されている。 However, the technique disclosed in Patent Document 1 has a problem that the deviation (variation) of the magnetic characteristics in the coil after finish annealing is large. Therefore, as a technique for solving this problem, Patent Document 2 discloses that a steel sheet is subjected to a sulfurizing treatment in the temperature rising process of the finish annealing process by containing a sulfide and / or a sulfate in the annealing separator. In this case, the concentration of sulfide and / or sulfate in the annealing separator applied from the innermost coil portion to a position where the coil diameter is 90% of the coil outer diameter, the coil diameter is the coil outer diameter Increase by 50% or more and 400% or less of the concentration of sulfide and / or sulfate in the annealing separator applied to a position from more than 90% of the A technique has been proposed for reducing the deviation of the magnetic properties in the steel sheet by suppressing the difference between the maximum value and the minimum value of the amount of vulcanization in the coil at 800 ° C. to 30 ppm or less.
上記特許文献２に開示の技術を用いることで、コイル内の磁気特性の偏差をある程度は小さくすることができる。しかし、発明者らの知見では、上記改善効果は、コイルによってバラツキが大きく、特に、製品板厚が０．２３ｍｍ以下の場合には、安定して磁気特性に優れる製品を製造することが難しいという問題があった。 By using the technology disclosed in Patent Document 2, the deviation of the magnetic characteristics in the coil can be reduced to a certain extent. However, according to the findings of the inventors, the improvement effect has a large variation depending on the coil, and in particular, it is difficult to stably produce a product having excellent magnetic characteristics when the product thickness is 0.23 mm or less. There was a problem.
本発明は、従来技術が抱える上記問題点に鑑みてなされたものであり、その目的は、特許文献１や特許文献２に開示された増硫法を適用した方向性電磁鋼板の製造方法において、コイル内の磁気特性の偏差を安定して低減することができる方向性電磁鋼板の製造方法を提案することにある。 The present invention has been made in view of the above problems of the prior art, and an object thereof is a method of manufacturing a grain-oriented electrical steel sheet to which the vulcanization method disclosed in Patent Document 1 or Patent Document 2 is applied, An object of the present invention is to propose a method of manufacturing a grain-oriented electrical steel sheet capable of stably reducing the deviation of the magnetic characteristics in the coil.
発明者らは、上記課題の解決に向けて、一次再結晶焼鈍後の鋼板と、焼鈍分離剤中に含まれるＳ含有量に着目して鋭意検討を重ねた。その結果、一次再結晶焼鈍後の鋼板の平均結晶粒径と焼鈍分離剤中に含まれるＳ含有量との関係を適正化することで、増硫効果が安定化し、ひいては、磁気特性に優れる方向性電磁鋼板を安定して得ることができることを見出し、本発明を開発するに至った。 In order to solve the above-mentioned subject, the inventors repeated earnestly examination paying attention to the steel plate after primary recrystallization annealing, and S content contained in an annealing separator. As a result, by optimizing the relationship between the average grain size of the steel sheet after primary recrystallization annealing and the S content contained in the annealing separator, the effect of vulcanization is stabilized and, consequently, the direction in which the magnetic characteristics are excellent It has been found that stable magnetic steel sheets can be obtained stably, and the present invention has been developed.
すなわち、本発明は、Ｃ：０．０８ｍａｓｓ％以下、Ｓｉ：４．５ｍａｓｓ％以下、Ｍｎ：０．５ｍａｓｓ％以下、ｓｏｌ．Ａｌ：０．０１００ｍａｓｓ％未満、Ｎ：０．０１００ｍａｓｓ％未満、Ｓ：０．０１００ｍａｓｓ％以下、Ｓｅ：０．０１００ｍａｓｓ％以下およびＯ：０．００５０ｍａｓｓ％以下を含有し、残部がＦｅおよび不可避的不純物からなる成分組成を有する鋼スラブを熱間圧延して熱延板とし、１回または中間焼鈍を挟む２回以上の冷間圧延して最終板厚の冷延板とし、脱炭焼鈍を兼ねた一次再結晶焼鈍し、ＭｇＯを主体とする焼鈍分離剤を塗布し、仕上焼鈍を施す一連の工程からなる方向性電磁鋼板の製造方法において、上記一次再結晶焼鈍後の結晶粒の平均粒径ｄを１０〜２５μｍとし、上記焼鈍分離剤として、Ｓｒ，Ｍｇ，Ｃａ，Ｂａ，Ｔｉ，ＳｂおよびＳｎの硫酸塩ならびに硫化物のうちから選ばれる１種または２種以上を、Ｓ含有量ｓで０．２〜２ｍａｓｓ％の範囲で含有し、かつ、上記Ｓ含有量ｓと上記ｄが下記式；
２．０≦（ｓ／ｄ）×１００≦１２．０
を満たして含有するものを用いることを特徴とする方向性電磁鋼板の製造方法を提案する。
That is, in the present invention, C: 0.08 mass% or less, Si: 4.5 mass% or less, Mn: 0.5 mass% or less, sol. Al: less than 0.0100 mass%, N: less than 0.0100 mass%, S: not more than 0.0100 mass%, Se: not more than 0.0100 mass% and O: not more than 0.0050 mass%, the balance being Fe and unavoidable impurities The steel slab having the component composition comprising the following composition was hot-rolled to form a hot-rolled sheet, and cold-rolled to a final thickness by cold-rolling once or twice or more with intermediate In the method of manufacturing a grain-oriented electrical steel sheet comprising a series of steps of applying primary annealing and annealing separation agent mainly comprising MgO and applying finish annealing, average grain diameter d of crystal grains after primary recrystallization annealing Is 10 to 25 μm, and one or more selected from sulfates and sulfides of Sr, Mg, Ca, Ba, Ti, Sb and Sn as the above-mentioned annealing separator, contains S, Contained in a range of 0.2～2Mass% in s, and the S content s and the d satisfies the following formula;
2.0 ≦ (s / d) × 100 ≦ 12.0
We propose a method of manufacturing a grain-oriented electrical steel sheet characterized by using a material that satisfies
本発明の上記方向性電磁鋼板の製造方法に用いる上記鋼スラブは、上記成分組成に加えてさらに、Ｎｉ：０．０５〜０．５ｍａｓｓ％、Ｓｎ：０．０１〜０．５ｍａｓｓ％、Ｓｂ：０．０１〜０．５ｍａｓｓ％、Ｐ：０．０１〜０．２ｍａｓｓ％、Ｃｒ：０．０１〜０．５ｍａｓｓ％、Ｃｕ：０．０１〜０．５ｍａｓｓ％、Ｎｂ：０．００２〜０．０１ｍａｓｓ％およびＭｏ：０．０１〜０．２ｍａｓｓ％のうちから選ばれる１種または２種以上を含有することを特徴とする。 In addition to the above component compositions, the above-described steel slab used in the method of the present invention for producing a grain-oriented electrical steel sheet further includes Ni: 0.05 to 0.5 mass%, Sn: 0.01 to 0.5 mass%, Sb: 0.01 to 0.5 mass%, P: 0.01 to 0.2 mass%, Cr: 0.01 to 0.5 mass%, Cu: 0.01 to 0.5 mass%, Nb: 0.002 to 0.. It is characterized in that it contains one or more selected from 01 mass% and Mo: 0.01 to 0.2 mass%.
