JPH07278827A - Low-iron-loss grain-oriented silicon steel sheet having magnesium oxide-aluminum oxide composite coating film and its production - Google Patents
Low-iron-loss grain-oriented silicon steel sheet having magnesium oxide-aluminum oxide composite coating film and its productionInfo
- Publication number
- JPH07278827A JPH07278827A JP7361494A JP7361494A JPH07278827A JP H07278827 A JPH07278827 A JP H07278827A JP 7361494 A JP7361494 A JP 7361494A JP 7361494 A JP7361494 A JP 7361494A JP H07278827 A JPH07278827 A JP H07278827A
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- Prior art keywords
- steel sheet
- aluminum oxide
- silicon steel
- magnesium oxide
- composite coating
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鋼板に大きな張力を付
与する被膜を表面に有することで、鉄損が低減された一
方向性珪素鋼板およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a unidirectional silicon steel sheet having reduced iron loss by having a coating on its surface which imparts a large tension to the steel sheet, and a method for producing the same.
【０００２】[0002]
【従来の技術】一方向性珪素鋼板は、（１１０），〔０
０１〕を主方位とする結晶組織を有し、磁気鉄芯材料と
して多用されており、特にエネルギーロスを少なくする
ために鉄損の小さい材料が求められている。一方向性珪
素鋼板の鉄損を低減する手段としては、仕上げ焼鈍後の
鋼板表面にレーザービームを照射して局部的な歪を与
え、それによって磁区を細分化する方法が特開昭５８−
２６４０５号公報に開示されている。また鉄芯加工後の
歪取り焼鈍（応力除去焼鈍）を施した後もその効果が消
失しない磁区細分化手段が、例えば特開昭６２−８６１
７５号公報に開示されている。2. Description of the Related Art One-directional silicon steel sheets are (110), [0
[01] is mainly used as a magnetic iron core material, and a material having a small iron loss is required to reduce energy loss. As a means for reducing the iron loss of a unidirectional silicon steel sheet, there is a method of irradiating a laser beam on the surface of the steel sheet after finish annealing to give a local strain, and thereby subdividing the magnetic domain.
It is disclosed in Japanese Patent No. 26405. Further, there is a magnetic domain subdivision means which does not lose its effect even after strain relief annealing (stress relief annealing) after iron core processing is disclosed in, for example, JP-A-62-861.
No. 75 publication.
【０００３】一方で、鉄および珪素を含有する鉄合金は
結晶磁気異方性が大きいため、外部張力を付加すると磁
区の細分化が起こり、鉄損の主要素である渦電流損失を
低下させることができる。したがって、５％以下の珪素
を含有する一方向性珪素鋼板の鉄損の低減には鋼板に張
力を付与することが有効であり、１．５kgf/mm2 程度ま
での張力付与によって効果的に鉄損が低減できることが
知られている。この張力は通常、表面に形成された被膜
によって付与されている。On the other hand, since iron alloys containing iron and silicon have large crystal magnetic anisotropy, application of external tension causes subdivision of magnetic domains, which reduces eddy current loss which is a main factor of iron loss. You can Therefore, it is effective to apply tension to the steel sheet in order to reduce the iron loss of the unidirectional silicon steel sheet containing 5% or less of silicon, and it is effective to apply the tension up to about 1.5 kgf / mm 2. It is known that the loss can be reduced. This tension is usually applied by a film formed on the surface.
【０００４】従来、一方向性珪素鋼板には、仕上げ焼鈍
工程で鋼板表面の酸化物と焼鈍分離剤とが反応して生成
するフォルステライトを主体とする１次被膜、および特
開昭４８−３９３３８号公報等に開示されたコロイド状
シリカとりん酸塩とを主体とするコーティング液を焼き
付けることによって生成する２次被膜の２層の被膜によ
って１．０kgf/mm2 程度の張力が付与されている。した
がって、これら現行被膜の場合、より大きな張力付与に
よる鉄損改善の余地は残されているものの、被膜を厚く
することによる付与張力の増加は占積率の低下をもたら
すため好ましくない。Conventionally, for unidirectional silicon steel sheets, a primary coating mainly composed of forsterite formed by a reaction between an oxide on the surface of the steel sheet and an annealing separator in the finish annealing step, and Japanese Patent Laid-Open No. 48-39338. A tension of about 1.0 kgf / mm 2 is given by the two-layer coating film, which is a secondary coating film produced by baking the coating liquid mainly containing colloidal silica and phosphate disclosed in Japanese Patent Publication No. . Therefore, in the case of these existing coatings, there is still room for iron loss improvement by applying a larger tension, but increasing the applied tension by thickening the coating leads to a decrease in space factor, which is not preferable.
