JP2003293149A - Grain-oriented silicon steel sheet with excellent adhesion to tension-imparting insulation film, and manufacturing method therefor - Google Patents
Grain-oriented silicon steel sheet with excellent adhesion to tension-imparting insulation film, and manufacturing method thereforInfo
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- JP2003293149A JP2003293149A JP2002105175A JP2002105175A JP2003293149A JP 2003293149 A JP2003293149 A JP 2003293149A JP 2002105175 A JP2002105175 A JP 2002105175A JP 2002105175 A JP2002105175 A JP 2002105175A JP 2003293149 A JP2003293149 A JP 2003293149A
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- tension
- film
- steel sheet
- insulating film
- imparting
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、フォルステライト
(Mg2SiO4)等で構成される無機鉱物質皮膜の生成
を意図的に防止して製造したり、あるいは、研削や酸洗
等の手段によって除去したり、更には、鏡面光沢を呈す
るまで表面を平坦化させたりして調製した仕上げ焼鈍済
みの一方向性珪素鋼板に対し、張力付与性の絶縁性皮膜
を形成させた一方向性珪素鋼板とその製造方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended for production by intentionally preventing the formation of an inorganic mineral film composed of forsterite (Mg 2 SiO 4 ) or the like, or means for grinding or pickling. Of the unidirectional silicon steel sheet which has been subjected to finish annealing and which has been prepared by removing it by the above method or further flattening the surface until it exhibits a mirror gloss, The present invention relates to a steel plate and a manufacturing method thereof.
【0002】[0002]
【従来の技術】一方向性珪素鋼板は磁気鉄芯材料として
多用されており、特にエネルギ−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。鉄損の低減には
鋼板に張力を付与することが有効であることから、鋼板
に比べ熱膨張係数の小さい材質からなる皮膜を高温で形
成することによって鋼板に張力を付与し、鉄損低減が図
られてきた。2. Description of the Related Art Unidirectional silicon steel sheets are widely used as magnetic iron core materials, and in particular, materials having a low iron loss are required to reduce energy loss. Since it is effective to apply tension to the steel sheet to reduce iron loss, tension is applied to the steel sheet by forming a film made of a material having a smaller coefficient of thermal expansion than the steel sheet at high temperature, which reduces iron loss. It has been planned.
【0003】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系皮膜
は、鋼板に張力を与えることができ、皮膜密着性も優れ
ている。特開昭48−39338号公報で開示されたコ
ロイド状シリカとリン酸塩を主体とするコーティング液
を鋼板表面に塗布し、焼き付けることによって絶縁皮膜
を形成する方法は、鋼板に対する張力付与の効果が大き
く、鉄損低減に有効である。The forsterite type coating formed by the reaction between the oxide on the surface of the steel sheet and the annealing separator in the finish annealing step can give tension to the steel sheet and has excellent coating adhesion. The method of forming an insulating film by applying the coating liquid containing colloidal silica and phosphate as a main component, which is disclosed in JP-A-48-39338, on the surface of the steel sheet and baking the coating solution has the effect of applying tension to the steel sheet. Large and effective in reducing iron loss.
【0004】そこで、仕上げ焼鈍工程で生じたフォルス
テライト系皮膜を残した上でリン酸塩を主体とする絶縁
皮膜を形成することが、一般的な一方向性珪素鋼板の製
造方法となっている。Therefore, a general method for producing a unidirectional silicon steel sheet is to leave the forsterite film formed in the finish annealing step and then to form an insulating film mainly containing phosphate. .
【0005】近年、フォルステライト系皮膜と地鉄の乱
れた界面構造が、皮膜張力による鉄損改善効果をある程
度減少させていることが明らかになってきた。そこで、
例えば、特開昭49−96920号公報に開示されてい
る如く、仕上げ焼鈍工程で生ずるフォルステライト系皮
膜を除去したり、更に鏡面化仕上げを行った後、改めて
張力皮膜を形成することにより、更なる鉄損低減を試み
る技術が開発された。In recent years, it has become clear that the disordered interface structure between the forsterite coating and the base iron reduces the iron loss improving effect due to the coating tension to some extent. Therefore,
For example, as disclosed in JP-A-49-96920, by removing the forsterite-based film generated in the finish annealing step, further performing mirror finishing, and then forming a tension film again, Has been developed.
【0006】しかしながら、上記絶縁皮膜は、フォルス
テライトを主体とする皮膜の上に形成された場合は、か
なりの密着性を呈するものの、フォルステライト系皮膜
を除去したり、あるいは、仕上げ焼鈍工程で意図的にフ
ォルステライト形成を行わなかったものに対しては、皮
膜密着性が十分ではない。[0006] However, although the above-mentioned insulating film exhibits a considerable adhesiveness when formed on a film mainly composed of forsterite, it is intended to remove the forsterite-based film or to be used in the finish annealing process. The film adhesion is not sufficient for those for which forsterite formation was not performed.
【0007】フォルステライト系皮膜の除去を行った場
合には、コ−ティング液を塗布して形成させる張力付与
型絶縁皮膜のみで所要の皮膜張力を確保する必要があ
り、必然的に厚膜化しなければならず、より一層の密着
性が必要である。したがって、従来の皮膜形成法では鏡
面化の効果を十分に引き出すほどの皮膜張力を達成し、
かつ、皮膜密着性をも確保することは困難であり、十分
な鉄損低減が図られていなかった。When the forsterite-based film is removed, it is necessary to secure the required film tension only with the tension-imparting insulating film formed by applying the coating liquid. It is necessary to further improve the adhesion. Therefore, the conventional film forming method achieves a film tension sufficient to bring out the effect of mirror-finishing,
At the same time, it is difficult to secure the film adhesion, and the iron loss has not been sufficiently reduced.
【0008】そこで、張力付与性絶縁皮膜の密着性を確
保するための技術として、張力付与性絶縁皮膜の形成に
先立ち、仕上げ焼鈍済みの一方向性珪素鋼板の表面に酸
化膜を形成させる方法が、例えば、特開昭60−131
976号公報、特開平6−184762号公報、特開平
7−278833号公報、特開平8−191010号公
報、特開平9−078252号公報、において開示され
た。Therefore, as a technique for ensuring the adhesion of the tension-imparting insulating film, there is a method of forming an oxide film on the surface of the finish-annealed unidirectional silicon steel sheet prior to the formation of the tension-imparting insulating film. , For example, JP-A-60-131
976, JP-A-6-184762, JP-A-7-278833, JP-A-8-191010, and JP-A-9-078252.
【0009】特開昭60−131976号公報は、鏡面
化した仕上げ焼鈍済みの一方向性珪素鋼板を鏡面化した
後、鋼板表面付近を内部酸化させる方法で、この内部酸
化層によって張力皮膜の密着性を向上させ、内部酸化、
即ち鏡面度減退で生じる鉄損劣化を皮膜密着性向上によ
ってもたらされる付与張力の増大で補おうとする方法で
ある。Japanese Patent Laid-Open No. 60-131976 discloses a method in which a mirror-finished finish-annealed unidirectional silicon steel sheet is mirror-finished and then the surface of the steel sheet is internally oxidized. Improve the internal properties, internal oxidation,
That is, this is a method of compensating for the iron loss deterioration caused by the decrease in specularity by increasing the applied tension brought about by the improvement of the film adhesion.
【0010】特開平6−184762号公報は、鏡面化
ないしはそれに近い状態に調製した仕上げ焼鈍済みの一
方向性珪素鋼板に対し、温度ごとに特定の雰囲気で焼鈍
を施すことにより鋼板表面に外部酸化型の酸化膜を形成
し、この酸化膜でもって張力付与性絶縁皮膜の皮膜と鋼
板との皮膜密着性を確保する方法である。Japanese Unexamined Patent Publication (Kokai) No. 6-184762 discloses that a finish-annealed unidirectional silicon steel sheet prepared to have a mirror-like finish or a state close to that is annealed in a specific atmosphere at each temperature to externally oxidize the steel sheet surface. This is a method of forming an oxide film of a mold and ensuring the film adhesion between the film of the tension-imparting insulating film and the steel sheet with this oxide film.
