JPH11152516A - Manufacture of grain oriented silicon steel sheet - Google Patents
Manufacture of grain oriented silicon steel sheetInfo
- Publication number
- JPH11152516A JPH11152516A JP9314779A JP31477997A JPH11152516A JP H11152516 A JPH11152516 A JP H11152516A JP 9314779 A JP9314779 A JP 9314779A JP 31477997 A JP31477997 A JP 31477997A JP H11152516 A JPH11152516 A JP H11152516A
- Authority
- JP
- Japan
- Prior art keywords
- annealing
- compound
- steel sheet
- weight
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、主として変圧器そ
の他の電気機器の鉄芯として利用される方向性電磁鋼板
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a grain-oriented electrical steel sheet mainly used as an iron core of a transformer or other electric equipment.
【０００２】[0002]
【従来の技術】方向性電磁鋼板は、磁気鉄芯として多く
の電気機器に利用されている。方向性電磁鋼板は、製品
の結晶方位を｛１１０｝＜００１＞方位（ＧＯＳＳ 方
位とも称される) に高度に集積させたものである。方向
性電磁鋼板の製造技術には古くて永い歴史がある。N.P.
Gossによる日本特許第１２９４０９号（昭和１３年公告
第５０４６号，米国特許１９６５５５９号) において、
熱延板に対して、焼鈍をはさむ二回冷延と続く、高温仕
上焼鈍によって方向性電磁鋼板が造れることが開示され
た。しかしながら、この当時、Ｓｉ以外の成分組成の制
御、鉄損を改善する脱炭焼鈍および仕上バッチ焼鈍のた
めの焼鈍分離剤塗布の考えは無かったようである。その
後、V.W.Carpenter による米国特許第２２８７４６６号
で、仕上焼鈍前のＣ量を低く制限することが、ＧＯＳＳ
方位の形成に有利であることが発見され、脱炭の手段と
して熱延板のミルスケール付きのままの焼鈍（スケール
脱炭）が提案された。彼は、バッチの脱炭焼鈍で０．０
１％以下のＣ量を確認している。2. Description of the Related Art Oriented magnetic steel sheets are used as magnetic iron cores in many electric appliances. A grain-oriented electrical steel sheet is a product in which the crystal orientation of a product is highly integrated in a {110} <001> orientation (also referred to as a GOSS orientation). The production technology of grain-oriented electrical steel sheets has an old and long history. NP
In Japanese Patent No. 129409 by Goss (No. 5046 published in 1938, U.S. Pat. No. 1,965,559),
It has been disclosed that a grain-oriented electrical steel sheet can be produced by performing high-temperature finish annealing, followed by twice cold rolling including annealing on a hot-rolled sheet. However, at this time, there seems to be no idea of controlling the composition of components other than Si, decarburizing annealing for improving iron loss, and applying an annealing separator for finish batch annealing. Subsequently, in US Patent No. 2,287,466 to VW Carpenter, it was proposed to limit the amount of carbon before finish annealing to a low value by GOSS.
It was found to be advantageous for forming the orientation, and as a means of decarburization, annealing of a hot-rolled sheet with mill scale (scale decarburization) was proposed. He found that the decarburizing annealing of the batch was 0.0
A C content of 1% or less has been confirmed.
【０００３】今日のような冷延後の鋼板を連続焼鈍で脱
炭する最初の特許は、V.W.Carpenter による米国特許第
２２８７４６７号であろう。更に、V.W.Carpenter 等
は、日本特許第１９６２４４号（特公昭２７−２４０９
号，米国特許第２４９２６８２号）において、最終冷延
板を脱炭焼鈍するに際して、鋼板表層にシリカを形成さ
せてから、焼鈍隔離剤マグネシヤを塗布し、続く、高温
のバッチ焼鈍（仕上焼鈍の意味）においてシリカと酸化
マグネシュウムを反応させフォルステライトを絶縁皮膜
となす、脱炭焼鈍、焼鈍分離剤と絶縁皮膜の組み合わせ
発明を開示した。この脱炭焼鈍を省略した場合、皮膜の
形成に悪影響があるだけでなく、仕上焼鈍では炭素量が
むらがあると記載されている。The first patent to decarburize a cold rolled steel sheet by continuous annealing, such as today, would be US Pat. No. 2,287,467 to VW Carpenter. Further, VW Carpenter et al. Discloses Japanese Patent No. 196244 (Japanese Patent Publication No. 27-2409).
No. 2,492,682), when decarburizing and annealing the final cold-rolled sheet, silica is formed on the surface layer of the steel sheet, and then an annealing separator magnesium is applied, followed by high-temperature batch annealing (meaning of finish annealing). ) Discloses a decarburizing annealing, a combined invention of an annealing separator and an insulating film, wherein silica and magnesium oxide are reacted to form forsterite as an insulating film. It is described that omitting the decarburizing annealing not only adversely affects the formation of the film, but also results in an uneven carbon content in the finish annealing.
