JPH06299366A - Production of low iron loss grain oriented silicon steel sheet - Google Patents
Production of low iron loss grain oriented silicon steel sheetInfo
- Publication number
- JPH06299366A JPH06299366A JP8483393A JP8483393A JPH06299366A JP H06299366 A JPH06299366 A JP H06299366A JP 8483393 A JP8483393 A JP 8483393A JP 8483393 A JP8483393 A JP 8483393A JP H06299366 A JPH06299366 A JP H06299366A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- film
- iron loss
- oxide
- metal salt
- 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.)
- Granted
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鋼板に張力を付与する
皮膜が密着性良く鋼板表面に形成された方向性電磁鋼板
の製造方法に関する。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 a coating for applying tension to the steel sheet formed on the surface of the steel sheet with good adhesion.
【０００２】[0002]
【従来の技術】方向性電磁鋼板は（１１０）〔００１〕
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、エネルギーロスを少なくするために鉄損
の少ない材料が求められている。鉄および５％以下の珪
素を含有する鉄合金は結晶磁気異方性が大きいので、外
部張力を付与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。従っ
て、５％以下の珪素を含有する方向性珪素鋼板の鉄損低
減には鋼板に張力を付与することが有効である。2. Description of the Related Art Grain-oriented electrical steel sheets are (110) [001].
It is used as a magnetic iron core material because it has a crystal structure with the main direction being, and a material with less iron loss is required to reduce energy loss. Since an iron alloy containing iron and 5% or less of silicon has a large magnetocrystalline anisotropy, application of external tension causes subdivision of magnetic domains, which can reduce eddy current loss which is a main factor of iron loss. . Therefore, it is effective to apply tension to the steel sheet in order to reduce the iron loss of the grain-oriented silicon steel sheet containing 5% or less of silicon.
【０００３】ここで、皮膜形成による鋼板への付与張力
は、一定の鋼板厚さに対し、皮膜厚さが大きくなるに従
って増大するが、厚膜化は占積率の低下をまねく。従っ
て、なるべく薄い膜厚で鋼板への付与張力の大きい皮膜
が好ましい。従来より工業的に行われている方法とし
て、仕上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皮膜
（グラス皮膜）は、鋼板に与える張力が大きく、鉄損低
減に効果がある。さらに、特開昭４８−３９３３８号公
報で開示されたコロイド状シリカと燐酸塩を主成分とす
るコーティング液を焼き付けることによって、絶縁皮膜
を形成する方法は、鋼板に対して張力付与の効果が大き
く、鉄損低減に有効である。従って、仕上焼鈍工程で生
じた皮膜を残したうえで張力性の絶縁コーティングを施
すことが一般的な方向性電磁鋼板の製造方法となってい
る。Here, the tension applied to the steel sheet due to the film formation increases as the film thickness increases for a given steel plate thickness, but increasing the film thickness leads to a decrease in the space factor. Therefore, a film having a film thickness as thin as possible and having a large tension applied to the steel sheet is preferable. As a method that has been conventionally performed industrially, a film (glass film) mainly composed of forsterite produced by the reaction between the oxide on the surface of the steel sheet and the annealing separator in the finish annealing step (glass film) has a tension applied to the steel sheet. Large and effective in reducing iron loss. Furthermore, the method of forming an insulating film by baking the coating liquid containing colloidal silica and phosphate as the main components disclosed in JP-A-48-39338 has a large effect of applying tension to the steel sheet. It is effective in reducing iron loss. Therefore, a general method for producing a grain-oriented electrical steel sheet is to apply a tensile insulating coating after leaving the film produced in the finish annealing step.
【０００４】しかしながら、この方法によって得られた
鋼板は、セラミック皮膜／鋼板地鉄の界面の構造が乱れ
ており、これが磁区の移動の障害となって鋼板の鉄損低
減に限界を来していた。そこで鋼板表面に上述のグラス
皮膜等がない、鏡面化ないしは平坦化した鋼板表面にセ
ラミック質の張力皮膜を形成しようとする試みが近年数
多くなされている。これらの試みに見られる共通の技術
課題は、如何に密着性の高い皮膜を鋼板上に形成するか
である。However, in the steel sheet obtained by this method, the structure of the interface between the ceramic coating and the steel sheet base metal is disordered, which becomes an obstacle to the movement of magnetic domains, and the iron loss of the steel sheet is limited. . Therefore, in recent years, many attempts have been made to form a ceramic tension film on a mirror-finished or flattened steel plate surface without the above-mentioned glass film on the steel plate surface. A common technical problem seen in these attempts is how to form a highly adherent coating on a steel sheet.