また、本発明の上記方向性電磁鋼板の製造方法は、上記冷延板の最終板厚を０．２３ｍｍ以下とすることを特徴とする。 In the method of manufacturing a grain-oriented electrical steel sheet according to the present invention, the final thickness of the cold-rolled sheet is 0.23 mm or less.
本発明によれば、磁気特性に優れる方向性電磁鋼板を、工業的に安定してかつ安価に製造することが可能になる。 According to the present invention, it is possible to industrially stably and inexpensively manufacture a grain-oriented electrical steel sheet having excellent magnetic properties.
まず、本発明を開発するに至った実験について説明する。
Ｃ：０．０３ｍａｓｓ％、Ｓｉ：３．５ｍａｓｓ％、Ｍｎ：０．０５ｍａｓｓ％、ｓｏｌ．Ａｌ：０．００７５ｍａｓｓ％、Ｎ：０．００５０ｍａｓｓ％、Ｓ：０．００２０ｍａｓｓ％、Ｓｅ：０．００１０ｍａｓｓ％およびＯ：０．００１０ｍａｓｓ％を含有し、残部がＦｅおよび不可避的不純物からなる成分組成を有する連続鋳造製のスラブを、１２００℃に再加熱した後、熱間圧延して板厚２．２ｍｍの熱延板とし、その後、１０５０℃×３０秒の熱延板焼鈍を施した。
次いで、１回目の冷間圧延で中間板厚１．５ｍｍとし、１０５０℃×１２０秒の中間焼鈍を施した後、２回目の冷間圧延で最終板厚０．１８、０．２３ｍｍまたは０．２７ｍｍ厚の冷延板とし、その後、７８０〜９００℃の温度範囲で１２０秒間均熱保持する脱炭を兼ねた一次再結晶焼鈍を、ｖｏｌ％比でＨ２：Ｎ２＝５０：５０、露点６０℃の雰囲気下で施し、一次再結晶焼鈍後の結晶粒の平均粒径ｄを８〜２６μｍの範囲で種々に変化させた。ここで、上記平均粒径は、ＪＩＳ Ｇ０５５１に規定された計数法によって得た平均粒径である。
次いで、上記一次再結晶焼鈍後の鋼板表面に、ＭｇＯを主体とし、硫酸Ｍｇ（硫酸塩）を、焼鈍分離剤中に含まれるＳ含有量ｓで０．１〜１．５ｍａｓｓ％の範囲で種々に変化させて添加した焼鈍分離剤を、一次再結晶焼鈍後の鋼板表面に１２．５ｇ／ｍ２（両面）塗布し、乾燥した。
次いで、Ｎ２ガス雰囲気下で、昇温速度１５℃／ｈｒで昇温し、１１６０℃×５ｈｒの均熱処理する仕上焼鈍を施した。
First, the experiments that led to the development of the present invention will be described.
C: 0.03 mass%, Si: 3.5 mass%, Mn: 0.05 mass%, sol. Al: 0.0075 mass%, N: 0.0050 mass%, S: 0.0020 mass%, Se: 0.0010 mass% and O: 0.0010 mass%, with the balance containing Fe and unavoidable impurities The continuous casting slab was reheated to 1200 ° C., and then hot rolled to a hot-rolled sheet having a thickness of 2.2 mm, and then subjected to hot-rolled sheet annealing at 1050 ° C. for 30 seconds.
Next, after making the intermediate plate thickness 1.5 mm in the first cold rolling and subjecting to intermediate annealing at 1050 ° C. × 120 seconds, the final thickness 0.18, 0.23 mm or 0. 27% thick cold rolled sheet, then, primary recrystallization annealing combined with decarburization holding soaking at 120 ° C. for 120 seconds at temperature range of 780 to 900 ° C. H 2 : N 2 = 50: 50 by vol% ratio, dew point C. to 60.degree. C. The average grain diameter d of the crystal grains after primary recrystallization annealing was variously changed in the range of 8 to 26 .mu.m. Here, the average particle size is an average particle size obtained by the counting method defined in JIS G0551.
Next, on the steel sheet surface after the above primary recrystallization annealing, MgO is mainly contained, and Mg sulfate (sulfate) is variously in the range of 0.1 to 1.5 mass% with S content s contained in the annealing separating agent The annealing separator added to the above was applied to the surface of the steel sheet after primary recrystallization annealing at 12.5 g / m 2 (both sides) and dried.
Then, the temperature was raised at a temperature rising rate of 15 ° C./hr under a N 2 gas atmosphere, and a finish annealing for soaking at 1160 ° C. × 5 hr was performed.
斯くして得た製品板の磁気特性（磁束密度Ｂ８）をＪＩＳ Ｃ２５５６に規定された方法で測定した。
図１は、板厚が０．２３ｍｍおよび０．１８ｍｍにおける一次再結晶焼鈍後の結晶粒の平均粒径ｄと焼鈍分離剤中に含まれるＳ含有量ｓが磁気特性に及ぼす影響を示したグラフである。この図から、一次再結晶焼鈍後の結晶粒の平均粒径ｄと焼鈍分離剤中に含まれるＳ含有量ｓには適正範囲が存在し、一次再結晶粒の平均粒径ｄが大きくなるほど、適正な焼鈍分離剤中のＳ含有量ｓが大きくなることがわかる。
The magnetic properties (magnetic flux density B 8 ) of the product plate thus obtained were measured by the method defined in JIS C2556.
FIG. 1 is a graph showing the influence of the average grain diameter d of the crystal grains after primary recrystallization annealing at a plate thickness of 0.23 mm and 0.18 mm and the S content s contained in the annealing separator on the magnetic characteristics. It is. From this figure, an appropriate range exists for the average grain size d of the crystal grains after primary recrystallization annealing and the S content s contained in the annealing separator, and the larger the average grain size d of the primary recrystallized grains, It can be seen that the S content s in the proper annealing separator increases.
上記のように、一次再結晶後の結晶粒の平均粒径ｄと焼鈍分離剤中Ｓ含有量ｓとが関係する理由は、まだ十分に明らかとなっていないが、発明者らは以下のように考えている。
仕上焼鈍時に、焼鈍分離剤中に添加した硫酸塩や硫化物から分解したＳが鋼板内部へ侵入するときは、体拡散よりも粒界拡散が支配的となると考えられ、粒界が多いほど、つまり、一次再結晶粒が小さいほど、焼鈍分離剤に添加したＳの鋼中への侵入が促進され、逆に、一次再結晶粒が大きいほど、上記Ｓの鋼中への侵入は進み難くなる。
そのため、一次再結晶粒が小さく、鋼中へのＳ侵入が進みやすい場合でかつ焼鈍分離剤中へのＳ添加量が多い場合には、鋼中へのＳの侵入が過剰となり、磁気特性に悪影響が出る。一方、一次再結晶粒が大きく、鋼中へのＳ侵入が進み難い場合には、Ｓ添加量を多くしないと、増硫の効果が得られ難くなる、と考えられる。
As described above, the reason why the average grain size d of the crystal grains after primary recrystallization and the S content s in the annealing separator are not yet sufficiently clarified, but the inventors have as follows: I am thinking about it.