【０００４】現在、工業化されている方向性電磁鋼板の
製造プロセスは、最終冷延板を脱炭焼鈍させてから、表
層に薄いシリカ主体の層を形成させ、酸化マグネシュウ
ム主体のコーティングを施し、仕上焼鈍でフォルステラ
イトを生成させるこの発明方法が採用されている。この
脱炭焼鈍は、通常、最終冷延の０．１〜０．６mm厚で、
７００〜９００℃の温度で湿潤水素・窒素気流中で１〜
５分実施されるものである。しかしながら、連続焼鈍炉
で均熱時間を１〜５分とすることは、炉長を長くする必
要があるし、また、生産性にも問題があったため、脱炭
焼鈍工程を省略することが長年の課題であった。At present, the manufacturing process of grain-oriented electrical steel sheets, which has been industrialized, is to decarburize the final cold-rolled sheet, form a thin layer mainly composed of silica on the surface layer, apply a coating mainly composed of magnesium oxide, and finish the coating. The method of the present invention in which forsterite is formed by annealing is employed. This decarburization annealing is usually 0.1 to 0.6 mm thick of the final cold rolling,
In a wet hydrogen / nitrogen stream at a temperature of 700 to 900 ° C,
Run for 5 minutes. However, setting the soaking time in a continuous annealing furnace to 1 to 5 minutes requires a longer furnace length, and also has a problem in productivity. Was an issue.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記の点に鑑
み、現行の脱炭焼鈍を実施するプロセスで製造された品
質特性を維持または改善させて、且つ、最終冷延後に採
用されて来た脱炭焼鈍を省略するプロセスを提供し、製
造コストを低減するものである。SUMMARY OF THE INVENTION In view of the above, the present invention maintains or improves the quality characteristics produced by current decarburization annealing processes and has been employed after final cold rolling. It is intended to provide a process for omitting the decarburization annealing and reduce the production cost.
【０００６】[0006]
【課題を解決するための手段】本発明の要旨は、以下の
通りである◎ （１） 通常の方向性電磁鋼板の製造方法において、熱
延板に焼鈍を施すか或いは施すことなく、中間焼鈍をは
さむ二回の冷間圧延により所定の製品板厚とし、成分組
成が重量％で、 Ｃ ：０．００５〜０．０６％、 Ｓｉ：２〜４％、 Ａｌ≦０．０１％、 Ｍｎ：０．０３〜０．２％、 Ｓ又はＳｅ：０．０１〜０．０４％、Ｎ ≦０．０１％ を含有し、残部が実質的にＦｅである冷延板に対して、
脱炭焼鈍を実施することなしに、アルミナを主成分とし
て、Ｃａ化合物又はＮａ化合物の一種或いは二種を０．
５〜３０重量％、Ｓｂ化合物又はＳｒ化合物の一種或い
は二種を０．０２〜１０重量％添加した焼鈍隔離剤をド
ライコーティングしてから、非酸化性雰囲気中で高温バ
ッチ焼鈍を行うことを特徴とする一次皮膜のない方向性
電磁鋼板の製造方法。SUMMARY OF THE INVENTION The gist of the present invention is as follows: (1) In a normal method for manufacturing a grain-oriented electrical steel sheet, a hot-rolled sheet is subjected to or without intermediate annealing. A predetermined product thickness is obtained by cold rolling twice, and the composition of the components is% by weight, C: 0.005 to 0.06%, Si: 2 to 4%, Al ≦ 0.01%, Mn: 0.03% to 0.2%, S or Se: 0.01% to 0.04%, N ≦ 0.01%, and the balance is substantially Fe.
Without carrying out decarburization annealing, one or two kinds of Ca compounds or Na compounds containing alumina as a main component were added.
Dry coating of an annealing separator containing 5 to 30% by weight of Sb compound or Sr compound or 0.02 to 10% by weight of one or two kinds of Sr compounds, and then performing high-temperature batch annealing in a non-oxidizing atmosphere. Method for producing a grain-oriented electrical steel sheet without a primary coating.
【０００７】（２） 前記（１）記載の冷延板が、更
に、成分組成として重量％で、 Ｃｕ≦０．３％、 Ｓｎ≦０．３、 Ｓｂ≦０．１％、 Ｍｏ≦０．２％ の一種又は二種以上を含有する請求項１記載の方向性電
磁鋼板の製造方法。(2) The cold-rolled sheet according to the above (1) further comprises Cu ≦ 0.3%, Sn ≦ 0.3, Sb ≦ 0.1%, Mo ≦ 0% by weight as a component composition. The method for producing a grain-oriented electrical steel sheet according to claim 1, wherein one or more of 2% or more are contained.
【０００８】（３） 前記（１）又は（２）記載の焼鈍
隔離剤が、更に、Ｂｉ化合物を３０重量％以下添加した
ものであることを特徴とする前記（１）又は（２）記載
の一次皮膜のない方向性電磁鋼板の製造方法。(3) The annealing separator according to (1) or (2), wherein the annealing compound according to (1) or (2) further comprises a Bi compound added in an amount of 30% by weight or less. A method for producing grain-oriented electrical steel sheets without a primary coating.
【０００９】本発明のポイントは、６点ある。第１点
は、従来のプロセスで行われてきた、湿潤水素、窒素雰
囲気中での脱炭焼鈍工程を省略することである。脱炭焼
鈍工程を省略することで、方向性電磁鋼板の生産性を向
上し、製造コストを低減することができる。なお、従来
のプロセスにおける脱炭焼鈍の目的は、Ｃ量を磁気時効
の面から０．００３％以下とすること、一次再結晶をさ
せること、鋼板表層にシリカを形成さすことにあった。There are six points of the present invention. The first point is that the decarburizing annealing step in a wet hydrogen and nitrogen atmosphere, which has been performed in the conventional process, is omitted. By omitting the decarburizing annealing step, the productivity of grain-oriented electrical steel sheets can be improved, and the manufacturing cost can be reduced. The purpose of the decarburization annealing in the conventional process was to reduce the C content to 0.003% or less from the viewpoint of magnetic aging, to perform primary recrystallization, and to form silica on the surface layer of the steel sheet.
【００１０】第２点は、高温のバッチ仕上焼鈍工程にお
いて、鋼板の純化（脱Ｃ、脱Ｓ又はＳｅ及び脱Ｎ）と一
次再結晶とを、従来行われてきた二次再結晶と不純物の
除去に加えて実施することである。The second point is that in the high-temperature batch finish annealing step, the steel sheet is purified (de-C, de-S or Se and de-N) and primary recrystallization is performed by the conventional secondary recrystallization and impurity removal. It is to be carried out in addition to the removal.