【０００５】これらの試みのうちの一つの技術領域とし
て、ドライプロセスによる皮膜形成があり、例えば特公
昭５６−４１５０号公報、特開昭６１−２０１７３２号
公報、特公昭６３−５４７６７号公報、特開平２−２１
３４８３号公報等に記載されている。これらは具体的に
は真空蒸着、化学蒸着、スパッタリング、イオンプレー
ティング、イオンインプランテーション、溶射等による
プロセスである。これらドライプロセスの技術的な特徴
は、鏡面化ないしは平坦化された鋼板の金属表面に、例
えば予備酸化処理等の下地処理を施さずとも、直接容易
に密着性の高い皮膜を形成することができることにあ
る。この方法の利点は、鋼板地鉄と皮膜の界面が平滑で
あるので鉄損等鋼板の磁気的性質に悪い影響を与える可
能性がないことである。One of the technical areas of these attempts is film formation by a dry process. For example, JP-B-56-4150, JP-A-61-201732, JP-B-63-54767, and JP-B-63-54767. Kaihei 2-21
No. 3483, etc. Specifically, these are processes such as vacuum deposition, chemical vapor deposition, sputtering, ion plating, ion implantation, and thermal spraying. The technical feature of these dry processes is that a highly adherent film can be easily formed directly on the mirror-finished or flattened metal surface of a steel plate without any pretreatment such as preliminary oxidation treatment. It is in. The advantage of this method is that the interface between the steel sheet and the coating is smooth, so there is no possibility of adversely affecting the magnetic properties of the steel sheet such as iron loss.
【０００６】しかしながら、ドライプロセスによる張力
皮膜にはかなりの効果が認められるものの、方法によっ
ては高真空を必要としたり、また実用に供する膜厚を得
るには長時間が必要であったり等生産性が極めて低く、
高いコストを要する等の問題点を抱えており、電磁鋼板
に対しては工業的な皮膜形成方法とはなりがたい。However, although the tension film produced by the dry process is considerably effective, depending on the method, high vacuum is required, and it takes a long time to obtain a film thickness for practical use. Is extremely low,
Since it has problems such as high cost, it is difficult to use an industrial film forming method for magnetic steel sheets.
【０００７】また、これらの試みのうち他の技術領域と
して、近年ゾル・ゲル法を用いた皮膜形成方法が考案さ
れている。例えば、特開平２−２４３７７０号公報には
ゾル・ゲル法による酸化物皮膜の形成について、また特
開平３−１３０３７６号公報には平滑化した鋼板の表面
にゾル・ゲル法によりゲル膜を形成し、その薄膜上に絶
縁皮膜を形成する技術が開示されている。これらの技術
では従来の塗布・焼き付けの工業的プロセスによる皮膜
形成が可能であるものの、鏡面化ないしは平滑化された
鋼板に対して皮膜を形成しなければならないため、焼き
付け時あるいはゲル化、乾燥等の工程で剥離が生じるこ
とが多く、密着性の良好な皮膜、特に鋼板に大きな張力
を付与できるほどのある程度厚い皮膜（例えば０．５μ
ｍ以上の厚みの膜）を形成することは困難であるという
問題があった。従ってこの場合は、鋼板地鉄と張力皮膜
を強固に密着させることが必須となる。Further, as another technical area of these attempts, a film forming method using a sol-gel method has been devised in recent years. For example, JP-A-2-243770 discloses formation of an oxide film by the sol-gel method, and JP-A-3-130376 discloses formation of a gel film by a sol-gel method on the surface of a smoothed steel sheet. , A technique of forming an insulating film on the thin film is disclosed. With these technologies, it is possible to form a film by the conventional industrial process of coating and baking, but since it is necessary to form a film on a steel plate that has been mirror-finished or smoothed, during baking or gelation, drying, etc. Peeling often occurs in the step of, and a film with good adhesion, especially a film that is thick enough to give a large tension to the steel sheet (for example, 0.5 μm).
It is difficult to form a film having a thickness of m or more). Therefore, in this case, it is essential to firmly adhere the steel plate base iron and the tension film.
【０００８】[0008]
【発明が解決しようとする課題】本発明は仕上焼鈍後の
方向性電磁鋼板上に、張力を付与する酸化物系皮膜を形
成する際に、皮膜に鋼板への高い密着性を与えることを
課題とするものであり、結果として鋼板に高い張力を有
効に付与できる皮膜を有する方向性電磁鋼板を提供する
ことを目的とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a film with high adhesion to a steel sheet when forming an oxide-based coating film that gives tension on a grain-oriented electrical steel sheet after finish annealing. Accordingly, it is an object of the present invention to provide a grain-oriented electrical steel sheet having a coating capable of effectively applying high tension to the steel sheet.