At the time of finish annealing, when S decomposed from sulfates and sulfides added to the annealing separating agent penetrates into the inside of the steel sheet, it is thought that grain boundary diffusion becomes dominant rather than body diffusion, and the more grain boundaries there are, That is, the smaller the primary recrystallized grains, the more the penetration of S added to the annealing separator into the steel is promoted, and conversely, the larger the primary recrystallized grains, the harder it is for the penetration of S into the steel to proceed .
Therefore, when primary recrystallized grains are small, it is easy to proceed with S penetration into steel, and when the amount of S added to the annealing separator is large, the penetration of S into steel becomes excessive, resulting in the magnetic characteristics. There is an adverse effect. On the other hand, when the primary recrystallized grains are large and it is difficult for the penetration of S into the steel, it is considered that the effect of the vulcanization can not be obtained unless the amount of S is increased.
一方、図２は、板厚が０．２７ｍｍにおける一次再結晶焼鈍後の結晶粒の平均粒径ｄと焼鈍分離剤中に含まれるＳ含有量ｓが磁気特性に及ぼす影響を示したグラフである。この図から、板厚０．２７ｍｍでは、磁気特性は、一次再結晶焼鈍後の結晶粒の平均粒径ｄと焼鈍分離剤中に含まれるＳ含有量ｓに影響されず、ｓが０．２ｍａｓｓ％をこえる領域で良好な磁気特性が得られている。 On the other hand, FIG. 2 is a graph showing the influence of the average grain diameter d of the crystal grains after primary recrystallization annealing at a thickness of 0.27 mm and the S content s contained in the annealing separator on the magnetic characteristics. . From this figure, at a plate thickness of 0.27 mm, the magnetic characteristics are not affected by the average grain diameter d of the crystal grains after primary recrystallization annealing and the S content s contained in the annealing separator, and s is 0.2 mass. Good magnetic properties are obtained in the region of more than 10%.
このように、板厚０．２７ｍｍでは、ｓを０．２ｍａｓｓ％で良好な磁気特性が得られるのに対し、板厚が０．２３ｍｍ以下の方向性電磁鋼板では、増硫法の効果が安定しない理由について、発明者らは以下のように考えている。
方向性電磁鋼板の製品品質（磁気特性）に及ぼす製造条件の変動、特に、製鋼工程における成分変動や焼鈍工程における温度変動などの影響は、一般に、板厚が薄いほど受けやすいため、一次再結晶焼鈍後の結晶粒の大きさも上記製造条件の変動によって大きく変化する。そのため、板厚が０．２３ｍｍ以下の方向性電磁鋼板は、焼鈍分離剤中に含まれるＳ含有量の変動の影響も受けて、磁気特性が安定しなかったものと考えられる。
本発明は、上記の新規な知見に基き、開発したものである。
As described above, when the thickness is 0.27 mm, good magnetic characteristics can be obtained with s of 0.2 mass%, but in the case of a grain-oriented electrical steel sheet having a thickness of 0.23 mm or less, the effect of the vulcanization method is stable. The inventors consider as follows about the reason for not doing.
In general, the smaller the thickness of the sheet, the more easily it is affected by fluctuations in the manufacturing conditions that affect the product quality (magnetic properties) of the grain-oriented electrical steel sheet, in particular, component fluctuations in the steelmaking process and temperature fluctuations in the annealing process. The size of the crystal grain after annealing also largely changes due to the fluctuation of the manufacturing conditions. Therefore, the grain-oriented electrical steel sheet having a thickness of 0.23 mm or less is also considered to be unstable in the magnetic characteristics, also affected by the fluctuation of the S content contained in the annealing separator.
The present invention has been developed based on the above novel findings.
次に、本発明の方向性電磁鋼板の製造に用いる鋼素材（スラブ）の成分組成について説明する。
Ｃ：０．０８ｍａｓｓ％以下
Ｃは、一次再結晶集合組織を改善するのに有用な元素であるため、０．００１０ｍａｓｓ％以上含有させることが好ましい。しかし、０．０８ｍａｓｓ％を超えると、却って一次再結晶集合組織の劣化を招くので、上限は０．０８ｍａｓｓ％とする。なお、良好な磁気特性を得る観点からは、０．０１〜０．０６ｍａｓｓ％の範囲が好ましい。
Next, the component composition of the steel material (slab) used for manufacturing the grain-oriented electrical steel sheet of the present invention will be described.
C: 0.08 mass% or less Since C is an element useful for improving primary recrystallization texture, it is preferable to contain 0.0010 mass% or more. However, if it exceeds 0.08 mass%, the primary recrystallized texture will rather deteriorate, so the upper limit is made 0.08 mass%. In addition, from a viewpoint of obtaining a favorable magnetic characteristic, the range of 0.01-0.06 mass% is preferable.
Ｓｉ：４．５ｍａｓｓ％以下
Ｓｉは、鋼の比抵抗を高め、鉄損を低減する有用元素であるので、２．０ｍａｓｓ％以上含有させるのが好ましい。しかし、４．５ｍａｓｓ％を超えると、冷間圧延性が著しく悪化するので、上限は４．５ｍａｓｓ％とする。なお、良好な鉄損特性を得る観点からは、２．０〜４．０ｍａｓｓ％の範囲が好ましい。
Si: 4.5 mass% or less Since Si is a useful element which raises the specific resistance of steel and reduces iron loss, it is preferable to contain 2.0 mass% or more. However, if it exceeds 4.5 mass%, the cold rolling property is significantly deteriorated, so the upper limit is set to 4.5 mass%. In addition, from a viewpoint of obtaining a favorable iron loss characteristic, the range of 2.0-4.0 mass% is preferable.
Ｍｎ：０．５ｍａｓｓ％以下
Ｍｎは、製造時における熱間加工性を向上させる効果があるので、０．０１ｍａｓｓ％以上含有させるのが好ましい。しかし、０．５ｍａｓｓ％を超えると、一次再結晶集合組織が悪化し、磁気特性の劣化を招くので、Ｍｎの上限は０．５ｍａｓｓ％とする。好ましくは、０．２ｍａｓｓ％以下、さらに好ましくは０．１ｍａｓｓ％以下である。
Mn: 0.5 mass% or less Since Mn has an effect of improving the hot workability at the time of production, it is preferable to contain 0.01 mass% or more. However, if it exceeds 0.5 mass%, the primary recrystallization texture is deteriorated to cause deterioration of the magnetic properties, so the upper limit of Mn is made 0.5 mass%. Preferably, it is 0.2 mass% or less, more preferably 0.1 mass% or less.
ｓｏｌ．Ａｌ：０．０１００ｍａｓｓ％未満
Ａｌは、鋼中に過剰に存在すると二次再結晶の発現を阻害する。特に、ｓｏｌ．Ａｌ量で０．０１００ｍａｓｓ％以上になると、低温スラブ加熱の製造条件では、二次再結晶が起こり難くなって磁気特性が劣化する。よって、Ａｌはｓｏｌ．Ａｌ量で０．０１００ｍａｓｓ％未満に制限する。
sol. Al: less than 0.0100 mass% Al, when present in excess in steel, inhibits the development of secondary recrystallization. In particular, sol. When the Al content is 0.0100 mass% or more, secondary recrystallization hardly occurs under the production conditions of low temperature slab heating, and the magnetic characteristics are degraded. Therefore, Al is sol. The amount of Al is limited to less than 0.0100 mass%.