【０００５】また、一方向性珪素鋼板の鉄損を改善する
もうひとつの方法として、仕上げ焼鈍後の鋼板表面の凹
凸や表面近傍の内部酸化層を除去して鏡面仕上げを行
い、その表面に金属メッキを施す方法が特公昭５２−２
４４９９号公報に、さらにその表面に張力被膜を形成す
る方法が例えば特公昭５６−４１５０号公報、特開昭６
１−２０１７３２号公報、特公昭６３−５４７６７号公
報、特開平２−２１３４８８号公報等に開示されてい
る。これらの場合においても、被膜による鋼板への張力
付与の大きい方が鉄損改善効果が大きい。これらのこと
から、密着性に優れ、薄くて鋼板に大きな張力が付与で
きる被膜が望まれていた。As another method for improving the iron loss of a unidirectional silicon steel sheet, the unevenness of the surface of the steel sheet after finish annealing and the internal oxide layer near the surface are removed to give a mirror finish, and the surface is made of metal. The method of plating is Japanese Patent Publication Sho 52-2
4499 discloses a method of further forming a tension film on the surface thereof, for example, JP-B-56-4150 and JP-A-6-61.
No. 1-201732, JP-B-63-54767, JP-A-2-213488, and the like. Even in these cases, the larger the tension applied to the steel sheet by the coating, the greater the iron loss improving effect. From these things, a coating film which is excellent in adhesion, thin, and capable of imparting a large tension to a steel sheet has been desired.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、これら従来
技術における問題点を解決し、鋼板に大きな張力を付与
する被膜を表面に有することにより鉄損が低減された一
方向性珪素鋼板、およびその製造方法を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention solves these problems in the prior art, and has a coating film that gives a large tension to the steel sheet on the surface thereof. It is an object to provide a manufacturing method thereof.
【０００７】[0007]
【課題を解決するための手段】本発明は、表面に酸化
マグネシウム−酸化アルミニウム系複合被膜を有する一
方向性珪素鋼板、酸化マグネシウム−酸化アルミニウ
ム系複合被膜が結晶質スピネルを含有する一方向性珪素
鋼板、表面に酸化マグネシウム−酸化アルミニウム−
非晶質酸化物系複合被膜を有する一方向性珪素鋼板、
酸化マグネシウム−酸化アルミニウム−非晶質酸化物系
複合被膜が、結晶質スピネル、および／または珪素、ほ
う素、りんの少なくとも１種を成分として含む非晶質相
を含有する一方向性珪素鋼板を要旨とする。DISCLOSURE OF THE INVENTION The present invention is directed to a unidirectional silicon steel sheet having a magnesium oxide-aluminum oxide composite coating on its surface, and a unidirectional silicon having a magnesium oxide-aluminum oxide composite coating containing crystalline spinel. Steel plate, magnesium oxide on the surface-aluminum oxide-
A unidirectional silicon steel sheet having an amorphous oxide composite coating,
A magnesium oxide-aluminum oxide-amorphous oxide-based composite coating comprises a unidirectional silicon steel sheet containing a crystalline spinel and / or an amorphous phase containing at least one of silicon, boron and phosphorus as a component. Use as a summary.
【０００８】また、仕上げ焼鈍が完了した鋼板表面に酸
化マグネシウム前駆体化合物、酸化アルミニウム前駆体
化合物を含む懸濁液を塗布、乾燥後、５００〜１３５０
℃の温度で焼き付け、酸化物被膜を形成せしめることを
特徴とする製造方法を要旨とする。さらに、酸化アルミ
ニウム前駆体化合物が酸化アルミニウム前駆体ゾルであ
る製造方法を要旨とする。Further, a suspension containing a magnesium oxide precursor compound and an aluminum oxide precursor compound is applied to the surface of the steel sheet that has been subjected to finish annealing, dried, and then 500 to 1350.
The gist is a manufacturing method characterized by baking at a temperature of ° C to form an oxide film. Furthermore, the gist is a manufacturing method in which the aluminum oxide precursor compound is an aluminum oxide precursor sol.
【０００９】[0009]
【作用】以下に本発明を詳細に説明する。本発明の一方
向性珪素鋼板は、その表面に酸化マグネシウム−酸化ア
ルミニウム系複合被膜を有している。従来より、珪素鋼
板への張力付与には熱膨張係数の小さい被膜材質を選択
し、鋼板との熱膨張係数差によって冷却時に生じる応力
を利用していた。しかしながら、熱膨張係数だけではな
く、被膜材質のヤング率も鋼板への張力付与に影響をお
よぼす因子であることが指摘されている。本発明の被膜
構成成分の役割を明確に規定することは不可能である
が、酸化アルミニウム成分はヤング率が比較的大きく、
これに酸化マグネシウムを複合化することで鋼板に大き
な張力が付与されていると推察している。The present invention will be described in detail below. The unidirectional silicon steel sheet of the present invention has a magnesium oxide-aluminum oxide composite coating on its surface. Conventionally, a film material having a small coefficient of thermal expansion has been selected for applying tension to a silicon steel sheet, and stress generated during cooling due to a difference in coefficient of thermal expansion from the steel sheet has been used. However, it has been pointed out that not only the thermal expansion coefficient, but also the Young's modulus of the coating material is a factor that affects the application of tension to the steel sheet. Although it is impossible to clearly define the role of the constituent components of the coating film of the present invention, the Young's modulus of the aluminum oxide component is relatively large,
It is speculated that a large amount of tension is applied to the steel sheet by combining this with magnesium oxide.