【0011】特開平7−278833号公報は、張力付
与性の絶縁皮膜が結晶質である場合において、無機鉱物
質皮膜のない仕上げ焼鈍済みの一方向性珪素鋼板の表面
に非晶質の酸化物の下地皮膜を形成させることで、結晶
質の張力付与性絶縁皮膜が形成される際に起こる鋼板酸
化、即ち、鏡面度減退を防止する技術である。Japanese Unexamined Patent Publication (Kokai) No. 7-278833 discloses that when the tension-imparting insulating film is crystalline, an amorphous oxide is formed on the surface of the finish-annealed unidirectional silicon steel plate without the inorganic mineral film. This is a technique for preventing the steel sheet oxidation that occurs when the crystalline tension-imparting insulating film is formed, that is, the decrease in specularity, by forming the undercoating film.
【0012】特開平8−191010号公報は、非金属
物質を除去した仕上げ焼鈍済みの一方向性珪素鋼板の表
面に結晶性のファイヤライトを形成させることでファイ
ヤライト結晶による張力付与効果と張力付与性の絶縁皮
膜との密着性向上効果により鉄損低減を図る方法であ
る。Japanese Unexamined Patent Publication (Kokai) No. Hei 8-191010 discloses a method of forming a crystalline firelite on the surface of a finish-annealed unidirectional silicon steel sheet from which non-metallic substances have been removed, thereby providing a tensioning effect and a tensioning force by the firelite crystal. This is a method for reducing iron loss by the effect of improving the adhesiveness with a conductive insulating film.
【0013】特開平9−078252号公報は、無機鉱
物質皮膜のない仕上げ焼鈍済みの一方向性珪素鋼板の表
面に形成させる下地シリカ層の量を100mg/m2以
下にすることで張力皮膜の密着性確保だけでなく、良好
な鉄損値をも実現しようとする方法である。Japanese Unexamined Patent Publication (Kokai) No. 9-078252 discloses that the amount of an underlying silica layer formed on the surface of a finish-annealed unidirectional silicon steel sheet having no inorganic mineral film is 100 mg / m 2 or less, thereby forming a tension film. This is a method that not only ensures adhesion but also achieves a good iron loss value.
【0014】[0014]
【発明が解決しようとする課題】上述の技術を適用し、
無機鉱物質のない一方向性珪素鋼板の表面に酸化膜を形
成させることで、皮膜密着性の改善効果や鉄損値の低減
効果が得られることはそれなりに認められる。しかしな
がら、張力付与性絶縁皮膜の皮膜密着性は必ずしも完全
ではなかった。Applying the above-mentioned technique,
It is recognized that forming an oxide film on the surface of a unidirectional silicon steel sheet free of inorganic minerals has the effect of improving the film adhesion and the effect of reducing the iron loss value. However, the film adhesion of the tension-imparting insulating film was not always perfect.
【0015】[0015]
【課題を解決するための手段】本発明は上述の問題点を
解決し、無機鉱物質皮膜のない仕上げ焼鈍済みの一方向
性珪素鋼板に対し、十分な皮膜密着性を得ることができ
るよう張力付与型の絶縁性皮膜を形成した張力付与性絶
縁皮膜密着性に優れる一方向性珪素鋼板とその製造方法
である。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and provides a tension so that sufficient film adhesion can be obtained for a finish-annealed unidirectional silicon steel sheet without an inorganic mineral film. A unidirectional silicon steel sheet excellent in adhesion to a tension-imparting insulating film formed with an imparting type insulating film, and a method for producing the same.
【0016】本発明の要旨は次のとおりである。The gist of the present invention is as follows.
【0017】(1)フォルステライト等の無機鉱物質皮
膜を酸洗等の手段により除去したりあるいはその生成を
意図的に防止して製造した後、張力付与性絶縁皮膜を形
成した一方向性珪素鋼板であって、張力付与性絶縁皮膜
と鋼板との界面に、膜厚が2nm以上500nm以下の
シリカ主体の外部酸化型酸化膜を有し、かつ、該酸化膜
の張力付与性絶縁皮膜との界面部分の密度低下層の平均
厚さが該酸化膜全厚の30%以下であることを特徴とす
る張力付与性絶縁皮膜密着性に優れる一方向性珪素鋼
板。(1) Unidirectional silicon having a tension imparting insulating film formed after the inorganic mineral film such as forsterite is removed by means such as pickling or intentionally prevented from producing. A steel sheet having an external oxidation type oxide film mainly composed of silica having a thickness of 2 nm or more and 500 nm or less at the interface between the tension-imparting insulating film and the steel sheet, and A unidirectional silicon steel sheet having excellent adhesion to a tension-imparting insulating film, characterized in that the average thickness of the density-reduced layer at the interface is 30% or less of the total thickness of the oxide film.
【0018】(2)前記張力付与性絶縁皮膜が、リン酸
塩とコロイド状シリカを主体とする塗布液を焼き付ける
ことによって形成した張力付与性絶縁皮膜であることを
特徴とする前記(1)記載の張力付与性絶縁皮膜密着性
に優れる一方向性珪素鋼板。(2) The above-mentioned (1), wherein the tension-imparting insulating film is a tension-imparting insulating film formed by baking a coating liquid mainly containing phosphate and colloidal silica. A unidirectional silicon steel sheet with excellent tensile strength and insulating film adhesion.
【0019】(3)前記張力付与性絶縁皮膜が、アルミ
ナゾルとほう酸を主体とする塗布液を焼き付けることに
よって形成した張力付与性絶縁皮膜であることを特徴と
する前記(1)記載の張力付与性絶縁皮膜密着性に優れ
る一方向性珪素鋼板。(3) The tension imparting insulating film according to the above (1), wherein the tension imparting insulating film is a tension imparting insulating film formed by baking a coating liquid mainly containing alumina sol and boric acid. A unidirectional silicon steel plate with excellent insulation film adhesion.
【0020】(4)フォルステライト等の無機鉱物質皮
膜を酸洗等の手段により除去したりあるいはその生成を
意図的に防止して製造した仕上げ焼鈍済み一方向性珪素
鋼板に対し、張力付与性絶縁皮膜と鋼板との密着性を確
保するため、張力付与性絶縁皮膜の形成に先立ち、シリ
カを主体とする外部酸化型酸化膜を形成させた後、張力
付与性絶縁皮膜形成用の塗布液を塗布し、焼き付けるこ
とによって張力付与性絶縁皮膜を形成して、一方向性珪
素鋼板を製造する方法において、張力付与性絶縁皮膜形
成用塗布液とシリカ主体の外部酸化型酸化膜を形成させ
た鋼板とが100℃以下の温度域で接触している時間を
20秒以下にして、張力付与性絶縁皮膜を製造すること
を特徴とする張力付与性絶縁皮膜密着性に優れる一方向
性珪素鋼板の製造方法。(4) Tension imparting property to the finish-annealed unidirectional silicon steel sheet produced by removing the inorganic mineral film such as forsterite by means such as pickling or intentionally preventing its formation. In order to secure the adhesion between the insulating film and the steel sheet, prior to forming the tension-imparting insulating film, an external oxidation type oxide film mainly composed of silica is formed, and then a coating liquid for forming the tension-imparting insulating film is applied. A method for producing a unidirectional silicon steel sheet by forming a tension-imparting insulating film by coating and baking, and a steel sheet having a coating liquid for forming a tension-imparting insulating film and an external oxidation type oxide film mainly composed of silica. A unidirectional silicon steel sheet having excellent adhesion to a tension-imparting insulating film, characterized in that the tension-imparting insulating film is manufactured by keeping the time of contact with 100 ° C. or less for 20 seconds or less. Law.
【0021】[0021]
【発明の実施の形態】以下、発明の詳細について説明す
る。DETAILED DESCRIPTION OF THE INVENTION The details of the invention will be described below.