【０００９】[0009]
【課題を解決するための手段】本発明は、仕上焼鈍後の
方向性電磁鋼板表面に酸化物系の張力皮膜を形成するに
あたり、該張力皮膜形成のための塗布原料に金属塩の微
粒子、および／または水溶性の金属塩を０．１〜５重量
％添加した液を塗布し乾燥後、５００〜１３５０℃で焼
き付け、酸化物皮膜を形成する低鉄損方向性電磁鋼板の
製造方法である。また、該金属塩の塩が酸化物、水酸化
物、硝酸塩、酢酸塩であり、該金属塩の金属がＶ，Ｃ
ｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｓｎであ
る。MEANS FOR SOLVING THE PROBLEMS In the present invention, in forming an oxide-based tension film on the surface of a grain-oriented electrical steel sheet after finish annealing, fine particles of a metal salt are used as a coating material for forming the tension film, and And / or is a method for producing a low iron loss grain-oriented electrical steel sheet, which comprises applying a solution containing 0.1 to 5% by weight of a water-soluble metal salt, drying it, and baking it at 500 to 1350 ° C. to form an oxide film. Further, the salts of the metal salts are oxides, hydroxides, nitrates and acetates, and the metal of the metal salts is V, C.
r, Mn, Fe, Co, Ni, Cu, Zn, Sn.
【００１０】[0010]
【作用】電磁鋼板上に張力皮膜を形成する方法として、
工業的には前記したように湿式法、すなわちコーティン
グ液を鋼板に塗布して、乾燥・焼き付ける方法が有用で
ある。この場合、酸化物系の皮膜は特に限定されるもの
ではなく、基本的にはいかなる材質の皮膜も適用可能で
ある。しかしながら、できるだけ大きな張力を付与する
ことが電磁鋼板の鉄損値をより低減し、かつ占積率を増
加させるために有効である。そのため、この皮膜の材質
としては、従来から知られているように熱膨張係数の小
さいものを適用するのが好ましいと考えられ、例えば、
酸化アルミニウム、酸化アルミニウム−酸化硼素系、酸
化アルミニウム−シリカ系、コージェライト系等が好適
に用いられる。[Operation] As a method for forming a tension film on an electromagnetic steel sheet,
Industrially, as described above, a wet method, that is, a method of applying a coating liquid to a steel sheet and drying / baking is useful. In this case, the oxide-based coating is not particularly limited, and basically any material coating can be applied. However, it is effective to apply as much tension as possible in order to further reduce the iron loss value of the electrical steel sheet and increase the space factor. Therefore, as the material of this coating, it is considered preferable to apply a material having a small coefficient of thermal expansion as conventionally known.
Aluminum oxide, aluminum oxide-boron oxide type, aluminum oxide-silica type, cordierite type and the like are preferably used.
【００１１】また、本発明において張力皮膜を形成すべ
き鋼板は仕上焼鈍が完了したものであれば、いかなる鋼
板も使用可能である。代表的に用いられる鋼板として
は、マグネシア粉末を焼鈍分離剤として仕上焼鈍を行っ
たもの、またこの鋼板から表面に生成したフォルステラ
イト層（グラス皮膜）を酸に浸漬して除去したもの等で
ある。さらに、これに水素中で平坦化焼鈍を施すかある
いは化学研磨、電解研磨等の鏡面化処理を施す等の平坦
化処理をすると鉄損値が著しく低減される場合には、こ
れらの処理を施した鋼板も好適に使用される。また酸化
アルミニウム等皮膜形成に対して不活性な粉末を塗布し
て皮膜を形成させない条件で仕上焼鈍を行って得た、表
面に殆ど皮膜の存在しない鋼板も特に支障なく使用可能
である。In the present invention, any steel sheet can be used as the steel sheet on which the tension film is to be formed as long as the finish annealing is completed. Typical steel sheets used are those obtained by performing finish annealing using magnesia powder as an annealing separator, and those obtained by immersing the forsterite layer (glass film) formed on the surface of this steel sheet in an acid to remove it. . Further, if the iron loss value is remarkably reduced by performing flattening annealing in hydrogen or performing flattening treatment such as chemical polishing, electrolytic polishing, etc., these treatments are performed. A steel sheet made from the above materials is also preferably used. Further, a steel sheet obtained by applying a powder such as aluminum oxide which is inactive to form a film and performing finish annealing under the condition that the film is not formed can be used without any particular problem on the surface.