【００１１】第３点は、最終冷延後の鋼板にアルミナ隔
離剤をドライコーティングすることである。このように
すれば、バッチ仕上焼鈍で脱炭を行わせることが可能で
あり、二次再結晶も安定する。すなわち、仕上焼鈍で脱
炭を行うためには、従来の脱炭焼鈍板表層にあるような
緻密なシリカ層が鋼板表層にあってはならず、またバッ
チ仕上焼鈍中の鋼板表層にシリカや従来のフォルステラ
イトなどの酸化層があってはならない。The third point is that the steel sheet after final cold rolling is dry-coated with an alumina sequestering agent. In this manner, decarburization can be performed by batch finish annealing, and secondary recrystallization is also stabilized. In other words, in order to perform decarburization by finish annealing, a dense silica layer as in the surface layer of a conventional decarburized annealed sheet must not be present on the surface layer of the steel sheet. There should be no oxide layer such as forsterite.
【００１２】第４点は、上記アルミナ隔離剤に脱Ｓ又は
Ｓｅ促進剤を添加することである。隔離剤にアルミナの
みを用いた場合の難点は、鋼板の脱Ｓ又はＳｅが不十分
となり、鉄損が劣化することである。この対策として、
本発明では脱Ｓ又はＳｅ促進剤として、例えばＣａＯや
Ｎａ2 Ｏを添加して脱Ｓ又はＳｅを行う。The fourth point is that a de-S or Se accelerator is added to the above-mentioned alumina sequestering agent. A disadvantage when only alumina is used as the isolating agent is that the removal of S or Se from the steel sheet becomes insufficient, and iron loss deteriorates. As a measure against this,
In the present invention, S or Se is removed by adding, for example, CaO or Na 2 O as a S or Se promoter.
【００１３】第５点は、上記アルミナ隔離剤にＳｂ又は
Ｓｒ化合物を微量添加して、鋼板の磁気特性を向上させ
ていることである。The fifth point is that a small amount of a Sb or Sr compound is added to the above-mentioned alumina sequestrant to improve the magnetic properties of the steel sheet.
【００１４】第６点は、上記アルミナ隔離剤にＢｉ化合
物の添加して、鋼板表面を鏡面にし、鉄損を改善させて
いることである。The sixth point is that a Bi compound is added to the above-mentioned alumina sequestering agent to make the surface of the steel sheet a mirror surface and improve iron loss.
【００１５】[0015]
【発明の実施の形態】以下、本発明の限定理由について
説明する。先ず、鋼成分について説明する。最終冷延板
のＣ量は、０．００５〜０．０６％に制限する。最終冷
延板のＣ量は、０．００５％未満並びに０．０６％を超
えると二次再結晶不良となる。このため、最終冷延板の
Ｃを０．００５〜０．０６％とする。この最終冷延板の
Ｃ量は、従来プロセスのＣ量とほとんど同じである。な
お、スラブでのＣ量は、とくに制限するものでないが、
従来の０．０２〜０．１％が好ましい。また、製品のＣ
量は、０．００３％以下が従来通り好ましい。０．００
３％超では、磁気時効の問題があるからである。DESCRIPTION OF THE PREFERRED EMBODIMENTS The reasons for limiting the present invention will be described below. First, the steel composition will be described. The C content of the final cold rolled sheet is limited to 0.005 to 0.06%. If the C content of the final cold-rolled sheet is less than 0.005% or more than 0.06%, secondary recrystallization failure occurs. For this reason, C of the final cold rolled sheet is set to 0.005 to 0.06%. The C content of this final cold rolled sheet is almost the same as the C content of the conventional process. In addition, although the amount of C in the slab is not particularly limited,
Conventionally, 0.02 to 0.1% is preferable. The product C
The amount is preferably 0.003% or less conventionally. 0.00
If it exceeds 3%, there is a problem of magnetic aging.
【００１６】Ｓｉ量は、２〜４％とする。Ｓｉは鋼板の
固有抵抗を増やしてうず電流損を低減させるのに有効で
ある。下限を２％とするのは、２％未満ではα−γ変態
を高温仕上焼鈍中に生じるためＧｏｓｓ方位が形成され
ないし、変態を避けるため仕上焼鈍を低温で実施すれば
不純物の除去に長時間をかけざるを得なくなり工業的で
ない。また、４％を超えると冷延での破断や電気部品へ
の打抜き工程での割れの問題が大きくなる。このため、
Ｓｉ量は、２〜４％に制限する。The amount of Si is set to 2 to 4%. Si is effective for increasing the specific resistance of the steel sheet to reduce eddy current loss. When the lower limit is set to 2%, if less than 2%, the α-γ transformation occurs during the high-temperature finish annealing, so that the Goss orientation is not formed. Is not industrial. On the other hand, if it exceeds 4%, the problem of breakage in cold rolling and cracking in the step of punching an electric component will increase. For this reason,
The amount of Si is limited to 2 to 4%.
【００１７】Ａｌ量は、０．０１％以下に制限する。Ａ
ｌが、０．０１％超では二次再結晶不良となるので避け
る。The amount of Al is limited to 0.01% or less. A
If l exceeds 0.01%, secondary recrystallization failure will occur, so avoid it.
【００１８】Ｍｎ量は、０．０３〜０．２％とする。Ｍ
ｎは、ＭｎＳを二次再結晶に利用するため必須である。
Ｍｎが、０．０３％未満と０．２％超では二次再結晶が
不安定なので避ける。The amount of Mn is 0.03 to 0.2%. M
n is essential for utilizing MnS for secondary recrystallization.