【0022】発明者らは、皮膜密着性が必ずしも完全で
はない原因として外部酸化型酸化膜を形成させた後、張
力付与性絶縁皮膜を形成させる工程に問題があるのでは
ないかと考えた。中でも、張力付与性絶縁皮膜形成用の
塗布液を鋼板に塗布し焼き付ける時の、塗布液と鋼板と
が低温温度域において接触している時間が影響している
のではないかと推定した。The inventors have suspected that there is a problem in the step of forming the tension-imparting insulating film after forming the external oxidation type oxide film as a cause that the film adhesion is not always perfect. In particular, it was estimated that the time during which the coating liquid and the steel sheet are in contact with each other in the low temperature temperature range may be affected when the coating liquid for forming the tension imparting insulating film is applied to the steel plate and baked.
【0023】つまり、鋼板と塗布液との接触時間によっ
て外部酸化型酸化膜と張力付与性絶縁皮膜との界面構
造、特に、外部酸化型酸化膜側に差異が生じ、そのため
張力付与性の絶縁皮膜の密着性が変動するのではないか
と考えた。That is, the interface structure between the external oxidation type oxide film and the tension-imparting insulating film, especially on the side of the external oxidation type oxide film, is different depending on the contact time between the steel sheet and the coating liquid, and therefore the tension-imparting insulating film. I thought that the adhesiveness of would fluctuate.
【0024】そこで、次に述べるような実験を行い、皮
膜密着性に対する塗布液と外部酸化型酸化膜付き鋼板と
の接触時間と外部酸化型酸化膜構造の関係を調べた。な
お、ここでの外部酸化型酸化膜とは、鋼板上に形成され
た酸化物であって、その酸化物が鋼板表面の70%以上
を被覆している場合に、その酸化物のことをいう。Therefore, the following experiment was conducted to examine the relationship between the coating time and the contact time between the coating solution and the steel sheet with the external oxidation type oxide film and the structure of the external oxidation type oxide film. In addition, the external oxidation type oxide film here is an oxide formed on a steel plate, and when the oxide covers 70% or more of the steel plate surface, it means the oxide. .
【0025】実験用素材として、板厚0.225mmの
脱炭焼鈍板に対し、アルミナを主体とする焼鈍分離剤を
塗布して仕上げ焼鈍を行い、二次再結晶させ、鏡面光沢
を有する一方向性珪素鋼板を準備した。この鋼板に対
し、窒素20%、水素80%、露点+2℃の雰囲気にお
いて均熱時間8秒で、かつ、種々の温度で熱処理を施
し、シリカを主体とする外部酸化型酸化膜を形成させ
た。As a material for experimentation, a decarburized annealed plate having a plate thickness of 0.225 mm was coated with an annealing separator containing alumina as a main component, subjected to finish annealing, secondary recrystallized, and one direction having a mirror gloss. Silicon steel sheet was prepared. This steel sheet was heat-treated in an atmosphere of nitrogen 20%, hydrogen 80%, dew point + 2 ° C. for a soaking time of 8 seconds and at various temperatures to form an external oxidation type oxide film mainly composed of silica. .
【0026】ついで、張力付与性の絶縁皮膜を形成する
ため、リン酸アルミニウム、クロム酸、コロイダルシリ
カを主体とする塗布液を塗布し、窒素雰囲気中で835
℃で30秒間焼き付けた。この時、塗布液が100℃以
下の温度で鋼板と接触している時間を変えて張力付与性
絶縁皮膜を形成させた。このようにして作製した鋼板の
皮膜密着性を調べた。Then, in order to form an insulating film having a tension imparting property, a coating liquid mainly containing aluminum phosphate, chromic acid and colloidal silica is applied, and 835 is applied in a nitrogen atmosphere.
Baked at 30 ° C for 30 seconds. At this time, the tension-imparting insulating film was formed by changing the time during which the coating solution was in contact with the steel plate at a temperature of 100 ° C. or lower. The film adhesion of the steel sheet thus produced was examined.
【0027】皮膜密着性は直径20mmの円筒に試料を
巻き付けた時、鋼板から剥離せず、鋼板と皮膜が密着し
たままであった部分の面積率(以後、皮膜残存面積率と
称する)で評価した。密着性が不良で皮膜が完全に剥離
した場合は0%、皮膜密着性が良好で皮膜が全く剥離し
なかった場合を100%と判定した。評価は皮膜残存面
積率が90%以下の場合を×、90%超95%以下のも
のを○、95%超100%以下のものを◎とした。The coating adhesion is evaluated by the area ratio (hereinafter referred to as the coating residual area ratio) of the portion where the coating was not peeled from the steel sheet and the coating remained in contact when the sample was wound around a cylinder having a diameter of 20 mm. did. The case where the adhesion was poor and the film was completely peeled off was judged as 0%, and the case where the film adhesion was good and the film was not peeled at all was judged as 100%. In the evaluation, when the film residual area ratio was 90% or less, x was given, when more than 90% and 95% or less was given, and when more than 95% and 100% or less, was given.
【0028】また、外部酸化型酸化膜を含む張力付与性
絶縁皮膜と鋼板との界面構造を調べるため、集束イオン
ビ−ム法(以下、FIB法と称する)によって試料を作
製し、透過型電子顕微鏡(以下、TEMと称する)で断
面構造を観察した。また、シリカを主体とする外部酸化
型酸化膜の膜厚方向の密度分布を電子エネルギ−損失分
光法(以下、EELS法と称する)によって調べた。Further, in order to investigate the interface structure between the steel sheet and the tension-imparting insulating film including the external oxidation type oxide film, a sample was prepared by the focused ion beam method (hereinafter referred to as FIB method), and the transmission electron microscope was used. The cross-sectional structure was observed with (hereinafter referred to as TEM). Further, the density distribution in the film thickness direction of the external oxidation type oxide film mainly composed of silica was examined by electron energy-loss spectroscopy (hereinafter referred to as EELS method).
【0029】FIB法とは、鋼板上に形成した厚さ数μ
mの皮膜を断面方向から観察できるよう、皮膜付き鋼板
試料の所望の位置から厚さ数μmの薄片状試料を作製・
採取する手法である。The FIB method is the thickness of several μ formed on a steel plate.
A thin sample with a thickness of several μm was prepared from the desired position of the coated steel plate sample so that the film of m could be observed from the cross-sectional direction.
This is a method of collecting.
【0030】EELS法とは、FIB法等で作製した薄
片状試料に対し、厚さ方向に電子線を照射した時、散乱
されてくる電子線強度を損失エネルギ−に対して計測す
る方法で、弾性散乱強度と非弾性散乱強度の比率が膜を
構成する物質の密度に比例することを利用し、両者の強
度比でもって密度を算出する手法である。The EELS method is a method of measuring the intensity of scattered electron beam against the loss energy when a thin sample prepared by the FIB method or the like is irradiated with an electron beam in the thickness direction. This method utilizes the fact that the ratio of the elastic scattering intensity and the inelastic scattering intensity is proportional to the density of the substance constituting the film, and calculates the density by the intensity ratio of both.
【0031】FIB法で薄膜試料を作製し、TEM−E
ELS法でシリカ主体の外部酸化型酸化膜中の密度を調
べたところ、密度分布が観察された。特に、シリカ主体
の外部酸化型酸化膜と張力付与性絶縁皮膜との界面近傍
において、外部酸化型酸化膜の密度が、該酸化膜中心部
や鋼板側界面部と比較し、低くなっていることが観測さ
れた。A thin film sample was prepared by the FIB method, and TEM-E
When the density in the external oxidation type oxide film mainly composed of silica was examined by the ELS method, a density distribution was observed. In particular, the density of the external oxidation type oxide film in the vicinity of the interface between the silica-based external oxidation type oxide film and the tension-imparting insulating film is lower than that of the oxide film center part or the steel plate side interface part. Was observed.
