JPH0754155A - Production of ultralow core loss grain-oriented silicon steel sheet - Google Patents
Production of ultralow core loss grain-oriented silicon steel sheetInfo
- Publication number
- JPH0754155A JPH0754155A JP32305993A JP32305993A JPH0754155A JP H0754155 A JPH0754155 A JP H0754155A JP 32305993 A JP32305993 A JP 32305993A JP 32305993 A JP32305993 A JP 32305993A JP H0754155 A JPH0754155 A JP H0754155A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- annealing
- bismuth
- iron loss
- oriented electrical
- 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.)
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- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鉄損が極めて低い方向
性電磁鋼板の製造法に関するものである。特にその表面
にフォルステライト（以下、グラスという）被膜を形成
させずに二次再結晶工程（仕上焼鈍工程）を完了させ、
その後、磁区細分化、張力コーティング等の処理を行
い、鉄損特性の改善を図る方向性電磁鋼板の製造法であ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a grain-oriented electrical steel sheet having extremely low iron loss. In particular, complete the secondary recrystallization process (finish annealing process) without forming a forsterite (hereinafter referred to as glass) film on the surface,
After that, magnetic domain subdivision, tension coating, and other treatments are performed to produce a grain-oriented electrical steel sheet for improving iron loss characteristics.
【０００２】[0002]
【従来の技術】方向性電磁鋼板は、電気機器の磁気鉄芯
として多用され、エネルギーロスを少なくすべく、改善
が繰り返されてきた。方向性電磁鋼板の鉄損を低減する
手段として、仕上焼鈍後の材料表面にレーザービームを
照射し局部歪を与え、それによって磁区を細分化して鉄
損を低下させる方法が例えば特開昭５８−２６４０５号
公報に開示されている。また、応力除去焼鈍しても磁区
細分化効果が消失しない手段が、例えば特開昭６２−８
６１７号公報に開示されている。これらの技術により鉄
損レベルは極めて良好なものとなってきたが、さらに鉄
損値の低減を図るためには鋼板表面近傍の磁区の動きを
阻害する地鉄表面の凹凸を取り除くこと（平滑化）が重
要であるとの認識が生まれてきた。しかしながら、珪素
鋼板を通常の製造工程で処理した場合、仕上焼鈍後の鋼
板表面にはグラス被膜が生成されており、表面平滑化の
ためにはグラス被膜を除去する必要がある。2. Description of the Related Art Grain-oriented electrical steel sheets are frequently used as magnetic iron cores for electric equipment and have been repeatedly improved in order to reduce energy loss. As a means for reducing the iron loss of grain-oriented electrical steel sheets, there is a method of irradiating a laser beam on the surface of the material after finish annealing to give local strain, thereby subdividing magnetic domains to reduce the iron loss. It is disclosed in Japanese Patent No. 26405. Further, means for preventing the magnetic domain refining effect from disappearing even when stress-relief annealing is disclosed in, for example, JP-A-62-8.
No. 617 is disclosed. These technologies have made the iron loss level extremely good, but in order to further reduce the iron loss value, the irregularities on the surface of the base metal that obstruct the movement of magnetic domains near the surface of the steel sheet should be removed (smoothing). ) Has come to be recognized as important. However, when a silicon steel sheet is processed in a normal manufacturing process, a glass coating film is formed on the surface of the steel sheet after finish annealing, and it is necessary to remove the glass coating film for surface smoothing.
【０００３】グラス被膜を除去する方法としては酸洗等
の技術が古くからあり、その後表面平滑化する方法とし
て特開昭６４−８３６２０号公報に開示されている化学
研磨、電解研磨等がある。平滑な表面を得るために、一
度生成されたグラス被膜を除去しさらに化学研磨・機械
研磨等を行うことは種々の困難を伴う。グラス被膜は地
鉄中にその根を深くおろしているため、酸洗によって除
去しなければならない量は鋼板板厚で１μｍ以上もあり
生産性が極めて悪い。さらに酸洗設備設置に伴い例えば
薬剤濃度管理、排水処理等の環境問題等もある。Techniques such as pickling have long been known as methods for removing the glass coating, and chemical polishing, electrolytic polishing, etc. disclosed in Japanese Patent Laid-Open No. 64-83620 are known as methods for smoothing the surface thereafter. In order to obtain a smooth surface, it is accompanied by various difficulties to remove the glass film once formed and further carry out chemical polishing, mechanical polishing and the like. Since the roots of the glass coating are deeply laid in the ground iron, the amount that must be removed by pickling is 1 μm or more in plate thickness of the steel plate, and productivity is extremely poor. Furthermore, with the installation of pickling equipment, there are environmental problems such as chemical concentration control and wastewater treatment.