If Mn is less than 0.03% or more than 0.2%, secondary recrystallization is unstable and is avoided.
【００１９】Ｓ量は、０．０１〜０．０４％に制限す
る。Ｓは，ＭｎＳとして二次再結晶に利用するので有効
であるが、０．０１％未満並びに、０．０４％超では二
次再結晶が不安定となるので避けなければならない。The amount of S is limited to 0.01 to 0.04%. S is effective because it is used for secondary recrystallization as MnS, but if it is less than 0.01% or more than 0.04%, the secondary recrystallization becomes unstable and must be avoided.
【００２０】Ｓｅ量は、０．０１〜０．０４％に制限す
る。Ｓｅは，ＭｎＳｅとして二次再結晶に利用するので
有効であるが、０．０１％未満並びに、０．０４％超で
は二次再結晶が不安定となるので避けなければならな
い。なお、公知の如く、ＳとＳｅの併用は二次再結晶の
不安定化を招くいため、Ｓ或いはＳｅの単独添加が好ま
しい。The Se content is limited to 0.01 to 0.04%. Se is effective because it is used for secondary recrystallization as MnSe, but if it is less than 0.01% or more than 0.04%, the secondary recrystallization becomes unstable and must be avoided. As is well known, the combined use of S and Se causes instability of the secondary recrystallization, so that S or Se alone is preferably added.
【００２１】Ｎ量は、０．０１％以下に制限する。０．
０１％超ではブリスターと称されるＮ2 ガスによる鋼板
表面のふくれが生じるので避けなければならない。The amount of N is limited to 0.01% or less. 0.
If the content exceeds 01%, blisters on the steel sheet surface due to N 2 gas called blister must be avoided.
【００２２】Ｃｕは、公知のＣｕx Ｓを二次再結晶に利
用するのに有効であるため必要に応じて添加するが、
０．３％超では添加コストの問題があるので、０．３％
以下とする。Cu is added as necessary because it is effective for utilizing known Cu x S for secondary recrystallization.
If it exceeds 0.3%, there is a problem of addition cost.
The following is assumed.
【００２３】Ｓｎは、必要に応じて添加するが、その添
加量は０．３％以下に制限する。Ｓｎは、粒界偏析型の
元素として二次再結晶の安定化に有効であるが、添加量
が多くなると、熱延板での耳割れが大きくなるので上限
を０．３％とする。Sn is added as needed, but its amount is limited to 0.3% or less. Sn is effective as a grain boundary segregation type element for stabilizing secondary recrystallization, but when the addition amount is large, the edge cracks in the hot-rolled sheet become large, so the upper limit is made 0.3%.
【００２４】Ｓｂは、必要に応じて添加するが、その添
加量は０．１％以下に制限する。Ｓｂも粒界偏析型の元
素として二次再結晶の安定化に有効であるが、添加量が
多くなりすぎると、熱延板表面で擦り傷状の欠陥が多く
なるので、上限を０．１％とする。Sb is added as needed, but its amount is limited to 0.1% or less. Sb is also effective for stabilizing secondary recrystallization as a grain boundary segregation type element. However, if the addition amount is too large, scratch-like defects increase on the hot rolled sheet surface, so the upper limit is 0.1%. And
【００２５】Ｍｏ量は、必要に応じて添加するが、その
添加量は０．２％以下に制限する。ＭｏはＳｂやＳｅを
添加した系での熱延でのへげ疵を低減するのに効果があ
るが、添加量が多くなると添加コストの問題があるため
０．２％以下とする。The amount of Mo is added as needed, but the amount is limited to 0.2% or less. Mo is effective in reducing the flaws caused by hot rolling in a system to which Sb or Se is added. However, if the amount of Mo increases, there is a problem in the cost of addition.
【００２６】なお、上記Ｃｕ，Ｓｎ，Ｓｂ，Ｍｏは一種
のみ添加してもよいし、二種以上を複合添加するように
してもよい。The above Cu, Sn, Sb and Mo may be added alone or in combination of two or more.
【００２７】次に、本発明のプロセスについて説明す
る。熱延は、公知の条件で行う。スラブ加熱温度は、通
常の１２５０〜１４５０℃である。Next, the process of the present invention will be described. Hot rolling is performed under known conditions. The slab heating temperature is usually 1250-1450 ° C.
【００２８】熱延板の焼鈍は、二次再結晶の安定化に効
果があるが、焼鈍コストがかかるので必要に応じて行え
ばよい。熱延板焼鈍を行う場合の焼鈍温度は、公知の８
００〜１２００℃で行えばよく、一般的な連続焼鈍で行
ってもよい。このとき、公知のスケール脱炭、若しく
は、酸化雰囲気で脱炭させることも可能である。Annealing of the hot-rolled sheet is effective in stabilizing the secondary recrystallization, but annealing cost is high, so it may be performed as needed. The annealing temperature when performing hot-rolled sheet annealing is a known 8
It may be carried out at 00 to 1200 ° C., and may be carried out by general continuous annealing. At this time, it is also possible to perform decarburization in a known scale or in an oxidizing atmosphere.
【００２９】続いて行う冷延工程は、中間焼鈍を挟む２
回の冷延で行う。冷延工程は、少なくとも１パスにおい
て、公知の１００〜４００℃の温間圧延を行ってもよ
い。中間焼鈍は、通常の連続焼鈍で温度は７００〜１１
００℃で行う。中間焼鈍の雰囲気は、通常の水素窒素混
合雰囲気で行えばよく、ドライでもウエットでもよい。The subsequent cold-rolling step is carried out by sandwiching the intermediate annealing 2
Perform cold rolling. In the cold rolling step, known hot rolling at 100 to 400 ° C. may be performed in at least one pass. Intermediate annealing is performed by ordinary continuous annealing at a temperature of 700-11.