【0032】外部酸化型酸化膜の鋼板との界面近傍部分
の密度をDiとしたときに、測定した外部酸化型酸化膜
の密度Dsが0.8Di以下となる部分を密度低下部分
とし、この密度低下部分が外部酸化型酸化膜中で占める
平均膜厚を求め、外部酸化型酸化膜の全厚に対する比率
とし、これを密度低下層比率とした。When the density of the portion of the external oxidation type oxide film near the interface with the steel sheet is Di, the portion where the measured external oxidation type oxide film density Ds is 0.8 Di or less is defined as the density reduced portion, and this density The average film thickness occupied by the reduced portion in the external oxidation type oxide film was determined and defined as the ratio to the total thickness of the external oxidation type oxide film, which was defined as the density reduced layer ratio.
【0033】なお、全厚とは外部酸化型酸化膜全体の厚
さを意味し、TEMによる断面観察像において外部酸化
型酸化膜と鋼板との界面から、上記外部酸化型酸化膜と
張力付与性絶縁皮膜との界面までの距離を指す。The total thickness means the total thickness of the external oxidation type oxide film, and from the interface between the external oxidation type oxide film and the steel sheet in the cross-sectional observation image by TEM, the external oxidation type oxide film and the tension imparting property are obtained. Indicates the distance to the interface with the insulating film.
【0034】このようにして調べた結果を表1および表
2(表1のつづき)にまとめた。The results of the examinations thus made are summarized in Table 1 and Table 2 (continued from Table 1).
【0035】[0035]
【表1】 [Table 1]
【0036】[0036]
【表2】 [Table 2]
【0037】表1および表2から、張力付与性絶縁皮膜
の密着性を確保できる条件を求めると次のようになる。From Tables 1 and 2, the conditions for ensuring the adhesion of the tension-imparting insulating film are as follows.
【0038】まず、シリカ主体の外部酸化型酸化膜付き
の鋼板と塗布液との接触時間の長短に関わらず、外部酸
化型酸化膜の膜厚が2nm未満の試料番号1から試料番
号5の熱処理温度500℃の条件では、皮膜密着性が確
保できない。一方、外部酸化型酸化膜の膜厚が2nm以
上の試料番号6から試料番号40の熱処理温度が600
℃から1150℃の条件においては、概ね、皮膜密着性
が確保できるようになる。First, heat treatment of Sample Nos. 1 to 5 in which the film thickness of the external oxidation type oxide film is less than 2 nm is irrespective of the length of the contact time between the coating liquid and the steel plate mainly composed of silica and having the external oxidation type oxide film. Under the condition of a temperature of 500 ° C, the film adhesion cannot be secured. On the other hand, the heat treatment temperature of Sample No. 6 to Sample No. 40 having the thickness of the external oxidation type oxide film of 2 nm or more is 600
Under the conditions of ℃ to 1150 ℃, the film adhesion can be generally secured.
【0039】特に、試料番号26から試料番号40の外
部酸化型酸化膜の膜厚が40nm以上の熱処理温度が1
000℃以上の条件では皮膜密着性が格段に良好であ
る。In particular, the heat treatment temperature of the sample No. 26 to sample No. 40 at which the thickness of the external oxidation type oxide film is 40 nm or more is 1
Under conditions of 000 ° C or higher, the film adhesion is remarkably good.
【0040】但し、シリカ主体の外部酸化型酸化膜付き
の鋼板と塗布液との接触時間が20秒以下で、外部酸化
型酸化膜中の密度低下層の比率が30%以下の条件で
は、皮膜密着性が良好であるが、接触時間30秒で密度
低下層比率が30%よりも大きい条件では外部酸化型酸
化膜の膜厚が厚くとも、皮膜密着性が必ずしも完全とは
言えず、皮膜残存面積率で90%となった。However, under the conditions that the contact time between the steel sheet having a silica-based external oxidation type oxide film and the coating solution is 20 seconds or less and the ratio of the density-reduced layer in the external oxidation type oxide film is 30% or less, the coating film Adhesiveness is good, but under the condition that the contact time is 30 seconds and the density-reduced layer ratio is larger than 30%, even if the film thickness of the external oxidation type oxide film is thick, the film adhesion cannot be said to be perfect and the film remains. The area ratio was 90%.
【0041】表1および表2から張力付与性絶縁皮膜の
皮膜密着性を確保するためには外部酸化型酸化膜の膜厚
が2nm以上で、かつ、外部酸化型酸化膜における密度
低下層比率が30%以下であることが必須であり、こう
した外部酸化型酸化膜を形成させるためには、外部酸化
型酸化膜を形成するための熱処理工程において、熱処理
温度を600℃以上、特に好ましくは1000℃以上で
行ない、かつ、張力付与性絶縁皮膜を形成させる工程に
おいて、外部酸化型酸化膜付き鋼板と張力付与性絶縁皮
膜形成用塗布液との接触時間を20秒以下にする必要が
あることがわかる。From Tables 1 and 2, in order to secure the film adhesion of the tension imparting insulating film, the thickness of the external oxidation type oxide film is 2 nm or more, and the density reduction layer ratio in the external oxidation type oxide film is It is indispensable to be 30% or less. In order to form such an external oxidation type oxide film, in the heat treatment step for forming the external oxidation type oxide film, the heat treatment temperature is 600 ° C. or higher, particularly preferably 1000 ° C. It can be seen that in the step of forming the tension-imparting insulating film as described above, the contact time between the steel sheet with the external oxidation type oxide film and the coating solution for forming the tension-imparting insulating film needs to be 20 seconds or less. .
【0042】また、表1および表2には記載されていな
いが、外部酸化型酸化膜の膜厚が500nm以上になる
と、張力付与性絶縁皮膜による張力が外部酸化型酸化膜
によって著しく緩和されて鋼板に十分な張力が付与され
ないため、たとえ張力付与性絶縁皮膜密着性が優れてい
たとしても商品特性としては好ましくない。従って、外
部酸化型酸化膜の膜厚の上限は500nmとした。Although not described in Tables 1 and 2, when the film thickness of the external oxidation type oxide film is 500 nm or more, the tension due to the tension imparting insulating film is remarkably relaxed by the external oxidation type oxide film. Since sufficient tension is not applied to the steel sheet, even if the adhesion property of the tension-imparting insulating film is excellent, it is not preferable as a product property. Therefore, the upper limit of the thickness of the external oxidation type oxide film is set to 500 nm.
【0043】外部酸化型酸化膜付き鋼板と張力付与性絶
縁皮膜形成用塗布液との接触時間の下限については現在
のところ明らかではないが、0.1秒よりも短いと鋼板
と塗布液の両者がなじむ時間がなく、いわゆる塗布ムラ
を生じ易くなる可能性が考えられるので、鋼板と塗布液
との100℃以下での接触時間は0.1秒以上がよい。The lower limit of the contact time between the steel sheet with an external oxidation type oxide film and the coating liquid for forming the tension-imparting insulating film is not clear at present, but if it is shorter than 0.1 seconds, both the steel plate and the coating liquid will be used. Since it is considered that there is no time for the sheet to fit in, and so-called coating unevenness is likely to occur, the contact time between the steel sheet and the coating liquid at 100 ° C. or lower is preferably 0.1 seconds or longer.
【0044】このように皮膜密着性について外部酸化型
酸化膜の膜厚や密度低下層比率が大きく影響しているこ
とについて、発明者らはその機構を次のように考えてい
る。As described above, the inventors consider the mechanism that the film thickness and the density-reduced layer ratio of the external oxidation type oxide film have a great influence on the film adhesion.
【0045】まず、外部酸化型酸化膜の膜厚依存性につ
いて述べる。First, the film thickness dependence of the external oxidation type oxide film will be described.
