JP2698549B2 - Low iron loss unidirectional silicon steel sheet having magnesium oxide-aluminum oxide composite coating and method for producing the same - Google Patents
Low iron loss unidirectional silicon steel sheet having magnesium oxide-aluminum oxide composite coating and method for producing the sameInfo
- Publication number
- JP2698549B2 JP2698549B2 JP6073614A JP7361494A JP2698549B2 JP 2698549 B2 JP2698549 B2 JP 2698549B2 JP 6073614 A JP6073614 A JP 6073614A JP 7361494 A JP7361494 A JP 7361494A JP 2698549 B2 JP2698549 B2 JP 2698549B2
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- JP
- Japan
- Prior art keywords
- steel sheet
- silicon steel
- aluminum oxide
- iron loss
- magnesium oxide
- 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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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 directionally oriented silicon steel sheet having a coating that imparts a large tension to the steel sheet to reduce iron loss, and a method of manufacturing 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 Oriented silicon steel sheets are (110), [0
[01], and is widely used as a magnetic iron core material. In particular, 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, a method of irradiating a laser beam to a steel sheet surface after finish annealing to give local strain and thereby subdivide the magnetic domain is disclosed in
26405. Further, a magnetic domain refining means which does not lose its effect even after performing stress relief annealing (stress relief annealing) after iron core processing is disclosed in, for example, JP-A-62-26161.
No. 75 discloses this.
【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, an iron alloy containing iron and silicon has a large crystal magnetic anisotropy. Therefore, when an external tension is applied, the magnetic domain is subdivided and the eddy current loss which is a main element of iron loss is reduced. Can be. Therefore, it is effective to apply a tension to the steel sheet to reduce iron loss of a unidirectional silicon steel sheet containing 5% or less of silicon, and it is effective to apply a tension up to about 1.5 kgf / mm 2 to effectively reduce iron loss. It is known that loss can be reduced. This tension is usually provided by a coating 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, a unidirectional silicon steel sheet has a primary coating mainly composed of forsterite produced by a reaction between an oxide on the steel sheet surface and an annealing separator in a finish annealing step, and Japanese Patent Application Laid-Open No. 48-39338. A tension of about 1.0 kgf / mm 2 is given by a two-layer coating of a secondary coating formed by baking a coating liquid mainly composed of colloidal silica and phosphate disclosed in Japanese Patent Application Laid-Open Publication No. H10-163,086. . Therefore, in the case of these existing coatings, although there is room for improving iron loss by applying a larger tension, an increase in the applied tension by increasing the thickness of the coating is not preferable because it results in a decrease in the space factor.
【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。Further, as another method for improving iron loss of a grain-oriented silicon steel sheet, mirror finishing is performed by removing irregularities on the surface of the steel sheet after finish annealing and an internal oxide layer near the surface, and performing metal finishing on the surface. The method of plating is Japanese Patent Publication No. 52-2.
No. 4499, a method of forming a tension film on the surface is disclosed in, for example, Japanese Patent Publication No.
These are disclosed in Japanese Patent Application Laid-Open No. 1-2201732, Japanese Patent Publication No. 63-54767, Japanese Patent Application Laid-Open No. Hei 2-213488, and the like. In these cases as well, the greater the tension applied to the steel sheet by the coating, the greater the effect of improving iron loss. For these reasons, there has been a demand for a coating film having excellent adhesion and being thin and capable of applying a large tension to a steel sheet.
【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 provides a unidirectional silicon steel sheet in which iron loss is reduced by providing a coating that imparts a large tension to the steel sheet, and It is an object of the present invention to provide a manufacturing method thereof.
【０００７】[0007]
【課題を解決するための手段】本発明は、仕上げ焼鈍
後の表面に、酸化マグネシウム、酸化アルミニウムそれ
ぞれの成分を被膜全体に対する重量割合で１０重量％以
上含有してなる、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、仕上げ焼鈍後の表面に酸
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。SUMMARY OF THE INVENTION The present invention provides a finish annealing process.