Ｎ：０．０１００ｍａｓｓ％未満
Ｎは、ｓｏｌ．Ａｌと同様、鋼中に過剰に存在すると二次再結晶の発現を阻害する。特にＮ量が０．０１００ｍａｓｓ％以上になると、二次再結晶が起こり難くなって、磁気特性が劣化する。よって、Ｎは０．０１００ｍａｓｓ％未満に制限する。好ましくは０．０７０ｍａｓｓ％以下である。
N: less than 0.0100 mass% N is sol. Like Al, excessive presence in steel inhibits the development of secondary recrystallization. In particular, when the N content is 0.0100 mass% or more, secondary recrystallization hardly occurs and the magnetic characteristics deteriorate. Therefore, N is limited to less than 0.0100 mass%. Preferably it is 0.070 mass% or less.
Ｓ：０．０１００ｍａｓｓ％以下、Ｓｅ：０．０１００ｍａｓｓ％以下
Ｓ，Ｓｅは、Ａｌ，Ｎと同様、鋼中に過剰に存在すると二次再結晶の発現を阻害する元素であり、それぞれ０．０１００ｍａｓｓ％を超えると、スラブ加熱時に粗大化したＭｎＳやＭｎＳｅが一次再結晶組織を不均一にするため、磁気特性が劣化する。よって、ＳおよびＳｅは、それぞれ０．０１００ｍａｓｓ％以下に制限する。好ましくはそれぞれ０．００５０ｍａｓｓ％以下である。
S: 0.0100 mass% or less, Se: 0.0100 mass% or less S and Se, like Al and N, are elements that, when present in excess in steel, inhibit the development of secondary recrystallization, each of 0.0100 mass When it exceeds 10%, the MnS and MnSe coarsened at the time of slab heating make the primary recrystallized structure non-uniform, so that the magnetic properties deteriorate. Therefore, S and Se are each limited to 0.0100 mass% or less. Preferably, they are each 0.0050 mass% or less.
Ｏ：０．００５０ｍａｓｓ％以下
Ｏは、Ｓ，Ｓｅと同様、０．００５０ｍａｓｓ％以上になると、粗大な酸化物を形成し、二次再結晶を阻害するので、上限は０．００５０ｍａｓｓ％とする。好ましくは０．００３０ｍａｓｓ％以下である。
O: not more than 0.0050 mass% O, like S and Se, forms coarse oxides when it is not less than 0.0050 mass% and inhibits secondary recrystallization, so the upper limit is made 0.0050 mass%. Preferably it is 0.0030 mass% or less.
本発明に用いる鋼スラブは、上記成分に加えてさらに、以下に説明する成分のうちから選ばれる１種または２種以上を含有することができる。
Ｎｉ：０．０５〜０．５ｍａｓｓ％
Ｎｉは、熱延板組織の均一性を高め、磁気特性を改善する効果がある。しかし、０．０５ｍａｓｓ％未満では、上記効果に乏しく、一方、０．５ｍａｓｓ％を超えると二次再結晶が不安定となり、逆に磁気特性が劣化するので、添加する場合には、０．０５〜０．５ｍａｓｓ％の範囲とするのが好ましい。より好ましくは０．０７〜０．２ｍａｓｓ％の範囲である。
The steel slab used in the present invention may further contain one or more selected from the components described below, in addition to the above components.
Ni: 0.05 to 0.5 mass%
Ni has the effect of improving the uniformity of the hot-rolled sheet structure and improving the magnetic properties. However, if the content is less than 0.05 mass%, the above effect is scarce, while if it exceeds 0.5 mass%, secondary recrystallization becomes unstable and the magnetic properties deteriorate, so 0.05 is added. It is preferable to set it as -0.5 mass%. More preferably, it is in the range of 0.07 to 0.2 mass%.
Ｓｎ：０．０１〜０．５ｍａｓｓ％、Ｓｂ：０．０１〜０．５ｍａｓｓ％、Ｐ：０．００１〜０．２ｍａｓｓ％およびＣｒ：０．０１〜０．５ｍａｓｓ％
これらの元素は、いずれも、鉄損の改善に有効に寄与する元素であるが、含有量が上記下限値に満たないと、その添加効果に乏しく、一方、上記上限値を超えると、二次再結晶粒の発達が抑制される。そのため、それぞれ上記の範囲で含有させることが好ましい。より好ましくは、Ｓｎ：０．０２〜０．２ｍａｓｓ％、Ｓｂ：０．０２〜０．２ｍａｓｓ％、Ｐ：０．０４〜０．１２ｍａｓｓ％およびＣｒ：０．０３〜０．２ｍａｓｓ％の範囲である。
Sn: 0.01 to 0.5 mass%, Sb: 0.01 to 0.5 mass%, P: 0.001 to 0.2 mass% and Cr: 0.01 to 0.5 mass%
These elements are all elements that effectively contribute to the improvement of iron loss, but if the content is less than the above lower limit value, the addition effect is scarce, while if the above upper limit value is exceeded, the secondary The development of recrystallized grains is suppressed. Therefore, it is preferable to contain each in the above-mentioned range. More preferably, Sn: 0.02 to 0.2 mass%, Sb: 0.02 to 0.2 mass%, P: 0.04 to 0.12 mass% and Cr: 0.03 to 0.2 mass%. is there.
Ｃｕ：０．０１〜０．５ｍａｓｓ％
Ｃｕは、仕上焼鈍中における鋼板の窒化や酸化を抑制し、Ｇｏｓｓ方位粒の優先的な成長を促進して、磁気特性を効果的に向上させる働きがある。しかし、０．０１ｍａｓｓ％未満では、上記添加効果が小さく、一方、０．５ｍａｓｓ％を超える添加は、熱間圧延性を悪化する。よって、Ｃｕは０．０１〜０．５ｍａｓｓ％の範囲で添加するのが好ましい。より好ましくは０．０２〜０．２ｍａｓｓ％の範囲である。
Cu: 0.01 to 0.5 mass%
Cu has the function of suppressing nitriding and oxidation of the steel sheet during finish annealing, promoting preferential growth of Goss oriented grains, and effectively improving the magnetic properties. However, if the amount is less than 0.01 mass%, the addition effect is small, while the addition exceeding 0.5 mass% deteriorates the hot-rollability. Therefore, it is preferable to add Cu in 0.01 to 0.5 mass%. More preferably, it is in the range of 0.02 to 0.2 mass%.
Ｎｂ：０．００２〜０．０１ｍａｓｓ％
Ｎｂは、一次再結晶粒の成長を抑制し、良好な結晶方位を有する二次再結晶粒の成長を促進して磁気特性を向上させる効果がある。上記効果は０．００２ｍａｓｓ％以上の添加で発現するが、０．０１ｍａｓｓ％を超えて添加すると、仕上焼鈍後も地鉄中に残留し、鉄損を劣化させる。よって、Ｎｂは０．００２〜０．０１ｍａｓｓ％の範囲で含有させるのが好ましい。より好ましくは０．００２〜０．００８ｍａｓｓ％の範囲である。
Nb: 0.002 to 0.01 mass%
Nb has an effect of suppressing the growth of primary recrystallized grains and promoting the growth of secondary recrystallized grains having a favorable crystal orientation to improve the magnetic properties. The above effect is manifested by the addition of 0.002 mass% or more, but when it is added in excess of 0.01 mass%, it remains in the base iron even after finish annealing and degrades the iron loss. Therefore, Nb is preferably contained in a range of 0.002 to 0.01 mass%. More preferably, it is in the range of 0.002 to 0.008 mass%.