【００１０】酸化マグネシウムはペリクレースとよばれ
るものだけが結晶相として知られているが、酸化アルミ
ニウムには、α−，γ−，δ−，θ−等いくつかの結晶
系が存在し、鋼板への張力付与効果はそれぞれの結晶系
において必ずしも同一ではない。しかしながら、本発明
の酸化アルミニウムはこのいずれであっても差し支えな
い。またいずれの化合物とも必ずしも良好な結晶性を有
する結晶である必要はなく、結晶性のあまり良くない非
晶質的なもの、あるいは結晶の前駆体となるような化合
物であっても構わない。Although only what is called periclase is known as a crystalline phase of magnesium oxide, aluminum oxide has several crystal systems such as α-, γ-, δ-, and θ-. The effect of imparting the tension is not necessarily the same in each crystal system. However, the aluminum oxide of the present invention may be any of these. Further, any of the compounds does not necessarily have to be crystals having good crystallinity, and may be an amorphous compound having poor crystallinity or a compound that serves as a crystal precursor.
【００１１】またこれらの被膜中に結晶質スピネルを含
有することでより大きな張力付与が可能となる場合があ
る。スピネルは、ＭｇＯ・Ａｌ2 Ｏ3 の化学式で表記さ
れる結晶であり、すでに述べた低熱膨張係数、高いヤン
グ率という性質によって鋼板に対して高い張力付与をも
たらしていると推察される。スピネルには１：１組成を
中心にアルミナ過剰側に固溶域が存在することが知られ
ているが、本発明の被膜中に存在する結晶質スピネル
は、定比組成、固溶体のいずれであってもまったく支障
なく用いることができる。Further, the inclusion of crystalline spinel in these coatings may make it possible to apply a larger tension. Spinel is a crystal represented by the chemical formula of MgO.Al 2 O 3 , and it is presumed that it imparts high tension to the steel sheet due to the properties of the low thermal expansion coefficient and high Young's modulus described above. It is known that the spinel has a solid solution region on the alumina excess side centering on a 1: 1 composition, but the crystalline spinel present in the coating film of the present invention is either a stoichiometric composition or a solid solution. However, it can be used without any problems.
【００１２】本発明の複合被膜中の酸化マグネシウムと
酸化アルミニウムの存在割合は、比較的幅広い範囲とす
ることが可能であり、いかなる割合とすることもでき
る。しかしながら複合被膜の特長を最大限に発揮させる
ためにはそれぞれの成分を最低でも被膜全体に対する重
量割合で５％、好ましくは１０％以上含有させるのが良
い。また、結晶質スピネルの量もいかなる割合とするこ
ともでき、この化合物をできるだけ多く含有させること
でより高い張力の付与が可能となるが、被膜の表面性状
が悪くなる傾向があるため、必要に応じて最適な量を決
定することが好ましい。結晶質スピネルの好ましい含有
量としては、被膜全体に対する重量割合で９０％以下、
より好ましくは８０％以下であり、通常は、５〜７５％
程度の範囲から選択される。The proportion of magnesium oxide and aluminum oxide present in the composite coating of the present invention can be in a relatively wide range, and can be any proportion. However, in order to maximize the features of the composite coating, it is preferable that the respective components are contained in a weight ratio of at least 5%, preferably 10% or more with respect to the entire coating. Further, the amount of the crystalline spinel can be set to any ratio, and higher tension can be imparted by containing this compound as much as possible, but the surface quality of the coating tends to be deteriorated, so that it is necessary. It is preferable to determine the optimum amount accordingly. The preferable content of the crystalline spinel is 90% or less by weight ratio to the entire coating,
It is more preferably 80% or less, and usually 5 to 75%.
It is selected from a range of degrees.
【００１３】本発明のもうひとつの一方向性珪素鋼板表
面には、酸化マグネシウム−酸化アルミニウム−非晶質
酸化物系複合被膜を有している。酸化マグネシウム成
分、酸化アルミニウム成分の役割はすでに述べたとおり
であるが、非晶質酸化物成分の役割として、鋼板への張
力付与にはそれほど大きな効果はなく、表面平滑性、下
地鋼板との密着性等を大きく改善していると推察してい
る。なかでも、珪素、ほう素、りんの少なくとも１種を
成分として含む非晶質相がとりわけこの効果が顕著であ
ることを見い出した。特にガラス状物質を形成している
ときに著しく大きな効果が得られる。非晶質相中の珪
素、ほう素、りんの含有量は、それぞれの酸化物換算の
合計で非晶質相全体に対する重量割合で５０％以上、好
ましくは７０％以上である。On the surface of another unidirectional silicon steel sheet of the present invention, a magnesium oxide-aluminum oxide-amorphous oxide composite coating film is provided. The roles of the magnesium oxide component and aluminum oxide component are as described above, but as the role of the amorphous oxide component, there is not a great effect on the tension application to the steel sheet, and the surface smoothness and adhesion to the base steel sheet It is presumed that the sex is greatly improved. Among them, it has been found that this effect is particularly remarkable in an amorphous phase containing at least one of silicon, boron and phosphorus as a component. In particular, a remarkably large effect is obtained when forming a glassy substance. The content of silicon, boron, and phosphorus in the amorphous phase is 50% or more, preferably 70% or more in terms of the total weight of the respective oxides in terms of the weight ratio to the entire amorphous phase.