Magnesium oxide, aluminum oxide on the back surface
10% by weight or less of each component in weight ratio to the whole coating
Comprising upper, magnesium oxide - oriented silicon steel sheet having an aluminum oxide-based composite coating, magnesium oxide - oriented silicon steel sheet having an aluminum oxide-based composite coating contains the crystalline spinel, the oxidation on the surface after the finish annealing A unidirectional silicon steel sheet having a magnesium-aluminum oxide-amorphous oxide-based composite coating, a magnesium oxide-aluminum oxide-amorphous oxide-based composite coating formed of crystalline spinel, and / or silicon, boron, phosphorus The present invention is directed to a unidirectional silicon steel sheet containing an amorphous phase containing at least one of the above as a component.
【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 which has been subjected to the finish annealing, dried, and then dried at 500 to 1350.
A gist of the present invention is a manufacturing method characterized by baking at a temperature of ° C. to form an oxide film. Furthermore, a gist of the present invention is a production 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 below in detail. The grain-oriented silicon steel sheet of the present invention has a magnesium oxide-aluminum oxide-based composite coating on its surface. Conventionally, a coating material having a small thermal expansion coefficient has been selected for applying tension to a silicon steel sheet, and a stress generated during cooling due to a difference in thermal expansion coefficient from the steel sheet has been used. However, it has been pointed out that not only the coefficient of thermal expansion 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 coating components of the present invention, the aluminum oxide component has a relatively large Young's modulus,
It is presumed that the composite of magnesium oxide with this gives a large tension to the steel sheet.
【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。[0010] Magnesium oxide is only known as periclase as a crystal phase, but aluminum oxide has several crystal systems such as α-, γ-, δ-, θ-, Is not necessarily the same in each crystal system. However, the aluminum oxide of the present invention may be any of these. In addition, each of the compounds does not necessarily need to be a crystal having good crystallinity, and may be an amorphous compound having poor crystallinity, or a compound that is a precursor of the crystal.
【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。In some cases, the inclusion of a crystalline spinel in these films makes it possible to impart a greater tension. Spinel is a crystal represented by the chemical formula of MgO.Al 2 O 3 , and is presumed to have given a high tension to the steel sheet due to the above-mentioned properties of a low thermal expansion coefficient and a high Young's modulus. It is known that a spinel has a solid solution region on the alumina excess side with a 1: 1 composition as the center, but the crystalline spinel present in the coating of the present invention may be either a stoichiometric composition or a solid solution. It can be used without any problem.
【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 proportions of magnesium oxide and aluminum oxide 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 characteristics of the composite coating, it is preferable that each component is contained at least 5% by weight, preferably 10% or more based on the whole coating. In addition, the amount of the crystalline spinel can be any ratio, and by containing this compound as much as possible, a higher tension can be applied.However, since the surface properties of the coating tend to deteriorate, It is preferred to determine the optimal amount accordingly. The preferred content of the crystalline spinel is 90% or less by weight relative to the whole coating,
More preferably 80% or less, 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。The surface of another unidirectional silicon steel sheet according to the present invention has a magnesium oxide-aluminum oxide-amorphous oxide-based composite coating. The role of the magnesium oxide and aluminum oxide components has already been described, but the role of the amorphous oxide component has no significant effect on the application of tension to the steel sheet, and the surface smoothness and adhesion to the base steel sheet It is speculated that the properties have been greatly improved. Among them, it has been found that an amorphous phase containing at least one of silicon, boron and phosphorus as a component has a remarkable effect. Particularly when a glassy substance is formed, a remarkably great effect can be obtained. The content of silicon, boron, and phosphorus in the amorphous phase is 50% or more, and preferably 70% or more, in terms of the total weight of the respective oxides in terms of oxide.
【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。The amorphous phase may contain a small amount of components other than silicon, boron and phosphorus. Possible elements include A, which is the main component of the film.
l, Mg, Fe as a constituent material of a base material, Ti, Mn, and S as primary coating components, as well as 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, and Sn, Pb, Bi, and Sb. The content of the entire amorphous phase is not particularly limited. However, if the content is too large, the tension is not sufficiently applied to the steel sheet. . If the amount is too small, a sufficiently smooth surface of the coating and good adhesion may not be obtained in some cases.
【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 grain-oriented silicon steel sheet of the present invention is:
If it is too thick, the space factor will decrease, so it is better to be as thin as possible according to the purpose. One guideline is 5% or less of the thickness of the steel sheet. More preferably, 2% of the steel sheet thickness
It is as follows. Further, from the viewpoint of imparting tension, if the thickness is extremely thin, a sufficient effect cannot be obtained, and the thickness is desirably 0.1 μm or more.
