JP2664337B2 - Method for forming insulating film on unidirectional silicon steel sheet - Google Patents
Method for forming insulating film on unidirectional silicon steel sheetInfo
- Publication number
- JP2664337B2 JP2664337B2 JP6077204A JP7720494A JP2664337B2 JP 2664337 B2 JP2664337 B2 JP 2664337B2 JP 6077204 A JP6077204 A JP 6077204A JP 7720494 A JP7720494 A JP 7720494A JP 2664337 B2 JP2664337 B2 JP 2664337B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- insulating film
- film
- forming
- tension
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based alloys in the form of sheets with insulating coating
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Soft Magnetic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面にフォルステライト
等、無機鉱物質皮膜を有しない仕上げ焼鈍済みの一方向
性珪素鋼板、更には鏡面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、絶縁性およ
び張力付与性の優れた皮膜を形成する方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a finish-annealed unidirectional silicon steel sheet having no inorganic mineral film such as forsterite on its surface, and a finish-annealed unidirectional steel sheet prepared to a mirror surface or a state close to it. The present invention relates to a method for forming a film having excellent insulating properties and tension imparting properties on a silicon steel sheet.
【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が知られて
いる。鋼板に張力を付与するためには、鋼板より熱膨張
係数の小さい材質からなる皮膜を高温で形成することが
有効である。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。2. Description of the Related Art A grain-oriented silicon steel sheet is widely used as a magnetic iron core material. In particular, a material having a small iron loss is required to reduce energy loss. It is known that applying a tension to a steel sheet is effective in reducing iron loss. In order to impart tension to a steel sheet, it is effective to form a film made of a material having a smaller coefficient of thermal expansion than the steel sheet at a high temperature. The forsterite-based coating formed by the reaction between the oxide on the steel sheet surface and the annealing separator in the finish annealing step can give tension to the steel sheet and has excellent coating adhesion.
【０００３】更に、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。従って、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
る絶縁コーティングを施す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。Further, the method of forming an insulating film by baking a coating solution mainly composed of colloidal silica and phosphate disclosed in Japanese Patent Application Laid-Open No. 48-39338 has a large effect of applying tension to a steel sheet. It is effective for reducing iron loss. Therefore, it is a general method for producing a unidirectional silicon steel sheet to apply a phosphate-based insulating coating while leaving the forsterite-based film generated in the finish annealing step.
【０００４】一方、最近、フォルステライト系皮膜と地
鉄の乱れた界面構造が、鉄損に対する皮膜張力効果をあ
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させることにより、更なる鉄損低減
を試みる技術が開発された。On the other hand, it has recently become clear that the disordered interface structure between the forsterite-based coating and the ground iron has reduced the effect of the coating tension on iron loss to some extent. Therefore, for example, as disclosed in Japanese Patent Application Laid-Open No. 49-96920, by removing a forsterite-based film generated in the finish annealing step, or performing a mirror finish, and then forming a tension film again. Technology to further reduce iron loss has been developed.
【０００５】ところで、一方向性珪素鋼板製造において
張力付与性の絶縁皮膜形成は、一般に、皮膜原料となる
物質を水溶液あるいは水懸濁液の状態に調製し、それを
鋼板表面に塗布し、その後高温で焼き付けるという手法
が取られる。そのため焼き付け工程において鋼板表面に
塗布された水溶液あるいは水懸濁液から水分の蒸発が起
こり、炉内の雰囲気露点はおよそ＋１０℃から＋４０℃
前後になっているものと推定される。焼き付け炉の雰囲
気ガスは窒素を主体とし、これに数％の水素を含むのが
通常である。従って、水蒸気−窒素−水素が主体で珪素
鋼に対し酸化性の雰囲気となる焼き付け炉の中で張力付
与型の絶縁皮膜を形成され、一方向性珪素鋼板製品とな
る。[0005] In the production of a unidirectional silicon steel sheet, the formation of a tension-imparting insulating film is generally carried out by preparing a material to be a coating material in the form of an aqueous solution or an aqueous suspension, applying it to the surface of the steel sheet, and then applying it. The technique of baking at high temperature is adopted. Therefore, in the baking process, water evaporates from the aqueous solution or water suspension applied to the steel sheet surface, and the atmosphere dew point in the furnace is approximately + 10 ° C to + 40 ° C.
It is presumed that they are before and after. The atmosphere gas of the baking furnace is mainly composed of nitrogen, and usually contains several% of hydrogen. Therefore, a tension-imparting insulating film is formed in a baking furnace in which steam-nitrogen-hydrogen is mainly contained and the atmosphere is oxidizing to silicon steel, and a unidirectional silicon steel sheet product is obtained.
【０００６】このようにして完成した一方向性珪素鋼板
は所望の寸法に剪断され、鉄芯等の製品に加工される。
剪断や加工の際に発生する歪は一方向性珪素鋼板の鉄損
を劣化させるため、歪取り焼鈍と称される焼鈍が施され
る。このとき所定の形状に鋼板同士を積層し、焼鈍され
るのが通常である。従来の張力付与型の絶縁皮膜は非晶
質の状態にあり、熱的には準安定状態にある。そのた
め、歪取り焼鈍の間に積層された鋼板表面で絶縁皮膜同
士が融着し、製品としての組み立てが困難になるという
問題がある。従って、熱的安定性を考えた場合、張力付
与型の絶縁皮膜の主体は熱安定性に優れた結晶質である
ことが望ましい。[0006] The unidirectional silicon steel sheet thus completed is sheared to a desired size and processed into a product such as an iron core.
Since the strain generated during shearing and working deteriorates the iron loss of the unidirectional silicon steel sheet, annealing called strain relief annealing is performed. At this time, the steel sheets are usually laminated in a predetermined shape and then annealed. The conventional tension type insulating film is in an amorphous state and is in a thermally metastable state. Therefore, there is a problem that the insulating films are fused together on the surface of the steel sheets laminated during the strain relief annealing, and it is difficult to assemble the product. Therefore, in consideration of thermal stability, it is desirable that the main component of the tension-imparting insulating film be crystalline having excellent thermal stability.