【0046】鋼板と張力付与性絶縁皮膜との密着性は、
両者の界面に形成させた外部酸化型酸化膜によって決ま
る。一般に外部酸化型酸化膜は金属原子が鋼中から表面
に拡散し、表面で酸化性ガスと反応することで成長する
と言われている。そのため、酸化膜の成長速度は原子の
拡散速度によって決まる。原子の拡散は熱エネルギ−に
よって高められる。したがって、温度が高いほど原子の
拡散が促進され、外部酸化型酸化膜はより成長する。The adhesion between the steel sheet and the tension-imparting insulating film is
It depends on the external oxidation type oxide film formed at the interface between the two. It is generally said that the external oxidation type oxide film grows when metal atoms diffuse from the steel to the surface and react with the oxidizing gas on the surface. Therefore, the growth rate of the oxide film is determined by the diffusion rate of atoms. Atomic diffusion is enhanced by thermal energy. Therefore, the higher the temperature, the more the diffusion of atoms is promoted, and the external oxidation type oxide film grows more.
【0047】こうした機構のため熱処理温度が500℃
と低い条件では、外部酸化型の酸化膜の成長が十分では
ないため、皮膜密着性が十分ではなく、一方、熱処理温
度が600℃以上では、十分に外部酸化型酸化膜が成長
するので皮膜密着性は良好で、更に1000℃以上では
更に酸化膜が成長し易くなるので、皮膜密着性が極めて
良好となるものと考えられる。Due to such a mechanism, the heat treatment temperature is 500 ° C.
Under low conditions, the growth of the external oxidation type oxide film is not sufficient, so the film adhesion is insufficient. On the other hand, when the heat treatment temperature is 600 ° C or higher, the external oxidation type oxide film grows sufficiently, so the film adhesion It is considered that the adhesiveness is excellent, and further that the oxide film is more likely to grow at 1000 ° C. or higher, so that the film adhesion is extremely good.
【0048】こうした推測が妥当であることがTEMを
使った外部酸化型酸化膜の膜厚測定の結果からわかる。
即ち、膜厚が1nmで、外部酸化型酸化膜の成長が十分
でない熱処理温度500℃の条件では、張力付与性絶縁
皮膜の密着性が不良であるのに対し、膜厚2nm以上
で、外部酸化型酸化膜が成長した熱処理温度600℃以
上の条件では、皮膜密着性は良好である。It can be seen from the result of the film thickness measurement of the external oxidation type oxide film using the TEM that this estimation is valid.
That is, the adhesion of the tension-imparting insulating film is poor under the condition of the heat treatment temperature of 500 ° C. where the thickness of the film is 1 nm and the growth of the external oxidation type oxide film is not sufficient, while the film thickness of 2 nm or more is sufficient for the external oxidation. The film adhesion is good under the condition that the heat treatment temperature at which the mold oxide film is grown is 600 ° C. or higher.
【0049】次に張力付与性絶縁皮膜の密着性と外部酸
化型酸化膜に存在する密度低下層比率との関係について
述べる。Next, the relationship between the adhesion of the tension-imparting insulating film and the density-reduced layer ratio existing in the external oxidation type oxide film will be described.
【0050】外部酸化型酸化膜中にの密度低下層が形成
される機構については、その詳細が未だ不明であるが、
現在のところ、発明者らは次のように考えている。Although the details of the mechanism of forming the density-reduced layer in the external oxidation type oxide film are unknown,
At present, the inventors think as follows.
【0051】発明者らは、外部酸化型酸化膜付きの鋼板
に張力付与性絶縁皮膜形成用塗布液を塗布した際、外部
酸化型酸化膜において、一種の膨潤反応が起こり、外部
酸化型酸化膜の構造緩和が生じるのではないかと考えて
いる。このような構造緩和は塗布液に含まる水分などに
よって引き起こされるものと推測している。The inventors of the present invention, when a coating liquid for forming a tension-imparting insulating film is applied to a steel sheet with an external oxidation type oxide film, a kind of swelling reaction occurs in the external oxidation type oxide film, and the external oxidation type oxide film I think that structural relaxation of will occur. It is speculated that such structural relaxation is caused by water contained in the coating liquid.
【0052】そのため、外部酸化型酸化膜の中でも断面
方向から見て、塗布液と接している界面側で起こるもの
と推測される。実際、FIB法で試料を作製し、TEM
−EELS法で断面の密度分布を測定した場合、外部酸
化型酸化膜が張力付与性絶縁皮膜と接している部分で密
度低下が観測された。Therefore, it is presumed that, even in the external oxidation type oxide film, when viewed from the cross-sectional direction, it occurs on the interface side in contact with the coating liquid. Actually, a sample was prepared by the FIB method, and TEM
When the density distribution of the cross section was measured by the -EELS method, a decrease in density was observed in the portion where the external oxidation type oxide film was in contact with the tension imparting insulating film.
【0053】次に、こうした密度低下層の酸化膜全膜厚
に対する比率と塗布液との接触時間の関係について述べ
る。Next, the relationship between the ratio of the density reducing layer to the total thickness of the oxide film and the contact time with the coating solution will be described.
【0054】まず、鋼板と塗布液との100℃以下での
接触時間が短い場合、塗布液中に含まれる水分等による
外部酸化型酸化膜の膨潤様反応が起こりにくいため、密
度低下層比率は低い。一方、鋼板と塗布液との100℃
以下での接触時間が長い場合、塗布液中に含まれる水分
等による外部酸化型酸化膜の膨潤様反応が起こり易いた
め、密度低下層比率が高くなる。First, when the contact time between the steel sheet and the coating liquid at 100 ° C. or lower is short, the swelling-like reaction of the external oxidation type oxide film due to the moisture contained in the coating liquid is unlikely to occur, so that the density decreasing layer ratio is Low. On the other hand, 100 ° C between the steel plate and the coating liquid
If the contact time below is long, a swelling-like reaction of the external oxidation type oxide film due to water contained in the coating solution or the like is likely to occur, and the density-reduced layer ratio increases.
【0055】次に張力付与性絶縁皮膜の鋼板密着性と外
部酸化型酸化膜における密度低下層比率との関係を述べ
る。Next, the relationship between the adhesion of the tension imparting insulating film to the steel sheet and the density-reduced layer ratio in the external oxidation type oxide film will be described.
【0056】張力付与性絶縁皮膜による鋼板への張力付
与は張力付与性絶縁皮膜と鋼板との熱膨張係数の差によ
ってもたらされる。この時、張力付与性絶縁皮膜と鋼板
との界面には多大な応力が発生する。この応力に耐え、
鋼板と張力付与性絶縁皮膜の密着性を確保するのが外部
酸化型酸化膜である。The application of tension to the steel sheet by the tension-providing insulating film is brought about by the difference in the coefficient of thermal expansion between the tension-providing insulating film and the steel sheet. At this time, a large amount of stress is generated at the interface between the tension imparting insulating film and the steel sheet. Withstand this stress,
The external oxidation type oxide film secures the adhesion between the steel sheet and the tension-imparting insulating film.
【0057】発明者らは、こうした応力耐性に関し、一
種の欠陥部分である密度低下層が影響しているのではな
いかと推測している。つまり、外部酸化型酸化膜におけ
る密度低下層が少なく、酸化膜全膜厚に対する比率にし
て30%以下の場合、応力に耐えうるが、密度低下層比
率が多く、比率にして30%よりも多い場合、外部酸化
型酸化膜が、張力付与性絶縁皮膜によって押しかかる応
力に耐えることができず、外部酸化型酸化膜が破壊され
てしまうのではないかと考えている。The inventors have speculated that the stress-resistance may be affected by the density-reduced layer, which is a kind of defective portion. That is, when the density reduction layer in the external oxidation type oxide film is small and the ratio to the total thickness of the oxide film is 30% or less, it can withstand stress, but the density reduction layer ratio is high and the ratio is higher than 30%. In this case, the external oxidation type oxide film cannot withstand the stress applied by the tension imparting insulating film, and the external oxidation type oxide film may be destroyed.