【００１２】本発明の要点は、張力皮膜形成のための酸
化物の主原料に、金属塩の微粒子、および／または水溶
性の金属塩を添加しておくことにある。これらの金属塩
（焼き付け後は概ねそれぞれの金属の酸化物になる）
は、適度に設定された酸素分圧の雰囲気下で起こる下地
物質（珪素鋼表面、ないしはフォルステライト等のセラ
ミックス表面）との反応により、張力皮膜の下地物質と
の接着力を高めることを発明者らは見い出した。この目
的のため、これらの金属塩の添加量は０．１〜５重量％
が適当であり、より好ましくは０．３〜３重量％であ
る。添加量が０．１％未満では張力皮膜の下地への密着
に対して効果がない。他方、添加量が５％を超えると張
力皮膜が変性しすぎて皮膜の鋼板への張力付与効果が小
さくなって好ましくない。The point of the present invention is to add fine particles of a metal salt and / or a water-soluble metal salt to the main raw material of the oxide for forming the tension film. These metal salts (after baking, they become oxides of each metal)
Is to increase the adhesive force of the tension film with the underlying substance by reacting with the underlying substance (silicon steel surface or ceramic surface such as forsterite) that occurs in an atmosphere of an appropriately set oxygen partial pressure. Found out. For this purpose, the addition amount of these metal salts is 0.1 to 5% by weight.
Is suitable, and more preferably 0.3 to 3% by weight. If the addition amount is less than 0.1%, there is no effect on the adhesion of the tension film to the base. On the other hand, if the addition amount exceeds 5%, the tension film is excessively modified and the effect of imparting tension to the steel sheet by the film becomes small, which is not preferable.
【００１３】ここでいう金属塩の金属は、鋼板界面な
り、グラス皮膜等の表面なりに残存することにより鋼板
の磁気特性に好ましくない影響を与えるものでなければ
特に限定されるものではないが、前記したように工業的
に設定しやすい酸素分圧の雰囲気下での反応にあずかる
という点から、好ましくは鉄族の遷移金属であるＶ，Ｃ
ｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ等や、これ以外にＺ
ｎ，Ｓｎ等が好ましい。またそれらの金属の塩としては
特に限定しないものの、好ましくは酸化物、水酸化物、
硝酸塩、酢酸塩等が一般的には利用しやすい。The metal of the metal salt referred to here is not particularly limited as long as it does not adversely affect the magnetic properties of the steel sheet by remaining at the steel sheet interface or the surface of the glass film or the like. As described above, from the viewpoint of participating in the reaction under the atmosphere of oxygen partial pressure which is industrially easy to set, V and C which are transition metals of the iron group are preferable.
r, Mn, Fe, Co, Ni, Cu, etc., and Z
n, Sn and the like are preferable. The metal salt is not particularly limited, but is preferably an oxide, a hydroxide,
Nitrate, acetate, etc. are generally easy to use.
【００１４】張力皮膜形成のための酸化物主原料の形態
としては、前記した適当な材質（例えば、酸化アルミニ
ウム−酸化硼素系）の微粒子が均一に良く分散した液
（いわゆるゾル等）を使用することができる。これは、
鋼板上に均一に塗布するためには細かい微粒子が良く、
好ましくは数nmから数十nmサイズの微粒子である。微粒
子径が大きくなって１００nmを顕著に超えると、焼き付
け後の皮膜が不均一なものとなる傾向がある。これらの
原料液に上記した金属塩の微粒子、および／または水溶
性の金属塩を添加した後、良く撹拌・混合して塗布液を
作製する。As the form of the oxide main raw material for forming the tension film, a liquid (so-called sol or the like) in which fine particles of the above-mentioned appropriate material (for example, aluminum oxide-boron oxide) are uniformly and well dispersed is used. be able to. this is,
Fine particles are good for uniform application on the steel plate,
The fine particles are preferably several nm to several tens of nm in size. If the size of the fine particles becomes large and significantly exceeds 100 nm, the coating film after baking tends to be non-uniform. After the above-mentioned metal salt fine particles and / or water-soluble metal salt are added to these raw material liquids, they are well stirred and mixed to prepare a coating liquid.