【０００４】一方、一度生成されたグラス被膜を除去す
るのでなく、仕上焼鈍時にグラス被膜を生成させない方
法として、Ｕ．Ｓ．Ｐａｔｅｎｔ ３７８５８８２に開
示されるＡｌ２Ｏ３、特公昭５６−３４１４号公報に開
示される含水珪酸塩鉱物粉末等、ＳｉＯ２と反応しない
焼鈍分離剤を用いる方法がある。この方法は、生成した
グラス被膜を酸洗除去する方法よりも優れている。しか
しながら、この方法においても脱炭焼鈍時に形成された
ＳｉＯ２等の酸化物が表面に残存するため、表面を平滑
化するために化学研磨・機械研磨等の処理が必要であ
る。化学的方法においては、前述の酸洗と同じく薬剤濃
度管理、排水処理等の環境問題があり、また機械研磨等
物理的方法においては工業的に大きな面積を持つ表面を
同一基準で平滑化することに困難がある。さらに特開昭
６４−６２４１７号、特開平２−２２８４８１号公報に
開示される、塩化物を焼鈍分離剤中に添加し仕上焼鈍時
にＭｇＯとＳｉＯ２との反応を抑制する方法がある。こ
の方法は現在のところ最も工業的に優れているが、薄い
酸化膜が残存する点、得られる表面粗度が化学研磨を用
いた場合よりも粗い点が鉄損低減の妨げとなっていた。On the other hand, as a method of not forming a glass coating film once formed, but not forming a glass coating film during finish annealing, U.S. Pat. S. There is a method of using an annealing separator which does not react with SiO 2 , such as Al 2 O 3 disclosed in Patent 3785882 and hydrous silicate mineral powder disclosed in Japanese Patent Publication No. 56-3414. This method is superior to the method of pickling and removing the produced glass film. However, even in this method, since oxides such as SiO 2 formed during decarburization annealing remain on the surface, it is necessary to carry out treatments such as chemical polishing and mechanical polishing in order to smooth the surface. In the chemical method, there are environmental problems such as chemical concentration control and wastewater treatment as in the above pickling. In the physical method such as mechanical polishing, the surface having an industrially large area should be smoothed by the same standard. Have difficulty. Further JP 64-62417, is disclosed in JP-A-2-228481, there is a method of suppressing the reaction between MgO and SiO 2 upon addition to finish annealing chloride in annealing separator. This method is currently the most industrially excellent, but the point that a thin oxide film remains and the obtained surface roughness is rougher than that when chemical polishing is used has been an obstacle to iron loss reduction.
【０００５】[0005]
【発明が解決しようとする課題】本発明は従来法におけ
る上記問題を解消した、電磁鋼板の表面を平滑化し低鉄
損を得るための工業的手段を提供することを目的とす
る。本発明は、珪素鋼の仕上焼鈍において脱炭焼鈍時に
形成された酸化被膜を除去し、かつ鋼板表面を平滑化し
た後に張力被膜付与あるいは磁区細分化を施すことによ
り鉄損を極限まで低減した超低鉄損方向性電磁鋼板の製
造方法を提供するものである。SUMMARY OF THE INVENTION An object of the present invention is to provide an industrial means for smoothing the surface of an electromagnetic steel sheet to obtain a low iron loss, which solves the above problems in the conventional method. The present invention removes the oxide film formed during decarburization annealing in finish annealing of silicon steel, and smoothes the surface of the steel sheet, and then imparts a tension film or subdivides the magnetic domain to reduce the iron loss to the maximum. A method for manufacturing a low iron loss grain-oriented electrical steel sheet is provided.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、種々の塩
素を含む化合物を焼鈍分離剤中に添加し、仕上焼鈍中の
鋼板表面の酸化膜が除去される過程を詳細に調査した。
その結果、添加される塩化物がＢｉ（ビスマス）の塩化
物である場合に限って、かつ添加量が塩素重量部で０．
２部以上の場合に仕上焼鈍後の鋼板表面が鏡面のように
平滑化されることを見いだした。さらに発明者等は検討
を加えたところ、Ｂｉを含む化合物と金属の塩化物を焼
鈍分離剤に添加すれば同様の効果が得られることが分か
った。これらの方向性電磁鋼板の鉄損特性は酸洗してグ
ラス被膜を除去したもの、特開昭６４−６２４１７号、
特開平２−２２８４８１号公報に開示される塩化物を用
いて酸化膜を除去したものに比べて低くなることを見い
だし本発明を完成させた。Means for Solving the Problems The present inventors have investigated in detail the process of adding various chlorine-containing compounds to the annealing separator to remove the oxide film on the surface of the steel sheet during finish annealing.
As a result, only when the chloride to be added is Bi (bismuth) chloride, and the addition amount is 0.
It has been found that the steel sheet surface after finish annealing is smoothed like a mirror surface in the case of 2 parts or more. Further, the inventors have made further studies and found that the same effect can be obtained by adding a compound containing Bi and a metal chloride to the annealing separator. The iron loss characteristics of these grain-oriented electrical steel sheets are those obtained by pickling to remove the glass coating, JP-A-64-62417,
The present invention has been completed by discovering that it is lower than that obtained by removing the oxide film using chloride disclosed in JP-A-2-228481.
【０００７】本発明の要旨とするところは、重量％で、
２〜７％のＳｉを含有する珪素鋼スラブを熱延し、必要
に応じて焼鈍を施し、１回の冷延または中間焼鈍を挟む
２回以上の冷延を行い、脱炭焼鈍後焼鈍分離剤を塗布、
乾燥し仕上焼鈍を行う方向性電磁鋼板の製造方法におい
て、ビスマスの塩化物を焼鈍分離剤１００重量部に対し
て、塩素重量部で０．２重量部以上１５重量部以下を含
む焼鈍分離剤を用いて仕上焼鈍する、またはビスマス単
体あるいはビスマスの化合物及び金属の塩素化合物を含
む焼鈍分離剤を用いて仕上焼鈍するところにある。ビス
マスの化合物としては、酸化ビスマス、水酸化ビスマ
ス、硫化ビスマス、硫酸ビスマス、リン酸ビスマス、炭
酸ビスマス、硝酸ビスマス、有機酸ビスマス、ハロゲン
化ビスマスの１種あるいは２種以上の混合物が有効であ
る。The gist of the present invention is that, by weight%,
A silicon steel slab containing 2 to 7% of Si is hot-rolled, annealed as required, and cold-rolled once or two or more times with intermediate annealing sandwiched between them, followed by decarburization-annealing-annealing separation Apply the agent,
In a method for producing a grain-oriented electrical steel sheet which is dried and finish-annealed, an annealing separator containing bismuth chloride in an amount of 0.2 parts by weight or more and 15 parts by weight or less in terms of chlorine parts is used with respect to 100 parts by weight of the annealing separator. Finish annealing is carried out by using it, or finish annealing is carried out by using an annealing separating agent containing bismuth alone or a compound of bismuth and a chlorine compound of metal. As the bismuth compound, one or a mixture of bismuth oxide, bismuth hydroxide, bismuth sulfide, bismuth sulfate, bismuth phosphate, bismuth carbonate, bismuth nitrate, organic acid bismuth, and bismuth halide is effective.