【0058】[0058]
【実施例】(実施例1)板厚0.225mm、Si濃度
3.30%の一方向性珪素鋼板製造用の冷延板に脱炭焼
鈍を施した後、表面酸化層を弗化アンモニウムと硫酸の
混合溶液中で酸洗し溶解除去した。EXAMPLES Example 1 A cold rolled sheet for producing a unidirectional silicon steel sheet having a sheet thickness of 0.225 mm and a Si concentration of 3.30% was subjected to decarburization annealing, and then the surface oxide layer was formed with ammonium fluoride. The solution was removed by dissolution by pickling in a mixed solution of sulfuric acid.
【0059】ついで、アルミナ粉末を静電塗布法で塗布
し、乾燥水素雰囲気中、1200℃、20時間の仕上げ
焼鈍を行なった。こうして調製した二次再結晶の完了し
た一方向性珪素鋼板の表面には無機鉱物質がなく、か
つ、鏡面光沢を有する。Then, alumina powder was applied by an electrostatic coating method, and finish annealing was performed at 1200 ° C. for 20 hours in a dry hydrogen atmosphere. The surface of the thus-prepared secondary recrystallized unidirectional silicon steel sheet is free of inorganic minerals and has a specular gloss.
【0060】この鋼板に対し、窒素25%、水素75
%、露点−3℃の雰囲気中、温度900℃で熱処理を行
なうことで外部酸化型酸化膜を形成させた。ついで、調
製した鋼板に対し、濃度50%のリン酸マグネシウム/
アルミニウム水溶液50ml、濃度30%のコロイダル
シリカ水分散液66ml、無水クロム酸5gからなる混
合液を塗布し、850℃で30秒間焼き付け、張力付与
性の絶縁皮膜を形成させた。With respect to this steel sheet, nitrogen 25%, hydrogen 75
%, The external oxidation type oxide film was formed by performing heat treatment at a temperature of 900 ° C. in an atmosphere having a dew point of −3 ° C. Then, with respect to the prepared steel sheet, magnesium phosphate having a concentration of 50% /
A mixed solution of 50 ml of an aluminum aqueous solution, 66 ml of an aqueous dispersion of colloidal silica having a concentration of 30%, and 5 g of chromic anhydride was applied and baked at 850 ° C. for 30 seconds to form a tension-imparting insulating film.
【0061】この時、鋼板と塗布液との100℃以下に
おける接触時間を3秒(実施例1)と35秒(比較例
1)で行なった。At this time, the contact time between the steel sheet and the coating liquid at 100 ° C. or lower was 3 seconds (Example 1) and 35 seconds (Comparative Example 1).
【0062】こうして調製した絶縁皮膜付き一方向性珪
素鋼板について、直径20mmの円筒に試料を巻き付け
た時の張力付与性絶縁皮膜残存面積率で皮膜密着性を評
価した。結果を表3に示す。With respect to the unidirectional silicon steel sheet with an insulating film thus prepared, the film adhesion was evaluated by the tension-providing insulating film remaining area ratio when the sample was wound around a cylinder having a diameter of 20 mm. The results are shown in Table 3.
【0063】[0063]
【表3】 [Table 3]
【0064】表3から、接触時間35秒、密度低下層比
率40%で張力付与性絶縁皮膜残存面積率90%である
比較例1に比べ、接触時間3秒、密度低下層比率5%で
張力付与性絶縁皮膜残存面積率100%である実施例1
のほうが皮膜密着性が良好で優れていることが解る。From Table 3, as compared with Comparative Example 1 in which the contact time is 35 seconds, the density-reduced layer ratio is 40%, and the tension-providing insulating film residual area ratio is 90%, the contact time is 3 seconds and the density-reduced layer ratio is 5%. Example 1 in which the residual area ratio of the impartable insulating film is 100%
It can be seen that the film has better film adhesion and is superior.
【0065】(実施例2)板厚0.225mm、Si濃
度3.35%の一方向性珪素鋼板製造用の冷延板に脱炭
焼鈍を施し、表面にマグネシアと塩化ビスマスを主体と
する焼鈍分離剤の水スラリ−を塗布し、乾燥した。つい
で、乾燥水素雰囲気中、1200℃、20時間の仕上げ
焼鈍を行ない、表面に無機鉱物質のほとんどない二次再
結晶の完了した一方向性珪素鋼板を得た。Example 2 A cold rolled sheet for producing a unidirectional silicon steel sheet having a sheet thickness of 0.225 mm and a Si concentration of 3.35% was subjected to decarburization annealing, and the surface was annealed mainly with magnesia and bismuth chloride. A water slurry as a separating agent was applied and dried. Then, finish annealing was performed at 1200 ° C. for 20 hours in a dry hydrogen atmosphere to obtain a unidirectional silicon steel sheet in which secondary recrystallization with almost no inorganic mineral substance on the surface was completed.
【0066】この鋼板に対し、窒素25%、水素75
%、露点−15℃の雰囲気中、温度1150℃で熱処理
を行なうことでシリカを主体とする外部酸化型酸化膜を
形成させた。ついで、調製した鋼板に対し、濃度50%
のリン酸マグネシム水溶液50ml、濃度20%のコロ
イダルシリカ水分散液100ml、無水クロム酸5gか
らなる混合液を塗布し、850℃で30秒間焼き付け、
張力付与性の絶縁皮膜を形成させた。この時、鋼板と塗
布液との100℃以下における接触時間を10秒(実施
例2)と25秒(比較例2)で行なった。With respect to this steel sheet, nitrogen 25%, hydrogen 75
%, A heat treatment was performed at a temperature of 1150 ° C. in an atmosphere having a dew point of −15 ° C. to form an external oxidation type oxide film mainly composed of silica. Then, the concentration of the prepared steel sheet is 50%
50 ml of an aqueous magnesium phosphate solution, 100 ml of a 20% aqueous colloidal silica dispersion, and 5 g of chromic anhydride were applied, and baked at 850 ° C. for 30 seconds.
An insulating film having a tension imparting property was formed. At this time, the contact time between the steel sheet and the coating liquid at 100 ° C. or lower was 10 seconds (Example 2) and 25 seconds (Comparative Example 2).
【0067】こうして調製した絶縁皮膜付き一方向性珪
素鋼板について、直径20mmの円筒に試料を巻き付け
た時の張力付与性絶縁皮膜残存面積率で絶縁皮膜の密着
性を評価した。結果を表4に示す。With respect to the unidirectional silicon steel sheet with an insulating coating thus prepared, the adhesion of the insulating coating was evaluated by the tension-providing insulating coating remaining area ratio when the sample was wound around a cylinder having a diameter of 20 mm. The results are shown in Table 4.
【0068】[0068]
【表4】 [Table 4]
【0069】表4から、接触時間25秒、密度低下層比
率35%で張力付与性絶縁皮膜残存面積率90%である
比較例2に比べ、接触時間10秒、密度低下層比率10
%で張力付与性絶縁皮膜残存面積率100%である実施
例2のほうが皮膜密着性が良好で優れていることが解
る。From Table 4, as compared with Comparative Example 2 in which the contact time is 25 seconds, the density-reduced layer ratio is 35%, and the tension-applying insulating film remaining area ratio is 90%, the contact time is 10 seconds and the density-reduced layer ratio is 10.
It can be seen that in Example 2 in which the residual area ratio of the tension-imparting insulating film is 100% in%, the film adhesion is better and superior.
【0070】(実施例3)板厚0.225mm、Si濃
度3.25%の一方向性珪素鋼板製造用の冷延板に脱炭
焼鈍を施し、表面にアルミナを主体とする焼鈍分離剤の
水スラリ−を塗布し、乾燥した。ついで、乾燥水素雰囲
気中、1200℃、20時間の仕上げ焼鈍を行ない、表
面に無機鉱物質がほとんどなく、鏡面光沢を有する二次
再結晶の完了した一方向性珪素鋼板を得た。Example 3 A cold-rolled sheet for producing a unidirectional silicon steel sheet having a plate thickness of 0.225 mm and a Si concentration of 3.25% was subjected to decarburization annealing, and the surface of an annealing separator containing alumina as a main component was used. A water slurry was applied and dried. Then, finish annealing was carried out at 1200 ° C. for 20 hours in a dry hydrogen atmosphere to obtain a unidirectional silicon steel sheet having almost no inorganic mineral substance on the surface and having secondary gloss re-crystallization having a mirror gloss.