【０００７】発明者らはこの認識をもとに、種々の絶縁
皮膜原料をフォルステライト系皮膜のない、あるいは更
に鏡面化した鋼板の表面に塗布し、窒素ガスが主体で、
露点が＋１０℃から＋４０℃前後の酸化性雰囲気の中で
焼き付け、その鉄損低減効果を調べた。その結果、焼き
付け中に結晶化する皮膜材質の場合、鉄損低減効果が十
分に発揮されないことがわかった。この点を更に検討し
たところ、焼き付け中に結晶化する皮膜の場合、雰囲気
中の酸化性ガスが皮膜を通して侵入し、鋼板が内部酸化
されることを知見した。一旦、内部酸化が生じると鏡面
化の効果が減退する。[0007] Based on this recognition, the inventors applied various insulating coating materials to the surface of a steel plate having no forsterite coating or having a mirror surface, and mainly using nitrogen gas.
Baking was performed in an oxidizing atmosphere having a dew point of about + 10 ° C. to about + 40 ° C., and the effect of reducing iron loss was examined. As a result, it was found that in the case of a film material that crystallized during baking, the effect of reducing iron loss was not sufficiently exhibited. Further examination of this point has revealed that in the case of a film that crystallizes during baking, an oxidizing gas in the atmosphere penetrates through the film, and the steel sheet is internally oxidized. Once the internal oxidation occurs, the effect of mirror finishing is reduced.
【０００８】そのため、たとえ張力を付与できる絶縁皮
膜を形成させたとしても期待できるほどの鉄損低減効果
が得られない。従って、フォルステライト系皮膜をなく
したり、鏡面化等を施した鋼板に対し、結晶化の起こる
張力付与性の絶縁皮膜を形成する場合、従来の方法だけ
では期待できる鉄損低減効果を十分に引き出すことは困
難であった。For this reason, even if an insulating film capable of imparting tension is formed, an effect of reducing iron loss as expected cannot be obtained. Therefore, in the case where a forsterite-based coating is eliminated or a tension-imparting insulating coating in which crystallization occurs is formed on a steel sheet subjected to mirror finishing, etc., the iron loss reduction effect that can be expected only by the conventional method is sufficiently brought out. It was difficult.
【０００９】[0009]
【発明が解決しようとする課題】本発明はフォルステラ
イト等無機鉱物質皮膜のない鋼板表面に、内部酸化を起
こさず、結晶質の絶縁皮膜を形成させる方法を提供する
ことを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a crystalline insulating film without causing internal oxidation on the surface of a steel sheet having no inorganic mineral material such as forsterite.
【００１０】[0010]
【課題を解決するための手段】本発明は鋼板表面に無機
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、あらかじめ非晶質の酸化物皮膜を形成させ、しかる
後に結晶質の張力付与型の絶縁皮膜を形成することによ
り、内部酸化を起こさせない方法を提供するものであ
る。According to the present invention, an amorphous oxide film is previously formed on a finish-annealed unidirectional silicon steel sheet having no inorganic mineral substance film on the surface of the steel sheet, and thereafter, a crystalline tension is applied. An object of the present invention is to provide a method for preventing internal oxidation by forming an application-type insulating film.
【００１１】本発明の要旨は、次の通りである。 （１）鋼板表面に無機鉱物質皮膜のない仕上げ焼鈍済み
一方向性珪素鋼板に結晶質の張力付与型の絶縁皮膜を形
成する方法において、該鋼板表面に非晶質酸化物皮膜を
形成させた後、結晶質の張力付与型の絶縁皮膜を形成す
ることを特徴とする、一方向性珪素鋼板の絶縁皮膜形成
方法。The gist of the present invention is as follows. (1) In a method of forming a crystalline tension-imparting insulating film on a finish-annealed unidirectional silicon steel sheet having no inorganic mineral substance film on the steel sheet surface, an amorphous oxide film is formed on the steel sheet surface. Thereafter, a method of forming an insulating film on a unidirectional silicon steel sheet, comprising forming a crystalline tension-imparting insulating film.
【００１２】（２）非晶質酸化物皮膜として鋼板片面当
たり１０mg／ｍ2 以上の外部酸化状のＳｉＯ2 を形成す
ることを特徴とする（１）に記載の絶縁皮膜形成方法。 （３）非晶質酸化物皮膜として鋼板片面当たり１ｇ／ｍ
2 以上のリン酸塩を主体とした皮膜を形成することを特
徴とする（１）に記載の絶縁皮膜形成方法。 （４）張力付与型の絶縁皮膜のコーティング液がホウ酸
化合物とアルミナゾルを主体とすることを特徴とする
（１），（２），（３）の何れかに記載の絶縁皮膜形成
方法。(2) The method for forming an insulating film according to (1), wherein an external oxidized SiO 2 of 10 mg / m 2 or more per one side of the steel sheet is formed as an amorphous oxide film. (3) 1 g / m per side of steel sheet as amorphous oxide film
The method for forming an insulating film according to (1), wherein a film mainly composed of two or more phosphates is formed. (4) The method for forming an insulating film according to any one of (1), (2) and (3), wherein the coating liquid for the tension imparting type insulating film is mainly composed of a boric acid compound and alumina sol.
【００１３】[0013]
【作用】結晶質の張力付与型の絶縁皮膜と鋼板との間
に、あらかじめ雰囲気シール性のある皮膜を形成するな
らば、内部酸化を防止できるのではないかと発明者らは
考え検討を重ねた。その結果、鋼板表面にあらかじめ非
晶質の酸化物皮膜を形成させた上で結晶質の絶縁皮膜を
形成させるならば、内部酸化を防止できることを確認し
た。The present inventors have repeatedly studied and thought that if a film having an atmosphere sealing property is formed in advance between a crystalline tension-imparting insulating film and a steel sheet, internal oxidation can be prevented. . As a result, it was confirmed that internal oxidation can be prevented if a crystalline insulating film is formed after an amorphous oxide film is formed on the steel sheet surface in advance.
【００１４】まず、発明者らは非晶質の中間皮膜として
ＳｉＯ2 に着目した。一方向性珪素鋼板は通常３％程度
のＳｉを含有しているので、無機鉱物質皮膜のない一方
向性珪素鋼板を熱処理すれば表面にＳｉＯ2 を形成させ
ることができる。その際、内部酸化状でなく外部酸化状
のＳｉＯ2 が生成するように熱処理条件を選択する必要
がある。First, the inventors focused on SiO 2 as an amorphous intermediate film. Since the grain-oriented silicon steel sheet usually contains about 3% of Si, if a grain-oriented silicon steel sheet without an inorganic mineral substance film is heat-treated, SiO 2 can be formed on the surface. At this time, it is necessary to select heat treatment conditions so that SiO 2 is formed in an external oxidized form instead of an internal oxidized form.