Hereinafter, a method for suitably producing the grain-oriented 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。A suspension containing a magnesium oxide precursor compound and an aluminum oxide precursor compound is applied to the steel sheet surface after the finish annealing, dried, and baked at a temperature of 500 to 1350 ° C. to form an oxide film. Is a manufacturing method. The steel sheet which has been subjected to the finish annealing herein means: a steel sheet on which a finish annealing has been performed by a conventionally known method to form a forsterite primary coating on the surface.
: Steel sheet obtained by immersing the primary coating and the accompanying oxide layer in acid to remove it, steel sheet obtained by flattening and annealing the steel sheet obtained in hydrogen, or chemical polishing, electrolytic polishing, etc. A polished steel plate, which is coated with a conventionally known annealing separator containing a small amount of an additive such as alumina powder or a chloride which is inert to film formation, and under conditions that do not form a primary film. Refers to steel sheets subjected to 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 which become magnesium oxide after baking (heat treatment). Point to. Similarly, the aluminum oxide precursor compound is a generic name of a compound that becomes aluminum oxide after baking (heat treatment), and is not limited to aluminum oxide, but also to Al 2 O 3.
Includes aluminum oxide hydrate represented by nH 2 O, aluminum hydroxide, or various aluminum salts such as aluminum nitrate and aluminum chloride.
【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). The dispersion medium is most preferably water from the viewpoints of workability, cost and the like, but an organic solvent or a mixture thereof can be used unless there is any particular problem in other steps. Certain of the raw materials may dissolve at the time the slurry is made, but this is no problem.
【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 thus obtained slurry is applied to the surface of the unidirectional silicon steel sheet which has been finish-annealed by a conventionally known method such as a coater such as a roll coater, dipping, spraying or electrophoresis. After drying, 500 ~
By baking at 1350 ° C., an oxide film is formed on the surface. The atmosphere at the time of baking is preferably a reducing atmosphere such as an inert gas atmosphere such as nitrogen or a nitrogen-hydrogen mixed atmosphere. An atmosphere containing air or oxygen is not preferable because it may oxidize the steel sheet. There is no particular limitation on the dew point of the atmospheric gas. If the baking temperature is lower than 500 ° C., the applied precursor may not become an oxide, and the baking temperature is low, so that sufficient tension is not developed, which is not preferable. On the other hand, when the temperature exceeds 1350 ° C., it is not economical, although there is no particular inconvenience, and the temperature is 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。In the above-mentioned slurry, a thin, uniform coating film having good adhesion may be obtained by using a fine particle dispersion system called a sol as an aluminum oxide precursor. This is particularly remarkable when a non-metallic substance does not exist on the surface and a film is formed directly on the metal surface. In such a case, the above-described sol containing fine particles or a sol containing a soluble component is preferably used. When a sol solution is used as the coating liquid, the above-described boehmite sol is used as the aluminum oxide precursor compound, and / or
Alternatively, a material called 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 may be a magnesium oxide ultrafine powder produced by a gas phase method or the like, a fine powder produced by a liquid phase method or the like. It is preferable to use those in a state of being dispersed and soluble magnesium salts, thereby realizing uniform mixing at an extremely microscopic level. Also in the use of the aluminum oxide precursor sol, it is possible to disperse it in a dispersion medium, particularly water, as in the case of the above-mentioned slurry, and use it. In order to obtain particularly good dispersibility, pH control of the coating solution by addition of an acid, an alkali or the like is a frequently used technique, and can be performed without any particular problem in the present invention. Also, there is no problem at all in adding a trace amount of a surfactant or the like for improving the applicability to the steel sheet. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these 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 thereto to prepare a slurry. This was applied to a 0.2-mm-thick finish-annealed unidirectional silicon steel sheet (having a forsterite primary coating) containing 3.2% of Si so as to have a surface of 4 g / m 2 and dried. Later, H 2
Was baked at 800 ° C. for 5 minutes in an N 2 atmosphere containing 5 vol% to form an oxide film on the surface.