【０００８】また、金属の塩素化合物としては沸点ある
いは昇華点が１８３℃以上である塩素化合物を用いる、
特に塩化鉄、塩化コバルト、塩化ニッケル等が有効であ
る。添加量は焼鈍分離剤１００重量部に対して、塩素重
量部で０．２部以上１５部以下含めることが必要であ
る。仕上焼鈍後、焼鈍分離剤を除去し、磁区細分化処理
及び張力被膜を付与することにより、鉄損は極小とな
る。この技術による仕上焼鈍後の鋼板表面は、グラス被
膜を酸洗除去しさらに化学研磨を行った鋼板表面と同等
の平滑度を示す。磁壁の移動に対して障害となるような
表面の凹凸がない、磁気的に理想的な表面になる。As the metal chlorine compound, a chlorine compound having a boiling point or sublimation point of 183 ° C. or higher is used.
In particular, iron chloride, cobalt chloride, nickel chloride and the like are effective. It is necessary to add 0.2 parts by weight or more and 15 parts or less by weight of chlorine to 100 parts by weight of the annealing separator. After the finish annealing, the annealing separator is removed, and the magnetic domain refinement treatment and the tension coating are applied to minimize the iron loss. The surface of the steel sheet after finish annealing by this technique shows the same smoothness as the surface of the steel sheet after the glass film is pickled and removed and chemical polishing is performed. The surface is magnetically ideal without any surface irregularities that hinder the movement of the domain wall.
【０００９】ここでいう焼鈍分離剤とは、１２００℃ま
での温度域で凝結せずかつ鉄とも焼き付かない公知の高
融点化合物、例えば酸化物、窒化物等を指す。中でもＢ
ａＯ，ＣａＯ，ＭｇＯ，ＳｒＯ等アルカリ土類金属の酸
化物及びＡｌ２Ｏ３は、工業的に利用価値が高い。ま
た、ビスマスの塩化物とはＢｉＣｌ，ＢｉＯＣｌ，Ｂｉ
Ｃｌ３等を指す。The term "annealing separating agent" as used herein refers to a known high melting point compound which does not condense in the temperature range up to 1200 ° C. and does not seize with iron, such as oxides and nitrides. Above all, B
aO-, CaO, MgO, SrO or the like oxide and Al 2 O 3 of the alkaline earth metal is industrially high utility value. Bismuth chloride means BiCl, BiOCl, Bi
Refers to Cl 3, etc.
【００１０】以下、本発明について詳細に説明する。珪
素鋼中の珪素は極めて酸化されやすく、通常の仕上焼鈍
では鋼板表面にグラス被膜が形成される。発明者らは、
仕上焼鈍中にグラス被膜を形成させない方法の中でまず
特開昭６４−６２４１７号、特開平２−２２８４８１号
公報に開示される塩化物を焼鈍分離剤中に添加し仕上焼
鈍時にＭｇＯとＳｉＯ２との反応を抑制する方法を検討
した。しかしながらこの技術は、鋼板表面のグラス被膜
除去による打抜性改善を目的としていたため、充分な表
面平滑度・鉄損が得られるものではなかった。The present invention will be described in detail below. Silicon in silicon steel is extremely susceptible to oxidation, and a glass film is formed on the surface of the steel sheet by ordinary finish annealing. The inventors
Among the methods in which the glass film is not formed during the finish annealing, first, the chlorides disclosed in JP-A-64-62417 and JP-A-2-228481 are added to the annealing separator, and MgO and SiO 2 are added during the finish annealing. The method of suppressing the reaction with was investigated. However, since this technique aims at improving the punching property by removing the glass coating on the surface of the steel sheet, sufficient surface smoothness and iron loss cannot be obtained.
【００１１】本発明者等は、種々の金属塩化物を焼鈍分
離剤中に添加し、仕上焼鈍中の鋼板表面を詳細に調査し
た。その結果、添加される物質がビスマスの塩化物で
ある場合、及びＡ群：ビスマス単体あるいはビスマス
の化合物及びＢ群：金属の塩素化合物とするときＡ群及
びＢ群両方を含む場合に限って、かつ添加量が塩素重量
部で０．２部以上の場合に、酸化膜はその根ごと除去さ
れること、引き続く高温焼鈍中に表面が平滑化されるこ
とを見いだした。The present inventors have added various metal chlorides to the annealing separator and investigated the surface of the steel sheet during finish annealing in detail. As a result, only when the added substance is a chloride of bismuth, and when the group A: a bismuth simple substance or a compound of bismuth and a group B: a chlorine compound of a metal, both groups A and B are included, It was also found that when the added amount was 0.2 parts by weight or more by weight of chlorine, the oxide film was removed together with its roots, and the surface was smoothed during the subsequent high temperature annealing.