【００１４】また、非晶質相には、珪素、ほう素、りん
以外に微量の成分を含有していても一向に差し支えな
い。可能性のある元素としては、被膜主成分であるＡ
ｌ，Ｍｇ、母材構成成分であるＦｅ、１次被膜成分であ
るＴｉ，Ｍｎ，Ｓの他に、Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｓ
ｒ，Ｂａ，Ｖ，Ｃｒ，Ｎｉ，Ｃｏ，Ｃｕをはじめとする
アルカリ金属、アルカリ土類金属、遷移金属元素、ある
いはＳｎ，Ｐｂ，Ｂｉ，Ｓｂ等があげられる。非晶質相
全体としての含有量は特に制限はないが、あまり多くな
りすぎると鋼板への張力付与が十分でなくなるため、被
膜全体に対する重量割合で９０％以下、より好ましくは
７０％以下である。また少なすぎる場合には、十分に平
滑な被膜表面、良好な密着性が得られない場合があるた
め、被膜全体に対する重量割合で５％以上、より好まし
くは１０％以上含有することが望ましい。Further, the amorphous phase may contain a trace amount of components other than silicon, boron and phosphorus. As a possible element, the main component of the film is A
l, Mg, Fe as a base material constituent, and Ti, Mn, S as primary film constituents, Li, Na, K, Ca, S
Examples thereof include alkali metals such as r, Ba, V, Cr, Ni, Co and Cu, alkaline earth metals, transition metal elements, Sn, Pb, Bi and Sb. The content of the amorphous phase as a whole is not particularly limited, but if the amount is too large, the tensile strength of the steel sheet will not be sufficient, so the weight ratio to the entire coating is 90% or less, more preferably 70% or less. . On the other hand, if the amount is too small, a sufficiently smooth coating surface and good adhesion may not be obtained in some cases. Therefore, it is desirable that the content is 5% or more, and more preferably 10% or more by weight ratio to the entire coating.
【００１５】本発明の一方向性珪素鋼板表面の被膜は、
厚すぎる場合には占積率が低下するため目的に応じてで
きるだけ薄いものが良く、ひとつの目安としては鋼板厚
さの５％以下である。より好ましくは、鋼板厚さの２％
以下である。また張力付与の観点からは、極端に薄くて
は十分な効果が得られず、０．１μｍ以上が望ましい。
以下に、本発明の一方向性珪素鋼板を好適に製造する方
法について述べる。The coating on the surface of the unidirectional silicon steel sheet according to the present invention is
If it is too thick, the space factor will decrease, so that it should be as thin as possible depending on the purpose, and one guideline is 5% or less of the steel plate thickness. More preferably, 2% of steel plate thickness
It is the following. Further, from the viewpoint of applying tension, if it is extremely thin, a sufficient effect cannot be obtained, and 0.1 μm or more is desirable.
Hereinafter, a method for suitably manufacturing the unidirectional silicon steel sheet of the present invention will be described.
【００１６】仕上げ焼鈍が完了した鋼板表面に、酸化マ
グネシウム前駆体化合物、酸化アルミニウム前駆体化合
物を含む懸濁液を塗布、乾燥後、５００〜１３５０℃の
温度で焼き付け、酸化物被膜を形成することによる製造
方法である。ここでいう仕上げ焼鈍が完了した鋼板と
は、：従来公知の方法によって仕上げ焼鈍を行い、表
面にフォルステライト質の１次被膜が形成された鋼板、
：１次被膜、および付随的に生成している酸化層を酸
に浸漬して除去した鋼板、：で得た鋼板を水素中で
平坦化焼鈍を行った鋼板、あるいは化学研磨、電解研磨
等の研磨を施した鋼板、：被膜生成に対して不活性で
あるアルミナ粉末等、または塩化物等の微量添加物を添
加した従来公知の焼鈍分離剤を塗布し、１次被膜を生成
させない条件下で仕上げ焼鈍を行った鋼板、等を指す。Applying a suspension containing a magnesium oxide precursor compound and an aluminum oxide precursor compound to the surface of the steel sheet that has been subjected to finish annealing, drying and baking at a temperature of 500 to 1350 ° C. to form an oxide film. Is a manufacturing method. The steel sheet that has been subjected to finish annealing as used herein means: a steel sheet that has been subjected to finish annealing by a conventionally known method and has a forsterite primary coating formed on its surface,
A steel sheet obtained by immersing an acid layer in a primary coating and an oxide layer that is additionally formed, and a steel sheet obtained by: being flattened and annealed in hydrogen, or by chemical polishing, electrolytic polishing, or the like. Polished steel plate: Alumina powder, which is inactive to form a film, or a conventionally known annealing separator containing a trace amount of additives such as chloride is applied under the condition that a primary film is not formed. This refers to steel sheets that have undergone finish annealing.