【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 microscope, and the like, it was found that the obtained coating was mainly composed of MgO, α-Al 2 O 3 , and spinel. A winding test was performed around a 20 mmφ cylinder so that the angle was 180 degrees, and the adhesion of the coating evaluated from the peeling state was extremely good. The coating on one side was removed, and the applied tension to the steel sheet measured from the bending of the sheet and the magnetic properties are shown in Table 1. From the results shown in Table 1, it can be seen that unidirectional silicon steel sheets having remarkably low iron loss are obtained. The chemical stability of the 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 proportions shown in Table 2, and distilled water was added thereto to prepare a mixed sol. This was replaced with 3.2
%, Aluminum oxide was applied as an annealing separator, and mirror-finished simultaneously with secondary recrystallization.
After coating and drying on a unidirectional silicon steel sheet having a thickness of 4 g / m 2 on one side and baking at 1000 ° C. for 10 minutes in an N 2 atmosphere containing 10 vol% of H 2 , an oxide film is formed 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 phase of the film measured from the results of chemical analysis, X-ray diffraction, electron microscope and the like. In all the compositions in the table, formation of spinel was confirmed. The adhesion of the coating evaluated in the same manner as in Example 1 was extremely good. The coating on one side was removed, and the applied tension to the steel sheet measured from the bending of the sheet and the magnetic properties were also shown in Table 2. Table 2
From the results, it can be seen that a unidirectional silicon steel sheet having significantly low iron loss was obtained in each case. The chemical stability of the 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 thereto to form a mixed sol. Produced. This was coated on a 0.2 g-thick unidirectional silicon steel sheet containing 3.2% of Si (with a primary coating of forsterite) having a finish annealing of 4 g / m2 on one side.
2 so as coated, after drying, 850 ° C. in a N 2 atmosphere containing H 2 3 vol%, to form an oxide film on the surface by baking for 3 minutes.
【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 film measured from the results of chemical analysis, X-ray diffraction, electron microscope and the like. The absence of the crystalline phase containing boron and silicon indicates that the boron and silicon components are present in an amorphous phase. The adhesion of the coating evaluated in the same manner as in Example 1 was extremely good. The coating on one side was removed, and the applied tension to the steel sheet and the magnetic properties measured from the bending of the sheet were also shown in Table 3. From the results shown in Table 3, it can be seen that unidirectional silicon steel sheets having significantly low iron loss were obtained. The chemical stability of the 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, a coating of a specific component is provided,
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 shows good properties especially for conventionally used steel sheets having a primary coating or mirror-finished steel sheets for the purpose of remarkably reducing iron loss. The effect is enormous.
Claims (6)
に、酸化マグネシウム、酸化アルミニウムそれぞれの成
分を被膜全体に対する重量割合で１０重量％以上含有す
ることを特徴とする、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。1. The surface of a grain-oriented silicon steel sheet after finish annealing
Of magnesium oxide and aluminum oxide
At least 10% by weight based on the total weight of the coating
A low iron loss unidirectional silicon steel sheet having a magnesium oxide-aluminum oxide composite coating film , characterized in that:
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.
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低鉄損一方向性珪素鋼板。3. A low-loss unidirectional silicon steel sheet having a magnesium oxide-aluminum oxide-amorphous oxide-based composite coating on the surface of the unidirectional silicon steel sheet after the finish annealing .
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 a crystalline spinel and / or
4. 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 grain-oriented silicon steel sheet on which the finish annealing has been completed, dried, and then dried.
A method for producing a low iron loss unidirectional silicon steel sheet which is baked 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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07278827A JPH07278827A (en) | 1995-10-24 |
| JP2698549B2 true JP2698549B2 (en) | 1998-01-19 |
Family
ID=13523395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6073614A Expired - Fee Related 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 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2698549B2 (en) |
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| CN110088307A (en) * | 2016-12-21 | 2019-08-02 | Posco公司 | Oriented electrical steel annealing separator composition, oriented electrical steel and its manufacturing method |
| CN110088307B (en) * | 2016-12-21 | 2020-12-25 | Posco公司 | Annealing separator composition for grain-oriented electrical steel sheet, and method for manufacturing same |
| KR101906962B1 (en) | 2016-12-22 | 2018-10-11 | 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 |
| WO2018117673A1 (en) * | 2016-12-22 | 2018-06-28 | 주식회사 포스코 | Annealing separator composition for grain-oriented electrical steel sheet, grain-oriented electrical steel sheet, and method for producing grain-oriented electrical steel sheet |
| 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 |
| 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 |
| KR20180083295A (en) * | 2018-07-12 | 2018-07-20 | 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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| JPH07278827A (en) | 1995-10-24 |
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