Ｍｏ：０．０１〜０．２ｍａｓｓ％
Ｍｏは、粒界に偏析して一次再結晶粒の成長を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を向上させる効果がある。上記効果は０．０１ｍａｓｓ％以上の添加で発現し、一方、０．２ｍａｓｓ％を超える添加は、冷間圧延性を悪化させる。よって、Ｍｏは０．０１〜０．２ｍａｓｓ％の範囲で添加するのが好ましい。より好ましくは０．０２〜０．０８ｍａｓｓ％の範囲である。
Mo: 0.01 to 0.2 mass%
Mo is segregated at grain boundaries to suppress the growth of primary recrystallized grains, and has an effect of promoting secondary recrystallization of crystal grains having a favorable crystal orientation to improve magnetic properties. The above effect is manifested by the addition of 0.01 mass% or more, while the addition exceeding 0.2 mass% deteriorates the cold rolling property. Therefore, it is preferable to add Mo in the range of 0.01 to 0.2 mass%. More preferably, it is in the range of 0.02 to 0.08 mass%.
次に、本発明の方向性電磁鋼板の製造方法について説明する。
本発明の方向性電磁鋼板の製造方法は、上記成分組成を有する鋼素材（スラブ）を、熱間圧延して熱延板とし、１回または中間焼鈍を挟む２回以上の冷間圧延して最終板厚の冷延板とし、脱炭焼鈍を兼ねた一次再結晶焼鈍し、ＭｇＯを主体とする焼鈍分離剤を塗布し、仕上焼鈍を施す一連の工程からなる。ここで、上記スラブは、本発明に適合する上記成分組成に調整した鋼を、通常公知の精錬プロセス等で溶製した後、常法の連続鋳造法等により鋼素材（スラブ）とする。
Next, the method for producing the grain-oriented electrical steel sheet of the present invention will be described.
In the method of manufacturing a grain-oriented electrical steel sheet of the present invention, a steel material (slab) having the above-described composition is hot-rolled into a hot-rolled sheet and cold-rolled once or twice or more with intermediate annealing interposed. A cold rolled sheet having a final thickness, primary recrystallization annealing also serving as decarburization annealing, an annealing separating agent mainly composed of MgO is applied, and a series of steps of finish annealing are performed. Here, the above-mentioned slab is made of a steel adjusted to the above-mentioned composition suitable for the present invention by a generally known refining process or the like, and then made into a steel material (slab) by a continuous casting method or the like.
その後、上記スラブを、再加熱した後、あるいは、再加熱せずに、熱間圧延し、熱延板とする。なお、スラブを再加熱する場合には、再加熱温度は１０００〜１３００℃の範囲とするのが好ましい。１０００℃未満では、熱間圧延における圧延荷重が高くなり過ぎ、圧延することが困難となる。一方、１３００℃を超える加熱は、インヒビタを含まない本発明では無意味であり、また、結晶粒が巨大化するため、磁気特性の劣化を招くからである。 Thereafter, the slab is hot-rolled into a hot-rolled sheet after reheating or without reheating. In addition, when reheating a slab, it is preferable to make reheating temperature into the range of 1000-1300 degreeC. If it is less than 1000 ° C., the rolling load in hot rolling becomes too high, and rolling becomes difficult. On the other hand, heating exceeding 1300 ° C. is meaningless in the present invention not containing any inhibitor, and the crystal grains become gigantic, which causes deterioration of the magnetic properties.
次いで、上記熱延板は、必要に応じて熱延板焼鈍を施したのち、１回または中間焼鈍を挟む２回以上の冷間圧延により、最終板厚の冷延板とする。なお、上記最終板厚は、０．２３ｍｍ以下とするのが好ましい。０．２３ｍｍ以下で、本発明の効果がより発現するからである。 Next, the hot-rolled sheet is subjected to hot-rolled sheet annealing if necessary, and then made into a cold-rolled sheet of final thickness by cold rolling once or twice or more with intermediate annealing interposed. The final plate thickness is preferably 0.23 mm or less. This is because the effects of the present invention are more manifested at 0.23 mm or less.
次いで、上記冷延板は、脱炭焼鈍を兼ねた一次再結晶焼鈍を施し、鋼板に含まれるＣを０．００５０ｍａｓｓ％未満に低減する。０．００５０ｍａｓｓ％以上含まれると、製品板が磁気時効を起こして鉄損が劣化するからである。好ましくは０．００３０ｍａｓｓ％以下である。なお、脱炭焼鈍時の雰囲気は、湿水素窒素または湿水素アルゴン雰囲気とするのが好ましい。 Next, the cold rolled sheet is subjected to primary recrystallization annealing which also serves as decarburization annealing to reduce C contained in the steel sheet to less than 0.0050 mass%. If the content is 0.0050% by mass or more, the product plate is subjected to magnetic aging to deteriorate the iron loss. Preferably it is 0.0030 mass% or less. The atmosphere for decarburizing annealing is preferably wet hydrogen nitrogen or wet hydrogen argon.
上記脱炭焼鈍を兼ねた一次再結晶焼鈍後、鋼板表面にマグネシア（ＭｇＯ）を主体とする焼鈍分離剤を塗布する。
この際、上記焼鈍分離剤は、一次再結晶焼鈍後から二次再結晶完了までの間に、地鉄中のＳ量を増加（増硫処理）させるため、硫酸塩あるいは硫化物を、Ｓ含有量ｓが０．２〜２．０ｍａｓｓ％となる範囲で、かつ、焼鈍分離剤を塗布する一次再結晶後の結晶粒の平均粒径ｄとの間で、下記式；
２．０≦（ｓ／ｄ）×１００≦１２．０
の関係を満たして含有するものであることが必要である。
上記Ｓ含有量ｓが０．２ｍａｓｓ％未満であったり、（ｓ／ｄ）×１００が２．０未満では、増硫による磁気特性の向上効果が小さく、一方、上記Ｓ含有量ｓが２．０ｍａｓｓ％超えであったり、（ｓ／ｄ）×１００が１２．０超えでは、鋼板中へのＳの侵入が過剰となり、却って磁気特性に悪影響を及ぼすからである。なお、好ましいＳ含有量ｓは０．３〜１．０ｍａｓｓ％の範囲、好ましい（ｓ／ｄ）×１００は５．０〜１０．０の範囲である。
After the primary recrystallization annealing also serving as the decarburization annealing, an annealing separator mainly composed of magnesia (MgO) is applied to the surface of the steel sheet.