【００１５】内部酸化防止効果のあるＳｉＯ2 量を調べ
るため、３％のＳｉを含有する板厚０．１５mmの仕上げ
焼鈍済みの一方向性電磁鋼板について実験を行った。こ
の試料は脱炭焼鈍後、表面に生成した酸化層を酸洗によ
り除去した後、アルミナ粉末をふりかけて仕上げ焼鈍
し、フォルステライト系皮膜の生成を防止している。こ
のようにして調製した試料の表面は鏡面状態を呈する。In order to examine the amount of SiO 2 having an internal oxidation preventing effect, an experiment was performed on a 0.15 mm-thick finish-annealed unidirectional electrical steel sheet containing 3% Si. In this sample, after decarburizing annealing, an oxide layer formed on the surface is removed by pickling, and then alumina powder is sprinkled to finish-anneal to prevent the formation of a forsterite-based film. The surface of the sample thus prepared exhibits a mirror surface state.
【００１６】次に、作製した鋼板を窒素２５％、水素７
５％、露点０℃以下の雰囲気中で温度７００℃から９５
０℃、時間３０秒から６００秒の種々の条件で焼鈍し、
表面に外部酸化状のＳｉＯ2 を形成させた。形成させた
外部酸化状ＳｉＯ2 は電解抽出法によって採取しＩＣＰ
分析法で定量した。比較例として表面にＳｉＯ2 を形成
させない試料も作製した。Next, the prepared steel sheet was nitrogen 25% and hydrogen 7
5%, temperature from 700 ° C to 95% in an atmosphere with a dew point of 0 ° C or less
Annealing under various conditions of 0 ° C., time 30 seconds to 600 seconds,
External oxidized SiO 2 was formed on the surface. The formed external oxidized SiO 2 is sampled by electrolytic extraction and ICP
It was quantified by an analytical method. As a comparative example, a sample in which SiO 2 was not formed on the surface was also prepared.
【００１７】次に、メタホウ酸とコロイダルアルミナを
主成分とするコーティング液を塗布し、窒素９７％、水
素３％の雰囲気中、８５０℃で９０秒間焼き付けを行っ
た。焼き付けの際、雰囲気露点を１０℃と２０℃にして
焼き付けた。このようにして形成した皮膜は２Ａｌ2 Ｏ
3 ・Ｂ2 Ｏ3 の結晶質を主成分とする皮膜となる。Next, a coating liquid containing metaboric acid and colloidal alumina as main components was applied, and baked at 850 ° C. for 90 seconds in an atmosphere of 97% nitrogen and 3% hydrogen. At the time of baking, baking was performed with the atmospheric dew point set at 10 ° C. and 20 ° C. The coating thus formed is 2Al 2 O
3. A film mainly composed of B 2 O 3 is formed.
【００１８】比較例のＳｉＯ2 を形成させなかった試料
についても、塗布、焼き付けを行い、２Ａｌ2 Ｏ3 ・Ｂ
2 Ｏ3 を主体とする皮膜を形成させた。鋼板の内部酸化
の状況は断面を光学顕微鏡で観察しその有無を判定し
た。結果を図１に示す。図１の中で、○は内部酸化がな
いことを表し、×は内部酸化が起こっていることを表
す。The sample in which SiO 2 was not formed in the comparative example was also coated and baked to obtain 2Al 2 O 3 .B
A film mainly composed of 2 O 3 was formed. The state of the internal oxidation of the steel sheet was determined by observing the cross section with an optical microscope to determine the presence or absence thereof. The results are shown in FIG. In FIG. 1, ○ indicates that there is no internal oxidation, and x indicates that internal oxidation has occurred.
【００１９】焼き付け雰囲気の露点が＋１０℃、＋２０
℃の何れの場合でも、絶縁皮膜形成に先だって、鋼板表
面に１０mg／ｍ2 以上の外部酸化状ＳｉＯ2 を形成させ
るならば、内部酸化を防止できることがわかる。また、
鋼板表面に１０mg／ｍ2 の外部酸化状のＳｉＯ2 を形成
させた場合、絶縁皮膜の密着性も良好であった。なお、
皮膜量の上限値は現在のところ確定できていないが、外
部酸化状であれば占積率を損なわない限りいくら厚くて
も問題ない。Dew point of baking atmosphere is + 10 ° C., +20
It can be seen that in any case of ° C, internal oxidation can be prevented if an external oxidized SiO 2 of 10 mg / m 2 or more is formed on the surface of the steel sheet prior to the formation of the insulating film. Also,
When 10 mg / m 2 of external oxidized SiO 2 was formed on the surface of the steel sheet, the adhesion of the insulating film was also good. In addition,
The upper limit of the coating amount has not been determined at present, but if it is in the form of external oxidation, it does not matter how thick it is, as long as the space factor is not impaired.
【００２０】内部酸化を防止する非晶質酸化物としてＳ
ｉＯ2 以外にも検討を進めた。発明者らは非晶質酸化物
としてリン酸塩について検討した。実験は３％のＳｉを
含有する０．１５mm板厚の仕上げ焼鈍済みの一方向性電
磁鋼板について行った。この試料は脱炭焼鈍後、表面に
生成した酸化層を酸洗により除去した後、アルミナをふ
りかけて仕上げ焼鈍しフォルステライト系皮膜の生成を
防止している。このようにして作製した試料の表面は鏡
面状態を呈している。S as an amorphous oxide for preventing internal oxidation
Investigations other than iO 2 were conducted. The inventors studied phosphate as an amorphous oxide. The experiment was performed on a 0.15 mm-thick finish-annealed grain-oriented electrical steel sheet containing 3% Si. In this sample, after decarburizing annealing, an oxide layer formed on the surface is removed by pickling, and then alumina is sprinkled to finish annealing to prevent formation of a forsterite-based film. The surface of the sample thus prepared has a mirror surface state.