【００１５】これらの塗布液をロールコーター等のコー
ター法、ディップ法、あるいは電気泳動法等従来公知の
方法によって鋼板表面に塗布し、乾燥後、５００〜１３
５０℃の温度で焼き付けることによって密着背の高い張
力皮膜が形成される。焼き付け時の雰囲気は窒素等の不
活性ガス雰囲気、窒素−水素混合ガス等の還元性雰囲気
等から選択することができる。このような非酸化性雰囲
気を設定した場合でも、工業的な焼き付け工程において
は塗布液から蒸発する水蒸気や、焼き付け炉内に不可避
的に取り込まれる空気により、下地物質／塗布皮膜界面
には適度の酸素分圧の雰囲気が供給される。焼き付け温
度が５００℃未満の場合、塗布した前駆体等の原料が緻
密なセラミックスとならない場合があり、また焼き付け
温度と使用温度（多くの場合常温付近）との差が小さい
ため張力が充分に付与されないので好ましくない。一
方、１３５０℃超の場合、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。These coating solutions are applied on the surface of the steel sheet by a conventionally known method such as a coater method such as a roll coater, a dipping method, or an electrophoresis method, and after drying, 500 to 13
Baking at a temperature of 50 ° C. forms a tension film having a high adhesion. The atmosphere during baking can be selected from an inert gas atmosphere such as nitrogen and a reducing atmosphere such as a nitrogen-hydrogen mixed gas. Even when such a non-oxidizing atmosphere is set, water vapor that evaporates from the coating solution in the industrial baking process and air that is inevitably taken into the baking furnace cause the substrate / coating film interface to have an appropriate amount. An oxygen partial pressure atmosphere is supplied. If the baking temperature is less than 500 ° C, the applied precursors and other raw materials may not be dense ceramics, and the difference between the baking temperature and the operating temperature (often around room temperature) is small, so sufficient tension is applied. It is not preferred because it is not done On the other hand, if it is higher than 1350 ° C, it is not economical although it is not particularly inconvenient, and it is more preferably 1250 ° C or lower.
【００１６】以上の工程を経ることにより、特に塗布・
焼き付けの繰り返しを必要とせずに均質で、かつ大きな
張力が付与できる高密着性の皮膜を容易に形成すること
ができる。ここでいう密着性とは、かかる皮膜を表面に
形成した鋼板を、例えば２０mmφのロール棒を用いてこ
の棒の周りに１８０度の角度ほど曲げる試験を行った場
合に皮膜が全く剥離しない程度の密着性である。以下に
本発明を実施例を用いて説明するが、本発明はかかる実
施例に限定されない。By the above steps, especially coating /
It is possible to easily form a uniform and highly adherent film that can impart a large tension without requiring repeated baking. The term "adhesion" as used herein means that a steel sheet having such a coating formed on its surface is such that the coating does not peel off at all when a test is performed by bending a roll rod of 20 mmφ around this rod by an angle of 180 degrees. Adhesiveness. The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００１７】[0017]
【実施例】 実施例１ Ｓｉを３．２％含有する脱炭焼鈍済みの方向性電磁鋼板
に、皮膜形成に対して不活性である粉末を塗布、仕上焼
鈍を施すことにより鏡面二次再結晶材を得た。次いで、
この鋼板上に、市販のアルミナゾル（固形分１０％を含
む）１００重量部、メタ硼酸５重量部、ＦｅＯＯＨの微
粒子を０．２重量部、および蒸留水よりなるコーティン
グ液を片面４ｇ／ｍ2 となるように塗布し、乾燥・ゲル
化後、８５０℃で３分間、乾燥したＮ2 中で焼き付けを
行い、厚み１．５μｍの張力皮膜を形成した。Example 1 A decarburization-oriented grain-oriented electrical steel sheet containing 3.2% of Si was coated with a powder inactive to form a film and subjected to finish annealing to perform secondary mirror surface recrystallization. I got the material. Then
On this steel plate, 100 parts by weight of commercially available alumina sol (including 10% solid content), 5 parts by weight of metaboric acid, 0.2 parts by weight of FeOOH fine particles, and 4 g / m 2 of distilled water were coated on one side. After coating and drying and gelling, the film was baked in dry N 2 at 850 ° C. for 3 minutes to form a tension film having a thickness of 1.5 μm.
【００１８】得られた鋼板は、張力皮膜である硼酸アル
ミニウムが鋼板に付いていることが表面部分のＸ線回折
および電子顕微鏡観察によりわかった。皮膜の鋼板への
密着性は極めて良好であり、２０mmφのロール棒による
１８０度曲げ試験によっても皮膜の剥離は全く認められ
なかった。また、張力皮膜形成前と形成後の鉄損Ｗ17
/50 を測定したところ、それぞれ１．０３w/kgおよび
０．７７w/kgであり、張力皮膜による顕著な鉄損低減効
果が得られた。It was found by X-ray diffraction and electron microscope observation of the surface portion of the obtained steel sheet that aluminum borate, which is a tension film, was attached to the steel sheet. The adhesion of the coating to the steel sheet was extremely good, and no peeling of the coating was observed even in the 180-degree bending test using a roll rod of 20 mmφ. In addition, the iron loss W 17 before and after the formation of the tension film
When / 50 was measured, they were 1.03 w / kg and 0.77 w / kg, respectively, and a remarkable iron loss reducing effect by the tension film was obtained.