【００１７】酸化マグネシウム前駆体化合物は、焼き付
け後（熱処理）に酸化マグネシウムとなる化合物の総称
であり、酸化マグネシウムはもとより、水酸化マグネシ
ウム、あるいは硝酸マグネシウム、塩化マグネシウムを
はじめとする各種のマグネシウム塩等を指す。酸化アル
ミニウム前駆体化合物も同様に焼き付け後（熱処理）に
酸化アルミニウムとなる化合物の総称であり、酸化アル
ミニウムはもとより、ベーマイトのようなＡｌ2 Ｏ3 ・
ｎＨ2 Ｏで表記される酸化アルミニウムの水和物、水酸
化アルミニウム、あるいは硝酸アルミニウム、塩化アル
ミニウムをはじめとする各種のアルミニウム塩等を含
む。The magnesium oxide precursor compound is a general term for compounds that become magnesium oxide after baking (heat treatment). In addition to magnesium oxide, magnesium hydroxide, or various magnesium salts such as magnesium nitrate and magnesium chloride. Refers to. Similarly, the aluminum oxide precursor compound is a generic term for compounds that become aluminum oxide after baking (heat treatment). Not only aluminum oxide but also Al 2 O 3 · such as boehmite.
Aluminum oxide hydrate represented by nH 2 O, aluminum hydroxide, or various aluminum salts such as aluminum nitrate and aluminum chloride are included.
【００１８】これらの原料を分散媒に分散させて懸濁液
（スラリー）を作製する。分散媒は作業性、コスト等の
点から水が最も好適であるが、他の工程で特に支障がな
ければ有機溶媒、あるいはこれらの混合物が使用でき
る。スラリーを作製した時点で原料のうちのある種のも
のは溶解する可能性があるが、これは一向に差し支えな
い。These raw materials are dispersed in a dispersion medium to prepare a suspension (slurry). Water is most suitable as the dispersion medium from the viewpoints of workability and cost, but an organic solvent or a mixture thereof can be used if there is no particular problem in other steps. Some of the raw materials may dissolve at the time of making the slurry, but this is all right.
【００１９】こうして得たスラリーをロールコーター等
のコーター、ディップ法、スプレー吹き付け、あるいは
電気泳動等従来公知の方法によって仕上げ焼鈍が完了し
た一方向性珪素鋼板表面に塗布する。乾燥後、５００〜
１３５０℃で焼き付けることによって表面に酸化物被膜
を形成する。焼き付け時の雰囲気は、窒素等の不活性ガ
ス雰囲気、窒素−水素混合雰囲気等の還元雰囲気が好ま
しく、空気、あるいは酸素を含む雰囲気は鋼板を酸化さ
せる可能性があり、好ましくない。雰囲気ガスの露点に
ついては特に制限はない。焼き付け温度が５００℃未満
の場合、塗布した前駆体が酸化物とならない場合があ
り、また焼き付け温度が低いため十分な張力が発現せ
ず、好ましくない。一方、１３５０℃を超える場合、特
に大きな不都合はないものの経済的でなく、より好まし
くは１２５０℃以下である。The slurry thus obtained is applied to the surface of the unidirectional silicon steel sheet on which finish annealing has been completed by a conventionally known method such as a coater such as a roll coater, a dipping method, spraying, or electrophoresis. After drying, 500 ~
An oxide film is formed on the surface by baking at 1350 ° C. The atmosphere during baking is preferably an inert gas atmosphere such as nitrogen, a reducing atmosphere such as a nitrogen-hydrogen mixed atmosphere, and an atmosphere containing air or oxygen may oxidize the steel sheet, which is not preferable. There is no particular limitation on the dew point of the atmospheric gas. When the baking temperature is lower than 500 ° C., the applied precursor may not become an oxide, and since the baking temperature is low, sufficient tension is not expressed, which is not preferable. On the other hand, when the temperature exceeds 1350 ° C, it is not economical although it is not particularly inconvenient, and more preferably 1250 ° C or less.
【００２０】前述のスラリーのうち、酸化アルミニウム
前駆体として、いわゆるゾルとよばれる微粒子分散系を
用いることにより薄くて均一、かつ密着性の良い被膜が
得られる場合がある。これは表面に非金属物質が存在せ
ず、金属面上に直接被膜を形成するような場合に特に顕
著である。かかるときには上述の微粒子分散系ゾル、あ
るいは可溶性成分を含んだゾルが好適に用いられる。塗
布液としてゾル溶液を用いる場合には、酸化アルミニウ
ム前駆体化合物として上述のベーマイトゾル、および／
またはアルミナゾルとよばれているものが作業性、ある
いは価格の点から特に好適に用いられる。Of the above-mentioned slurries, a thin and uniform coating having good adhesion may be obtained by using a so-called sol fine particle dispersion system as the aluminum oxide precursor. This is particularly remarkable when a non-metal substance does not exist on the surface and a film is directly formed on the metal surface. In this case, the fine particle dispersed sol described above or a sol containing a soluble component is preferably used. When a sol solution is used as the coating liquid, the above boehmite sol as the aluminum oxide precursor compound, and /
Alternatively, what is called an alumina sol is particularly preferably used from the viewpoint of workability and cost.