Perform at 00 ° C. The atmosphere for the intermediate annealing may be performed in a normal hydrogen-nitrogen mixed atmosphere, and may be dry or wet.
【００３０】この冷延工程によって鋼板は所定の製品板
厚とされるが、本発明における製品板厚は通常の０．１
〜０．６mmである。また、最終冷延はレバース圧延でも
タンデム圧延でも可能であるが、レバース圧延のほうが
得られる製品磁束密度が少し高いので好ましく、温間圧
延を実施することも好ましい。なお、従来は最終冷延に
続いて脱炭のための連続焼鈍が行われてきたが、本発明
ではこれを省略して生産性を向上し、製造コストの低減
を図る。The steel sheet is made to have a predetermined product thickness by the cold rolling process.
０．６0.6 mm. Further, the final cold rolling can be performed by reversal rolling or tandem rolling, but reversing rolling is preferable because the obtained product magnetic flux density is slightly higher, and warm rolling is also preferable. Conventionally, continuous annealing for decarburization has been performed following the final cold rolling, but this is omitted in the present invention to improve productivity and reduce manufacturing costs.
【００３１】次に、上記冷延工程によって得られた冷延
板に、焼鈍隔離剤を塗布する。通常実施される塗布前の
冷延板脱脂は、本発明では基本的には不要であるが、圧
延油の不均一性による塗布むら等の問題があれば脱脂し
ても問題はない。焼鈍隔離剤の塗布方法は、ドライコー
ティング法に限定する。具体的なドライコーティングの
方法としては、例えば、公知の特開昭５４−１０６００
９号による静電塗装の方法や、簡単な粉末の振り掛け方
式でも良い。本発明プロセスの仕上焼鈍で脱炭を促進す
るためには、鋼板表面には仕上焼鈍過程でもシリカ層を
極力形成させないことが重要であるため、スラリーでの
塗布・乾燥は不可で、水分を含まないドライコーティン
グでなければならない。Next, an annealing isolating agent is applied to the cold rolled sheet obtained in the above cold rolling step. Degreasing of a cold rolled sheet before coating, which is usually performed, is basically unnecessary in the present invention. However, if there is a problem such as coating unevenness due to uneven rolling oil, there is no problem even if degreasing. The method of applying the annealing separator is limited to the dry coating method. A specific dry coating method is described in, for example, Japanese Patent Application Laid-Open No. 54-10600.
The method of electrostatic coating according to No. 9 or a simple powder sprinkling method may be used. In order to promote decarburization in the finish annealing of the process of the present invention, it is important not to form a silica layer on the steel sheet surface as much as possible even in the finish annealing process. Not have to be a dry coating.
【００３２】焼鈍隔離剤の種類としては、続く、高温の
仕上焼鈍で鋼板表面に緻密な酸化膜を形成させないもの
が選択される。即ち、公知の酸化アルミニュウム（例え
ば、特公昭４８−１９０５０号，米国特許３７８５８８
２号参照）である。As the kind of the annealing isolating agent, one that does not form a dense oxide film on the steel sheet surface by the subsequent high-temperature finish annealing is selected. That is, a known aluminum oxide (for example, Japanese Patent Publication No. 48-19050, US Pat. No. 378588).
No. 2).
【００３３】アルミナ（酸化アルミニュウム）の粉末の
塗布量は、１〜５００ｇ／ｍ2 が好ましい。アルミナの
塗布量は、多い方が仕上焼鈍で脱Ｓ又は脱Ｓｅし易く、
１ｇ／ｍ2 未満では鋼板同士の焼き付きを防止できな
い。しかし、必要以上に多くなると塗布コストがかかる
ので５００ｇ／ｍ2 以下とする。なお、仕上焼鈍の脱炭
に関しては、アルミナを焼鈍隔離剤として使用する限
り、塗布量に依存せず問題なく行うことができる。The amount of the alumina (aluminum oxide) powder applied is preferably from 1 to 500 g / m 2 . The larger the amount of alumina applied, the easier it is to remove S or Se by finish annealing,
If it is less than 1 g / m 2 , seizure between steel sheets cannot be prevented. However, if the amount is more than necessary, the coating cost increases, so the amount is set to 500 g / m 2 or less. The decarburization in the finish annealing can be performed without any problem as long as alumina is used as the annealing separator, regardless of the coating amount.
【００３４】ここで、焼鈍隔離剤に脱Ｓ又は脱Ｓｅ促進
剤を添加すれば、薄いコーティングでも脱Ｓ又は脱Ｓｅ
を容易に起こさせることができる。添加する脱Ｓ又は脱
Ｓｅ促進剤としては、公知のＣａＯ，Ｎａ2 Ｏ等の酸化
物が有効である。また、炭酸塩やリン酸塩、硝酸塩、硼
酸塩、塩化物なども有効で、これらの一種または二種以
上の混合剤が使用できる。Ｃａ化合物またはＮａ化合物
の添加量は、０．５〜３０重量％とする。０．５重量％
未満では、仕上焼鈍での脱Ｓ又はＳｅが不足し、３０重
量％超では、添加コストの問題がある。Here, if a de-S or de-Se promoter is added to the annealing isolating agent, even a thin coating can be de-S or de-Se.
Can be easily caused. Known oxides such as CaO and Na 2 O are effective as the de-S or De-Se accelerator. In addition, carbonates, phosphates, nitrates, borates, chlorides, and the like are also effective, and one or more of these can be used. The addition amount of the Ca compound or the Na compound is 0.5 to 30% by weight. 0.5% by weight
If it is less than 30%, the removal of S or Se in the finish annealing is insufficient.