At this time, the above-mentioned annealing separating agent increases the amount of S in the base iron (intensification treatment) between the primary recrystallization annealing and the completion of the secondary recrystallization. In the range of 0.2 to 2.0 mass% of the amount s, and between the average particle diameter d of the crystal grains after primary recrystallization to which the annealing separator is applied, the following formula;
2.0 ≦ (s / d) × 100 ≦ 12.0
It is necessary to satisfy the relationship of
When the S content s is less than 0.2 mass% or (s / d) × 100 is less than 2.0, the effect of improving the magnetic properties by vulcanization is small, while the S content s is less than 2. If the content exceeds 0 mass% or (s / d) × 100 exceeds 12.0, the penetration of S into the steel sheet becomes excessive, which adversely affects the magnetic properties. In addition, preferable S content s is the range of 0.3-1.0 mass%, preferable (s / d) x100 is the range of 5.0-10.0.
上記焼鈍分離剤を塗布した鋼板は、その後、仕上焼鈍を施す。この仕上焼鈍の条件は、常法に従って行えば良く、特に制限はない。この仕上焼鈍中に、焼鈍分離剤中の添加した硫酸塩あるいは硫化物が分解して増硫効果を発揮し、ゴス方位に高度に集積した結晶組織が形成され、良好な磁気特性が得られる。 The steel sheet coated with the above-mentioned annealing separator is then subjected to finish annealing. The conditions for this finish annealing may be performed according to a conventional method, and are not particularly limited. During this final annealing, the added sulfate or sulfide in the annealing separator decomposes to exhibit a hypertensive effect, forming a highly integrated crystal structure in the Goss orientation, and good magnetic characteristics can be obtained.
上記仕上焼鈍後の鋼板は、その後、必要に応じて、また、用途に応じて、平坦化焼鈍および適当な絶縁被膜を被成した後、製品板とする。 The steel sheet after the above-mentioned finish annealing is thereafter made into a product sheet after forming a flattening annealing and an appropriate insulating film, if necessary and depending on the application.
なお、本発明の方向性電磁鋼板は、鉄損をより低減させるため、磁区細分化処理を施すことが望ましい。磁区細分化の方法としては、一般的に実施されている方法、例えば、最終板厚に冷間圧延した鋼板や中間工程の鋼板の表面にエッチング加工を施して溝を形成したり、製品板の鋼板表面に電子ビームやレーザビームを照射したりする方法等を用いることができる。 In addition, as for the directionality electromagnetic steel sheet of this invention, in order to reduce an iron loss more, it is desirable to perform a magnetic domain refinement process. As a method of magnetic domain fragmentation, a method which is generally carried out, for example, etching a surface of a steel plate cold rolled to a final thickness or a steel plate of an intermediate step to form a groove, or forming a product plate A method of irradiating an electron beam or a laser beam on the surface of the steel plate can be used.
表１に示した種々の成分組成を有するスラブを、１２００℃に再加熱した後、熱間圧延して板厚２．２ｍｍの熱延板とし、１０５０℃×３０秒の熱延板焼鈍を施した後、１回目の冷間圧延で中間板厚１．８ｍｍとし、１０５０℃×１２０秒の中間焼鈍を施した後、２回目の冷間圧延で最終板厚０．２０ｍｍの冷延板とした。
その後、脱炭焼鈍を兼ねた一次再結晶焼鈍を施した。ここで、上記一次再結晶焼鈍における脱炭処理は、Ｈ２：５５ｖｏｌ％＋Ｎ２：４５ｖｏｌ％、露点５０℃の雰囲気下で、８５０℃×１００秒間保持する条件で行った。
なお、それぞれのコイルについて、一次再結晶粒の平均粒径を、ＪＩＳ Ｇ０５５１に規定された計数法で測定したところ、成分の違いなどにより、表１に示す違いが生じていた。
次いで、上記一次再結晶焼鈍後の鋼板表面に、ＭｇＯを主体とし、硫酸Ｍｇを、表１に示す量を添加した焼鈍分離剤を塗布・乾燥した後、Ｎ２ガス雰囲気下で、昇温速度１５℃／ｈｒで加熱し、１１６０℃×５ｈｒの均熱処理する仕上焼鈍を施した。
次いで、上記仕上焼鈍後の鋼板表面に、リン酸塩系の絶縁張力コーティングを塗布し、焼付と形状矯正を兼ねた平坦化焼鈍を施して方向性電磁鋼板の製品板とした。
The slabs having various component compositions shown in Table 1 are reheated to 1200 ° C. and then hot rolled to form a hot-rolled sheet having a thickness of 2.2 mm and subjected to hot-rolled sheet annealing at 1050 ° C. × 30 seconds Then, after making the thickness of the intermediate plate 1.8 mm in the first cold rolling, subjected to intermediate annealing at 1050 ° C × 120 seconds, it was made a cold-rolled sheet with a final thickness 0.20 mm in the second cold rolling .
Then, the primary recrystallization annealing which served as decarburization annealing was given. Here, the decarburizing treatment in the primary recrystallization annealing was performed under the condition of holding at 850 ° C. for 100 seconds under an atmosphere of H 2 : 55 vol% + N 2 : 45 vol% and a dew point of 50 ° C.
In addition, when the average particle diameter of primary recrystallized grain was measured by the counting method prescribed | regulated to JIS G0551 about each coil, the difference shown in Table 1 had arisen by the difference of a component, etc.
Then, after applying and drying an annealing separator to the surface of the steel sheet after the above primary recrystallization annealing, to which MgO is mainly added and Mg sulfate is added in the amount shown in Table 1, the temperature rising rate is under N 2 gas atmosphere It heated at 15 ° C./hr and was subjected to finish annealing for soaking at 1160 ° C. × 5 hr.
Next, a phosphate-based insulation tension coating was applied to the surface of the steel sheet after the above-described finish annealing, and flattening annealing was carried out which also performed baking and shape correction, to obtain a product sheet of a grain-oriented electrical steel sheet.
上記のようにして得た製品板から、試験片を採取し、ＪＩＳ Ｃ２５５６に規定された方法で磁気特性（磁束密度Ｂ８、鉄損Ｗ１７／５０）を測定し、その測定結果を、表１中に併記した。表１から、一次再結晶粒の平均粒径ｄと焼鈍分離剤中のＳ含有量ｓの比（ｓ／ｄ）×１００が２．０〜１２．０の範囲にある場合に良好な磁気特性が得られていることがわかる。 Test pieces are collected from the product plate obtained as described above, and magnetic characteristics (magnetic flux density B 8 , iron loss W 17/50 ) are measured by the method defined in JIS C2556, and the measurement results are shown in the table. It is written together in 1. From Table 1, when the ratio (s / d) x 100 of the average particle diameter d of the primary recrystallized grains and the S content s in the annealing separator is in the range of 2.0 to 12.0, good magnetic properties It can be seen that
表２に示した種々の成分組成を有するスラブを、１２００℃に再加熱した後、熱間圧延して板厚２．２ｍｍの熱延板とし、１０５０℃×３０秒の熱延板焼鈍を施した後、１回目の冷間圧延で中間板厚１．７ｍｍとし、１０５０℃×１２０秒の中間焼鈍を施した後、２回目の冷間圧延で最終板厚０．２０ｍｍの冷延板とした。
その後、脱炭焼鈍を兼ねた一次再結晶焼鈍を施した。ここで、上記一次再結晶焼鈍における脱炭処理は、Ｈ２：５５ｖｏｌ％＋Ｎ２：４５ｖｏｌ％、露点５０℃の雰囲気下で、８５０℃×１００秒間保持する条件で行った。
なお、それぞれのコイルについて、一次再結晶粒の平均粒径を、ＪＩＳ Ｇ０５５１に規定された計数法で測定したところ、成分の違いなどにより、表２に示す違いが生じていた。
次いで、上記一次再結晶焼鈍後の鋼板表面に、ＭｇＯを主体とし、硫酸塩や硫化物を表２に示す量で添加した焼鈍分離剤を塗布・乾燥した後、Ｎ２ガス雰囲気下で、昇温速度１５℃／ｈｒで加熱し、１１６０℃×５ｈｒの均熱処理する仕上焼鈍を施した。
次いで、上記仕上焼鈍後の鋼板表面に、リン酸塩系の絶縁張力コーティングを塗布し、焼付と形状矯正を兼ねた平坦化焼鈍を施して方向性電磁鋼板の製品板とした。
The slabs having various component compositions shown in Table 2 are reheated to 1200 ° C. and hot rolled to form a hot-rolled sheet having a thickness of 2.2 mm and subjected to hot-rolled sheet annealing at 1050 ° C. × 30 seconds. Then, after making the thickness of the intermediate plate 1.7 mm in the first cold rolling, subjected to intermediate annealing at 1050 ° C × 120 seconds, it was made a cold-rolled plate with a final thickness 0.20 mm in the second cold rolling .