【００２１】この鋼板の上にリン酸アルミニウムを主成
分とするコーティング液を塗布量をかけて塗布し、窒素
９７％、水素３％の雰囲気中、８５０℃で３０秒間焼き
付けを行った。この上に、メタホウ酸とコロイダルアル
ミナを主成分とするコーティング液を塗布し、窒素９７
％、水素３％の雰囲気中、８５０℃で９０秒間焼き付け
を行い、結晶質皮膜を形成させた。焼き付けの際、雰囲
気露点を＋３０℃、＋４０℃にして焼き付けを行った。
鋼板表面の内部酸化の状況は断面を光学顕微鏡で観察
し、その有無を判定した。A coating solution containing aluminum phosphate as a main component was applied on the steel plate in an applied amount, and baked at 850 ° C. for 30 seconds in an atmosphere of 97% nitrogen and 3% hydrogen. On top of this, a coating liquid containing metaboric acid and colloidal alumina as main components is applied, and nitrogen 97
% And hydrogen at 3% for 90 seconds to form a crystalline film. At the time of baking, baking was performed with the atmospheric dew point set at + 30 ° C and + 40 ° C.
The state of the internal oxidation of the steel sheet surface was determined by observing the cross section with an optical microscope to determine the presence or absence thereof.
【００２２】図２は、内部酸化に対するリン酸アルミニ
ウムの皮膜量とメタホウ酸とコロイダルアルミナを主成
分とするコーティング液を焼き付けるときの雰囲気露点
の影響を示す。○は内部酸化がないことを、×は内部酸
化が起こっていることを表す。結晶質の強力付与型の絶
縁皮膜形成に先だって、鋼板表面に１ｇ／ｍ2 以上のリ
ン酸アルミニウム皮膜を形成させた場合、何れの焼き付
け露点においても内部酸化を防止できることがわかる。
なお、リン酸アルミニウム皮膜の量の上限値は確定でき
ていないが、占積率を損なわない範囲であればいくら厚
くても問題ない。FIG. 2 shows the effect of the amount of aluminum phosphate coating on the internal oxidation and the dew point of the atmosphere when baking a coating solution containing metaboric acid and colloidal alumina as main components. ○ indicates no internal oxidation, and x indicates that internal oxidation has occurred. It can be seen that when an aluminum phosphate film of 1 g / m 2 or more was formed on the surface of the steel sheet prior to the formation of the crystalline strength-imparting insulating film, internal oxidation could be prevented at any baking dew point.
Although the upper limit of the amount of the aluminum phosphate film has not been determined, any thickness can be used as long as the space factor is not impaired.
【００２３】現在のところ、非晶質の下地皮膜形成によ
って内部酸化が防止できる理由を次のように推定してい
る。結晶質の張力付与型絶縁皮膜の場合、焼き付け中に
結晶粒界を通って雰囲気中の酸化性ガスが侵入する。こ
こに鋼板が直接、接していると鋼板が内部酸化を受け
る。一方、鋼板との界面に結晶粒界をもたない非晶質皮
膜があると酸化性ガスがこれ以上侵入できない。その結
果、鋼板の内部酸化が防止される。At present, the reason why the internal oxidation can be prevented by the formation of the amorphous undercoat is estimated as follows. In the case of a crystalline tension-imparting insulating film, an oxidizing gas in the atmosphere enters through a crystal grain boundary during baking. If the steel sheet is in direct contact with it, the steel sheet undergoes internal oxidation. On the other hand, if there is an amorphous film having no crystal grain boundary at the interface with the steel sheet, the oxidizing gas cannot enter any more. As a result, internal oxidation of the steel sheet is prevented.
【００２４】張力付与性の結晶質絶縁皮膜を形成するの
に先立ち、鋼板表面の内部酸化を防止する目的で形成す
る酸化物は、外部酸化状のＳｉＯ2 とリン酸アルミニウ
ム皮膜に限定されるものではなく、非晶質酸化物であれ
ば良い。リン酸塩についてもその結晶構造が非晶質であ
れば、金属はアルミニウム（Ａｌ）に限定されるもので
はなく、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）や
その他の金属であってかまわない。Prior to the formation of the tension-imparting crystalline insulating film, the oxides formed for the purpose of preventing internal oxidation of the steel sheet surface are limited to externally oxidized SiO 2 and aluminum phosphate films. Instead, any amorphous oxide may be used. If the crystal structure of the phosphate is also amorphous, the metal is not limited to aluminum (Al), but may be magnesium (Mg), calcium (Ca), or another metal.
【００２５】また、これらのリン酸塩はその金属が１種
または２種以上の混合であってもかまわない。更に、非
晶質のリン酸塩皮膜を形成させるためのコーティング液
にはリン酸塩の原料のほかに、皮膜の結晶性を非晶質に
保つもの、例えばクロム酸やコロイダルシリカ等が含ま
れても良い。更に、外部酸化状のＳｉＯ2 形成と非晶質
リン酸塩形成は組み合わせて実施しても良い。These phosphates may be used alone or in combination of two or more metals. Further, the coating liquid for forming the amorphous phosphate film contains, in addition to the raw material of the phosphate, one that keeps the crystallinity of the film amorphous, such as chromic acid or colloidal silica. May be. Further, the formation of external oxidized SiO 2 and the formation of amorphous phosphate may be performed in combination.
【００２６】[0026]
【実施例】 実施例１ Ｓｉを３％含有する最終板厚０．２３mmに圧延された珪
素鋼に対し、脱炭焼鈍を兼ねて珪素鋼表面にＳｉＯ2 を
含む酸化層を形成させた後、ＭｇＯを主体とする焼鈍分
離剤を塗布し、最終仕上げ焼鈍を行った。このようにし
て焼鈍した一方向性珪素鋼板表面にはフォルステライト
を主体とする皮膜が存在している。このフォルステライ
ト系皮膜付きの鋼板を硫酸とフッ化アンモニウムの水溶
液に浸漬することによりフォルステライト系皮膜を除去
し、更にフッ酸と過酸化水素水の水溶液中で化学研磨し
表面を鏡面状態に仕上げた。Example 1 An oxide layer containing SiO 2 was formed on the surface of a silicon steel containing 3% of Si and rolled to a final thickness of 0.23 mm to serve as decarburization annealing. An annealing separator mainly composed of MgO was applied, and final annealing was performed. A coating mainly composed of forsterite exists on the surface of the annealed silicon steel sheet thus annealed. The steel plate with the forsterite coating is immersed in an aqueous solution of sulfuric acid and ammonium fluoride to remove the forsterite coating, and then chemically polished in an aqueous solution of hydrofluoric acid and hydrogen peroxide to finish the surface to a mirror finish. Was.