【００１９】比較例１ コーティング液中にＦｅＯＯＨ微粒子を含有させないこ
と以外は、実施例１と全く同様のことを行った。得られ
た鋼板は、Ｘ線回折や電子顕微鏡による観察の結果、結
晶性の低い硼酸アルミニウムの皮膜（厚み約１．５μ
ｍ）が鋼板上に形成されていた。この鋼板を２０mmφの
ロール棒による１８０度曲げ試験に供したところ、全面
積の合計約４０％の部分から皮膜の剥離が観察された。Comparative Example 1 The same operation as in Example 1 was carried out except that FeOOH fine particles were not contained in the coating liquid. As a result of observation by X-ray diffraction and an electron microscope, the obtained steel sheet had a film of aluminum borate having a low crystallinity (thickness of about 1.5 μm).
m) was formed on the steel plate. When this steel sheet was subjected to a 180-degree bending test using a roll bar of 20 mmφ, peeling of the film was observed from a total of about 40% of the total area.
【００２０】実施例２ 実施例１と同じ鏡面二次再結晶材を得た後、この鋼板上
に市販のアルミナゾル（固形分１０％を含む）１００重
量部、メタ硼酸５重量部、硝酸ニッケル０．１重量部、
および蒸留水よりなるゾルを片面５ｇ／ｍ2 となるよう
に塗布し、乾燥・ゲル化後、１０００℃で２分間、乾燥
したＮ2 ：Ｈ2 ＝９５％：５％中で焼き付けを行った。Example 2 After obtaining the same mirror secondary recrystallized material as in Example 1, 100 parts by weight of a commercially available alumina sol (containing 10% of solid content), 5 parts by weight of metaboric acid, and 0% of nickel nitrate were obtained on this steel plate. .1 part by weight,
And a sol consisting of distilled water were coated on one side at 5 g / m 2 , dried and gelled, and baked at 1000 ° C. for 2 minutes in dried N 2 : H 2 = 95%: 5%. .
【００２１】得られた鋼板は、張力皮膜である硼酸アル
ミニウムが鋼板に付いており、実施例１と同様な曲げ試
験を行った結果、皮膜の剥離は全く認められず、密着性
は極めて良好であった。張力皮膜の厚みは約２μｍであ
った。また、張力皮膜形成前と形成後の鉄損Ｗ17/50 を
測定したところ、それぞれ１．０５w/kgおよび０．７８
w/kgであり、皮膜形成により顕著な鉄損低減効果が得ら
れた。The obtained steel sheet had aluminum borate as a tension film attached to the steel sheet. As a result of the same bending test as in Example 1, no peeling of the film was observed and the adhesion was very good. there were. The thickness of the tension film was about 2 μm. The iron loss W 17/50 before and after the formation of the tension film was measured to be 1.05 w / kg and 0.78, respectively.
w / kg, and a significant iron loss reduction effect was obtained due to the film formation.
【００２２】比較例２ コーティング液中に硝酸ニッケルを含有させないこと以
外は実施例２と全く同様のことを行った。得られた鋼板
は、Ｘ線回折や電子顕微鏡による観察の結果、硼酸アル
ミニウムの皮膜（厚み約２μｍ）が鋼板上に形成されて
いたが、２０mmφロールによる１８０度曲げ試験の結
果、全面積の３０％の部分から皮膜の剥離が観察され
た。Comparative Example 2 The same procedure as in Example 2 was carried out except that nickel nitrate was not contained in the coating liquid. The obtained steel sheet had an aluminum borate film (thickness of about 2 μm) formed on the steel sheet as a result of observation by X-ray diffraction and an electron microscope, but as a result of a 180-degree bending test using a 20 mmφ roll, the total area was 30 The peeling of the film was observed from the% portion.
【００２３】実施例３ Ｓｉを３．２％含有する仕上焼鈍後のグラス皮膜（フォ
ルステライト皮膜）を有する方向性電磁鋼板に、実施例
１と同様にして調製したＦｅＯＯＨ微粒子を含むコーテ
ィング液を片面４ｇ／ｍ2 となるように塗布し、乾燥・
ゲル化後、８５０℃で３分間、乾燥したＮ2 中で焼き付
けを行った。Example 3 A grain-oriented electrical steel sheet having a glass film (forsterite film) after finish annealing containing 3.2% of Si was coated with a coating solution containing FeOOH fine particles prepared in the same manner as in Example 1 on one side. Apply 4 g / m 2 and dry.
After gelation, baking was performed at 850 ° C. for 3 minutes in dry N 2 .