【００１２】酸化膜が除去され、表面が鏡面状態になる
機構についてはまだ明らかではないが、我々は次のよう
に考えている。Ａ群：ビスマス単体あるいはビスマスの
化合物及びＢ群：金属の塩素化合物とするときＡ群及び
Ｂ群両方を含む焼鈍分離剤では少なくとも１８３℃以上
でＢｉの塩化物：ＢｉＯＣｌを形成する。このＢｉＯＣ
ｌは仕上焼鈍の昇温中にＢｉＣｌ３の蒸気を発生しつつ
分解する。ＢｉＣｌ３は平衡解離塩素分圧が高いので、
コイル板間で容易にＣｌガスを発生する。Ｃｌガスは鋼
板表面の酸化層を拡散し、地鉄に達するとＦｅ＋２Ｃｌ
→ＦｅＣｌ２の反応に従ってＦｅＣｌ２の蒸気を発生す
る。The mechanism by which the oxide film is removed and the surface becomes a mirror surface is not yet clear, but we consider it as follows. Group A: Bismuth simple substance or bismuth compound and Group B: metal chlorine compound, the annealing separator containing both Group A and Group B forms Bi chloride: BiOCl at 183 ° C. or higher. This BiOC
1 decomposes while generating vapor of BiCl 3 during the temperature rise of finish annealing. Since BiCl 3 has a high equilibrium dissociation chlorine partial pressure,
Cl gas is easily generated between the coil plates. Cl gas diffuses in the oxide layer on the surface of the steel sheet and reaches Fe + 2Cl when it reaches the base iron.
→ FeCl 2 vapor is generated according to the reaction of FeCl 2 .
【００１３】酸化膜／地鉄界面である体積のＦｅＣｌ２
ガスが生成されると、酸化層と地鉄が剥離する。地鉄表
面は酸化層と分離するため、表面Ｆｅ原子の移動が容易
になり１０００℃以上の高温で鏡面状態になるものと推
測している。Ｂｉの塩化物を用いるときも同様で、Ｂｉ
の塩化物を水と混合させ、乾燥するとＢｉＯＣｌを形成
する。以下、前記同様の反応により鏡面化すると推測し
ている。Volume of FeCl 2 at the oxide film / base iron interface
When the gas is generated, the oxide layer and the base iron are separated. Since the surface of the base iron is separated from the oxide layer, it is presumed that the surface Fe atoms are easily moved and become a mirror surface state at a high temperature of 1000 ° C. or higher. The same applies when using Bi chloride.
Of the chloride is mixed with water and dried to form BiOCl. Hereafter, it is speculated that the same reaction as described above will give a mirror finish.
【００１４】Ｂ群：金属の塩素化合物に用いる金属の塩
化物は、沸点あるいは昇華点が１８３℃以上あることが
必要である。これは塩化第２スズ（ＳｎＣｌ４）のよう
に低い沸点（１１４℃）ではＡ群と反応する以前にガス
化して体積が増大し消失してしまうからである。有効な
塩化物としては塩化鉄（ＦｅＣｌ２，ＦｅＣｌ３）、塩
化コバルト（ＣｏＣｌ２，ＣｏＣｌ３）、塩化ニッケル
（ＮｉＣｌ２）、塩化アンチモン等があり、これらは混
合して用いても良い。なお、塩化アルミニウム（ＡｌＣ
ｌ３）昇華点：１８３℃、三塩化アンチモン（ＳｂＣｌ
３）沸点：２２１℃、塩化ニッケル（ＮｉＣｌ２）沸
点：９９３℃、塩化鉄（ＦｅＣｌ２）沸点：１０２４
℃、塩化コバルト（ＣｏＣｌ２）沸点：１０４９℃であ
り、鏡面化に有効である。Group B: The metal chloride used as the metal chlorine compound must have a boiling point or sublimation point of 183 ° C. or higher. This is because at a low boiling point (114 ° C.) such as stannic chloride (SnCl 4 ), it is gasified and increases in volume before it reacts with the group A and disappears. Examples of effective chlorides include iron chloride (FeCl 2 , FeCl 3 ), cobalt chloride (CoCl 2 , CoCl 3 ), nickel chloride (NiCl 2 ), antimony chloride and the like, and these may be mixed and used. Aluminum chloride (AlC
l 3 ) Sublimation point: 183 ° C., antimony trichloride (SbCl
3 ) Boiling point: 221 ° C., nickel chloride (NiCl 2 ) boiling point: 993 ° C., iron chloride (FeCl 2 ) boiling point: 1024
C, boiling point of cobalt chloride (CoCl 2 ): 1049 ° C., which is effective for mirroring.
【００１５】Ａ群：ビスマス単体あるいはビスマスの化
合物は、Ｂｉ元素が含まれれば良く、特にビスマスの化
合物が、Ｂｉ粉末、酸化ビスマス、水酸化ビスマス、硫
化ビスマス、硫酸ビスマス、リン酸ビスマス、炭酸ビス
マス、硝酸ビスマス、有機酸ビスマス、ハロゲン化ビス
マスの１種あるいは２種以上の混合物が有効である。Group A: Bismuth simple substance or bismuth compound may contain Bi element, and especially bismuth compound is Bi powder, bismuth oxide, bismuth hydroxide, bismuth sulfide, bismuth sulfate, bismuth phosphate, bismuth carbonate. , Bismuth nitrate, bismuth organic acid, bismuth halide, or a mixture of two or more thereof is effective.