【００２７】次に、この試料を水素７５％、窒素２５
％、露点０℃の雰囲気中で９５０℃、６００秒間焼鈍
し、表面に片面当たり５０mg／ｍ2 の非晶質の外部酸化
状のＳｉＯ2 を形成させた。続いて、この鋼板表面にア
ルミナゾル３０重量部、メタホウ酸１５重量部、および
蒸留水を混合した懸濁液を塗布した。これを窒素、水
素、露点２０℃の雰囲気中で８５０℃で９０秒間焼き付
け、結晶質の２Ａｌ2 Ｏ3 ・Ｂ2 Ｏ3 を主体とする皮膜
を形成させた。鋼板表面に非晶質の外部酸化状のＳｉＯ
2 を形成させなかった試料にも同様にメタホウ酸とアル
ミナゾルを主体とする懸濁液を塗布し、焼き付けを行っ
た。結果を表１に示す。絶縁皮膜の焼き付けに先立ち鋼
板表面に非晶質の外部酸化状のＳｉＯ2 を形成させた場
合、内部酸化が防止され、良好な鉄損値をもつ一方向性
珪素鋼板を得ることができる。Next, this sample was subjected to 75% hydrogen and 25% nitrogen.
%, And annealed at 950 ° C. for 600 seconds in an atmosphere having a dew point of 0 ° C. to form 50 mg / m 2 of amorphous external oxidized SiO 2 per surface on the surface. Subsequently, a suspension obtained by mixing 30 parts by weight of alumina sol, 15 parts by weight of metaboric acid, and distilled water was applied to the surface of the steel sheet. This nitrogen, hydrogen, baked for 90 seconds at 850 ° C. in an atmosphere of a dew point of 20 ° C., to form a film mainly composed of 2Al 2 O 3 · B 2 O 3 crystalline. Amorphous external oxidized SiO on the steel plate surface
Similarly, a suspension mainly composed of metaboric acid and alumina sol was applied to the sample in which No. 2 was formed, and baked. Table 1 shows the results. When amorphous external oxidized SiO 2 is formed on the surface of the steel sheet prior to the baking of the insulating film, internal oxidation is prevented and a unidirectional silicon steel sheet having a good iron loss value can be obtained.
【００２８】[0028]
【表１】 [Table 1]
【００２９】実施例２ Ｓｉを３％含有する最終板厚０．１５mmに圧延された珪
素鋼に対し、脱炭焼鈍を行った。続いて脱炭焼鈍の際、
珪素鋼表面に生成するＳｉＯ2 を含む酸化層を酸洗によ
って除去した。次に、アルミナをふりかけ仕上げ焼鈍を
行った。このような方法で調製した鋼板はその表面にフ
ォルステライトをもたず、表面は鏡面状態を呈する。続
いて、この試料を水素７５％、窒素２５％、露点０℃の
雰囲気中で９５０℃、３６０秒間焼鈍し、片面当たり２
０mg／ｍ2 の非晶質の外部酸化状のＳｉＯ2 を形成させ
た。Example 2 Decarburization annealing was performed on a silicon steel containing 3% of Si and rolled to a final thickness of 0.15 mm. Then, at the time of decarburization annealing,
The oxide layer containing SiO 2 formed on the silicon steel surface was removed by pickling. Next, finish annealing was performed by sprinkling alumina. The steel sheet prepared by such a method has no forsterite on its surface, and the surface exhibits a mirror-like state. Subsequently, the sample was annealed at 950 ° C. for 360 seconds in an atmosphere of 75% hydrogen, 25% nitrogen, and a dew point of 0 ° C.
0 mg / m 2 of amorphous external oxidized SiO 2 was formed.
【００３０】次に、この鋼板表面にアルミナゾル３０重
量部、メタホウ酸１５重量部、および蒸留水を混合した
懸濁液を塗布した。これを窒素、水素、露点１０℃の雰
囲気中で８５０℃で９０秒間焼き付け、結晶質の２Ａｌ
2 Ｏ3 ・Ｂ2 Ｏ3 を主体とする皮膜を形成させた。非晶
質の外部酸化状のＳｉＯ2 を形成させなかった試料にも
同様にメタホウ酸とアルミナゾルを主体とする懸濁液を
塗布し、焼き付けを行った。結果を表２に示す。絶縁皮
膜の焼き付けに先立ち鋼板表面に非晶質の外部酸化状の
ＳｉＯ2 を形成させた場合、内部酸化が防止され、良好
な鉄損値を得ることができる。Next, a suspension prepared by mixing 30 parts by weight of alumina sol, 15 parts by weight of metaboric acid, and distilled water was applied to the surface of the steel sheet. This is baked at 850 ° C. for 90 seconds in an atmosphere of nitrogen, hydrogen and a dew point of 10 ° C. to obtain crystalline 2Al
A film mainly composed of 2 O 3 · B 2 O 3 was formed. Similarly, a suspension mainly composed of metaboric acid and alumina sol was applied to a sample on which amorphous external oxidized SiO 2 was not formed, and baked. Table 2 shows the results. When amorphous external oxidized SiO 2 is formed on the surface of the steel sheet prior to the baking of the insulating film, internal oxidation is prevented, and a good iron loss value can be obtained.