【００２４】得られた鋼板は、硼酸アルミニウムの皮膜
が下地のグラス皮膜と密着しており、実施例１と同様な
曲げ試験を行った結果、皮膜の剥離は全く認められず、
密着性は極めて良好であった。張力皮膜の厚みは１．５
μｍであった。また、張力皮膜形成前と形成後の鉄損Ｗ
17/50 を測定したところ、それぞれ０．９６w/kgおよび
０．８３w/kgであり、顕著な鉄損低減効果が得られた。The obtained steel sheet had the aluminum borate film adhered to the underlying glass film, and the same bending test as in Example 1 was carried out. As a result, no peeling of the film was observed.
The adhesion was extremely good. The thickness of the tension film is 1.5
was μm. Also, the iron loss W before and after forming the tension film
When 17/50 was measured, they were 0.96 w / kg and 0.83 w / kg, respectively, and a remarkable iron loss reduction effect was obtained.
【００２５】比較例３ コーティング液中にＦｅＯＯＨ微粒子を含有させないこ
と以外は、実施例３と全く同様のことを行った。得られ
た鋼板は、Ｘ線回折や電子顕微鏡による観察の結果、結
晶性の低い硼酸アルミニウムの皮膜（厚み約１．５μ
ｍ）が下地のグラス皮膜上に形成されていたが、この鋼
板を２０mmφのロール棒による１８０度曲げ試験に供し
たところ、全面積の合計約２０％の部分から皮膜の剥離
が観察された。Comparative Example 3 The same operation as in Example 3 was carried out except that FeOOH fine particles were not contained in the coating liquid. As a result of observation by X-ray diffraction and an electron microscope, the obtained steel sheet had a film of aluminum borate having a low crystallinity (thickness of about 1.5 μm).
m) was formed on the underlying glass film, but when this steel sheet was subjected to a 180-degree bending test using a 20 mmφ roll bar, film peeling was observed from a total of about 20% of the total area.
【００２６】実施例４ Ｓｉを３．２％含有する仕上焼鈍後のグラス皮膜（フォ
ルステライト皮膜）を有する方向性電磁鋼板に、市販の
アルミナゾル（固形分１０％を含む）１００重量部、メ
タ硼酸５重量部、酢酸スズ０．２重量部、および蒸留水
よりなるコーティング液を片面４ｇ／ｍ2 となるように
塗布し、乾燥・ゲル化後、８５０℃で３分間、乾燥した
Ｎ2 中で焼き付けを行った。Example 4 100 parts by weight of commercially available alumina sol (containing 10% of solid content) and metaboric acid were added to a grain-oriented electrical steel sheet having a glass film (forsterite film) after finish annealing containing 3.2% of Si. A coating solution consisting of 5 parts by weight, 0.2 parts by weight of tin acetate, and distilled water was applied on one side to 4 g / m 2 , dried and gelled, and then dried at 850 ° C. for 3 minutes in dried N 2 . I baked it.
【００２７】得られた鋼板は、Ｘ線回折や電子顕微鏡観
察の結果、張力皮膜（厚み約１．５μｍ）の硼酸アルミ
ニウムが下地のグラス皮膜に密着していることがわかっ
た。この密着性は極めて良好であり、２０mmφのロール
棒による１８０度曲げ試験によっても皮膜の剥離は全く
認められなかった。また、この張力皮膜形成前と形成後
の鉄損Ｗ17/50 を測定したところ、それぞれ０．９６w/
kgおよび０．８４w/kgであり、張力皮膜による顕著な鉄
損低減効果が得られた。As a result of X-ray diffraction and electron microscope observation, it was found that the obtained steel sheet had aluminum borate as a tension film (thickness of about 1.5 μm) adhered to the underlying glass film. This adhesion was extremely good, and no peeling of the film was observed even in the 180-degree bending test using a roll bar of 20 mmφ. The iron loss W 17/50 before and after the formation of the tension film was measured to be 0.96 w /
kg and 0.84 w / kg, and a remarkable effect of reducing iron loss by the tension film was obtained.
【００２８】比較例４ コーティング液中に酢酸スズを含有させないこと以外
は、実施例４と全く同様なことを行った。得られた鋼板
はＸ線回折や電子顕微鏡観察の結果、結晶性の低い硼酸
アルミニウムの皮膜（厚み約１．５μｍ）が下地のグラ
ス皮膜上に形成されていたが、この鋼板を２０mmφのロ
ール棒による１８０度曲げ試験に供したところ、全面積
の合計約２０％の部分から皮膜の剥離が観察された。Comparative Example 4 The same operation as in Example 4 was carried out except that the coating solution did not contain tin acetate. As a result of X-ray diffraction and electron microscopic observation, the obtained steel sheet had a film of aluminum borate having low crystallinity (thickness of about 1.5 μm) formed on the underlying glass film. When subjected to a 180-degree bending test according to the above, peeling of the film was observed from a total of about 20% of the total area.