【００１６】添加物が塩素重量部で０．２部よりも少な
い場合には、コイル幅方向全域に渡って酸化膜を除去す
ることができない。添加量を多くしても板間に存在し得
るＣｌガスの体積は一定であるので、余分に添加された
ＢｉＣｌ３はコイル板間より流出し、効果を持たない。
また、仕上焼鈍中に鋼板焼き付きが発生しないために
は、ビスマス塩化物が蒸発した後に分離剤がある程度残
存していることも必要である。従って、Ｂｉ塩化物の添
加量の上限は、塩素重量部で１５部とした。When the amount of the additive is less than 0.2 parts by weight of chlorine, the oxide film cannot be removed over the entire width direction of the coil. Since the volume of Cl gas that can exist between the plates is constant even if the added amount is increased, the excessively added BiCl 3 flows out from between the coil plates and has no effect.
Further, in order to prevent seizure of the steel sheet during the finish annealing, it is necessary that the separating agent remains to some extent after the bismuth chloride is evaporated. Therefore, the upper limit of the amount of Bi chloride added is 15 parts by weight of chlorine.
【００１７】本発明により得られる鋼板表面は鏡のよう
な光沢を保ち、従来のアルカリ金属及びアルカリ土類金
属の塩化物を利用する技術に比べて、鋼板表面の平滑度
が良くなり鉄損が低減される。本発明は低鉄損を得るこ
とを目的とするものであるが、それ以外の目的で、例え
ば二次再結晶を安定化する等の目的でビスマスの塩化物
以外の化合物すなわち窒化物、硫化物等を添加しても良
い。分離剤の塗布方法は公知の方法で良く、特に限定し
ない。水へ添加・撹拌して塗っても、静電塗布しても良
い。The surface of the steel sheet obtained by the present invention retains a mirror-like luster, and the surface of the steel sheet has better smoothness and less iron loss than the conventional technique using chlorides of alkali metals and alkaline earth metals. Will be reduced. The present invention is intended to obtain a low iron loss, but for other purposes, for example, compounds other than chloride of bismuth for the purpose of stabilizing secondary recrystallization, that is, nitrides, sulfides Etc. may be added. The method of applying the separating agent may be a known method and is not particularly limited. It may be added to water with stirring and applied, or electrostatically applied.
【００１８】本発明に供される方向性電磁鋼板は、公知
の方法によって鋳造、熱延、冷延、焼鈍を施される電磁
鋼板である。低鉄損を得る目的でＳｉを２％以上７％以
下添加したスラブを用いる。上限は工業的に圧延が可能
なＳｉ量であり、下限は鏡面化を生じさせ得る高温仕上
焼鈍で変態を生じさせないＳｉ量である。仕上焼鈍まま
の状態では、鋼板表面は金属面が露出しているため、板
と板を積層したときの板間の絶縁を保つために公知の方
法により絶縁張力被膜を付与する。占積率を高めるため
にＰＶＤ，ＣＶＤ，イオンプレーティング等の薄手高張
力被膜を形成する技術を用いても良い。The grain-oriented electrical steel sheet used in the present invention is an electrical steel sheet which is cast, hot rolled, cold rolled or annealed by a known method. A slab containing 2% or more and 7% or less of Si is used for the purpose of obtaining a low iron loss. The upper limit is the amount of Si that can be industrially rolled, and the lower limit is the amount of Si that does not cause transformation in high-temperature finishing annealing that can cause mirror finish. Since the metal surface is exposed on the surface of the steel sheet in the state of finish annealing, an insulating tension film is applied by a known method to maintain insulation between the sheets when the sheets are laminated. A technique for forming a thin high-strength coating film such as PVD, CVD, or ion plating may be used to increase the space factor.
【００１９】さらに鉄損を低減するために、張力被膜を
形成した後に公知の磁区細分化技術を併用する。この組
み合わせ技術により極めて低い鉄損を得ることができ
る。図１の（ａ）は従来法で酸洗した鋼板表面と、
（ｂ）は本発明により得られる鋼板表面の写真（倍率×
１）である。本発明材の表面が黒く見えるのは、表面が
鏡のように平滑で光の反射率が高いためである。一方、
従来の酸洗では表面が荒れるため光が散乱し白く見えて
いる。本発明により得られる鋼板表面が、従来の酸洗技
術により得られる表面と全く異なることがわかる。In order to further reduce the iron loss, a known magnetic domain refining technique is used together after forming the tension film. With this combination technique, extremely low iron loss can be obtained. FIG. 1A shows a steel sheet surface pickled by a conventional method,
(B) is a photograph of the surface of the steel sheet obtained by the present invention (magnification ×
1). The surface of the material of the present invention looks black because the surface is smooth like a mirror and has a high light reflectance. on the other hand,
In conventional pickling, the surface is rough, so light is scattered and it looks white. It can be seen that the steel sheet surface obtained by the present invention is completely different from the surface obtained by the conventional pickling technique.
【００２０】[0020]
（実施例１） Ｃ：０．０４％、Ｓｉ：３．２５％、Ｍｎ：０．１５
％、Ｓ：０．００７％、Ａｌ：０．０２７％、Ｎ：０．
００７％を含むスラブを、１１５０℃で加熱後熱延し、
１．８ｍｍの熱延板とした。１１２０℃で熱延板を焼鈍
後０．１６ｍｍまで冷延し、８３０℃で脱炭焼鈍を行っ
た。表１に示す組成の焼鈍分離剤をスラリー状で塗布
し、１２００℃で２０時間の仕上焼鈍を行った。塩素化
合物の添加は、塩素重量部で、すべて１．５重量部であ
る。(Example 1) C: 0.04%, Si: 3.25%, Mn: 0.15
%, S: 0.007%, Al: 0.027%, N: 0.