【００３１】[0031]
【表２】 [Table 2]
【００３２】実施例３ Ｓｉを３％含有する最終板厚０．１５mmに圧延された珪
素鋼に対し、脱炭焼鈍を行った後、ＭｇＯを主成分とす
る焼鈍分離剤を塗布し仕上げ焼鈍した。このフォルステ
ライト皮膜付きの鋼板を硫酸とフッ化アンモニウムの水
溶液に浸漬することにより、フォルステライト皮膜を除
去した。更にフッ酸と過酸化水素水の水溶液中で化学研
磨し表面を鏡面状態に仕上げた。この試料にリン酸アル
ミニウム５０重量部を含む塗布液を塗布し８５０℃、３
０秒間焼鈍し、片面当たり２．４ｇ／ｍ2 の非晶質のリ
ン酸アルミニウム皮膜を形成させた。Example 3 After decarburizing annealing was performed on a silicon steel containing 3% of Si and rolled to a final thickness of 0.15 mm, an annealing separator containing MgO as a main component was applied and finish annealing was performed. . The forsterite film was removed by immersing the steel sheet with the forsterite film in an aqueous solution of sulfuric acid and ammonium fluoride. Furthermore, the surface was mirror-finished by chemical polishing in an aqueous solution of hydrofluoric acid and hydrogen peroxide. A coating solution containing 50 parts by weight of aluminum phosphate was applied to this sample,
Annealing was performed for 0 second to form an amorphous aluminum phosphate film of 2.4 g / m 2 per side.
【００３３】続いて、これにアルミナゾル３０重量部、
メタホウ酸１５重量部、および蒸留水を混合した懸濁液
を塗布した。これを窒素、水素、露点４０℃の雰囲気中
で８５０℃で９０秒間焼き付け、結晶質の２Ａｌ2 Ｏ3
・Ｂ2 Ｏ3 を主体とする皮膜を形成させた。比較例とし
て鋼板表面にリン酸アルミニウム皮膜を形成させず、直
接、アルミナゾルとメタホウ酸を主成分とするコーティ
ング液を塗布、焼き付けした試料も作製した。結果を表
３に示す。表３から張力付与性の結晶質絶縁皮膜の焼き
付けに先立ち、鋼板表面に非晶質のリン酸アルミニウム
を形成させた場合、内部酸化が防止され、良好な鉄損が
得られる。Subsequently, 30 parts by weight of alumina sol was added thereto,
A suspension in which 15 parts by weight of metaboric acid and distilled water were mixed was applied. This is baked at 850 ° C. for 90 seconds in an atmosphere of nitrogen, hydrogen and a dew point of 40 ° C. to obtain crystalline 2Al 2 O 3
The · B 2 O 3 to form a film mainly. As a comparative example, a sample prepared by directly applying and baking a coating solution containing alumina sol and metaboric acid as main components without forming an aluminum phosphate film on the steel sheet surface was also prepared. Table 3 shows the results. According to Table 3, when amorphous aluminum phosphate is formed on the surface of the steel sheet prior to the baking of the crystalline insulating film capable of imparting tension, internal oxidation is prevented and good iron loss is obtained.
【００３４】[0034]
【表３】 [Table 3]
【００３５】実施例４ Ｓｉを３％含有する最終板厚０．２３mmに圧延された珪
素鋼に対し、脱炭焼鈍を行った。続いて脱炭焼鈍の際、
珪素鋼表面に生成するＳｉＯ2 を含む酸化層を酸洗によ
って除去した。次に、アルミナをふりかけ仕上げ焼鈍を
行った。このような方法で調製した鋼板はその表面にフ
ォルステライトをもたず、表面は鏡面状態を呈する。こ
の試料にリン酸アルミニウム５０重量部を主体とし、こ
れにクロム酸とコロイダルシリカを含む塗布液を塗布
し、８５０℃で３０秒間焼き付け、片面当たり１．５ｇ
／ｍ2 の非晶質のリン酸アルミニウム皮膜を形成させ
た。Example 4 Decarburization annealing was performed on a silicon steel containing 3% of Si and rolled to a final thickness of 0.23 mm. Then, at the time of decarburization annealing,
The oxide layer containing SiO 2 formed on the silicon steel surface was removed by pickling. Next, finish annealing was performed by sprinkling alumina. The steel sheet prepared by such a method has no forsterite on its surface, and the surface exhibits a mirror-like state. A coating liquid containing 50 parts by weight of aluminum phosphate as a main component and containing chromic acid and colloidal silica was applied to the sample, baked at 850 ° C. for 30 seconds, and 1.5 g per side.
/ M 2 of an amorphous aluminum phosphate film.
【００３６】続いて、これにアルミナゾル３０重量部、
メタホウ酸１５重量部、および蒸留水を混合した懸濁液
を塗布した。これを窒素、水素、露点３０℃の雰囲気中
で８５０℃で９０秒間焼き付け、２Ａｌ2 Ｏ3 ・Ｂ2 Ｏ
3 の結晶質を主体とする皮膜を形成させた。比較例とし
てリン酸アルミニウム皮膜を形成させず、アルミナゾル
とメタホウ酸を主成分とするコーティング液を塗布、焼
き付けした試料も作製した。結果を表４に示す。表４か
ら張力付与性の結晶質絶縁皮膜の焼き付けに先立ち、鋼
板表面に非晶質のリン酸アルミニウム皮膜を形成させた
場合、内部酸化が防止され、良好な鉄損が得られる。な
お、何れの実施例においても本発明に比べ、比較例の方
が皮膜形成後の磁束密度（Ｂ8 ）が低い。これは鋼板表
面に内部酸化層が形成され、鋼板断面積に占める鉄の割
合が減少することが原因で、皮膜形成前の素材特性によ
るものではない。本発明はかかる実施例に限定されるも
のではない。Subsequently, 30 parts by weight of alumina sol was added thereto,
A suspension in which 15 parts by weight of metaboric acid and distilled water were mixed was applied. This nitrogen, hydrogen, baked for 90 seconds at 850 ° C. in an atmosphere of a dew point of 30 ℃, 2Al 2 O 3 · B 2 O
A film mainly composed of crystalline 3 was formed. As a comparative example, a sample was also prepared in which an aluminum phosphate film was not formed, and a coating solution containing alumina sol and metaboric acid as main components was applied and baked. Table 4 shows the results. According to Table 4, when an amorphous aluminum phosphate film is formed on the surface of the steel sheet prior to the baking of the crystalline insulating film having a tension imparting property, internal oxidation is prevented and good iron loss is obtained. In each of the examples, the magnetic flux density (B 8 ) of the comparative example after the film formation was lower than that of the present invention. This is due to the fact that an internal oxide layer is formed on the surface of the steel sheet and the ratio of iron to the cross-sectional area of the steel sheet is reduced, and is not due to the material properties before the film is formed. The present invention is not limited to such an embodiment.