【００３５】焼鈍隔離剤には、さらにＳｂ化合物または
Ｓｒ化合物を０．０２〜１０重量％添加する。Ｓｂ化合
物またはＳｒ化合物は、磁束密度を高める働きがある。
この効果は、０．０２重量％以上の添加で得られるが、
あまり多くなると添加コストの問題があるため１０重量
％以下とする。Ｓｂ化合物またはＳｒ化合物としては、
塩化物、酸化物、硫化物、水酸化物、弗化物、硝酸塩、
硼酸塩並びにこれの混合物を用いることができる。The annealing isolating agent is further added with an Sb compound or an Sr compound in an amount of 0.02 to 10% by weight. The Sb compound or Sr compound has the function of increasing the magnetic flux density.
This effect can be obtained by adding 0.02% by weight or more,
If it is too large, there is a problem of addition cost, so the content is set to 10% by weight or less. As the Sb compound or Sr compound,
Chlorides, oxides, sulfides, hydroxides, fluorides, nitrates,
Borates and mixtures thereof can be used.
【００３６】また焼鈍隔離剤には必要に応じてＢｉ化合
物を添加するが、その添加量は３０重量％以下とする。
Ｂｉ化合物は仕上焼鈍での酸化層形成を防止して鉄損を
改善する働きがある。必要以上に添加量が多いと、添加
コストの問題があるので３０重量％以下とする。Ｂｉ化
合物としては、塩化物、酸化物、硫化物、水酸化物、弗
化物、硝酸塩、硼酸塩並びにこれの混合物を用いること
ができる以上のようにして焼鈍隔離剤を塗布した冷延板
に高温バッチ焼鈍、すなわち仕上焼鈍を行うが、仕上焼
鈍は従来の通常条件で行えばよい。即ち、通常の非酸化
雰囲気、例えば、水素、窒素混合気流中でバッチ焼鈍さ
れる。二次再結晶後のＳやＮの除去のための９００℃以
上での高温部の焼鈍は純水素中で行われる。特に、昇温
中に留意すべきことは、水分などにより鋼板表面が酸化
されると表層に酸化層が形成されて脱炭しなくなるの
で、雰囲気は非酸化性雰囲気である必要がある。脱炭作
用は、９００℃以上の高温で行われる。A Bi compound is added to the annealing separator as needed, but the amount of addition is limited to 30% by weight or less.
The Bi compound has the function of preventing the formation of an oxide layer during finish annealing and improving iron loss. If the addition amount is more than necessary, there is a problem of addition cost. As the Bi compound, chlorides, oxides, sulfides, hydroxides, fluorides, nitrates, borates and mixtures thereof can be used. Batch annealing, that is, finish annealing is performed, and the finish annealing may be performed under conventional ordinary conditions. That is, batch annealing is performed in a normal non-oxidizing atmosphere, for example, a mixed gas stream of hydrogen and nitrogen. Annealing of the high temperature portion at 900 ° C. or higher for removal of S and N after the secondary recrystallization is performed in pure hydrogen. In particular, it should be noted that the atmosphere must be a non-oxidizing atmosphere, because if the surface of the steel sheet is oxidized by moisture or the like, an oxidized layer will be formed on the surface layer and decarburization will not occur. The decarburization is performed at a high temperature of 900 ° C. or more.
【００３７】仕上焼鈍後は、焼鈍隔離剤の除去を水洗ま
たは軽酸洗で行った後、従来のセラミック系絶縁皮膜が
塗布され、この乾燥とコイルセット並びに耳波や中伸び
の形状矯正を兼ねて、連続の張力焼鈍が７００〜１００
０℃で実施される。なお、打抜き用の小型トランスや大
型回転機用として、セラミック系の皮膜に代えて、無方
向性電磁鋼板の絶縁皮膜である有機・無機混合系のコー
ティングとすることもできる。After the finish annealing, the annealing isolating agent is removed by washing with water or light acid, and then a conventional ceramic insulating film is applied. The drying and coil setting and the correction of the shape of ear waves and middle elongation are performed. And the continuous tension annealing is 700-100.
Performed at 0 ° C. It should be noted that, for a small transformer or a large rotating machine for punching, an organic / inorganic mixed coating which is an insulating coating of a non-oriented electrical steel sheet can be used instead of the ceramic coating.
【００３８】また、仕上焼鈍前または後に、磁区制御を
実施することも本発明によって得られる鋼板の鉄損を改
善する手段として有効である。It is also effective to control the magnetic domain before or after the finish annealing as a means for improving the iron loss of the steel sheet obtained by the present invention.
【００３９】[0039]
【実施例】以下、本発明の実施例について説明する。 ［実施例１］重量％で、Ｃ：０．０６３％，Ｓｉ：２．
５％，Ｍｎ：０．０７％，Ｓｅ：０．０３％，Ｓ：０．
００１１％，Ｎ：０．００４％，Ａｌ：０．００５％，
Ｓｂ：０．０３％，Ｍｏ：０．１％を含み残部が実質的
にＦｅからなるスラブを、１４２０℃に加熱して、２．
３mm厚の熱延板とした。次に熱延板焼鈍を９００℃で１
分間実施してから酸洗した。これを１．１mmに冷延し、
中間焼鈍として連続焼鈍を８５０℃で１分間、湿潤水素
２０％，窒素８０％の雰囲気で実施し、製品板厚である
０．２mmまで冷延した。得られた冷延板を脱脂して成分
分析した結果、Ｃ：０．０５７％であったが他の元素は
スラブ成分と一致していた。Embodiments of the present invention will be described below. [Example 1] C: 0.063%, Si: 2.
5%, Mn: 0.07%, Se: 0.03%, S: 0.
0011%, N: 0.004%, Al: 0.005%,
A slab containing 0.03% of Sb and 0.1% of Mo and substantially consisting of Fe is heated to 1420 ° C.