【００２１】酸化アルミニウム前駆体化合物として酸化
アルミニウム前駆体ゾルを用いる場合、酸化マグネシウ
ム前駆体化合物としては気相法等によって作製した酸化
マグネシウム超微粉末、液相法等によって作製した微粉
末あるいはそれを分散させたままの状態のもの、可溶性
マグネシウム塩類を用いることが好ましく、これによっ
てきわめてミクロなレベルでの均一混合が実現する。酸
化アルミニウム前駆体ゾルの使用においても、前述のス
ラリーの場合と同様に分散媒、特に水に分散させて使用
することが可能である。特に良好な分散性を得るため
に、酸、アルカリ等の添加による塗布液のｐＨ制御等は
しばしば用いられる手法であり、本発明においても特に
支障なく行うことができる。また、鋼板への塗布性を改
善するための極微量の界面活性剤等の添加についてもま
ったく問題がない。以下に本発明を実施例を用いて具体
的に説明するが、本発明はかかる実施例にのみ限定され
るものではない。When an aluminum oxide precursor sol is used as the aluminum oxide precursor compound, the magnesium oxide precursor compound is ultrafine magnesium oxide powder produced by a vapor phase method or the like, or fine powder produced by a liquid phase method or the like. It is preferable to use as-dispersed magnesium salts and soluble magnesium salts, which realizes uniform mixing at a very micro level. Also when using the aluminum oxide precursor sol, it is possible to disperse it in a dispersion medium, especially water, as in the case of the above-mentioned slurry. In order to obtain particularly good dispersibility, pH control of the coating solution by addition of acid, alkali or the like is a technique often used, and the present invention can be carried out without any particular problems. In addition, there is no problem in adding a very small amount of a surfactant or the like to improve the coating property on the steel sheet. The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
【００２２】[0022]
実施例１ 市販の酸化マグネシウム微粉末、酸化アルミニウム粉末
（α−Ａｌ2 Ｏ3 ）を表１に示した割合に混合し、これ
に蒸留水を加えてスラリーを作製した。これを、Ｓｉを
３．２％含有する厚さ０．２mmの仕上げ焼鈍が完了した
一方向性珪素鋼板（フォルステライト質の１次被膜あ
り）に片面４ｇ／ｍ2 となるように塗布、乾燥後、Ｈ2
を５ vol％含有するＮ2 雰囲気中で８００℃、５分間焼
き付けることによって表面に酸化物被膜を形成した。Example 1 Commercially available magnesium oxide fine powder and aluminum oxide powder (α-Al 2 O 3 ) were mixed in the proportions shown in Table 1, and distilled water was added to this to prepare a slurry. This was applied to a 0.2 mm-thick finish-annealed unidirectional silicon steel sheet (having a primary coating of forsterite) containing 3.2% of Si so that one side was 4 g / m 2 and dried. After that, H 2
Oxide film was formed on the surface by baking at 800 ° C. for 5 minutes in an N 2 atmosphere containing 5 vol.
【００２３】化学分析、Ｘ線回折、電子顕微鏡等の結果
から、得られた被膜はＭｇＯ，α−Ａｌ2 Ｏ3 ，スピネ
ルを主体としていることがわかった。２０mmφの円柱の
周囲に、その角度が１８０度となるように巻き付け試験
を行い、その剥離状況から評価した被膜の密着性はきわ
めて良好であった。片面の被膜を除去し、板の曲がりか
ら測定した鋼板への付与張力、および磁気特性を表１に
記した。表１の結果から、いずれも著しく鉄損の低い一
方向性珪素鋼板が得られていることがわかる。また表面
に形成された被膜の化学的安定性もきわめて良好であっ
た。From the results of chemical analysis, X-ray diffraction, electron microscopy, etc., it was found that the obtained coating mainly contained MgO, α-Al 2 O 3 and spinel. A winding test was conducted around a 20 mmφ cylinder so that the angle was 180 degrees, and the adhesion of the coating film evaluated from the peeling condition was very good. Table 1 shows the tension applied to the steel sheet measured from the bending of the sheet after removing the coating on one side and the magnetic properties. From the results in Table 1, it can be seen that the grain-oriented silicon steel sheets having significantly low iron loss are obtained. The chemical stability of the coating film formed on the surface was also very good.
【００２４】[0024]
【表１】 [Table 1]
【００２５】実施例２ 市販の酸化マグネシウム微粉末、ベーマイト粉末（平均
粒径：１００nm）を表２に示した割合に混合しこれに蒸
留水を加えて混合ゾルを作製した。これをＳｉを３．２
％含有し、酸化アルミニウムを焼鈍分離剤として塗布
し、２次再結晶と同時に鏡面化処理を施した厚さ０．２
mmの一方向性珪素鋼板に片面４ｇ／ｍ2 となるように塗
布、乾燥後、Ｈ2 を１０ vol％含有するＮ2 雰囲気中で
１０００℃、１０分間焼き付けることによって表面に酸
化物被膜を形成した。Example 2 Commercially available magnesium oxide fine powder and boehmite powder (average particle size: 100 nm) were mixed in the ratio shown in Table 2, and distilled water was added to this to prepare a mixed sol. This is Si 3.2
%, Aluminum oxide applied as an annealing separator, and subjected to secondary recrystallization and mirror-finishing at a thickness of 0.2
on a unidirectional silicon steel sheet of 4 g / m 2 on one side, dried, and baked at 1000 ° C. for 10 minutes in an N 2 atmosphere containing 10 vol% of H 2 to form an oxide film on the surface. did.