A slab containing 007% is heated at 1150 ° C. and then hot rolled,
It was a hot rolled sheet of 1.8 mm. The hot-rolled sheet was annealed at 1120 ° C, cold-rolled to 0.16 mm, and decarburized at 830 ° C. The annealing separator having the composition shown in Table 1 was applied in a slurry form, and finish annealing was performed at 1200 ° C. for 20 hours. Chlorine compounds are added by 1.5 parts by weight of chlorine, all by weight.
【００２１】焼鈍後鋼板表面を水洗し、グラス被膜が形
成されたものは硝酸によりこれを除去し歪取焼鈍後、単
板で磁気測定を行った。結果を表１に示す。本発明技術
によれば、仕上焼鈍後酸洗で酸化膜を除去するよりも低
い鉄損が得られることがわかる。これは前述したように
表面が平滑になったことによって、磁壁移動が容易にな
ったためと考えている。After the annealing, the surface of the steel sheet was washed with water, and the glass film was removed by nitric acid. After strain relief annealing, magnetic measurement was performed on the single plate. The results are shown in Table 1. According to the technique of the present invention, it can be seen that a lower iron loss can be obtained as compared with removing the oxide film by pickling after finish annealing. This is considered to be because the domain wall movement was facilitated by the smooth surface as described above.
【００２２】[0022]
【表１】 [Table 1]
【００２３】（実施例２）実施例１の素材に、リン酸ア
ルミニウムとコロイダルシリカを主成分とする溶液を塗
布・乾燥し、張力被膜を形成した。単板で磁気測定を行
った結果を表２に示す。張力被膜形成により鉄損が改善
されるが、本発明ではその到達鉄損値が最も低い。表面
が平滑化され磁壁移動が容易になった効果は、張力被膜
形成後も残っている。Example 2 The material of Example 1 was coated with a solution containing aluminum phosphate and colloidal silica as main components and dried to form a tension film. Table 2 shows the results of magnetic measurement performed on a single plate. Although iron loss is improved by forming a tension film, the achieved iron loss value is the lowest in the present invention. The effect of smoothing the surface and facilitating domain wall movement remains after the tension film is formed.
【００２４】[0024]
【表２】 [Table 2]
【００２５】（実施例３）実施例２の素材の圧延方向と
直角方向に、５ｍｍの間隔でレーザー照射した。単板で
磁気測定を行った結果を表３に示す。張力被膜形成後の
レーザー照射により鉄損がさらに改善されるが、本発明
ではその到達鉄損値が最も低い。表面が平滑化され磁壁
移動が容易になった効果は、張力被膜形成・レーザー照
射による磁区細分化後も残っている。(Example 3) The material of Example 2 was irradiated with laser light at a distance of 5 mm in the direction perpendicular to the rolling direction. Table 3 shows the results of magnetic measurement performed on a single plate. Although the iron loss is further improved by the laser irradiation after forming the tension film, the reached iron loss value is the lowest in the present invention. The effect of smoothing the surface and facilitating domain wall movement remains after the magnetic domain subdivision by forming the tension film and irradiating the laser.
【００２６】[0026]
【表３】 [Table 3]
【００２７】（実施例４）実施例１中Ｎｏ．１と６につ
いて分離剤を水洗除去した後、エッチングにより鋼板圧
延方向と直角方向に４ｍｍ間隔で深さ７μｍの溝を形成
した。引き続きリン酸アルミニウムとコロイダルシリカ
を主成分とする溶液を塗布・乾燥し、張力被膜を形成し
た素材について単板で磁気測定を行った。結果を表４に
示す。溝形成による磁区細分化後も、表面が平滑化され
磁壁移動が容易になった効果が残ることがわかる。(Embodiment 4) No. 1 in Embodiment 1. After removing the separating agent with respect to 1 and 6 with water, grooves having a depth of 7 μm were formed at intervals of 4 mm in the direction perpendicular to the steel plate rolling direction by etching. Subsequently, a solution containing aluminum phosphate and colloidal silica as main components was applied and dried, and the tension-coated material was subjected to magnetic measurement with a single plate. The results are shown in Table 4. It can be seen that the effect that the surface is smoothed and the domain wall movement is facilitated remains after the magnetic domain is subdivided by the groove formation.
【００２８】[0028]
【表４】 [Table 4]
【００２９】（実施例５）実施例１中Ｎｏ．１と６につ
いて分離剤を水洗除去した後、歯車型ロールにより板表
面に圧延方向と直角方向に破線状の凹部を形成した。引
き続きリン酸アルミニウムとコロイダルシリカを主成分
とする溶液を塗布・焼鈍した。焼鈍温度は８００℃であ
る。単板磁気測定結果を表５に示す。凹部形成後の焼鈍
で導入された異方位微小粒による磁区細分化後も、表面
が平滑化され磁壁移動が容易になった効果が残ることが
わかる。(Embodiment 5) No. 1 in Embodiment 1. After removing the separating agent with respect to Nos. 1 and 6 by water, a gear-shaped roll was used to form a broken line-shaped recess on the surface of the plate in a direction perpendicular to the rolling direction. Subsequently, a solution containing aluminum phosphate and colloidal silica as main components was applied and annealed. The annealing temperature is 800 ° C. Table 5 shows the results of the single plate magnetic measurement. It can be seen that the effect of facilitating the domain wall movement by smoothing the surface remains even after the domain refinement by the differently oriented fine grains introduced by the annealing after forming the recesses.