【００２９】[0029]
【発明の効果】本発明は、仕上焼鈍後の方向性電磁鋼板
上に極めて密着性の良いセラミック質張力皮膜が形成さ
れた方向性電磁鋼板を得るものであり、その工業的効果
は甚大である。INDUSTRIAL APPLICABILITY The present invention is to obtain a grain-oriented electrical steel sheet having a ceramic tension film having excellent adhesion formed on the grain-oriented electrical steel sheet after finish annealing, and its industrial effect is enormous. .
Claims (3)
物系の張力皮膜を形成するにあたり、該張力皮膜形成の
ための酸化物原料に金属塩の微粒子、および／または水
溶性の金属塩を０．１〜５重量％添加した液を塗布し乾
燥後、５００〜１３５０℃で焼き付け、酸化物皮膜を形
成することを特徴とする低鉄損方向性電磁鋼板の製造方
法。1. When forming an oxide-based tension film on the surface of a grain-oriented electrical steel sheet after finish annealing, fine particles of a metal salt and / or a water-soluble metal salt are used as an oxide raw material for forming the tension film. Is applied and dried, and then baked at 500 to 1350 ° C. to form an oxide film, thereby producing a low iron loss grain-oriented electrical steel sheet.
塩、酢酸塩である請求項１記載の低鉄損方向性電磁鋼板
の製造方法。2. The method for producing a low iron loss grain oriented electrical steel sheet according to claim 1, wherein the salt of the metal salt is an oxide, a hydroxide, a nitrate or an acetate.
Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｓｎである請求項１記載の低
鉄損方向性電磁鋼板の製造方法。3. The metal of the metal salt is V, Cr, Mn, Fe,
The method for producing a low iron loss grain-oriented electrical steel sheet according to claim 1, which is Co, Ni, Cu, Zn, or Sn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8483393A JP2667098B2 (en) | 1993-04-12 | 1993-04-12 | Manufacturing method of low iron loss grain-oriented electrical steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8483393A JP2667098B2 (en) | 1993-04-12 | 1993-04-12 | Manufacturing method of low iron loss grain-oriented electrical steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06299366A true JPH06299366A (en) | 1994-10-25 |
| JP2667098B2 JP2667098B2 (en) | 1997-10-22 |
Family
ID=13841788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8483393A Expired - Fee Related JP2667098B2 (en) | 1993-04-12 | 1993-04-12 | Manufacturing method of low iron loss grain-oriented electrical steel sheet |
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| Country | Link |
|---|---|
| JP (1) | JP2667098B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262431A (en) * | 2006-03-27 | 2007-10-11 | Nippon Steel Corp | Electrical steel sheet with good film adhesion and excellent magnetic property, its manufacturing method and its usage |
| JP2008031499A (en) * | 2006-07-26 | 2008-02-14 | Nippon Steel Corp | Electromagnetic steel sheet provided with multilayer film having superior adhesiveness and excellent magnetic property, and manufacturing method therefor |
| JP2008069412A (en) * | 2006-09-14 | 2008-03-27 | Nippon Steel Corp | Electrical part composed of electrical steel sheet with multilayer film having excellent film adhesion and satisfactory magnetic property, and method for producing the same |
| CN111684106A (en) * | 2018-02-06 | 2020-09-18 | 杰富意钢铁株式会社 | Electromagnetic steel sheet with insulating coating and method for producing same |
-
1993
- 1993-04-12 JP JP8483393A patent/JP2667098B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262431A (en) * | 2006-03-27 | 2007-10-11 | Nippon Steel Corp | Electrical steel sheet with good film adhesion and excellent magnetic property, its manufacturing method and its usage |
| JP2008031499A (en) * | 2006-07-26 | 2008-02-14 | Nippon Steel Corp | Electromagnetic steel sheet provided with multilayer film having superior adhesiveness and excellent magnetic property, and manufacturing method therefor |
| JP2008069412A (en) * | 2006-09-14 | 2008-03-27 | Nippon Steel Corp | Electrical part composed of electrical steel sheet with multilayer film having excellent film adhesion and satisfactory magnetic property, and method for producing the same |
| CN111684106A (en) * | 2018-02-06 | 2020-09-18 | 杰富意钢铁株式会社 | Electromagnetic steel sheet with insulating coating and method for producing same |
| CN111684106B (en) * | 2018-02-06 | 2022-06-07 | 杰富意钢铁株式会社 | Electromagnetic steel sheet with insulating coating and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2667098B2 (en) | 1997-10-22 |
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