It was a hot-rolled sheet having a thickness of 3 mm. Next, hot rolled sheet annealing was performed at 900 ° C for 1 hour.
After picking for a minute, it was pickled. This was rolled to 1.1mm,
As intermediate annealing, continuous annealing was performed at 850 ° C. for 1 minute in an atmosphere of 20% of wet hydrogen and 80% of nitrogen, and cold-rolled to a product sheet thickness of 0.2 mm. The resulting cold-rolled sheet was degreased and analyzed for components. As a result, the content of C was 0.057%, but the other elements were consistent with the slab components.
【００４０】この冷延板に、焼鈍隔離剤として、冷延板
片面あたり７ｇ／ｍ2 のアルミナに酸化ナトリウムと硫
酸アンチモンとオキシ塩化ビスマスとを表１に示す重量
％で添加した粉末を鋼板に振り掛けた。次に、焼鈍隔離
剤を塗布した冷延板を仕上焼鈍するに際し、８５０℃で
５０時間均熱してから１１７０℃まで１８℃／時間で昇
温し１０時間均熱してから、炉冷する熱サイクルをとっ
た。仕上焼鈍の雰囲気は、１１７０℃までの昇温は３０
％水素７０％窒素気流中で、９００℃に到達してからは
１００％水素に切り替えて最後まで行った。A powder obtained by adding sodium oxide, antimony sulfate, and bismuth oxychloride to alumina of 7 g / m 2 per one side of the cold-rolled sheet as an annealing separator to the cold-rolled sheet was added to a steel sheet. Sprinkled. Next, when the cold-rolled sheet coated with the annealing isolating agent is subjected to finish annealing, it is heated at 850 ° C. for 50 hours, then heated up to 1170 ° C. at 18 ° C./hour, soaked for 10 hours, and then cooled in a furnace. Was taken. The atmosphere for the finish annealing is 30 ° C in temperature up to 1170 ° C.
After the temperature reached 900 ° C. in a 70% nitrogen gas stream, the operation was switched to 100% hydrogen until the end.
【００４１】その後、燐酸アルミ、コロイダルシリカ、
クロム酸系の絶縁皮膜を塗布・乾燥した。乾燥は鋼板の
形状矯正を兼ねて９００℃×２分で行った。その後、エ
プスタイン試料を切り出し、８００℃で２時間の窒素中
で歪取焼鈍してから、磁性を測定し表１を得た。なお、
実験Ｎｏ．９のＮａ2 Ｏに代えて、ＣａＯ、硫酸アンチ
モンに代えて、硫酸ストロンチュウムとする実験も実施
したが、実験Ｎｏ．９と同じ分析、磁性結果が得られ
た。Thereafter, aluminum phosphate, colloidal silica,
A chromic acid-based insulating film was applied and dried. Drying was performed at 900 ° C. for 2 minutes also to correct the shape of the steel sheet. Thereafter, an Epstein sample was cut out and subjected to strain relief annealing in nitrogen at 800 ° C. for 2 hours. In addition,
Experiment No. An experiment was also conducted in which strontium sulfate was used instead of CaO and antimony sulfate in place of Na 2 O of Experiment No. 9, The same analysis and magnetic results as in Example 9 were obtained.
【００４２】[0042]
【表１】 [Table 1]
【００４３】表１に示すように、Ｎａ2 Ｏ添加量が本発
明範囲の０．５％以上で、脱ＳおよびＳｅが良好で鉄損
が優れており、更に、硫酸Ｓｂの０．０２％以上の添加
で磁気特性が改善された、更に、オキシ塩化Ｂｉ添加で
鉄損が向上することが分かった。As shown in Table 1, when the added amount of Na 2 O is 0.5% or more of the range of the present invention, the removal of S and Se are good and the iron loss is excellent. It was found that the magnetic properties were improved by the above addition, and that the iron loss was improved by the addition of Bi oxychloride.
【００４４】[0044]
【発明の効果】本発明によれば、従来の連続焼鈍による
脱炭焼鈍工程を省略する製造プロセスで高位安定した磁
気特性を有する方向性電磁鋼板が得られた。According to the present invention, a grain-oriented electrical steel sheet having high and stable magnetic properties can be obtained by a manufacturing process in which the conventional decarburizing annealing step by continuous annealing is omitted.
Claims (3)
て、熱延板に焼鈍を施すか或いは施すことなく、中間焼
鈍をはさむ二回の冷間圧延により所定の製品板厚とし、
成分組成が重量％で、 Ｃ ：０．００５〜０．０６％、 Ｓｉ：２〜４％、 Ａｌ≦０．０１％、 Ｍｎ：０．０３〜０．２％、 Ｓ又はＳｅ：０．０１〜０．０４％、Ｎ ≦０．０１％ を含有し、残部が実質的にＦｅである冷延板に対して、
脱炭焼鈍を実施することなしに、アルミナを主成分とし
て、Ｃａ化合物又はＮａ化合物の一種或いは二種を０．
５〜３０重量％、Ｓｂ化合物又はＳｒ化合物の一種或い
は二種を０．０２〜１０重量％添加した焼鈍隔離剤をド
ライコーティングしてから、非酸化性雰囲気中で高温バ
ッチ焼鈍を行うことを特徴とする一次皮膜のない方向性
電磁鋼板の製造方法。In a normal method for producing a grain-oriented electrical steel sheet, a hot rolled sheet is subjected to annealing or not, without being subjected to intermediate annealing, to a predetermined product sheet thickness by two times of cold rolling,
Component composition is% by weight, C: 0.005 to 0.06%, Si: 2 to 4%, Al ≦ 0.01%, Mn: 0.03 to 0.2%, S or Se: 0.01 ０．０0.04%, N ≦ 0.01%, with the balance being substantially Fe,
Without carrying out decarburization annealing, one or two kinds of Ca compounds or Na compounds containing alumina as a main component were added.