【００３０】[0030]
【表５】 （実施例６）Ｃ：０．０５％、Ｓｉ：３．３％、Ｍｎ：
０．１４％、Ｓ：０．００７％、Ａｌ：０．０２８％、
Ｎ：０．００８％を含むスラブを、１１５０℃で加熱後
熱延し、１．８ｍｍの熱延板とした。１１２０℃で熱延
板を焼鈍後０．１６ｍｍまで冷延し、８３０℃で脱炭焼
鈍を行った。表６に示す組成の焼鈍分離剤をスラリー状
で塗布し、１２００℃で２０時間の仕上焼鈍を行った。
焼鈍分離剤はマグネシア（ＭｇＯ）：１００重量部に対
して、Ｂｉの化合物：５重量部、金属の塩素化合物：５
重量部である。仕上焼鈍後の素材に、リン酸アルミニウ
ムとコロイダルシリカを主成分とする溶液を塗布・乾燥
し、張力被膜を形成した。[Table 5] (Example 6) C: 0.05%, Si: 3.3%, Mn:
0.14%, S: 0.007%, Al: 0.028%,
A slab containing N: 0.008% was heated at 1150 ° C. and then hot-rolled to obtain a 1.8 mm hot-rolled sheet. The hot-rolled sheet was annealed at 1120 ° C, cold-rolled to 0.16 mm, and decarburized at 830 ° C. The annealing separator having the composition shown in Table 6 was applied in a slurry form, and finish annealing was performed at 1200 ° C. for 20 hours.
The annealing separator is magnesia (MgO): 100 parts by weight, Bi compound: 5 parts by weight, metal chlorine compound: 5
Parts by weight. A solution containing aluminum phosphate and colloidal silica as a main component was applied to the material after the finish annealing and dried to form a tension film.
【００３１】さらに圧延方向と直角方向に、５ｍｍの間
隔でレーザー照射した。単板で磁気測定を行った結果を
表６に示す。本発明例ではその到達鉄損値が低い。表面
が平滑化され磁壁移動が容易になった効果は、張力被膜
形成・レーザー照射による磁区細分化後も残っている。Further, laser irradiation was performed in the direction perpendicular to the rolling direction at intervals of 5 mm. Table 6 shows the results of magnetic measurement performed on a single plate. In the example of the present invention, the achieved iron loss value is low. The effect of smoothing the surface and facilitating domain wall movement remains after the magnetic domain subdivision by forming the tension film and irradiating the laser.
【００３２】[0032]
【表６】 [Table 6]
【００３３】[0033]
【発明の効果】本発明によれば、一度生成されたグラス
被膜を酸洗する必要がなくかつグラス被膜を酸洗したも
のよりも優れた鉄損値が得られるので工業的価値は極め
て大きい。Industrial Applicability According to the present invention, it is not necessary to pickle a glass film once formed, and an iron loss value superior to that obtained by pickling a glass film is obtained, so that the industrial value is extremely large.
【図１】（ａ）は従来法で酸洗した鋼板表面写真（倍率
×１）、（ｂ）は本発明例により得られる鋼板表面の写
真（倍率×１）である。FIG. 1 (a) is a photograph of a steel sheet surface pickled by a conventional method (magnification × 1), and FIG. 1 (b) is a photograph of a steel sheet surface obtained by an example of the present invention (magnification × 1).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村上 建一 富津市新富20−１ 新日本製鐵株式会社技 術開発本部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Murakami 20-1 Shintomi, Futtsu City Nippon Steel Corporation Technical Development Division
Claims (13)
鋼スラブを熱延し、必要に応じて焼鈍を施し、１回の冷
延または中間焼鈍を挟む２回以上の冷延を行い、脱炭焼
鈍後焼鈍分離剤を塗布、乾燥し仕上焼鈍を行う方向性電
磁鋼板の製造方法において、焼鈍分離剤１００重量部に
対して、ビスマスの塩化物を、塩素重量部で０．２部以
上１５部以下含めることを特徴とする超低鉄損方向性電
磁鋼板の製造法。1. A silicon steel slab containing 2 to 7% by weight of Si is hot-rolled, annealed as required, and cold-rolled once or twice or more with intermediate annealing interposed. In the method for producing a grain-oriented electrical steel sheet, which comprises performing decarburization annealing, applying an annealing separator, then drying and performing finish annealing, bismuth chloride is added in an amount of 0.2 parts by weight of chlorine based on 100 parts by weight of the annealing separator. A method for manufacturing an ultra-low iron loss grain-oriented electrical steel sheet, characterized by including not less than 15 parts and not more than 15 parts.
去し、絶縁張力被膜を表面に形成することを特徴とする
請求項１記載の超低鉄損方向性電磁鋼板の製造法。2. The method for producing an ultra-low iron loss grain-oriented electrical steel sheet according to claim 1, wherein after the finish annealing, the annealing separator is removed and an insulating tension film is formed on the surface.
ービーム、電子ビーム、プラズマ放電から選んだ１種ま
たは２種以上のビームを、コイル幅方向に線状または断
続した線状に照射し磁区の細分化することを特徴とする
請求項２記載の超低鉄損方向性電磁鋼板の製造法。3. After forming the insulating tension film, the surface of the steel sheet is irradiated with one or more kinds of beams selected from a laser beam, an electron beam and a plasma discharge linearly or intermittently in the coil width direction to form magnetic domains. 3. The method for manufacturing an ultra-low iron loss grain-oriented electrical steel sheet according to claim 2, wherein
去し、次いで圧延方向を横切って延びる連続または断続
した線状に鋼板表面の地鉄の一部を除去し、さらに鋼板
表面に張力被膜を形成することを特徴とする請求項２記
載の超低鉄損方向性電磁鋼板の製造法。4. After finishing annealing, the annealing separating agent is removed, and then a part of the base metal on the surface of the steel sheet is removed in a continuous or intermittent linear shape extending across the rolling direction, and the steel sheet surface is tensioned. The method for producing an ultra-low iron loss grain-oriented electrical steel sheet according to claim 2, wherein a coating film is formed.