Then, the primary recrystallization annealing which served as decarburization annealing was given. Here, the decarburizing treatment in the primary recrystallization annealing was performed under the condition of holding at 850 ° C. for 100 seconds under an atmosphere of H 2 : 55 vol% + N 2 : 45 vol% and a dew point of 50 ° C.
In addition, when the average particle diameter of primary recrystallized grain was measured by the counting method prescribed | regulated to JIS G0551 about each coil, the difference shown in Table 2 had arisen by the difference of a component, etc.
Then, after applying and drying an annealing separator which is mainly composed of MgO and to which sulfates and sulfides are added in the amount shown in Table 2 on the steel sheet surface after the above primary recrystallization annealing, it is raised under N 2 gas atmosphere It heated at a temperature rate of 15 ° C./hr and was subjected to finish annealing for soaking at 1160 ° C. × 5 hr.
Next, a phosphate-based insulation tension coating was applied to the surface of the steel sheet after the above-described finish annealing, and flattening annealing was carried out which also performed baking and shape correction, to obtain a product sheet of a grain-oriented electrical steel sheet.
上記のようにして得た製品板から、試験片を採取し、ＪＩＳ Ｃ２５５６に規定された方法で磁気特性（磁束密度Ｂ８、鉄損Ｗ１７／５０）を測定し、その測定結果を、表２中に併記した。表２から、Ｓｒ，Ｍｇ，Ｃａ，Ｂａ，Ｔｉ，ＳｂおよびＳｎの硫酸塩ならびに硫化物のいずれか１種以上を添加した場合でも、一次再結晶粒の平均粒径ｄと焼鈍分離剤中のＳ含有量ｓの比（ｓ／ｄ）×１００が２．０〜１２．０の範囲にある場合に良好な磁気特性が得られていることがわかる。 Test pieces are collected from the product plate obtained as described above, and magnetic characteristics (magnetic flux density B 8 , iron loss W 17/50 ) are measured by the method defined in JIS C2556, and the measurement results are shown in the table. It is written together in 2. From Table 2, even when any one or more of Sr, Mg, Ca, Ba, Ti, Sb and Sn sulfates and sulfides are added, the average grain diameter d of primary recrystallized grains and the content in the annealing separator It can be seen that good magnetic characteristics are obtained when the ratio (s / d) × 100 of the S content s is in the range of 2.0 to 12.0.
表３に示した種々の成分組成を有するスラブを、１２００℃に再加熱した後、熱間圧延して板厚１．７ｍｍの熱延板とし、１０３０℃×３０秒の熱延板焼鈍を施した後、１回目の冷間圧延で中間板厚１．５ｍｍとし、１０５０℃×１２０秒の中間焼鈍を施した後、２回目の冷間圧延で最終板厚０．１８ｍｍの冷延板とした。
その後、脱炭焼鈍を兼ねた一次再結晶焼鈍を施した。ここで、上記一次再結晶焼鈍における脱炭処理は、Ｈ２：５５ｖｏｌ％＋Ｎ２：４５ｖｏｌ％、露点５０℃の雰囲気下で、８５０℃×１００秒間保持する条件で行った。
なお、それぞれのコイルについて、一次再結晶粒の平均粒径を、ＪＩＳ Ｇ０５５１に規定された計数法で測定したところ、成分の違いなどにより、表３に示す違いが生じていた。
次いで、上記一次再結晶焼鈍後の鋼板表面に、ＭｇＯを主体とし、硫酸マグネシウムを、表３に示す量を添加した焼鈍分離剤を塗布・乾燥した後、Ｎ２ガス雰囲気下で、昇温速度１５℃／ｈｒで加熱し、１１６０℃×５ｈｒの均熱処理する仕上焼鈍を施した。
次いで、上記仕上焼鈍後の鋼板表面に、リン酸塩系の絶縁張力コーティングを塗布し、焼付と形状矯正を兼ねた平坦化焼鈍を施して方向性電磁鋼板の製品板とした。
さらに、上記絶縁被膜被成後の鋼板表面に、電子ビーム照射による磁区細分化処理を施し、方向性電磁鋼板の製品板とした。なお、電子ビームの照射は、鋼板の片表面に、加速電圧１００ｋＶ、ビーム電流３ｍＡの条件で、圧延方向の照射間隔を５ｍｍとして、圧延直角方向に連続照射した。
The slabs having various component compositions shown in Table 3 are reheated to 1200 ° C. and then hot-rolled to form a hot-rolled sheet having a thickness of 1.7 mm and subjected to hot-rolled sheet annealing at 1030 ° C. × 30 seconds Then, after making the thickness of the intermediate plate 1.5 mm in the first cold rolling, subjected to intermediate annealing at 1050 ° C × 120 seconds, and made a cold-rolled sheet with a final thickness of 0.18 mm in the second cold rolling .
Then, the primary recrystallization annealing which served as decarburization annealing was given. Here, the decarburizing treatment in the primary recrystallization annealing was performed under the condition of holding at 850 ° C. for 100 seconds under an atmosphere of H 2 : 55 vol% + N 2 : 45 vol% and a dew point of 50 ° C.
In addition, when the average particle diameter of primary recrystallized grain was measured by the counting method prescribed | regulated to JIS G0551 about each coil, the difference shown in Table 3 had arisen by the difference of a component, etc.
Then, an annealing separator containing mainly MgO and magnesium sulfate in an amount shown in Table 3 is applied to the steel sheet surface after the above primary recrystallization annealing and dried, and then the temperature rising rate is performed under an N 2 gas atmosphere. It heated at 15 ° C./hr and was subjected to finish annealing for soaking at 1160 ° C. × 5 hr.
Next, a phosphate-based insulation tension coating was applied to the surface of the steel sheet after the above-described finish annealing, and flattening annealing was carried out which also performed baking and shape correction, to obtain a product sheet of a grain-oriented electrical steel sheet.