【0071】この鋼板に対し、窒素30%、水素70
%、露点−10℃の雰囲気中、温度800℃で熱処理を
行なう事で外部酸化型酸化膜を形成させた。ついで、調
製した鋼板に対し、濃度50%のリン酸アルミニウム水
溶液50ml、濃度20%のコロイダルシリカ水分散液
100ml、無水クロム酸5gからなる混合液を塗布
し、850℃で30秒間焼き付け、張力付与性の絶縁皮
膜を形成させた。With respect to this steel sheet, nitrogen 30%, hydrogen 70%
%, The external oxidation type oxide film was formed by performing heat treatment at a temperature of 800 ° C. in an atmosphere having a dew point of −10 ° C. Then, to the prepared steel sheet, a mixed solution consisting of 50 ml of an aqueous solution of aluminum phosphate having a concentration of 50%, 100 ml of an aqueous dispersion of colloidal silica having a concentration of 20%, and 5 g of chromic anhydride was applied, and baked at 850 ° C. for 30 seconds to apply tension. Formed an insulating film.
【0072】この時、鋼板と塗布液との100℃以下に
おける接触時間を1秒(実施例3)と40秒(比較例
3)で行なった。At this time, the contact time between the steel sheet and the coating liquid at 100 ° C. or lower was 1 second (Example 3) and 40 seconds (Comparative Example 3).
【0073】こうして調製した絶縁皮膜付き一方向性珪
素鋼板について、直径20mmの円筒に試料を巻き付け
た時の張力付与性絶縁皮膜残存面積率で皮膜密着性を評
価した。結果を表5に示す。With respect to the unidirectional silicon steel sheet with an insulating film thus prepared, the film adhesion was evaluated by the tension-providing insulating film remaining area ratio when the sample was wound around a cylinder having a diameter of 20 mm. The results are shown in Table 5.
【0074】[0074]
【表5】 [Table 5]
【0075】表5から、接触時間40秒、密度低下層比
率35%で張力付与性絶縁皮膜残存面積率90%である
比較例3に比べ、接触時間1秒、密度低下層比率5%で
張力付与性絶縁皮膜残存面積率100%である実施例3
のほうが皮膜密着性が良好で優れていることが解る。From Table 5, as compared with Comparative Example 3 in which the contact time is 40 seconds, the density-reduced layer ratio is 35%, and the tension-providing insulating film residual area ratio is 90%, the contact time is 1 second and the density-reduced layer ratio is 5%. Example 3 in which the remaining area ratio of the impartable insulating film is 100%
It can be seen that the film has better film adhesion and is superior.
【0076】(実施例4)板厚0.23mm、Si濃度
3.30%の一方向性珪素鋼板製造用の冷延板に脱炭焼
鈍を施し、表面にマグネシアを主体とする焼鈍分離剤の
水スラリ−を塗布し、乾燥した後、乾燥水素雰囲気中、
1200℃、20時間の仕上げ焼鈍を行なった。こうし
て調製した二次再結晶の完了した一方向性珪素鋼板の表
面にはフォルステライトを主体とする皮膜が生成してい
る。Example 4 A cold-rolled sheet for producing a unidirectional silicon steel sheet having a sheet thickness of 0.23 mm and a Si concentration of 3.30% was subjected to decarburization annealing, and the surface of the annealing separator mainly composed of magnesia was used. After applying a water slurry and drying, in a dry hydrogen atmosphere,
Finish annealing was performed at 1200 ° C. for 20 hours. On the surface of the thus-prepared secondary recrystallized unidirectional silicon steel sheet, a film mainly composed of forsterite is formed.
【0077】ついで、ふっ化アンモニムと硫酸の混合溶
液中で酸洗し、表面皮膜を溶解除去した後、ふっ酸と過
酸化水素水の混合溶液中で化学研磨し、鋼板表面に無機
鉱物質がなく、かつ鏡面光沢をもつ鋼板を得た。この鋼
板に対し、窒素50%、水素50%、露点−10℃の雰
囲気中、温度1050℃で熱処理を行なう事で外部酸化
型酸化膜を形成させた。Then, after pickling in a mixed solution of ammonium fluoride and sulfuric acid to dissolve and remove the surface film, chemical polishing was carried out in a mixed solution of hydrofluoric acid and hydrogen peroxide solution, and the surface of the steel sheet was covered with inorganic mineral substances. A steel plate having no specular gloss was obtained. This steel sheet was heat-treated at a temperature of 1050 ° C. in an atmosphere of nitrogen 50%, hydrogen 50% and a dew point of −10 ° C. to form an external oxidation type oxide film.
【0078】ついで、調製した鋼板に対し、10%濃度
のコロイダルアルミナ水分散液100ml、不定形アル
ミナ粉末10g、ホウ酸5g、水200mlからなる混
合液を塗布し、900℃で30秒間焼き付け、張力付与
性の絶縁皮膜を形成させた。この時塗布液との接触時間
を0.5秒(実施例4)と50秒(比較例4)の条件で
行なった。Next, to the prepared steel sheet, a mixed solution of 100 ml of 10% aqueous colloidal alumina dispersion, 10 g of amorphous alumina powder, 5 g of boric acid, and 200 ml of water was applied, and baked at 900 ° C. for 30 seconds to give a tension. An imparting insulating film was formed. At this time, the contact time with the coating liquid was 0.5 seconds (Example 4) and 50 seconds (Comparative Example 4).
【0079】こうして調製した絶縁皮膜付き一方向性珪
素鋼板について、直径20mmの円筒に試料を巻き付け
た時の張力付与性絶縁皮膜残存面積率で皮膜密着性を評
価した。結果を表6に示す。With respect to the thus prepared unidirectional silicon steel sheet with an insulating film, the film adhesion was evaluated by the tension-providing insulating film remaining area ratio when the sample was wound around a cylinder having a diameter of 20 mm. The results are shown in Table 6.
【0080】[0080]
【表6】 [Table 6]
【0081】表6から、接触時間50秒、密度低下層比
率35%で張力付与性絶縁皮膜残存面積率90%である
比較例4に比べ、接触時間0.5秒、密度低下層比率1
%で張力付与性絶縁皮膜残存面積率100%である実施
例4のほうが皮膜密着性が良好で優れていることが解
る。From Table 6, as compared with Comparative Example 4 in which the contact time is 50 seconds, the density-reduced layer ratio is 35%, and the residual area ratio of the tension-giving insulating film is 90%, the contact time is 0.5 seconds and the density-reduced layer ratio is 1.
It can be seen that the adhesiveness of the film of Example 4 in which the residual area ratio of the tension-imparting insulating film is 100% is better and the film adhesion is better.