去し、次いで鋼板表面に圧延方向を横切って延びる連続
または断続した線状の金属メッキを施した後、さらに鋼
板表面に張力被膜を形成することを特徴とする請求項２
記載の超低鉄損方向性電磁鋼板の製造法。5. After finishing annealing, the annealing separating agent is removed, and then a continuous or intermittent linear metal plating extending across the rolling direction is applied to the surface of the steel sheet, and then a tension coating is further applied to the surface of the steel sheet. It is formed, It is characterized by the above-mentioned.
A method for producing the described ultra-low iron loss grain-oriented electrical steel sheet.
鋼板表面に押圧により凹部を形成した後、張力被膜を７
５０℃以上の温度で形成することを特徴とする請求項２
記載の超低鉄損方向性電磁鋼板の製造法。6. After the finish annealing, the annealing separating agent is removed, and then a depression is formed on the surface of the steel sheet by pressing, and then a tension coating is applied to the surface of the steel sheet.
The film is formed at a temperature of 50 ° C. or higher.
A method for producing the described ultra-low iron loss grain-oriented electrical steel sheet.
を熱延後、必要に応じて焼鈍し、１回の冷延または中間
焼鈍を挟む２回以上の冷延を行い、脱炭焼鈍後、焼鈍分
離剤を塗布、乾燥して仕上焼鈍を行う方向性電磁鋼板の
製造方法において、ビスマス単体あるいはビスマスの化
合物及び金属の塩素化合物を含む焼鈍分離剤を用いるこ
とを特徴とする超低鉄損方向性電磁鋼板の製造法。7. A silicon steel slab containing Si: 2 to 7% by weight is hot-rolled and then annealed, if necessary, once cold-rolled or twice or more cold-rolled with an intermediate annealing to decarburize. After annealing, in a method for producing a grain-oriented electrical steel sheet which is applied with an annealing separator and is then dried and finish-annealed, an ultra-low characteristic of using an annealing separator containing bismuth simple substance or a bismuth compound and a chlorine compound of metal Iron loss direction electrical steel sheet manufacturing method.
ス、水酸化ビスマス、硫化ビスマス、硫酸ビスマス、リ
ン酸ビスマス、炭酸ビスマス、硝酸ビスマス、有機酸ビ
スマス、ハロゲン化ビスマスの１種あるいは２種以上の
混合物を用いることを特徴とする請求項７記載の超低鉄
損方向性電磁鋼板の製造法。8. The bismuth compound is one or a mixture of bismuth oxide, bismuth hydroxide, bismuth sulfide, bismuth sulfate, bismuth phosphate, bismuth carbonate, bismuth nitrate, bismuth organic acid and bismuth halide. The method for manufacturing an ultra-low iron loss grain-oriented electrical steel sheet according to claim 7, wherein
る金属の塩素化合物を用いることを特徴とする請求項７
または８記載の超低鉄損方向性電磁鋼板の製造法。9. A metal chlorine compound having a boiling point or sublimation point of 183 ° C. or higher is used.
Alternatively, the method for manufacturing an ultra-low iron loss grain-oriented electrical steel sheet according to 8.
コバルト、塩化ニッケルの１種あるいは２種以上の混合
物を用いることを特徴とする請求項７または８記載の超
低鉄損方向性電磁鋼板の製造法。10. The ultra-low iron loss grain oriented electrical steel sheet according to claim 7, wherein one or a mixture of two or more of iron chloride, cobalt chloride and nickel chloride is used as the metal chlorine compound. Manufacturing method.
力被膜を付与することを特徴とする請求項７乃至１０の
いずれかに記載の超低鉄損方向性電磁鋼板の製造法。11. The method for producing an ultra-low iron loss grain oriented electrical steel sheet according to claim 7, wherein the annealing separator is removed after the finish annealing and a tension coating is applied.
区細分化処理をすることを特徴とする請求項７乃至１０
のいずれかに記載の超低鉄損方向性電磁鋼板の製造法。12. The method according to claim 7, wherein after the finish annealing, the annealing separating agent is removed and the magnetic domain is refined.
The method for producing an ultra-low iron loss grain-oriented electrical steel sheet according to any one of 1.
区細分化処理及び張力被膜を付与することを特徴とする
請求項７乃至１０のいずれかに記載の超低鉄損方向性電
磁鋼板の製造法。13. The ultra-low iron loss grain-oriented electrical steel sheet according to claim 7, wherein after the finish annealing, the annealing separator is removed, and the magnetic domain refinement treatment and the tension coating are applied. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32305993A JP2664333B2 (en) | 1993-06-07 | 1993-11-16 | Manufacturing method for ultra-low iron loss grain-oriented electrical steel sheets |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-173556 | 1993-06-07 | ||
| JP17355693 | 1993-06-07 | ||
| JP32305993A JP2664333B2 (en) | 1993-06-07 | 1993-11-16 | Manufacturing method for ultra-low iron loss grain-oriented electrical steel sheets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0754155A true JPH0754155A (en) | 1995-02-28 |
| JP2664333B2 JP2664333B2 (en) | 1997-10-15 |
Family
ID=26495488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32305993A Expired - Lifetime JP2664333B2 (en) | 1993-06-07 | 1993-11-16 | Manufacturing method for ultra-low iron loss grain-oriented electrical steel sheets |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2664333B2 (en) |
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- 1993-11-16 JP JP32305993A patent/JP2664333B2/en not_active Expired - Lifetime
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