【００２６】化学分析、Ｘ線回折、電子顕微鏡等の結果
から測定した被膜の結晶相を表２に記した。表中の全て
の組成において、スピネルの生成が確認された。実施例
１と同様に評価した被膜の密着性はきわめて良好であっ
た。片面の被膜を除去し、板の曲がりから測定した鋼板
への付与張力、および磁気特性を表２に併記した。表２
の結果から、いずれも著しく鉄損の低い一方向性珪素鋼
板が得られていることがわかる。また表面に形成された
被膜の化学的安定性もきわめて良好であった。Table 2 shows the crystal phases of the coating film measured from the results of chemical analysis, X-ray diffraction, electron microscopy and the like. Formation of spinel was confirmed in all the compositions in the table. The adhesion of the coating film evaluated in the same manner as in Example 1 was extremely good. Table 2 shows the tension applied to the steel sheet measured from the bending of the sheet after removing the coating on one side and the magnetic properties. Table 2
From the results, it can be seen that a unidirectional silicon steel sheet having a significantly low iron loss was obtained. The chemical stability of the coating film formed on the surface was also very good.
【００２７】[0027]
【表２】 [Table 2]
【００２８】実施例３ 市販の酸化マグネシウム微粉末、ベーマイト粉末（平均
粒径：１００nm）、テトラエトキシシラン、ほう酸試薬
を表３に示した割合に混合し、これに蒸留水を加えて混
合ゾルを作製した。これを、Ｓｉを３．２％含有する厚
さ０．２mmの仕上げ焼鈍が完了した一方向性珪素鋼板
（フォルステライト質の１次被膜あり）に片面４ｇ／ｍ
2 となるように塗布、乾燥後、Ｈ2 を３ vol％含有する
Ｎ2 雰囲気中で８５０℃、３分間焼き付けることによっ
て表面に酸化物被膜を形成した。Example 3 Commercially available magnesium oxide fine powder, boehmite powder (average particle size: 100 nm), tetraethoxysilane and boric acid reagent were mixed in the proportions shown in Table 3, and distilled water was added to this to prepare a mixed sol. It was made. This was applied to a unidirectional silicon steel sheet (containing a forsterite primary coating) containing 3.2% of Si and having a thickness of 0.2 mm and finished by finishing, 4 g / m on each side.
After being coated so as to have a thickness of 2 and dried, it was baked at 850 ° C. for 3 minutes in an N 2 atmosphere containing 3 vol% of H 2 to form an oxide film on the surface.
【００２９】化学分析、Ｘ線回折、電子顕微鏡等の結果
から測定した被膜の結晶相を表３に記した。ほう素、珪
素を含有する結晶質相が観察されないことより、ほう
素、珪素成分は非晶質相となって存在していることがわ
かる。実施例１と同様に評価した被膜の密着性はきわめ
て良好であった。片面の被膜を除去し、板の曲がりから
測定した鋼板への付与張力、および磁気特性を表３に併
記した。表３の結果から、いずれも著しく鉄損の低い一
方向性珪素鋼板が得られていることがわかる。また表面
に形成された被膜の化学的安定性もきわめて良好であっ
た。Table 3 shows the crystal phase of the coating film measured from the results of chemical analysis, X-ray diffraction, electron microscopy and the like. Since no crystalline phase containing boron and silicon is observed, it is understood that the boron and silicon components exist as an amorphous phase. The adhesion of the coating film evaluated in the same manner as in Example 1 was extremely good. Table 3 shows the tension applied to the steel sheet measured from the bending of the sheet after removing the coating on one surface and the magnetic properties. From the results in Table 3, it can be seen that the grain-oriented silicon steel sheets having extremely low iron loss are obtained. The chemical stability of the coating film formed on the surface was also very good.
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【発明の効果】本発明により、特定成分の被膜を有し、
化学的に安定で、かつその張力付与効果によって鉄損が
著しく改善された一方向性珪素鋼板、およびその製造方
法を提供することができる。本発明は特に、従来から用
いられている１次被膜を有する鋼板、あるいは著しい低
鉄損化を目的とした鏡面化鋼板のいずれに対しても良好
な特性を示し、汎用性の観点からも工業的効果は甚大で
ある。According to the present invention, it has a film of a specific component,
It is possible to provide a unidirectional silicon steel sheet which is chemically stable and whose iron loss is remarkably improved by its tension-imparting effect, and a method for producing the same. The present invention particularly exhibits good characteristics with respect to both a steel sheet having a primary coating that has been conventionally used and a mirror-finished steel sheet for the purpose of significantly reducing iron loss. The effect is enormous.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成７年６月１４日[Submission date] June 14, 1995
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の名称[Name of item to be amended] Title of invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の名称】 酸化マグネシウム−酸化アルミニウム
系複合被膜を有する低鉄損一方向性珪素鋼板およびその
製造方法Title: Low iron loss unidirectional silicon steel sheet having magnesium oxide-aluminum oxide composite coating and method for producing the same
Claims (6)
ウム系複合被膜を有する低鉄損一方向性珪素鋼板。1. A low iron loss unidirectional silicon steel sheet having a magnesium oxide-aluminum oxide composite coating on its surface.
複合被膜が結晶質スピネルを含有する請求項１に記載の
低鉄損一方向性珪素鋼板。2. The low iron loss unidirectional silicon steel sheet according to claim 1, wherein the magnesium oxide-aluminum oxide composite coating contains a crystalline spinel.