【００３７】[0037]
【表４】 [Table 4]
【００３８】[0038]
【発明の効果】本願の絶縁皮膜形成方法により、鋼板表
面にフォルステライト等の無機鉱物質皮膜のない仕上げ
焼鈍済み一方向性珪素鋼板、更には鏡面状態の仕上げ焼
鈍済み一方向性珪素鋼板に対しても結晶質の張力付与性
の絶縁皮膜を形成でき、一方向性珪素鋼板の鉄損値の低
減が可能になるのでその工業的効果は甚大である。According to the method for forming an insulating film of the present invention, a finish-annealed unidirectional silicon steel sheet having no inorganic mineral film such as forsterite on the steel sheet surface and a finish-annealed unidirectional silicon steel sheet having a mirror-finished state can be obtained. However, since the crystalline tension-imparting insulating film can be formed and the iron loss value of the unidirectional silicon steel sheet can be reduced, the industrial effect is enormous.
【図面の簡単な説明】[Brief description of the drawings]
【図１】内部酸化に対する外部酸化状ＳｉＯ2 の量と皮
膜焼き付け時の露点の影響を示す図表。○は内部酸化が
起こっていないことを表し、×は内部酸化が起こってい
ることを表す。FIG. 1 is a chart showing the influence of the amount of externally oxidized SiO 2 on internal oxidation and the dew point during baking of a film. O indicates that internal oxidation has not occurred, and X indicates that internal oxidation has occurred.
【図２】内部酸化に対するリン酸アルミニウム皮膜の量
と皮膜焼き付け時の露点の影響を示す図表。○は内部酸
化が起こっていないことを表し、×は内部酸化が起こっ
ていることを表す。FIG. 2 is a chart showing the effect of the amount of aluminum phosphate film on internal oxidation and the dew point during film baking. O indicates that internal oxidation has not occurred, and X indicates that internal oxidation has occurred.
Claims (4)
焼鈍済み一方向性珪素鋼板に結晶質の張力付与型の絶縁
皮膜を形成する方法において、該鋼板表面に非晶質酸化
物皮膜を形成させた後、結晶質の張力付与型の絶縁皮膜
を形成することを特徴とする一方向性珪素鋼板の絶縁皮
膜形成方法。1. A method for forming a crystalline tension-imparting insulating film on a finish-annealed unidirectional silicon steel sheet having no inorganic mineral substance film on the surface of the steel sheet, wherein an amorphous oxide film is formed on the surface of the steel sheet. Forming a crystalline tension-imparting insulating film after forming the insulating film.
１０mg／ｍ2 以上の外部酸化状のＳｉＯ2 を形成するこ
とを特徴とする請求項１に記載の絶縁皮膜形成方法。 2. The method for forming an insulating film according to claim 1, wherein an external oxidized SiO 2 of 10 mg / m 2 or more per one side of the steel sheet is formed as the amorphous oxide film.
１ｇ／ｍ2 以上のリン酸塩を主体とした皮膜を形成する
ことを特徴とする請求項１に記載の絶縁皮膜形成方法。3. The method for forming an insulating film according to claim 1, wherein a film mainly composed of phosphate of 1 g / m 2 or more per one side of the steel sheet is formed as the amorphous oxide film.
がホウ酸化合物とアルミナゾルを主体とすることを特徴
とする請求項１，２，３の何れかに記載の絶縁皮膜形成
方法。4. The method for forming an insulating film according to claim 1, wherein the coating liquid for the tension-imparting insulating film is mainly composed of a boric acid compound and alumina sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6077204A JP2664337B2 (en) | 1994-04-15 | 1994-04-15 | Method for forming insulating film on unidirectional silicon steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6077204A JP2664337B2 (en) | 1994-04-15 | 1994-04-15 | Method for forming insulating film on unidirectional silicon steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07278833A JPH07278833A (en) | 1995-10-24 |
| JP2664337B2 true JP2664337B2 (en) | 1997-10-15 |
Family
ID=13627304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6077204A Expired - Fee Related JP2664337B2 (en) | 1994-04-15 | 1994-04-15 | Method for forming insulating film on unidirectional silicon steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2664337B2 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3324632B2 (en) * | 1996-01-30 | 2002-09-17 | 新日本製鐵株式会社 | Grain-oriented electrical steel sheet with excellent adhesion and method for forming its insulating film |
| JP3406801B2 (en) * | 1997-05-06 | 2003-05-19 | 新日本製鐵株式会社 | Method for producing low iron loss unidirectional silicon steel sheet |
| JP4025514B2 (en) * | 2001-04-09 | 2007-12-19 | 新日本製鐵株式会社 | Insulating film forming method for unidirectional silicon steel sheet with excellent magnetic properties and film adhesion |
| JP3895943B2 (en) * | 2001-04-13 | 2007-03-22 | 新日本製鐵株式会社 | Method for forming insulating film on grain-oriented electrical steel sheet |
| JP4288022B2 (en) * | 2001-06-08 | 2009-07-01 | 新日本製鐵株式会社 | Unidirectional silicon steel sheet and manufacturing method thereof |
| JP3930696B2 (en) * | 2001-04-23 | 2007-06-13 | 新日本製鐵株式会社 | Unidirectional silicon steel sheet excellent in film adhesion of tension imparting insulating film and method for producing the same |
| JP4044781B2 (en) * | 2002-04-08 | 2008-02-06 | 新日本製鐵株式会社 | Unidirectional silicon steel sheet with excellent tension-providing insulating film adhesion and method for producing the same |
| JP4473489B2 (en) * | 2002-04-25 | 2010-06-02 | 新日本製鐵株式会社 | Unidirectional silicon steel sheet and manufacturing method thereof |
| JP4236431B2 (en) * | 2002-09-05 | 2009-03-11 | 新日本製鐵株式会社 | Method for forming insulating film on grain-oriented electrical steel sheet |
| KR101596446B1 (en) | 2014-08-07 | 2016-03-07 | 주식회사 포스코 | Pre-coating composition for forsterite film-eliminated grain oriented electrical steels, grain oriented electrical steels manufactured by using the same, and method for manufacturing the same grain oriented electrical steels |
| JP6954351B2 (en) | 2017-07-13 | 2021-10-27 | 日本製鉄株式会社 | Directional electrical steel sheet |
| PL3653758T3 (en) | 2017-07-13 | 2022-07-04 | Nippon Steel Corporation | Grain-oriented electrical steel sheet |
| JP6876280B2 (en) | 2017-07-13 | 2021-05-26 | 日本製鉄株式会社 | Directional electrical steel sheet |
| JP6828820B2 (en) | 2017-07-13 | 2021-02-10 | 日本製鉄株式会社 | Manufacturing method of grain-oriented electrical steel sheet and grain-oriented electrical steel sheet |
| WO2019013354A1 (en) | 2017-07-13 | 2019-01-17 | 新日鐵住金株式会社 | Oriented electromagnetic steel plate |