Further, the surface of the steel plate after the formation of the insulating coating is subjected to magnetic domain fragmentation treatment by electron beam irradiation to obtain a product plate of a directional electromagnetic steel plate. The irradiation of the electron beam was continuously performed in the direction perpendicular to rolling on the surface of one side of the steel plate under the conditions of an acceleration voltage of 100 kV and a beam current of 3 mA with an irradiation interval of 5 mm in the rolling direction.
上記のようにして得た製品板から、試験片を採取し、ＪＩＳ Ｃ２５５６に規定された方法で磁気特性（磁束密度Ｂ８、鉄損Ｗ１７／５０）を測定し、その測定結果を、表３中に併記した。表３から、本発明に適合する成分組成を有する鋼素材を用い、本発明に適合する方法で製造した方向性電磁鋼板は、優れた磁気特性を有することがわかる。 Test pieces are collected from the product plate obtained as described above, and magnetic characteristics (magnetic flux density B 8 , iron loss W 17/50 ) are measured by the method defined in JIS C2556, and the measurement results are shown in the table. It was written in 3 together. It can be seen from Table 3 that a grain-oriented electrical steel sheet manufactured by a method compatible with the present invention using a steel material having a component composition compatible with the present invention has excellent magnetic properties.
表４に示した種々の成分組成を有するスラブを、１２００℃に再加熱した後、熱間圧延して板厚１．９ｍｍの熱延板とし、１０００℃×３０秒の熱延板焼鈍を施した後、１回の冷間圧延により最終板厚０．２３ｍｍの冷延板とした。次いで、表４に示したように、上記冷延板の一部の鋼板表面（片面）に、圧延方向に対して直角方向に、幅：１８０μｍ×深さ：１５μｍの溝を圧延方向に５ｍｍ間隔で形成する磁区細分化処理を施した。その後、脱炭焼鈍を兼ねた一次再結晶焼鈍を施した。ここで、上記一次再結晶焼鈍における脱炭処理は、Ｈ２：５５ｖｏｌ％＋Ｎ２：４５ｖｏｌ％、露点５０℃の雰囲気下で、８５０℃×１００秒間保持する条件で行った。
次いで、上記一次再結晶焼鈍後の鋼板表面に、ＭｇＯを主体とし、硫酸マグネシウムを、表４に示す量を添加した焼鈍分離剤を塗布・乾燥した後、Ｎ２ガス雰囲気下で、昇温速度１５℃／ｈｒで加熱し、１１６０℃×５ｈｒの均熱処理する仕上焼鈍を施した。
次いで、上記仕上焼鈍後の鋼板表面に、リン酸塩系の絶縁張力コーティングを塗布し、焼付と形状矯正を兼ねた平坦化焼鈍を施して方向性電磁鋼板の製品板とした。
The slabs having various component compositions shown in Table 4 are reheated to 1200 ° C. and then hot-rolled to form a hot-rolled sheet having a thickness of 1.9 mm and subjected to hot-rolled sheet annealing at 1000 ° C. × 30 seconds Then, a cold-rolled sheet with a final thickness of 0.23 mm was formed by one cold rolling. Next, as shown in Table 4, on the surface (one side) of a part of the steel sheet (one side) of the cold-rolled sheet, grooves with a width of 180 μm and a depth of 15 μm are separated by 5 mm in the rolling direction Domain refinement processing to be formed. Then, the primary recrystallization annealing which served as decarburization annealing was given. Here, the decarburizing treatment in the primary recrystallization annealing was performed under the condition of holding at 850 ° C. for 100 seconds under an atmosphere of H 2 : 55 vol% + N 2 : 45 vol% and a dew point of 50 ° C.
Then, an annealing separator containing mainly MgO and magnesium sulfate in an amount shown in Table 4 is coated and dried on the steel sheet surface after the above primary recrystallization annealing, and then the temperature rising rate is performed under an N 2 gas atmosphere. It heated at 15 ° C./hr and was subjected to finish annealing for soaking at 1160 ° C. × 5 hr.
Next, a phosphate-based insulation tension coating was applied to the surface of the steel sheet after the above-described finish annealing, and flattening annealing was carried out which also performed baking and shape correction, to obtain a product sheet of a grain-oriented electrical steel sheet.
上記のようにして得た製品板から、試験片を採取し、ＪＩＳ Ｃ２５５６に規定された方法で磁気特性（磁束密度Ｂ８、鉄損Ｗ１７／５０）を測定し、その測定結果を、表４中に併記した。表４から、本発明に適合する成分組成を有する鋼素材を用い、本発明に適合する方法で製造した方向性電磁鋼板は、磁区細分化処理の有無にかかわらず優れた磁気特性を有することがわかる。 Test pieces are collected from the product plate obtained as described above, and magnetic characteristics (magnetic flux density B 8 , iron loss W 17/50 ) are measured by the method defined in JIS C2556, and the measurement results are shown in the table. I wrote it in 4 together. From Table 4, it is found that a grain-oriented electrical steel sheet manufactured by a method compatible with the present invention using a steel material having a component composition compatible with the present invention has excellent magnetic properties regardless of the presence or absence of magnetic domain refining treatment Recognize.
Claims (2)
上記冷延板の最終板厚を０．２０ｍｍ以下とし、
上記一次再結晶焼鈍後の結晶粒の平均粒径ｄを１０〜２５μｍとし、
上記焼鈍分離剤として、Ｓｒ，Ｍｇ，Ｃａ，Ｂａ，Ｔｉ，ＳｂおよびＳｎの硫酸塩ならびに硫化物のうちから選ばれる１種または２種以上を、Ｓ含有量ｓで０．２〜２ｍａｓｓ％の範囲で含有し、かつ、上記Ｓ含有量ｓと上記ｄが下記式を満たすものを用いることを特徴とする方向性電磁鋼板の製造方法。
記
２．０≦（ｓ／ｄ）×１００≦１２．０ C: 0.08 mass% or less, Si: 4.5 mass% or less, Mn: 0.5 mass% or less, sol. Al: less than 0.0100 mass%, N: less than 0.0100 mass%, S: not more than 0.0100 mass%, Se: not more than 0.0100 mass% and O: not more than 0.0050 mass%, the balance being Fe and unavoidable impurities The steel slab having the component composition comprising the following composition was hot-rolled to form a hot-rolled sheet, and cold-rolled to a final thickness by cold-rolling once or twice or more with intermediate In a method of manufacturing a grain-oriented electrical steel sheet comprising a series of steps of: primary recrystallization annealing; applying an annealing separator mainly composed of MgO;
The final thickness of the cold rolled sheet is 0.20 mm or less ,
The average grain diameter d of the crystal grains after the above primary recrystallization annealing is set to 10 to 25 μm,
As the above-mentioned annealing separator, one or two or more selected from sulfates and sulfides of Sr, Mg, Ca, Ba, Ti, Sb and Sn, with S content s of 0.2 to 2 mass% A method for producing a grain-oriented electrical steel sheet, characterized in that the material is contained in a range, and the S content s and the d satisfy the following formula.
Description 2.0 ≦ (s / d) × 100 ≦ 12.0
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