Dry coating of an annealing separator containing 5 to 30% by weight of Sb compound or Sr compound or 0.02 to 10% by weight of Sr compound is added, and then high temperature batch annealing is performed in a non-oxidizing atmosphere. Method for producing a grain-oriented electrical steel sheet without a primary coating.
成として重量％で、 Ｃｕ≦０．３％、 Ｓｎ≦０．３、 Ｓｂ≦０．１％、 Ｍｏ≦０．２％ の一種又は二種以上を含有する請求項１記載の方向性電
磁鋼板の製造方法。2. The cold-rolled sheet according to claim 1, further comprising: Cu ≦ 0.3%, Sn ≦ 0.3, Sb ≦ 0.1%, Mo ≦ 0.2% by weight as a component composition. The method for producing a grain-oriented electrical steel sheet according to claim 1, comprising one or more of the following.
に、Ｂｉ化合物を３０重量％以下添加したものであるこ
とを特徴とする請求項１又は２記載の一次皮膜のない方
向性電磁鋼板の製造方法。3. The directional electromagnetic wave without a primary coating according to claim 1 or 2, wherein the annealing separator according to claim 1 or 2 further comprises a Bi compound added in an amount of 30% by weight or less. Steel plate manufacturing method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9314779A JPH11152516A (en) | 1997-11-17 | 1997-11-17 | Manufacture of grain oriented silicon steel sheet |
| KR1019980000708A KR100262761B1 (en) | 1997-01-17 | 1998-01-13 | A method for manufacturing a grain oriented electrical steel plate having no primary film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9314779A JPH11152516A (en) | 1997-11-17 | 1997-11-17 | Manufacture of grain oriented silicon steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11152516A true JPH11152516A (en) | 1999-06-08 |
Family
ID=18057500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9314779A Withdrawn JPH11152516A (en) | 1997-01-17 | 1997-11-17 | Manufacture of grain oriented silicon steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11152516A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013167000A (en) * | 2012-02-16 | 2013-08-29 | Hitachi Metals Ltd | Metal powder, method for producing the same, and dust core |
| CN113981196A (en) * | 2021-11-02 | 2022-01-28 | 无锡普天铁心股份有限公司 | Annealing separant for improving quality of ultrahigh magnetic induction oriented silicon steel bottom layer and preparation method and application thereof |
-
1997
- 1997-11-17 JP JP9314779A patent/JPH11152516A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013167000A (en) * | 2012-02-16 | 2013-08-29 | Hitachi Metals Ltd | Metal powder, method for producing the same, and dust core |
| CN113981196A (en) * | 2021-11-02 | 2022-01-28 | 无锡普天铁心股份有限公司 | Annealing separant for improving quality of ultrahigh magnetic induction oriented silicon steel bottom layer and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3932236A (en) | Method for producing a super low watt loss grain oriented electrical steel sheet | |
| KR101294624B1 (en) | A method of manufacturing oriented si steel containing cu | |
| JP3456862B2 (en) | Manufacturing method of grain-oriented electrical steel sheet with extremely low iron loss | |
| JP3392669B2 (en) | Manufacturing method of grain-oriented electrical steel sheet with extremely low iron loss | |
| JP3336555B2 (en) | Method for producing grain-oriented electrical steel sheet without glass coating with excellent surface properties | |
| JP2663229B2 (en) | Method for producing grain-oriented electrical steel sheet having a uniform glass film and extremely excellent magnetic properties | |
| JPH02294428A (en) | Production of grain-oriented silicon steel sheet having high magnetic flux density | |
| JPH11152516A (en) | Manufacture of grain oriented silicon steel sheet | |
| JPH1136018A (en) | Manufacture of grain oriented silicon steel sheet having extremely excellent glass film and magnetic property | |
| JP2724094B2 (en) | Manufacturing method of grain-oriented silicon steel sheet | |
| JP3921807B2 (en) | Method for producing grain-oriented silicon steel sheet | |
| JP2671084B2 (en) | High magnetic flux density grain-oriented electrical steel sheet having excellent iron loss characteristics and method for producing the same | |
| JP7392848B2 (en) | Method for producing grain-oriented electrical steel sheet and annealing separator used therein | |
| JP2647334B2 (en) | Manufacturing method of high magnetic flux density, low iron loss grain-oriented electrical steel sheet | |
| JPH0832928B2 (en) | Method for producing unidirectional electrical steel sheet with excellent magnetic properties and glass film properties | |
| JP2706039B2 (en) | Method for manufacturing mirror-oriented silicon steel sheet | |
| JPH11100616A (en) | Manufacture of grain oriented silicon steel sheet | |
| JP3456869B2 (en) | Manufacturing method of unidirectional electrical steel sheet | |
| KR100940719B1 (en) | Method for manufacturing non-oriented electrical steel sheet having higher magnetic induction after stress relief annealing | |
| JP3952711B2 (en) | Method for producing grain-oriented electrical steel sheet | |
| JPH10204532A (en) | Production of grain oriented magnetic steel sheet | |
| KR20030052139A (en) | Manufacturing method for non-oriented electrical steel sheet having low core loss and high magnetic induction after stress relief annealing | |
| JPS6396218A (en) | Production of extremely low iron loss grain oriented silicon steel sheet | |
| KR100262761B1 (en) | A method for manufacturing a grain oriented electrical steel plate having no primary film | |
| JP2757719B2 (en) | Manufacturing method of non-oriented electrical steel sheet with excellent magnetic properties and surface properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20050201 |