| US11450460B2 (en) | 2017-07-13 | 2022-09-20 | Nippon Steel Corporation | Grain-oriented electrical steel sheet |
| BR112020000266A2 (en) * | 2017-07-13 | 2020-07-14 | Nippon Steel Corporation | oriented electromagnetic steel sheet |
| JP6911598B2 (en) * | 2017-07-13 | 2021-07-28 | 日本製鉄株式会社 | Original plate for grain-oriented electrical steel sheet without glass coating and its manufacturing method and manufacturing method of grain-oriented electrical steel sheet with good adhesion of insulating coating |
| KR102419354B1 (en) | 2017-07-13 | 2022-07-13 | 닛폰세이테츠 가부시키가이샤 | Grain-oriented electrical steel sheet and its manufacturing method |
| JP7027925B2 (en) * | 2018-02-06 | 2022-03-02 | 日本製鉄株式会社 | Electrical steel sheet and its manufacturing method |
| BR112020026927B1 (en) | 2018-07-13 | 2023-10-24 | Nippon Steel Corporation | ELECTRIC STEEL SHEET WITH GRAIN ORIENTED AND PRODUCTION METHOD THEREOF |
| BR112020027000B1 (en) | 2018-07-13 | 2023-10-24 | Nippon Steel Corporation | ELECTRICAL STEEL SHEET WITH GRAIN ORIENTED AND PRODUCTION METHOD OF THE SAME |
| WO2020149342A1 (en) | 2019-01-16 | 2020-07-23 | 日本製鉄株式会社 | Grain-oriented electrical steel sheet |
| EP3913075A4 (en) | 2019-01-16 | 2022-09-07 | Nippon Steel Corporation | Grain-oriented electromagnetic steel sheet and method for manufacturing same |
| WO2020149331A1 (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 |
| KR20210111280A (en) | 2019-01-16 | 2021-09-10 | 닛폰세이테츠 가부시키가이샤 | Grain-oriented electrical steel sheet, intermediate steel sheet for grain-oriented electrical steel sheet, and manufacturing method thereof |
| WO2020149344A1 (en) | 2019-01-16 | 2020-07-23 | 日本製鉄株式会社 | Grain-oriented electromagnetic steel sheet having no forsterite film and exhibiting excellent insulating film adhesion |
| US20220316022A1 (en) * | 2020-04-17 | 2022-10-06 | Nippon Steel Corporation | Non-oriented electrical steel sheet and method for producing same |
| WO2023204269A1 (en) * | 2022-04-21 | 2023-10-26 | 日本製鉄株式会社 | Grain-oriented electromagnetic steel sheet and method for manufacturing same |
-
1994
- 1994-04-15 JP JP6077204A patent/JP2664337B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07278833A (en) | 1995-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2664337B2 (en) | Method for forming insulating film on unidirectional silicon steel sheet | |
| JP3272211B2 (en) | Method of forming insulating film on magnetic domain controlled unidirectional silicon steel sheet | |
| JP4288022B2 (en) | Unidirectional silicon steel sheet and manufacturing method thereof | |
| JP3930696B2 (en) | Unidirectional silicon steel sheet excellent in film adhesion of tension imparting insulating film and method for producing the same | |
| JP4473489B2 (en) | Unidirectional silicon steel sheet and manufacturing method thereof | |
| EP3561085A2 (en) | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet | |
| EP1382717A1 (en) | Unidirectional silicon steel sheet excellent in adhesion of insulating coating film imparting tensile force | |
| JPH05311453A (en) | Production of ultralow iron loss grain-oriented electrical steel sheet | |
| JPH05279864A (en) | Formation of insulated film for grain oriented silicon steel sheet | |
| JP4116702B2 (en) | Method for producing grain-oriented electrical steel sheet | |
| JPH1171683A (en) | Grain oriented silicon steel sheet having high-tension insulating coating film and its treatment | |
| KR102577485B1 (en) | Manufacturing method of grain-oriented electrical steel sheet | |
| JP3172025B2 (en) | Method for forming insulating film on unidirectional silicon steel sheet with good adhesion | |
| JP2698501B2 (en) | Method for forming insulating film on unidirectional silicon steel sheet | |
| JP3272210B2 (en) | Method for forming insulating film on unidirectional silicon steel sheet | |
| JP4044781B2 (en) | Unidirectional silicon steel sheet with excellent tension-providing insulating film adhesion and method for producing the same | |
| JP3406801B2 (en) | Method for producing low iron loss unidirectional silicon steel sheet | |
| JP3065908B2 (en) | Low iron loss unidirectional silicon steel sheet | |
| JP3280844B2 (en) | Method for forming insulating film on unidirectional silicon steel sheet | |
| JP4025514B2 (en) | Insulating film forming method for unidirectional silicon steel sheet with excellent magnetic properties and film adhesion | |
| JP2009019274A (en) | Production method of grain-oriented electromagnetic steel sheet with excellent adhesion to insulating film and extremely low core loss | |
| JP4479047B2 (en) | Method for producing unidirectional electrical steel sheet with extremely low iron loss | |
| JPH06287765A (en) | Formation of tension coating film of grain oriented silicon steel sheet | |
| JP2671084B2 (en) | High magnetic flux density grain-oriented electrical steel sheet having excellent iron loss characteristics and method for producing the same | |
| JP3461712B2 (en) | Unidirectional electrical steel sheet and method for forming insulating film on unidirectional electrical steel sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19970520 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080620 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090620 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090620 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100620 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100620 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110620 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110620 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120620 Year of fee payment: 15 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130620 Year of fee payment: 16 |
|
| LAPS | Cancellation because of no payment of annual fees |