ウム−非晶質酸化物系複合被膜を有する低鉄損一方向性
珪素鋼板。3. A low iron loss unidirectional silicon steel sheet having a magnesium oxide-aluminum oxide-amorphous oxide composite coating on its surface.
非晶質酸化物系複合被膜が、結晶質スピネル、および／
または珪素、ほう素、りんの少なくとも１種を成分とし
て含む非晶質相を含有する請求項３に記載の低鉄損一方
向性珪素鋼板。4. Magnesium oxide-aluminum oxide-
The amorphous oxide-based composite coating is crystalline spinel, and / or
The low iron loss unidirectional silicon steel sheet according to claim 3, further comprising an amorphous phase containing at least one of silicon, boron and phosphorus as a component.
表面に、酸化マグネシウム前駆体化合物、酸化アルミニ
ウム前駆体化合物を含む懸濁液を塗布、乾燥後、５００
〜１３５０℃の温度で焼き付け、酸化物被膜を形成せし
める低鉄損一方向性珪素鋼板の製造方法。5. A suspension containing a magnesium oxide precursor compound and an aluminum oxide precursor compound is applied to the surface of the unidirectional silicon steel sheet that has been subjected to finish annealing, dried, and then 500
A method for producing a low iron loss unidirectional silicon steel sheet, which comprises baking at a temperature of ˜1350 ° C. to form an oxide film.
ルミニウム前駆体ゾルである請求項５に記載の低鉄損一
方向性珪素鋼板の製造方法。6. The method for producing a low iron loss unidirectional silicon steel sheet according to claim 5, wherein the aluminum oxide precursor compound is an aluminum oxide precursor sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6073614A JP2698549B2 (en) | 1994-04-12 | 1994-04-12 | Low iron loss unidirectional silicon steel sheet having magnesium oxide-aluminum oxide composite coating and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6073614A JP2698549B2 (en) | 1994-04-12 | 1994-04-12 | Low iron loss unidirectional silicon steel sheet having magnesium oxide-aluminum oxide composite coating and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH07278827A true JPH07278827A (en) | 1995-10-24 |
| JP2698549B2 JP2698549B2 (en) | 1998-01-19 |
Family
ID=13523395
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|---|---|---|---|
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| Country | Link |
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| JP (1) | JP2698549B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100320282B1 (en) * | 1997-04-14 | 2002-01-15 | 래리 디. 맥밀란 | Method of forming magnesium oxide films on glass substrate for use in plasma display panels |
| JP2002535234A (en) * | 1999-01-29 | 2002-10-22 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method for producing anionic clay using boehmite |
| KR20190078165A (en) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | Grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
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| KR101944901B1 (en) * | 2016-12-21 | 2019-02-01 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
| KR101919546B1 (en) * | 2018-07-12 | 2018-11-16 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297575A (en) * | 1986-12-22 | 1988-12-05 | マリーン マグネシウム カンパニー | Improvement in magnesium oxide steel coating agent |
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1994
- 1994-04-12 JP JP6073614A patent/JP2698549B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297575A (en) * | 1986-12-22 | 1988-12-05 | マリーン マグネシウム カンパニー | Improvement in magnesium oxide steel coating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100320282B1 (en) * | 1997-04-14 | 2002-01-15 | 래리 디. 맥밀란 | Method of forming magnesium oxide films on glass substrate for use in plasma display panels |
| JP2002535234A (en) * | 1999-01-29 | 2002-10-22 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method for producing anionic clay using boehmite |
| EP3561084A4 (en) * | 2016-12-21 | 2019-10-30 | Posco | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
| US11174525B2 (en) | 2016-12-21 | 2021-11-16 | Posco | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
| CN110073011B (en) * | 2016-12-22 | 2021-11-02 | Posco公司 | Annealing separator composition for grain-oriented electrical steel sheet, and method for manufacturing same |
| JP2020509216A (en) * | 2016-12-22 | 2020-03-26 | ポスコＰｏｓｃｏ | Annealing separator composition for grain-oriented electrical steel sheet, grain-oriented electrical steel sheet, and method for producing grain-oriented electrical steel sheet |
| CN110073011A (en) * | 2016-12-22 | 2019-07-30 | Posco公司 | Oriented electrical steel annealing separator composition, oriented electrical steel and its manufacturing method |
| US11773462B2 (en) | 2016-12-22 | 2023-10-03 | Posco Co., Ltd | Annealing separator composition for grain-oriented electrical steel sheet, grain-oriented electrical steel sheet, and method for producing grain-oriented electrical steel sheet |
| KR20190078165A (en) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | Grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
| WO2020130643A1 (en) * | 2018-12-19 | 2020-06-25 | 주식회사 포스코 | Annealing separator composition for grain-oriented electrical steel sheet, grain-oriented electrical steel sheet, and method for manufacturing grain-oriented electrical steel sheet |
| KR20200076516A (en) * | 2018-12-19 | 2020-06-29 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
| CN113227411A (en) * | 2018-12-19 | 2021-08-06 | Posco公司 | Annealing separator composition for grain-oriented electrical steel sheet, and method for manufacturing same |
| JP2022514938A (en) * | 2018-12-19 | 2022-02-16 | ポスコ | Annealing Separator Composition for Electrical Steel Sheets, Manufacturing Methods for Electrical Steel Sheets and Electrical Steel Sheets |
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