【0082】[0082]
【発明の効果】本発明により、張力付与性絶縁皮膜密着
性に優れる一方向性珪素鋼板を製造し、エネルギーロス
の少ない磁気鉄芯材料を提供することができる。According to the present invention, it is possible to produce a unidirectional silicon steel sheet having excellent adhesion to a tension-imparting insulating film and provide a magnetic iron core material with less energy loss.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村上 健一 福岡県北九州市戸畑区飛幡町1−1 新日 本製鐵株式会社八幡製鐵所内 (72)発明者 牛神 義行 千葉県富津市新富20−1 新日本製鐵株式 会社技術開発本部内 (72)発明者 中村 修一 千葉県富津市新富20−1 新日本製鐵株式 会社技術開発本部内 (72)発明者 杉山 昌章 千葉県富津市新富20−1 新日本製鐵株式 会社技術開発本部内 Fターム(参考) 4K026 AA03 AA22 BA03 BA12 BB05 CA16 CA23 CA41 DA02 EA04 EA07 EB11 5E041 AA02 BC01 BC08 CA01 HB11 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kenichi Murakami 1-1 Tobata-cho, Tobata-ku, Kitakyushu, Fukuoka Inside the Yawata Works of Hontan Works (72) Inventor Yoshiyuki Ushigami 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares Company Technology Development Division (72) Inventor Shuichi Nakamura 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares Company Technology Development Division (72) Inventor Masaaki Sugiyama 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares Company Technology Development Division F term (reference) 4K026 AA03 AA22 BA03 BA12 BB05 CA16 CA23 CA41 DA02 EA04 EA07 EB11 5E041 AA02 BC01 BC08 CA01 HB11
Claims (4)
酸洗等の手段により除去したりあるいはその生成を意図
的に防止して製造した後、張力付与性絶縁皮膜を形成し
た一方向性珪素鋼板であって、張力付与性絶縁皮膜と鋼
板との界面に、膜厚が2nm以上500nm以下のシリ
カ主体の外部酸化型酸化膜を有し、かつ、該酸化膜の張
力付与性絶縁皮膜との界面部分の密度低下層の平均厚さ
が該酸化膜全厚の30%以下であることを特徴とする張
力付与性絶縁皮膜密着性に優れる一方向性珪素鋼板。1. A unidirectional silicon steel sheet on which a tension imparting insulating film is formed after the inorganic mineral film such as forsterite is removed by means such as pickling or intentionally prevented from producing the film. And an interface between the tension-imparting insulating film and the steel sheet has an external oxidation type oxide film mainly composed of silica and having a thickness of 2 nm or more and 500 nm or less, and the interface of the oxide film with the tension-imparting insulating film. A unidirectional silicon steel sheet having excellent adhesion to a tension-imparting insulating film, characterized in that the average thickness of the density-reduced layer in a portion is 30% or less of the total thickness of the oxide film.
コロイド状シリカを主体とする塗布液を焼き付けること
によって形成した張力付与性絶縁皮膜であることを特徴
とする請求項1記載の張力付与性絶縁皮膜密着性に優れ
る一方向性珪素鋼板。2. The tension-imparting insulating film according to claim 1, wherein the tension-imparting insulating film is formed by baking a coating liquid mainly containing phosphate and colloidal silica. A unidirectional silicon steel sheet with excellent adhesion to the insulating coating.
ルとほう酸を主体とする塗布液を焼き付けることによっ
て形成した張力付与性絶縁皮膜であることを特徴とする
請求項1記載の張力付与性絶縁皮膜密着性に優れる一方
向性珪素鋼板。3. The tension-imparting insulation film according to claim 1, wherein the tension-imparting insulation film is formed by baking a coating solution mainly containing alumina sol and boric acid. Unidirectional silicon steel sheet with excellent adhesion.
酸洗等の手段により除去したりあるいはその生成を意図
的に防止して製造した仕上げ焼鈍済み一方向性珪素鋼板
に対し、張力付与性絶縁皮膜と鋼板との密着性を確保す
るため、張力付与性絶縁皮膜の形成に先立ち、シリカを
主体とする外部酸化型酸化膜を形成させた後、張力付与
性絶縁皮膜形成用の塗布液を塗布し、焼き付けることに
よって張力付与性絶縁皮膜を形成して一方向性珪素鋼板
を製造する方法において、張力付与性絶縁皮膜形成用塗
布液とシリカ主体の外部酸化型酸化膜を形成させた鋼板
とが100℃以下の温度域で接触している時間を20秒
以下にして、張力付与性絶縁皮膜を形成することを特徴
とする張力付与性絶縁皮膜密着性に優れる一方向性珪素
鋼板の製造方法。4. A tension-imparting insulation for a finish-annealed unidirectional silicon steel sheet produced by removing an inorganic mineral film such as forsterite by means such as pickling or intentionally preventing its formation. In order to secure the adhesion between the film and the steel sheet, an external oxidation type oxide film mainly composed of silica is formed before the formation of the tension-imparting insulating film, and then a coating liquid for forming the tension-imparting insulating film is applied. Then, in the method for producing a unidirectional silicon steel sheet by forming a tension-imparting insulating coating by baking, a coating solution for forming a tension-imparting insulating coating and a steel sheet on which a silica-based external oxidation type oxide film is formed are used. A method for producing a unidirectional silicon steel sheet having excellent adhesion to a tension-imparting insulating film, which comprises forming the tension-imparting insulating film for 20 seconds or less in a temperature range of 100 ° C. or less.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019013354A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel plate |
WO2019013352A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel plate |
WO2019013355A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel plate |
WO2019013348A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel sheet |
WO2020149349A1 (en) * | 2019-01-16 | 2020-07-23 | 日本製鉄株式会社 | Grain-oriented electromagnetic steel sheet and method for manufacturing same |
WO2020149342A1 (en) | 2019-01-16 | 2020-07-23 | 日本製鉄株式会社 | Grain-oriented electrical steel sheet |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5848630A (en) * | 1981-09-17 | 1983-03-22 | Nippon Steel Corp | Heat treatment of directional electrical steel plate in treatment of insulating coat |
JPH02267276A (en) * | 1989-04-07 | 1990-11-01 | Nippon Steel Corp | Treatment of insulating film of grain oriented electrical steel sheet having excellent magnetic characteristic and film characteristic |
JPH0356679A (en) * | 1989-07-21 | 1991-03-12 | Nkk Corp | Method for baking insulating coating film for electrical steel sheet |
JPH06184762A (en) * | 1992-08-25 | 1994-07-05 | Nippon Steel Corp | Formation of insulated film on grain-oriented silicon steel sheet |
JPH07278833A (en) * | 1994-04-15 | 1995-10-24 | Nippon Steel Corp | Method for forming insulating film on grain-oriented silicon steel sheet |
JPH08191010A (en) * | 1995-01-06 | 1996-07-23 | Kawasaki Steel Corp | Orientation silicon steel plate of excellent magnetic characteristic and its manufacturing method |
JPH0978252A (en) * | 1995-09-13 | 1997-03-25 | Nippon Steel Corp | Formation of insulating film on grain-oriented silicon steel sheet |
JPH10110271A (en) * | 1996-10-04 | 1998-04-28 | Kawasaki Steel Corp | Formation of insulating coating film excellent in corrosion resistance on surface of non-oriented silicon steel sheet |
-
2002
- 2002-04-08 JP JP2002105175A patent/JP4044781B2/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5848630A (en) * | 1981-09-17 | 1983-03-22 | Nippon Steel Corp | Heat treatment of directional electrical steel plate in treatment of insulating coat |
JPH02267276A (en) * | 1989-04-07 | 1990-11-01 | Nippon Steel Corp | Treatment of insulating film of grain oriented electrical steel sheet having excellent magnetic characteristic and film characteristic |
JPH0356679A (en) * | 1989-07-21 | 1991-03-12 | Nkk Corp | Method for baking insulating coating film for electrical steel sheet |
JPH06184762A (en) * | 1992-08-25 | 1994-07-05 | Nippon Steel Corp | Formation of insulated film on grain-oriented silicon steel sheet |
JPH07278833A (en) * | 1994-04-15 | 1995-10-24 | Nippon Steel Corp | Method for forming insulating film on grain-oriented silicon steel sheet |
JPH08191010A (en) * | 1995-01-06 | 1996-07-23 | Kawasaki Steel Corp | Orientation silicon steel plate of excellent magnetic characteristic and its manufacturing method |
JPH0978252A (en) * | 1995-09-13 | 1997-03-25 | Nippon Steel Corp | Formation of insulating film on grain-oriented silicon steel sheet |
JPH10110271A (en) * | 1996-10-04 | 1998-04-28 | Kawasaki Steel Corp | Formation of insulating coating film excellent in corrosion resistance on surface of non-oriented silicon steel sheet |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20200022016A (en) | 2017-07-13 | 2020-03-02 | 닛폰세이테츠 가부시키가이샤 | Directional electronic steel sheet |
WO2019013355A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel plate |
WO2019013354A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel plate |
US11225706B2 (en) | 2017-07-13 | 2022-01-18 | Nippon Steel Corporation | Grain-oriented electrical steel sheet |
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